JP7037224B1 - Additives for hydraulic compositions and hydraulic compositions - Google Patents
Additives for hydraulic compositions and hydraulic compositions Download PDFInfo
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- JP7037224B1 JP7037224B1 JP2021119504A JP2021119504A JP7037224B1 JP 7037224 B1 JP7037224 B1 JP 7037224B1 JP 2021119504 A JP2021119504 A JP 2021119504A JP 2021119504 A JP2021119504 A JP 2021119504A JP 7037224 B1 JP7037224 B1 JP 7037224B1
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- 239000000203 mixture Substances 0.000 title claims abstract description 119
- 239000000654 additive Substances 0.000 title claims abstract description 69
- 230000000996 additive effect Effects 0.000 claims abstract description 60
- 125000004432 carbon atom Chemical group C* 0.000 claims description 132
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 74
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 125000006353 oxyethylene group Chemical group 0.000 claims description 44
- 239000003638 chemical reducing agent Substances 0.000 claims description 37
- -1 benzyl phenyl group Chemical group 0.000 claims description 33
- 239000000470 constituent Substances 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 30
- 150000002430 hydrocarbons Chemical group 0.000 claims description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 125000003342 alkenyl group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 4
- 229910052751 metal Chemical group 0.000 claims description 4
- 239000002184 metal Chemical group 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 claims description 4
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 claims description 4
- 229920006163 vinyl copolymer Polymers 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000010419 fine particle Substances 0.000 abstract description 47
- 239000004927 clay Substances 0.000 abstract description 13
- 238000010586 diagram Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 18
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- 238000011156 evaluation Methods 0.000 description 15
- 238000005227 gel permeation chromatography Methods 0.000 description 15
- 238000013329 compounding Methods 0.000 description 14
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- 235000019441 ethanol Nutrition 0.000 description 9
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- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 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 6
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- 238000003786 synthesis reaction Methods 0.000 description 6
- 125000006032 3-methyl-3-butenyl group Chemical group 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 5
- 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 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 5
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000006038 hexenyl group Chemical group 0.000 description 5
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 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 5
- 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 5
- 125000001196 nonadecyl 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])[H] 0.000 description 5
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 5
- 125000001400 nonyl 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])[H] 0.000 description 5
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 5
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 5
- 125000002347 octyl 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])[H] 0.000 description 5
- 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 5
- 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 5
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 5
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 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 5
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 5
- 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 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
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- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002511 behenyl 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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003901 ceryl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229940097037 decylene glycol Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- 125000000755 henicosyl 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])C([H])([H])[H] 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000002463 lignoceryl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000002819 montanyl 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])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
- 125000001802 myricyl 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])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
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- YLQLIQIAXYRMDL-UHFFFAOYSA-N propylheptyl alcohol Chemical compound CCCCCC(CO)CCC YLQLIQIAXYRMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- TYWMIZZBOVGFOV-UHFFFAOYSA-N tetracosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCO TYWMIZZBOVGFOV-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229940057402 undecyl alcohol Drugs 0.000 description 1
- 230000000007 visual effect Effects 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
- C04B24/02—Alcohols; Phenols; Ethers
-
- 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
- C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
-
- 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
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Lubricants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
【課題】品質が十分でなく粘土質等の微粒成分等の含有量のばらつきが大きい骨材を使用しても、微粒成分等の多少に起因する性状の変化が抑制され、一定の性状（粘性、流動性等）が得られ、更に、その使用量が少なくても良い水硬性組成物用添加剤を提供する。【解決手段】一般式（１）で示されるＡ成分と、一般式（２）で示されるＢ成分と、を含有することを特徴とする水硬性組成物用添加剤。【選択図】なしPROBLEM TO BE SOLVED: To suppress a change in properties due to a certain amount of fine particles and the like even if an aggregate having insufficient quality and a large variation in the content of fine particles such as clay is used, and certain properties (viscosity). , Fluidity, etc.), and further provides an additive for a hydraulic composition which may be used in a small amount. An additive for a hydraulic composition, which comprises an A component represented by the general formula (1) and a B component represented by the general formula (2). [Selection diagram] None
Description
本発明は、水硬性組成物用添加剤及び水硬性組成物に関する。更に詳しくは、コンクリート等の水硬性組成物に添加される水硬性組成物用添加剤及びこれが添加された水硬性組成物に関する。 The present invention relates to an additive for a hydraulic composition and a hydraulic composition. More specifically, the present invention relates to an additive for a hydraulic composition added to a hydraulic composition such as concrete, and a hydraulic composition to which the additive is added.
近年、川砂等における良質な細骨材が枯渇しつつあり、それに起因して、以前は使用されていなかった品質が十分でない細骨材が採用される傾向がある。つまり、細骨材として、粘土質等の微粒成分等の含有量のばらつきが大きいものが使用される傾向がある。このような細骨材を用いると、得られる水硬性組成物は、例えば、通常の水セメント比（Ｗ／Ｃ）であってもフレッシュ状態（粘性、流動性等）がばらつき、作業性が低下する。 In recent years, high-quality fine aggregates such as river sand are being depleted, and as a result, there is a tendency for fine aggregates of insufficient quality that have not been used before to be adopted. That is, as the fine aggregate, there is a tendency to use a material having a large variation in the content of fine particles such as clay. When such a fine aggregate is used, the obtained hydraulic composition has, for example, a variation in fresh state (viscosity, fluidity, etc.) even at a normal water-cement ratio (W / C), resulting in reduced workability. do.
このようなフレッシュ状態のばらつきは、水硬性組成物用減水剤として汎用的に使用されているポリカルボン酸系共重合体が特に顕著な影響を受けるために生じることが分かっている。そして、これが、近年の水硬性組成物の品質安定性の低下の原因の一つとなっている。 It has been found that such variations in the fresh state occur because polycarboxylic acid-based copolymers, which are generally used as water reducing agents for hydraulic compositions, are particularly significantly affected. And this is one of the causes of the deterioration of the quality stability of the hydraulic composition in recent years.
そこで、粘土質等の微粒成分等の含有量のばらつきが大きい細骨材を使用する場合にも、流動保持性やフレッシュ時の粘性やモルタルの状態を改善でき、コンクリート等の水硬性組成物に優れた性状を与えることのできる水硬性組成物用添加剤（例えば、特許文献１参照）等が報告されている。 Therefore, even when a fine aggregate having a large variation in the content of fine particles such as clay can be used, the fluid retention property, the viscosity at the time of freshness, and the state of mortar can be improved, and the hydraulic composition such as concrete can be used. Additives for hydraulic compositions that can give excellent properties (see, for example, Patent Document 1) and the like have been reported.
また、流動性が高い生コンクリートや生モルタルを製造するために、球状凝固体からなる特定の細骨材を使用することが報告されている（例えば、特許文献２参照）。 Further, it has been reported that a specific fine aggregate made of a spherical solid body is used to produce ready-mixed concrete and ready-made mortar having high fluidity (see, for example, Patent Document 2).
しかしながら、特許文献１に記載の水硬性組成物用添加剤は、更なる改良の余地があり、また、特許文献２の記載の細骨材を採用することは、細骨材の供給面や費用面等から現実的でない。そのため、品質が十分でなく粘土質等の微粒成分等の含有量のばらつきが大きい骨材を使用しても、粘性、流動性等の性状が維持される新たな水硬性組成物用添加剤の開発が求められていた。 However, the additive for hydraulic composition described in Patent Document 1 has room for further improvement, and the adoption of the fine aggregate described in Patent Document 2 has a supply aspect and cost of the fine aggregate. It is not realistic from the aspect. Therefore, a new additive for hydraulic composition that maintains properties such as viscosity and fluidity even when aggregates with insufficient quality and large variations in the content of fine particles such as clay are used. Development was required.
そこで、本発明は、上記実情に鑑み、品質が十分でなく粘土質等の微粒成分等の含有量のばらつきが大きい骨材を使用しても、微粒成分等の多少に起因する性状の変化が抑制され、一定の性状（粘性、流動性等）が得られ、更に、その使用量が少なくても良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。 Therefore, in view of the above circumstances, in the present invention, even if an aggregate having insufficient quality and a large variation in the content of fine particles such as clay is used, the properties of the present invention may change due to the slightness of the fine particles and the like. It is an object of the present invention to provide an additive for a hydraulic composition which is suppressed and has constant properties (viscosity, fluidity, etc.) and may be used in a small amount.
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、所定のＡ成分及びＢ成分を配合することによって上記課題を解決できることを見出した。本発明によれば、以下の水硬性組成物用添加剤及び水硬性組成物が提供される。 As a result of diligent research to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by blending a predetermined A component and B component. According to the present invention, the following additives for hydraulic composition and hydraulic composition are provided.
［１］ ポリカルボン酸系減水剤と併用され、
下記一般式（１）で示されるＡ成分と、
下記一般式（２）で示されるＢ成分と、を含有し、
前記Ａ成分及び前記Ｂ成分の含有割合の合計を１００質量部としたとき、前記Ａ成分を１５～８５質量部の割合で含有し、前記Ｂ成分を１５～８５質量部の割合で含有することを特徴とする水硬性組成物用添加剤。
[1] Used in combination with a polycarboxylic acid-based water reducing agent,
A component represented by the following general formula (1) and
Containing the B component represented by the following general formula (2),
When the total content ratio of the A component and the B component is 100 parts by mass, the A component is contained in a ratio of 15 to 85 parts by mass, and the B component is contained in a ratio of 15 to 85 parts by mass. An additive for a hydraulic composition characterized by.
［２］ 前記一般式（１）におけるＲ２Ｏは、全オキシアルキレン基中の１５～９０モル％が炭素数２のオキシエチレン基であり、全オキシアルキレン基中の１０～８５モル％が炭素数３のオキシプロピレン基である、前記［１］に記載の水硬性組成物用添加剤。 [ 2 ] In R2O in the general formula (1), 15 to 90 mol% of the total oxyalkylene group is an oxyethylene group having 2 carbon atoms, and 10 to 85 mol% of the total oxyalkylene group is carbon. The additive for a water-hard composition according to the above [1], which is an oxypropylene group of number 3.
［３］ 前記Ｂ成分は、前記一般式（２）におけるＲ４が炭素数１４のモノスチレン化フェニル基であるもの、前記一般式（２）におけるＲ４が炭素数２２のジスチレン化フェニル基であるもの、及び、前記一般式（２）におけるＲ４が炭素数３０のトリスチレン化フェニル基であるものから選択される少なくとも１つを含む、前記［１］または［２］に記載の水硬性組成物用添加剤。 [3] In the component B, R 4 in the general formula (2) is a monostyrenated phenyl group having 14 carbon atoms, and R 4 in the general formula (2) is a distyrene phenyl group having 22 carbon atoms. The water-hardness according to the above [1] or [2], which comprises at least one selected from those having an element and one in which R4 in the general formula (2) is a tristyrenated phenyl group having 30 carbon atoms. Additives for compositions.
［４］ 前記Ｂ成分は、前記一般式（２）におけるＲ４が炭素数３０のトリスチレン化フェニル基であるものを含む、前記［１］～［３］のいずれかに記載の水硬性組成物用添加剤。 [4] The hydraulic composition according to any one of [1] to [3] above, wherein the component B comprises a tristyrene phenyl group having 30 carbon atoms in R4 in the general formula (2). Additives for products.
削除delete
［５］ 更に、下記一般式（３）で示されるＣ成分、及び、下記一般式（４）で示されるＤ成分から選択される少なくとも１つを含有する、前記［１］～［４］のいずれかに記載の水硬性組成物用添加剤。 [ 5 ] Further, the above-mentioned [1] to [4], further containing at least one selected from the C component represented by the following general formula (3) and the D component represented by the following general formula (4). Additive for hydraulic composition according to any one.
［６］ 前記Ａ成分、前記Ｂ成分、及び前記Ｃ成分を含み、前記Ａ成分、前記Ｂ成分、及び前記Ｃ成分の含有割合の合計を１００質量部としたとき、
前記Ａ成分を１０～８０質量部、前記Ｂ成分を１０～８０質量部、及び前記Ｃ成分を０．１～４０質量部の割合で含有する、前記［５］に記載の水硬性組成物用添加剤。
[ 6 ] When the A component, the B component, and the C component are contained, and the total content ratio of the A component, the B component, and the C component is 100 parts by mass.
The hydraulic composition according to the above [ 5 ], which contains the component A in an amount of 10 to 80 parts by mass, the component B in an amount of 10 to 80 parts by mass, and the component C in a proportion of 0.1 to 40 parts by mass. Additive.
［７］ 前記Ａ成分、前記Ｂ成分、及び前記Ｄ成分を含み、前記Ａ成分、前記Ｂ成分、及び前記Ｄ成分の含有割合の合計を１００質量部としたとき、
前記Ａ成分を１０～８０質量部、前記Ｂ成分を１０～８０質量部、及び前記Ｄ成分を０．１～２０質量部の割合で含有する、前記［５］に記載の水硬性組成物用添加剤。
[ 7 ] When the A component, the B component, and the D component are contained, and the total content ratio of the A component, the B component, and the D component is 100 parts by mass.
The hydraulic composition according to the above [ 5 ], which contains the component A in an amount of 10 to 80 parts by mass, the component B in an amount of 10 to 80 parts by mass, and the component D in a proportion of 0.1 to 20 parts by mass. Additive.
［８］ 前記Ａ成分、前記Ｂ成分、前記Ｃ成分、及び前記Ｄ成分を含み、前記Ａ成分、前記Ｂ成分、前記Ｃ成分、及び前記Ｄ成分の含有割合の合計を１００質量部としたとき、
前記Ａ成分を１０～８０質量部、前記Ｂ成分を１０～８０質量部、前記Ｃ成分を０．１～４０質量部、及び前記Ｄ成分を０．１～２０質量部の割合で含有する、前記［５］に記載の水硬性組成物用添加剤。
[ 8 ] When the A component, the B component, the C component, and the D component are contained, and the total content ratio of the A component, the B component, the C component, and the D component is 100 parts by mass. ,
The component A is contained in an amount of 10 to 80 parts by mass, the component B is contained in an amount of 10 to 80 parts by mass, the component C is contained in an amount of 0.1 to 40 parts by mass, and the component D is contained in a proportion of 0.1 to 20 parts by mass. The additive for a hydraulic composition according to the above [ 5 ].
［９］ 下記ポリカルボン酸系減水剤と併用される、前記［１］～［８］に記載の水硬性組成物用添加剤。
ポリカルボン酸系減水剤：下記の一般式（５）で示される化合物から形成される構成単位１、及びビニル基を有するカルボン酸単量体から形成される構成単位２を含み、分子中に占める前記構成単位１及び前記構成単位２の構成割合の合計を１００質量％としたとき、前記構成単位１が１～９９質量％、及び前記構成単位２が９９～１質量％であり、更に、質量平均分子量が１，０００～１，０００，０００であるビニル共重合体。
[ 9 ] The additive for a hydraulic composition according to the above [1] to [ 8 ], which is used in combination with the following polycarboxylic acid-based water reducing agent.
Polycarboxylic acid-based water reducing agent: Containing a structural unit 1 formed of a compound represented by the following general formula (5) and a structural unit 2 formed of a carboxylic acid monomer having a vinyl group, and occupying the molecule. When the total of the constituent ratios of the constituent unit 1 and the constituent unit 2 is 100% by mass, the constituent unit 1 is 1 to 99% by mass, the constituent unit 2 is 99 to 1% by mass, and further, the mass is A vinyl copolymer having an average molecular weight of 1,000 to 1,000,000.
［１０］ 前記［１］～［９］のいずれかに記載の水硬性組成物用添加剤を含有することを特徴とする水硬性組成物。 [ 10 ] A hydraulic composition comprising the additive for a hydraulic composition according to any one of the above [1] to [ 9 ].
本発明の水硬性組成物用添加剤は、品質が十分でなく粘土質等の微粒成分等の含有量のばらつきが大きい骨材を使用しても、微粒成分等の多少に起因する性状の変化が抑制され、一定の性状（粘性、流動性等）が得られ、更に、その使用量が少なくてもよいという効果を奏するものである。 In the additive for hydraulic composition of the present invention, even if an aggregate having insufficient quality and a large variation in the content of fine particles such as clay is used, changes in properties due to some of the fine particles and the like are used. Is suppressed, certain properties (viscosity, fluidity, etc.) can be obtained, and further, the amount used may be small.
本発明の水硬性組成物は、水硬性組成物用添加剤の使用量が少なく、更に、品質が十分でなく粘土質等の微粒成分等の含有量のばらつきが大きい骨材を使用しても、微粒成分等の多少に起因する性状の変化が抑制され、一定の性状（粘性、流動性等）が得られるという効果を奏するものである。 In the hydraulic composition of the present invention, even if an aggregate is used in which the amount of the additive for the hydraulic composition is small, the quality is not sufficient, and the content of fine particles such as clay is large. , Changes in properties due to the amount of fine particles and the like are suppressed, and certain properties (viscosity, fluidity, etc.) can be obtained.
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 mean parts by mass.
（１）水硬性組成物用添加剤：
本発明の水硬性組成物用添加剤は、ポリカルボン酸系減水剤と併用され、一般式（１）で示されるＡ成分と、一般式（２）で示されるＢ成分と、を含有するものである。
(1) Additives for hydraulic composition:
The additive for a hydraulic composition of the present invention is used in combination with a polycarboxylic acid-based water reducing agent and contains a component A represented by the general formula (1) and a component B represented by the general formula (2). Is.
このような水硬性組成物用添加剤は、品質が十分でなく粘土質等の微粒成分等の含有量のばらつきが大きい骨材を使用しても、微粒成分等の多少に起因する性状の変化が抑制され、一定の性状（粘性、流動性等）が得られる。つまり、ロバスト性の高いものである。更に、その使用量が少なくても良好な効果が発揮されるものである。 Even if an aggregate having insufficient quality and a large variation in the content of fine particles such as clay is used, such an additive for a hydraulic composition changes in properties due to some of the fine particles and the like. Is suppressed, and certain properties (viscosity, fluidity, etc.) can be obtained. In other words, it is highly robust. Further, even if the amount used is small, a good effect can be exhibited.
具体的には、従来、粘土質（泥分）を含む微粒成分等を含有する骨材を水硬性組成物に使用した場合、この水硬性組成物の流動性が低下することがある。また、微粒成分等を含む水硬性組成物は、その粘性が上昇し、ポンプ圧送性等の作業性が低下するという問題がある。このような問題に対して、本発明の水硬性組成物用添加剤は、上記構成を採用することにより、水硬性組成物の流動性の低下を抑制するとともに、粘性を低減することで作業性を確保できるものである。更には、骨材の品質にばらつきがあると、それに起因して、得られる水硬性組成物の品質にも差が生じてしまうが、本発明の水硬性組成物用添加剤によれば、水硬性組成物の品質の安定化を図ることができる。 Specifically, when an aggregate containing a fine particle component containing clay (mud) or the like is conventionally used for a hydraulic composition, the fluidity of the hydraulic composition may decrease. Further, the hydraulic composition containing fine particles and the like has a problem that its viscosity increases and workability such as pumping property decreases. In response to such problems, the additive for hydraulic composition of the present invention suppresses the decrease in fluidity of the hydraulic composition by adopting the above configuration and reduces the viscosity to workability. Can be secured. Further, if the quality of the aggregate varies, the quality of the obtained hydraulic composition also differs due to the variation. However, according to the additive for hydraulic composition of the present invention, water The quality of the rigid composition can be stabilized.
ここで、「微粒成分等の含有量にばらつきがある」とは、コンクリート等の水硬性組成物において、その流動性等の性状に大きな差異を生じるような「含有量のばらつき」があることを意味する。つまり、微粒成分等の具体的な含有量の大小に着目するのではなく、水硬性組成物の流動性等の性状を大きく変化させる程に含有量に振れ幅がある場合、「含有量にばらつきがある」ということになる。 Here, "the content of fine particles and the like varies" means that there is a "variation in the content" of a hydraulic composition such as concrete that causes a large difference in properties such as fluidity. means. In other words, instead of paying attention to the specific magnitude of the content of the fine particle component, etc., if the content varies widely enough to significantly change the properties such as the fluidity of the hydraulic composition, "the content varies. There is. "
（１－１）Ａ成分：
Ａ成分は、一般式（１）で示される化合物である。このＡ成分をＢ成分とともに配合することで、微粒成分等の含有量のばらつきが大きい骨材を使用しても、微粒成分等の多少に起因する性状の変化が抑制され、一定の性状（粘性、流動性等）が得られる。更に、その使用量が少なくても良好な効果が発揮されるという効果が発揮される。
(1-1) A component:
The component A is a compound represented by the general formula (1). By blending this A component together with the B component, even if an aggregate having a large variation in the content of the fine particle component or the like is used, the change in the property due to the slight amount of the fine particle component or the like is suppressed, and a certain property (viscosity) is suppressed. , Liquidity, etc.). Further, the effect that a good effect is exhibited even if the amount used is small is exhibited.
Ｒ１は、水素原子、または炭素数１～３０の１～３価アルコールから水酸基を除いた残基である。 R 1 is a residue obtained by removing a hydroxyl group from a hydrogen atom or a 1 to trihydric alcohol having 1 to 30 carbon atoms.
Ｒ１の炭素数１～３０の１～３価アルコールから水酸基を除いた残基としては、例えば、メチルアルコール、エチルアルコール、プロピルアルコール、イソプロピルアルコール、ブチルアルコール、ペンチルアルコール、ヘキシルアルコール、ヘプチルアルコール、オクチルアルコール、２－エチル－ヘキシルアルコール、ノニルアルコール、デシルアルコール、２－プロピル－ヘプチルアルコール、ウンデシルアルコール、ドデシルアルコール、２－ブチル－オクチルアルコール、トリデシルアルコール、テトラデシルアルコール、ヘキサデシルアルコール、オクタデシルアルコール、イソオクタデシルアルコール、オクタデセニルアルコール、エイコシルアルコール、ドコシルアルコール、テトラコシルアルコール、ヘキサコシルアルコール、オクタコシルアルコール、トリアコンチルアルコール、メチレングリコール、エチレングリコール、プロピレングリコール、ブチレングリコール、ペンチレングリコール、ヘキシレングリコール、オクチレングリコール、デシレングリコール、グリセリン、トリメチロールエタン、トリメチロールプロパン、１，３，５－ペンタトリオールから水酸基を除いた残基等を挙げることができる。 Examples of the residue obtained by removing the hydroxyl group from the 1 to trihydric alcohol having 1 to 30 carbon atoms of R 1 include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, and heptyl alcohol. Octyl alcohol, 2-ethyl-hexyl alcohol, nonyl alcohol, decyl alcohol, 2-propyl-heptyl alcohol, undecyl alcohol, dodecyl alcohol, 2-butyl-octyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl Alcohol, isooctadecyl alcohol, octadecenyl alcohol, eikosyl alcohol, docosyl alcohol, tetracosyl alcohol, hexacosyl alcohol, octacosyl alcohol, triacity alcohol, methylene glycol, ethylene glycol, propylene glycol, butylene Examples thereof include glycol, pentylene glycol, hexylene glycol, octylene glycol, decylene glycol, glycerin, trimethylolethane, trimethylolpropane, and residues obtained by removing hydroxyl groups from 1,3,5-pentatriol.
Ｒ２Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独または２種以上とすることができる）であり、炭素数２～４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、オキシブチレン基等が挙げられる。 R2O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of the oxyalkylene groups are present, it may be one kind alone or two or more kinds), and is an oxy having 2 to 4 carbon atoms. Examples of the alkylene group include an oxyethylene group, an oxypropylene group, an oxybutylene group and the like.
Ｒ２Ｏが、２種以上の場合は、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良い。 When there are two or more types of R 2 O, it may be in any form of a random adduct, a block adduct, and an alternate adduct.
このＲ２Ｏは、全オキシアルキレン基中の１５～９０モル％が炭素数２のオキシエチレン基であることが好ましく、全オキシアルキレン基中の１０～８５モル％が炭素数３のオキシプロピレン基であることが好ましい。更に、Ｒ２Ｏは、全オキシアルキレン基中の１５～８０モル％が炭素数２のオキシエチレン基であることが更に好ましく、全オキシアルキレン基中の２０～８５モル％が炭素数３のオキシプロピレン基であることが更に好ましい。このような割合であると、水硬性組成物において更に一定の性状（粘性、流動性等）が得られ、更に、添加剤の使用量がより少なくても良好な効果が得られる。 It is preferable that 15 to 90 mol% of the total oxyalkylene group is an oxyethylene group having 2 carbon atoms, and 10 to 85 mol% of the total oxyalkylene group is an oxypropylene group having 3 carbon atoms. Is preferable. Further, in R2O, it is more preferable that 15 to 80 mol% of the total oxyalkylene group is an oxyethylene group having 2 carbon atoms, and 20 to 85 mol% of the total oxyalkylene group is an oxy having 3 carbon atoms. It is more preferably a propylene group. With such a ratio, more constant properties (viscosity, fluidity, etc.) can be obtained in the hydraulic composition, and a good effect can be obtained even if the amount of the additive used is smaller.
Ｒ３は、水素原子、または炭素数１～２０の炭化水素基であり、水素原子であることが好ましい。 R 3 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and is preferably a hydrogen atom.
Ｒ３の炭素数１～２０の炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ペンチル基、へキシル基、ヘプチル基、オクチル基、イソオクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、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、エチニル基、プロペニル基、ブテニル基、ヘキセニル基、オクテニル基、ノネニル基、デセニル基、ドデセニル基、テトラデセニル基、ヘキサデセニル基、オクタデセニル基等を挙げることができる。 Examples of the hydrocarbon group having 1 to 20 carbon atoms of R 3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group and a nonyl group. , Decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, ethynyl group, propenyl group, butenyl group, hexenyl group, octenyl group, nonenyl group, decenyl Examples thereof include a group, a dodecenyl group, a tetradecenyl group, a hexadecenyl group, an octadecenyl group and the like.
ｍは、１～２００の数であり、１０～２００の数であることが好ましい。なお、ｍは、Ｒ２Ｏの数を示し、式：ｍ＝平均付加モル数／ａで算出される値である。 m is a number of 1 to 200, preferably a number of 10 to 200. In addition, m represents the number of R2O, and is a value calculated by the formula: m = average number of added moles / a.
ａは、１～３の整数である。 a is an integer of 1 to 3.
ａ×ｍは、Ｒ２Ｏの平均付加モル数であり、１～２００を満たし、３０～２００を満たすことが好ましく、６０～２００を満たすことがより好ましい。このような範囲を満たすことにより、水硬性組成物において更に一定の性状（粘性、流動性等）が得られ、更に、添加剤の使用量がより少なくても良好な効果が得られる。一方、ａ×ｍ（即ち、Ｒ２Ｏの平均付加モル数）が２００超であると、得られる水硬性組成物の粘性が上昇してしまい、作業性が低下する。 a × m is the average number of moles of R2O added, preferably 1 to 200 , preferably 30 to 200, and more preferably 60 to 200. By satisfying such a range, more constant properties (viscosity, fluidity, etc.) can be obtained in the hydraulic composition, and a good effect can be obtained even if the amount of the additive used is smaller. On the other hand, when a × m (that is, the average number of moles of R2O added) exceeds 200 , the viscosity of the obtained hydraulic composition increases and the workability decreases.
本明細書において「平均付加モル数」は、製造時の各原料の仕込み比から計算される、ヒドロキシ基や、アミノ基等を有する出発物質（アルコール類、アミン類）１モル当たりに対する、アルキレンオキシドのモル数を意味するものとする。 In the present specification, the "average number of added moles" is an alkylene oxide per mole of a starting substance (alcohols, amines) having a hydroxy group, an amino group, etc., which is calculated from the charging ratio of each raw material at the time of production. It shall mean the number of moles of.
平均付加モル数は、１Ｈ－ＮＭＲを用いて求めることもできる。 The average number of moles added can also be determined using 1 H-NMR.
Ａ成分は、公知の方法を採用して適宜作製することができる。 The component A can be appropriately produced by adopting a known method.
（１－２）Ｂ成分：
Ｂ成分は、一般式（２）で示される化合物である。このＢ成分をＡ成分とともに配合することで、微粒成分等の含有量のばらつきが大きい骨材を使用しても、微粒成分等の多少に起因する性状の変化が抑制され、一定の性状（粘性、流動性等）が得られる。更に、その使用量が少なくても良好な効果が発揮されるという効果が発揮される。
(1-2) B component:
The B component is a compound represented by the general formula (2). By blending this component B together with the component A, even if an aggregate having a large variation in the content of the fine particle component or the like is used, the change in the property due to the amount of the fine particle component or the like is suppressed, and a certain property (viscosity) is suppressed. , Liquidity, etc.). Further, the effect that a good effect is exhibited even if the amount used is small is exhibited.
Ｒ４は、炭素数１３～２７のベンジルフェニル基、炭素数１４～３０のスチレン化フェニル基、またはｐ－クミルフェノールから水酸基を除いた残基である。このような残基であると、得られる水硬性組成物は一定の性状（粘性、流動性等）が得られる。 R4 is a benzylphenyl group having 13 to 27 carbon atoms, a styrated phenyl group having 14 to 30 carbon atoms, or a residue obtained by removing a hydroxyl group from p-cumylphenol. With such residues, the obtained hydraulic composition has certain properties (viscosity, fluidity, etc.).
このＢ成分は、一般式（２）におけるＲ４が炭素数１４のモノスチレン化フェニル基であるもの、一般式（２）におけるＲ４が炭素数２２のジスチレン化フェニル基であるもの、及び、一般式（２）におけるＲ４が炭素数３０のトリスチレン化フェニル基であるものから選択される少なくとも１つを含むものであることが好ましい。このようにＲ４が所定のスチレン化フェニル基を含むものであると、得られる水硬性組成物はより一定の性状（粘性、流動性等）が得られる。 In the B component, R 4 in the general formula (2) is a monostyrene phenyl group having 14 carbon atoms, R 4 in the general formula (2) is a distyrene phenyl group having 22 carbon atoms, and It is preferable that R 4 in the general formula (2) contains at least one selected from those having a tristyrene phenyl group having 30 carbon atoms. When R 4 contains a predetermined styrenated phenyl group as described above, the obtained hydraulic composition has more constant properties (viscosity, fluidity, etc.).
また、Ｂ成分は、一般式（２）におけるＲ４が炭素数３０のトリスチレン化フェニル基であるものを含んでいることが好ましい。つまり、スチレン化フェニル基は、モノ体、ジ体、トリ体が有るが、これらのうちでも、上記トリ体を含んでいることがよい。 Further, the B component preferably contains a tristyrene phenyl group having 30 carbon atoms in R4 in the general formula (2). That is, the styrenated phenyl group includes a mono-form, a di-form, and a tri-form, and among these, it is preferable to include the above-mentioned tri-form.
更には、Ｂ成分は、一般式（２）におけるＲ４が炭素数１４のモノスチレン化フェニル基であるもの（ｂ１成分）、及び、一般式（２）におけるＲ４が炭素数２２のジスチレン化フェニル基であるもの（ｂ２成分）から選択される少なくとも１つと、一般式（２）におけるＲ４が炭素数３０のトリスチレン化フェニル基であるもの（ｂ３成分）と、を含み、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）分析において、ｂ１成分、ｂ２成分、及び、ｂ３成分のピーク面積の総和に占めるｂ３成分のピーク面積の割合が３０％以上であることが好ましく、５０％以上であることが更に好ましい。このような条件を満たすことにより、水硬性組成物用添加剤の使用量がより少なくても良好な効果が発揮される。 Further, as the B component, R 4 in the general formula (2) is a monostyrene phenyl group having 14 carbon atoms (b1 component), and R 4 in the general formula (2) is distyreneized with 22 carbon atoms. A gel permeation comprising at least one selected from those which are phenyl groups (b2 component) and those in which R4 in the general formula (2) is a tristylated phenyl group having 30 carbon atoms (b3 component). In the chromatographic (GPC) analysis, the ratio of the peak area of the b3 component to the total peak areas of the b1 component, the b2 component, and the b3 component is preferably 30% or more, and more preferably 50% or more. preferable. By satisfying such conditions, a good effect can be exhibited even if the amount of the additive for the hydraulic composition used is smaller.
スチレン化フェニル基において、モノ体であるもの（ｂ１成分）、ジ体であるもの（ｂ２成分）、トリ体であるもの（ｂ３成分）の構成比の測定は、上記のようにゲルパーミエーションクロマトグラフィー（ＧＰＣ）によって行うことができる。 Among the styrenated phenyl groups, the measurement of the composition ratio of the mono-form (b1 component), the di-form (b2 component), and the tri-form (b3 component) is performed by gel permeation chromatography as described above. It can be done by imaging (GPC).
Ｒ５Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独または２種以上とすることができる）であり、炭素数２～４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、オキシブチレン基等が挙げられる。 R5 O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of the oxyalkylene groups are present, one type alone or two or more types can be used), and oxy having 2 to 4 carbon atoms. Examples of the alkylene group include an oxyethylene group, an oxypropylene group, an oxybutylene group and the like.
Ｒ５Ｏが、２種以上の場合は、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良い。 When there are two or more types of R5O, it may be in any form of a random adduct, a block adduct, and an alternate adduct.
このようなＲ５Ｏは、全オキシアルキレン基中の１５～９９モル％が炭素数２のオキシエチレン基であることが好ましく、全オキシアルキレン基中の１～８５モル％が炭素数３のオキシプロピレン基であることが好ましい。このような割合であると、水硬性組成物において更に一定の性状（粘性、流動性等）が得られ、更に、添加剤の使用量がより少なくても良好な効果が得られる。 In such R5O, it is preferable that 15 to 99 mol% of the total oxyalkylene group is an oxyethylene group having 2 carbon atoms, and 1 to 85 mol% of the total oxyalkylene group is an oxy having 3 carbon atoms. It is preferably a propylene group. With such a ratio, more constant properties (viscosity, fluidity, etc.) can be obtained in the hydraulic composition, and a good effect can be obtained even if the amount of the additive used is smaller.
Ｒ６は、水素原子、または炭素数１～２０の炭化水素基であり、水素原子、または炭素数１～１０の炭化水素基であることが好ましく、水素原子であることがより好ましい。 R 6 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and more preferably a hydrogen atom.
Ｒ６の炭素数１～２０の炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ペンチル基、へキシル基、ヘプチル基、オクチル基、イソオクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、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、エチニル基、プロペニル基、ブテニル基、ヘキセニル基、オクテニル基、ノネニル基、デセニル基、ドデセニル基、テトラデセニル基、ヘキサデセニル基、オクタデセニル基等を挙げることができる。 Examples of the hydrocarbon group having 1 to 20 carbon atoms of R 6 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group and a nonyl group. , Decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, ethynyl group, propenyl group, butenyl group, hexenyl group, octenyl group, nonenyl group, decenyl Examples thereof include a group, a dodecenyl group, a tetradecenyl group, a hexadecenyl group, an octadecenyl group and the like.
ｎは、Ｒ５Ｏの平均付加モル数であり、１～１５０の数であり、１～１００の数であることが好ましく、１～５０の数であることがより好ましい。このような範囲を満たすことにより、水硬性組成物において更に一定の性状（粘性、流動性等）が得られ、更に、添加剤の使用量がより少なくても良好な効果が得られる。一方、ｎが１５０超であると、得られる水硬性組成物の粘性が上昇してしまい、作業性が低下する。 n is the average number of added moles of R5O, which is a number of 1 to 150, preferably a number of 1 to 100, and more preferably a number of 1 to 50. By satisfying such a range, more constant properties (viscosity, fluidity, etc.) can be obtained in the hydraulic composition, and a good effect can be obtained even if the amount of the additive used is smaller. On the other hand, when n is more than 150, the viscosity of the obtained hydraulic composition increases, and the workability decreases.
Ｂ成分は、公知の方法を採用して適宜作製することができる。 The B component can be appropriately produced by adopting a known method.
（１－３）Ｃ成分及びＤ成分：
本発明の水硬性組成物用添加剤は、更に、下記一般式（３）で示されるＣ成分、及び、下記一般式（４）で示されるＤ成分から選択される少なくとも１つを含有することが好ましい。このようなＣ成分またはＤ成分、或いは、Ｃ成分とＤ成分の両方を含有することで、微粒成分等の含有量のばらつきが大きい骨材を使用しても、微粒成分等の多少に起因する性状の変化が更に抑制され、より安定した性状（粘性、流動性等）の水硬性組成物が得られる。更に、添加剤の使用量がより少なくても良好な効果が得られる。
(1-3) C component and D component:
The additive for a hydraulic composition of the present invention further contains at least one selected from the C component represented by the following general formula (3) and the D component represented by the following general formula (4). Is preferable. Even if an aggregate having a large variation in the content of the fine particle component or the like is used because the C component or the D component or both the C component and the D component are contained, the amount of the fine particle component or the like is caused. Changes in properties are further suppressed, and a hydraulic composition having more stable properties (viscosity, fluidity, etc.) can be obtained. Further, a good effect can be obtained even if the amount of the additive used is smaller.
（１－３ａ）Ｃ成分：
Ｃ成分は、一般式（３）で示される化合物である。このＣ成分を含有することにより、更に高いロバスト性を付与することができる。更に、減水剤に対する水硬性組成物用添加剤の溶解性（相溶性）を改善することができる。
(1-3a) C component:
The C component is a compound represented by the general formula (3). By containing this C component, even higher robustness can be imparted. Further, the solubility (compatibility) of the additive for the hydraulic composition with respect to the water reducing agent can be improved.
Ｒ７は、炭素数１～３０のアルキル基または炭素数２～３０のアルケニル基であり、炭素数６～２２のアルキル基または炭素数６～２２のアルケニル基であることが好ましい。 R 7 is an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms, and is preferably an alkyl group having 6 to 22 carbon atoms or an alkenyl group having 6 to 22 carbon atoms.
Ｒ７の炭素数１～３０のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ペンチル基、へキシル基、ヘプチル基、オクチル基、イソオクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、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、ヘンイコシル基、ドコシル基、テトラコシル基、ヘキサコシル基、オクタコシル基、トリアコンチル基等を挙げることができる。Ｒ７の炭素数２～３０のアルケニル基としては、例えば、エチニル基、プロペニル基、ブテニル基、ヘキセニル基、オクテニル基、ノネニル基、デセニル基、ドデセニル基、テトラデセニル基、ヘキサデセニル基、オクタデセニル基等を挙げることができる。 Examples of the alkyl group having 1 to 30 carbon atoms of R 7 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group and a nonyl group. A decyl group, an undecyl group, a dodecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henicosyl group, a docosyl group, a tetracosyl group, a hexacosyl group, an octacosyl group, a triacontyl group and the like. be able to. Examples of the alkenyl group having 2 to 30 carbon atoms of R 7 include an ethynyl group, a propenyl group, a butenyl group, a hexenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, a tetradecenyl group, a hexadecenyl group, an octadecenyl group and the like. Can be mentioned.
Ｒ８Ｏ，Ｒ９Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独または２種以上とすることができる）であり、炭素数２～４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、オキシブチレン基等が挙げられる。 R 8 O and R 9 O are oxyalkylene groups having 2 to 4 carbon atoms (however, when a plurality of the oxyalkylene groups are present, one kind alone or two or more kinds can be used), and the number of carbon atoms is 2. Examples of the oxyalkylene group of 4 to 4 include an oxyethylene group, an oxypropylene group, an oxybutylene group and the like.
Ｒ８Ｏ及びＲ９Ｏが、２種以上の場合は、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良い。 When there are two or more types of R 8 O and R 9 O, they may be in any form of a random adduct, a block adduct, and an alternate adduct.
Ｒ８Ｏ及びＲ９Ｏは、これらの合計のオキシアルキレン基中の５０モル％以上が、炭素数２のオキシエチレン基であり、７０モル％以上が炭素数２のオキシエチレン基であることが好ましく、９０モル％以上が炭素数２のオキシエチレン基であることが更に好ましい。 In R 8 O and R 9 O, 50 mol% or more of these total oxyalkylene groups are oxyethylene groups having 2 carbon atoms, and 70 mol% or more are oxyethylene groups having 2 carbon atoms. It is preferable that 90 mol% or more is an oxyethylene group having 2 carbon atoms.
ｐは、０～１００の数であり、１～５０の数であることが好ましい。 p is a number from 0 to 100, preferably a number from 1 to 50.
ｑは、０～１００の数であり、１～５０の数であることが好ましい。 q is a number from 0 to 100, preferably a number from 1 to 50.
ｐ＋ｑは、Ｒ８Ｏ及びＲ９Ｏで示される炭素数２～４のオキシアルキレン基の平均付加モル数である。そして、０≦ｐ＋ｑ≦１００の条件を満たし、２≦ｐ＋ｑ≦７０の条件を満たすことが好ましく、３≦ｐ＋ｑ≦５０の条件を満たすことがより好ましい。このような条件を満たすことにより、更に高いロバスト性を付与することができる。 p + q is the average number of moles of oxyalkylene groups having 2 to 4 carbon atoms represented by R 8 O and R 9 O. Then, it is preferable that the condition of 0 ≦ p + q ≦ 100 is satisfied, the condition of 2 ≦ p + q ≦ 70 is satisfied, and the condition of 3 ≦ p + q ≦ 50 is more preferable. By satisfying such conditions, even higher robustness can be imparted.
（１－３ｂ）Ｄ成分：
Ｄ成分は、一般式（４）で示される化合物である。このＤ成分を含有することにより、消泡剤としても作用し、空気量のばらつきを小さくすることができ、更に、流動性を改善することが想定される。
(1-3b) D component:
The D component is a compound represented by the general formula (4). By containing this D component, it also acts as a defoaming agent, it is possible to reduce the variation in the amount of air, and it is expected that the fluidity will be further improved.
Ｒ１０は、炭素数１０～２０のアルキル基、または炭素数１０～２０のアルケニル基であり、１４～１８のアルキル基、または炭素数１４～１８のアルケニル基であることが好ましい。 R 10 is an alkyl group having 10 to 20 carbon atoms or an alkenyl group having 10 to 20 carbon atoms, and preferably an alkyl group having 14 to 18 carbon atoms or an alkenyl group having 14 to 18 carbon atoms.
Ｒ１０の炭素数１０～２０のアルキル基としては、例えば、デシル基、ウンデシル基、ドデシル基、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、イコシル基等を挙げることができる。Ｒ１０の炭素数１０～２０のアルケニル基としては、例えば、デセニル基、ドデセニル基、テトラデセニル基、ヘキサデセニル基、オクタデセニル基等を挙げることができる。 Examples of the alkyl group having 10 to 20 carbon atoms of R 10 include a decyl group, an undecyl group, a dodecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and an icosyl group. can. Examples of the alkenyl group having 10 to 20 carbon atoms of R 10 include a decenyl group, a dodecenyl group, a tetradecenyl group, a hexadecenyl group, an octadecenyl group and the like.
Ｒ１１Ｏ，Ｒ１２Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独または２種以上とすることができる）であり、炭素数２～４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、オキシブチレン基等が挙げられる。 R 11 O and R 12 O are oxyalkylene groups having 2 to 4 carbon atoms (however, when a plurality of the oxyalkylene groups are present, one type alone or two or more types can be used), and the number of carbon atoms is 2. Examples of the oxyalkylene group of 4 to 4 include an oxyethylene group, an oxypropylene group, an oxybutylene group and the like.
Ｒ１１Ｏ及びＲ１２Ｏが２種以上の場合は、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良い。 When there are two or more types of R 11 O and R 12 O, any of the random adduct, the block adduct, and the alternate adduct may be used.
Ｒ１１Ｏ及びＲ１２Ｏは、これらの合計のオキシアルキレン基中の６５モル％以上が、炭素数３または４のオキシアルキレン基であり、７０モル％以上が炭素数３のオキシアルキレン基であることが好ましく、７５モル％以上が炭素数３のオキシアルキレン基であることが更に好ましい。 In R 11 O and R 12 O, 65 mol% or more of these total oxyalkylene groups are oxyalkylene groups having 3 or 4 carbon atoms, and 70 mol% or more are oxyalkylene groups having 3 carbon atoms. It is preferable, and it is more preferable that 75 mol% or more is an oxyalkylene group having 3 carbon atoms.
Ｒ１３は、水素原子、または炭素数１～１０の炭化水素基であり、水素原子であることが好ましい。 R 13 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and is preferably a hydrogen atom.
Ｒ１４は、水素原子、または炭素数１～１０の炭化水素基であり、水素原子であることが好ましい。 R 14 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and is preferably a hydrogen atom.
Ｒ１３、Ｒ１４における炭素数１～１０の炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ペンチル基、へキシル基、ヘプチル基、オクチル基、イソオクチル基、ノニル基、デシル基、エチニル基、プロペニル基、ブテニル基、ヘキセニル基、オクテニル基、ノネニル基、デセニル基等を挙げることができる。 Examples of the hydrocarbon group having 1 to 10 carbon atoms in R 13 and R 14 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and an isooctyl group. , Nonyl group, decyl group, ethynyl group, propenyl group, butenyl group, hexenyl group, octenyl group, nonenyl group, decenyl group and the like.
ｒは、０～１００の数であり、１～７０の数であることが好ましい。 r is a number from 0 to 100, preferably a number from 1 to 70.
ｓは、０～１００の数であり、１～７０の数であることが好ましい。 s is a number from 0 to 100, preferably a number from 1 to 70.
ｒ＋ｓは、Ｒ１１Ｏ及びＲ１２Ｏで示される炭素数２～４のオキシアルキレン基の平均付加モル数である。そして、２０≦ｒ＋ｓ≦１００の条件を満たし、２５≦ｒ＋ｓ≦８０の条件を満たすことが好ましく、３０≦ｒ＋ｓ≦７０の条件を満たすことがより好ましい。このような条件を満たすことにより、より空気量のばらつきを小さくすることができ、更に流動性を改善することができる。 r + s is the average number of moles of oxyalkylene groups having 2 to 4 carbon atoms represented by R 11 O and R 12 O. Then, it is preferable that the condition of 20 ≦ r + s ≦ 100 is satisfied, the condition of 25 ≦ r + s ≦ 80 is satisfied, and the condition of 30 ≦ r + s ≦ 70 is more preferable. By satisfying such conditions, the variation in the amount of air can be further reduced, and the fluidity can be further improved.
Ｃ成分及びＤ成分は、それぞれ公知の方法を採用して適宜作製することができる。 The C component and the D component can be appropriately produced by adopting known methods.
（１－４）各成分の配合割合：
Ａ成分及びＢ成分の含有割合の合計を１００質量部としたとき、Ａ成分を１５～８５質量部の割合で含有し、Ｂ成分を１５～８５質量部の割合で含有し、Ａ成分を２５～７５質量部、Ｂ成分を２５～７５質量部の割合で含有することが好ましい。このような範囲とすると、微粒成分等の含有量のばらつきが大きい骨材を使用しても、微粒成分等の多少に起因する性状の変化が更に抑制され、一定の性状（粘性、流動性等）が得られ、更に、その使用量が更に少なくても十分に効果が得られる。
(1-4) Mixing ratio of each component:
When the total content of the A component and the B component is 100 parts by mass, the A component is contained in a ratio of 15 to 85 parts by mass, the B component is contained in a ratio of 15 to 85 parts by mass, and the A component is contained in 25 parts by mass. It is preferable to contain the component B in an amount of up to 75 parts by mass and a component B in an amount of 25 to 75 parts by mass. Within such a range, even if an aggregate having a large variation in the content of fine particles and the like is used, changes in the properties due to the slightness of the fine particles and the like are further suppressed, and certain properties (viscosity, fluidity, etc.) are suppressed. ) Is obtained, and even if the amount used is smaller, a sufficient effect can be obtained.
Ａ成分、Ｂ成分、及びＣ成分を含み（但し、Ｄ成分は含まない場合）、Ａ成分、Ｂ成分、及びＣ成分の含有割合の合計を１００質量部としたとき、Ａ成分を１０～８０質量部、Ｂ成分を１０～８０質量部、及びＣ成分を０．１～４０質量部の割合で含有することが好ましく、Ａ成分を２０～７０質量部、Ｂ成分を２０～７０質量部、Ｃ成分を０．１～２０質量部の割合で含有することが更に好ましい。このような範囲とすると、微粒成分等の含有量のばらつきが大きい骨材を使用しても、微粒成分等の多少に起因する性状の変化が更に抑制され、一定の性状（粘性、流動性等）が得られ、更に、その使用量が更に少なくても十分に効果が得られる。 When the total content ratio of the A component, the B component, and the C component is 100 parts by mass, the A component is 10 to 80 parts, including the A component, the B component, and the C component (provided that the D component is not contained). It is preferable to contain 10 to 80 parts by mass of the B component and 0.1 to 40 parts by mass of the C component, 20 to 70 parts by mass of the A component, and 20 to 70 parts by mass of the B component. It is more preferable to contain the C component in a proportion of 0.1 to 20 parts by mass. Within such a range, even if an aggregate having a large variation in the content of fine particles and the like is used, changes in the properties due to the slightness of the fine particles and the like are further suppressed, and certain properties (viscosity, fluidity, etc.) are suppressed. ) Is obtained, and even if the amount used is smaller, a sufficient effect can be obtained.
Ａ成分、Ｂ成分、及びＤ成分を含み（但し、Ｃ成分は含まない場合）、Ａ成分、Ｂ成分、及びＤ成分の含有割合の合計を１００質量部としたとき、Ａ成分を１０～８０質量部、Ｂ成分を１０～８０質量部、及びＤ成分を０．１～２０質量部の割合で含有することが好ましく、Ａ成分を２０～７０質量部、Ｂ成分を２０～７０質量部、Ｄ成分を０．１～１５質量部の割合で含有することが更に好ましい。このような範囲とすると、微粒成分等の含有量のばらつきが大きい骨材を使用しても、微粒成分等の多少に起因する性状の変化が更に抑制され、一定の性状（粘性、流動性等）が得られ、更に、その使用量が更に少なくても十分に効果が得られる。 When the total content ratio of the A component, the B component, and the D component is 100 parts by mass, the A component is 10 to 80 parts, including the A component, the B component, and the D component (provided that the C component is not contained). It is preferable to contain 10 to 80 parts by mass of the B component and 0.1 to 20 parts by mass of the D component, 20 to 70 parts by mass of the A component, and 20 to 70 parts by mass of the B component. It is more preferable to contain the D component in a proportion of 0.1 to 15 parts by mass. Within such a range, even if an aggregate having a large variation in the content of fine particles and the like is used, changes in the properties due to the slightness of the fine particles and the like are further suppressed, and certain properties (viscosity, fluidity, etc.) are suppressed. ) Is obtained, and even if the amount used is smaller, a sufficient effect can be obtained.
Ａ成分、Ｂ成分、Ｃ成分、及びＤ成分を含み、Ａ成分、Ｂ成分、Ｃ成分、及びＤ成分の含有割合の合計を１００質量部としたとき、Ａ成分を１０～８０質量部、Ｂ成分を１０～８０質量部、Ｃ成分を０．１～４０質量部、及びＤ成分を０．１～２０質量部の割合で含有することが好ましく、Ａ成分を２０～７０質量部、Ｂ成分を２０～７０質量部、Ｃ成分を０．１～２０質量部、Ｄ成分を０．１～１５質量部の割合で含有することが更に好ましい。このような範囲とすると、微粒成分等の含有量のばらつきが大きい骨材を使用しても、微粒成分等の多少に起因する性状の変化が更に抑制され、一定の性状（粘性、流動性等）が得られ、更に、その使用量が更に少なくても十分に効果が得られる。 It contains A component, B component, C component, and D component, and when the total content ratio of A component, B component, C component, and D component is 100 parts by mass, A component is 10 to 80 parts by mass, B. It is preferable to contain 10 to 80 parts by mass of the component, 0.1 to 40 parts by mass of the C component, and 0.1 to 20 parts by mass of the D component, and 20 to 70 parts by mass of the A component and the B component. Is more preferably contained in a proportion of 20 to 70 parts by mass, the C component in an amount of 0.1 to 20 parts by mass, and the D component in an amount of 0.1 to 15 parts by mass. Within such a range, even if an aggregate having a large variation in the content of fine particles and the like is used, changes in the properties due to the slightness of the fine particles and the like are further suppressed, and certain properties (viscosity, fluidity, etc.) are suppressed. ) Is obtained, and even if the amount used is smaller, a sufficient effect can be obtained.
（１－５）その他の成分：
本発明の水硬性組成物用添加剤は、上述したＡ成分～Ｄ成分以外に、効果が損なわれない範囲内で、その他の成分を更に含有していてもよい。このようなその他の成分としては、例えば、糖類や、オキシカルボン酸塩等からなる凝結遅延成分、リグニンスルホン酸ナトリウム等からなる分散作用を有する成分、陰イオン界面活性剤等からなるＡＥ剤、オキシアルキレン系化合物等からなる消泡剤、アルカノールアミン等からなる硬化促進剤、ポリオキシアルキレンアルキルエーテル等からなる収縮低減剤、セルロースエーテル系化合物等からなる増粘剤、イソチアゾリン系化合物等からなる防腐剤、亜硝酸塩等からなる防錆剤等を挙げることができる。
(1-5) Other ingredients:
The additive for a hydraulic composition of the present invention may further contain other components in addition to the above-mentioned components A to D as long as the effect is not impaired. Examples of such other components include saccharides, a setting retarding component made of oxycarboxylate and the like, a component having a dispersing action made of sodium lignin sulfonate and the like, an AE agent made of an anionic surfactant and the like, and oxy. A defoaming agent made of an alkylene compound or the like, a curing accelerator made of an alkanolamine or the like, a shrinkage reducing agent made of a polyoxyalkylene alkyl ether or the like, a thickener made of a cellulose ether compound or the like, a preservative made of an isothiazoline compound or the like. , A rust inhibitor composed of nitrite and the like can be mentioned.
その他の成分の含有割合としては、例えば、本発明の水硬性組成物用添加剤全体の０～２０質量％とすることができる。 The content ratio of the other components may be, for example, 0 to 20% by mass of the total additive for the hydraulic composition of the present invention.
更に、本発明の水硬性組成物用添加剤は、水や溶剤で希釈された形態で使用してもよい。 Further, the additive for a hydraulic composition of the present invention may be used in a form diluted with water or a solvent.
（１－６）水硬性組成物用添加剤の使用：
本発明の水硬性組成物用添加剤は、下記ポリカルボン酸系減水剤と併用されることが好ましい。本発明の水硬性組成物用添加剤は、このポリカルボン酸系減水剤と併用することにより、微粒成分等との材料相性を有するポリカルボン酸系減水剤の材料相性を低減させることができ、減水剤の使用量を少なくすることができるとともに、良好な性状（粘性、流動性等）の水硬性組成物が得られる。
(1-6) Use of Additives for Hydraulic Composition:
The additive for a hydraulic composition of the present invention is preferably used in combination with the following polycarboxylic acid-based water reducing agent. When the additive for a water-hardening composition of the present invention is used in combination with this polycarboxylic acid-based water reducing agent, the material compatibility of the polycarboxylic acid-based water reducing agent having material compatibility with fine particle components and the like can be reduced. The amount of the water reducing agent used can be reduced, and a water-hard composition having good properties (viscosity, fluidity, etc.) can be obtained.
ポリカルボン酸系減水剤は、下記の一般式（５）で示される化合物から形成される構成単位１、及びビニル基を有するカルボン酸単量体から形成される構成単位２を含み、分子中に占める構成単位１及び構成単位２の構成割合の合計を１００質量％としたとき、構成単位１が１～９９質量％、及び構成単位２が９９～１質量％である。そして、上記ポリカルボン酸系減水剤は、更に、質量平均分子量が１，０００～１，０００，０００のビニル共重合体である。 The polycarboxylic acid-based water reducing agent contains a structural unit 1 formed of a compound represented by the following general formula (5) and a structural unit 2 formed of a carboxylic acid monomer having a vinyl group in the molecule. When the total of the constituent ratios of the constituent unit 1 and the constituent unit 2 is 100% by mass, the constituent unit 1 is 1 to 99% by mass and the constituent unit 2 is 99 to 1% by mass. The polycarboxylic acid-based water reducing agent is further a vinyl copolymer having a mass average molecular weight of 1,000 to 1,000,000.
（１－６ａ）構成単位１：
構成単位１は、上記一般式（５）で示される化合物から形成されるものである。具体的には、構成単位１は、一般式（５）で示される化合物であるモノマーを材料の１つとして得られるポリマーを構成する１つの構成単位（一般式（５）で示される化合物に由来する構成単位）である。
(1-6a) Constituent unit 1:
The structural unit 1 is formed from the compound represented by the above general formula (5). Specifically, the structural unit 1 is derived from one structural unit (compound represented by the general formula (5)) constituting a polymer obtained by using a monomer which is a compound represented by the general formula (5) as one of the materials. It is a structural unit to be used.
Ｒ１５，Ｒ１６，Ｒ１７は、水素原子、メチル基、及び－（ＣＨ２）ｔＣＯＯＭで示される有機基（但し、ｔは０～２の整数であり、Ｍは水素原子、または金属原子である）である。但し、Ｒ１５，Ｒ１６，Ｒ１７のうち少なくとも１つは、水素原子またはメチル基である。 R 15 , R 16 and R 17 are a hydrogen atom, a methyl group, and an organic group represented by-(CH 2 ) t COMO (where t is an integer of 0 to 2 and M is a hydrogen atom or a metal atom. Is). However, at least one of R 15 , R 16 and R 17 is a hydrogen atom or a methyl group.
Ｒ１８Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独または２種以上とすることができる）であり、炭素数２～４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、オキシブチレン基等が挙げられる。 R 18 O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of the oxyalkylene groups are present, it may be one kind alone or two or more kinds), and is an oxy having 2 to 4 carbon atoms. Examples of the alkylene group include an oxyethylene group, an oxypropylene group, an oxybutylene group and the like.
Ｒ１８Ｏが２種以上の場合は、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良い。 When there are two or more types of R 18 O, any of the random adduct, the block adduct, and the alternate adduct may be used.
Ｒ１９は、水素原子、または炭素数１～２０の炭化水素基であり、水素原子、または炭素数１～５の炭化水素基であることが好ましい。 R 19 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and is preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms.
Ｒ１９の炭素数１～２０の炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ペンチル基、へキシル基、ヘプチル基、オクチル基、イソオクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、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、エチニル基、プロペニル基、ブテニル基、ヘキセニル基、オクテニル基、ノネニル基、デセニル基、ドデセニル基、テトラデセニル基、ヘキサデセニル基、オクタデセニル基等を挙げることができる。 Examples of the hydrocarbon group having 1 to 20 carbon atoms of R 19 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group and a nonyl group. , Decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, ethynyl group, propenyl group, butenyl group, hexenyl group, octenyl group, nonenyl group, decenyl Examples thereof include a group, a dodecenyl group, a tetradecenyl group, a hexadecenyl group, an octadecenyl group and the like.
ｘは０～５の整数であり、０～２の整数であることが好ましい。 x is an integer of 0 to 5, preferably an integer of 0 to 2.
ｙは０または１の整数である。 y is an integer of 0 or 1.
ｚは、Ｒ１８Ｏの平均付加モル数であり、１～３００の数であり、１～２００の数であることが好ましく、１～１５０の数であることがより好ましい。 z is the average number of added moles of R 18 O, which is a number of 1 to 300, preferably a number of 1 to 200, and more preferably a number of 1 to 150.
一般式（５）で示される化合物としては、具体的には、α－アリル－ω－メトキシ－（ポリ）オキシエチレン、α－アリル－ω－メトキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－アリル－ω－ヒドロキシ－（ポリ）オキシエチレン、α－アリル－ω－ヒドロキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－メタリル－ω－ヒドロキシ－（ポリ）オキシエチレン、α－メタリル－ω－メトキシ－（ポリ）オキシエチレン、α－メタリル－ω－ヒドロキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－メタリル－ω－アセチル－（ポリ）オキシエチレン、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－（ポリ）オキシエチレン、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－（３－メチル－３－ブテニル）－ω－ブトキシ－（ポリ）オキシエチレン、α－（３－メチル－３－ブテニル）－ω－アセチル－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－アクリロイル－ω－ヒドロキシ－（ポリ）オキシエチレン、α－アクリロイル－ω－ヒドロキシ－（ポリ）オキシプロピレン、α－アクリロイル－ω－メトキシ－（ポリ）オキシエチレン、α－アクリロイル－ω－メトキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－アクリロイル－ω－ブトキシ－（ポリ）オキシエチレン、α－メタクリロイル－ω－ヒドロキシ－（ポリ）オキシエチレン、α－メタクリロイル－ω－ヒドロキシ－（ポリ）オキシプロピレン、α－メタクリロイル－ω－ヒドロキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－メタクリロイル－ω－メトキシ－（ポリ）オキシエチレン、α－メタクリロイル－ω－メトキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－メタクリロイル－ω－ブトキシ－（ポリ）オキシエチレン、α－ビニル－ω－ヒドロキシ－（ポリ）オキシブチレン（ポリ）オキシエチレン等を挙げることができる。 Specific examples of the compound represented by the general formula (5) include α-allyl-ω-methoxy- (poly) oxyethylene, α-allyl-ω-methoxy- (poly) oxyethylene (poly) oxypropylene, and the like. α-allyl-ω-hydroxy- (poly) oxyethylene, α-allyl-ω-hydroxy- (poly) oxyethylene (poly) oxypropylene, α-metharyl-ω-hydroxy- (poly) oxyethylene, α-metharyl -Ω-methoxy- (poly) oxyethylene, α-metharyl-ω-hydroxy- (poly) oxyethylene (poly) oxypropylene, α-metharyl-ω-acetyl- (poly) oxyethylene, α- (3-methyl) -3-Butenyl) -ω-hydroxy- (poly) oxyethylene, α- (3-methyl-3-butenyl) -ω-hydroxy- (poly) oxyethylene (poly) oxypropylene, α- (3-methyl- 3-Butenyl) -ω-Butoxy- (Poly) Oxyethylene, α- (3-Methyl-3-Butenyl) -ω-Acetyl- (Poly) Oxyethylene (Poly) Oxypropylene, α-Acryloyl-ω-Hydroxy- (Poly) Oxyethylene, α-acryloyl-ω-hydroxy- (poly) oxypropylene, α-acryloyl-ω-methoxy- (poly) oxyethylene, α-acryloyl-ω-methoxy- (poly) oxyethylene (poly) Oxypropylene, α-acryloyl-ω-butoxy- (poly) oxyethylene, α-methacryloyl-ω-hydroxy- (poly) oxyethylene, α-methacryloyl-ω-hydroxy- (poly) oxypropylene, α-methacryloyl-ω -Hydroxy- (poly) oxyethylene (poly) oxypropylene, α-methacryloyl-ω-methoxy- (poly) oxyethylene, α-methacryl-ω-methoxy- (poly) oxyethylene (poly) oxypropylene, α-methacryloyl Examples thereof include -ω-butoxy- (poly) oxyethylene, α-vinyl-ω-hydroxy- (poly) oxybutylene (poly) oxyethylene and the like.
（１－６ｂ）構成単位２：
構成単位２は、ビニル基を有するカルボン酸単量体から形成されるものである。つまり、構成単位２は、ビニル基を有するカルボン酸単量体を材料の１つとして得られるポリマーを構成する１つの構成単位（ビニル基を有するカルボン酸単量体に由来する構成単位）である。
(1-6b) Constituent unit 2:
The structural unit 2 is formed of a carboxylic acid monomer having a vinyl group. That is, the structural unit 2 is one structural unit (a structural unit derived from the carboxylic acid monomer having a vinyl group) constituting the polymer obtained by using the carboxylic acid monomer having a vinyl group as one of the materials. ..
ビニル基を有するカルボン酸単量体としては、具体的には、（メタ）アクリル酸、クロトン酸、（無水）マレイン酸、（無水）イタコン酸、フマル酸、それらの塩から選ばれるもの等を挙げることができる。 Specific examples of the carboxylic acid monomer having a vinyl group include (meth) acrylic acid, crotonic acid, (maleic anhydride) maleic acid, (anhydrous) itaconic acid, fumaric acid, and salts thereof. Can be mentioned.
（１－６ｃ）構成単位３：
上記ビニル共重合体は、更に、分子中に任意の構成単位として、構成単位１及び構成単位２と共重合可能な構成単位３を含んでいてもよい。構成単位３を形成する単量体としては、例えば、（メタ）アリルスルホン酸およびその塩、（メタ）アクリルアミド、アクリロニトリル、（メタ）アクリル酸アルキルエステル等を用いることができる。構成単位３は、１種または２種以上から形成されていてもよい。
(1-6c) Constituent unit 3:
The vinyl copolymer may further contain a structural unit 1 and a structural unit 3 copolymerizable with the structural unit 2 as arbitrary structural units in the molecule. As the monomer forming the structural unit 3, for example, (meth) allylsulfonic acid and a salt thereof, (meth) acrylamide, acrylonitrile, (meth) acrylic acid alkyl ester and the like can be used. The structural unit 3 may be formed of one type or two or more types.
（１－６ｄ）構成割合：
上記ポリカルボン酸系減水剤は、分子中に占める構成単位１及び構成単位２の構成割合の合計を１００質量％としたとき、構成単位１が１～９９質量％、及び構成単位２が９９～１質量％であり、更に、構成単位１が７０～９９質量％、構成単位２が１～３０質量％とすることができる。また、任意の構成単位である構成単位３の構成割合は、分子中に占める構成単位１、構成単位２及び構成単位３の構成割合の合計を１００質量％としたとき、０～２０質量％であり、０～１０質量％とすることができる。
(1-6d) Composition ratio:
In the polycarboxylic acid-based water reducing agent, when the total of the constituent units 1 and 2 in the molecule is 100% by mass, the constituent unit 1 is 1 to 99% by mass and the constituent unit 2 is 99 to 99. It is 1% by mass, and further, the constituent unit 1 can be 70 to 99% by mass, and the constituent unit 2 can be 1 to 30% by mass. Further, the constituent ratio of the constituent unit 3 which is an arbitrary constituent unit is 0 to 20% by mass when the total of the constituent ratios of the constituent unit 1, the constituent unit 2 and the constituent unit 3 in the molecule is 100% by mass. Yes, it can be 0 to 10% by mass.
（１－６ｅ）質量平均分子量：
上記ポリカルボン酸系減水剤は、その質量平均分子量が１，０００～１，０００，０００であり、５，０００～２００，０００とすることが好ましく、５，０００～１００，０００とすることがより好ましい。なお、ポリカルボン酸系減水剤の質量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定することができる。
(1-6e) Mass average molecular weight:
The polycarboxylic acid-based water reducing agent has a mass average molecular weight of 1,000 to 1,000,000, preferably 5,000 to 200,000, and preferably 5,000 to 100,000. More preferred. The mass average molecular weight of the polycarboxylic acid-based water reducing agent can be measured by gel permeation chromatography (GPC).
（１－６ｆ）製造方法：
上記ポリカルボン酸系減水剤は、従来公知の方法を採用して適宜製造することができる。
(1-6f) Manufacturing method:
The polycarboxylic acid-based water reducing agent can be appropriately produced by adopting a conventionally known method.
（２）水硬性組成物：
本発明の水硬性組成物は、本発明の水硬性組成物用添加剤を含有するものである。このような水硬性組成物は、水硬性組成物用添加剤の使用量が少なく、更に、品質が十分でなく粘土質等の微粒成分等の含有量のばらつきが大きい骨材が使用されていても、微粒成分等の多少に起因する性状の変化が抑制され、一定の性状（粘性、流動性等）が得られるものである。
(2) Hydraulic composition:
The hydraulic composition of the present invention contains the additive for the hydraulic composition of the present invention. In such a hydraulic composition, an aggregate is used in which the amount of the additive for the hydraulic composition is small, the quality is not sufficient, and the content of fine particles such as clay is greatly varied. In addition, changes in properties due to the amount of fine particles and the like are suppressed, and constant properties (viscosity, fluidity, etc.) can be obtained.
本発明の水硬性組成物は、従来公知の水硬性組成物と同様に、結合材、水、細骨材、及び粗骨材を含むものとすることができる。 The hydraulic composition of the present invention may contain a binder, water, fine aggregate, and coarse aggregate in the same manner as the conventionally known hydraulic composition.
本発明の水硬性組成物は、本発明の水硬性組成物用添加剤の含有割合について特に制限はなく適宜設定することができるが、本発明の水硬性組成物用添加剤の含有割合は、例えば、結合材１００質量％に対して、固形分換算で、０．００１～３．０質量％の割合とすることができる。 The water-hardening composition of the present invention can be appropriately set without particular limitation on the content ratio of the additive for the water-hardening composition of the present invention, but the content ratio of the additive for the water-hardening composition of the present invention can be appropriately set. For example, the ratio can be 0.001 to 3.0% by mass in terms of solid content with respect to 100% by mass of the binder.
結合材としては、例えば、普通ポルトランドセメント、中庸熱ポルトランドセメント、低熱ポルトランドセメント、早強ポルトランドセメント、耐硫酸塩ポルトランドセメント等の各種ポルトランドセメント、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のセメントを挙げることができる。 Examples of the binder include various Portland cements such as ordinary Portland cement, moderate heat Portland cement, low heat Portland cement, early strength Portland cement, and sulfate resistant Portland cement, and various cements such as blast furnace cement, fly ash cement, and silica fume cement. Can be mentioned.
更に、結合材は、フライアッシュ、高炉スラグ微粉末、石灰石微粉末、石粉、シリカフューム、膨張材等の各種混和材を上述した各種セメントと併用してもよい。 Further, as the binder, various admixtures such as fly ash, blast furnace slag fine powder, limestone fine powder, stone powder, silica fume, and expansion material may be used in combination with the above-mentioned various cements.
細骨材としては、例えば、川砂、山砂、陸砂、海砂、珪砂、砕砂、各種スラグ細骨材等が挙げられるが、粘土質等の微粒成分等を含むものであってもよい。本発明においては、粘土質等の微粒成分等の含有量のばらつきが大きいものであっても良好に使用することができる。 Examples of the fine aggregate include river sand, mountain sand, land sand, sea sand, silica sand, crushed sand, various slag fine aggregates, etc., but may contain fine particles such as clay. In the present invention, even those having a large variation in the content of fine particles such as clay can be used satisfactorily.
ここで、細骨材中における「微粒成分等の含有量にばらつきがある」とは、コンクリート等の水硬性組成物において、その流動性等の性状に大きな差異を生じさせるような「含有量のばらつき」を意味する。つまり、例えば、微粒成分等の含有量が１割程度減少するだけであっても、流動性等の性状が、大きく変化することがある。微粒成分等の許容量の範囲（十分な性状の水硬性組成物が得られる範囲）は、比較的狭く、僅かな含有量の違いであっても、「含有量にばらつきがある」と言えることがある。 Here, "the content of fine particles and the like varies" in the fine aggregate means that "the content of the hydraulic composition such as concrete causes a large difference in properties such as fluidity". It means "variation". That is, for example, even if the content of the fine particle component or the like is reduced by only about 10%, the properties such as fluidity may be significantly changed. The allowable range of fine particles and the like (the range in which a hydraulic composition having sufficient properties can be obtained) is relatively narrow, and even a slight difference in content can be said to be "variation in content". There is.
粗骨材としては、例えば、川砂利、山砂利、陸砂利、砕石、各種スラグ粗骨材、軽量骨材等が挙げられる。 Examples of the coarse aggregate include river gravel, mountain gravel, land gravel, crushed stone, various slag coarse aggregates, and lightweight aggregates.
本発明の水硬性組成物は、効果が損なわれない範囲内で、適宜その他の成分を更に含有していてもよい。このようなその他の成分としては、例えば、糖類や、オキシカルボン酸塩等からなる凝結遅延成分、リグニンスルホン酸ナトリウム等からなる分散作用を有する成分、陰イオン界面活性剤等からなるＡＥ剤、オキシアルキレン系化合物等からなる消泡剤、アルカノールアミン等からなる硬化促進剤、ポリオキシアルキレンアルキルエーテル等からなる収縮低減剤、セルロースエーテル系化合物等からなる増粘剤、イソチアゾリン系化合物等からなる防腐剤、亜硝酸塩等からなる防錆剤等を挙げることができる。 The hydraulic composition of the present invention may further contain other components as appropriate, as long as the effect is not impaired. Examples of such other components include saccharides, a setting retarding component made of oxycarboxylate and the like, a component having a dispersing action made of sodium lignin sulfonate and the like, an AE agent made of an anionic surfactant and the like, and oxy. A defoaming agent made of an alkylene compound or the like, a curing accelerator made of an alkanolamine or the like, a shrinkage reducing agent made of a polyoxyalkylene alkyl ether or the like, a thickener made of a cellulose ether compound or the like, a preservative made of an isothiazoline compound or the like. , A rust inhibitor composed of nitrite and the like can be mentioned.
その他の成分の含有割合としては、例えば、結合材１００質量％に対して、固形分換算で０～５質量％とすることができる。 The content ratio of the other components may be, for example, 0 to 5% by mass in terms of solid content with respect to 100% by mass of the binder.
本発明の水硬性組成物は、その水と結合材の比率（水／結合材比）としては従来公知の割合を適宜採用することができるが、例えば、２５～７０質量％とすることができる。 In the hydraulic composition of the present invention, a conventionally known ratio can be appropriately adopted as the ratio of the water to the binder (water / binder ratio), but it can be, for example, 25 to 70% by mass. ..
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.
まず、使用したＡ成分～Ｄ成分について、以下の表１～表４に示す。 First, the components A to D used are shown in Tables 1 to 4 below.
（Ａ成分）
下記表１には、使用したＡ成分（Ａ－１～Ａ－６、ＲＡ－１）を示す。
(Component A)
Table 1 below shows the A components (A-1 to A-6, RA-1) used.
（Ｂ成分）
下記表２には、使用したＢ成分（Ｂ－１）～（Ｂ－６）を示す。
(B component)
Table 2 below shows the B components (B-1) to (B-6) used.
（スチレン化フェノール中のモノ、ジ、トリ体の構成比の測定）
スチレン化フェノール中のモノ、ジ、トリ体の構成比の測定条件について、下記に示す測定条件に従ってゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて測定した。
＜測定条件＞
装置：ＨＬＣ－８３２０ＧＰＣ（東ソー社製）
検出器：示差屈折計（ＲＩ）
カラム：ＴＳＫ ｇｅｌ ＳｕｐｅｒＨ４０００＋Ｈ３０００＋Ｈ２０００（東ソー社製）
溶離液：ＴＨＦ
流速：０．５ｍＬ／分
カラム温度：４０℃
標準物質：ポリスチレン（東ソー社製）
(Measurement of composition ratio of mono, di, and bird bodies in styrenated phenol)
The measurement conditions for the composition ratios of mono, di, and triforms in the styrenated phenol were measured by gel permeation chromatography (GPC) according to the measurement conditions shown below.
<Measurement conditions>
Equipment: HLC-8320GPC (manufactured by Tosoh)
Detector: Differential Refractometer (RI)
Column: TSK gel Super H4000 + H3000 + H2000 (manufactured by Tosoh)
Eluent: THF
Flow velocity: 0.5 mL / min Column temperature: 40 ° C
Standard material: Polystyrene (manufactured by Tosoh)
（Ｃ成分）
下記表３には、使用したＣ成分（Ｃ－１）～（Ｃ－５）を示す。
(C component)
Table 3 below shows the C components (C-1) to (C-5) used.
（Ｄ成分）
下記表４には、使用したＤ成分（Ｄ－１）～（Ｄ－５）を示す。
(D component)
Table 4 below shows the D components (D-1) to (D-5) used.
（作製例１～４５）
次に、表５に示すように、各成分を混合して水硬性組成物用添加剤（Ｘ－１～Ｘ－４０、ＲＸ－１～ＲＸ－５）を作製した。
(Production Examples 1 to 45)
Next, as shown in Table 5, additives for hydraulic composition (X-1 to X-40, RX-1 to RX-5) were prepared by mixing each component.
次に、表６には、ポリカルボン酸系減水剤（Ｐ－１）～（Ｐ－３）の構成単位について示す。 Next, Table 6 shows the constituent units of the polycarboxylic acid-based water reducing agents (P-1) to (P-3).
表６中、Ｌ－１～Ｌ－４、Ｍ－１、及び、Ｍ－２は、以下の化合物を示し、各構成単位は当該化合物に由来するものである。
Ｌ－１：α－メタクリロイル－ω－メトキシ－ポリ（平均４５モル）オキシエチレン
Ｌ－２：α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（平均５３モル）オキシエチレン
Ｌ－３：α－メタリル－ω－ヒドロキシ－ポリ（平均５３モル）オキシエチレン
Ｌ－４：２－ヒドロキシエチルアクリレート
Ｍ－１：メタクリル酸
Ｍ－２：アクリル酸
In Table 6, L-1 to L-4, M-1 and M-2 indicate the following compounds, and each structural unit is derived from the compound.
L-1: α-methacryloyl-ω-methoxy-poly (average 45 mol) oxyethylene L-2: α- (3-methyl-3-butenyl) -ω-hydroxy-poly (average 53 mol) oxyethylene L- 3: α-Metalyl-ω-hydroxy-poly (average 53 mol) oxyethylene L-4: 2-hydroxyethyl acrylate M-1: methacrylic acid M-2: acrylic acid
以下に、各ポリカルボン酸系減水剤（Ｐ－１）～（Ｐ－３）の合成方法を説明する。 Hereinafter, a method for synthesizing each of the polycarboxylic acid-based water reducing agents (P-1) to (P-3) will be described.
（合成例１）ポリカルボン酸系減水剤（Ｐ－１）の合成：
上水道水４１５．８ｇ、α－メタクリロイル－ω－メトキシ－ポリ（平均４５モル）オキシエチレン３４６．３ｇ、メタクリル酸４４．７ｇ、３－メルカプトプロピオン酸３．９ｇを、温度計、攪拌機、滴下ロート、及び窒素導入管を備えた反応容器に仕込んだ。そして、攪拌しながら均一に溶解した後、雰囲気を窒素置換し、反応系の温度を温水浴にて７０℃に保持した。
(Synthesis Example 1) Synthesis of polycarboxylic acid-based water reducing agent (P-1):
Tap water 415.8 g, α-methacryloyl-ω-methoxy-poly (average 45 mol) oxyethylene 346.3 g, methacrylic acid 44.7 g, 3-mercaptopropionic acid 3.9 g, thermometer, stirrer, dropping funnel, And charged in a reaction vessel equipped with a nitrogen inlet tube. Then, after uniformly dissolving with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was maintained at 70 ° C. in a warm water bath.
次に、上記反応系に１％過酸化水素水溶液５４．８ｇを投入し、２時間かけてラジカル共重合反応を行った。２時間経過後、１％過酸化水素水溶液１３．７ｇを投入し、更に２時間反応を行った後、重合反応を終了した。その後、反応系に３０％水酸化ナトリウム水溶液を投入してｐＨを５に調整し、その後、上水道水にて濃度を４０％に調整して反応混合物を得た。 Next, 54.8 g of a 1% hydrogen peroxide aqueous solution was added to the above reaction system, and a radical copolymerization reaction was carried out over 2 hours. After 2 hours, 13.7 g of a 1% hydrogen peroxide aqueous solution was added, and the reaction was further carried out for 2 hours, and then the polymerization reaction was completed. Then, a 30% aqueous sodium hydroxide solution was added to the reaction system to adjust the pH to 5, and then the concentration was adjusted to 40% with tap water to obtain a reaction mixture.
この反応混合物をゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて分析したところ、質量平均分子量が２５，０００であった。この反応物をポリカルボン酸系減水剤（Ｐ－１）とした。 When this reaction mixture was analyzed by gel permeation chromatography (GPC), the mass average molecular weight was 25,000. This reaction product was designated as a polycarboxylic acid-based water reducing agent (P-1).
（合成例２）ポリカルボン酸系減水剤（Ｐ－２）の合成：
上水道水２０７．４ｇ、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（平均５３モル）オキシエチレン４５６．８ｇを、温度計、攪拌機、滴下ロート、及び窒素導入管を備えた反応容器に仕込んだ。そして、攪拌しながら均一に溶解した後、雰囲気を窒素置換し、反応系の温度を温水浴にて７０℃に保持した。
(Synthesis Example 2) Synthesis of polycarboxylic acid-based water reducing agent (P-2):
207.4 g of tap water, 456.8 g of α- (3-methyl-3-butenyl) -ω-hydroxy-poly (53 mol on average) oxyethylene, equipped with a thermometer, stirrer, dripping funnel, and nitrogen introduction tube. It was charged in a reaction vessel. Then, after uniformly dissolving with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was maintained at 70 ° C. in a warm water bath.
次に、上記反応系に３．５％過酸化水素水溶液２４．８ｇを３時間かけて滴下し、それと同時に、「上水道水１９８．６ｇにアクリル酸３９．７ｇを均一に溶解させた水溶液」を３時間かけて滴下し、更にそれと同時に、「上水道水２１．８ｇにＬ－アスコルビン酸２．０ｇと３－メルカプトプロピオン酸３．５ｇを溶解させた水溶液」を４時間かけて滴下した。その後、反応系の温度を７０℃に２時間維持し、重合反応を終了した。その後、反応系に３０％水酸化ナトリウム水溶液を加えてｐＨが５になるように調整し、その後、上水道水を加えて濃度を４０％に調整して反応混合物を得た。 Next, 24.8 g of a 3.5% hydrogen peroxide aqueous solution was added dropwise to the reaction system over 3 hours, and at the same time, "an aqueous solution in which 39.7 g of acrylic acid was uniformly dissolved in 198.6 g of tap water" was added. The solution was added dropwise over 3 hours, and at the same time, "an aqueous solution prepared by dissolving 2.0 g of L-ascorbic acid and 3.5 g of 3-mercaptopropionic acid in 21.8 g of tap water" was added dropwise over 4 hours. Then, the temperature of the reaction system was maintained at 70 ° C. for 2 hours to complete the polymerization reaction. Then, a 30% aqueous sodium hydroxide solution was added to the reaction system to adjust the pH to 5, and then tap water was added to adjust the concentration to 40% to obtain a reaction mixture.
この反応混合物をゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて分析したところ、質量平均分子量が３５，０００であった。この反応物をポリカルボン酸系減水剤（Ｐ－２）とした。 When this reaction mixture was analyzed by gel permeation chromatography (GPC), the mass average molecular weight was 35,000. This reaction product was designated as a polycarboxylic acid-based water reducing agent (P-2).
（合成例３）ポリカルボン酸系減水剤（Ｐ－３）の合成：
上水道水２３１．１ｇ、α－メタリル－ω－ヒドロキシ－ポリ（平均５３モル）オキシエチレン４２９．２ｇを、温度計、攪拌機、滴下ロート、及び窒素導入管を備えた反応容器に仕込んだ。そして、攪拌しながら均一に溶解した後、雰囲気を窒素置換し、反応系の温度を温水浴にて７０℃に保持した。
(Synthesis Example 3) Synthesis of polycarboxylic acid-based water reducing agent (P-3):
231.1 g of tap water and 429.2 g of α-metharyl-ω-hydroxy-poly (53 mol on average) oxyethylene were charged into a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a nitrogen introduction tube. Then, after uniformly dissolving with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was maintained at 70 ° C. in a warm water bath.
次に、上記反応系に３．５％過酸化水素水溶液２９．２ｇを３時間かけて滴下し、それと同時に、「上水道水４２．０ｇにアクリル酸４８．８ｇ、２－ヒドロキシエチルアクリレート９．８ｇを均一に溶解させた水溶液」を３時間かけて滴下し、更にそれと同時に、「上水道水２７．３ｇにＬ－アスコルビン酸２．０ｇと３－メルカプトプロピオン酸４．９ｇを溶解させた水溶液」を４時間かけて滴下した。その後、反応系の温度を７０℃に２時間維持し、重合反応を終了した。その後、反応系に３０％水酸化ナトリウム水溶液を加えてｐＨが５になるように調整し、その後、上水道水にて濃度を４０％に調整して反応混合物を得た。 Next, 29.2 g of a 3.5% aqueous hydrogen peroxide solution was added dropwise to the above reaction system over 3 hours, and at the same time, "42.0 g of tap water, 48.8 g of acrylic acid, and 9.8 g of 2-hydroxyethyl acrylate" were added. Was added dropwise over 3 hours, and at the same time, "an aqueous solution in which 2.0 g of L-ascorbic acid and 4.9 g of 3-mercaptopropionic acid were dissolved in 27.3 g of tap water" was added. It was dropped over 4 hours. Then, the temperature of the reaction system was maintained at 70 ° C. for 2 hours to complete the polymerization reaction. Then, a 30% aqueous sodium hydroxide solution was added to the reaction system to adjust the pH to 5, and then the concentration was adjusted to 40% with tap water to obtain a reaction mixture.
この反応混合物をゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて分析したところ、質量平均分子量が３０，０００であった。この反応物をポリカルボン酸系減水剤（Ｐ－３）とした。 When this reaction mixture was analyzed by gel permeation chromatography (GPC), the mass average molecular weight was 30,000. This reaction product was designated as a polycarboxylic acid-based water reducing agent (P-3).
（質量平均分子量）
合成したポリカルボン酸系減水剤（Ｐ－１）～（Ｐ－３）の質量平均分子量の測定におけるゲルパーミエーションクロマトグラフィー（ＧＰＣ）の条件を以下に示す。
＜測定条件＞
装置：Ｓｈｏｄｅｘ ＧＰＣ－１０１（昭和電工社製）
カラム：ＯＨｐａｋ ＳＢ－Ｇ＋ＳＢ－８０６Ｍ ＨＱ＋ＳＢ－８０６Ｍ ＨＱ（昭和電工社製）
検出器：示差屈折計（ＲＩ）
溶離液：５０ｍＭ硝酸ナトリウム水溶液
流量：０．７ｍＬ／分
カラム温度：４０℃
試料濃度：試料濃度０．５質量％の溶離液溶液
標準物質：ＰＥＧ／ＰＥＯ（アジレント・テクノロジー社製）
(Mass average molecular weight)
The conditions of gel permeation chromatography (GPC) in the measurement of the mass average molecular weight of the synthesized polycarboxylic acid-based water reducing agents (P-1) to (P-3) are shown below.
<Measurement conditions>
Equipment: Shodex GPC-101 (manufactured by Showa Denko KK)
Column: OHpak SB-G + SB-806M HQ + SB-806M HQ (manufactured by Showa Denko KK)
Detector: Differential Refractometer (RI)
Eluent: 50 mM sodium nitrate aqueous solution Flow rate: 0.7 mL / min Column temperature: 40 ° C
Sample concentration: Eluent solution with sample concentration of 0.5% by mass Standard substance: PEG / PEO (manufactured by Agilent Technologies)
（実施例１～５６、比較例１～７）
次に、作製した水硬性組成物用添加剤（表５参照）を用い、表７に示す配合Ｎｏ．１～３（配合Ｎｏ．１－１、２－１、３－１（多量配合パターン）、及び、配合Ｎｏ．１－２、２－２、３－２（少量配合パターン））を採用して各コンクリート（水硬性組成物）を作製した。なお、表８、表９には、ポリカルボン酸系減水剤の使用量と水硬性組成物用添加剤の使用量を示す。
(Examples 1 to 56, Comparative Examples 1 to 7)
Next, using the prepared additive for hydraulic composition (see Table 5), the formulation No. shown in Table 7 was used. Adopting 1-3 (formulation Nos. 1-1, 2-1 and 3-1 (large amount compounding pattern) and compounding Nos. 1-2, 2-2, 3-2 (small amount compounding pattern)) Each concrete (hydraulic composition) was prepared. Tables 8 and 9 show the amount of the polycarboxylic acid-based water reducing agent used and the amount of the additive for the hydraulic composition.
その後、表８、表９に示すように、コンクリートの基本評価を行った。基本評価は、具体的には、多量配合パターンのコンクリートについては、スランプ、スランプフロー、及び、空気量の測定を行った。また、少量配合パターンのコンクリートについては、スランプフロー、及び、空気量の測定を行った。更に、表１０、表１１には、添加剤の使用量の評価、コンクリートの粘性、及びスランプフロー変化量の各評価結果について示す。 Then, as shown in Tables 8 and 9, the basic evaluation of concrete was performed. In the basic evaluation, specifically, for concrete with a large amount of compounding pattern, slump, slump flow, and air volume were measured. In addition, the slump flow and the amount of air were measured for concrete with a small amount of compounding pattern. Further, Tables 10 and 11 show the evaluation results of the amount of the additive used, the viscosity of the concrete, and the amount of change in the slump flow.
各実施例及び比較例では、多量配合パターンと少量配合パターンの両方のパターンで水硬性組成物の調製を行い、スランプフロー変化量の評価を行った。この評価によってコンクリートの流動性が維持されるか否かが分かる。 In each Example and Comparative Example, the hydraulic composition was prepared in both the large amount compounding pattern and the small amount compounding pattern, and the amount of change in the slump flow was evaluated. This evaluation shows whether or not the fluidity of concrete is maintained.
なお、ベントナイト、カオリナイト、細骨材微粒分の微粒成分等の含有量は、多量配合パターンと少量配合パターンで比較すると、１割程度の差異となるが、スランプフロー等の変化には大きな違いを生じさせる。例えば、比較例１では、ベントナイトの配合量が２ｋｇ／ｍ３（多量配合パターン）と１．８ｋｇ／ｍ３（少量配合パターン）である。その含有量の差異は大きくないようにも見えるが、これらのスランプフロー変化量は９．５ｃｍとなり、コンクリート（水硬性組成物）の性状としては大きな違いである。 The content of bentonite, kaolinite, fine particles of fine aggregate, etc. is about 10% different between the large amount compounding pattern and the small amount compounding pattern, but there is a big difference in changes such as slump flow. Causes. For example, in Comparative Example 1, the blending amounts of bentonite are 2 kg / m 3 (large amount blending pattern) and 1.8 kg / m 3 (small amount blending pattern). Although the difference in the contents does not seem to be large, the amount of change in these slump flows is 9.5 cm, which is a big difference in the properties of concrete (hydraulic composition).
以下に、具体的なコンクリート（水硬性組成物）の調製方法を示す。表７に示した配合条件で、２０℃の試験室内で５０Ｌのパン型強制練りミキサーに、普通ポルトランドセメント（太平洋セメント社製、宇部三菱セメント社製、及び住友大阪セメント社製等量混合、密度＝３．１６ｇ／ｃｍ３）からなる水硬性結合材と、細骨材として陸砂（大井川水系産、密度＝２．５８ｇ／ｃｍ３）と、微粒成分等として、ベントナイト（クニミネ工業社製、クニピア－Ｆ、真比重＝２．６ｇ／ｃｍ３）、カオリナイト（竹原化学工業社製、ＲＣ－１、真比重＝２．６ｇ／ｃｍ３）、または細骨材微粒分と、粗骨材として砕石（岡崎産砕石、密度＝２．６８ｇ／ｃｍ３）と、を投入した。なお、細骨材微粒分は、細骨材に含まれる成分であり、ＪＩＳ Ａ １１０３に規定された７５μｍふるいを通過したもの（密度＝２．５８ｇ／ｃｍ３として計算）を用いた。 A specific method for preparing concrete (hydraulic composition) is shown below. Under the compounding conditions shown in Table 7, ordinary Portland cement (manufactured by Taiheiyo Cement, Ube Mitsubishi Cement, and Sumitomo Osaka Cement) is mixed and densified in a 50 L pan-type forced kneading mixer in a test room at 20 ° C. = 3.16 g / cm 3 ) water-hard binder, land sand (Oigawa water system, density = 2.58 g / cm 3 ) as fine aggregate, and bentnite (manufactured by Kunimine Kogyo Co., Ltd.) as fine particle components. Kunipia-F, true specific gravity = 2.6 g / cm 3 ), kaolinite (manufactured by Takehara Chemical Industry Co., Ltd., RC-1, true specific gravity = 2.6 g / cm 3 ), or fine aggregate fine particles and coarse aggregate As a result, crushed stone (crushed stone from Okazaki, density = 2.68 g / cm 3 ) was added. The fine aggregate fine particles were components contained in the fine aggregate and passed through a 75 μm sieve specified in JIS A 1103 (calculated assuming that the density = 2.58 g / cm 3 ).
更に、水硬性組成物用減水剤、及び水硬性組成物用添加剤（表５参照）を表８、表９に示す使用量で配合し、更に、所定の空気量となるように、消泡剤「ＡＦＫ－２（竹本油脂社製）」を練混ぜ水（蒲郡市上水道水）の一部として計量してミキサーに投入して９０秒間練り混ぜた。そして、スランプが２１±１ｃｍ、連行空気量が２．０％以下の範囲となるようコンクリート組成物（水硬性組成物）を調製した。なお、水硬性組成物用減水剤は、ポリカルボン酸系減水剤（Ｐ－１）／ポリカルボン酸系減水剤（Ｐ－２）／ポリカルボン酸系減水剤（Ｐ－３）／グルコン酸ナトリウム＝２５／２５／２５／２５（質量比）として混合したものを使用した。 Further, a water reducing agent for a hydraulic composition and an additive for a hydraulic composition (see Table 5) are blended in the amounts shown in Tables 8 and 9, and further, defoaming is performed so as to have a predetermined air amount. The agent "AFK-2 (manufactured by Takemoto Oil & Fat Co., Ltd.)" was weighed as a part of kneading water (Gamagori City tap water), put into a mixer, and kneaded for 90 seconds. Then, a concrete composition (hydraulic composition) was prepared so that the slump was 21 ± 1 cm and the entrained air amount was in the range of 2.0% or less. The water reducing agent for the water-hard composition is a polycarboxylic acid-based water reducing agent (P-1) / a polycarboxylic acid-based water reducing agent (P-2) / a polycarboxylic acid-based water reducing agent (P-3) / sodium gluconate. The mixture was used as = 25/25/25/25 (mass ratio).
次に、コンクリートの基本評価の評価方法は、以下の通りである。 Next, the evaluation method of the basic evaluation of concrete is as follows.
・スランプ（ｃｍ）：
練り混ぜ直後のコンクリートについて、ＪＩＳ Ａ １１０１に準拠して測定した。
・ Slump (cm):
The concrete immediately after kneading was measured according to JIS A 1101.
・スランプフロー（ｃｍ）：
練り混ぜ直後のコンクリートについて、ＪＩＳ Ａ １１５０に準拠して測定した。
・ Slump flow (cm):
The concrete immediately after kneading was measured according to JIS A 1150.
・空気量（容積％）：
スランプ及びスランプフローの測定と同時に、ＪＩＳ Ａ １１２８に準拠して測定した。
・ Air volume (volume%):
At the same time as the measurement of slump and slump flow, it was measured according to JIS A 1128.
次に、添加剤の使用量の評価、コンクリートの粘性、及びスランプフロー変化量の各評価の評価方法は、以下の通りである。なお、添加剤の使用量の評価及びコンクリートの粘性は、微粒成分等の含有量が多い多量配合パターンの配合時のものを採用して評価を行っている。 Next, the evaluation methods for the evaluation of the amount of the additive used, the viscosity of the concrete, and the amount of change in the slump flow are as follows. The amount of the additive used and the viscosity of the concrete are evaluated by adopting the one at the time of blending a large amount of blending pattern having a large content of fine particles and the like.
・添加剤の使用量の評価
所定の空気量となるように水硬性組成物を調製した際における水硬性組成物用添加剤の使用量について、評価を行った。
-Evaluation of the amount of additive used The amount of additive used for the hydraulic composition when the hydraulic composition was prepared so as to have a predetermined air amount was evaluated.
評価基準は、以下の通りである。水硬性組成物用添加剤の使用量が０．０６％以上で０．０７％未満である場合を「Ｓ」とした。上記使用量が０．０７％以上で０．０８％未満である場合を「Ａ」とした。上記使用量が０．０８％以上で０．０９％未満である場合を「Ｂ」とした。上記使用量が０．０９％以上で０．１０％未満である場合を「Ｃ」とした。上記使用量が０．１０％以上である場合を「Ｄ」とした。 The evaluation criteria are as follows. The case where the amount of the additive for the hydraulic composition used was 0.06% or more and less than 0.07% was defined as "S". The case where the amount used was 0.07% or more and less than 0.08% was designated as "A". The case where the amount used was 0.08% or more and less than 0.09% was designated as "B". The case where the amount used was 0.09% or more and less than 0.10% was designated as "C". The case where the amount used was 0.10% or more was designated as "D".
・コンクリートの粘性
コンクリートの粘性は、５人の試験者による官能評価で確認した。具体的には、得られたコンクリートをスコップで切り返してもらい、目視による印象及びハンドリング性に基づいて最高１０点（１～１０点の１０段階評価）で採点した。その後、試験者の平均値（得点平均）を０．５点刻みで示し、この得点平均に応じて評価した。
-Concrete viscosity The viscosity of concrete was confirmed by sensory evaluation by five testers. Specifically, the obtained concrete was cut back with a shovel and scored on a maximum of 10 points (10-point evaluation of 1 to 10 points) based on the visual impression and handleability. Then, the average value (score average) of the examiners was shown in increments of 0.5 points, and the evaluation was made according to the average score.
評価基準を以下に示す。９．０点以上で１０．０点以下の場合、粘性が最も低いとして「Ｓ」とした。８．０点以上で９．０点未満の場合、粘性が特に低いとして「Ａ」とした。７．０点以上で８．０点未満の場合、粘性が低いとして「Ｂ」とした。７．０点未満の場合、粘性が高いとして「Ｃ」とした。 The evaluation criteria are shown below. When the score was 9.0 or higher and 10.0 or lower, the viscosity was considered to be the lowest and was rated as "S". When the score was 8.0 or higher and less than 9.0, it was rated as "A" because the viscosity was particularly low. When the score was 7.0 or higher and less than 8.0, it was rated as "B" because of its low viscosity. When the score was less than 7.0, it was rated as "C" because of its high viscosity.
・スランプフロー変化量
多量配合パターンにおけるスランプフローと少量配合パターンにおけるスランプフローの差（式：「少量配合パターンにおけるスランプフロー」－「多量配合パターンにおけるスランプフロー」）を算出し、スランプフロー変化量とした。この変化量について評価を行った。変化量の値が小さい程、一定の性状が維持されることを示す。
・ Slump flow change amount Calculate the difference between the slump flow in the large amount compounding pattern and the slump flow in the small amount compounding pattern (formula: "slump flow in the small amount compounding pattern"-"slump flow in the large amount compounding pattern"), and use it as the slump flow change amount. did. This amount of change was evaluated. The smaller the value of the amount of change, the more constant the properties are maintained.
評価基準を以下に示す。スランプフロー変化量が±３ｃｍ未満である場合を「Ｓ」とした。スランプフロー変化量が±３ｃｍ以上で±５ｃｍ未満である場合を「Ａ」とした。スランプフロー変化量が±５ｃｍ以上で±７ｃｍ未満である場合を「Ｂ」とした。スランプフロー変化量が±７ｃｍ以上である場合を「Ｃ」とした。 The evaluation criteria are shown below. The case where the amount of change in slump flow was less than ± 3 cm was defined as “S”. The case where the amount of change in slump flow was ± 3 cm or more and less than ± 5 cm was defined as “A”. The case where the amount of change in slump flow was ± 5 cm or more and less than ± 7 cm was defined as “B”. The case where the amount of change in slump flow was ± 7 cm or more was defined as “C”.
なお、表７中、細骨材率は、ベントナイト、カオリナイト、及び細骨材微粒分を細骨材として見積もって計算した。 In Table 7, the fine aggregate ratio was calculated by estimating the bentonite, kaolinite, and fine aggregate fine particles as fine aggregate.
なお、表９中、「※」で示す比較例７の添加剤は、ポリ（ジアリルジメチルアンモニウムクロライド）であり、質量平均分子量は１００，０００である。 In Table 9, the additive of Comparative Example 7 shown by “*” is poly (diallyldimethylammonium chloride) and has a mass average molecular weight of 100,000.
表８、表９中、水硬組成物用減水剤及び水硬性組成物用添加剤の使用量は、全て固形分表記とした。 In Tables 8 and 9, the amounts of the water reducing agent for the hydraulic composition and the additive for the hydraulic composition are all expressed in solid content.
（結果）
表１０、表１１に示すように、本実施例の水硬性組成物用添加剤を水硬性組成物に配合することで、品質が十分でなく粘土質等の微粒成分等の含有量のばらつきが大きい骨材を使用しても、微粒成分等の多少に起因する性状の変化が抑制され、一定の性状（粘性、流動性等）が得られることが確認された。更に、その使用量が少なくても十分に効果が得られることが確認された。
(result)
As shown in Tables 10 and 11, by blending the additive for the hydraulic composition of this example into the hydraulic composition, the quality is not sufficient and the content of fine particles such as clay varies. It was confirmed that even if a large aggregate was used, changes in properties due to some fine particles and the like were suppressed, and constant properties (viscosity, fluidity, etc.) could be obtained. Furthermore, it was confirmed that a sufficient effect can be obtained even if the amount used is small.
本発明の水硬性組成物用添加剤は、コンクリート等の水硬性組成物に添加される添加剤として利用することができる。また、本発明の水硬性組成物は、コンクリート等の硬化物を作製するものとして利用することができる。
The additive for a hydraulic composition of the present invention can be used as an additive added to a hydraulic composition such as concrete. Further, the hydraulic composition of the present invention can be used for producing a cured product such as concrete.
Claims (10)
下記一般式（１）で示されるＡ成分と、
下記一般式（２）で示されるＢ成分と、を含有し、
前記Ａ成分及び前記Ｂ成分の含有割合の合計を１００質量部としたとき、前記Ａ成分を１５～８５質量部の割合で含有し、前記Ｂ成分を１５～８５質量部の割合で含有することを特徴とする水硬性組成物用添加剤。
A component represented by the following general formula (1) and
Containing the B component represented by the following general formula (2),
When the total content ratio of the A component and the B component is 100 parts by mass, the A component is contained in a ratio of 15 to 85 parts by mass, and the B component is contained in a ratio of 15 to 85 parts by mass. An additive for a hydraulic composition characterized by.
前記Ａ成分を１０～８０質量部、前記Ｂ成分を１０～８０質量部、及び前記Ｃ成分を０．１～４０質量部の割合で含有する、請求項５に記載の水硬性組成物用添加剤。 When the A component, the B component, and the C component are contained, and the total content ratio of the A component, the B component, and the C component is 100 parts by mass.
The addition for a hydraulic composition according to claim 5 , wherein the component A is contained in an amount of 10 to 80 parts by mass, the component B is contained in an amount of 10 to 80 parts by mass, and the component C is contained in a proportion of 0.1 to 40 parts by mass. Agent.
前記Ａ成分を１０～８０質量部、前記Ｂ成分を１０～８０質量部、及び前記Ｄ成分を０．１～２０質量部の割合で含有する、請求項５に記載の水硬性組成物用添加剤。 When the A component, the B component, and the D component are contained, and the total content ratio of the A component, the B component, and the D component is 100 parts by mass.
The addition for a hydraulic composition according to claim 5 , wherein the component A is contained in an amount of 10 to 80 parts by mass, the component B is contained in an amount of 10 to 80 parts by mass, and the component D is contained in a proportion of 0.1 to 20 parts by mass. Agent.
前記Ａ成分を１０～８０質量部、前記Ｂ成分を１０～８０質量部、前記Ｃ成分を０．１～４０質量部、及び前記Ｄ成分を０．１～２０質量部の割合で含有する、請求項５に記載の水硬性組成物用添加剤。 When the A component, the B component, the C component, and the D component are contained, and the total content ratio of the A component, the B component, the C component, and the D component is 100 parts by mass.
The component A is contained in an amount of 10 to 80 parts by mass, the component B is contained in an amount of 10 to 80 parts by mass, the component C is contained in an amount of 0.1 to 40 parts by mass, and the component D is contained in a proportion of 0.1 to 20 parts by mass. The additive for a hydraulic composition according to claim 5 .
ポリカルボン酸系減水剤：下記の一般式（５）で示される化合物から形成される構成単位１、及びビニル基を有するカルボン酸単量体から形成される構成単位２を含み、分子中に占める前記構成単位１及び前記構成単位２の構成割合の合計を１００質量％としたとき、前記構成単位１が１～９９質量％、及び前記構成単位２が９９～１質量％であり、更に、質量平均分子量が１，０００～１，０００，０００であるビニル共重合体。
Polycarboxylic acid-based water reducing agent: Containing a structural unit 1 formed of a compound represented by the following general formula (5) and a structural unit 2 formed of a carboxylic acid monomer having a vinyl group, and occupying the molecule. When the total of the constituent ratios of the constituent unit 1 and the constituent unit 2 is 100% by mass, the constituent unit 1 is 1 to 99% by mass, the constituent unit 2 is 99 to 1% by mass, and further, the mass is A vinyl copolymer having an average molecular weight of 1,000 to 1,000,000.
A hydraulic composition comprising the additive for a hydraulic composition according to any one of claims 1 to 9 .
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