WO2022162979A1 - Additive for hydraulic compositions, and hydraulic composition - Google Patents
Additive for hydraulic compositions, and hydraulic composition Download PDFInfo
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- WO2022162979A1 WO2022162979A1 PCT/JP2021/029061 JP2021029061W WO2022162979A1 WO 2022162979 A1 WO2022162979 A1 WO 2022162979A1 JP 2021029061 W JP2021029061 W JP 2021029061W WO 2022162979 A1 WO2022162979 A1 WO 2022162979A1
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- 239000000654 additive Substances 0.000 title claims abstract description 55
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- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 2
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- 238000005886 esterification reaction Methods 0.000 description 2
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- 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 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 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 2
- 125000004370 n-butenyl group Chemical group [H]\C([H])=C(/[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 150000002826 nitrites Chemical class 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 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 2
- 239000003960 organic solvent Substances 0.000 description 2
- 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 2
- 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 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
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- 230000000379 polymerizing effect Effects 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- MHVJRKBZMUDEEV-KRFUXDQASA-N sandaracopimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-KRFUXDQASA-N 0.000 description 2
- YZVSLDRKXBZOMY-KNOXWWKRSA-N sandaracopimaric acid Natural products CC(=C)[C@]1(C)CCC[C@]2(C)[C@H]3CC[C@](C)(C=C)C=C3CC[C@@H]12 YZVSLDRKXBZOMY-KNOXWWKRSA-N 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- 239000000176 sodium gluconate Substances 0.000 description 2
- 235000012207 sodium gluconate Nutrition 0.000 description 2
- 229940005574 sodium gluconate Drugs 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 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 2
- 239000005720 sucrose Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
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- 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 2
- YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 description 2
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 description 1
- DNYWXJPIRSNXIP-UHFFFAOYSA-N 2-bromo-1,1,1-trichloroethane Chemical compound ClC(Cl)(Cl)CBr DNYWXJPIRSNXIP-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 241000218641 Pinaceae Species 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 229930004069 diterpene Natural products 0.000 description 1
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- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
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- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
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- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- LWNSNYBMYBWJDN-UHFFFAOYSA-N octyl 3-sulfanylpropanoate Chemical compound CCCCCCCCOC(=O)CCS LWNSNYBMYBWJDN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- HEZHYQDYRPUXNJ-UHFFFAOYSA-L potassium dithionite Chemical compound [K+].[K+].[O-]S(=O)S([O-])=O HEZHYQDYRPUXNJ-UHFFFAOYSA-L 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 229940043349 potassium metabisulfite Drugs 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 description 1
- 229940075931 sodium dithionate Drugs 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/02—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
- C04B24/08—Fats; Fatty oils; Ester type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
-
- 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
- C04B24/16—Sulfur-containing compounds
-
- 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
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Abstract
The present invention provides an additive for hydraulic compositions, which is added to a hydraulic composition to reduce the change in fluidability of the hydraulic composition over time regardless of the temperature of the use of the hydraulic composition, enable the proper control of the amount of air, and prevent the undue delay of the setting time of the hydraulic composition. Provided is an additive for hydraulic compositions, characterized by comprising a specific component A, a specific component B, and at least one component selected from a specific component C and a specific component D.
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 a hydraulic composition additive and a hydraulic composition. More particularly, it relates to a hydraulic composition additive added to a hydraulic composition such as concrete and a hydraulic composition to which the additive is added.
従来、コンクリート等の硬化物は、水硬性組成物を所定の型枠内へ充填し、その後、硬化させることによって製造されている。
Conventionally, hardened materials such as concrete are manufactured by filling a predetermined mold with a hydraulic composition and then hardening it.
この水硬性組成物は、型枠内への充填などの作業性等の観点から十分な流動性を有することが重要となる。
It is important for this hydraulic composition to have sufficient fluidity from the viewpoint of workability such as filling into the formwork.
そこで、水硬性組成物の流動性を向上させるための添加剤が開発されている。具体的には、ポリカルボン酸系重合体（Ａ）と、アミド結合に由来しない窒素原子を有する化合物（Ｂ）とを含んでなり、ポリカルボン酸系重合体（Ａ）と、該アミド結合に由来しない窒素原子を有する化合物（Ｂ）との質量比（Ａ／Ｂ）が所定であるセメント混和剤（例えば、特許文献１参照）、セメント及びクレイに対する吸着量が所定の条件を満たすポリマーを含有するもの（例えば、特許文献２参照）などが報告されている。
Therefore, additives have been developed to improve the fluidity of hydraulic compositions. Specifically, it comprises a polycarboxylic acid-based polymer (A) and a compound (B) having a nitrogen atom not derived from an amide bond, and the polycarboxylic acid-based polymer (A) and the amide bond Contains a cement admixture having a predetermined mass ratio (A/B) with a compound (B) having a nitrogen atom not derived from it (see, for example, Patent Document 1), and a polymer that satisfies predetermined conditions for the amount of adsorption to cement and clay. (see, for example, Patent Document 2) have been reported.
ここで、上述の通り、型枠内への充填などの作業性等の観点からすると、十分な流動性を有することが、水硬性組成物には重要な要素の一つである。一方で、水硬性組成物は、充填後には所望の時間で（即ち、比較的短時間で）凝結して硬化し、強度等において十分な性能を発揮することが要求される。
Here, as described above, from the viewpoint of workability such as filling into the mold, it is one of the important factors for the hydraulic composition to have sufficient fluidity. On the other hand, the hydraulic composition is required to set and harden in a desired time (that is, in a relatively short time) after filling, and to exhibit sufficient performance in terms of strength and the like.
このように流動性の保持と凝結時間を過度に遅延させないことの両方を満足することは簡単ではなく、一般的に、流動性の保持が良い水硬性組成物は、凝結時間が長く、硬化に時間が必要になることが多い。このようなことから、水硬性組成物の流動性を保持しつつ、凝結時間を過度に遅延させない添加剤の開発が行われている（例えば、特許文献３参照）。
Thus, it is not easy to satisfy both the maintenance of fluidity and the prevention of excessive delay in setting time. It often takes time. For this reason, an additive has been developed that does not excessively delay the setting time while maintaining the fluidity of the hydraulic composition (see, for example, Patent Document 3).
特許文献１～３に記載の水硬性組成物等の添加剤は、水硬性組成物等における流動性、粘度等の状態を改善するものである。しかし、これらの添加剤は、未だ改善の余地があり、新たな水硬性組成物用添加剤の開発が求められていた。具体的には、使用温度に関わらず、経時による流動性の変化が少なく空気量の調整が適宜可能でありながら、凝結時間を過度に遅延させない添加剤の開発が求められていた。
The additives for the hydraulic composition described in Patent Documents 1 to 3 improve the fluidity, viscosity, etc. of the hydraulic composition. However, these additives still have room for improvement, and development of new additives for hydraulic compositions has been desired. Specifically, there has been a demand for the development of an additive that does not excessively delay the setting time, while the change in fluidity over time is small and the amount of air can be appropriately adjusted, regardless of the operating temperature.
そこで、本発明は、上記実情に鑑み、使用温度に関わらず、経時による流動性の変化が少なく空気量の調整が適宜可能でありながら、凝結時間を過度に遅延させない添加剤（水硬性組成物用の添加剤）の提供を課題とするものである。
Therefore, in view of the above-mentioned circumstances, the present invention provides an additive (hydraulic composition) that does not excessively delay the setting time, while the fluidity does not change over time and the air amount can be adjusted appropriately, regardless of the operating temperature. The object is to provide an additive for
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成分に加え、更に、Ｃ成分及びＤ成分の少なくとも一つ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。
The present inventors have made intensive studies to solve the above problems, and found that the above problems can be solved by adding at least one of the C component and the D component in addition to the predetermined A component and B component. Found it. According to the present invention, the following hydraulic composition additive and hydraulic composition are provided.
［１］ 下記Ａ成分と、
下記Ｂ成分と、
下記Ｃ成分及び下記Ｄ成分から選択される少なくとも１つと、
を含有することを特徴とする水硬性組成物用添加剤。 [1] the following A component,
the following B component,
At least one selected from the following C component and the following D component,
An additive for a hydraulic composition characterized by containing
下記Ｂ成分と、
下記Ｃ成分及び下記Ｄ成分から選択される少なくとも１つと、
を含有することを特徴とする水硬性組成物用添加剤。 [1] the following A component,
the following B component,
At least one selected from the following C component and the following D component,
An additive for a hydraulic composition characterized by containing
＜Ａ成分＞
ポリアリルアミン、ポリアリルアミン塩、ポリアルキレンイミン、ポリアルキレンイミンのアルキレンオキシド付加物、ジアリルアミン重合体、ジアリルアミン塩重合体、ジアリルアミン・二酸化硫黄共重合体、ジアリルアミン塩・二酸化硫黄共重合体、及びポリビニルピロリドンから選択される少なくとも１つ。 <A component>
From polyallylamine, polyallylamine salt, polyalkyleneimine, alkylene oxide adduct of polyalkyleneimine, diallylamine polymer, diallylamine salt polymer, diallylamine/sulfur dioxide copolymer, diallylamine salt/sulfur dioxide copolymer, and polyvinylpyrrolidone At least one selected.
ポリアリルアミン、ポリアリルアミン塩、ポリアルキレンイミン、ポリアルキレンイミンのアルキレンオキシド付加物、ジアリルアミン重合体、ジアリルアミン塩重合体、ジアリルアミン・二酸化硫黄共重合体、ジアリルアミン塩・二酸化硫黄共重合体、及びポリビニルピロリドンから選択される少なくとも１つ。 <A component>
From polyallylamine, polyallylamine salt, polyalkyleneimine, alkylene oxide adduct of polyalkyleneimine, diallylamine polymer, diallylamine salt polymer, diallylamine/sulfur dioxide copolymer, diallylamine salt/sulfur dioxide copolymer, and polyvinylpyrrolidone At least one selected.
＜Ｂ成分＞
下記一般式（１）で示される化合物である単量体１から形成された構成単位１、及び、下記一般式（２）で示される化合物である単量体２から形成された構成単位２を含み、
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５０～９９質量％、前記構成単位２が５０～１質量％の割合であり、
更に、質量平均分子量が５，０００以上で１００，０００以下であるビニル共重合体。 <B component>
A structural unit 1 formed from a monomer 1 which is a compound represented by the following general formula (1), and a structural unit 2 formed from a monomer 2 which is a compound represented by the following general formula (2) including
When the total composition ratio of the structural unit 1 and the structural unit 2 is 100% by mass, the structural unit 1 is 50 to 99% by mass and the structural unit 2 is 50 to 1% by mass,
Furthermore, a vinyl copolymer having a weight average molecular weight of 5,000 or more and 100,000 or less.
下記一般式（１）で示される化合物である単量体１から形成された構成単位１、及び、下記一般式（２）で示される化合物である単量体２から形成された構成単位２を含み、
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５０～９９質量％、前記構成単位２が５０～１質量％の割合であり、
更に、質量平均分子量が５，０００以上で１００，０００以下であるビニル共重合体。 <B component>
A structural unit 1 formed from a monomer 1 which is a compound represented by the following general formula (1), and a structural unit 2 formed from a monomer 2 which is a compound represented by the following general formula (2) including
When the total composition ratio of the structural unit 1 and the structural unit 2 is 100% by mass, the structural unit 1 is 50 to 99% by mass and the structural unit 2 is 50 to 1% by mass,
Furthermore, a vinyl copolymer having a weight average molecular weight of 5,000 or more and 100,000 or less.
＜Ｃ成分＞
下記一般式（３）で示される化合物。 <C component>
A compound represented by the following general formula (3).
下記一般式（３）で示される化合物。 <C component>
A compound represented by the following general formula (3).
＜Ｄ成分＞
下記一般式（４）で示される化合物である単量体３から形成された構成単位３、及び、下記一般式（５）で示される化合物である単量体４から形成された構成単位４を含み、
前記構成単位３と前記構成単位４の構成割合の合計を１００質量％としたとき、前記構成単位３が５０～９９質量％、前記構成単位４が５０～１質量％であり、
更に、質量平均分子量が１００，０００超で６００，０００以下であるビニル共重合体。 <D component>
A structural unit 3 formed from a monomer 3 which is a compound represented by the following general formula (4), and a structural unit 4 formed from a monomer 4 which is a compound represented by the following general formula (5) including
When the total composition ratio of the structural unit 3 and the structural unit 4 is 100% by mass, the structural unit 3 is 50 to 99% by mass and the structural unit 4 is 50 to 1% by mass,
Furthermore, a vinyl copolymer having a weight average molecular weight of more than 100,000 and not more than 600,000.
下記一般式（４）で示される化合物である単量体３から形成された構成単位３、及び、下記一般式（５）で示される化合物である単量体４から形成された構成単位４を含み、
前記構成単位３と前記構成単位４の構成割合の合計を１００質量％としたとき、前記構成単位３が５０～９９質量％、前記構成単位４が５０～１質量％であり、
更に、質量平均分子量が１００，０００超で６００，０００以下であるビニル共重合体。 <D component>
A structural unit 3 formed from a monomer 3 which is a compound represented by the following general formula (4), and a structural unit 4 formed from a monomer 4 which is a compound represented by the following general formula (5) including
When the total composition ratio of the structural unit 3 and the structural unit 4 is 100% by mass, the structural unit 3 is 50 to 99% by mass and the structural unit 4 is 50 to 1% by mass,
Furthermore, a vinyl copolymer having a weight average molecular weight of more than 100,000 and not more than 600,000.
［２］ 前記一般式（３）における－（ＡＯ）ｓ－が、炭素数２～４のオキシアルキレン基の構成割合の合計を１００モル％とすると、
炭素数２のオキシアルキレン基を９０モル％以上の割合で有するものである、前記［１］に記載の水硬性組成物用添加剤。 [2] Assuming that -(AO) s - in the general formula (3) contains 100% by mole of oxyalkylene groups having 2 to 4 carbon atoms,
The additive for hydraulic compositions according to the above [1], which contains 90 mol % or more of oxyalkylene groups having 2 carbon atoms.
炭素数２のオキシアルキレン基を９０モル％以上の割合で有するものである、前記［１］に記載の水硬性組成物用添加剤。 [2] Assuming that -(AO) s - in the general formula (3) contains 100% by mole of oxyalkylene groups having 2 to 4 carbon atoms,
The additive for hydraulic compositions according to the above [1], which contains 90 mol % or more of oxyalkylene groups having 2 carbon atoms.
［３］ 前記Ｄ成分が、
硫黄原子を含有する親水性連鎖移動剤に由来する構造単位（ＴＡ）を更に含有する、前記［１］または［２］に記載の水硬性組成物用添加剤。 [3] The D component is
The additive for hydraulic compositions according to the above [1] or [2], which further contains a structural unit (TA) derived from a hydrophilic chain transfer agent containing a sulfur atom.
硫黄原子を含有する親水性連鎖移動剤に由来する構造単位（ＴＡ）を更に含有する、前記［１］または［２］に記載の水硬性組成物用添加剤。 [3] The D component is
The additive for hydraulic compositions according to the above [1] or [2], which further contains a structural unit (TA) derived from a hydrophilic chain transfer agent containing a sulfur atom.
［４］ 前記Ｄ成分が、
硫黄原子を含有する疎水性連鎖移動剤に由来する構造単位（ＴＢ）を更に含有する、前記［３］に記載の水硬性組成物用添加剤。 [4] The D component is
The additive for hydraulic composition according to [3] above, further comprising a structural unit (TB) derived from a hydrophobic chain transfer agent containing a sulfur atom.
硫黄原子を含有する疎水性連鎖移動剤に由来する構造単位（ＴＢ）を更に含有する、前記［３］に記載の水硬性組成物用添加剤。 [4] The D component is
The additive for hydraulic composition according to [3] above, further comprising a structural unit (TB) derived from a hydrophobic chain transfer agent containing a sulfur atom.
［５］ 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１～７０質量部、前記Ｂ成分を２９～９８質量部、及び前記Ｃ成分を０．０５～１０質量部の割合で含有する、前記［１］～［４］のいずれかに記載の水硬性組成物用添加剤。 [5] When the total content of the A component, the B component and the C component is included, and the total content of the A component, the B component and the C component is 100 parts by mass,
Any of the above [1] to [4], which contains 1 to 70 parts by mass of the A component, 29 to 98 parts by mass of the B component, and 0.05 to 10 parts by mass of the C component. Additive for hydraulic compositions as described.
前記Ａ成分を１～７０質量部、前記Ｂ成分を２９～９８質量部、及び前記Ｃ成分を０．０５～１０質量部の割合で含有する、前記［１］～［４］のいずれかに記載の水硬性組成物用添加剤。 [5] When the total content of the A component, the B component and the C component is included, and the total content of the A component, the B component and the C component is 100 parts by mass,
Any of the above [1] to [4], which contains 1 to 70 parts by mass of the A component, 29 to 98 parts by mass of the B component, and 0.05 to 10 parts by mass of the C component. Additive for hydraulic compositions as described.
［６］ 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１～６０質量部、前記Ｂ成分を１９～９８質量部、及び前記Ｄ成分を０．５～４０質量部の割合で含有する、前記［１］～［４］のいずれかに記載の水硬性組成物用添加剤。 [6] When the total content of the A component, the B component and the D component is included, and the total content of the A component, the B component and the D component is 100 parts by mass,
Any of the above [1] to [4], containing 1 to 60 parts by mass of the A component, 19 to 98 parts by mass of the B component, and 0.5 to 40 parts by mass of the D component. Additive for hydraulic compositions as described.
前記Ａ成分を１～６０質量部、前記Ｂ成分を１９～９８質量部、及び前記Ｄ成分を０．５～４０質量部の割合で含有する、前記［１］～［４］のいずれかに記載の水硬性組成物用添加剤。 [6] When the total content of the A component, the B component and the D component is included, and the total content of the A component, the B component and the D component is 100 parts by mass,
Any of the above [1] to [4], containing 1 to 60 parts by mass of the A component, 19 to 98 parts by mass of the B component, and 0.5 to 40 parts by mass of the D component. Additive for hydraulic compositions as described.
［７］ 前記Ａ成分、前記Ｂ成分、前記Ｃ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１～６０質量部、前記Ｂ成分を１９～９８質量部、前記Ｃ成分を０．０５～１０質量部、及び前記Ｄ成分を０．５～４０質量部の割合で含有する、前記［１］～［４］のいずれかに記載の水硬性組成物用添加剤。 [7] When the total content of the A component, the B component, the C and the D component is included, and the total content of the A component, the B component, the C component and the D component is 100 parts by mass,
1 to 60 parts by mass of the A component, 19 to 98 parts by mass of the B component, 0.05 to 10 parts by mass of the C component, and 0.5 to 40 parts by mass of the D component, The additive for hydraulic compositions according to any one of [1] to [4].
前記Ａ成分を１～６０質量部、前記Ｂ成分を１９～９８質量部、前記Ｃ成分を０．０５～１０質量部、及び前記Ｄ成分を０．５～４０質量部の割合で含有する、前記［１］～［４］のいずれかに記載の水硬性組成物用添加剤。 [7] When the total content of the A component, the B component, the C and the D component is included, and the total content of the A component, the B component, the C component and the D component is 100 parts by mass,
1 to 60 parts by mass of the A component, 19 to 98 parts by mass of the B component, 0.05 to 10 parts by mass of the C component, and 0.5 to 40 parts by mass of the D component, The additive for hydraulic compositions according to any one of [1] to [4].
［８］ 前記［１］～［７］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。
[8] A hydraulic composition characterized by containing the additive for a hydraulic composition according to any one of [1] to [7].
本発明の水硬性組成物用添加剤は、使用温度に関わらず、経時による流動性の変化が少なく空気量の調整が適宜可能でありながら、凝結時間を過度に遅延させないという効果を奏するものである。
The additive for a hydraulic composition of the present invention has the effect of not excessively delaying the setting time while allowing the air content to be appropriately adjusted with little change in fluidity over time, regardless of the operating temperature. be.
本発明の水硬性組成物は、使用温度に関わらず、経時による流動性の変化が少なく空気量の調整が適宜可能でありながら、凝結時間が過度に遅延しないという効果を奏するものである。
The hydraulic composition of the present invention has little change in fluidity over time, regardless of the temperature of use, and the amount of air can be adjusted appropriately, while the setting time is not delayed excessively.
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。
Embodiments of the present invention will be described below. However, the present invention is not limited to the following embodiments. Therefore, it should be understood that modifications, improvements, etc., can be made to the following embodiments as appropriate 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, % means % by mass, and part means part by mass, unless otherwise specified.
（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、所定のＡ成分と、所定のＢ成分と、所定のＣ成分及び所定のＤ成分から選択される少なくとも１つと、を含有するものである。別言すれば、所定のＡ成分及び所定のＢ成分を含有し、更に、所定のＣ成分及び所定のＤ成分の一方、または、所定のＣ成分及び所定のＤ成分の両方が配合されたものである。 (1) Additive for hydraulic composition:
The additive for hydraulic compositions of the present invention contains a prescribed A component, a prescribed B component, and at least one selected from a prescribed C component and a prescribed D component. In other words, it contains the prescribed A component and the prescribed B component, and further contains one of the prescribed C component and the prescribed D component, or both the prescribed C component and the prescribed D component. is.
本発明の水硬性組成物用添加剤は、所定のＡ成分と、所定のＢ成分と、所定のＣ成分及び所定のＤ成分から選択される少なくとも１つと、を含有するものである。別言すれば、所定のＡ成分及び所定のＢ成分を含有し、更に、所定のＣ成分及び所定のＤ成分の一方、または、所定のＣ成分及び所定のＤ成分の両方が配合されたものである。 (1) Additive for hydraulic composition:
The additive for hydraulic compositions of the present invention contains a prescribed A component, a prescribed B component, and at least one selected from a prescribed C component and a prescribed D component. In other words, it contains the prescribed A component and the prescribed B component, and further contains one of the prescribed C component and the prescribed D component, or both the prescribed C component and the prescribed D component. is.
このような水硬性組成物用添加剤は、水硬性組成物に配合することで、当該水硬性組成物は、使用温度に関わらず、経時による流動性の変化が少なく空気量の調整が適宜可能となる。特に、通常は高温（例えば、３０℃以上）の環境下では、経時による流動性の変化が大きく、高温下である程、早くに流動性が低下する。しかし、本発明の水硬性組成物用添加剤を添加することで、高温環境下であっても経時による流動性の変化が少なくなる。このようなことから、使用温度が高くなるような気温の高い国や地域、即ち、気温が３０℃以上となるような気温の高い国や地域でも良好に使用することができる。
By blending such a hydraulic composition additive into a hydraulic composition, the hydraulic composition has little change in fluidity over time regardless of the operating temperature, and the amount of air can be appropriately adjusted. becomes. In particular, in a high-temperature environment (for example, 30° C. or higher), fluidity changes greatly over time, and the higher the temperature, the faster the fluidity decreases. However, by adding the additive for hydraulic compositions of the present invention, the change in fluidity over time is reduced even in a high-temperature environment. For this reason, it can be used satisfactorily in countries and regions where the temperature is high, that is, in countries and regions where the temperature is 30° C. or higher.
また、一方で、水硬性組成物は、コテ等による仕上げや、型枠の脱型等の関係から、適度な時間で凝結することが求められる。即ち、水硬性組成物は、凝結時間が長過ぎず適当であることが望まれる。この点、本発明の水硬性組成物用添加剤は、使用温度に関わらず、水硬性組成物の凝結時間を過度に遅延させないという利点がある。ここで、凝結時間を過度に遅延させないとは、添加剤を配合することで、水硬性組成物の流動性が練り混ぜから数時間程度（例えば、１～２時間程度）保持されて、凝結開始を遅延させることができ、一方で、練り混ぜから数時間程度で、流動性が低下し凝結が開始することを意味するものである。
On the other hand, the hydraulic composition is required to set in an appropriate amount of time due to finishing with a trowel, etc., and removal of the formwork. That is, the hydraulic composition is desired to have a suitable setting time that is not too long. In this regard, the additive for hydraulic compositions of the present invention has the advantage of not excessively delaying the setting time of the hydraulic composition regardless of the temperature of use. Here, not excessively delaying the setting time means that the fluidity of the hydraulic composition is maintained for about several hours after kneading (for example, about 1 to 2 hours) by adding the additive, and the setting starts. On the other hand, it means that the fluidity will decrease and coagulation will start in about several hours after kneading.
具体的には、生コンクリート（水硬性組成物）の製造後、直ぐに生コンクリートの打ち込みを行うことができることがよい。しかし、通常は、生コンクリートの製造から作業現場での打ち込みまでには、生コンクリート工場から作業現場までの運搬時間や、作業現場での待機時間などの時間を要する。この生コンクリート工場から作業現場までの時間は、数時間程度かかることがある。そのため、練り混ぜから数時間程度（例えば、１～２時間程度）保持されることが望まれる。一方で、生コンクリートの打ち込み後には、凝結が開始されることが望まれる。このように、運搬等の時間を考慮して所定時間は流動性が確保されつつ、所定時間の経過後、適切に凝結が開始することが望まれる。
Specifically, it is preferable that ready-mixed concrete (hydraulic composition) can be poured immediately after production. However, usually, it takes time such as transportation time from the ready-mixed concrete factory to the work site, standby time at the work site, and the like from the time the ready-mixed concrete is manufactured to the time it is placed at the work site. The time from the ready-mixed concrete factory to the work site may take several hours. Therefore, it is desired that the mixture is kept for about several hours (for example, about 1 to 2 hours) after kneading. On the other hand, it is desired that after the ready-mixed concrete has been placed, it will begin to set. In this way, it is desired that the fluidity is ensured for a predetermined period of time in consideration of the time required for transportation, and the coagulation starts appropriately after the predetermined period of time has elapsed.
なお、既存の遅延剤（例えば、糖類、オキシカルボン酸塩等）を多量に用いることによって、流動性をある程度保持することは可能である。しかし、その場合は、凝結が過度に遅延し硬化不良を生じ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を用いることで、流動性を保持することができる。そして同時に、多量に遅延剤を用いた場合のように過度な凝結遅延が生じることを防止することができる。
It should be noted that it is possible to maintain fluidity to some extent by using a large amount of existing retarders (eg, sugars, oxycarboxylates, etc.). However, in that case, there is a problem that the setting is delayed excessively, resulting in poor curing. To solve such problems, fluidity can be maintained by using the additive for hydraulic composition of the present invention. At the same time, it is possible to prevent excessive retardation of setting as in the case of using a large amount of retarder.
（１－１）Ａ成分：
Ａ成分は、ポリアリルアミン、ポリアリルアミン塩、ポリアルキレンイミン、ポリアルキレンイミンのアルキレンオキシド付加物、ジアリルアミン重合体、ジアリルアミン塩重合体、ジアリルアミン・二酸化硫黄共重合体、ジアリルアミン塩・二酸化硫黄共重合体、及びポリビニルピロリドンから選択される少なくとも１つである。このＡ成分を他の成分（Ｂ成分、及び、Ｃ成分とＤ成分の少なくとも一方）とともに配合することで、使用温度に関わらず、経時による流動性の変化が少なく空気量の調整が適宜可能でありながら、凝結時間を過度に遅延させないという効果が発揮される。 (1-1) A component:
Component A includes polyallylamine, polyallylamine salt, polyalkyleneimine, alkylene oxide adduct of polyalkyleneimine, diallylamine polymer, diallylamine salt polymer, diallylamine/sulfur dioxide copolymer, diallylamine salt/sulfur dioxide copolymer, and polyvinylpyrrolidone. By blending this A component with other components (B component and at least one of C component and D component), it is possible to appropriately adjust the amount of air with little change in fluidity over time regardless of the operating temperature. However, the effect of not delaying the setting time excessively is exhibited.
Ａ成分は、ポリアリルアミン、ポリアリルアミン塩、ポリアルキレンイミン、ポリアルキレンイミンのアルキレンオキシド付加物、ジアリルアミン重合体、ジアリルアミン塩重合体、ジアリルアミン・二酸化硫黄共重合体、ジアリルアミン塩・二酸化硫黄共重合体、及びポリビニルピロリドンから選択される少なくとも１つである。このＡ成分を他の成分（Ｂ成分、及び、Ｃ成分とＤ成分の少なくとも一方）とともに配合することで、使用温度に関わらず、経時による流動性の変化が少なく空気量の調整が適宜可能でありながら、凝結時間を過度に遅延させないという効果が発揮される。 (1-1) A component:
Component A includes polyallylamine, polyallylamine salt, polyalkyleneimine, alkylene oxide adduct of polyalkyleneimine, diallylamine polymer, diallylamine salt polymer, diallylamine/sulfur dioxide copolymer, diallylamine salt/sulfur dioxide copolymer, and polyvinylpyrrolidone. By blending this A component with other components (B component and at least one of C component and D component), it is possible to appropriately adjust the amount of air with little change in fluidity over time regardless of the operating temperature. However, the effect of not delaying the setting time excessively is exhibited.
Ａ成分としては、ポリアリルアミン、ポリアリルアミン塩、及びポリビニルピロリドンから選択される少なくとも１つであることが好ましい。Ａ成分としての、ポリアリルアミン、ポリアリルアミン塩、及びポリビニルピロリドンから選択される少なくとも１つは、その質量平均分子量が１，０００以上で１，２００，０００以下であることが好ましく、１，０００以上で９００，０００以下であることがより好ましく、１，０００以上で３００，０００以下であることが更に好ましい。
The A component is preferably at least one selected from polyallylamine, polyallylamine salts, and polyvinylpyrrolidone. At least one selected from polyallylamine, polyallylamine salt, and polyvinylpyrrolidone as component A has a weight average molecular weight of preferably 1,000 or more and 1,200,000 or less, preferably 1,000 or more. is more preferably 900,000 or less, and more preferably 1,000 or more and 300,000 or less.
（１－２）Ｂ成分：
Ｂ成分は、所定のビニル共重合体である。このＢ成分を他の成分（Ａ成分、及び、Ｃ成分とＤ成分の少なくとも一方）とともに配合することで、使用温度に関わらず、経時による流動性の変化が少なく空気量の調整が適宜可能でありながら、凝結時間を過度に遅延させないという効果が発揮される。 (1-2) B component:
The B component is a specified vinyl copolymer. By blending this B component with other components (A component and at least one of C component and D component), it is possible to appropriately adjust the amount of air with little change in fluidity over time regardless of the operating temperature. However, the effect of not delaying the setting time excessively is exhibited.
Ｂ成分は、所定のビニル共重合体である。このＢ成分を他の成分（Ａ成分、及び、Ｃ成分とＤ成分の少なくとも一方）とともに配合することで、使用温度に関わらず、経時による流動性の変化が少なく空気量の調整が適宜可能でありながら、凝結時間を過度に遅延させないという効果が発揮される。 (1-2) B component:
The B component is a specified vinyl copolymer. By blending this B component with other components (A component and at least one of C component and D component), it is possible to appropriately adjust the amount of air with little change in fluidity over time regardless of the operating temperature. However, the effect of not delaying the setting time excessively is exhibited.
Ｂ成分は、一般式（１）で示される化合物である単量体１から形成された構成単位１、及び、一般式（２）で示される化合物である単量体２から形成された構成単位２を含むものである。そして、構成単位１の構成割合と構成単位２の構成割合の合計を１００質量％としたとき、構成単位１の割合が５０～９９質量％、構成単位２の割合が５０～１質量％のビニル共重合体である。
Component B is a structural unit 1 formed from a monomer 1, which is a compound represented by the general formula (1), and a structural unit formed from a monomer 2, which is a compound represented by the general formula (2). 2. Then, when the total of the composition ratio of the structural unit 1 and the composition ratio of the structural unit 2 is 100% by mass, the ratio of the structural unit 1 is 50 to 99% by mass and the ratio of the structural unit 2 is 50 to 1% by mass. It is a copolymer.
この構成単位１の割合は、６０～９９質量％とすることが好ましく、７０～９５質量％とすることが更に好ましい。また、構成単位２の割合は、４０～１質量％とすることが好ましく、３０～５質量％とすることが更に好ましい。
The proportion of this structural unit 1 is preferably 60 to 99% by mass, more preferably 70 to 95% by mass. Also, the proportion of structural unit 2 is preferably 40 to 1% by mass, more preferably 30 to 5% by mass.
（１－２ａ）構成単位１：
構成単位１は、下記一般式（１）で示される化合物である単量体１から形成されたものである。 (1-2a) Structural unit 1:
Structural unit 1 is formed from monomer 1, which is a compound represented by the following general formula (1).
構成単位１は、下記一般式（１）で示される化合物である単量体１から形成されたものである。 (1-2a) Structural unit 1:
Structural unit 1 is formed from monomer 1, which is a compound represented by the following general formula (1).
一般式（１）におけるＲ４は、水素原子又は炭素数１～２０の炭化水素基である。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、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－オクチル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基等の直鎖又は分岐アルキル基が挙げられる。これらの中でも、水素原子又は、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基等の炭素数１～５の炭化水素基であることが好ましい。
R 4 in general formula (1) is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of hydrocarbon groups having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group and n-hexyl group. , n-octyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and icosyl group. Among these, a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, etc. is preferably
一般式（１）におけるＲ５Ｏは、炭素数２～４のオキシアルキレン基（ただし、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、オキシブチレン基が挙げられる。
R 5 O in the general formula (1) is an oxyalkylene group having 2 to 4 carbon atoms (however, when there are a plurality of such oxyalkylene groups, one type or two or more types can be used), and carbon Examples of the oxyalkylene group of numbers 2 to 4 include oxyethylene group, oxypropylene group and oxybutylene group.
Ｒ５Ｏが２種類以上の場合は、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よい。
When there are two or more types of R 5 O, it may be in any form of random adduct, block adduct, and alternating adduct.
一般式（１）におけるａは、０～５の整数であり、０～２の整数であることが好ましい。
"a" in the general formula (1) is an integer of 0 to 5, preferably an integer of 0 to 2.
一般式（１）におけるｃは、１～３００の整数であり、１～２００の整数であることが好ましく、１～１５０の整数であることが更に好ましい。
c in the general formula (1) is an integer of 1-300, preferably an integer of 1-200, more preferably an integer of 1-150.
一般式（１）で示される化合物としては、例えば、α－アリル－ω－メトキシ－（ポリ）エチレングリコール、α－アリル－ω－メトキシ－（ポリ）エチレン（ポリ）プロピレングリコール、α－アリル－ω－ブトキシ－（ポリ）エチレングリコール、α－アリル－ω－ブトキシ－（ポリ）エチレン（ポリ）プロピレングリコール、α－アリル－ω－ヒドロキシ－（ポリ）エチレングリコール、α－アリル－ω－ヒドロキシ－（ポリ）エチレン（ポリ）プロピレングリコール、α－ビニル－ω－メトキシ－（ポリ）エチレングリコール、α－ビニル－ω－メトキシ－（ポリ）エチレン（ポリ）プロピレングリコール、α－ビニル－ω－ヒドロキシ－（ポリ）エチレングリコール、α－ビニル－ω－ヒドロキシ－（ポリ）エチレン（ポリ）プロピレングリコール、α－ビニル－ω－ヒドロキシ－（ポリ）エチレン（ポリ）ブチレングリコール、α－メタリル－ω－メトキシ－（ポリ）エチレングリコール、α－メタリル－ω－メトキシ－（ポリ）エチレン（ポリ）プロピレングリコール、α－メタリル－ω－ヒドロキシ－（ポリ）エチレングリコール、α－メタリル－ω－ヒドロキシ－（ポリ）エチレン（ポリ）プロピレングリコール、α－（３－メチル－３－ブテニル）－ω－メトキシ－（ポリ）エチレングリコール、α－（３－メチル－３－ブテニル）－ω－メトキシ－（ポリ）エチレン（ポリ）プロピレングリコール、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－（ポリ）エチレングリコール、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－（ポリ）エチレン（ポリ）プロピレングリコール、α－アクリロイル－ω－メトキシ－（ポリ）エチレングリコール、α－アクリロイル－ω－メトキシ－（ポリ）エチレン（ポリ）プロピレングリコール、α－アクリロイル－ω－ヒドロキシ－（ポリ）エチレングリコール、α－アクリロイル－ω－ヒドロキシ－（ポリ）プロピレンングリコール、α－アクリロイル－ω－ヒドロキシ－（ポリ）エチレン（ポリ）プロピレングリコール、α－メタクリロイル－ω－メトキシ－（ポリ）エチレングリコール、α－メタクリロイル－ω－メトキシ－（ポリ）エチレン（ポリ）プロピレングリコール、α－メタクリロイル－ω－ヒドロキシ－（ポリ）エチレングリコール、α－メタクリロイル－ω－ヒドロキシ－（ポリ）エチレン（ポリ）プロピレングリコール等が挙げられる。
Examples of compounds represented by general formula (1) include α-allyl-ω-methoxy-(poly)ethylene glycol, α-allyl-ω-methoxy-(poly)ethylene (poly)propylene glycol, α-allyl- ω-butoxy-(poly)ethylene glycol, α-allyl-ω-butoxy-(poly)ethylene (poly)propylene glycol, α-allyl-ω-hydroxy-(poly)ethylene glycol, α-allyl-ω-hydroxy- (Poly)ethylene (poly)propylene glycol, α-vinyl-ω-methoxy-(poly)ethylene glycol, α-vinyl-ω-methoxy-(poly)ethylene (poly)propylene glycol, α-vinyl-ω-hydroxy- (Poly)ethylene glycol, α-vinyl-ω-hydroxy-(poly)ethylene (poly)propylene glycol, α-vinyl-ω-hydroxy-(poly)ethylene (poly)butylene glycol, α-methallyl-ω-methoxy- (Poly)ethylene glycol, α-methallyl-ω-methoxy-(poly)ethylene (poly)propylene glycol, α-methallyl-ω-hydroxy-(poly)ethylene glycol, α-methallyl-ω-hydroxy-(poly)ethylene (Poly)propylene glycol, α-(3-methyl-3-butenyl)-ω-methoxy-(poly)ethylene glycol, α-(3-methyl-3-butenyl)-ω-methoxy-(poly)ethylene (poly ) propylene glycol, α-(3-methyl-3-butenyl)-ω-hydroxy-(poly)ethylene glycol, α-(3-methyl-3-butenyl)-ω-hydroxy-(poly)ethylene (poly)propylene glycol, α-acryloyl-ω-methoxy-(poly)ethylene glycol, α-acryloyl-ω-methoxy-(poly)ethylene (poly)propylene glycol, α-acryloyl-ω-hydroxy-(poly)ethylene glycol, α- Acryloyl-ω-hydroxy-(poly)propylene glycol, α-acryloyl-ω-hydroxy-(poly)ethylene (poly)propylene glycol, α-methacryloyl-ω-methoxy-(poly)ethylene glycol, α-methacryloyl-ω -Methoxy-(poly)ethylene (poly)propylene glycol, α-methacryloyl-ω-hydroxy-(poly)ethylene glycol, α-methacryloyl-ω-hydroxy-(poly)ethylene (poly)propylene glycol, etc. is mentioned.
（１－２ｂ）構成単位２：
構成単位２は、下記一般式（２）で示される化合物である単量体２から形成されたものである。 (1-2b) Structural unit 2:
Structural unit 2 is formed from monomer 2, which is a compound represented by the following general formula (2).
構成単位２は、下記一般式（２）で示される化合物である単量体２から形成されたものである。 (1-2b) Structural unit 2:
Structural unit 2 is formed from monomer 2, which is a compound represented by the following general formula (2).
一般式（２）におけるＭ１及び、上記有機基におけるＭ３は、水素原子、アルカリ金属、アルカリ土類金属（１／２原子）又は有機アミンである。アルカリ金属としては、例えば、ナトリウム、カリウム等が挙げられ、アルカリ土類金属としては、マグネシウム、カルシウム等が挙げられ、有機アミン塩としては、アンモニウム塩、第一級アミン塩、第二級アミン塩、第三級アミン塩等が挙げられる。
M1 in the general formula ( 2 ) and M3 in the above organic group are a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), or an organic amine. Examples of alkali metals include sodium, potassium, etc. Examples of alkaline earth metals include magnesium, calcium, etc. Examples of organic amine salts include ammonium salts, primary amine salts, and secondary amine salts. , tertiary amine salts and the like.
一般式（２）で示される化合物としては、例えば、（メタ）アクリル酸、（無水）マレイン酸、フマル酸、（無水）イタコン酸、クロトン酸、これらの塩（例えば、（メタ）アクリル酸塩）等が挙げられる。なお、これらの塩については特に制限するものではないが、ナトリウムやカリウム等のアルカリ金属塩、マグネシウムやカルシウム等のアルカリ土類金属塩、有機アミン塩等が挙げられる。
Examples of compounds represented by the general formula (2) include (meth)acrylic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, crotonic acid, salts thereof (e.g., (meth)acrylate ) and the like. These salts are not particularly limited, but examples include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium and calcium, and organic amine salts.
（１－２ｃ）質量平均分子量：
Ｂ成分は、その質量平均分子量が５，０００以上で１００，０００以下であり、６，０００以上で７０，０００以下であることが好ましい。Ｂ成分の質量平均分子量が下限値未満であると、調製直後の水硬性組成物において流動性が十分に確保できない。同様に、Ｂ成分の質量平均分子量が上限値超であると、調製直後の水硬性組成物において流動性が十分に確保できない不具合が生じる。特に、Ｄ成分を配合する場合には、Ｂ成分は、Ｄ成分と作用が重複する部分もあり、本発明の効果が十分に得られなくなる。但し、Ｂ成分とＤ成分を比べると、調製直後の水硬性組成物に十分な流動性を付与する点で、質量平均分子量が低いＢ成分の方を必須とすることが重要となる。 (1-2c) mass average molecular weight:
Component B has a weight average molecular weight of 5,000 or more and 100,000 or less, preferably 6,000 or more and 70,000 or less. If the mass-average molecular weight of the B component is less than the lower limit, sufficient fluidity cannot be ensured in the hydraulic composition immediately after preparation. Similarly, if the mass average molecular weight of the B component exceeds the upper limit, there arises a problem that sufficient fluidity cannot be ensured in the hydraulic composition immediately after preparation. In particular, when the D component is blended, the B component partially overlaps with the D component, and the effect of the present invention cannot be obtained sufficiently. However, when comparing the B component and the D component, it is important that the B component, which has a low mass average molecular weight, is essential in terms of imparting sufficient fluidity to the hydraulic composition immediately after preparation.
Ｂ成分は、その質量平均分子量が５，０００以上で１００，０００以下であり、６，０００以上で７０，０００以下であることが好ましい。Ｂ成分の質量平均分子量が下限値未満であると、調製直後の水硬性組成物において流動性が十分に確保できない。同様に、Ｂ成分の質量平均分子量が上限値超であると、調製直後の水硬性組成物において流動性が十分に確保できない不具合が生じる。特に、Ｄ成分を配合する場合には、Ｂ成分は、Ｄ成分と作用が重複する部分もあり、本発明の効果が十分に得られなくなる。但し、Ｂ成分とＤ成分を比べると、調製直後の水硬性組成物に十分な流動性を付与する点で、質量平均分子量が低いＢ成分の方を必須とすることが重要となる。 (1-2c) mass average molecular weight:
Component B has a weight average molecular weight of 5,000 or more and 100,000 or less, preferably 6,000 or more and 70,000 or less. If the mass-average molecular weight of the B component is less than the lower limit, sufficient fluidity cannot be ensured in the hydraulic composition immediately after preparation. Similarly, if the mass average molecular weight of the B component exceeds the upper limit, there arises a problem that sufficient fluidity cannot be ensured in the hydraulic composition immediately after preparation. In particular, when the D component is blended, the B component partially overlaps with the D component, and the effect of the present invention cannot be obtained sufficiently. However, when comparing the B component and the D component, it is important that the B component, which has a low mass average molecular weight, is essential in terms of imparting sufficient fluidity to the hydraulic composition immediately after preparation.
なお、Ｂ成分としてのビニル共重合体は、構成単位１及び構成単位２の他に、一般式（１）で示される化合物及び一般式（２）で示される化合物とは異なるその他の単量体から形成された構成単位を含有していてもよい。その他の単量体としては、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。その他の構成単位は、１種又は２種以上から形成されていてもよい。その他の構成単位の共重合割合は、全構成単位中、２０質量％以下が好ましく、１０質量％以下が更に好ましい。
In addition to the structural unit 1 and the structural unit 2, the vinyl copolymer as the B component contains other monomers different from the compound represented by the general formula (1) and the compound represented by the general formula (2). It may contain structural units formed from. Other monomers that can be used include, for example, (meth)allylsulfonic acid and salts thereof, (meth)acrylamide, acrylonitrile, and (meth)acrylic acid alkyl esters. Other structural units may be formed from one or two or more. The copolymerization ratio of other structural units is preferably 20% by mass or less, more preferably 10% by mass or less, in all structural units.
更に、Ｂ成分としてのビニル共重合体は公知の方法で製造することができる。例えば、このようなビニル共重合体としては、ラジカル重合にて合成され、上記の構成単位１を形成する一般式（１）で示される化合物である単量体１、構成単位２を形成する一般式（２）で示される化合物である単量体２、及びその他の構成単位を形成するその他の単量体、及びラジカル開始剤を混合（加熱）することにより得られる。
Furthermore, the vinyl copolymer as the B component can be produced by a known method. For example, as such a vinyl copolymer, a monomer 1, which is a compound represented by the general formula (1) that is synthesized by radical polymerization and forms the above structural unit 1, and a general compound that forms the structural unit 2 It is obtained by mixing (heating) the monomer 2, which is the compound represented by formula (2), other monomers forming other structural units, and a radical initiator.
使用するラジカル開始剤としては、例えば、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の過硫酸塩、過酸化水素、２，２’－アゾビス（２－メチルブチロニトリル）、２，２’－アゾビスイソブチロニトリル等のアゾ系化合物等が挙げられる。これらは、亜硫酸塩やアスコルビン酸等の還元性物質、更にはアミン等と組み合わせ、レドックス開始剤系として用いることもできる。また、得られる共重合体の質量平均分子量を所望の範囲とするため、２－メルカプトエタノール、２－メルカプトプロピオン酸、３－メルカプトプロピオン酸、チオグリセロール、チオグリコール酸等の連鎖移動剤を使用してもよい。また、重合は、溶媒に水や有機溶媒を用いてもよく、無溶媒であってもよい。
Examples of radical initiators to be used include persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, hydrogen peroxide, 2,2′-azobis(2-methylbutyronitrile), 2,2′- Examples include azo compounds such as azobisisobutyronitrile. These can also be used as redox initiator systems in combination with reducing substances such as sulfites and ascorbic acid, as well as amines and the like. In order to set the weight average molecular weight of the resulting copolymer within the desired range, a chain transfer agent such as 2-mercaptoethanol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thioglycerol, and thioglycolic acid is used. may Moreover, water or an organic solvent may be used as a solvent for the polymerization, or no solvent may be used.
（１－３）Ｃ成分：
Ｃ成分は、下記一般式（３）で示される化合物である。このＣ成分を他の成分（Ａ成分及びＢ成分、必要に応じてＤ成分）とともに配合することで、使用温度に関わらず、経時による流動性の変化が更に少なく空気量の調整が適宜可能でありながら、凝結時間をより過度に遅延させないという効果が発揮される。特に、このＣ成分を配合することで、練り混ぜ後、６０分程度から９０分程度の間における流動性の保持が非常に優れることになる。 (1-3) C component:
Component C is a compound represented by the following general formula (3). By blending this C component with other components (A component and B component, D component if necessary), regardless of the operating temperature, the change in fluidity over time is further reduced and the amount of air can be adjusted appropriately. However, the effect of not delaying the setting time more excessively is exhibited. In particular, by incorporating this C component, the retention of fluidity for about 60 to 90 minutes after kneading is extremely excellent.
Ｃ成分は、下記一般式（３）で示される化合物である。このＣ成分を他の成分（Ａ成分及びＢ成分、必要に応じてＤ成分）とともに配合することで、使用温度に関わらず、経時による流動性の変化が更に少なく空気量の調整が適宜可能でありながら、凝結時間をより過度に遅延させないという効果が発揮される。特に、このＣ成分を配合することで、練り混ぜ後、６０分程度から９０分程度の間における流動性の保持が非常に優れることになる。 (1-3) C component:
Component C is a compound represented by the following general formula (3). By blending this C component with other components (A component and B component, D component if necessary), regardless of the operating temperature, the change in fluidity over time is further reduced and the amount of air can be adjusted appropriately. However, the effect of not delaying the setting time more excessively is exhibited. In particular, by incorporating this C component, the retention of fluidity for about 60 to 90 minutes after kneading is extremely excellent.
一般式（３）におけるＲ９は、ロジンのアシル残基である。ここで、ロジンとは、樹脂酸（ロジン酸）と称されるジテルペン系化合物をいう。このようなロジンとして、例えば、天然ロジン、変性ロジン、重合ロジンなどが挙げられる。
R9 in general formula ( 3 ) is an acyl residue of rosin. Here, rosin refers to a diterpene compound called resin acid (rosin acid). Examples of such rosin include natural rosin, modified rosin, polymerized rosin and the like.
天然ロジンは、マツ科植物から得られる樹脂油から、精油等の揮発性物質を留去した残留物中に存在する樹脂酸の混合物であり、製造方法により、ガムロジン、ウッドロジン、トール油ロジンに分類される。
Natural rosin is a mixture of resin acids present in the residue obtained by distilling off volatile substances such as essential oils from resin oil obtained from plants of the Pinaceae family. It is classified into gum rosin, wood rosin and tall oil rosin according to the manufacturing method. be done.
ガムロジンは、松の木に切り傷をつけ、そこから流出する生松脂をろ過精製し、水蒸気蒸留によりテレビン油を除去して得られる。ウッドロジンは、松の切株のチップを溶剤抽出して得られる。トール油ロジンは、松材からクラフトパルプ法でパルプを製造する工程で副生する粗トール油を蒸留精製して得られる。
Gum rosin is obtained by cutting a pine tree, filtering and refining the raw pine resin that flows out from the cut, and removing the turpentine oil by steam distillation. Wood rosin is obtained by solvent extraction of pine stump chips. Tall oil rosin is obtained by distilling and refining crude tall oil, which is a by-product in the process of producing pulp from pine wood by the kraft pulp method.
ロジンは、主成分の樹脂酸として、アビエチン酸を含み、その他の成分の樹脂酸として、ネオアビエチン酸、デヒドロアビエチン酸、テトラヒドロアビエチン酸、パラストリン酸、ピマール酸、イソピマール酸、サンダラコピマール酸、レボピマール酸等を含む。
Rosin contains abietic acid as a main resin acid, and other resin acids such as neoabietic acid, dehydroabietic acid, tetrahydroabietic acid, parastric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, and levopimaric acid. Including acids, etc.
変性ロジンとは、天然ロジンを変性したものをいい、例えば、天然ロジンを高圧化でニッケル触媒、白金触媒、パラジウム触媒等の貴金属触媒等を使用して水素添加して、分子内の二重結合を消失若しくは減少させた水添ロジン、天然ロジンを貴金属触媒又はハロゲン触媒の存在下に高温加熱することにより分子内の不安定な共役二重結合を消失させた不均化ロジンが挙げられる。
Modified rosin refers to a modified natural rosin. For example, natural rosin is hydrogenated under high pressure using a nickel catalyst, platinum catalyst, palladium catalyst, or other noble metal catalyst to form double bonds in the molecule. and a disproportionated rosin obtained by heating a natural rosin to a high temperature in the presence of a noble metal catalyst or a halogen catalyst to eliminate unstable conjugated double bonds in the molecule.
重合ロジンとは、天然ロジン又は変性ロジン同士を反応させたものであり、これらの２量化物、３量化物をいう。
Polymerized rosin is a product obtained by reacting natural rosin or modified rosin with each other, and refers to dimerized products and trimerized products thereof.
なお、このようなロジンとして、入手の容易さの観点から、天然ロジンが好ましい。このような天然ロジンとしては、より好ましくは、ガムロジンである。ロジンは、様々な化合物の混合物として扱うことが一般的であり、カルボン酸量については、酸価を測定することで定量化される。酸価は、日本工業規格ＪＩＳ Ｋ ００７０（１９９２）により測定することで求められる。
As such rosin, natural rosin is preferable from the viewpoint of easy availability. Gum rosin is more preferred as such a natural rosin. Rosin is generally treated as a mixture of various compounds, and the amount of carboxylic acid is quantified by measuring the acid value. The acid value is determined by measuring according to Japanese Industrial Standards JIS K 0070 (1992).
一般式（３）におけるＲ１０は、水素原子、炭素数１～２０のアルキル基、又は炭素数２～２０のアルケニル基である。この炭素数１～２０のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－オクチル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基等の直鎖又は分岐アルキル基が挙げられる。炭素数２～２０のアルケニル基としては、エテニル基、ｎ－プロペニル基、ｎ－ブテニル基、ｎ－ペンテニル基、ｎ－ヘキセニル基、ｎ－ヘプテニル基、ｎ－オクテニル基、ｎ－ノネル基、ｎ－デセニル基、ｎ－ウンデセニル基、ｎ－ドデセニル基、ｎ－トリデセニル基、ｎ－テトラデセニル基、ｎ－ペンタデセニル基、ｎ－ヘキサデセニル基、ｎ－ヘプタデセニル基、ｎ－オクタデセニル基、ｎ－ノナデセニル基、ｎ－イコセニル基等が挙げられる。これらの中でも、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基等の炭素数１～５のアルキル基、エテニル基、ｎ－プロペニル基、ｎ－ブテニル基、ｎ－ペンテニル基等の炭素数２～５のアルケニル基が好ましい。
R 10 in general formula (3) is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group and n-hexyl group. , n-octyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and icosyl group. Examples of alkenyl groups having 2 to 20 carbon atoms include ethenyl, n-propenyl, n-butenyl, n-pentenyl, n-hexenyl, n-heptenyl, n-octenyl, n-nonel, n -decenyl group, n-undecenyl group, n-dodecenyl group, n-tridecenyl group, n-tetradecenyl group, n-pentadecenyl group, n-hexadecenyl group, n-heptadecenyl group, n-octadecenyl group, n-nonadecenyl group, n -icosenyl group and the like. Among these, alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, ethenyl group, n Alkenyl groups having 2 to 5 carbon atoms such as -propenyl group, n-butenyl group and n-pentenyl group are preferred.
一般式（３）におけるＡＯは、炭素数２～４のオキシアルキレン基（ただし、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、オキシブチレン基が挙げられる。
AO in the general formula (3) is an oxyalkylene group having 2 to 4 carbon atoms (however, when there are a plurality of the oxyalkylene groups, it may be one type alone or two or more types), and has 2 carbon atoms. Examples of the oxyalkylene group of -4 include an oxyethylene group, an oxypropylene group and an oxybutylene group.
ＡＯが２種類以上の場合は、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よい。
When there are two or more types of AO, it may be in any form of random adduct, block adduct, or alternating adduct.
一般式（３）におけるｓは、１～２００の整数であり、１～１５０の整数であることが好ましく、５～１００の整数であることが更に好ましい。
s in the general formula (3) is an integer of 1 to 200, preferably an integer of 1 to 150, and more preferably an integer of 5 to 100.
Ｃ成分は、一般式（３）における－（ＡＯ）ｓ－について、炭素数２～４のオキシアルキレン基の構成割合の合計を１００モル％とするとき、炭素数２のオキシアルキレン基を９０モル％以上の割合で有するものであることが好ましい。
Component C is 90 moles of an oxyalkylene group having 2 carbon atoms, given that the total proportion of oxyalkylene groups having 2 to 4 carbon atoms in -(AO) s - in the general formula (3) is 100 mol%. % or more.
一般式（３）で表される化合物の製造方法は特に限定されない。一般式（３）で表される化合物の製造方法としては、例えば、アビエチン酸、ネオアビエチン酸、デヒドロアビエチン酸、テトラヒドロアビエチン酸、パラストリン酸、ピマール酸、イソピマール酸、サンダラコピマール酸、レボピマール酸等の樹脂酸の混合物であるロジンに、触媒等を用いることで常法によりアルキレンオキサイドを付加させて、一般式（３）で表されるロジンポリオキシアルキレン付加物を製造する方法や、Ｒ１０に相当するアルコールに、予め、触媒等を用いることで常法によりアルキレンオキシドを付加し、その後ロジンとエステル化させることにより、一般式（３）で表される化合物を製造する方法等が挙げられる。
The method for producing the compound represented by formula (3) is not particularly limited. Examples of methods for producing the compound represented by the general formula (3) include abietic acid, neoabietic acid, dehydroabietic acid, tetrahydroabietic acid, parastric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, and levopimaric acid. A method for producing a rosin polyoxyalkylene adduct represented by the general formula ( 3 ) by adding an alkylene oxide to rosin, which is a mixture of resin acids, by a conventional method using a catalyst or the like, or Examples include a method of producing a compound represented by the general formula (3) by previously adding an alkylene oxide to the corresponding alcohol by a conventional method using a catalyst or the like, and then esterifying it with rosin.
（１－４）Ｄ成分：
Ｄ成分は、上記Ｂ成分とは異なる所定のビニル共重合体である。このＤ成分を他の成分（Ａ成分及びＢ成分、必要に応じてＣ成分）とともに配合することで、使用温度に関わらず、経時による流動性の変化が少なく空気量の調整が適宜可能でありながら、凝結時間を過度に遅延させないという効果が発揮される。なお、このＤ成分は、Ｂ成分（所定のビニル共重合体）よりも質量平均分子量が大きなビニル共重合体である。 (1-4) D component:
The D component is a predetermined vinyl copolymer different from the B component. By blending this D component with other components (A component and B component, and C component if necessary), regardless of the operating temperature, the change in fluidity over time is small and the amount of air can be adjusted appropriately. However, the effect of not delaying the setting time excessively is exhibited. The D component is a vinyl copolymer having a larger weight average molecular weight than the B component (predetermined vinyl copolymer).
Ｄ成分は、上記Ｂ成分とは異なる所定のビニル共重合体である。このＤ成分を他の成分（Ａ成分及びＢ成分、必要に応じてＣ成分）とともに配合することで、使用温度に関わらず、経時による流動性の変化が少なく空気量の調整が適宜可能でありながら、凝結時間を過度に遅延させないという効果が発揮される。なお、このＤ成分は、Ｂ成分（所定のビニル共重合体）よりも質量平均分子量が大きなビニル共重合体である。 (1-4) D component:
The D component is a predetermined vinyl copolymer different from the B component. By blending this D component with other components (A component and B component, and C component if necessary), regardless of the operating temperature, the change in fluidity over time is small and the amount of air can be adjusted appropriately. However, the effect of not delaying the setting time excessively is exhibited. The D component is a vinyl copolymer having a larger weight average molecular weight than the B component (predetermined vinyl copolymer).
ここで、このＤ成分を配合することで、練り混ぜ後、０分（即ち、練り混ぜ直後）から６０分程度の間における流動性が非常に優れることになる。
Here, by blending this D component, the fluidity is extremely excellent in the period from 0 minutes (that is, immediately after kneading) to about 60 minutes after kneading.
なお、Ｃ成分とＤ成分の両方を配合すると、練り混ぜ後、０分（即ち、練り混ぜ直後）から９０分程度の間において非常に優れた流動性が保持されることになる。そして、その後の凝結も良好に開始されることになる。
It should be noted that when both the C component and the D component are blended, extremely excellent fluidity is maintained for about 0 minutes (that is, immediately after kneading) to about 90 minutes after kneading. Then the subsequent setting will also start well.
このようにＣ成分とＤ成分では、優れた流動性が発揮される時間帯が異なるため、これらを使い分けることで、打ち込み時における適切な流動性を確保することができる。また、これらの両方を配合することで、両方の機能を十分に発揮させることができ、流動性の保持時間を長くすること、即ち、練り混ぜ後、０分（即ち、練り混ぜ直後）から９０分程度の間の流動性を確保することができる。
In this way, the C component and the D component have different time zones during which excellent fluidity is exhibited, so by using these properly, it is possible to ensure appropriate fluidity during driving. In addition, by blending both of these, it is possible to sufficiently exhibit both functions, and the retention time of fluidity can be extended, that is, after kneading, 0 minutes (that is, immediately after kneading) to 90 minutes Liquidity can be secured for about a minute.
Ｄ成分は、一般式（４）で示される化合物である単量体３から形成された構成単位３、及び、一般式（５）で示される化合物である単量体４から形成された構成単位４を含むものである。そして、構成単位３の構成割合と構成単位４の構成割合の合計を１００質量％としたとき、構成単位３の割合が５０～９９質量％、構成単位４の割合が５０～１質量％のビニル共重合体である。
Component D is a structural unit 3 formed from a monomer 3, which is a compound represented by the general formula (4), and a structural unit formed from a monomer 4, which is a compound represented by the general formula (5). 4. Then, when the total of the composition ratio of the structural unit 3 and the composition ratio of the structural unit 4 is 100% by mass, the ratio of the structural unit 3 is 50 to 99% by mass and the ratio of the structural unit 4 is 50 to 1% by mass. It is a copolymer.
この構成単位３の割合は、７０～９９質量％とすることが好ましく、８０～９５質量％とすることが更に好ましい。また、構成単位４の割合は、１～３０質量％とすることが好ましく、５～２０質量％とすることが更に好ましい。
The proportion of this structural unit 3 is preferably 70 to 99% by mass, more preferably 80 to 95% by mass. Also, the proportion of the structural unit 4 is preferably 1 to 30% by mass, more preferably 5 to 20% by mass.
（１－４ａ）構成単位３：
構成単位３は、下記一般式（４）で示される化合物である単量体３から形成されたものである。 (1-4a) Structural unit 3:
Structural unit 3 is formed from monomer 3, which is a compound represented by the following general formula (4).
構成単位３は、下記一般式（４）で示される化合物である単量体３から形成されたものである。 (1-4a) Structural unit 3:
Structural unit 3 is formed from monomer 3, which is a compound represented by the following general formula (4).
一般式（４）におけるＲ１４は、水素原子又は炭素数１～２０の炭化水素基であり、例えば、一般式（１）におけるＲ４の炭化水素基として例示した上記炭化水素基と同様のものなどが挙げられる。これらの中でも、水素原子又は炭素数１～５の炭化水素基であることが好ましい。
R 14 in general formula (4) is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, for example, the same hydrocarbon group as the hydrocarbon group for R 4 in general formula (1). etc. Among these, a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms is preferred.
一般式（４）におけるＲ１５Ｏは、炭素数２～４のオキシアルキレン基（ただし、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、オキシブチレン基が挙げられる。
R 15 O in the general formula (4) is an oxyalkylene group having 2 to 4 carbon atoms (however, when there are a plurality of such oxyalkylene groups, one type or two or more types can be used), and carbon Examples of the oxyalkylene group of numbers 2 to 4 include oxyethylene group, oxypropylene group and oxybutylene group.
一般式（４）におけるｄは、０～５の整数であり、０～２の整数であることが好ましい。
d in the general formula (4) is an integer of 0 to 5, preferably an integer of 0 to 2.
一般式（４）におけるｆは、１～３００の整数であり、１～２００の整数であることが好ましく、１～１５０の整数であることが更に好ましい。
f in the general formula (4) is an integer of 1-300, preferably an integer of 1-200, more preferably an integer of 1-150.
一般式（４）で示される化合物としては、例えば、一般式（１）で示される化合物として例示した上記化合物と同様のものなどが挙げられる。
Examples of the compound represented by the general formula (4) include those similar to the above compounds exemplified as the compound represented by the general formula (1).
（１－４ｂ）構成単位４：
構成単位４は、下記一般式（５）で示される化合物である単量体４から形成されたものである。 (1-4b) Structural unit 4:
Structural unit 4 is formed from monomer 4, which is a compound represented by the following general formula (5).
構成単位４は、下記一般式（５）で示される化合物である単量体４から形成されたものである。 (1-4b) Structural unit 4:
Structural unit 4 is formed from monomer 4, which is a compound represented by the following general formula (5).
一般式（５）におけるＭ２及び、上記有機基におけるＭ４は、水素原子、アルカリ金属、アルカリ土類金属（１／２原子）又は有機アミンである。アルカリ金属としては、例えば、ナトリウム、カリウム等が挙げられ、アルカリ土類金属としては、マグネシウム、カルシウム等が挙げられ、有機アミン塩としては、アンモニウム塩、第一級アミン塩、第二級アミン塩、第三級アミン塩等が挙げられる。
M2 in the general formula ( 5 ) and M4 in the above organic group are a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), or an organic amine. Examples of alkali metals include sodium, potassium, etc. Examples of alkaline earth metals include magnesium, calcium, etc. Examples of organic amine salts include ammonium salts, primary amine salts, and secondary amine salts. , tertiary amine salts and the like.
一般式（５）で示される化合物としては、（メタ）アクリル酸、（無水）マレイン酸、フマル酸、（無水）イタコン酸、クロトン酸、これらの塩（例えば、（メタ）アクリル酸塩）等が挙げられる。これらの塩については、特に制限するものではないが、ナトリウムやカリウム等のアルカリ金属塩、マグネシウムやカルシウム等のアルカリ土類金属塩、有機アミン塩等が挙げられる。
Examples of compounds represented by the general formula (5) include (meth)acrylic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, crotonic acid, salts thereof (e.g., (meth)acrylic acid salts), and the like. is mentioned. These salts are not particularly limited, but include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium and calcium, and organic amine salts.
（１－４ｃ）質量平均分子量：
Ｄ成分は、その質量平均分子量が１００，０００超で６００，０００以下であり、１５０，０００超で５００，０００以下であることが好ましい。Ｄ成分の質量平均分子量が下限値未満であると、流動保持性が低下する。この場合、Ｂ成分と重複することになり、Ｃ成分が含まれない場合には本発明の効果が十分に得られ難くなる傾向がある。また、Ｄ成分を配合することで、質量平均分子量が小さいＢ成分（ビニル共重合体）以外に、これよりも質量平均分子量が大きな所定のビニル共重合体が共存することになり、これにより本発明の効果が良好に発揮されることになる。そして、Ｄ成分の質量平均分子量が上限値超であると、調製直後の水硬性組成物において流動性が十分に確保できない。 (1-4c) mass average molecular weight:
Component D preferably has a weight average molecular weight of more than 100,000 and 600,000 or less, more preferably more than 150,000 and 500,000 or less. If the mass-average molecular weight of component D is less than the lower limit, the fluidity retention is reduced. In this case, it overlaps with the B component, and when the C component is not included, it tends to be difficult to sufficiently obtain the effects of the present invention. Further, by blending the D component, in addition to the B component (vinyl copolymer) having a small mass average molecular weight, a predetermined vinyl copolymer having a larger mass average molecular weight coexists, thereby making the present invention. The effect of the invention is exhibited satisfactorily. And when the mass average molecular weight of the D component exceeds the upper limit, sufficient fluidity cannot be ensured in the hydraulic composition immediately after preparation.
Ｄ成分は、その質量平均分子量が１００，０００超で６００，０００以下であり、１５０，０００超で５００，０００以下であることが好ましい。Ｄ成分の質量平均分子量が下限値未満であると、流動保持性が低下する。この場合、Ｂ成分と重複することになり、Ｃ成分が含まれない場合には本発明の効果が十分に得られ難くなる傾向がある。また、Ｄ成分を配合することで、質量平均分子量が小さいＢ成分（ビニル共重合体）以外に、これよりも質量平均分子量が大きな所定のビニル共重合体が共存することになり、これにより本発明の効果が良好に発揮されることになる。そして、Ｄ成分の質量平均分子量が上限値超であると、調製直後の水硬性組成物において流動性が十分に確保できない。 (1-4c) mass average molecular weight:
Component D preferably has a weight average molecular weight of more than 100,000 and 600,000 or less, more preferably more than 150,000 and 500,000 or less. If the mass-average molecular weight of component D is less than the lower limit, the fluidity retention is reduced. In this case, it overlaps with the B component, and when the C component is not included, it tends to be difficult to sufficiently obtain the effects of the present invention. Further, by blending the D component, in addition to the B component (vinyl copolymer) having a small mass average molecular weight, a predetermined vinyl copolymer having a larger mass average molecular weight coexists, thereby making the present invention. The effect of the invention is exhibited satisfactorily. And when the mass average molecular weight of the D component exceeds the upper limit, sufficient fluidity cannot be ensured in the hydraulic composition immediately after preparation.
なお、Ｄ成分としてのビニル共重合体は、構成単位３及び構成単位４の他に、一般式（４）で示される化合物及び一般式（５）で示される化合物とは異なるその他の単量体から形成された構成単位（その他の構成単位）を含有していてもよい。そして、その他の単量体としては、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。その他の構成単位は、１種又は２種以上から形成されていてもよい。その他の構成単位の共重合割合は、全構成単位中、２０質量％以下が好ましく、さらには１０質量％以下が更に好ましい。
In addition to the structural unit 3 and the structural unit 4, the vinyl copolymer as the component D contains other monomers different from the compound represented by the general formula (4) and the compound represented by the general formula (5). It may contain structural units (other structural units) formed from. As other monomers, for example, (meth)allylsulfonic acid and salts thereof, (meth)acrylamide, acrylonitrile, (meth)acrylic acid alkyl esters, and the like can be used. Other structural units may be formed from one or two or more. The copolymerization ratio of other structural units is preferably 20% by mass or less, more preferably 10% by mass or less, in all structural units.
更に、Ｄ成分としてのビニル共重合体は公知の方法で製造することができる。例えば、このビニル共重合体は、ラジカル重合にて合成され、上記の構成単位３を形成する一般式（４）で示される化合物である単量体３、構成単位４を形成する一般式（５）で示される化合物である単量体４、及びその他の構成単位を形成するその他の単量体、及びラジカル開始剤を混合（加熱）することにより得ることができる。
Furthermore, the vinyl copolymer as component D can be produced by a known method. For example, this vinyl copolymer is synthesized by radical polymerization, and monomer 3, which is a compound represented by general formula (4) forming structural unit 3, and general formula (5 ), other monomers forming other structural units, and a radical initiator can be mixed (heated).
使用するラジカル開始剤としては、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の過硫酸塩、過酸化水素、２，２’－アゾビス（２－メチルブチロニトリル）、２，２’－アゾビスイソブチロニトリル等のアゾ系化合物等が挙げられる。これらは、亜硫酸塩やアスコルビン酸等の還元性物質、更にはアミン等と組み合わせ、レドックス開始剤系として用いることもできる。また、重合は溶媒に水や有機溶媒を用いてもよく、無溶媒であってもよい。
Radical initiators to be used include persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, hydrogen peroxide, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis Examples include azo compounds such as isobutyronitrile. These can also be used as redox initiator systems in combination with reducing substances such as sulfites and ascorbic acid, as well as amines and the like. Moreover, water or an organic solvent may be used as a solvent for the polymerization, or no solvent may be used.
（１－４ｄ）連鎖移動剤に由来する構成単位：
Ｄ成分は、構成単位３及び構成単位４以外に、硫黄原子を含有する親水性連鎖移動剤（ＴＡ）に由来する構成単位や、硫黄原子を含有する疎水性連鎖移動剤（ＴＢ）などの連鎖移動剤に由来する構成単位を更に含有していてもよく、これらの中でも、硫黄原子を含有する親水性連鎖移動剤（ＴＡ）に由来する構成単位、及び硫黄原子を含有する疎水性連鎖移動剤（ＴＢ）に由来する構成単位の少なくとも一方を含有することがよい。特に、硫黄原子を含有する親水性連鎖移動剤（ＴＡ）に由来する構成単位を含有していることが好ましい。 (1-4d) a structural unit derived from a chain transfer agent:
In addition to structural unit 3 and structural unit 4, component D is a structural unit derived from a hydrophilic chain transfer agent (TA) containing a sulfur atom, and a chain such as a hydrophobic chain transfer agent (TB) containing a sulfur atom. It may further contain a structural unit derived from a transfer agent, and among these, a structural unit derived from a hydrophilic chain transfer agent (TA) containing a sulfur atom and a hydrophobic chain transfer agent containing a sulfur atom. It is preferable to contain at least one of structural units derived from (TB). In particular, it preferably contains structural units derived from a hydrophilic chain transfer agent (TA) containing a sulfur atom.
Ｄ成分は、構成単位３及び構成単位４以外に、硫黄原子を含有する親水性連鎖移動剤（ＴＡ）に由来する構成単位や、硫黄原子を含有する疎水性連鎖移動剤（ＴＢ）などの連鎖移動剤に由来する構成単位を更に含有していてもよく、これらの中でも、硫黄原子を含有する親水性連鎖移動剤（ＴＡ）に由来する構成単位、及び硫黄原子を含有する疎水性連鎖移動剤（ＴＢ）に由来する構成単位の少なくとも一方を含有することがよい。特に、硫黄原子を含有する親水性連鎖移動剤（ＴＡ）に由来する構成単位を含有していることが好ましい。 (1-4d) a structural unit derived from a chain transfer agent:
In addition to structural unit 3 and structural unit 4, component D is a structural unit derived from a hydrophilic chain transfer agent (TA) containing a sulfur atom, and a chain such as a hydrophobic chain transfer agent (TB) containing a sulfur atom. It may further contain a structural unit derived from a transfer agent, and among these, a structural unit derived from a hydrophilic chain transfer agent (TA) containing a sulfur atom and a hydrophobic chain transfer agent containing a sulfur atom. It is preferable to contain at least one of structural units derived from (TB). In particular, it preferably contains structural units derived from a hydrophilic chain transfer agent (TA) containing a sulfur atom.
ここで、「連鎖移動剤に由来する構成単位を含有する」とは、ビニル共重合体の末端に硫黄原子を含有する連鎖移動剤に由来する構造を有することであり、ビニル共重合体主鎖の水素ラジカルの引き抜き後の連鎖移動反応により、主鎖に、導入された連鎖移動剤に由来する構造を含むことをいう。より具体的には、例えば硫黄原子を含有する場合、連鎖移動剤に由来する構造が、硫黄原子を介して、ビニル系単量体由来の構造の主鎖末端の少なくとも一つと結合した構造を有していることを意味する。つまり、硫黄原子を含有する親水性連鎖移動剤（ＴＡ）と硫黄原子を含有する疎水性連鎖移動剤（ＴＢ）の場合には、主として、それぞれの硫黄原子を介して、構成単位３及び構成単位４を含む主鎖の末端と結合している。
Here, "containing a structural unit derived from a chain transfer agent" means that the vinyl copolymer has a structure derived from a chain transfer agent containing a sulfur atom at the end of the vinyl copolymer. It means that the structure derived from the introduced chain transfer agent is included in the main chain by the chain transfer reaction after abstraction of the hydrogen radical of. More specifically, for example, when a sulfur atom is contained, the structure derived from the chain transfer agent has a structure bonded to at least one main chain end of the structure derived from the vinyl monomer through the sulfur atom. means that That is, in the case of a hydrophilic chain transfer agent (TA) containing a sulfur atom and a hydrophobic chain transfer agent (TB) containing a sulfur atom, the structural unit 3 and the structural unit It binds to the ends of the main chain containing 4.
硫黄原子を含有する親水性連鎖移動剤（ＴＡ）としては、例えば、２－メルカプトエタノール、チオグリセロール、チオグリコール酸、２－メルカプトプロピオン酸、３－メルカプトプロピオン酸、チオリンゴ酸、２－メルカプトエタンスルホン酸等が挙げられる。これらの中でも、３－メルカプトプロピオン酸、チオグリコール酸、チオグリセロールが好ましい。また、硫黄原子を含有する親水性連鎖移動剤（ＴＡ）は、１種又は２種以上を併用してもよい。
Hydrophilic chain transfer agents (TA) containing sulfur atoms include, for example, 2-mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, 2-mercaptoethanesulfone acids and the like. Among these, 3-mercaptopropionic acid, thioglycolic acid and thioglycerol are preferred. Moreover, the hydrophilic chain transfer agent (TA) containing a sulfur atom may be used singly or in combination of two or more.
構成単位３及び構成単位４以外に、硫黄原子を含有する親水性連鎖移動剤（ＴＡ）に由来する構成単位を更に含有しているビニル共重合体は、構成単位３を構成する一般式（４）で示される化合物である単量体３、構成単位４を構成する一般式（５）で示される化合物である単量体４、及び硫黄原子を含有する親水性連鎖移動剤（ＴＡ）の存在下において、水中又は無溶媒で重合させて製造されるものである。
A vinyl copolymer further containing a structural unit derived from a hydrophilic chain transfer agent (TA) containing a sulfur atom, in addition to the structural units 3 and 4, is represented by the general formula (4 ), the monomer 4 which is a compound represented by the general formula (5) constituting the structural unit 4, and the presence of a hydrophilic chain transfer agent (TA) containing a sulfur atom It is produced by polymerizing in water or in the absence of a solvent as described below.
硫黄原子を含有する親水性連鎖移動剤（ＴＡ）に由来する構成単位は、構成単位３と構成単位４の合計に対する割合が、０．００１～４質量％であることが好ましい。
The proportion of structural units derived from a hydrophilic chain transfer agent (TA) containing a sulfur atom to the total of structural units 3 and 4 is preferably 0.001 to 4% by mass.
Ｄ成分は、更に、構成単位３及び構成単位４以外に、硫黄原子を含有する親水性連鎖移動剤（ＴＡ）に由来する構成単位と、硫黄原子を含有する疎水性連鎖移動剤（ＴＢ）に由来する構成単位の両方を含有していることが特に好ましい。
In addition to structural unit 3 and structural unit 4, component D further includes structural units derived from a hydrophilic chain transfer agent (TA) containing sulfur atoms and a hydrophobic chain transfer agent (TB) containing sulfur atoms. It is particularly preferred to contain both of the derived structural units.
硫黄原子を含有する疎水性連鎖移動剤（ＴＢ）としては、例えば、ｎ－ドデシルメルカプタン、ステアリルメルカプタン、セチルメルカプタン、２－エチルヘキシルメルカプタン、ｔｅｒｔ－ドデシルメルカプタン、ドコシルメルカプタンなどのアルキルメルカプタン、チオグリコール酸オクチル、３－メルカプトプロピオン酸オクチルなどのメルカプトカルボン酸アルキルエステルなどが挙げられる。特に、アルキルメルカプタンが好ましく、アルキル鎖の炭素数は、８～２２であることがより好ましい。これらの中でも、ｎ－ドデシルメルカプタン、ステアリルメルカプタン、セチルメルカプタン、２－エチルヘキシルメルカプタン、ｔｅｒｔ－ドデシルメルカプタン、ドコシルメルカプタンが好ましい。また、硫黄原子を含有する疎水性連鎖移動剤（ＴＢ）は１種又は２種以上を併用してもよい。
Hydrophobic chain transfer agents (TB) containing sulfur atoms include, for example, n-dodecyl mercaptan, stearyl mercaptan, cetyl mercaptan, 2-ethylhexyl mercaptan, tert-dodecyl mercaptan, docosyl mercaptan and other alkyl mercaptans, and thioglycolic acid. and mercaptocarboxylic acid alkyl esters such as octyl and octyl 3-mercaptopropionate. Alkyl mercaptans are particularly preferred, and the number of carbon atoms in the alkyl chain is more preferably 8 to 22. Among these, n-dodecylmercaptan, stearylmercaptan, cetylmercaptan, 2-ethylhexylmercaptan, tert-dodecylmercaptan and docosylmercaptan are preferred. Moreover, the hydrophobic chain transfer agent (TB) containing a sulfur atom may be used singly or in combination of two or more.
また、構成単位３及び構成単位４以外に、硫黄原子を含有する親水性連鎖移動剤（ＴＡ）に由来する構成単位と、硫黄原子を含有する疎水性連鎖移動剤（ＴＢ）に由来する構成単位との両方を含有しているビニル共重合体は、構成単位３を構成する一般式（４）で示される化合物である単量体３、構成単位４を構成する一般式（５）で示される化合物である単量体４、硫黄原子を含有する親水性連鎖移動剤（ＴＡ）及び、硫黄原子を含有する疎水性連鎖移動剤（ＴＢ）の存在下において、水中又は無溶媒で重合させて製造することができる。
In addition to structural unit 3 and structural unit 4, a structural unit derived from a hydrophilic chain transfer agent (TA) containing a sulfur atom and a structural unit derived from a hydrophobic chain transfer agent (TB) containing a sulfur atom A vinyl copolymer containing both of and is represented by the general formula (5) constituting the monomer 3 and the structural unit 4, which is a compound represented by the general formula (4) constituting the structural unit 3. Manufactured by polymerizing in water or in the absence of a solvent in the presence of a compound monomer 4, a hydrophilic chain transfer agent (TA) containing a sulfur atom, and a hydrophobic chain transfer agent (TB) containing a sulfur atom can do.
硫黄原子を含有する親水性連鎖移動剤（ＴＡ）に由来する構成単位と、硫黄原子を含有する疎水性連鎖移動剤（ＴＢ）に由来する構成単位の合計は、構成単位３と構成単位４の合計に対する割合が、０．００１～４質量％であることが好ましい。
The sum of structural units derived from a hydrophilic chain transfer agent (TA) containing a sulfur atom and structural units derived from a hydrophobic chain transfer agent (TB) containing a sulfur atom is the structural unit 3 and the structural unit 4. The ratio to the total is preferably 0.001 to 4% by mass.
また、硫黄原子を含有する疎水性連鎖移動剤（ＴＢ）に由来する構成単位は、硫黄原子を含有する親水性連鎖移動剤（ＴＡ）に由来する構成単位と、硫黄原子を含有する疎水性連鎖移動剤（ＴＢ）に由来する構成単位との合計に対する割合が、１０～９９質量％であることが好ましく、４０～９５質量％であることがより好ましい。
Further, the structural unit derived from the hydrophobic chain transfer agent containing a sulfur atom (TB) is a structural unit derived from a hydrophilic chain transfer agent containing a sulfur atom (TA) and a hydrophobic chain containing a sulfur atom. The ratio to the total of the structural units derived from the transfer agent (TB) is preferably 10 to 99% by mass, more preferably 40 to 95% by mass.
また、Ｄ成分は、その他の（即ち、硫黄原子を含有するもの以外の）疎水性連鎖移動剤や親水性連鎖移動剤等の連鎖移動剤を併用してもよい。このような連鎖移動剤としては特に限定するものではないが、例えば、２－アミノプロパン－１－オール等の第１級アルコール；イソプロパノール等の第２級アルコール；亜リン酸、次亜リン酸、その塩（次亜リン酸ナトリウム、次亜リン酸カリウム等）や、亜硫酸、亜硫酸水素、亜二チオン酸、メタ重亜硫酸、その塩（亜硫酸ナトリウム、亜硫酸カリウム、亜硫酸水素ナトリウム、亜硫酸水素カリウム、亜二チオン酸ナトリウム、亜二チオン酸カリウム、メタ重亜硫酸ナトリウム、メタ重亜硫酸カリウム等）の低級酸化物、その塩、四塩化炭素、四臭化炭素、塩化メチレン、ブロモホルム、ブロモトリクロロエタン等のハロゲン化物；α－メチルスチレンダイマー、α－テルピネン、γ－テルピネン、ジペンテン、ターピノーレン等の不飽和炭化水素化合物等が挙げられる。
In addition, component D may be used in combination with other chain transfer agents (that is, other than those containing sulfur atoms) such as hydrophobic chain transfer agents and hydrophilic chain transfer agents. Although such chain transfer agents are not particularly limited, examples include primary alcohols such as 2-aminopropan-1-ol; secondary alcohols such as isopropanol; phosphorous acid, hypophosphorous acid, Its salts (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionous acid, metabisulfite, its salts (sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, nitrite) sodium dithionate, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.), lower oxides, salts thereof, halides such as carbon tetrachloride, carbon tetrabromide, methylene chloride, bromoform, bromotrichloroethane, etc. and unsaturated hydrocarbon compounds such as α-methylstyrene dimer, α-terpinene, γ-terpinene, dipentene and terpinolene.
その他の疎水性連鎖移動剤や親水性連鎖移動剤は、硫黄原子を含有する親水性連鎖移動剤（ＴＡ）に由来する構成単位と、硫黄原子を含有する疎水性連鎖移動剤（ＴＢ）に由来する構成単位との合計に対する割合が、２０質量％以下であることが好ましい。
Other hydrophobic chain transfer agents and hydrophilic chain transfer agents are derived from structural units derived from a hydrophilic chain transfer agent (TA) containing sulfur atoms and a hydrophobic chain transfer agent (TB) containing sulfur atoms. It is preferable that the proportion of the total amount of the constituent units is 20% by mass or less.
（１－５）各成分の配合割合：
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１～７０質量部、Ｂ成分を２９～９８質量部、及びＣ成分を０．０５～１０質量部の割合で含有することが好ましい。更に、Ａ成分を１～５０質量部、Ｂ成分を４９～９８質量部、及びＣ成分を０．０５～１０質量部の割合で含有することがより好ましく、Ａ成分を１～４０質量部、Ｂ成分を５９～９８質量部、及びＣ成分を０．０５～１０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、使用温度に関わらず、経時による流動性の変化が更に少なくなる。 (1-5) Mixing ratio of each component:
Including A component, B component and C component (however, when D component is not included), when the total content of A component, B component and C component is 100 parts by mass, 1 to 70 parts by mass of A component , 29 to 98 parts by mass of component B and 0.05 to 10 parts by mass of component C. Furthermore, it is more preferable to contain 1 to 50 parts by mass of component A, 49 to 98 parts by mass of component B, and 0.05 to 10 parts by mass of component C, and 1 to 40 parts by mass of component A, It is more preferable to contain 59 to 98 parts by mass of component B and 0.05 to 10 parts by mass of component C. Within such a range, change in fluidity over time is further reduced regardless of the operating temperature.
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１～７０質量部、Ｂ成分を２９～９８質量部、及びＣ成分を０．０５～１０質量部の割合で含有することが好ましい。更に、Ａ成分を１～５０質量部、Ｂ成分を４９～９８質量部、及びＣ成分を０．０５～１０質量部の割合で含有することがより好ましく、Ａ成分を１～４０質量部、Ｂ成分を５９～９８質量部、及びＣ成分を０．０５～１０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、使用温度に関わらず、経時による流動性の変化が更に少なくなる。 (1-5) Mixing ratio of each component:
Including A component, B component and C component (however, when D component is not included), when the total content of A component, B component and C component is 100 parts by mass, 1 to 70 parts by mass of A component , 29 to 98 parts by mass of component B and 0.05 to 10 parts by mass of component C. Furthermore, it is more preferable to contain 1 to 50 parts by mass of component A, 49 to 98 parts by mass of component B, and 0.05 to 10 parts by mass of component C, and 1 to 40 parts by mass of component A, It is more preferable to contain 59 to 98 parts by mass of component B and 0.05 to 10 parts by mass of component C. Within such a range, change in fluidity over time is further reduced regardless of the operating temperature.
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１～６０質量部、Ｂ成分を１９～９８質量部、及びＤ成分を０．５～４０質量部の割合で含有することが好ましい。更に、Ａ成分を１～５０質量部、Ｂ成分を４９～９８質量部、及びＤ成分を０．５～４０質量部の割合で含有することがより好ましく、Ａ成分を１～４０質量部、Ｂ成分を５９～９８質量部、及びＤ成分を０．５～４０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、使用温度に関わらず、経時による流動性の変化が更に少なくなる。
Including A component, B component and D component (however, when C component is not included), when the total content of A component, B component and D component is 100 parts by mass, 1 to 60 parts by mass of A component , 19 to 98 parts by mass of component B and 0.5 to 40 parts by mass of component D. Furthermore, it is more preferable to contain 1 to 50 parts by mass of component A, 49 to 98 parts by mass of component B, and 0.5 to 40 parts by mass of component D, and 1 to 40 parts by mass of component A, It is more preferable to contain 59 to 98 parts by mass of component B and 0.5 to 40 parts by mass of component D. Within such a range, change in fluidity over time is further reduced regardless of the operating temperature.
Ａ成分、Ｂ成分、Ｃ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１～６０質量部、Ｂ成分を１９～９８質量部、Ｃ成分を０．０５～１０質量部、及びＤ成分を０．５～４０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、使用温度に関わらず、経時による流動性の変化が特に少なくなる。
Including A component, B component, C and D component, when the total content of A component, B component, C component and D component is 100 parts by mass, 1 to 60 parts by mass of A component and 19 parts by mass of B component It is preferable to contain up to 98 parts by mass, 0.05 to 10 parts by mass of component C, and 0.5 to 40 parts by mass of component D. Within such a range, change in fluidity over time is particularly reduced regardless of the operating temperature.
（１－６）その他の成分：
本発明の水硬性組成物用添加剤は、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などを挙げることができる。 (1-6) Other components:
The additive for hydraulic composition of the present invention may further contain other components in addition to components A to D within a range in which the effect is not impaired. Such other components include, for example, setting retarding components such as sugars and oxycarboxylates, components having a dispersing action such as sodium ligninsulfonate, AE agents such as anionic surfactants, and oxycarboxylates. Antifoaming agents such as alkylene compounds, curing accelerators such as alkanolamines, shrinkage reducing agents such as polyoxyalkylene alkyl ethers, thickeners such as cellulose ether compounds, preservatives such as isothiazoline compounds , rust preventives such as nitrites, and the like.
本発明の水硬性組成物用添加剤は、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などを挙げることができる。 (1-6) Other components:
The additive for hydraulic composition of the present invention may further contain other components in addition to components A to D within a range in which the effect is not impaired. Such other components include, for example, setting retarding components such as sugars and oxycarboxylates, components having a dispersing action such as sodium ligninsulfonate, AE agents such as anionic surfactants, and oxycarboxylates. Antifoaming agents such as alkylene compounds, curing accelerators such as alkanolamines, shrinkage reducing agents such as polyoxyalkylene alkyl ethers, thickeners such as cellulose ether compounds, preservatives such as isothiazoline compounds , rust preventives such as nitrites, and the like.
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 of other components can be, for example, 0 to 20% by mass of the total additive for 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。
Furthermore, the additive for hydraulic compositions of the present invention may be used in a form diluted with water or a solvent.
（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、使用温度に関わらず、経時による流動性の変化が少なく空気量の調整が適宜可能でありながら、凝結時間が過度に遅延しないものである。 (2) Hydraulic composition:
The hydraulic composition of the present invention contains the additive for hydraulic compositions of the present invention. Such a hydraulic composition has little change in fluidity over time, regardless of the temperature of use, and the amount of air can be appropriately adjusted, while the setting time is not excessively delayed.
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、使用温度に関わらず、経時による流動性の変化が少なく空気量の調整が適宜可能でありながら、凝結時間が過度に遅延しないものである。 (2) Hydraulic composition:
The hydraulic composition of the present invention contains the additive for hydraulic compositions of the present invention. Such a hydraulic composition has little change in fluidity over time, regardless of the temperature of use, and the amount of air can be appropriately adjusted, while the setting time is not excessively delayed.
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は特に制限はなく適宜設定することができるが、例えば、結合材に対し、固形分換算で、０．００１～２．０質量％が好適であり、さらには０．０１～２．０質量％がより好適である。
In the hydraulic composition of the present invention, the content ratio of the additive for hydraulic compositions of the present invention is not particularly limited and can be set as appropriate. ~2.0% by mass is preferable, and 0.01 to 2.0% by mass is more preferable.
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 can contain a binder, water, fine aggregate, and coarse aggregate in the same manner as conventionally known hydraulic compositions.
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など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などの各種のセメントを挙げることができる。
Examples of binders include various Portland cements such as ordinary Portland cement, moderate heat Portland cement, low heat Portland cement, high-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、膨張材など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。
Furthermore, as binders, various admixtures such as fly ash, ground granulated blast furnace slag, ground limestone, stone powder, silica fume, and expansive agents may be used in combination with the various cements described above.
細骨材としては、例えば、川砂、山砂、陸砂、海砂、珪砂、砕砂、各種スラグ細骨材などが挙げられる。
Examples of fine aggregates include river sand, mountain sand, land sand, sea sand, silica sand, crushed sand, and various slag fine aggregates.
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、軽量骨材などが挙げられる。
Examples of coarse aggregates 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などを挙げることができる。
The hydraulic composition of the present invention may further contain other components as appropriate within a range in which the effects are not impaired. Such other components include, for example, setting retarding components such as sugars and oxycarboxylates, components having a dispersing action such as sodium ligninsulfonate, AE agents such as anionic surfactants, and oxycarboxylates. Antifoaming agents such as alkylene compounds, curing accelerators such as alkanolamines, shrinkage reducing agents such as polyoxyalkylene alkyl ethers, thickeners such as cellulose ether compounds, preservatives such as isothiazoline compounds , rust preventives such as nitrites, and the like.
その他の成分の含有割合としては、例えば、結合材に対して、固形分換算で０～５質量％とすることができる。
The content of other components can be, for example, 0 to 5% by mass in terms of solid content relative to 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。
For the hydraulic composition of the present invention, a conventionally known ratio can be suitably adopted as the ratio of water to binder (water/binder ratio).
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。
The present invention will be specifically described below 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５に示す。
First, the components A to D used are shown in Tables 1 to 5 below.
（Ａ成分）
下記表１には、使用したＡ成分（Ａ－１～Ａ－１１）を示す。 (A component)
Table 1 below shows the A components (A-1 to A-11) used.
下記表１には、使用したＡ成分（Ａ－１～Ａ－１１）を示す。 (A component)
Table 1 below shows the A components (A-1 to A-11) used.
（合成例１）Ａ－８の製造方法：
表１中のＡ－８は、以下のようにして製造した。まず、５Ｌのステンレス製の耐圧容器に、Ａ－７のテトラエチレンペンタミン２０００ｇを仕込んだ。そして、窒素置換後、７５±５℃でエチレンオキサイド９３０ｇを０．３ＭＰａ以下の条件で圧入し、そのままの温度で１時間熟成を行った。冷却後、回収し、Ａ－８（Ａ成分）を得た。 (Synthesis Example 1) Method for producing A-8:
A-8 in Table 1 was produced as follows. First, 2000 g of A-7 tetraethylenepentamine was placed in a 5 L stainless steel pressure vessel. After purging with nitrogen, 930 g of ethylene oxide was pressurized at 75±5° C. under conditions of 0.3 MPa or less, and aging was performed at that temperature for 1 hour. After cooling, it was recovered to obtain A-8 (component A).
表１中のＡ－８は、以下のようにして製造した。まず、５Ｌのステンレス製の耐圧容器に、Ａ－７のテトラエチレンペンタミン２０００ｇを仕込んだ。そして、窒素置換後、７５±５℃でエチレンオキサイド９３０ｇを０．３ＭＰａ以下の条件で圧入し、そのままの温度で１時間熟成を行った。冷却後、回収し、Ａ－８（Ａ成分）を得た。 (Synthesis Example 1) Method for producing A-8:
A-8 in Table 1 was produced as follows. First, 2000 g of A-7 tetraethylenepentamine was placed in a 5 L stainless steel pressure vessel. After purging with nitrogen, 930 g of ethylene oxide was pressurized at 75±5° C. under conditions of 0.3 MPa or less, and aging was performed at that temperature for 1 hour. After cooling, it was recovered to obtain A-8 (component A).
（Ｂ成分）
下記表２には、使用したＢ成分（Ｂ－１～Ｂ－３）を示す。 (B component)
Table 2 below shows the B components (B-1 to B-3) used.
下記表２には、使用したＢ成分（Ｂ－１～Ｂ－３）を示す。 (B component)
Table 2 below shows the B components (B-1 to B-3) used.
次に、表３には、Ｂ成分（Ｂ－１～Ｂ－３）を構成する各ビニル共重合体（ＰＣ－１～ＰＣ－４）について示す。
Next, Table 3 shows each vinyl copolymer (PC-1 to PC-4) constituting the B component (B-1 to B-3).
表３中、構成単位Ｎの「合計割合（質量％）」は、構成単位１と構成単位２の合計に対する割合（質量％）を意味するものである。
In Table 3, the "total ratio (% by mass)" of structural unit N means the ratio (% by mass) to the total of structural unit 1 and structural unit 2.
表３中、Ｌ－１～Ｌ－４、Ｍ－１、Ｍ－２、及び、Ｎ－１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（９モル）オキシエチレン
Ｌ－２：α－メタリル－ω－メトキシ－ポリ（５０モル）オキシエチレン
Ｌ－３：α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（５３モル）オキシエチレン
Ｌ－４：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
Ｎ－１：アクリル酸メチル In Table 3, L-1 to L-4, M-1, M-2, and N-1 represent the following compounds, and each structural unit is derived from the compound.
L-1: α-methacryloyl-ω-methoxy-poly (9 mol) oxyethylene L-2: α-methallyl-ω-methoxy-poly (50 mol) oxyethylene L-3: α-(3-methyl-3 -butenyl)-ω-hydroxy-poly (53 mol) oxyethylene L-4: hydroxyethyl acrylate M-1: methacrylic acid M-2: acrylic acid N-1: methyl acrylate
Ｌ－１：α－メタクリロイル－ω－メトキシ－ポリ（９モル）オキシエチレン
Ｌ－２：α－メタリル－ω－メトキシ－ポリ（５０モル）オキシエチレン
Ｌ－３：α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（５３モル）オキシエチレン
Ｌ－４：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
Ｎ－１：アクリル酸メチル In Table 3, L-1 to L-4, M-1, M-2, and N-1 represent the following compounds, and each structural unit is derived from the compound.
L-1: α-methacryloyl-ω-methoxy-poly (9 mol) oxyethylene L-2: α-methallyl-ω-methoxy-poly (50 mol) oxyethylene L-3: α-(3-methyl-3 -butenyl)-ω-hydroxy-poly (53 mol) oxyethylene L-4: hydroxyethyl acrylate M-1: methacrylic acid M-2: acrylic acid N-1: methyl acrylate
以下に、各共重合体（ＰＣ－１～ＰＣ－４）の合成方法を説明する。
The method for synthesizing each copolymer (PC-1 to PC-4) is described below.
（合成例２）ＰＣ－１の合成：
イオン交換水４２８．９ｇ、α－メタクリロイル－ω－メトキシ－ポリ（９モル）オキシエチレン３２９．８ｇ、メタクリル酸４５．０ｇ、３－メルカプトプロピオン酸３．７ｇを温度計、撹拌機、滴下ロート、及び窒素導入管を備えた反応容器に仕込み、撹拌しながら均一に溶解した。その後、雰囲気を窒素置換し、反応系の温度を温水浴にて６０℃とした。 (Synthesis Example 2) Synthesis of PC-1:
428.9 g of ion-exchanged water, 329.8 g of α-methacryloyl-ω-methoxy-poly(9 mol)oxyethylene, 45.0 g of methacrylic acid, and 3.7 g of 3-mercaptopropionic acid were added to a thermometer, stirrer, dropping funnel, and a reaction vessel equipped with a nitrogen inlet tube, and uniformly dissolved with stirring. After that, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 60°C in a hot water bath.
イオン交換水４２８．９ｇ、α－メタクリロイル－ω－メトキシ－ポリ（９モル）オキシエチレン３２９．８ｇ、メタクリル酸４５．０ｇ、３－メルカプトプロピオン酸３．７ｇを温度計、撹拌機、滴下ロート、及び窒素導入管を備えた反応容器に仕込み、撹拌しながら均一に溶解した。その後、雰囲気を窒素置換し、反応系の温度を温水浴にて６０℃とした。 (Synthesis Example 2) Synthesis of PC-1:
428.9 g of ion-exchanged water, 329.8 g of α-methacryloyl-ω-methoxy-poly(9 mol)oxyethylene, 45.0 g of methacrylic acid, and 3.7 g of 3-mercaptopropionic acid were added to a thermometer, stirrer, dropping funnel, and a reaction vessel equipped with a nitrogen inlet tube, and uniformly dissolved with stirring. After that, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 60°C in a hot water bath.
次に、２０％過硫酸ナトリウム水溶液２２．５ｇを加え重合反応を開始した。２時間後、２０％過硫酸ナトリウム水溶液１１．２ｇを加え、２時間、６０℃を維持し、重合反応を終了した。これに３０％水酸化ナトリウム水溶液を加え、ｐＨ７に調整し、イオン交換水にて濃度を４０％に調整した。この反応物をＰＣ－１とした。
Next, 22.5 g of a 20% sodium persulfate aqueous solution was added to initiate a polymerization reaction. After 2 hours, 11.2 g of a 20% sodium persulfate aqueous solution was added, and the temperature was maintained at 60°C for 2 hours to complete the polymerization reaction. A 30% sodium hydroxide aqueous solution was added to this to adjust the pH to 7, and ion-exchanged water was added to adjust the concentration to 40%. This reaction product was designated as PC-1.
（合成例３）ＰＣ－２の合成：
イオン交換水３４３．６ｇ、α－メタクリロイル－ω－メトキシ－ポリ（９モル）オキシエチレン２６６．１ｇ、メタクリル酸８８．７ｇ、アクリル酸メチル３．５ｇ、３－メルカプトプロピオン酸３．６ｇ、３０％水酸化ナトリウム水溶液７０．９ｇを温度計、撹拌機、滴下ロート、及び窒素導入管を備えた反応容器に仕込み、撹拌しながら均一に溶解した。その後、雰囲気を窒素置換し、反応系の温度を温水浴にて６０℃とした。 (Synthesis Example 3) Synthesis of PC-2:
Ion-exchanged water 343.6 g, α-methacryloyl-ω-methoxy-poly(9 mol)oxyethylene 266.1 g, methacrylic acid 88.7 g, methyl acrylate 3.5 g, 3-mercaptopropionic acid 3.6 g, 30% A reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a nitrogen inlet tube was charged with 70.9 g of an aqueous sodium hydroxide solution, and dissolved uniformly with stirring. After that, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 60°C in a hot water bath.
イオン交換水３４３．６ｇ、α－メタクリロイル－ω－メトキシ－ポリ（９モル）オキシエチレン２６６．１ｇ、メタクリル酸８８．７ｇ、アクリル酸メチル３．５ｇ、３－メルカプトプロピオン酸３．６ｇ、３０％水酸化ナトリウム水溶液７０．９ｇを温度計、撹拌機、滴下ロート、及び窒素導入管を備えた反応容器に仕込み、撹拌しながら均一に溶解した。その後、雰囲気を窒素置換し、反応系の温度を温水浴にて６０℃とした。 (Synthesis Example 3) Synthesis of PC-2:
Ion-exchanged water 343.6 g, α-methacryloyl-ω-methoxy-poly(9 mol)oxyethylene 266.1 g, methacrylic acid 88.7 g, methyl acrylate 3.5 g, 3-mercaptopropionic acid 3.6 g, 30% A reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a nitrogen inlet tube was charged with 70.9 g of an aqueous sodium hydroxide solution, and dissolved uniformly with stirring. After that, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 60°C in a hot water bath.
次に、２０％過硫酸ナトリウム水溶液３５．８ｇを加え重合反応を開始した。２時間後、２０％過硫酸ナトリウム水溶液１７．９ｇを加え２時間、６０℃を維持し、重合反応を終了した。これに３０％水酸化ナトリウム水溶液を加え、ｐＨ７に調整し、イオン交換水にて濃度を４０％に調整した。この反応物をＰＣ－２とした。
Next, 35.8 g of a 20% sodium persulfate aqueous solution was added to initiate the polymerization reaction. After 2 hours, 17.9 g of a 20% sodium persulfate aqueous solution was added, and the temperature was maintained at 60°C for 2 hours to complete the polymerization reaction. A 30% sodium hydroxide aqueous solution was added to this to adjust the pH to 7, and ion-exchanged water was added to adjust the concentration to 40%. This reaction product was designated as PC-2.
（合成例４）ＰＣ－３の合成：
イオン交換水１６２．７ｇ、α－メタリル－ω－メトキシ－ポリ（５０モル）オキシエチレン３４８．６ｇを温度計、撹拌機、滴下ロート、及び窒素導入管を備えた反応容器に仕込み、撹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６０℃とした。 (Synthesis Example 4) Synthesis of PC-3:
162.7 g of ion-exchanged water and 348.6 g of α-methallyl-ω-methoxy-poly(50 mol)oxyethylene were charged into a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a nitrogen inlet tube, and stirred. After uniformly dissolving, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 60°C in a hot water bath.
イオン交換水１６２．７ｇ、α－メタリル－ω－メトキシ－ポリ（５０モル）オキシエチレン３４８．６ｇを温度計、撹拌機、滴下ロート、及び窒素導入管を備えた反応容器に仕込み、撹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６０℃とした。 (Synthesis Example 4) Synthesis of PC-3:
162.7 g of ion-exchanged water and 348.6 g of α-methallyl-ω-methoxy-poly(50 mol)oxyethylene were charged into a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a nitrogen inlet tube, and stirred. After uniformly dissolving, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 60°C in a hot water bath.
次に、１０．０％過酸化水素水溶液１９．４ｇを３．０時間かけて滴下し、それと同時にイオン交換水１９３．６ｇにアクリル酸３１．０ｇ、ヒドロキシエチルアクリレート７．７ｇを溶解させた水溶液を３．０時間かけて滴下し、それと同時にイオン交換１５．５ｇに３－メルカプトプロピオン酸１．９ｇ、アスコルビン酸１．９ｇを溶解させた水溶液を４．０時間かけて滴下した。その後、０．５時間、６０℃を維持し、重合反応を終了した。これに３０％水酸化ナトリウム水溶液を加え、ｐＨ７に調整し、イオン交換水にて濃度を４０％に調整した。この反応物をＰＣ－３とした。
Next, 19.4 g of a 10.0% aqueous hydrogen peroxide solution was added dropwise over 3.0 hours, and at the same time, an aqueous solution prepared by dissolving 31.0 g of acrylic acid and 7.7 g of hydroxyethyl acrylate in 193.6 g of ion-exchanged water. was added dropwise over 3.0 hours, and at the same time, an aqueous solution prepared by dissolving 1.9 g of 3-mercaptopropionic acid and 1.9 g of ascorbic acid in 15.5 g of ion exchange was added dropwise over 4.0 hours. Thereafter, the temperature was maintained at 60° C. for 0.5 hours to complete the polymerization reaction. A 30% sodium hydroxide aqueous solution was added to this to adjust the pH to 7, and ion-exchanged water was added to adjust the concentration to 40%. This reaction was designated as PC-3.
（合成例５）ＰＣ－４の合成：
イオン交換水１５３．６ｇ、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（５３モル）オキシエチレン３３０．３ｇを温度計、撹拌機、滴下ロート、及び窒素導入管を備えた反応容器に仕込み、撹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６０℃とした。 (Synthesis Example 5) Synthesis of PC-4:
153.6 g of deionized water and 330.3 g of α-(3-methyl-3-butenyl)-ω-hydroxy-poly(53 mol)oxyethylene were equipped with a thermometer, a stirrer, a dropping funnel and a nitrogen inlet tube. After charging into a reaction vessel and uniformly dissolving with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 60°C in a hot water bath.
イオン交換水１５３．６ｇ、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（５３モル）オキシエチレン３３０．３ｇを温度計、撹拌機、滴下ロート、及び窒素導入管を備えた反応容器に仕込み、撹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６０℃とした。 (Synthesis Example 5) Synthesis of PC-4:
153.6 g of deionized water and 330.3 g of α-(3-methyl-3-butenyl)-ω-hydroxy-poly(53 mol)oxyethylene were equipped with a thermometer, a stirrer, a dropping funnel and a nitrogen inlet tube. After charging into a reaction vessel and uniformly dissolving with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 60°C in a hot water bath.
次に、１０．０％過酸化水素水溶液１９．２ｇを３．０時間かけて滴下し、それと同時にイオン交換水１９９．７ｇにアクリル酸２３．０ｇ、ヒドロキシエチルアクリレート３０．７ｇを溶解させた水溶液を３．０時間かけて滴下し、それと同時にイオン交換１５．４ｇに３－メルカプトプロピオン酸１．９ｇ、アスコルビン酸１．９ｇを溶解させた水溶液を４．０時間かけて滴下した。その後、０．５時間、６０℃を維持し、重合反応を終了した。これに３０％水酸化ナトリウム水溶液を加え、ｐＨ７に調整し、イオン交換水にて濃度を４０％に調整した。この反応物をＰＣ－４とした。
Next, 19.2 g of a 10.0% aqueous hydrogen peroxide solution was added dropwise over 3.0 hours, and at the same time, an aqueous solution prepared by dissolving 23.0 g of acrylic acid and 30.7 g of hydroxyethyl acrylate in 199.7 g of deionized water. was added dropwise over 3.0 hours, and at the same time, an aqueous solution prepared by dissolving 1.9 g of 3-mercaptopropionic acid and 1.9 g of ascorbic acid in 15.4 g of ion exchange was added dropwise over 4.0 hours. Thereafter, the temperature was maintained at 60° C. for 0.5 hours to complete the polymerization reaction. A 30% sodium hydroxide aqueous solution was added to this to adjust the pH to 7, and ion-exchanged water was added to adjust the concentration to 40%. This reaction was designated as PC-4.
（質量平均分子量）
合成した共重合体のＰＣ－１～ＰＣ－４の質量平均分子量について、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：Ｓｈｏｄｅｘ ＧＰＣ－１０１（昭和電工社製）
カラム：ＯＨｐａｋ 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 mass average molecular weights of PC-1 to PC-4 of the synthesized copolymers were measured by gel permeation chromatography (GPC) under the measurement conditions shown below.
<Measurement conditions>
Apparatus: Shodex GPC-101 (manufactured by Showa Denko)
Column: OHpak SB-806M HQ + SB-806M HQ (manufactured by Showa Denko)
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 a sample concentration of 0.5% by mass Standard substance: PEG/PEO (manufactured by Agilent Technologies)
合成した共重合体のＰＣ－１～ＰＣ－４の質量平均分子量について、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：Ｓｈｏｄｅｘ ＧＰＣ－１０１（昭和電工社製）
カラム：ＯＨｐａｋ 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 mass average molecular weights of PC-1 to PC-4 of the synthesized copolymers were measured by gel permeation chromatography (GPC) under the measurement conditions shown below.
<Measurement conditions>
Apparatus: Shodex GPC-101 (manufactured by Showa Denko)
Column: OHpak SB-806M HQ + SB-806M HQ (manufactured by Showa Denko)
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 a sample concentration of 0.5% by mass Standard substance: PEG/PEO (manufactured by Agilent Technologies)
測定の結果、ＰＣ－１の質量平均分子量は３６０００であり、ＰＣ－２の質量平均分子量は３２０００であり、ＰＣ－３の質量平均分子量は４００００であり、ＰＣ－４の質量平均分子量は３９０００であった。
As a result of measurement, the mass average molecular weight of PC-1 was 36,000, the mass average molecular weight of PC-2 was 32,000, the mass average molecular weight of PC-3 was 40,000, and the mass average molecular weight of PC-4 was 39,000. there were.
（Ｃ成分）
下記表４には、使用したＣ成分（Ｃ－１～Ｃ－５）、ＣＲ－１を示す。 (C component)
Table 4 below shows the C components (C-1 to C-5) and CR-1 used.
下記表４には、使用したＣ成分（Ｃ－１～Ｃ－５）、ＣＲ－１を示す。 (C component)
Table 4 below shows the C components (C-1 to C-5) and CR-1 used.
なお、表４中、「ＣＲ－１」としては、中華人民共和国産（以降、単に「中国産」と記す）の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を用いた。
In Table 4, as "CR-1", X grade (acid value: 171 mgKOH/g) of "gum rosin" made in the People's Republic of China (hereinafter simply referred to as "made in China") was used.
また、表４中、「ＥＯ」はオキシエチレン基、「ＰＯ」はオキシプロピレン基を表す。
Also, in Table 4, "EO" represents an oxyethylene group, and "PO" represents an oxypropylene group.
以下に、Ｃ成分（Ｃ－１～Ｃ－５）の合成方法を説明する。
The method for synthesizing the C components (C-1 to C-5) will be described below.
（合成例６）Ｃ－１の合成：
２Ｌのステンレス製の耐圧容器に、中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を５４２．２ｇと、水酸化カリウム２．０ｇを仕込み、１２０℃まで加熱し、撹拌しながら減圧脱水を１時間行った。窒素にて常圧に戻し、その後、１５０～１６０℃でエチレンオキサイド１４５５．８ｇを０．４ＭＰａの条件で圧入し、そのままの温度で１時間熟成を行った。その後、冷却し、９０％酢酸を３．５ｇ添加し、１２０℃にて減圧脱水の後、加圧濾過を行い、化合物（Ｃ－１）を得た。 (Synthesis Example 6) Synthesis of C-1:
542.2 g of X grade Chinese "gum rosin" (acid value: 171 mg KOH/g) and 2.0 g of potassium hydroxide were charged in a 2 L stainless steel pressure vessel, heated to 120 ° C., and stirred. Dehydration under reduced pressure was performed for 1 hour. After returning to normal pressure with nitrogen, 1455.8 g of ethylene oxide was pressurized at 150 to 160° C. under the condition of 0.4 MPa, and aging was performed at that temperature for 1 hour. After cooling, 3.5 g of 90% acetic acid was added, and after dehydration under reduced pressure at 120° C., filtration under pressure was carried out to obtain compound (C-1).
２Ｌのステンレス製の耐圧容器に、中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を５４２．２ｇと、水酸化カリウム２．０ｇを仕込み、１２０℃まで加熱し、撹拌しながら減圧脱水を１時間行った。窒素にて常圧に戻し、その後、１５０～１６０℃でエチレンオキサイド１４５５．８ｇを０．４ＭＰａの条件で圧入し、そのままの温度で１時間熟成を行った。その後、冷却し、９０％酢酸を３．５ｇ添加し、１２０℃にて減圧脱水の後、加圧濾過を行い、化合物（Ｃ－１）を得た。 (Synthesis Example 6) Synthesis of C-1:
542.2 g of X grade Chinese "gum rosin" (acid value: 171 mg KOH/g) and 2.0 g of potassium hydroxide were charged in a 2 L stainless steel pressure vessel, heated to 120 ° C., and stirred. Dehydration under reduced pressure was performed for 1 hour. After returning to normal pressure with nitrogen, 1455.8 g of ethylene oxide was pressurized at 150 to 160° C. under the condition of 0.4 MPa, and aging was performed at that temperature for 1 hour. After cooling, 3.5 g of 90% acetic acid was added, and after dehydration under reduced pressure at 120° C., filtration under pressure was carried out to obtain compound (C-1).
（合成例７）Ｃ－２の合成：
１Ｌのガラス製の反応容器にα－ブトキシ－ω－ヒドロキシ－ポリ（４５モル）オキシエチレン５００．０ｇと中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を７９．８ｇ、メタンスルホン酸７．２ｇを仕込み、窒素置換後、１５０℃、０．５ｋＰａで減圧脱水を行い、エステル化反応を行った。エステル化率が９９％以上となったところで反応を終了し、精製し、化合物Ｃ－２を得た。 (Synthesis Example 7) Synthesis of C-2:
In a 1 L glass reaction vessel, 500.0 g of α-butoxy-ω-hydroxy-poly(45 mol) oxyethylene and 79.8 g of X grade (acid value: 171 mg KOH/g) of “gum rosin” from China, methane 7.2 g of sulfonic acid was charged, and after purging with nitrogen, dehydration was performed under reduced pressure at 150° C. and 0.5 kPa to carry out an esterification reaction. When the esterification rate reached 99% or more, the reaction was terminated and purified to obtain compound C-2.
１Ｌのガラス製の反応容器にα－ブトキシ－ω－ヒドロキシ－ポリ（４５モル）オキシエチレン５００．０ｇと中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を７９．８ｇ、メタンスルホン酸７．２ｇを仕込み、窒素置換後、１５０℃、０．５ｋＰａで減圧脱水を行い、エステル化反応を行った。エステル化率が９９％以上となったところで反応を終了し、精製し、化合物Ｃ－２を得た。 (Synthesis Example 7) Synthesis of C-2:
In a 1 L glass reaction vessel, 500.0 g of α-butoxy-ω-hydroxy-poly(45 mol) oxyethylene and 79.8 g of X grade (acid value: 171 mg KOH/g) of “gum rosin” from China, methane 7.2 g of sulfonic acid was charged, and after purging with nitrogen, dehydration was performed under reduced pressure at 150° C. and 0.5 kPa to carry out an esterification reaction. When the esterification rate reached 99% or more, the reaction was terminated and purified to obtain compound C-2.
（合成例８）Ｃ－３の合成：
２Ｌのステンレス製の耐圧容器に、中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を１９２．２ｇと、水酸化カリウム２．０ｇを仕込み、１２０℃まで加熱し、撹拌しながら減圧脱水を１時間行った。窒素にて常圧に戻し、その後、１５０～１６０℃でエチレンオキサイド１８０５．８ｇを０．４ＭＰａの条件で圧入し、そのままの温度で１時間熟成を行った。その後、冷却し、吸着材（協和化学工業社製：キョーワード６００）を２０．０ｇ添加し、１２０℃にて減圧脱水の後、加圧濾過を行い、化合物（Ｃ－３）を得た。 (Synthesis Example 8) Synthesis of C-3:
192.2 g of Chinese "gum rosin" X grade (acid value: 171 mg KOH/g) and 2.0 g of potassium hydroxide are charged in a 2 L stainless steel pressure vessel, heated to 120 ° C., and stirred Dehydration under reduced pressure was performed for 1 hour. After returning to normal pressure with nitrogen, 1805.8 g of ethylene oxide was pressurized at 150 to 160° C. under the condition of 0.4 MPa, and aging was performed at that temperature for 1 hour. After cooling, 20.0 g of an adsorbent (Kyowa Kagaku Kogyo Co., Ltd.: Kyoward 600) was added, and after dehydration under reduced pressure at 120° C., pressure filtration was performed to obtain compound (C-3).
２Ｌのステンレス製の耐圧容器に、中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を１９２．２ｇと、水酸化カリウム２．０ｇを仕込み、１２０℃まで加熱し、撹拌しながら減圧脱水を１時間行った。窒素にて常圧に戻し、その後、１５０～１６０℃でエチレンオキサイド１８０５．８ｇを０．４ＭＰａの条件で圧入し、そのままの温度で１時間熟成を行った。その後、冷却し、吸着材（協和化学工業社製：キョーワード６００）を２０．０ｇ添加し、１２０℃にて減圧脱水の後、加圧濾過を行い、化合物（Ｃ－３）を得た。 (Synthesis Example 8) Synthesis of C-3:
192.2 g of Chinese "gum rosin" X grade (acid value: 171 mg KOH/g) and 2.0 g of potassium hydroxide are charged in a 2 L stainless steel pressure vessel, heated to 120 ° C., and stirred Dehydration under reduced pressure was performed for 1 hour. After returning to normal pressure with nitrogen, 1805.8 g of ethylene oxide was pressurized at 150 to 160° C. under the condition of 0.4 MPa, and aging was performed at that temperature for 1 hour. After cooling, 20.0 g of an adsorbent (Kyowa Kagaku Kogyo Co., Ltd.: Kyoward 600) was added, and after dehydration under reduced pressure at 120° C., pressure filtration was performed to obtain compound (C-3).
（合成例９）Ｃ－４の合成：
２Ｌのステンレス製の耐圧容器に、中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を６２６．２ｇと、水酸化カリウム２．０ｇを仕込み、１２０℃まで加熱し、撹拌しながら減圧脱水を１時間行った。窒素にて常圧に戻し、その後、１５０～１６０℃でエチレンオキサイド１２６０．９ｇを０．４ＭＰａの条件で圧入し、続いてプロピレンオキサイド１１０．９ｇを同条件で圧入し、そのままの温度で１時間熟成を行った。その後、冷却し、吸着材（協和化学工業社製：キョーワード６００）を２０．０ｇ添加し、１２０℃にて減圧脱水の後、加圧濾過を行い、化合物（Ｃ－４）を得た。 (Synthesis Example 9) Synthesis of C-4:
626.2 g of X grade Chinese "gum rosin" (acid value: 171 mg KOH/g) and 2.0 g of potassium hydroxide were charged in a 2 L stainless steel pressure vessel, heated to 120 ° C., and stirred. Dehydration under reduced pressure was performed for 1 hour. After returning to normal pressure with nitrogen, 1260.9 g of ethylene oxide was injected under the conditions of 0.4 MPa at 150 to 160° C., then 110.9 g of propylene oxide was injected under the same conditions, and the temperature was maintained for 1 hour. matured. After cooling, 20.0 g of an adsorbent (Kyowa Kagaku Kogyo Co., Ltd.: Kyoward 600) was added, and after dehydration under reduced pressure at 120° C., pressure filtration was performed to obtain compound (C-4).
２Ｌのステンレス製の耐圧容器に、中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を６２６．２ｇと、水酸化カリウム２．０ｇを仕込み、１２０℃まで加熱し、撹拌しながら減圧脱水を１時間行った。窒素にて常圧に戻し、その後、１５０～１６０℃でエチレンオキサイド１２６０．９ｇを０．４ＭＰａの条件で圧入し、続いてプロピレンオキサイド１１０．９ｇを同条件で圧入し、そのままの温度で１時間熟成を行った。その後、冷却し、吸着材（協和化学工業社製：キョーワード６００）を２０．０ｇ添加し、１２０℃にて減圧脱水の後、加圧濾過を行い、化合物（Ｃ－４）を得た。 (Synthesis Example 9) Synthesis of C-4:
626.2 g of X grade Chinese "gum rosin" (acid value: 171 mg KOH/g) and 2.0 g of potassium hydroxide were charged in a 2 L stainless steel pressure vessel, heated to 120 ° C., and stirred. Dehydration under reduced pressure was performed for 1 hour. After returning to normal pressure with nitrogen, 1260.9 g of ethylene oxide was injected under the conditions of 0.4 MPa at 150 to 160° C., then 110.9 g of propylene oxide was injected under the same conditions, and the temperature was maintained for 1 hour. matured. After cooling, 20.0 g of an adsorbent (Kyowa Kagaku Kogyo Co., Ltd.: Kyoward 600) was added, and after dehydration under reduced pressure at 120° C., pressure filtration was performed to obtain compound (C-4).
（合成例１０）Ｃ－５の合成：
２Ｌのステンレス製の耐圧容器に、中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を９６６．１ｇと、水酸化カリウム２．０ｇを仕込み、１２０℃まで加熱し、撹拌しながら減圧脱水を１時間行った。窒素にて常圧に戻し、その後、１５０～１６０℃でエチレンオキサイド５１８．８ｇを０．４ＭＰａの条件で圧入し、続いてプロピレンオキサイド５１３．２ｇを同条件で圧入し、そのままの温度で１時間熟成を行った。その後、冷却し、９０％酢酸を３．５ｇ添加し、１２０℃にて減圧脱水の後、加圧濾過を行い、化合物（Ｃ－５）を得た。 (Synthesis Example 10) Synthesis of C-5:
Into a 2 L stainless steel pressure vessel, 966.1 g of Chinese "gum rosin" X grade (acid value: 171 mg KOH / g) and 2.0 g of potassium hydroxide are charged, heated to 120 ° C., and stirred Dehydration under reduced pressure was performed for 1 hour. After returning to normal pressure with nitrogen, 518.8 g of ethylene oxide was injected under the conditions of 0.4 MPa at 150 to 160° C., and then 513.2 g of propylene oxide was injected under the same conditions, and the temperature was maintained for 1 hour. matured. After cooling, 3.5 g of 90% acetic acid was added, and after dehydration under reduced pressure at 120° C., filtration under pressure was carried out to obtain compound (C-5).
２Ｌのステンレス製の耐圧容器に、中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を９６６．１ｇと、水酸化カリウム２．０ｇを仕込み、１２０℃まで加熱し、撹拌しながら減圧脱水を１時間行った。窒素にて常圧に戻し、その後、１５０～１６０℃でエチレンオキサイド５１８．８ｇを０．４ＭＰａの条件で圧入し、続いてプロピレンオキサイド５１３．２ｇを同条件で圧入し、そのままの温度で１時間熟成を行った。その後、冷却し、９０％酢酸を３．５ｇ添加し、１２０℃にて減圧脱水の後、加圧濾過を行い、化合物（Ｃ－５）を得た。 (Synthesis Example 10) Synthesis of C-5:
Into a 2 L stainless steel pressure vessel, 966.1 g of Chinese "gum rosin" X grade (acid value: 171 mg KOH / g) and 2.0 g of potassium hydroxide are charged, heated to 120 ° C., and stirred Dehydration under reduced pressure was performed for 1 hour. After returning to normal pressure with nitrogen, 518.8 g of ethylene oxide was injected under the conditions of 0.4 MPa at 150 to 160° C., and then 513.2 g of propylene oxide was injected under the same conditions, and the temperature was maintained for 1 hour. matured. After cooling, 3.5 g of 90% acetic acid was added, and after dehydration under reduced pressure at 120° C., filtration under pressure was carried out to obtain compound (C-5).
（Ｄ成分）
下記表５には、使用したＤ成分（Ｄ－１～Ｄ－４）を示す。なお、Ｄ－４は、親水性連鎖移動剤のみの場合である。 (D component)
Table 5 below shows the D components (D-1 to D-4) used. Note that D-4 is the case of using only a hydrophilic chain transfer agent.
下記表５には、使用したＤ成分（Ｄ－１～Ｄ－４）を示す。なお、Ｄ－４は、親水性連鎖移動剤のみの場合である。 (D component)
Table 5 below shows the D components (D-1 to D-4) used. Note that D-4 is the case of using only a hydrophilic chain transfer agent.
表５中、「合計割合（質量％）」は、構成単位３と構成単位４の合計に対する割合（質量％）を意味する。
In Table 5, "total ratio (% by mass)" means the ratio (% by mass) to the total of structural unit 3 and structural unit 4.
表５中、Ｌ－３、Ｌ－５、Ｌ－６、Ｍ－１、Ｍ－２、ＴＡ－１、ＴＡ－２、及び、ＴＢ－１～ＴＢ－３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－３：α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（５３モル）オキシエチレン
Ｌ－５：α－メタクリロイル－ω－メトキシ－ポリ（４５モル）オキシエチレン
Ｌ－６：α－メタクリロイル－ω－メトキシ－ポリ（２３モル）オキシエチレン
Ｍ－１：メタクリル酸
Ｍ－２：アクリル酸
ＴＡ－１：３－メルカプトプロピオン酸
ＴＡ－２：チオグリコール酸
ＴＢ－１：ｎ－ドデシルメルカプタン
ＴＢ－２：ステアリルメルカプタン
ＴＢ－３：セチルメルカプタン In Table 5, L-3, L-5, L-6, M-1, M-2, TA-1, TA-2, and TB-1 to TB-3 represent the following compounds, each A structural unit is derived from the compound.
L-3: α-(3-methyl-3-butenyl)-ω-hydroxy-poly(53 mol) oxyethylene L-5: α-methacryloyl-ω-methoxy-poly(45 mol) oxyethylene L-6: α-methacryloyl-ω-methoxy-poly (23 mol) oxyethylene M-1: methacrylic acid M-2: acrylic acid TA-1: 3-mercaptopropionic acid TA-2: thioglycolic acid TB-1: n-dodecyl Mercaptan TB-2: Stearyl mercaptan TB-3: Cetyl mercaptan
Ｌ－３：α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（５３モル）オキシエチレン
Ｌ－５：α－メタクリロイル－ω－メトキシ－ポリ（４５モル）オキシエチレン
Ｌ－６：α－メタクリロイル－ω－メトキシ－ポリ（２３モル）オキシエチレン
Ｍ－１：メタクリル酸
Ｍ－２：アクリル酸
ＴＡ－１：３－メルカプトプロピオン酸
ＴＡ－２：チオグリコール酸
ＴＢ－１：ｎ－ドデシルメルカプタン
ＴＢ－２：ステアリルメルカプタン
ＴＢ－３：セチルメルカプタン In Table 5, L-3, L-5, L-6, M-1, M-2, TA-1, TA-2, and TB-1 to TB-3 represent the following compounds, each A structural unit is derived from the compound.
L-3: α-(3-methyl-3-butenyl)-ω-hydroxy-poly(53 mol) oxyethylene L-5: α-methacryloyl-ω-methoxy-poly(45 mol) oxyethylene L-6: α-methacryloyl-ω-methoxy-poly (23 mol) oxyethylene M-1: methacrylic acid M-2: acrylic acid TA-1: 3-mercaptopropionic acid TA-2: thioglycolic acid TB-1: n-dodecyl Mercaptan TB-2: Stearyl mercaptan TB-3: Cetyl mercaptan
以下に、Ｄ成分（Ｄ－１～Ｄ－４）の合成方法を説明する。
The method for synthesizing the D components (D-1 to D-4) will be described below.
（合成例１１）Ｄ－１の合成：
イオン交換水２７４．５ｇ、α－メタクリロイル－ω－メトキシ－ポリ（４５モル）オキシエチレン１７９．５ｇ、メタクリル酸１９．９ｇ、３－メルカプトプロピオン酸０．２ｇ、ｎ－ドデシルメルカプタン０．３８ｇを温度計、撹拌機、滴下ロート、及び窒素導入管を備えた反応容器に仕込み、撹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℃とした。 (Synthesis Example 11) Synthesis of D-1:
274.5 g of ion-exchanged water, 179.5 g of α-methacryloyl-ω-methoxy-poly(45 mol)oxyethylene, 19.9 g of methacrylic acid, 0.2 g of 3-mercaptopropionic acid, and 0.38 g of n-dodecylmercaptan were heated. The mixture was placed in a reaction vessel equipped with a meter, a stirrer, a dropping funnel, and a nitrogen inlet tube, and dissolved uniformly with stirring.
イオン交換水２７４．５ｇ、α－メタクリロイル－ω－メトキシ－ポリ（４５モル）オキシエチレン１７９．５ｇ、メタクリル酸１９．９ｇ、３－メルカプトプロピオン酸０．２ｇ、ｎ－ドデシルメルカプタン０．３８ｇを温度計、撹拌機、滴下ロート、及び窒素導入管を備えた反応容器に仕込み、撹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℃とした。 (Synthesis Example 11) Synthesis of D-1:
274.5 g of ion-exchanged water, 179.5 g of α-methacryloyl-ω-methoxy-poly(45 mol)oxyethylene, 19.9 g of methacrylic acid, 0.2 g of 3-mercaptopropionic acid, and 0.38 g of n-dodecylmercaptan were heated. The mixture was placed in a reaction vessel equipped with a meter, a stirrer, a dropping funnel, and a nitrogen inlet tube, and dissolved uniformly with stirring.
次に、３５％過酸化水素水溶液１．２ｇをイオン交換水１８．０ｇで希釈したものを加え重合反応を開始した。２時間後、３５％過酸化水素水溶液０．４ｇをイオン交換水６．０ｇで希釈したものを加え、２時間、７０℃を維持し、重合反応を終了した。イオン交換水にて濃度を２０％に調整した。この反応物をＤ－１とした。
Next, 1.2 g of a 35% hydrogen peroxide aqueous solution was diluted with 18.0 g of ion-exchanged water to initiate the polymerization reaction. After 2 hours, 0.4 g of 35% aqueous hydrogen peroxide solution diluted with 6.0 g of deionized water was added, and the temperature was maintained at 70° C. for 2 hours to complete the polymerization reaction. The concentration was adjusted to 20% with ion-exchanged water. This reactant was designated as D-1.
（合成例１２）Ｄ－２の合成：
イオン交換水４３６．８ｇ、α－メタクリロイル－ω－メトキシ－ポリ（２３モル）オキシエチレン３３８．９ｇ、メタクリル酸５９．６ｇ、３－メルカプトプロピオン酸０．４ｇ、ステアリルメルカプタン１．１ｇを温度計、撹拌機、滴下ロート、窒素導入管を備えた反応容器に仕込み、撹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℃とした。 (Synthesis Example 12) Synthesis of D-2:
436.8 g of ion-exchanged water, 338.9 g of α-methacryloyl-ω-methoxy-poly(23 mol) oxyethylene, 59.6 g of methacrylic acid, 0.4 g of 3-mercaptopropionic acid, and 1.1 g of stearyl mercaptan were added to a thermometer, The mixture was placed in a reaction vessel equipped with a stirrer, a dropping funnel, and a nitrogen inlet tube, and dissolved uniformly with stirring.
イオン交換水４３６．８ｇ、α－メタクリロイル－ω－メトキシ－ポリ（２３モル）オキシエチレン３３８．９ｇ、メタクリル酸５９．６ｇ、３－メルカプトプロピオン酸０．４ｇ、ステアリルメルカプタン１．１ｇを温度計、撹拌機、滴下ロート、窒素導入管を備えた反応容器に仕込み、撹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℃とした。 (Synthesis Example 12) Synthesis of D-2:
436.8 g of ion-exchanged water, 338.9 g of α-methacryloyl-ω-methoxy-poly(23 mol) oxyethylene, 59.6 g of methacrylic acid, 0.4 g of 3-mercaptopropionic acid, and 1.1 g of stearyl mercaptan were added to a thermometer, The mixture was placed in a reaction vessel equipped with a stirrer, a dropping funnel, and a nitrogen inlet tube, and dissolved uniformly with stirring.
次に、３５％過酸化水素水溶液２．４ｇをイオン交換水３５．８ｇで希釈したものを加え重合反応を開始した。２時間後、３５％過酸化水素水溶液０．８ｇをイオン交換水１１．９ｇで希釈したものを加え、２時間、７０℃を維持し、重合反応を終了した。イオン交換水にて濃度を２０％に調整した。この反応物をＤ－２とした。
Next, 2.4 g of a 35% hydrogen peroxide aqueous solution diluted with 35.8 g of deionized water was added to initiate the polymerization reaction. After 2 hours, 0.8 g of a 35% aqueous hydrogen peroxide solution diluted with 11.9 g of deionized water was added, and the temperature was maintained at 70° C. for 2 hours to complete the polymerization reaction. The concentration was adjusted to 20% with ion-exchanged water. This reaction product was designated as D-2.
（合成例１３）Ｄ－３の合成：
イオン交換水２１６．４ｇ、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（５３モル）オキシエチレン１６９．２ｇを温度計、撹拌機、滴下ロート、窒素導入管を備えた反応容器に仕込み、撹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℃とした。 (Synthesis Example 13) Synthesis of D-3:
216.4 g of ion-exchanged water and 169.2 g of α-(3-methyl-3-butenyl)-ω-hydroxy-poly(53 mol)oxyethylene were reacted with a thermometer, a stirrer, a dropping funnel and a nitrogen inlet tube. After charging into a container and uniformly dissolving with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 70°C in a warm water bath.
イオン交換水２１６．４ｇ、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（５３モル）オキシエチレン１６９．２ｇを温度計、撹拌機、滴下ロート、窒素導入管を備えた反応容器に仕込み、撹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℃とした。 (Synthesis Example 13) Synthesis of D-3:
216.4 g of ion-exchanged water and 169.2 g of α-(3-methyl-3-butenyl)-ω-hydroxy-poly(53 mol)oxyethylene were reacted with a thermometer, a stirrer, a dropping funnel and a nitrogen inlet tube. After charging into a container and uniformly dissolving with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 70°C in a warm water bath.
次に、３．５％過酸化水素水溶液１６．０ｇを３．０時間かけて滴下し、それと同時にアクリル酸２９．９ｇを３．０時間かけて滴下し、それと同時にチオグリコール酸０．０６ｇ、セチルメルカプタン０．３１ｇの混合物を４．０時間かけて滴下し、それと同時にアスコルビン酸１．３ｇをイオン交換水１１．７ｇで希釈したものを４．０時かけて滴下した。その後１．０時間７０℃を維持し、重合反応を終了した。イオン交換水にて濃度を２０％に調整した。この反応物をＤ－３とした。
Next, 16.0 g of a 3.5% aqueous hydrogen peroxide solution was added dropwise over 3.0 hours, and 29.9 g of acrylic acid was added dropwise over 3.0 hours. A mixture of 0.31 g of cetyl mercaptan was added dropwise over 4.0 hours, and at the same time, 1.3 g of ascorbic acid diluted with 11.7 g of deionized water was added dropwise over 4.0 hours. After that, the temperature was maintained at 70°C for 1.0 hour to complete the polymerization reaction. The concentration was adjusted to 20% with ion-exchanged water. This reaction product was designated as D-3.
（合成例１４）Ｄ－４の合成：
イオン交換水２７４．２ｇ、α－メタクリロイル－ω－メトキシ－ポリ（４５モル）オキシエチレン２１０．２ｇ、メタクリル酸２８．８ｇ、３－メルカプトプロピオン酸０．３６ｇを温度計、撹拌機、滴下ロート、窒素導入管を備えた反応容器に仕込み、撹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℃とした。 (Synthesis Example 14) Synthesis of D-4:
274.2 g of ion-exchanged water, 210.2 g of α-methacryloyl-ω-methoxy-poly(45 mol)oxyethylene, 28.8 g of methacrylic acid, and 0.36 g of 3-mercaptopropionic acid were charged with a thermometer, a stirrer, a dropping funnel, After charging into a reaction vessel equipped with a nitrogen inlet tube and uniformly dissolving with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 70°C in a hot water bath.
イオン交換水２７４．２ｇ、α－メタクリロイル－ω－メトキシ－ポリ（４５モル）オキシエチレン２１０．２ｇ、メタクリル酸２８．８ｇ、３－メルカプトプロピオン酸０．３６ｇを温度計、撹拌機、滴下ロート、窒素導入管を備えた反応容器に仕込み、撹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℃とした。 (Synthesis Example 14) Synthesis of D-4:
274.2 g of ion-exchanged water, 210.2 g of α-methacryloyl-ω-methoxy-poly(45 mol)oxyethylene, 28.8 g of methacrylic acid, and 0.36 g of 3-mercaptopropionic acid were charged with a thermometer, a stirrer, a dropping funnel, After charging into a reaction vessel equipped with a nitrogen inlet tube and uniformly dissolving with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 70°C in a hot water bath.
次に、３５％過酸化水素水溶液１．４ｇをイオン交換水１３．０ｇで希釈したものを加え重合反応を開始した。２時間後、３５％過酸化水素水溶液０．５ｇをイオン交換水４．３ｇで希釈したものを加え、２時間、７０℃を維持し、重合反応を終了した。イオン交換水にて濃度を２０％に調整した。この反応物をＤ－４とした。
Next, 1.4 g of a 35% hydrogen peroxide aqueous solution was diluted with 13.0 g of ion-exchanged water to initiate a polymerization reaction. After 2 hours, 0.5 g of 35% aqueous hydrogen peroxide solution diluted with 4.3 g of deionized water was added, and the temperature was maintained at 70° C. for 2 hours to complete the polymerization reaction. The concentration was adjusted to 20% with ion-exchanged water. This reaction product was designated as D-4.
（質量平均分子量）
合成した共重合体のＤ－１～Ｄ－４の質量平均分子量について、上述のＰＣ－１～ＰＣ－４と同様に、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。 (mass average molecular weight)
The mass average molecular weights of D-1 to D-4 of the synthesized copolymers were measured by gel permeation chromatography (GPC) in the same manner as PC-1 to PC-4 described above.
合成した共重合体のＤ－１～Ｄ－４の質量平均分子量について、上述のＰＣ－１～ＰＣ－４と同様に、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。 (mass average molecular weight)
The mass average molecular weights of D-1 to D-4 of the synthesized copolymers were measured by gel permeation chromatography (GPC) in the same manner as PC-1 to PC-4 described above.
測定の結果、Ｄ－１の質量平均分子量は３０００００であり、Ｄ－２の質量平均分子量は２８００００であり、Ｄ－３の質量平均分子量は２５００００であり、Ｄ－４の質量平均分子量は２０００００であった。
As a result of the measurement, the weight average molecular weight of D-1 was 300,000, the weight average molecular weight of D-2 was 280,000, the weight average molecular weight of D-3 was 250,000, and the weight average molecular weight of D-4 was 200,000. there were.
（実施例１～３４、比較例１，２）
次に、表６に示すように、各成分を混合して水硬性組成物用添加剤を作製した。なお、表６中、「水」の質量部は、水硬性組成物用添加剤１００質量部に対する質量部を示す。 (Examples 1 to 34, Comparative Examples 1 and 2)
Next, as shown in Table 6, each component was mixed to prepare an additive for a hydraulic composition. In addition, in Table 6, "parts by mass" of "water" indicates parts by mass with respect to 100 parts by mass of the additive for hydraulic composition.
次に、表６に示すように、各成分を混合して水硬性組成物用添加剤を作製した。なお、表６中、「水」の質量部は、水硬性組成物用添加剤１００質量部に対する質量部を示す。 (Examples 1 to 34, Comparative Examples 1 and 2)
Next, as shown in Table 6, each component was mixed to prepare an additive for a hydraulic composition. In addition, in Table 6, "parts by mass" of "water" indicates parts by mass with respect to 100 parts by mass of the additive for hydraulic composition.
（実施例３５～６８、比較例３～６）
次に、作製した水硬性組成物用添加剤を用い、表８に示す配合１を採用して、表７に示す各水硬性組成物を作製した。 (Examples 35-68, Comparative Examples 3-6)
Next, each hydraulic composition shown in Table 7 was produced using the produced additive for hydraulic composition and adopting formulation 1 shown in Table 8.
次に、作製した水硬性組成物用添加剤を用い、表８に示す配合１を採用して、表７に示す各水硬性組成物を作製した。 (Examples 35-68, Comparative Examples 3-6)
Next, each hydraulic composition shown in Table 7 was produced using the produced additive for hydraulic composition and adopting formulation 1 shown in Table 8.
具体的には、以下のようにして水硬性組成物（コンクリート組成物）を調製した。まず、５５Ｌの強制二軸ミキサーに、セメントとしての普通ポルトランドセメント（太平洋セメント社製、密度＝３．１６ｇ／ｃｍ３）と、フライアッシュとしての中部フライアッシュ（テクノ中部社製、密度＝２．３３ｇ／ｃｍ３、ＪＩＳ Ａ ６２０１フライアッシュＩＩ種）と、高炉スラグ微粉末としてのエスメント４０００（日鉄高炉セメント社製、密度＝２．８９ｇ／ｃｍ３、ＪＩＳ Ａ ６２０６高炉スラグ微粉末４０００）と、骨材としての細骨材（大井川水系産陸砂、密度＝２．５８ｇ／ｃｍ３）及び粗骨材（岡崎産砕石、密度＝２．６６ｇ／ｃｍ３）と、をそれぞれ表８に示す配合（配合１）処方で配合した。そして、これに各水硬性組成物用添加剤（Ｆ－１～３４、ＦＲ－１～２）を配合して、実施例３５～６８、比較例３～６の水硬性組成物を調製した（表７参照）。
Specifically, a hydraulic composition (concrete composition) was prepared as follows. First, ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd.; density = 3.16 g/cm 3 ) as cement and Chubu fly ash (manufactured by Techno Chubu Co., Ltd.; density = 2.0 g/cm 3 ) as fly ash were added to a 55 L forced twin-screw mixer. 33 g/cm 3 , JIS A 6201 fly ash type II), and Esment 4000 (manufactured by Nippon Steel Blast Furnace Cement Co., Ltd., density = 2.89 g/cm 3 , JIS A 6206 granulated blast furnace slag 4000) as ground granulated blast furnace slag. , fine aggregate (land sand from the Oi River water system, density = 2.58 g/cm 3 ) and coarse aggregate (crushed stone from Okazaki, density = 2.66 g/cm 3 ) as aggregates are shown in Table 8, respectively. Formulation (Formulation 1) Formulated according to the formula. Then, each hydraulic composition additive (F-1 to 34, FR-1 to 2) was added to this to prepare hydraulic compositions of Examples 35 to 68 and Comparative Examples 3 to 6 ( See Table 7).
なお、実施例３５～６８、比較例３～６の各水硬性組成物は、水硬性組成物用添加剤水溶液の添加量を調整して練り混ぜ直後のスランプが２１．０±１．５ｃｍの範囲内となるようにし、市販のＡＥ剤であるＡＥ－３００（竹本油脂社製）を適宜用い、更に、消泡剤であるＡＦＫ－２（竹本油脂社製）を結合材に対して０．００１質量％用いて、空気量が４．５±１．０％の範囲内となるように調整を行った。
The hydraulic compositions of Examples 35 to 68 and Comparative Examples 3 to 6 had a slump of 21.0±1.5 cm immediately after kneading by adjusting the amount of the additive aqueous solution for hydraulic compositions. Within the range, AE-300 (manufactured by Takemoto Yushi Co., Ltd.), which is a commercially available AE agent, is used as appropriate, and AFK-2 (manufactured by Takemoto Yushi Co., Ltd.), which is an antifoaming agent, is added to the binder at 0.00%. 001% by mass, the amount of air was adjusted to be within the range of 4.5±1.0%.
また、各水硬性組成物の調製は、２０℃及び３０℃環境下でそれぞれ行い、各水硬性組成物の練り上がり温度が、各環境温度の±２℃の範囲内になるように、調製前に各材料を温調した。
In addition, each hydraulic composition is prepared in an environment of 20 ° C. and 30 ° C., respectively, and the kneading temperature of each hydraulic composition is within the range of ± 2 ° C. of each environmental temperature. The temperature of each material was adjusted to .
なお、実施例３５～６８及び比較例３～６で採用した配合１は、水硬性粉体としてセメントを用いた配合である。
The formulation 1 employed in Examples 35-68 and Comparative Examples 3-6 is a formulation using cement as the hydraulic powder.
次に、作製した各水硬性組成物（コンクリート組成物）について、スランプ（ｃｍ）、空気量（容積％）、及び、コンクリート温度（℃）の測定を行った。結果を下記表７に示す。２０℃環境下と３０℃の環境下における各測定値を示す。表７中、「スランプ（ｃｍ）」は、練り混ぜ直後のスランプ（ｃｍ）を意味し、「空気量（％）」は、練り混ぜ直後の空気量（％）を意味し、「コンクリート温度（℃）」は、練り混ぜ直後のコンクリートの温度（℃）を意味する。
Next, the slump (cm), air content (volume %), and concrete temperature (°C) were measured for each hydraulic composition (concrete composition) that was prepared. The results are shown in Table 7 below. Measured values under 20° C. environment and 30° C. environment are shown. In Table 7, "slump (cm)" means the slump (cm) immediately after kneading, "air content (%)" means the air content (%) immediately after kneading, and "concrete temperature ( °C)” means the temperature of the concrete immediately after mixing (°C).
・スランプ（ｃｍ）：
コンクリート組成物について、ＪＩＳ－Ａ１１０１（２０２０）に準拠して測定した。 ・Slump (cm):
Concrete compositions were measured according to JIS-A1101 (2020).
コンクリート組成物について、ＪＩＳ－Ａ１１０１（２０２０）に準拠して測定した。 ・Slump (cm):
Concrete compositions were measured according to JIS-A1101 (2020).
・空気量（容積％）：
コンクリート組成物について、ＪＩＳ－Ａ１１２８（２０２０）に準拠して測定した。 ・Amount of air (% by volume):
Concrete compositions were measured according to JIS-A1128 (2020).
コンクリート組成物について、ＪＩＳ－Ａ１１２８（２０２０）に準拠して測定した。 ・Amount of air (% by volume):
Concrete compositions were measured according to JIS-A1128 (2020).
・コンクリート温度（℃）：
コンクリート組成物について、ＪＩＳ－Ａ１１５６（２０１４）に準拠して測定した。 ・Concrete temperature (°C):
Concrete compositions were measured according to JIS-A1156 (2014).
コンクリート組成物について、ＪＩＳ－Ａ１１５６（２０１４）に準拠して測定した。 ・Concrete temperature (°C):
Concrete compositions were measured according to JIS-A1156 (2014).
なお、比較例５は、ＡＥ剤を使用せず、消泡剤であるＡＦＫ－２を結合材に対して０．００５質量％用いても空気量が規定量以上となった。また、遅延剤水溶液は、グルコン酸ナトリウム（試薬：キシダ化学社製）４００ｇ、スクロース（試薬：キシダ化学社製）１００ｇ、及び、イオン交換水５００ｇを混合して調製した。
In Comparative Example 5, the amount of air was equal to or greater than the specified amount even when AFK-2, which is an antifoaming agent, was used in an amount of 0.005% by mass based on the binder without using an AE agent. An aqueous retardant solution was prepared by mixing 400 g of sodium gluconate (reagent: manufactured by Kishida Chemical Co., Ltd.), 100 g of sucrose (reagent: manufactured by Kishida Chemical Co., Ltd.), and 500 g of deionized water.
（評価結果）
作製した各水硬性組成物について、流動保持性の評価及び凝結時間の評価を行った。 (Evaluation results)
Evaluation of fluid retention and evaluation of setting time were performed for each of the produced hydraulic compositions.
作製した各水硬性組成物について、流動保持性の評価及び凝結時間の評価を行った。 (Evaluation results)
Evaluation of fluid retention and evaluation of setting time were performed for each of the produced hydraulic compositions.
（流動保持性）
練混ぜ直後（０分後）、練混ぜ直後から６０分後、及び、練混ぜ直後から９０分後のスランプ（ｃｍ）をそれぞれ、上記測定方法により測定し、その後、得られた測定値に基づき、「０分後と６０分後のスランプ差」、及び、「６０分後と９０分後のスランプ差」を算出した。そして、これらの「スランプ差」について以下の評価基準で評価を行い、これを流動保持性の評価とした。表９には、２０℃環境下における流動保持性の評価結果を示し、表１０には、３０℃環境下における流動保持性の評価結果を示す。 (Fluid retention)
The slump (cm) immediately after kneading (after 0 minutes), 60 minutes after kneading, and 90 minutes after kneading was measured by the above-described measurement method, and then based on the measured values obtained. , “difference in slump after 0 minute and after 60 minutes”, and “difference in slump after 60 minutes and after 90 minutes” were calculated. Then, these "slump differences" were evaluated according to the following evaluation criteria, and this was used as an evaluation of fluidity retention. Table 9 shows the evaluation results of fluidity retention in a 20°C environment, and Table 10 shows the evaluation results of fluidity retention in a 30°C environment.
練混ぜ直後（０分後）、練混ぜ直後から６０分後、及び、練混ぜ直後から９０分後のスランプ（ｃｍ）をそれぞれ、上記測定方法により測定し、その後、得られた測定値に基づき、「０分後と６０分後のスランプ差」、及び、「６０分後と９０分後のスランプ差」を算出した。そして、これらの「スランプ差」について以下の評価基準で評価を行い、これを流動保持性の評価とした。表９には、２０℃環境下における流動保持性の評価結果を示し、表１０には、３０℃環境下における流動保持性の評価結果を示す。 (Fluid retention)
The slump (cm) immediately after kneading (after 0 minutes), 60 minutes after kneading, and 90 minutes after kneading was measured by the above-described measurement method, and then based on the measured values obtained. , “difference in slump after 0 minute and after 60 minutes”, and “difference in slump after 60 minutes and after 90 minutes” were calculated. Then, these "slump differences" were evaluated according to the following evaluation criteria, and this was used as an evaluation of fluidity retention. Table 9 shows the evaluation results of fluidity retention in a 20°C environment, and Table 10 shows the evaluation results of fluidity retention in a 30°C environment.
・０分後と６０分後のスランプ差
Ｓ：差が２．０ｃｍ以下
Ａ：差が２．０ｃｍ超、４．０ｃｍ以下
Ｂ：差が４．０ｃｍ超、６．０ｃｍ以下
Ｃ：差が６．０ｃｍ超、７．５ｃｍ以下
Ｄ：差が７．５ｃｍ超 ・ Slump difference after 0 minutes and 60 minutes S: difference is 2.0 cm or less A: difference is more than 2.0 cm and 4.0 cm or less B: difference is more than 4.0 cm and 6.0 cm or less C: difference is 6 More than 0 cm and 7.5 cm or less D: Difference is more than 7.5 cm
Ｓ：差が２．０ｃｍ以下
Ａ：差が２．０ｃｍ超、４．０ｃｍ以下
Ｂ：差が４．０ｃｍ超、６．０ｃｍ以下
Ｃ：差が６．０ｃｍ超、７．５ｃｍ以下
Ｄ：差が７．５ｃｍ超 ・ Slump difference after 0 minutes and 60 minutes S: difference is 2.0 cm or less A: difference is more than 2.0 cm and 4.0 cm or less B: difference is more than 4.0 cm and 6.0 cm or less C: difference is 6 More than 0 cm and 7.5 cm or less D: Difference is more than 7.5 cm
・６０分後と９０分後のスランプ差
Ｓ：差が３．０ｃｍ以下
Ａ：差が３．０ｃｍ超、５．０ｃｍ以下
Ｂ：差が５．０ｃｍ超、７．０ｃｍ以下
Ｃ：差が７．０ｃｍ超、８．５ｃｍ以下
Ｄ：差が８．５ｃｍ超 ・ Slump difference after 60 minutes and 90 minutes S: difference is 3.0 cm or less A: difference is more than 3.0 cm and 5.0 cm or less B: difference is more than 5.0 cm and 7.0 cm or less C: difference is 7 More than 0 cm and 8.5 cm or less D: Difference is more than 8.5 cm
Ｓ：差が３．０ｃｍ以下
Ａ：差が３．０ｃｍ超、５．０ｃｍ以下
Ｂ：差が５．０ｃｍ超、７．０ｃｍ以下
Ｃ：差が７．０ｃｍ超、８．５ｃｍ以下
Ｄ：差が８．５ｃｍ超 ・ Slump difference after 60 minutes and 90 minutes S: difference is 3.0 cm or less A: difference is more than 3.0 cm and 5.0 cm or less B: difference is more than 5.0 cm and 7.0 cm or less C: difference is 7 More than 0 cm and 8.5 cm or less D: Difference is more than 8.5 cm
（凝結時間）
作製した各水硬性組成物（コンクリート組成物）について、以下のようにして凝結始発時間を測定し、その後、凝結時間の評価を行った。表９には、２０℃の環境下における凝結始発時間の評価結果を示し、表１０には、３０℃の環境下における凝結始発時間の評価結果を示す。 (setting time)
For each hydraulic composition (concrete composition) prepared, the initial setting time was measured as follows, and then the setting time was evaluated. Table 9 shows the evaluation results of the initial condensation time under the environment of 20°C, and Table 10 shows the evaluation result of the initial condensation time under the environment of 30°C.
作製した各水硬性組成物（コンクリート組成物）について、以下のようにして凝結始発時間を測定し、その後、凝結時間の評価を行った。表９には、２０℃の環境下における凝結始発時間の評価結果を示し、表１０には、３０℃の環境下における凝結始発時間の評価結果を示す。 (setting time)
For each hydraulic composition (concrete composition) prepared, the initial setting time was measured as follows, and then the setting time was evaluated. Table 9 shows the evaluation results of the initial condensation time under the environment of 20°C, and Table 10 shows the evaluation result of the initial condensation time under the environment of 30°C.
・凝結始発時間：
練り混ぜ直後のコンクリート組成物を用いて、ＪＩＳ－Ａ１１４７（２０１９）に準拠して凝結始発時間を測定した。 ・Start time of condensation:
Using the concrete composition immediately after kneading, the initial setting time was measured according to JIS-A1147 (2019).
練り混ぜ直後のコンクリート組成物を用いて、ＪＩＳ－Ａ１１４７（２０１９）に準拠して凝結始発時間を測定した。 ・Start time of condensation:
Using the concrete composition immediately after kneading, the initial setting time was measured according to JIS-A1147 (2019).
２０℃環境下と３０℃環境下における凝結始発時間の評価の評価基準を以下に示す。
The evaluation criteria for the evaluation of the initial condensation time under the 20°C environment and the 30°C environment are shown below.
・凝結時間（２０℃環境下）
Ａ：凝結の始発時間が７時間以内
Ｂ：凝結の始発時間が７時間超、８時間以内
Ｃ：凝結の始発時間が８時間超 ・Caking time (at 20°C)
A: The first time of coagulation is within 7 hours B: The time of first coagulation is more than 7 hours and less than 8 hours C: The time of first coagulation is more than 8 hours
Ａ：凝結の始発時間が７時間以内
Ｂ：凝結の始発時間が７時間超、８時間以内
Ｃ：凝結の始発時間が８時間超 ・Caking time (at 20°C)
A: The first time of coagulation is within 7 hours B: The time of first coagulation is more than 7 hours and less than 8 hours C: The time of first coagulation is more than 8 hours
・凝結時間（３０℃環境下）
Ａ：凝結の始発時間が６時間半以内
Ｂ：凝結の始発時間が６時間半超、７時間半以内
Ｃ：凝結の始発時間が７時間半超 ・Caking time (under 30°C environment)
A: The first time of condensation is within 6 hours and a half B: The time of the first time of condensation is over 6 hours and a half, within 7 hours and a half C: The time of the first time of condensation is over 7 hours and a half
Ａ：凝結の始発時間が６時間半以内
Ｂ：凝結の始発時間が６時間半超、７時間半以内
Ｃ：凝結の始発時間が７時間半超 ・Caking time (under 30°C environment)
A: The first time of condensation is within 6 hours and a half B: The time of the first time of condensation is over 6 hours and a half, within 7 hours and a half C: The time of the first time of condensation is over 7 hours and a half
なお、比較例４に示すように、Ｃ成分及びＤ成分のいずれも含まないような水硬性組成物用添加剤である場合、２０℃環境下と３０℃環境下を比較すると、高温である３０℃環境下の方が、スランプ差が大きくなり、高温環境下において流動性が大きく低下することが分かる。また、比較例５は、上述の通り、ＡＥ剤を使用せず、消泡剤であるＡＦＫ－２を結合材に対して０．００５質量％用いても空気量が規定量以上となり、空気量が過多のために調整が不可であったことから、表９及び表１０中、「－」を記載している。
As shown in Comparative Example 4, in the case of a hydraulic composition additive that does not contain either the C component or the D component, when comparing the 20 ° C. environment and the 30 ° C. environment, the high temperature is 30 °C environment, the slump difference is larger, and it can be seen that the fluidity is greatly reduced in the high-temperature environment. In addition, as described above, in Comparative Example 5, even if AFK-2, which is an antifoaming agent, is used in an amount of 0.005% by mass with respect to the binder without using an AE agent, the amount of air is equal to or greater than the specified amount. "-" is shown in Tables 9 and 10 because adjustment was not possible due to an excessive amount.
（実施例６９～７１、比較例７，８）
次に、作製した水硬性組成物用添加剤を用い、表１２に示す配合２を採用して、上述した配合１と同様の水硬性組成物の調製方法と、同様のスランプ、及び、空気量の調整方法を用いて、表１１に示す各水硬性組成物を作製した。なお、実施例６９～７１及び比較例７，８で採用した配合２は、水硬性粉体としてセメント、フライアッシュ、及び、高炉スラグ微粉末を用いた配合である。 (Examples 69-71, Comparative Examples 7 and 8)
Next, using the prepared hydraulic composition additive, formulation 2 shown in Table 12 was adopted, and the same hydraulic composition preparation method as formulation 1 described above, the same slump and air content Each hydraulic composition shown in Table 11 was prepared using the adjustment method of. In addition, formulation 2 employed in Examples 69 to 71 and Comparative Examples 7 and 8 is a formulation using cement, fly ash, and ground granulated blast furnace slag as hydraulic powders.
次に、作製した水硬性組成物用添加剤を用い、表１２に示す配合２を採用して、上述した配合１と同様の水硬性組成物の調製方法と、同様のスランプ、及び、空気量の調整方法を用いて、表１１に示す各水硬性組成物を作製した。なお、実施例６９～７１及び比較例７，８で採用した配合２は、水硬性粉体としてセメント、フライアッシュ、及び、高炉スラグ微粉末を用いた配合である。 (Examples 69-71, Comparative Examples 7 and 8)
Next, using the prepared hydraulic composition additive, formulation 2 shown in Table 12 was adopted, and the same hydraulic composition preparation method as formulation 1 described above, the same slump and air content Each hydraulic composition shown in Table 11 was prepared using the adjustment method of. In addition, formulation 2 employed in Examples 69 to 71 and Comparative Examples 7 and 8 is a formulation using cement, fly ash, and ground granulated blast furnace slag as hydraulic powders.
次に、作製した各水硬性組成物（コンクリート組成物）について、上述した配合１と同様の測定方法を採用して、スランプ（ｃｍ）、空気量（容積％）、及び、コンクリート温度（℃）の測定を行った。結果を下記表１１に示す。２０℃環境下と３０℃の環境下における各測定値を示す。表１１中、「スランプ（ｃｍ）」は、練り混ぜ直後のスランプ（ｃｍ）を意味し、「空気量（％）」は、練り混ぜ直後の空気量（％）を意味し、「コンクリート温度（℃）」は、練り混ぜ直後のコンクリートの温度（℃）を意味する。
Next, for each hydraulic composition (concrete composition) prepared, the same measurement method as in Formulation 1 described above was used to determine slump (cm), air content (% by volume), and concrete temperature (° C.). was measured. The results are shown in Table 11 below. Measured values under 20° C. environment and 30° C. environment are shown. In Table 11, "slump (cm)" means the slump (cm) immediately after kneading, "air content (%)" means the air content (%) immediately after kneading, and "concrete temperature ( °C)” means the temperature of the concrete immediately after mixing (°C).
表１１中、遅延剤水溶液は、グルコン酸ナトリウム（試薬：キシダ化学社製）４００ｇとスクロース（試薬：キシダ化学社製）１００ｇとイオン交換水５００ｇを混合して調製した。
In Table 11, the retarder aqueous solution was prepared by mixing 400 g of sodium gluconate (reagent: manufactured by Kishida Chemical Co., Ltd.), 100 g of sucrose (reagent: manufactured by Kishida Chemical Co., Ltd.), and 500 g of deionized water.
（評価結果）
（流動保持性）
練混ぜ直後（０分後）、練混ぜ直後から６０分後、及び、練混ぜ直後から９０分後のスランプ（ｃｍ）をそれぞれ、上記測定方法により測定し、その後、得られた測定値に基づき、「０分後と６０分後のスランプ差」、及び、「６０分後と９０分後のスランプ差」を算出した。そして、これらの「スランプ差」について以下の評価基準で評価を行い、これを流動保持性の評価とした。表１３には、２０℃環境下における流動保持性の評価結果を示し、表１４には、３０℃環境下における流動保持性の評価結果を示す。 (Evaluation results)
(Fluid retention)
The slump (cm) immediately after kneading (after 0 minutes), 60 minutes after kneading, and 90 minutes after kneading was measured by the above-described measurement method, and then based on the measured values obtained. , “difference in slump after 0 minute and after 60 minutes”, and “difference in slump after 60 minutes and after 90 minutes” were calculated. Then, these "slump differences" were evaluated according to the following evaluation criteria, and this was used as an evaluation of fluidity retention. Table 13 shows the evaluation results of fluidity retention in a 20°C environment, and Table 14 shows the evaluation results of fluidity retention in a 30°C environment.
（流動保持性）
練混ぜ直後（０分後）、練混ぜ直後から６０分後、及び、練混ぜ直後から９０分後のスランプ（ｃｍ）をそれぞれ、上記測定方法により測定し、その後、得られた測定値に基づき、「０分後と６０分後のスランプ差」、及び、「６０分後と９０分後のスランプ差」を算出した。そして、これらの「スランプ差」について以下の評価基準で評価を行い、これを流動保持性の評価とした。表１３には、２０℃環境下における流動保持性の評価結果を示し、表１４には、３０℃環境下における流動保持性の評価結果を示す。 (Evaluation results)
(Fluid retention)
The slump (cm) immediately after kneading (after 0 minutes), 60 minutes after kneading, and 90 minutes after kneading was measured by the above-described measurement method, and then based on the measured values obtained. , “difference in slump after 0 minute and after 60 minutes”, and “difference in slump after 60 minutes and after 90 minutes” were calculated. Then, these "slump differences" were evaluated according to the following evaluation criteria, and this was used as an evaluation of fluidity retention. Table 13 shows the evaluation results of fluidity retention in a 20°C environment, and Table 14 shows the evaluation results of fluidity retention in a 30°C environment.
・０分後と６０分後のスランプ差
Ｓ：差が１．５ｃｍ以下
Ａ：差が１．５ｃｍ超、３．０ｃｍ以下
Ｂ：差が３．０ｃｍ超、４．５ｃｍ以下
Ｃ：差が４．５ｃｍ超 ・ Slump difference after 0 minutes and 60 minutes S: difference is 1.5 cm or less A: difference is more than 1.5 cm and 3.0 cm or less B: difference is more than 3.0 cm and 4.5 cm or less C: difference is 4 over .5 cm
Ｓ：差が１．５ｃｍ以下
Ａ：差が１．５ｃｍ超、３．０ｃｍ以下
Ｂ：差が３．０ｃｍ超、４．５ｃｍ以下
Ｃ：差が４．５ｃｍ超 ・ Slump difference after 0 minutes and 60 minutes S: difference is 1.5 cm or less A: difference is more than 1.5 cm and 3.0 cm or less B: difference is more than 3.0 cm and 4.5 cm or less C: difference is 4 over .5 cm
・６０分後と９０分後のスランプ差
Ｓ：差が２．０ｃｍ以下
Ａ：差が２．０ｃｍ超、３．５ｃｍ以下
Ｂ：差が３．５ｃｍ超、５．０ｃｍ以下
Ｃ：差が５．０ｃｍ超 ・ Slump difference after 60 minutes and 90 minutes S: difference is 2.0 cm or less A: difference is more than 2.0 cm and 3.5 cm or less B: difference is more than 3.5 cm and 5.0 cm or less C: difference is 5 over 0.0 cm
Ｓ：差が２．０ｃｍ以下
Ａ：差が２．０ｃｍ超、３．５ｃｍ以下
Ｂ：差が３．５ｃｍ超、５．０ｃｍ以下
Ｃ：差が５．０ｃｍ超 ・ Slump difference after 60 minutes and 90 minutes S: difference is 2.0 cm or less A: difference is more than 2.0 cm and 3.5 cm or less B: difference is more than 3.5 cm and 5.0 cm or less C: difference is 5 over 0.0 cm
（凝結時間）
作製した各水硬性組成物（コンクリート組成物）について、以下のようにして凝結始発時間を測定し、その後、凝結時間の評価を行った。表１３には、２０℃の環境下における凝結始発時間の評価結果を示し、表１４には、３０℃の環境下における凝結始発時間の評価結果を示す。 (setting time)
For each hydraulic composition (concrete composition) prepared, the initial setting time was measured as follows, and then the setting time was evaluated. Table 13 shows the evaluation results of the initial condensation time under the environment of 20°C, and Table 14 shows the evaluation result of the initial condensation time under the environment of 30°C.
作製した各水硬性組成物（コンクリート組成物）について、以下のようにして凝結始発時間を測定し、その後、凝結時間の評価を行った。表１３には、２０℃の環境下における凝結始発時間の評価結果を示し、表１４には、３０℃の環境下における凝結始発時間の評価結果を示す。 (setting time)
For each hydraulic composition (concrete composition) prepared, the initial setting time was measured as follows, and then the setting time was evaluated. Table 13 shows the evaluation results of the initial condensation time under the environment of 20°C, and Table 14 shows the evaluation result of the initial condensation time under the environment of 30°C.
・凝結始発時間：
練り混ぜ直後のコンクリート組成物を用いて、上述した配合１と同様の測定方法を採用して、凝結始発時間を測定した。 ・Start time of condensation:
Using the concrete composition immediately after kneading, the initial setting time was measured by adopting the same measurement method as in Mixture 1 described above.
練り混ぜ直後のコンクリート組成物を用いて、上述した配合１と同様の測定方法を採用して、凝結始発時間を測定した。 ・Start time of condensation:
Using the concrete composition immediately after kneading, the initial setting time was measured by adopting the same measurement method as in Mixture 1 described above.
２０℃環境下と３０℃環境下における凝結始発時間の評価の評価基準を以下に示す。
The evaluation criteria for the evaluation of the initial condensation time under the 20°C environment and the 30°C environment are shown below.
・凝結時間（２０℃環境下）
Ａ：凝結の始発時間が８時間以内
Ｂ：凝結の始発時間が８時間超、９時間以内
Ｃ：凝結の始発時間が９時間超 ・Caking time (at 20°C)
A: The first time of coagulation is within 8 hours B: The time of first coagulation is over 8 hours and within 9 hours C: The time of first coagulation is over 9 hours
Ａ：凝結の始発時間が８時間以内
Ｂ：凝結の始発時間が８時間超、９時間以内
Ｃ：凝結の始発時間が９時間超 ・Caking time (at 20°C)
A: The first time of coagulation is within 8 hours B: The time of first coagulation is over 8 hours and within 9 hours C: The time of first coagulation is over 9 hours
・凝結時間（３０℃環境下）
Ａ：凝結の始発時間が７時間半以内
Ｂ：凝結の始発時間が７時間半超、８時間半以内
Ｃ：凝結の始発時間が８時間半超 ・Caking time (under 30°C environment)
A: Initial condensation time within 7.5 hours B: Initial condensation time over 7.5 hours, within 8.5 hours C: Initial condensation time over 8.5 hours
Ａ：凝結の始発時間が７時間半以内
Ｂ：凝結の始発時間が７時間半超、８時間半以内
Ｃ：凝結の始発時間が８時間半超 ・Caking time (under 30°C environment)
A: Initial condensation time within 7.5 hours B: Initial condensation time over 7.5 hours, within 8.5 hours C: Initial condensation time over 8.5 hours
（結果）
表９，表１０、表１３，表１４に示されるように、本発明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、使用時の環境温度に関わらず、水硬性組成物における経時による流動性の変化が少なく空気量の調整が適宜可能でありながら、水硬性組成物の凝結時間を過度に遅延させない水硬性組成物が得られることが確認された。また、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配合することで、使用時の環境温度に関わらず、水硬性組成物における経時による流動性の変化が少なく空気量の調整が適宜可能でありながら、その凝結時間が過度に遅延しないことが確認された。 (result)
As shown in Tables 9, 10, 13, and 14, by blending the additive for hydraulic composition of the present invention into the hydraulic composition, regardless of the environmental temperature during use, the hydraulic composition It has been confirmed that a hydraulic composition can be obtained that does not excessively delay the setting time of the hydraulic composition while the fluidity of the product changes little over time and the amount of air can be appropriately adjusted. In addition, the hydraulic composition of the present invention, by blending the additive for hydraulic compositions of the present invention, is less likely to change over time in the fluidity of the hydraulic composition regardless of the environmental temperature during use. It was confirmed that the setting time was not excessively delayed while adjusting the amount accordingly.
表９，表１０、表１３，表１４に示されるように、本発明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、使用時の環境温度に関わらず、水硬性組成物における経時による流動性の変化が少なく空気量の調整が適宜可能でありながら、水硬性組成物の凝結時間を過度に遅延させない水硬性組成物が得られることが確認された。また、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配合することで、使用時の環境温度に関わらず、水硬性組成物における経時による流動性の変化が少なく空気量の調整が適宜可能でありながら、その凝結時間が過度に遅延しないことが確認された。 (result)
As shown in Tables 9, 10, 13, and 14, by blending the additive for hydraulic composition of the present invention into the hydraulic composition, regardless of the environmental temperature during use, the hydraulic composition It has been confirmed that a hydraulic composition can be obtained that does not excessively delay the setting time of the hydraulic composition while the fluidity of the product changes little over time and the amount of air can be appropriately adjusted. In addition, the hydraulic composition of the present invention, by blending the additive for hydraulic compositions of the present invention, is less likely to change over time in the fluidity of the hydraulic composition regardless of the environmental temperature during use. It was confirmed that the setting time was not excessively delayed while adjusting the amount accordingly.
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 hydraulic compositions of the present invention can be used as an additive added to hydraulic compositions such as concrete. In addition, the hydraulic composition of the present invention can be used to prepare hardened materials such as concrete.
Claims (8)
- 下記Ａ成分と、
下記Ｂ成分と、
下記Ｃ成分及び下記Ｄ成分から選択される少なくとも１つと、
を含有することを特徴とする水硬性組成物用添加剤。
＜Ａ成分＞
ポリアリルアミン、ポリアリルアミン塩、ポリアルキレンイミン、ポリアルキレンイミンのアルキレンオキシド付加物、ジアリルアミン重合体、ジアリルアミン塩重合体、ジアリルアミン・二酸化硫黄共重合体、ジアリルアミン塩・二酸化硫黄共重合体、及びポリビニルピロリドンから選択される少なくとも１つ。
＜Ｂ成分＞
下記一般式（１）で示される化合物である単量体１から形成された構成単位１、及び、下記一般式（２）で示される化合物である単量体２から形成された構成単位２を含み、
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５０～９９質量％、前記構成単位２が５０～１質量％の割合であり、
更に、質量平均分子量が５，０００以上で１００，０００以下であるビニル共重合体。
＜Ｃ成分＞
下記一般式（３）で示される化合物。
＜Ｄ成分＞
下記一般式（４）で示される化合物である単量体３から形成された構成単位３、及び、下記一般式（５）で示される化合物である単量体４から形成された構成単位４を含み、
前記構成単位３と前記構成単位４の構成割合の合計を１００質量％としたとき、前記構成単位３が５０～９９質量％、前記構成単位４が５０～１質量％であり、
更に、質量平均分子量が１００，０００超で６００，０００以下であるビニル共重合体。
the following B component,
At least one selected from the following C component and the following D component,
An additive for a hydraulic composition characterized by containing
<A component>
From polyallylamine, polyallylamine salt, polyalkyleneimine, alkylene oxide adduct of polyalkyleneimine, diallylamine polymer, diallylamine salt polymer, diallylamine/sulfur dioxide copolymer, diallylamine salt/sulfur dioxide copolymer, and polyvinylpyrrolidone At least one selected.
<B component>
A structural unit 1 formed from a monomer 1 which is a compound represented by the following general formula (1), and a structural unit 2 formed from a monomer 2 which is a compound represented by the following general formula (2) including
When the total composition ratio of the structural unit 1 and the structural unit 2 is 100% by mass, the structural unit 1 is 50 to 99% by mass and the structural unit 2 is 50 to 1% by mass,
Furthermore, a vinyl copolymer having a weight average molecular weight of 5,000 or more and 100,000 or less.
<C component>
A compound represented by the following general formula (3).
<D component>
A structural unit 3 formed from a monomer 3 which is a compound represented by the following general formula (4), and a structural unit 4 formed from a monomer 4 which is a compound represented by the following general formula (5) including
When the total composition ratio of the structural unit 3 and the structural unit 4 is 100% by mass, the structural unit 3 is 50 to 99% by mass and the structural unit 4 is 50 to 1% by mass,
Furthermore, a vinyl copolymer having a weight average molecular weight of more than 100,000 and not more than 600,000.
- 前記一般式（３）における－（ＡＯ）ｓ－が、炭素数２～４のオキシアルキレン基の構成割合の合計を１００モル％とすると、
炭素数２のオキシアルキレン基を９０モル％以上の割合で有するものである、請求項１に記載の水硬性組成物用添加剤。 Assuming that -(AO) s - in the general formula (3) has a total composition ratio of oxyalkylene groups having 2 to 4 carbon atoms of 100 mol%,
2. The additive for hydraulic compositions according to claim 1, which contains 90 mol % or more of oxyalkylene groups having 2 carbon atoms. - 前記Ｄ成分が、
硫黄原子を含有する親水性連鎖移動剤に由来する構造単位（ＴＡ）を更に含有する、請求項１または２に記載の水硬性組成物用添加剤。 The D component is
3. The additive for hydraulic composition according to claim 1, further comprising a structural unit (TA) derived from a hydrophilic chain transfer agent containing a sulfur atom. - 前記Ｄ成分が、
硫黄原子を含有する疎水性連鎖移動剤に由来する構造単位（ＴＢ）を更に含有する、請求項３に記載の水硬性組成物用添加剤。 The D component is
4. The additive for hydraulic composition according to claim 3, further comprising a structural unit (TB) derived from a hydrophobic chain transfer agent containing a sulfur atom. - 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１～７０質量部、前記Ｂ成分を２９～９８質量部、及び前記Ｃ成分を０．０５～１０質量部の割合で含有する、請求項１～４のいずれか一項に記載の水硬性組成物用添加剤。 Including the A component, the B component and the C component, and when the total content of the A component, the B component and the C component is 100 parts by mass,
1 to 70 parts by mass of the A component, 29 to 98 parts by mass of the B component, and 0.05 to 10 parts by mass of the C component, according to any one of claims 1 to 4 Hydraulic composition additive. - 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１～６０質量部、前記Ｂ成分を１９～９８質量部、及び前記Ｄ成分を０．５～４０質量部の割合で含有する、請求項１～４のいずれか一項に記載の水硬性組成物用添加剤。 When the total content of the A component, the B component and the D component is included, and the total content of the A component, the B component and the D component is 100 parts by mass,
1 to 60 parts by mass of the A component, 19 to 98 parts by mass of the B component, and 0.5 to 40 parts by mass of the D component, according to any one of claims 1 to 4 Hydraulic composition additive. - 前記Ａ成分、前記Ｂ成分、前記Ｃ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１～６０質量部、前記Ｂ成分を１９～９８質量部、前記Ｃ成分を０．０５～１０質量部、及び前記Ｄ成分を０．５～４０質量部の割合で含有する、請求項１～４のいずれか一項に記載の水硬性組成物用添加剤。 When the total content of the A component, the B component, the C and the D component is included, and the total content of the A component, the B component, the C component and the D component is 100 parts by mass,
1 to 60 parts by mass of the A component, 19 to 98 parts by mass of the B component, 0.05 to 10 parts by mass of the C component, and 0.5 to 40 parts by mass of the D component, The additive for hydraulic compositions according to any one of claims 1 to 4. - 請求項１～７のいずれか一項に記載の水硬性組成物用添加剤を含有することを特徴とする水硬性組成物。 A hydraulic composition comprising the additive for a hydraulic composition according to any one of claims 1 to 7.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021011123A JP6918330B1 (en) | 2021-01-27 | 2021-01-27 | Additives for hydraulic compositions and hydraulic compositions |
| JP2021-011123 | 2021-01-27 |
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| Publication Number | Publication Date |
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| WO2022162979A1 true WO2022162979A1 (en) | 2022-08-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2021/029061 WO2022162979A1 (en) | 2021-01-27 | 2021-08-05 | Additive for hydraulic compositions, and hydraulic composition |
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| Country | Link |
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| JP (1) | JP6918330B1 (en) |
| WO (1) | WO2022162979A1 (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000063164A (en) * | 1998-06-11 | 2000-02-29 | Nippon Shokubai Co Ltd | Cement admixture |
| JP2004043284A (en) * | 2002-05-20 | 2004-02-12 | Nippon Shokubai Co Ltd | Cement admixture and method for manufacturing the same |
| WO2005066095A1 (en) * | 2004-01-06 | 2005-07-21 | Nippon Shokubai Co., Ltd. | Cement admixture |
| JP2005200298A (en) * | 2003-12-19 | 2005-07-28 | Nippon Shokubai Co Ltd | Cement admixture |
| JP2007270072A (en) * | 2006-03-31 | 2007-10-18 | Nippon Shokubai Co Ltd | Polycarboxylic acid-based polymer, method for producing the same and cement admixture |
| JP2010013320A (en) * | 2008-07-03 | 2010-01-21 | Nippon Shokubai Co Ltd | Silica fume cement composition |
| JP2017057101A (en) * | 2015-09-15 | 2017-03-23 | 花王株式会社 | Dispersant composition for gypsum |
| JP2020176045A (en) * | 2019-04-16 | 2020-10-29 | 株式会社日本触媒 | Cement additive, cement hardness improver, cement composition, and hardness improvement method of cement composition |
-
2021
- 2021-01-27 JP JP2021011123A patent/JP6918330B1/en active Active
- 2021-08-05 WO PCT/JP2021/029061 patent/WO2022162979A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000063164A (en) * | 1998-06-11 | 2000-02-29 | Nippon Shokubai Co Ltd | Cement admixture |
| JP2004043284A (en) * | 2002-05-20 | 2004-02-12 | Nippon Shokubai Co Ltd | Cement admixture and method for manufacturing the same |
| JP2005200298A (en) * | 2003-12-19 | 2005-07-28 | Nippon Shokubai Co Ltd | Cement admixture |
| WO2005066095A1 (en) * | 2004-01-06 | 2005-07-21 | Nippon Shokubai Co., Ltd. | Cement admixture |
| JP2007270072A (en) * | 2006-03-31 | 2007-10-18 | Nippon Shokubai Co Ltd | Polycarboxylic acid-based polymer, method for producing the same and cement admixture |
| JP2010013320A (en) * | 2008-07-03 | 2010-01-21 | Nippon Shokubai Co Ltd | Silica fume cement composition |
| JP2017057101A (en) * | 2015-09-15 | 2017-03-23 | 花王株式会社 | Dispersant composition for gypsum |
| JP2020176045A (en) * | 2019-04-16 | 2020-10-29 | 株式会社日本触媒 | Cement additive, cement hardness improver, cement composition, and hardness improvement method of cement composition |
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| JP6918330B1 (en) | 2021-08-11 |
| JP2022114716A (en) | 2022-08-08 |
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