JPWO2020196102A1 - Additives for hydraulic materials - Google Patents
Additives for hydraulic materials Download PDFInfo
- Publication number
- JPWO2020196102A1 JPWO2020196102A1 JP2021509127A JP2021509127A JPWO2020196102A1 JP WO2020196102 A1 JPWO2020196102 A1 JP WO2020196102A1 JP 2021509127 A JP2021509127 A JP 2021509127A JP 2021509127 A JP2021509127 A JP 2021509127A JP WO2020196102 A1 JPWO2020196102 A1 JP WO2020196102A1
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- mass
- structural unit
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 126
- 239000000654 additive Substances 0.000 title claims abstract description 75
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 162
- -1 aromatic vinyl compound Chemical class 0.000 claims abstract description 142
- 239000000839 emulsion Substances 0.000 claims abstract description 106
- 239000002245 particle Substances 0.000 claims abstract description 83
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 74
- 230000000996 additive effect Effects 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229920001577 copolymer Polymers 0.000 claims abstract description 61
- 239000000178 monomer Substances 0.000 claims abstract description 55
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 39
- 150000003839 salts Chemical class 0.000 claims abstract description 37
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 35
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920003122 (meth)acrylate-based copolymer Polymers 0.000 claims abstract description 23
- 230000009477 glass transition Effects 0.000 claims abstract description 19
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims description 54
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 21
- 150000003440 styrenes Chemical class 0.000 claims description 15
- 238000010276 construction Methods 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 5
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 239000011378 shotcrete Substances 0.000 claims description 5
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 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 claims description 4
- 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 claims description 4
- 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 claims description 4
- 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 claims description 4
- 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 claims description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 4
- 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 claims description 4
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical class C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 claims description 3
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical class C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 15
- 239000004567 concrete Substances 0.000 abstract description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 description 37
- 239000007864 aqueous solution Substances 0.000 description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 239000002253 acid Substances 0.000 description 20
- 239000002518 antifoaming agent Substances 0.000 description 20
- 239000004568 cement Substances 0.000 description 19
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 125000005702 oxyalkylene group Chemical group 0.000 description 16
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 239000011342 resin composition Substances 0.000 description 14
- 239000000523 sample Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000002270 dispersing agent Substances 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 238000005507 spraying Methods 0.000 description 10
- 239000003945 anionic surfactant Substances 0.000 description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 9
- 235000010265 sodium sulphite Nutrition 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 7
- 239000011398 Portland cement Substances 0.000 description 7
- 238000007664 blowing Methods 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000013530 defoamer Substances 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229920001732 Lignosulfonate Polymers 0.000 description 3
- 229920001214 Polysorbate 60 Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 125000005131 dialkylammonium group Chemical group 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 2
- 125000002270 phosphoric acid ester group Chemical group 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 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 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
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([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
- YKFLAYDHMOASIY-UHFFFAOYSA-N γ-terpinene Chemical compound CC(C)C1=CCC(C)=CC1 YKFLAYDHMOASIY-UHFFFAOYSA-N 0.000 description 2
- 239000001373 (E)-2-methylpent-2-enoic acid Substances 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- XPCQUZBJBFXAON-OWOJBTEDSA-N (e)-4-oxo-4-(2-sulfoethoxy)but-2-enoic acid Chemical compound OC(=O)\C=C\C(=O)OCCS(O)(=O)=O XPCQUZBJBFXAON-OWOJBTEDSA-N 0.000 description 1
- WCRQPXHVVCBDDT-PLNGDYQASA-N (z)-2-(3-sulfopropyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\CCCS(O)(=O)=O WCRQPXHVVCBDDT-PLNGDYQASA-N 0.000 description 1
- ICLYJLBTOGPLMC-KVVVOXFISA-N (z)-octadec-9-enoate;tris(2-hydroxyethyl)azanium Chemical compound OCCN(CCO)CCO.CCCCCCCC\C=C/CCCCCCCC(O)=O ICLYJLBTOGPLMC-KVVVOXFISA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- XIRPMPKSZHNMST-UHFFFAOYSA-N 1-ethenyl-2-phenylbenzene Chemical group C=CC1=CC=CC=C1C1=CC=CC=C1 XIRPMPKSZHNMST-UHFFFAOYSA-N 0.000 description 1
- ARIWANIATODDMH-AWEZNQCLSA-N 1-lauroyl-sn-glycerol Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)CO ARIWANIATODDMH-AWEZNQCLSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- OVPQPMTZOLCPHB-UHFFFAOYSA-N 2-(2-heptoxyethoxy)ethanol Chemical compound CCCCCCCOCCOCCO OVPQPMTZOLCPHB-UHFFFAOYSA-N 0.000 description 1
- WGIMXKDCVCTHGW-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCOCCO WGIMXKDCVCTHGW-UHFFFAOYSA-N 0.000 description 1
- FHCBFWPNQZFQAI-UHFFFAOYSA-N 2-(2-phosphonooxyphenyl)ethyl prop-2-enoate Chemical compound P(=O)(OC1=C(C=CC=C1)CCOC(C=C)=O)(O)O FHCBFWPNQZFQAI-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- JJYWRQLLQAKNAD-UHFFFAOYSA-N 2-Methyl-2-pentenoic acid Natural products CCC=C(C)C(O)=O JJYWRQLLQAKNAD-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- HXLLCROMVONRRO-UHFFFAOYSA-N 2-butoxyethenylbenzene Chemical compound CCCCOC=CC1=CC=CC=C1 HXLLCROMVONRRO-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 1
- FZHNODDFDJBMAS-UHFFFAOYSA-N 2-ethoxyethenylbenzene Chemical compound CCOC=CC1=CC=CC=C1 FZHNODDFDJBMAS-UHFFFAOYSA-N 0.000 description 1
- DDBYLRWHHCWVID-UHFFFAOYSA-N 2-ethylbut-1-enylbenzene Chemical compound CCC(CC)=CC1=CC=CC=C1 DDBYLRWHHCWVID-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- PJEKREDJLDASAE-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylpropanoate Chemical compound CCCCC(CC)COC(=O)C(C)S PJEKREDJLDASAE-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- JJYWRQLLQAKNAD-PLNGDYQASA-N 2-methyl-2-pentenoic acid Chemical compound CC\C=C(\C)C(O)=O JJYWRQLLQAKNAD-PLNGDYQASA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical compound NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 description 1
- LPIQIQPLUVLISR-UHFFFAOYSA-N 2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical group CC(=C)C1=NCCO1 LPIQIQPLUVLISR-UHFFFAOYSA-N 0.000 description 1
- ILYSKJPEZAABAA-UHFFFAOYSA-N 2-propoxyethenylbenzene Chemical compound CCCOC=CC1=CC=CC=C1 ILYSKJPEZAABAA-UHFFFAOYSA-N 0.000 description 1
- BHWWTWCFLZECFZ-UHFFFAOYSA-N 2-sulfanylethyl octanoate Chemical compound CCCCCCCC(=O)OCCS BHWWTWCFLZECFZ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- PLLWKXWNHKVGBR-UHFFFAOYSA-N 3-octadecoxy-1,2,4,3$l^{5}-trioxaphosphinane 3-oxide Chemical compound CCCCCCCCCCCCCCCCCCOP1(=O)OCCOO1 PLLWKXWNHKVGBR-UHFFFAOYSA-N 0.000 description 1
- AIMDYNJRXHEXEL-UHFFFAOYSA-N 3-phenylprop-1-enylbenzene Chemical compound C=1C=CC=CC=1CC=CC1=CC=CC=C1 AIMDYNJRXHEXEL-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RALRVIPTUXSBPO-UHFFFAOYSA-N 4-[4-chloro-3-(trifluoromethyl)phenyl]piperidin-4-ol Chemical compound C=1C=C(Cl)C(C(F)(F)F)=CC=1C1(O)CCNCC1 RALRVIPTUXSBPO-UHFFFAOYSA-N 0.000 description 1
- RRBONVXWAGQXDJ-UHFFFAOYSA-N 4-methoxybutyl 2-sulfanylacetate Chemical compound COCCCCOC(=O)CS RRBONVXWAGQXDJ-UHFFFAOYSA-N 0.000 description 1
- VIQGKXOVPDLASV-UHFFFAOYSA-N 4-methoxybutyl 2-sulfanylpropanoate Chemical compound COCCCCOC(=O)C(C)S VIQGKXOVPDLASV-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 102100026788 ATP synthase subunit C lysine N-methyltransferase Human genes 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical class OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 101000833848 Homo sapiens ATP synthase subunit C lysine N-methyltransferase Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- ARIWANIATODDMH-UHFFFAOYSA-N Lauric acid monoglyceride Natural products CCCCCCCCCCCC(=O)OCC(O)CO ARIWANIATODDMH-UHFFFAOYSA-N 0.000 description 1
- WSTYNZDAOAEEKG-UHFFFAOYSA-N Mayol Natural products CC1=C(O)C(=O)C=C2C(CCC3(C4CC(C(CC4(CCC33C)C)=O)C)C)(C)C3=CC=C21 WSTYNZDAOAEEKG-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- ZCZLQYAECBEUBH-UHFFFAOYSA-L calcium;octadec-9-enoate Chemical compound [Ca+2].CCCCCCCCC=CCCCCCCCC([O-])=O.CCCCCCCCC=CCCCCCCCC([O-])=O ZCZLQYAECBEUBH-UHFFFAOYSA-L 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical class [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- HLERILKGMXJNBU-UHFFFAOYSA-N norvaline betaine Chemical compound CCCC(C([O-])=O)[N+](C)(C)C HLERILKGMXJNBU-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- KHMYONNPZWOTKW-UHFFFAOYSA-N pent-1-enylbenzene Chemical compound CCCC=CC1=CC=CC=C1 KHMYONNPZWOTKW-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- KEOXNKSLFUFORO-UHFFFAOYSA-N phenoxymethylbenzene;sulfuric acid Chemical compound OS(O)(=O)=O.C=1C=CC=CC=1COC1=CC=CC=C1 KEOXNKSLFUFORO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- ONQDVAFWWYYXHM-UHFFFAOYSA-M potassium lauryl sulfate Chemical compound [K+].CCCCCCCCCCCCOS([O-])(=O)=O ONQDVAFWWYYXHM-UHFFFAOYSA-M 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect 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
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000646 scanning calorimetry Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 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
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- ZZMDMGNQUXYKQX-UHFFFAOYSA-L sodium;1-nonyl-2-(2-nonylphenoxy)benzene;sulfate Chemical compound [Na+].[O-]S([O-])(=O)=O.CCCCCCCCCC1=CC=CC=C1OC1=CC=CC=C1CCCCCCCCC ZZMDMGNQUXYKQX-UHFFFAOYSA-L 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- 229940117013 triethanolamine oleate Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
Abstract
本発明は、モルタル・コンクリート等におけるペースト分の骨材への粘着性を向上させ、かつ、併用する減水剤の添加量の増加を抑制することができる水硬性材料用添加剤を提供する。本発明は、（メタ）アクリレート系共重合体エマルション粒子を含む水硬性材料用添加剤であって、該共重合体エマルション粒子は、全構造単位１００質量％に対して、炭素数が１〜２０であるアルキル基を有するアルキル（メタ）アクリレート（Ａ）由来の構造単位（ａ）を４０〜９９．９質量％有し、（メタ）アクリル酸（塩）（Ｂ）由来の構造単位（ｂ）を０．１〜１０質量％有し、芳香族ビニル化合物（Ｃ）由来の構造単位（ｃ）の含有割合が０〜５９．９質量％であり、該アルキル（メタ）アクリレート（Ａ）、（メタ）アクリル酸（塩）（Ｂ）及び芳香族ビニル化合物（Ｃ）以外のその他の単量体（Ｄ）由来の構造単位（ｄ）の含有割合が０〜１０質量％であり、該共重合体エマルション粒子のガラス転移温度が−５０〜５℃以下であり、該共重合体エマルション粒子の平均粒子径が１３０ｎｍ以上であることを特徴とする水硬性材料用添加剤である。The present invention provides an additive for a hydraulic material that can improve the adhesiveness of a paste to an aggregate in mortar, concrete, etc., and can suppress an increase in the amount of a water reducing agent added in combination. The present invention is an additive for a water-hard material containing (meth) acrylate-based copolymer emulsion particles, and the copolymer emulsion particles have 1 to 20 carbon atoms with respect to 100% by mass of the total structural unit. The structural unit (a) derived from the alkyl (meth) acrylate (A) having an alkyl group is 40 to 99.9% by mass, and the structural unit (b) derived from (meth) acrylic acid (salt) (B). The content of the structural unit (c) derived from the aromatic vinyl compound (C) is 0 to 59.9% by mass, and the alkyl (meth) acrylate (A), ( The content ratio of the structural unit (d) derived from the other monomer (D) other than the meta) acrylic acid (salt) (B) and the aromatic vinyl compound (C) is 0 to 10% by mass, and the common weight thereof. It is an additive for a water-hard material, characterized in that the glass transition temperature of the combined emulsion particles is −50 to 5 ° C. or less, and the average particle size of the copolymer emulsion particles is 130 nm or more.
Description
本発明は、水硬性材料用添加剤に関する。より詳しくは、吹付モルタル・コンクリート等の用途に有用な水硬性材料用添加剤に関する。 The present invention relates to additives for hydraulic materials. More specifically, the present invention relates to additives for hydraulic materials useful for applications such as sprayed mortar and concrete.
（メタ）アクリレート系共重合体エマルションは、セメント等の水硬性材料組成物の改質性に優れ、硬化物の強度や耐久性等を向上させる作用等を有するため、土木・建築構造物等を構築するために好適に用いられる。
例えば特許文献１には、反応性不飽和基を有するノニオン性界面活性剤が乳化剤として用いられたことを特徴とするセメント混和用アクリル樹脂エマルションが開示されている。特許文献２には、カルボキシル基を有する不飽和単量体と、アクリル酸エステルおよびメタクリル酸エステルから選ばれる少なくとも一つの不飽和単量体とを含み、不飽和単量体の共重合体について重量分率法により算出したガラス転移温度が２２０〜２７０Ｋである混合物を、エチレン性不飽和結合とポリオキシアルキレン基とを有する分子を含む乳化剤を用いて乳化重合して得られるポリマーエマルションが開示されている。特許文献３には、不飽和二塩基酸のジメチルエステルおよび／またはメチルアクリレートを必須の単量体成分として用いて得られる、乳化重合体を必須の成分として含有することを特徴とする、セメント用組成物が開示されている。特許文献４には、少なくとも１種の水硬物質と、水硬物質１００重量部を基準にして、約２５〜約１３０重量部の水と、約０．０１〜約３０重量部の共重合体気泡安定剤とを含む発泡水硬組成物であって、前記共重合体気泡安定剤が、ａ）１種またはそれ以上の非イオン性のエチレン性不飽和単量体約０．１〜約９８重量％と、ｂ）少なくとも１種の単量体がカルボン酸を含有している、１種またはそれ以上のイオン性のまたはイオン化可能なエチレン性不飽和単量体約２〜約４０重量％とからなる共重合体である、前記組成物が開示されている。The (meth) acrylate-based copolymer emulsion is excellent in modifying a water-hard material composition such as cement, and has an action of improving the strength and durability of a cured product, so that it can be used for civil engineering, building structures, etc. Suitable for construction.
For example, Patent Document 1 discloses an acrylic resin emulsion for cement mixing, wherein a nonionic surfactant having a reactive unsaturated group is used as an emulsifier. Patent Document 2 contains an unsaturated monomer having a carboxyl group and at least one unsaturated monomer selected from an acrylic acid ester and a methacrylic acid ester, and the weight of the copolymer of the unsaturated monomer is included. A polymer emulsion obtained by emulsion polymerization of a mixture having a glass transition temperature of 220 to 270 K calculated by a fractional method using an emulsifier containing a molecule having an ethylenically unsaturated bond and a polyoxyalkylene group is disclosed. There is. Patent Document 3 describes, for cement, an emulsified polymer obtained by using an unsaturated dibasic acid dimethyl ester and / or methyl acrylate as an essential monomer component. The composition is disclosed. Patent Document 4 describes at least one type of water-hardening material, about 25 to about 130 parts by weight of water, and about 0.01 to about 30 parts by weight of a copolymer based on 100 parts by weight of the water-hardening material. A foamed water-hard composition containing a bubble stabilizer, wherein the copolymer bubble stabilizer is a) one or more nonionic ethylenically unsaturated monomers of about 0.1 to about 98. By weight% and b) about 2 to about 40% by weight of one or more ionic or ionizable ethylenically unsaturated monomers in which at least one monomer contains a carboxylic acid. The composition, which is a copolymer composed of the above, is disclosed.
ところで、例えばトンネルの一次覆工や、岩盤斜面・法面の保護・補強、コンクリート構造物の補修・補強等の土木・建築工事では、コンクリート（モルタル）を施工面に吹付ける吹付工法が広く用いられている。吹付工法の中でも、例えば湿式法では、急結剤以外の材料（水硬性材料、骨材、水、水硬性材料用添加剤等）を混合した後、圧縮空気又はポンプでノズル（吐出口）まで圧送し、ノズルの直前で別のポンプで送られた急結剤と混合して施工面に吹付ける。
吹付工法に用いられる水硬性材料に関して、例えば特許文献５には、セメント、細骨材及び軽量骨材より選ばれる骨材、繊維状鉱物、増粘剤、膨張材及びガラス転移温度−２０℃〜０℃のエマルションとを含むことを特徴とする水硬性組成物が開示されている。特許文献６には、岩盤の狭幅の割れ目又は／及び岩盤間の狭幅の継ぎ目に、フロー値が２５０以下のセメント組成物を噴霧することを特徴とする岩盤の安定化工法が開示されている。By the way, for example, in civil engineering and construction work such as primary lining of tunnels, protection and reinforcement of bedrock slopes and slopes, and repair and reinforcement of concrete structures, the spraying method of spraying concrete (mortar) on the construction surface is widely used. Has been done. Among the spraying methods, for example, in the wet method, materials other than the quick-setting admixture (hydraulic material, aggregate, water, additives for hydraulic material, etc.) are mixed, and then compressed air or a pump is used to reach the nozzle (discharge port). It is pumped, mixed with the quick-setting admixture sent by another pump just before the nozzle, and sprayed onto the construction surface.
Regarding hydraulic materials used in the spraying method, for example, Patent Document 5 describes aggregates selected from cement, fine aggregates and lightweight aggregates, fibrous minerals, thickeners, expansion materials and glass transition temperatures of -20 ° C to ~. A hydraulic composition comprising an emulsion at 0 ° C. is disclosed. Patent Document 6 discloses a rock stabilization method characterized by spraying a cement composition having a flow value of 250 or less on narrow cracks or / and narrow seams between rocks. There is.
上記吹付工法で用いられる水硬性材料組成物は、施工面に吹付けた際のはね返りによるロス分(リバウンド量)を低減させるために、モルタル・コンクリート等におけるペースト分の骨材への高い粘着性が求められていた。また、水硬性材料用添加剤は、減水剤と併用した場合に、減水剤の添加量が増加することを抑制することも求められていた。
従来の水硬性材料用添加剤は、水硬性材料組成物に用いた際のペースト分の骨材への粘着性と併用する減水剤の添加量の増加抑制との両立の点において充分ではなかった。The hydraulic material composition used in the above spraying method has high adhesiveness to the aggregate of the paste in mortar, concrete, etc. in order to reduce the loss (rebound amount) due to rebound when sprayed on the construction surface. Was required. In addition, the additive for hydraulic materials has also been required to suppress an increase in the amount of the water reducing agent added when used in combination with the water reducing agent.
The conventional additives for hydraulic materials are not sufficient in terms of both the adhesiveness of the paste to the aggregate when used in the hydraulic material composition and the suppression of the increase in the amount of the water reducing agent added in combination. ..
本発明は、上記現状に鑑みてなされたものであり、モルタル・コンクリート等におけるペースト分の骨材への粘着性を向上させ、かつ、併用する減水剤の添加量の増加を抑制することができる水硬性材料用添加剤を提供することを目的とする。 The present invention has been made in view of the above situation, and can improve the adhesiveness of the paste to the aggregate in mortar, concrete, etc., and suppress an increase in the amount of the water reducing agent added in combination. It is an object of the present invention to provide an additive for a hydraulic material.
本発明者は、水硬性材料用添加剤について種々検討したところ、炭素数が１〜２０であるアルキル基を有するアルキル（メタ）アクリレート由来の構造単位及び（メタ）アクリル酸（塩）由来の構造単位を特定の割合で有し、芳香族ビニル化合物由来の構造単位及びこれら以外のその他の単量体由来の構造単位の割合が特定の範囲であり、かつ、ガラス転移温度が−５０〜５℃であり、平均粒子径が１３０ｎｍ以上である共重合体エマルション粒子を含む水硬性材料用添加剤がモルタル・コンクリート等におけるペースト分の骨材への粘着性を向上させ、かつ、併用する減水剤の添加量の増加を抑制することができることを見いだし、上記課題をみごとに解決することができることに想到し、本発明に到達したものである。 As a result of various studies on additives for water-hard materials, the present inventor has found that structural units derived from alkyl (meth) acrylates having an alkyl group having 1 to 20 carbon atoms and structures derived from (meth) acrylic acid (salt). It has units in a specific ratio, the ratio of structural units derived from aromatic vinyl compounds and structural units derived from other monomers is in a specific range, and the glass transition temperature is -50 to 5 ° C. An additive for a water-hard material containing copolymer emulsion particles having an average particle size of 130 nm or more improves the adhesiveness of the paste to the aggregate in mortar, concrete, etc., and is a water-reducing agent used in combination. We have found that it is possible to suppress an increase in the amount of addition, and have come up with the idea that the above-mentioned problems can be solved brilliantly, and have arrived at the present invention.
すなわち本発明は、（メタ）アクリレート系共重合体エマルション粒子を含む水硬性材料用添加剤であって、該共重合体エマルション粒子は、全構造単位１００質量％に対して、炭素数が１〜２０であるアルキル基を有するアルキル（メタ）アクリレート（Ａ）由来の構造単位（ａ）を４０〜９９．９質量％有し、（メタ）アクリル酸（塩）（Ｂ）由来の構造単位（ｂ）を０．１〜１０質量％有し、芳香族ビニル化合物（Ｃ）由来の構造単位（ｃ）の含有割合が０〜５９．９質量％であり、上記アルキル（メタ）アクリレート（Ａ）、（メタ）アクリル酸（塩）（Ｂ）及び芳香族ビニル化合物（Ｃ）以外のその他の単量体（Ｄ）由来の構造単位（ｄ）の含有割合が０〜１０質量％であり、上記共重合体エマルション粒子のガラス転移温度が−５０〜５℃であり、上記共重合体エマルション粒子の平均粒子径が１３０ｎｍ以上である水硬性材料用添加剤である。 That is, the present invention is an additive for a water-hard material containing (meth) acrylate-based copolymer emulsion particles, and the copolymer emulsion particles have 1 to 1 carbon atoms with respect to 100% by mass of the total structural unit. It has 40 to 99.9% by mass of the structural unit (a) derived from the alkyl (meth) acrylate (A) having an alkyl group of 20, and the structural unit (b) derived from (meth) acrylic acid (salt) (B). ) Is 0.1 to 10% by mass, and the content ratio of the structural unit (c) derived from the aromatic vinyl compound (C) is 0 to 59.9% by mass. The content ratio of the structural unit (d) derived from the monomer (D) other than the (meth) acrylic acid (salt) (B) and the aromatic vinyl compound (C) is 0 to 10% by mass, and both of the above. It is an additive for a water-hard material in which the glass transition temperature of the polymer emulsion particles is −50 to 5 ° C. and the average particle size of the above-mentioned copolymer emulsion particles is 130 nm or more.
上記（メタ）アクリレート系共重合体エマルション粒子は、炭素数が３〜２０であるアルキル基を有するアルキル（メタ）アクリレート（Ａ２）由来の構造単位（ａ２）を有し、炭素数が１又は２であるアルキル基を有するアルキル（メタ）アクリレート（Ａ１）由来の構造単位（ａ１）を有していてもよく、該構造単位（ａ１）の割合が、構造単位（ａ２）１００質量％に対して０〜１４５質量％であることが好ましい。 The (meth) acrylate-based copolymer emulsion particles have a structural unit (a2) derived from an alkyl (meth) acrylate (A2) having an alkyl group having 3 to 20 carbon atoms, and have 1 or 2 carbon atoms. It may have a structural unit (a1) derived from an alkyl (meth) acrylate (A1) having an alkyl group, and the ratio of the structural unit (a1) is 100% by mass of the structural unit (a2). It is preferably 0 to 145% by mass.
上記（メタ）アクリレート系共重合体エマルション粒子は、炭素数が１又は２であるアルキル基を有するアルキル（メタ）アクリレート（Ａ１）由来の構造単位（ａ１）と炭素数が３〜２０であるアルキル基を有するアルキル（メタ）アクリレート（Ａ２）由来の構造単位（ａ２）とを有することが好ましい。 The (meth) acrylate-based copolymer emulsion particles have an alkyl (meth) acrylate (A1) -derived structural unit (a1) having an alkyl group having 1 or 2 carbon atoms and an alkyl having 3 to 20 carbon atoms. It is preferable to have a structural unit (a2) derived from an alkyl (meth) acrylate (A2) having a group.
上記構造単位（ａ）の割合が全構造単位１００質量％に対して４３〜９９．９質量％であることが好ましい。 The ratio of the structural unit (a) is preferably 43 to 99.9% by mass with respect to 100% by mass of all the structural units.
上記構造単位（ｂ）の割合が全構造単位１００質量％に対して０．１〜８質量％であることが好ましい。 The ratio of the structural unit (b) is preferably 0.1 to 8% by mass with respect to 100% by mass of all the structural units.
上記構造単位（ｃ）の割合が全構造単位１００質量％に対して０〜５７質量％であることが好ましい。 The ratio of the structural unit (c) is preferably 0 to 57% by mass with respect to 100% by mass of all the structural units.
上記構造単位（ａ１）の割合が構造単位（ａ２）１００質量％に対して５〜１４５質量％であることが好ましい。 The ratio of the structural unit (a1) is preferably 5 to 145% by mass with respect to 100% by mass of the structural unit (a2).
上記（メタ）アクリレート系共重合体エマルション粒子は、炭素数が１〜２０であるアルキル基を有するアルキル（メタ）アクリレート、（メタ）アクリル酸（塩）（Ｂ）及び芳香族ビニル化合物（Ｃ）以外のその他の単量体（Ｄ）由来の構造単位（ｄ）を有していてもよく、構造単位（ｄ）の含有割合の割合が全構造単位１００質量％に対して０〜１０質量％であることが好ましい。 The (meth) acrylate-based copolymer emulsion particles include an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms, a (meth) acrylic acid (salt) (B), and an aromatic vinyl compound (C). It may have a structural unit (d) derived from other monomers (D) other than the above, and the content ratio of the structural unit (d) is 0 to 10% by mass with respect to 100% by mass of all structural units. Is preferable.
上記（メタ）アクリレート系共重合体エマルション粒子は、ガラス転移温度が−４０〜５℃であることが好ましい。 The (meth) acrylate-based copolymer emulsion particles preferably have a glass transition temperature of -40 to 5 ° C.
上記（メタ）アクリレート系共重合体エマルション粒子は、平均粒子径が１５０〜４００ｎｍであることが好ましい。 The (meth) acrylate-based copolymer emulsion particles preferably have an average particle size of 150 to 400 nm.
上記アルキル（メタ）アクリレート（Ａ）は、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、テトラデシル（メタ）アクリレート、ペンタデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ヘプタデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、ノナデシル（メタ）アクリレート、イコシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレートからなる群より選択される少なくとも１種であることが好ましい。 The alkyl (meth) acrylate (A) includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and heptyl (meth). ) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) ) Acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecil (meth) acrylate , At least one selected from the group consisting of icosyl (meth) acrylate and cyclohexyl (meth) acrylate is preferable.
上記芳香族ビニル化合物（Ｃ）は、スチレン；アルキル置換スチレン；アルコキシ置換スチレン；芳香族基置換スチレン；ハロゲン置換スチレン；酸置換スチレン；ビニルナフタレン、ビニルアントラセンからなる群より選択される少なくとも１種であることが好ましい。 The aromatic vinyl compound (C) is at least one selected from the group consisting of styrene; alkyl-substituted styrene; alkoxy-substituted styrene; aromatic group-substituted styrene; halogen-substituted styrene; acid-substituted styrene; vinylnaphthalene and vinylanthracene. It is preferable to have.
上記水硬性材料用添加剤は、吹付けコンクリート用途に用いられることが好ましい。 The additive for hydraulic materials is preferably used for sprayed concrete applications.
本発明はまた、水硬性材料用添加剤と減水剤とを含む水硬性材料用添加剤組成物でもある。 The present invention is also an additive composition for hydraulic materials, which comprises an additive for hydraulic materials and a water reducing agent.
本発明はまた、上記水硬性材料用添加剤と水硬性材料とを含む水硬性材料組成物でもある。 The present invention is also a hydraulic material composition containing the above additive for a hydraulic material and a hydraulic material.
上記水硬性材料組成物は、更に減水剤を含むことが好ましい。 The hydraulic material composition preferably further contains a water reducing agent.
本発明は更に、上記水硬性材料用添加剤を水硬性材料とともに施工面に吹き付けて使用する方法でもある。 The present invention is also a method in which the additive for a hydraulic material is sprayed onto a construction surface together with the hydraulic material.
本発明の水硬性材料用添加剤は、上述の構成よりなり、モルタル・コンクリート等におけるペースト分の骨材への粘着性を向上させ、かつ、併用する減水剤の添加量の増加を抑制することができるため、吹付モルタル・コンクリート等に好適に用いることができる。 The additive for hydraulic materials of the present invention has the above-mentioned structure, improves the adhesiveness of the paste to the aggregate in mortar, concrete, etc., and suppresses an increase in the amount of the water reducing agent added in combination. Therefore, it can be suitably used for sprayed mortar, concrete and the like.
以下に本発明の好ましい形態について具体的に説明するが、本発明は以下の記載のみに限定されるものではなく、本発明の要旨を変更しない範囲において適宜変更して適用することができる。なお、以下に記載される本発明の個々の好ましい形態を２又は３以上組み合わせた形態も、本発明の好ましい形態に該当する。 Hereinafter, preferred embodiments of the present invention will be specifically described, but the present invention is not limited to the following description, and can be appropriately modified and applied without changing the gist of the present invention. A form in which two or three or more of the individual preferred forms of the present invention described below are combined also falls under the preferred form of the present invention.
＜（メタ）アクリレート系共重合体エマルション粒子＞
上記共重合体エマルション粒子は、全構造単位１００質量％に対して、炭素数が１〜２０であるアルキル基を有するアルキル（メタ）アクリレート由来の構造単位（ａ）を４０〜９９．９質量％有し、（メタ）アクリル酸（塩）由来の構造単位（ｂ）を０．１〜１０質量％有し、芳香族ビニル化合物（Ｃ）由来の構造単位（ｃ）の含有割合が０〜５９．９質量％である。構造単位（ａ）及び（ｂ）を上記割合で有し、構造単位（ｃ）の含有割合が上記範囲であることは、共重合体エマルション粒子のガラス転移温度が−５０〜５℃となることに寄与し、モルタル・コンクリート等におけるペースト分の骨材への粘着性を向上させる。これにより、施工面に水硬性材料組成物を吹き付けた際のリバウンド量を低減することができる。また、共重合体中の酸量が多い場合には、塩基性である水硬性材料と混合した際に高粘性となるため、吹付工法においては吹き付け直前に水硬性材料と混合する必要があるが、本発明の共重合体エマルション粒子は、構造単位（ａ）及び（ｂ）を上記割合で有し、構造単位（ｃ）の含有割合が上記範囲であることにより、塩基性である水硬性材料と混合した際にも高粘性となることを充分に抑制することができるため、水硬性材料と混合してから吹き付けまでの時間を充分に確保することもできる。<(Meta) acrylate-based copolymer emulsion particles>
The copolymer emulsion particles contain 40 to 99.9% by mass of a structural unit (a) derived from an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms with respect to 100% by mass of the total structural unit. It has 0.1 to 10% by mass of the structural unit (b) derived from (meth) acrylic acid (salt), and the content ratio of the structural unit (c) derived from the aromatic vinyl compound (C) is 0 to 59. It is 9.9% by mass. Having the structural units (a) and (b) in the above ratios and having the content ratio of the structural units (c) in the above range means that the glass transition temperature of the copolymer emulsion particles is −50 to 5 ° C. To improve the adhesiveness of the paste to the aggregate in mortar, concrete, etc. As a result, the amount of rebound when the hydraulic material composition is sprayed on the construction surface can be reduced. In addition, when the amount of acid in the copolymer is large, it becomes highly viscous when mixed with a basic hydraulic material, so in the spraying method, it is necessary to mix with the hydraulic material immediately before spraying. The copolymer emulsion particles of the present invention have the structural units (a) and (b) in the above proportions, and the content ratio of the structural units (c) is in the above range, so that the hydraulic material is basic. Since it is possible to sufficiently suppress the high viscosity even when mixed with the hydraulic material, it is possible to secure a sufficient time from mixing with the hydraulic material to spraying.
上記構造単位（ａ）の含有割合として好ましくは全構造単位１００質量％に対して４３〜９９．９質量％であることが好ましい。これにより本発明の作用効果をより充分に発揮することができる。より好ましくは４６〜９９．９質量％であり、更に好ましくは５０〜９９．９質量％である。
上記（メタ）アクリレート系共重合体エマルション粒子は、構造単位（ｃ）を有しないものであってもよく、その場合、構造単位（ａ）の含有割合として好ましくは８０〜９９．９質量％であり、より好ましくは８５〜９９．９質量％であり、更に好ましくは９０〜９９．９質量％であり、特に好ましくは９５〜９９．９質量％である。
上記（メタ）アクリレート系共重合体エマルション粒子が構造単位（ｃ）を有するものである場合、構造単位（ａ）の含有割合として好ましくは４３〜９９．９質量％であり、より好ましくは４６〜９０質量％であり、更に好ましくは５０〜８０量％である。The content ratio of the structural unit (a) is preferably 43 to 99.9% by mass with respect to 100% by mass of all structural units. Thereby, the action and effect of the present invention can be more fully exhibited. It is more preferably 46 to 99.9% by mass, and even more preferably 50 to 99.9% by mass.
The (meth) acrylate-based copolymer emulsion particles may not have the structural unit (c), and in that case, the content ratio of the structural unit (a) is preferably 80 to 99.9% by mass. It is more preferably 85 to 99.9% by mass, further preferably 90 to 99.9% by mass, and particularly preferably 95 to 99.9% by mass.
When the (meth) acrylate-based copolymer emulsion particles have the structural unit (c), the content ratio of the structural unit (a) is preferably 43 to 99.9% by mass, and more preferably 46 to 99.9% by mass. It is 90% by mass, more preferably 50 to 80% by mass.
上記（メタ）アクリレート系共重合体エマルション粒子は、炭素数が３〜２０であるアルキル基を有するアルキル（メタ）アクリレート（Ａ２）由来の構造単位（ａ２）を有することが好ましく、炭素数が１又は２であるアルキル基を有するアルキル（メタ）アクリレート（Ａ１）由来の構造単位（ａ１）を有していてもよく、該構造単位（ａ１）の割合は、構造単位（ａ２）１００質量％に対して０〜１４５質量％であることが好ましい。
また、上記（メタ）アクリレート系共重合体エマルション粒子は、炭素数が１又は２であるアルキル基を有するアルキル（メタ）アクリレート（Ａ１）由来の構造単位（ａ１）と炭素数が３〜２０であるアルキル基を有するアルキル（メタ）アクリレート（Ａ２）由来の構造単位（ａ２）とを有することが好ましい。これにより共重合体エマルション粒子のガラス転移温度をより好適な範囲とすることができる。更に、水硬性材料組成物の混錬時間が長くなることも充分に抑制することができる。上記（メタ）アクリレート系共重合体エマルション粒子が構造単位（ｃ）を有さず、構造単位（ａ１）と構造単位（ａ２）とを有する形態は、本発明の好適な実施形態の１つである。The (meth) acrylate-based copolymer emulsion particles preferably have a structural unit (a2) derived from an alkyl (meth) acrylate (A2) having an alkyl group having 3 to 20 carbon atoms, and have 1 carbon number. Alternatively, it may have a structural unit (a1) derived from an alkyl (meth) acrylate (A1) having an alkyl group of 2, and the ratio of the structural unit (a1) is 100% by mass of the structural unit (a2). On the other hand, it is preferably 0 to 145% by mass.
Further, the (meth) acrylate-based copolymer emulsion particles have a structural unit (a1) derived from an alkyl (meth) acrylate (A1) having an alkyl group having 1 or 2 carbon atoms and a carbon number of 3 to 20. It is preferable to have a structural unit (a2) derived from an alkyl (meth) acrylate (A2) having a certain alkyl group. This makes it possible to set the glass transition temperature of the copolymer emulsion particles in a more suitable range. Further, it is possible to sufficiently suppress that the kneading time of the hydraulic material composition becomes long. The form in which the (meth) acrylate-based copolymer emulsion particles do not have a structural unit (c) but have a structural unit (a1) and a structural unit (a2) is one of the preferred embodiments of the present invention. be.
上記（メタ）アクリレート系共重合体エマルション粒子が構造単位（ｃ）を有しないものである場合、構造単位（ａ１）の割合が、構造単位（ａ２）１００質量％に対して５〜１４５質量％であることが好ましい。より好ましくは２０〜１４５質量％であり、更に好ましくは３５〜１４５質量％である。 When the (meth) acrylate-based copolymer emulsion particles do not have the structural unit (c), the ratio of the structural unit (a1) is 5 to 145% by mass with respect to 100% by mass of the structural unit (a2). Is preferable. It is more preferably 20 to 145% by mass, and even more preferably 35 to 145% by mass.
上記構造単位（ｂ）の含有割合として好ましくは全構造単位１００質量％に対して０．１〜８質量％である。これにより本発明の作用効果をより充分に発揮することができる。より好ましくは０．１〜５質量％であり、更に好ましくは０．１〜３質量％である。 The content ratio of the structural unit (b) is preferably 0.1 to 8% by mass with respect to 100% by mass of all the structural units. Thereby, the action and effect of the present invention can be more fully exhibited. It is more preferably 0.1 to 5% by mass, and even more preferably 0.1 to 3% by mass.
上記共重合体エマルション粒子は、芳香族ビニル化合物（Ｃ）由来の構造単位（ｃ）を有していてもよく、構造単位（ｃ）の含有割合の割合は、全構造単位１００質量％に対して０〜５９．９質量％である。構造単位（ｃ）の含有割合として好ましくは、０〜５７質量％であり、より好ましくは０〜５４質量％であり、更に好ましくは０〜５０質量％である。
また、構造単位（ｃ）の含有割合が１〜５９．９質量％である場合、上記（メタ）アクリレート系共重合体エマルション粒子は、構造単位（ａ１）を有していなくてもよい。上記（メタ）アクリレート系共重合体エマルション粒子が、構造単位（ａ１）を有さず、構造単位（ａ２）と構造単位（ｃ）とを有する形態もまた、本発明の好適な実施形態の１つである。The above-mentioned copolymer emulsion particles may have a structural unit (c) derived from the aromatic vinyl compound (C), and the content ratio of the structural unit (c) is 100% by mass of the total structural unit. It is 0 to 59.9% by mass. The content ratio of the structural unit (c) is preferably 0 to 57% by mass, more preferably 0 to 54% by mass, and further preferably 0 to 50% by mass.
Further, when the content ratio of the structural unit (c) is 1 to 59.9% by mass, the (meth) acrylate-based copolymer emulsion particles do not have to have the structural unit (a1). The form in which the (meth) acrylate-based copolymer emulsion particles do not have the structural unit (a1) but have the structural unit (a2) and the structural unit (c) is also one of the preferred embodiments of the present invention. It is one.
上記共重合体エマルション粒子は、炭素数が１〜２０であるアルキル基を有するアルキル（メタ）アクリレート、（メタ）アクリル酸（塩）（Ｂ）及び芳香族ビニル化合物（Ｃ）以外のその他の単量体（Ｄ）由来の構造単位（ｄ）を有していてもよく、構造単位（ｄ）の含有割合の割合は、全構造単位１００質量％に対して０〜１０質量％である。
構造単位（ｄ）の含有割合として好ましくは、全構造単位１００質量％に対して０〜８質量％であり、より好ましくは０〜６質量％であり、更に好ましくは０〜５質量％であり、最も好ましくは０質量％である。The above-mentioned copolymer emulsion particles include alkyl (meth) acrylates having an alkyl group having 1 to 20 carbon atoms, (meth) acrylic acid (salt) (B), and other simple compounds other than the aromatic vinyl compound (C). It may have a structural unit (d) derived from the polymer (D), and the content ratio of the structural unit (d) is 0 to 10% by mass with respect to 100% by mass of the total structural unit.
The content ratio of the structural unit (d) is preferably 0 to 8% by mass, more preferably 0 to 6% by mass, and further preferably 0 to 5% by mass with respect to 100% by mass of the total structural unit. , Most preferably 0% by mass.
上記共重合体エマルション粒子は、ガラス転移温度が−５０〜５℃である。すなわち、共重合体エマルション粒子を構成する樹脂（ポリマー）のガラス転移温度が−５０〜５℃である。
これにより、モルタル・コンクリートにおけるペースト分の粘着性を向上させ、ペースト分の骨材への粘着性を向上させることができる。
ガラス転移温度として好ましくは−４０〜５℃である。これにより、水硬性材料組成物の混錬時間が長くなることをより充分に抑制することができる。ガラス転移温度としてより好ましくは−３０〜３℃であり、更に好ましくは−２０〜０℃である。
なお、共重合体エマルション粒子のガラス転移温度（Ｔｇ）は、後述する単量体成分の種類や使用割合によって制御することができ、次のＦＯＸの式（１）により求められる他、ＤＳＣ（示差走査熱量測定装置）やＤＴＡ（示差熱分析装置）によって求めることができる。The copolymer emulsion particles have a glass transition temperature of −50 to 5 ° C. That is, the glass transition temperature of the resin (polymer) constituting the copolymer emulsion particles is −50 to 5 ° C.
Thereby, the adhesiveness of the paste component in the mortar / concrete can be improved, and the adhesiveness of the paste component to the aggregate can be improved.
The glass transition temperature is preferably -40 to 5 ° C. As a result, it is possible to more sufficiently suppress the lengthening of the kneading time of the hydraulic material composition. The glass transition temperature is more preferably -30 to 3 ° C, still more preferably -20 to 0 ° C.
The glass transition temperature (Tg) of the copolymer emulsion particles can be controlled by the type and usage ratio of the monomer component described later, and can be obtained by the following FOX formula (1) or DSC (differential differential). It can be obtained by scanning calorimetry device) or DTA (differential thermal analysis device).
式中、Ｔｇ’は、共重合体エマルション粒子のＴｇ（絶対温度）である。Ｗ１’、Ｗ２’、・・・Ｗｎ’は、全単量体成分に対する各単量体の質量分率である。Ｔｇ１、Ｔｇ２、・・・Ｔｇｎは、各単量体成分からなるホモポリマー（単独重合体）のガラス転移温度（絶対温度）である。上記計算に用いるホモポリマーのガラス転移温度は、文献に記載されている値を用いることができ、例えば、「ＰＯＬＹＭＥＲ ＨＡＮＤＢＯＯＫ 第３版」（Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ, Ｉｎｃ．発行）などに記載されている。 In the formula, Tg'is the Tg (absolute temperature) of the copolymer emulsion particles. W1', W2', ... Wn'are the mass fractions of each monomer with respect to all the monomer components. Tg1, Tg2, ... Tgn is the glass transition temperature (absolute temperature) of the homopolymer (homopolymer) composed of each monomer component. As the glass transition temperature of the homopolymer used in the above calculation, the value described in the literature can be used, and for example, it is described in "POLYMER HANDBOOK 3rd Edition" (published by John Wiley & Sons, Inc.). ..
上記共重合体エマルション粒子は、平均粒子径が１３０ｎｍ以上である。これにより、減水剤を併用した際に、併用する減水剤の添加量が増加することを抑制することができる。共重合体エマルション粒子の平均粒子径が１３０ｎｍよりも小さいと、共重合体エマルション粒子の表面積が大きくなり、共重合体エマルション粒子と相互作用する減水剤の量が増加し、これにより、減水剤としての効果を発揮しないものの割合が増加すると考えられるが、共重合体エマルション粒子の平均粒子径が１３０ｎｍ以上であれば、共重合体エマルション粒子の表面積が大きくなることを抑制することができることに基づき、減水剤の添加量の増加を抑制することができる。共重合体エマルション粒子の平均粒子径として好ましくは、１５０〜４００ｎｍであり、より好ましくは１７０〜４００ｎｍであり、更に好ましくは２００〜４００ｎｍである。共重合体エマルション粒子の平均粒子径は、動的光散乱測定法により測定することができる。 The copolymer emulsion particles have an average particle size of 130 nm or more. As a result, when the water reducing agent is used in combination, it is possible to suppress an increase in the amount of the water reducing agent added in combination. When the average particle size of the copolymer emulsion particles is smaller than 130 nm, the surface area of the copolymer emulsion particles is increased, and the amount of the water reducing agent interacting with the copolymer emulsion particles is increased, whereby as a water reducing agent. However, if the average particle size of the copolymer emulsion particles is 130 nm or more, it is possible to suppress an increase in the surface area of the copolymer emulsion particles. It is possible to suppress an increase in the amount of the water reducing agent added. The average particle size of the copolymer emulsion particles is preferably 150 to 400 nm, more preferably 170 to 400 nm, and even more preferably 200 to 400 nm. The average particle size of the copolymer emulsion particles can be measured by a dynamic light scattering measurement method.
上記炭素数が１〜２０であるアルキル基を有するアルキル（メタ）アクリレートは、（メタ）アクリル酸の炭素数１〜２０のアルキルエステルである。上記アルキル（メタ）アクリレートは、（メタ）アクリル酸と炭素数が１〜２０であるアルキルアルコールとのエステルと同じ構造であれば、（メタ）アクリル酸と炭素数が１〜２０であるアルキルアルコールとがエステル反応して得られたものに限定されない。
上述のとおり、上記（メタ）アクリレート系共重合体エマルション粒子は、炭素数が１又は２であるアルキル基を有するアルキル（メタ）アクリレート（Ａ１）由来の構造単位（ａ１）と炭素数が３〜２０であるアルキル基を有するアルキル（メタ）アクリレート（Ａ２）由来の構造単位（ａ２）とを有することが好ましい。
上記アルキル（メタ）アクリレート（Ａ１）のアルキル基の炭素数として好ましくは１である。
上記アルキル（メタ）アクリレート（Ａ２）のアルキル基の炭素数として好ましくは３〜１８である。より好ましくは４〜１６であり、更に好ましくは４〜１４であり、特に好ましくは４〜１２である。The alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms is an alkyl ester having 1 to 20 carbon atoms of (meth) acrylic acid. If the alkyl (meth) acrylate has the same structure as the ester of (meth) acrylic acid and an alkyl alcohol having 1 to 20 carbon atoms, the alkyl (meth) acrylic acid and the alkyl alcohol having 1 to 20 carbon atoms have the same structure. Is not limited to the one obtained by the ester reaction with and.
As described above, the (meth) acrylate-based copolymer emulsion particles have a structural unit (a1) derived from an alkyl (meth) acrylate (A1) having an alkyl group having 1 or 2 carbon atoms and 3 to 3 carbon atoms. It is preferable to have a structural unit (a2) derived from an alkyl (meth) acrylate (A2) having an alkyl group of 20.
The number of carbon atoms of the alkyl group of the alkyl (meth) acrylate (A1) is preferably 1.
The alkyl group of the alkyl (meth) acrylate (A2) preferably has 3 to 18 carbon atoms. It is more preferably 4 to 16, still more preferably 4 to 14, and particularly preferably 4 to 12.
上記アルキル（メタ）アクリレートにおけるアルキル基として具体的には、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−ペンチル基（アミル基）、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ウンデシル基、ｎ−ドデシル基、ｎ−トリデシル基、ｎ−テトラデシル基、ｎ−ペンタデシル基、ｎ−ヘキサデシル基、ｎ−ヘプタデシル基、ｎ−オクタデシル基、ｎ−ノナデシル基、ｎ−エイコサニル基、ｉ−プロピル基、ｓｅｃ−ブチル基、ｉ−ブチル基、ｔ−ブチル基、１−メチルブチル基、１−エチルプロピル基、２−メチルブチル基、ｉ−アミル基、ネオペンチル基、１，２−ジメチルプロピル基、１，１−ジメチルプロピル基、ｔ−アミル基、１，３−ジメチルブチル基、３，３−ジメチルブチル基、２−エチルブチル基、２−エチル−２−メチルプロピル基、１−メチルヘプチル基、２−エチルヘキシル基、１，５−ジメチルヘキシル基、ｔ−オクチル基、分岐したノニル基、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、ステアリル基、イコシル基等の直鎖又は分岐鎖のアルキル基や、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等の環状アルキル基が挙げられる。 Specifically, as the alkyl group in the above alkyl (meth) acrylate, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group (amyl group), n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecil group, n-eicosanyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group , I-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group , 2-Ethyl-2-methylpropyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, decyl group, undecyl group, dodecyl group, tridecyl Examples include linear or branched alkyl groups such as groups, tetradecyl groups, pentadecyl groups, hexadecyl groups, heptadecyl groups, stearyl groups and icosyl groups, and cyclic alkyl groups such as cyclopropyl groups, cyclobutyl groups, cyclopentyl groups and cyclohexyl groups. Be done.
炭素数が１〜２０であるアルキル基を有するアルキル（メタ）アクリレートとして具体的には、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、テトラデシル（メタ）アクリレート、ペンタデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ヘプタデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、ノナデシル（メタ）アクリレート、イコシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等が挙げられる。
中でも好ましくは、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等であり、より好ましくはメチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、ブチルアクリレート、ペンチルアクリレート、ヘキシルアクリレート、ヘプチルアクリレート、オクチルアクリレート、イソオクチルアクリレート、２−エチルヘキシルアクリレート、ノニルアクリレート、イソノニルアクリレート、デシルアクリレート、イソデシルアクリレート、シクロヘキシル（メタ）アクリレートである。Specific examples of the alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth) acrylate. ) Acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) ) Acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate. , Octadecyl (meth) acrylate, nonadecil (meth) acrylate, icosyl (meth) acrylate, cyclohexyl (meth) acrylate and the like.
Of these, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, and octyl (meth) acrylate are preferable. Meta) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate Meta) acrylate, cyclohexyl (meth) acrylate and the like, more preferably methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate. , Isooctyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, isononyl acrylate, decyl acrylate, isodecyl acrylate, cyclohexyl (meth) acrylate.
上記共重合体エマルション粒子において、炭素数が１〜２０であるアルキル基を有するアルキル（メタ）アクリレートを１種用いても、２種以上用いてもよい。該アルキル（メタ）アクリレートを２種用いる形態は、本発明の好適な実施形態の１つである。 In the above-mentioned copolymer emulsion particles, one kind or two or more kinds of alkyl (meth) acrylates having an alkyl group having 1 to 20 carbon atoms may be used. The form using two kinds of the alkyl (meth) acrylate is one of the preferred embodiments of the present invention.
上記（メタ）アクリル酸（塩）とは、アクリル酸、アクリル酸塩、メタクリル酸、メタクリル酸塩を表し、これら（メタ）アクリル酸（塩）は、１種を用いてもよく、２種以上を用いてもよい。上記（メタ）アクリル酸（塩）における塩としては、金属塩、アンモニウム塩、有機アミン塩が挙げられる。これらの中でも、Ｌｉ、Ｎａ、Ｋ、Ｃａ等のアルカリ金属塩が好ましく、より好ましくは、ナトリウム塩またはカリウム塩である。 The above (meth) acrylic acid (salt) represents acrylic acid, acrylate, methacrylic acid, and methacrylic acid, and one type of these (meth) acrylic acid (salt) may be used, and two or more types may be used. May be used. Examples of the salt in the (meth) acrylic acid (salt) include metal salts, ammonium salts, and organic amine salts. Among these, alkali metal salts such as Li, Na, K and Ca are preferable, and sodium salt or potassium salt is more preferable.
上記芳香族ビニル化合物（Ｃ）は、エチレン性不飽和結合と芳香族基とを有するものであれば特に制限されないが、例えば、スチレン；α−メチルスチレン、ビニルトルエン、エチルスチレン、プロピルスチレン、イソプロピルスチレン、ブチルスチレン、ジメチルスチレン、ジエチルスチレン等のアルキル置換スチレン；メトキシスチレン、エトキシスチレン、プロポキシスチレン、ブトキシスチレン等のアルコキシ置換スチレン；ビニルビフェニル、ベンジルスチレン等の芳香族基置換スチレン；クロロスチレン、フルオロスチレン、ブロモスチレン、クロロ−メチルスチレン等のハロゲン置換スチレン；ビニル安息香酸、スチレンスルホン酸等の酸置換スチレン；等のスチレン系化合物の他、ビニルナフタレンや、ビニルアントラセン等が挙げられる。これらの中でも、スチレン系化合物が好適であり、より好ましくはスチレンである。 The aromatic vinyl compound (C) is not particularly limited as long as it has an ethylenically unsaturated bond and an aromatic group, and is, for example, styrene; α-methylstyrene, vinyltoluene, ethylstyrene, propylstyrene, isopropyl. Alkyl-substituted styrenes such as styrene, butylstyrene, dimethylstyrene, diethylstyrene; alkoxy-substituted styrenes such as methoxystyrene, ethoxystyrene, propoxystyrene, butoxystyrene; aromatic group-substituted styrenes such as vinylbiphenyl and benzylstyrene; chlorostyrene, fluoro Halogen-substituted styrenes such as styrene, bromostyrene and chloro-methylstyrene; acid-substituted styrenes such as vinyl benzoic acid and styrene sulfonic acid; and other styrene-based compounds, as well as vinylnaphthalene and vinylanthracene can be mentioned. Among these, styrene-based compounds are preferable, and styrene is more preferable.
上記共重合体エマルション粒子は、炭素数が１〜２０であるアルキル基を有するアルキル（メタ）アクリレート（Ａ）（メタ）アクリル酸（塩）（Ｂ）及び芳香族ビニル化合物（Ｃ）以外のその他の単量体（Ｄ）由来の構造単位（ｄ）を有していてもよく、その他の単量体（Ｄ）としては、上記アルキル（メタ）アクリレート及び（メタ）アクリル酸（塩）と共重合できる限り特に制限されない。
その他の単量体として具体的には、酢酸ビニル等のビニルエステル；メチルビニルエーテル等のビニルエーテル；クロトン酸、チグリン酸、３−メチルクロトン酸、２−メチル−２−ペンテン酸等の（メタ）アクリル酸（塩）以外のエチレン性不飽和モノカルボン酸類；マレイン酸、フマル酸、イタコン酸、メサコン酸、シトラコン酸、フマル酸等の不飽和多価カルボン酸類；マレイン酸モノエチル、イタコン酸モノエチル等のエチレン性不飽和多価カルボン酸の部分エステル化物等のカルボキシル基を有する単量体；ビニルスルホン酸、スチレンスルホン酸、スルホ（メタ）アクリレート等のスルホン酸基を有する単量体；２−（メタ）アクリロイルオキシエチルアシッドホスフェート、２−（メタ）アクリロイルオキシプロピルアシッドホスフェート、２−（メタ）アクリロイルオキシ−３−クロロプロピルアシッドホスフェート、２−（メタ）アクリロイルオキシエチルフェニルリン酸等の酸性リン酸エステル系単量体；The above-mentioned copolymer emulsion particles are other than alkyl (meth) acrylate (A) (meth) acrylic acid (salt) (B) and aromatic vinyl compound (C) having an alkyl group having 1 to 20 carbon atoms. May have a structural unit (d) derived from the monomer (D) of the above, and the other monomer (D) is the same as the above-mentioned alkyl (meth) acrylate and (meth) acrylic acid (salt). It is not particularly limited as long as it can be polymerized.
Specific examples of other monomers include vinyl esters such as vinyl acetate; vinyl ethers such as methyl vinyl ether; (meth) acrylics such as crotonic acid, tigric acid, 3-methylcrotonic acid, and 2-methyl-2-pentenoic acid. Ethylene unsaturated monocarboxylic acids other than acids (salts); unsaturated polyvalent carboxylic acids such as maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid; ethylene such as monoethyl maleate and monoethyl itacone. Monomer having a carboxyl group such as a partially esterified product of a sex unsaturated polyvalent carboxylic acid; Monomer having a sulfonic acid group such as vinyl sulfonic acid, styrene sulfonic acid, sulfo (meth) acrylate; 2- (meth) Acidic phosphate esters such as acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3-chloropropyl acid phosphate, 2- (meth) acryloyloxyethylphenyl phosphate Monomer;
アリルアルコール、メタリルアルコール、イソプロピルアルコール、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸とポリプロピレングリコールもしくはポリエチレングリコールとのモノエステル、α−（ヒドロキシルメチル）アクリル酸メチル等のヒドロキシル基を有する単量体；グリシジル（メタ）アクリレート等のエポキシ基を有する単量体；（メタ）アクリロニトリル等のニトリル基を有する単量体；Ｎ−モノメチル（メタ）アクリルアミド、Ｎ−モノエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、ジアセトンアクリルアミド、Ｎ−メチロールアクリルアミド等のアミド基を有する単量体；（メタ）アクリル酸ジメチルアミノエチル、アミノスチレン等のアミノ基を有する単量体；イソプロペニルオキサゾリン、ビニルピロリドン等のその他の官能基を有する単量体； Allyl alcohol, metalyl alcohol, isopropyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, monoester of (meth) acrylic acid with polypropylene glycol or polyethylene glycol, α- (hydroxyl) Monomer having a hydroxyl group such as methyl acrylate; Monomer having an epoxy group such as glycidyl (meth) acrylate; Monomer having a nitrile group such as (meth) acrylonitrile; N-monomethyl (meth) Monomers having an amide group such as acrylamide, N-monoethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, diacetone acrylamide, N-methylol acrylamide; dimethylaminoethyl (meth) acrylate, aminostyrene, etc. Monomer having an amino group; Monomer having other functional groups such as isopropenyloxazoline and vinylpyrrolidone;
（メタ）アクリル酸とエチレングリコール、プロピレングリコール、１，３−ブチレングリコール、ジエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール等の多価アルコールとのエステル；ジビニルベンゼン等の多官能ビニル化合物；（メタ）アクリル酸アリル等の（メタ）アクリル酸とアリルエステル；塩化ビニル、塩化ビニリデン、クロロスチレン、フッ化ビニル、フッ化ビニリデン、（メタ）アクリル酸パーフルオロオクチルエチル等のハロゲン成分を有する単量体が挙げられる。 Esters of (meth) acrylic acid with polyhydric alcohols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, trimerylpropane, pentaerythritol, dipentaerythritol; Polyfunctional vinyl compounds; (meth) acrylic acids such as allyl (meth) acrylate and allyl esters; vinyl chloride, vinylidene chloride, chlorostyrene, vinyl fluoride, vinylidene fluoride, perfluorooctylethyl (meth) acrylate, etc. Examples thereof include monomers having a halogen component.
＜共重合体エマルション＞
本発明はまた、上記共重合体エマルション粒子と溶媒とを含む樹脂分散体（以下、共重合体エマルションともいう）である。
上記溶媒としては、後述する共重合体エマルションの製造方法に記載の溶媒が挙げられる。<Copolymer emulsion>
The present invention is also a resin dispersion containing the above-mentioned copolymer emulsion particles and a solvent (hereinafter, also referred to as a copolymer emulsion).
Examples of the solvent include the solvents described in the method for producing a copolymer emulsion described later.
＜共重合体エマルションの製造方法＞
本発明の共重合体エマルションの製造は、特に制限されないが、単量体成分を乳化重合することにより製造することができる。乳化重合を行う形態としては特に限定されず、例えば、水性媒体中に単量体成分、重合開始剤及び乳化剤を適宜加えて重合することにより行うことができる。また、分子量調節のために重合連鎖移動剤等を用いてもよい。
本発明はまた、共重合体エマルション粒子を含む水硬性材料用添加剤を製造する方法であって、上記製造方法は、全単量体成分１００質量％に対して４０〜９９．９質量％の炭素数が１〜２０であるアルキル基を有するアルキル（メタ）アクリレート（Ａ）と、０．１〜１０質量％の（メタ）アクリル酸（塩）（Ｂ）と０〜５９．９質量％の芳香族ビニル化合物（Ｃ）とを含み、上記アルキル（メタ）アクリレート（Ａ）、（メタ）アクリル酸（塩）（Ｂ）及び芳香族ビニル化合物（Ｃ）以外のその他の単量体（Ｄ）の含有割合が０〜１０質量％である単量体成分を重合して、ガラス転移温度が−５０〜５℃であり、平均粒子径が１３０ｎｍ以上である共重合体エマルション粒子を形成する工程を含む水硬性材料用添加剤の製造方法でもある。また、上記共重合体エマルション粒子を形成する工程を行うことにより得られる水硬性材料用添加剤もまた、本発明の１つである。
上記単量体成分は、全単量体１００質量％に対して、炭素数が１〜２０であるアルキル基を有するアルキル（メタ）アクリレート（Ａ）を４０〜９９．９質量％含み、（メタ）アクリル酸（塩）（Ｂ）を０．１〜１０質量％含む。（メタ）アクリル酸（塩）（Ｂ）を上記割合で含むことにより、重合性が向上し、得られる共重合体エマルションの安定性が向上する。
単量体成分の具体例及び好ましい例、並びに、各単量体の好ましい割合は、上述のとおりである。<Method for producing copolymer emulsion>
The production of the copolymer emulsion of the present invention is not particularly limited, but can be produced by emulsion polymerization of the monomer component. The form of emulsion polymerization is not particularly limited, and for example, it can be carried out by appropriately adding a monomer component, a polymerization initiator and an emulsifier to an aqueous medium for polymerization. Further, a polymerization chain transfer agent or the like may be used for adjusting the molecular weight.
The present invention is also a method for producing an additive for a water-hard material containing copolymer emulsion particles, wherein the production method is 40 to 99.9% by mass based on 100% by mass of all monomer components. Alkyl (meth) acrylate (A) having an alkyl group having 1 to 20 carbon atoms, 0.1 to 10% by mass of (meth) acrylic acid (salt) (B), and 0 to 59.9% by mass. A monomer (D) containing an aromatic vinyl compound (C) other than the above alkyl (meth) acrylate (A), (meth) acrylic acid (salt) (B) and the aromatic vinyl compound (C). A step of polymerizing a monomer component having a content of 0 to 10% by mass to form copolymer emulsion particles having a glass transition temperature of −50 to 5 ° C. and an average particle size of 130 nm or more. It is also a method for producing an additive for a water-hard material containing the mixture. Further, an additive for a hydraulic material obtained by performing the step of forming the above-mentioned copolymer emulsion particles is also one of the present inventions.
The monomer component contains 40 to 99.9% by mass of an alkyl (meth) acrylate (A) having an alkyl group having 1 to 20 carbon atoms with respect to 100% by mass of all the monomers. ) Acrylic acid (salt) (B) is contained in an amount of 0.1 to 10% by mass. By containing (meth) acrylic acid (salt) (B) in the above ratio, the polymerizable property is improved and the stability of the obtained copolymer emulsion is improved.
Specific examples and preferable examples of the monomer components, and preferable ratios of each monomer are as described above.
上記水系溶媒としては特に限定されず、例えば、水、水と混じり合うことができる溶媒の１種又は２種以上の混合溶媒、このような溶媒に水が主成分となるように混合した混合溶媒等が挙げられる。これらの中でも、水が好ましい。 The aqueous solvent is not particularly limited, and is, for example, water, a mixed solvent of one or more kinds of solvents that can be mixed with water, and a mixed solvent in which water is the main component of such a solvent. And so on. Of these, water is preferable.
上記乳化剤としては、アニオン性（系）、カチオン性（系）、ノニオン性（系）、両性の各種界面活性剤、及び、高分子界面活性剤の１種又は２種以上を用いることができる。
上記アニオン系界面活性剤としては特に限定されず、例えば、ポリオキシアルキレンアルキルエーテル硫酸エステル塩、ポリオキシアルキレンオレイルエーテル硫酸ナトリウム塩、ポリオキシアルキレンアルキルフェニルエーテル硫酸エステル塩、アルキルジフェニルエーテルジスルホン酸塩、ポリオキシアルキレン（モノ、ジ、トリ）スチリルフェニルエーテル硫酸エステル塩、ポリオキシアルキレン（モノ、ジ、トリ）ベンジルフェニルエーテル硫酸エステル塩、アルケニルコハク酸ジ塩；ナトリウムドデシルサルフェート、カリウムドデシルサルフェート、アンモニウムアルキルサルフェート等のアルキルサルフェート塩；ナトリウムドデシルポリグリコールエーテルサルフェート；ナトリウムスルホリシノエート；スルホン化パラフィン塩等のアルキルスルホネート；ナトリウムドデシルベンゼンスルホネート、アルカリフェノールヒドロキシエチレンのアルカリ金属サルフェート等のアルキルスルホネート；高アルキルナフタレンスルホン酸塩；ナフタレンスルホン酸ホルマリン縮合物；ナトリウムラウレート、トリエタノールアミンオレエート、トリエタノールアミンアビエテート等の脂肪酸塩；ポリオキシアルキルエーテル硫酸エステル塩；ポリオキシエチレンカルボン酸エステル硫酸エステル塩；ポリオキシエチレンフェニルエーテル硫酸エステル塩；コハク酸ジアルキルエステルスルホン酸塩；ポリオキシエチレンアルキルアリールサルフェート塩等が挙げられる。これらの１種又は２種以上を用いることができる。As the emulsifier, one or more of anionic (system), cationic (system), nonionic (system), amphoteric surfactants, and polymer surfactants can be used.
The anionic surfactant is not particularly limited, and for example, polyoxyalkylene alkyl ether sulfate ester salt, polyoxyalkylene oleyl ether sulfate sodium salt, polyoxyalkylene alkylphenyl ether sulfate ester salt, alkyldiphenyl ether disulfonate, poly. Oxyalkylene (mono, di, tri) styrylphenyl ether sulfate, polyoxyalkylene (mono, di, tri) benzylphenyl ether sulfate, alkenyl succinate disalt; sodium dodecyl sulfate, potassium dodecyl sulfate, ammonium alkyl sulfate Alkyl sulfate salts such as; sodium dodecyl polyglycol ether sulfate; sodium sulforicinoate; alkyl sulfonates such as sulfonated paraffin salts; alkyl sulfonates such as sodium dodecylbenzene sulfonates, alkali metal sulfates of alkaliphenol hydroxyethylene; Acid salt; Naphthalene sulfonate formalin condensate; Fatty acid salts such as sodium laurate, triethanolamine oleate, triethanolamine aviateate; polyoxyalkyl ether sulfate ester salt; polyoxyethylene carboxylic acid ester sulfate ester salt; polyoxy Examples thereof include ethylene phenyl ether sulfate ester salt; succinic acid dialkyl ester sulfonate; polyoxyethylene alkyl aryl sulfate salt and the like. One or more of these can be used.
上記アニオン系界面活性剤として好適な市販品としては、例えば、ラテムルＷＸ、ラテムル１１８Ｂ、ペレックスＳＳ−Ｈ、エマルゲンＡ−６０、Ｂ−６６、レベノールＷＺ（花王社製）、ニューコール７０７ＳＦ、ニューコール７０７ＳＮ、ニューコール７１４ＳＦ、ニューコール７１４ＳＮ、ＡＢ−２６Ｓ、ＡＢＥＸ−２０１０、２０２０、２０３０、ＤＳＢ（ローディア日華社製）、ハイテノール１８Ｅ（第一工業製薬社製）等を挙げることができる。
また、これらのノニオンタイプに相当する界面活性剤も使用することができる。Examples of commercially available products suitable as the anionic surfactant include Latemul WX, Latemul 118B, Perex SS-H, Emargen A-60, B-66, Levenol WZ (manufactured by Kao Corporation), Newcol 707SF, and Newcol. 707SN, New Call 714SF, New Call 714SN, AB-26S, ABEX-2010, 2020, 2030, DSB (manufactured by Rhodia Nikka Co., Ltd.), High Tenor 18E (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like can be mentioned.
In addition, surfactants corresponding to these nonionic types can also be used.
上記アニオン系界面活性剤としては、また反応性界面活性剤として、反応性アニオン系界面活性剤、スルホコハク酸塩型反応性アニオン系界面活性剤、アルケニルコハク酸塩型反応性アニオン系界面活性剤等の１種又は２種以上を用いることができる。
スルホコハク酸塩型反応性アニオン系界面活性剤の市販品としては、ラテムルＳ−１２０、Ｓ−１２０Ａ、Ｓ−１８０及びＳ−１８０Ａ（いずれも商品名、花王社製）、エレミノールＪＳ−２（商品名、三洋化成工業社製）、アデカリアソープＳＲ−１０、ＳＲ−２０、ＳＲ−３０（ＡＤＥＫＡ社製）等が挙げられる。
アルケニルコハク酸塩型反応性アニオン系界面活性剤の市販品としては、ラテムルＡＳＫ（商品名、花王社製）等が挙げられる。
更に、（メタ）アクリル酸ポリオキシエチレンスルフォネート塩（例えば、三洋化成工業社製「エレミノールＲＳ−３０」、日本乳化剤社製「アントックスＭＳ−６０」等）、アリルオキシメチルアルキルオキシポリオキシエチレンのスルフォネー卜塩（例えば、第一工業製薬社製「アクアロンＫＨ−１０」等）等のアリル基を有する硫酸エステル（塩）、ポリオキシアルキレンアルケニルエーテル硫酸アンモニウム（例えば、花王社製「ラテムルＰＤ−１０４」等）等も用いることができる。As the above-mentioned anionic surfactant and as a reactive surfactant, a reactive anionic surfactant, a sulfosuccinate-type reactive anionic surfactant, an alkenyl succinate-type reactive anionic surfactant, etc. One or more of the above can be used.
Commercially available products of sulfosuccinate-type reactive anionic surfactants include Latemul S-120, S-120A, S-180 and S-180A (trade names, all manufactured by Kao) and Eleminor JS-2 (commodity). Name, Sanyo Kasei Kogyo Co., Ltd.), Adecaria Soap SR-10, SR-20, SR-30 (manufactured by ADEKA) and the like.
Examples of commercially available products of alkenyl succinate-type reactive anionic surfactants include Latemul ASK (trade name, manufactured by Kao Corporation).
Further, (meth) acrylate polyoxyethylene sulfonate salt (for example, "Eleminol RS-30" manufactured by Sanyo Chemical Industries, Ltd., "Antox MS-60" manufactured by Nippon Emulsion Co., Ltd., etc.), allyloxymethylalkyloxypolyoxy, etc. Sulfate ester (salt) having an allyl group such as a sulfone salt of ethylene (for example, "Aqualon KH-10" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyalkylene alkenyl ether ammonium sulfate (for example, "Latemul PD-" manufactured by Kao Co., Ltd.) 104 "etc.) and the like can also be used.
また、上記アニオン系界面活性剤としては、更に反応性界面活性剤として、下記の界面活性剤等も用いることができる。
炭素数３〜５の脂肪族不飽和カルボン酸のスルホアルキル（炭素数１〜４）エステル塩型界面活性剤、例えば、２−スルホエチル（メタ）アクリレートナトリウム塩、３−スルホプロピル（メタ）アクリレートアンモニウム塩等の（メタ）アクリル酸スルホアルキルエステル塩型界面活性剤；スルホプロピルマレイン酸アルキルエステルナトリウム塩、スルホプロピルマレイン酸ポリオキシエチレンアルキルエステルアンモニウム塩、スルホエチルフマル酸ポリオキシエチレンアルキルエステルアンモニウム塩等の脂肪族不飽和ジカルボン酸アルキルスルホアルキルジエステル塩型界面活性剤。Further, as the anionic surfactant, the following surfactants and the like can also be used as the reactive surfactant.
Sulfoalkyl (1 to 4 carbon atoms) ester salt type surfactant of aliphatic unsaturated carboxylic acid having 3 to 5 carbon atoms, for example, 2-sulfoethyl (meth) acrylate sodium salt, 3-sulfopropyl (meth) acrylate ammonium (Meta) acrylate sulfoalkyl ester salt type surfactants such as salts; sulfopropyl maleic acid alkyl ester sodium salt, sulfopropyl maleic acid polyoxyethylene alkyl ester ammonium salt, sulfoethyl fumarate polyoxyethylene alkyl ester ammonium salt, etc. Alibo unsaturated dicarboxylic acid alkyl sulfoalkyl diester salt type surfactant.
上記ノニオン系界面活性剤としては特に限定されず、例えば、ポリオキシエチレンアルキルエーテル；ポリオキシエチレンアルキルアリールエーテル；ソルビタン脂肪族エステル；ポリオキシエチレンソルビタン脂肪族エステル；グリセロールのモノラウレート等の脂肪族モノグリセライド；ポリオキシエチレンオキシプロピレン共重合体；エチレンオキサイドと脂肪族アミン、アミド又は酸との縮合生成物等が挙げられる。また、アリルオキシメチルアルコキシエチルヒドロキシポリオキシエチレン（例えば、ＡＤＥＫＡ社製「アデカリアソープＥＲ−２０」等）、ポリオキシアルキレンアルケニルエーテル（例えば、花王社製「ラテムルＰＤ−４２０」、「ラテムルＰＤ−４３０」等）等の反応性を有するノニオン系界面活性剤も用いることができる。これらの１種又は２種以上を用いることができる。 The nonionic surfactant is not particularly limited, and for example, polyoxyethylene alkyl ether; polyoxyethylene alkylaryl ether; sorbitan aliphatic ester; polyoxyethylene sorbitan aliphatic ester; aliphatic such as glycerol monolaurate. Examples thereof include monoglyceride; polyoxyethylene oxypropylene copolymer; and a condensation product of ethylene oxide and an aliphatic amine, amide or acid. In addition, allyloxymethylalkoxyethyl hydroxypolyoxyethylene (for example, "ADEKA Corporation" Adecaria Soap ER-20 ", etc.), polyoxyalkylene alkenyl ether (for example, Kao Co., Ltd." Latemul PD-420 "," Latemul PD- " Nonionic surfactants having reactivity such as 430 ”etc.) can also be used. One or more of these can be used.
上記カチオン系界面活性剤としては特に限定されず、例えば、ジアルキルジメチルアンモニウム塩、エステル型ジアルキルアンモニウム塩、アミド型ジアルキルアンモニウム塩、ジアルキルイミダゾリニウム塩等が挙げられ、これらの１種又は２種以上を用いることができる。 The cationic surfactant is not particularly limited, and examples thereof include a dialkyldimethylammonium salt, an ester-type dialkylammonium salt, an amide-type dialkylammonium salt, a dialkylimidazolinium salt, and the like, and one or more of these. Can be used.
上記両性界面活性剤としては特に限定されず、例えば、アルキルジメチルアミノ酢酸ベタイン、アルキルジメチルアミンオキサイド、アルキルカルボキシメチルヒドロキシエチルイミダゾリニウムベタイン、アルキルアミドプロピルベタイン、アルキルヒドロキシスルホベタイン等が挙げられ、これらの１種又は２種以上を用いることができる。 The amphoteric tenside is not particularly limited, and examples thereof include alkyldimethylaminoacetate betaine, alkyldimethylamine oxide, alkylcarboxymethylhydroxyethyl imidazolinium betaine, alkylamide propyl betaine, and alkylhydroxysulfobetaine. One or more of the above can be used.
上記高分子界面活性剤としては特に限定されず、例えば、ポリビニルアルコール及びその変性物；（メタ）アクリル系水溶性高分子；ヒドロキシエチル（メタ）アクリル系水溶性高分子；ヒドロキシプロピル（メタ）アクリル系水溶性高分子；ポリビニルピロリドン等が挙げられ、これらの１種又は２種以上を用いることができる。
上記界面活性剤の中でも、環境面からは、非ノニルフェニル型の界面活性剤を用いることが好適である。The polymer surfactant is not particularly limited, and for example, polyvinyl alcohol and its modified product; (meth) acrylic water-soluble polymer; hydroxyethyl (meth) acrylic water-soluble polymer; hydroxypropyl (meth) acrylic. Water-soluble polymers; polyvinylpyrrolidone and the like can be mentioned, and one or more of these can be used.
Among the above-mentioned surfactants, it is preferable to use a non-nonylphenyl type surfactant from the viewpoint of the environment.
上記重合開始剤としては、熱によって分解し、ラジカル分子を発生させる物質であれば特に限定されないが、例えば、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム等の過硫酸塩類；２，２’−アゾビス（２−アミジノプロパン）二塩酸塩、４，４’−アゾビス（４−シアノペンタン酸）、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、２，２’−アゾビス（２，４−ジメチルバレロニトリル）等のアゾ化合物；ｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート、ベンゾイルパーオキサイド、ジ−ｔｅｒｔ−ブチルパーオキサイド等の有機過酸化物；過酸化水素とアスコルビン酸、ｔ−ブチルヒドロパーオキサイドとロンガリット、過硫酸カリウムと金属塩、過硫酸アンモニウムと二亜硫酸ナトリウム等のレドックス系重合開始剤等が挙げられ、これらの１種又は２種以上を用いることができる。
上記重合開始剤の使用量としては特に限定されず、重合開始剤の種類等に応じて適宜設定すればよいが、例えば、重合体を形成するのに用いられる単量体成分の総量１００重量部に対して、０．１〜２重量部であることが好ましく、より好ましくは０．２〜１重量部である。The polymerization initiator is not particularly limited as long as it is a substance that decomposes by heat to generate radical molecules, but for example, persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; 2,2'-azobis (2-Amidinopropane) dihydrochloride, 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile , Azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile); organic peroxides such as tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, di-tert-butyl peroxide, etc. Substances; Redox-based polymerization initiators such as hydrogen peroxide and ascorbic acid, t-butylhydroperoxide and longalit, potassium persulfate and metal salt, ammonium persulfate and sodium disulfate, etc., and one or two of these. The above can be used.
The amount of the polymerization initiator used is not particularly limited and may be appropriately set according to the type of the polymerization initiator and the like. For example, the total amount of the monomer components used for forming the polymer is 100 parts by weight. On the other hand, it is preferably 0.1 to 2 parts by weight, more preferably 0.2 to 1 part by weight.
上記重合開始剤には、重合を促進させるため、必要に応じて還元剤を併用することができる。還元剤としては、例えば、アスコルビン酸、酒石酸、クエン酸、ブドウ糖等の還元性有機化合物；例えば、チオ硫酸ナトリウム、亜硫酸ナトリウム、重亜硫酸ナトリウム、メタ重亜硫酸ナトリウム、亜リン酸（塩)、次亜リン酸（塩）等の還元性無機化合物等が挙げられ、これらの１種又は２種以上を用いることができる。
上記還元剤の使用量としては特に限定されず、例えば、重合体を形成するのに用いられる単量体成分の総量１００重量部に対して、０．００１〜１重量部であることが好ましい。A reducing agent can be used in combination with the above-mentioned polymerization initiator in order to promote polymerization. Reducing agents include, for example, reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose; for example, sodium thiosulfate, sodium sulfite, sodium sulfite, sodium metabisulfite, phosphorous acid (salt), hypophosphite. Examples thereof include reducing inorganic compounds such as phosphorous acid (salt), and one or more of these can be used.
The amount of the reducing agent used is not particularly limited, and is preferably 0.001 to 1 part by weight with respect to 100 parts by weight of the total amount of the monomer components used for forming the polymer.
上記重合連鎖移動剤としては特に限定されず、例えば、３−メルカプトプロピオン酸、２−メルカプトプロピオン酸、ヘキシルメルカプタン、オクチルメルカプタン、ｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタン、ｎ−ヘキサデシルメルカプタン、ｎ−テトラデシルメルカプタン等のアルキルメルカプタン類；四塩化炭素、四臭化炭素、臭化エチレン等のハロゲン化炭化水素；メルカプト酢酸２−エチルヘキシルエステル、メルカプトプロピオン酸２−エチルヘキシルエステル、メルカプトピロピオン酸トリデシルエステル等のメルカプトカルボン酸アルキルエステル；メルカプト酢酸メトキシブチルエステル、メルカプトプロピオン酸メトキシブチルエステル等のメルカプトカルボン酸アルコキシアルキルエステル；オクタン酸２−メルカプトエチルエステル等のカルボン酸メルカプトアルキルエステルや、α−メチルスチレンダイマー、ターピノーレン、α−テルピネン、γ−テルピネン、ジペンテン、アニソール、アリルアルコール等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。これらの中でも、ヘキシルメルカプタン、オクチルメルカプタン、ｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタン、ｎ−ヘキサデシルメルカプタン、ｎ−テトラデシルメルカプタン等のアルキルメルカプタン類を用いることが好ましい。重合連鎖移動剤の使用量としては、例えば、全単量体成分１００重量部に対して、好ましくは２０重量部以下、より好ましくは、１０重量部以下である。更に好ましくは、５．０重量部以下、特に好ましくは２．０重量部以下、最も好ましくは１．０重量部以下である。 The polymerization chain transfer agent is not particularly limited, and for example, 3-mercaptopropionic acid, 2-mercaptopropionic acid, hexyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n- Alkyl mercaptans such as tetradecyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, carbon tetrabromide, ethylene bromide; mercaptoacetic acid 2-ethylhexyl ester, mercaptopropionic acid 2-ethylhexyl ester, mercaptopyrropionic acid tridecyl ester Mercaptocarboxylic acid alkyl ester such as mercaptocarboxylic acid alkyl ester; mercaptocarboxylic acid alkoxyalkyl ester such as mercaptoacetic acid methoxybutyl ester, mercaptopropionic acid methoxybutyl ester; carboxylic acid mercaptoalkyl ester such as octanoic acid 2-mercaptoethyl ester, α-methylstyrene dimer , Tarpinolene, α-terpinene, γ-terpinene, dipentene, anisole, allyl alcohol and the like. These may be used alone or in combination of two or more. Among these, alkyl mercaptans such as hexyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, and n-tetradecyl mercaptan are preferably used. The amount of the polymerization chain transfer agent used is, for example, preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of all the monomer components. More preferably, it is 5.0 parts by weight or less, particularly preferably 2.0 parts by weight or less, and most preferably 1.0 part by weight or less.
上記重合は、必要に応じて、エチレンジアミン四酢酸ナトリウム等のキレート剤、ポリアクリル酸ナトリウム等の分散剤や、無機塩等の存在下で行ってもよい。また、単量体成分や重合開始剤等の添加方法としては、例えば、一括添加法、連続添加法、多段添加法等の方法を適用することができる。また、これらの添加方法を適宜組み合わせてもよい。 The above polymerization may be carried out in the presence of a chelating agent such as sodium ethylenediaminetetraacetate, a dispersant such as sodium polyacrylate, an inorganic salt or the like, if necessary. Further, as a method for adding the monomer component, the polymerization initiator and the like, for example, a batch addition method, a continuous addition method, a multi-stage addition method and the like can be applied. Moreover, you may combine these addition methods as appropriate.
上記製造方法における重合条件に関し、重合温度としては特に限定されず、例えば、０〜１００℃であることが好ましく、より好ましくは４０〜９５℃である。また、重合時間も特に限定されず、例えば、１〜１５時間とすることが好適で、より好ましくは２〜１０時間である。
単量体成分や重合開始剤等の添加方法としては特に限定されず、例えば、一括添加法、連続添加法、多段添加法等の方法を適用することができる。また、これらの添加方法を適宜組み合わせてもよい。Regarding the polymerization conditions in the above production method, the polymerization temperature is not particularly limited, and is, for example, preferably 0 to 100 ° C, more preferably 40 to 95 ° C. The polymerization time is also not particularly limited, and is preferably 1 to 15 hours, more preferably 2 to 10 hours, for example.
The method for adding the monomer component, the polymerization initiator and the like is not particularly limited, and for example, a method such as a batch addition method, a continuous addition method, or a multi-stage addition method can be applied. Moreover, you may combine these addition methods as appropriate.
本発明の共重合体エマルションの製造方法においては、乳化重合によりエマルションを製造した後、中和剤によりエマルションを中和することが好ましい。これにより、エマルションが安定化されることになる。
中和剤としては特に限定されず、例えば、トリエタノールアミン、ジメチルエタノールアミン、ジエチルエタノールアミン、モルホリン等の三級アミン；ジグリコールアミン、アンモニア水；水酸化ナトリウム等を用いることができる。これらは単独で用いてもよく、２種以上を併用してもよい。In the method for producing a copolymer emulsion of the present invention, it is preferable to produce an emulsion by emulsion polymerization and then neutralize the emulsion with a neutralizing agent. This will stabilize the emulsion.
The neutralizing agent is not particularly limited, and for example, tertiary amines such as triethanolamine, dimethylethanolamine, diethylethanolamine and morpholine; diglycolamine, aqueous ammonia; sodium hydroxide and the like can be used. These may be used alone or in combination of two or more.
＜水硬性材料用添加剤及び水硬性材料組成物＞
本発明の水硬性材料用添加剤は、上記共重合体エマルション粒子を含むものであり、共重合体エマルション粒子を２種以上含んでいてもよい。上記水硬性材料用添加剤における上記共重合体の含有量（２種以上の共重合体エマルション粒子を含む場合は、その総含有量）は、特に制限されないが、水硬性材料用添加剤中の固形分（すなわち不揮発分）１００質量％中、５〜９０質量％であることが好ましい。より好ましくは２０〜９０質量％、更に好ましくは３０〜７５質量％である。
なお、本明細書中、「水硬性材料用添加剤」とは、セメントペースト、モルタル、コンクリート等の水硬性材料組成物へ添加される添加剤のことをいい、上記共重合体エマルションのみからなる剤であってもよいし、また、上記共重合体エマルションだけでなく、必要に応じて更に後述するその他の添加剤等を含む剤であってもよい。なお、本明細書中、固形分含量は、以下のようにして測定することができる。
＜固形分測定方法＞
１．アルミ皿を精秤する。
２．１で精秤したアルミ皿に固形分測定物を精秤する。
３．窒素雰囲気下１３０℃に調温した乾燥機に２で精秤した固形分測定物を１．５時間入れる。
４．１時間後、乾燥機から取り出し、室温のデシケーター内で１５分間放冷する。
５．１５分後、デシケーターから取り出し、アルミ皿＋測定物を精秤する。
６．５で得られた質量から１で得られたアルミ皿の質量を差し引き、２で得られた固形分測定物の質量で除することで固形分を測定する。<Additives for hydraulic materials and hydraulic material compositions>
The additive for a water-hard material of the present invention contains the above-mentioned copolymer emulsion particles, and may contain two or more kinds of copolymer emulsion particles. The content of the copolymer in the additive for water-hard material (when two or more kinds of copolymer emulsion particles are contained, the total content thereof) is not particularly limited, but is included in the additive for water-hard material. The solid content (that is, non-volatile content) is preferably 5 to 90% by mass based on 100% by mass. It is more preferably 20 to 90% by mass, still more preferably 30 to 75% by mass.
In the present specification, the "additive for water-hard material" refers to an additive added to a water-hard material composition such as cement paste, mortar, and concrete, and is composed of only the above-mentioned copolymer emulsion. It may be an agent, or may be an agent containing not only the above-mentioned copolymer emulsion but also other additives and the like, which will be further described later, if necessary. In the present specification, the solid content can be measured as follows.
<Solid content measurement method>
1. 1. Weigh the aluminum dish.
The solid content measurement object is precisely weighed in the aluminum dish precisely weighed in 2.1.
3. 3. The solid content measurement material precisely weighed in 2 is placed in a dryer whose temperature has been adjusted to 130 ° C. in a nitrogen atmosphere for 1.5 hours.
After 4.1 hours, remove from the dryer and allow to cool in a desiccator at room temperature for 15 minutes.
5. After 15 minutes, remove from the desiccator and weigh the aluminum dish + the object to be measured.
The solid content is measured by subtracting the mass of the aluminum plate obtained in 1 from the mass obtained in 6.5 and dividing by the mass of the solid content measurement product obtained in 2.
本発明の水硬性材料用添加剤は、減水剤と併用することが好ましい。すなわち、本発明は、水硬性材料用添加剤と減水剤とを含む水硬性材料用添加剤組成物でもある。
上記水硬性材料用添加剤組成物において、減水剤の割合は、水硬性材料用添加剤１００質量％に対して３〜９９質量％であることが好ましい。より好ましくは５〜９５質量％であり、更に好ましくは１０〜９０質量％である。The additive for hydraulic materials of the present invention is preferably used in combination with a water reducing agent. That is, the present invention is also an additive composition for a hydraulic material containing an additive for a hydraulic material and a water reducing agent.
In the additive composition for hydraulic materials, the proportion of the water reducing agent is preferably 3 to 99% by mass with respect to 100% by mass of the additive for hydraulic materials. It is more preferably 5 to 95% by mass, and even more preferably 10 to 90% by mass.
本発明の水硬性材料用添加剤は、水硬性材料を含む水硬性材料組成物に用いられることが好ましい。すなわち、水硬性材料用添加剤と水硬性材料とを含む水硬性材料組成物もまた、本発明の１つである。上記水硬性材料組成物が更に骨材を含む形態もまた、本発明の好ましい実施形態の１つである。 The additive for a hydraulic material of the present invention is preferably used in a hydraulic material composition containing a hydraulic material. That is, a hydraulic material composition containing an additive for a hydraulic material and a hydraulic material is also one of the present inventions. The form in which the hydraulic material composition further contains an aggregate is also one of the preferred embodiments of the present invention.
上記水硬性材料組成物において、本発明の水硬性材料用添加剤の配合割合としては、例えば、本発明の必須成分である共重合体エマルション粒子（複数含む場合はその合計量）の割合が、固形分換算で、水硬性材料の全量１００質量％に対して、０．００５〜１０質量％となるように設定することが好ましい。より好ましくは０．０１〜５質量％であり、更に好ましくは０．０２〜３質量％である。 In the above water-hard material composition, as the compounding ratio of the additive for water-hard material of the present invention, for example, the ratio of the copolymer emulsion particles (the total amount when a plurality of them are contained), which is an essential component of the present invention, is used. In terms of solid content, it is preferable to set it to be 0.005 to 10% by mass with respect to 100% by mass of the total amount of the water-hard material. It is more preferably 0.01 to 5% by mass, and even more preferably 0.02 to 3% by mass.
上記水硬性材料としては、水硬性又は潜在水硬性を有するものであれば特に限定されず、例えば、普通ポルトランドセメント、早強ポルトランドセメント、中庸熱ポルトランドセメント、低熱ポルトランドセメント等のポルトランドセメントや、シリカセメント、フライアッシュセメント、高炉セメント、アルミナセメント、ビーライト高含有セメント、各種混合セメント；珪酸三カルシウム、珪酸二カルシウム、アルミン酸三カルシウム、鉄アルミン酸四カルシウム等のセメントの構成成分；潜在水硬性を有するフライアッシュ、シリカヒューム、スラグ、石灰微粉等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。これらの中でも、普通ポルトランドセメントが通常よく使用され、好適に適用することができる。 The water-hardening material is not particularly limited as long as it has water-hardness or latent water-hardness. For example, ordinary Portland cement, early-strength Portland cement, moderate-heat Portland cement, low-heat Portland cement, or other Portland cement, or silica. Cement, fly ash cement, blast furnace cement, alumina cement, belite high content cement, various mixed cements; components of cement such as tricalcium silicate, dicalcium silicate, tricalcium aluminate, tetracalcium iron aluminate; latent hydraulic hardness Examples thereof include fly ash, silica fume, slag, lime fine powder and the like having the above. These may be used alone or in combination of two or more. Among these, ordinary Portland cement is usually commonly used and can be preferably applied.
上記骨材としては、砂利、砕石、水砕スラグ、再生骨材等以外に、珪石質、粘土質、ジルコン質、ハイアルミナ質、炭化珪素質、黒鉛質、クロム質、クロマグ質、マグネシア質等の耐火骨材等が挙げられる。 In addition to gravel, crushed stone, granulated slag, recycled aggregate, etc., the above-mentioned aggregates include silica stone, clay, zirconite, high alumina, silicon carbide, graphite, chromium, chromog, magnesia, etc. Fireproof aggregate and the like.
本発明の水硬性材料用添加剤は、水硬性材料組成物において、本発明の水硬性材料用添加剤以外のその他の添加剤と併用してもよく、その他の添加剤としては、通常使用されるセメント分散剤や減水剤、水溶性高分子物質、遅延剤、急結剤、早強剤・促進剤、鉱油系消泡剤、油脂系消泡剤、脂肪酸系消泡剤、脂肪酸エステル系消泡剤、オキシアルキレン系消泡剤、アルコール系消泡剤、アミド系消泡剤、リン酸エステル系消泡剤、金属石鹸系消泡剤、シリコーン系消泡剤、ＡＥ剤、界面活性剤、防水剤、防錆剤、防腐剤、ひび割れ低減剤、膨張材、セメント湿潤剤、増粘剤、分離低減剤、凝集剤、乾燥収縮低減剤、強度増進剤、セルフレベリング剤、着色剤、防カビ剤、高炉スラグ、フライアッシュ、シンダーアッシュ、クリンカーアッシュ、ハスクアッシュ、シリカヒューム、シリカ粉末、コロイダルシリカ、繊維、石膏、等のセメント添加剤（材）が挙げられる。 The additive for a water-hard material of the present invention may be used in combination with other additives other than the additive for a water-hard material of the present invention in a water-hard material composition, and is usually used as another additive. Cement dispersant, water reducing agent, water-soluble polymer substance, retarder, quick-setting agent, fast-strengthening agent / accelerator, mineral oil-based defoamer, oil-based defoamer, fatty acid-based defoamer, fatty acid ester-based defoamer Foaming agent, oxyalkylene defoaming agent, alcohol defoaming agent, amide defoaming agent, phosphoric acid ester defoaming agent, metal soap defoaming agent, silicone defoaming agent, AE agent, surfactant, Waterproofing agent, rust preventive, antiseptic, crack reducing agent, swelling material, cement wetting agent, thickener, separation reducing agent, coagulant, drying shrinkage reducing agent, strength enhancer, self-leveling agent, coloring agent, antifungal Examples thereof include cement additives (materials) such as agents, blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, colloidal silica, fibers, and plaster.
セメント分散剤（減水剤）としては特に限定されず、例えば、（ｉ）ナフタレンスルホン酸ホルムアルデヒド縮合物等のポリアルキルアリールスルホン酸塩系分散剤；メラミンスルホン酸ホルムアルデヒド縮合物等のメラミンホルマリン樹脂、スルホン酸塩系分散剤；アミノアリールスルホン酸−フェノール−ホルムアルデヒド縮合物等の芳香族アミノスルホン酸塩系分散剤；リグニンスルホン酸塩、変成リグニンスルホン酸塩等のリグニンスルホン酸塩系分散剤；ポリスチレンスルホン酸塩系分散剤；等の分子中にスルホン酸基を有する各種スルホン酸系分散剤（減水剤）；（ｉｉ）特公昭５９−１８３３８号公報、特開平７−２２３８５２号公報に記載の如く、ポリアルキレングリコールモノ（メタ）アクリル酸エステル系単量体、（メタ）アクリル酸系単量体、およびこれらの単量体と共重合可能な単量体から得られる共重合体；特開平１０−２３６８５８号公報、特開２００１−２２０４１７号公報、特開２００２−１２１０５５号公報、特開２００２−１２１０５６号公報に記載の如く、不飽和（ポリ）アルキレングリコールエーテル系単量体、マレイン酸系単量体または（メタ）アクリル酸系単量体から得られる共重合体；等の分子中に（ポリ）オキシアルキレン基とカルボキシル基とを有する各種ポリカルボン酸系分散剤（減水剤）；（ｉｉｉ）特開２００６−５２３８１号公報に記載の如く、（アルコキシ）ポリアルキレングリコールモノ（メタ）アクリレート、リン酸モノエステル系単量体、およびリン酸ジエステル系単量体から得られる共重合体等の、分子中に（ポリ）オキシアルキレン基とリン酸エステル基とを有する共重合体；特表２００８−５１７０８０号公報に記載の如く、（ポリ）オキシアルキレン基と芳香環族基及び／又は複素環式芳香族基とを有する単量体、リン酸（塩）基及び／又はリン酸エステル基と芳香環族基及び／又は複素環式芳香族基とを有する単量体、およびアルデヒド化合物からなる重縮合生成物；特表２０１５−５０８３８４号公報に記載の如く、芳香族トリアジン構造単位、ポリアルキレングリコール構造単位、およびリン酸エステル構造単位を有する分散剤；等の各種リン酸系分散剤（減水剤）等が挙げられる。
本発明の水硬性材料用添加剤は、上記その他の添加剤の中でも、減水剤と併用されることが好ましい。これによりペースト分の骨材への粘着性がより向上する。
すなわち、上記水硬性材料組成物は、更に減水剤を含むものであることが好ましく、このような形態は本発明の好ましい実施形態の１つである。The cement dispersant (water reducing agent) is not particularly limited, and for example, (i) a polyalkylaryl sulfonate-based dispersant such as naphthalene sulfonic acid formaldehyde condensate; melamine formalin resin such as melamine sulfonic acid formaldehyde condensate, sulfone. Acidate-based dispersant; Aromatic aminosulfonate-based dispersant such as aminoarylsulfonic acid-phenol-formaldehyde condensate; Ligninsulfonate-based dispersant such as ligninsulfonate and modified ligninsulfonate; Polystyrene sulfone Various sulfonic acid-based dispersants (water reducing agents) having a sulfonic acid group in the molecule such as acid acid-based dispersants; Polyalkylene glycol mono (meth) acrylic acid ester-based monomer, (meth) acrylic acid-based monomer, and copolymer obtained from a monomer copolymerizable with these monomers; JP-A-10- As described in JP-A-236858, JP-A-2001-220417, JP-A-2002-121055, and JP-A-2002-121056, unsaturated (poly) alkylene glycol ether-based monomers and maleic acid-based single amounts. Copolymers obtained from the body or (meth) acrylic acid-based monomers; various polycarboxylic acid-based dispersants (water reducing agents) having (poly) oxyalkylene group and carboxyl group in molecules such as; (iii) As described in JP-A-2006-52381, A copolymer having a (poly) oxyalkylene group and a phosphoric acid ester group in the molecule; as described in JP-A-2008-517080, a (poly) oxyalkylene group and an aromatic ring group and / or a heterocyclic type. A weight consisting of a monomer having an aromatic group, a monomer having a phosphoric acid (salt) group and / or a phosphoric acid ester group and an aromatic ring group and / or a heterocyclic aromatic group, and an aldehyde compound. Condensation products; as described in JP-A-2015-508384, various phosphate-based dispersants (water reducing agents) such as dispersants having aromatic triazine structural units, polyalkylene glycol structural units, and phosphoric acid ester structural units; ) Etc. can be mentioned.
Among the above-mentioned other additives, the additive for hydraulic materials of the present invention is preferably used in combination with a water reducing agent. As a result, the adhesiveness of the paste to the aggregate is further improved.
That is, the hydraulic material composition preferably further contains a water reducing agent, and such a form is one of the preferred embodiments of the present invention.
上記急結剤としては公知の急結剤であれば良く特に限定されない。用いる急結剤は粉体急結剤、液体急結剤でも、スラリータイプの急結剤でも良い。液体急結剤としては例えば硫酸アルミニウム、フッ素、及びアルカリ金属、さらに、これらとアルカノールアミンを含有するものが挙げられ、これらの１種または２種以上を用いることができる。また本発明で使用する液体急結剤には、既知の水溶性の水和促進剤を使用することが可能である。水和促進剤としては、例えば、ギ酸又はその塩、酢酸又はその塩、及び乳酸又はその塩等の有機系の水和促進剤や、水ガラス、硝酸塩、亜硝酸塩、チオ硫酸塩、及びチオシアン酸塩等の無機系の水和促進剤を使用することが可能である。粉体急結剤としては例えば、カルシウムアルミネート類、硫酸塩類、アルカリ金属アルミン酸塩類、アルカリ金属炭酸塩類、及びオキシカルボン酸類を含有してなるもの等が挙げられ、これらの１種または２種以上を用いることができる。 The quick-setting agent is not particularly limited as long as it is a known quick-setting agent. The quick-setting agent used may be a powder quick-setting agent, a liquid quick-setting agent, or a slurry-type quick-setting agent. Examples of the liquid quick-setting admixture include aluminum sulfate, fluorine, and alkali metals, and those containing these and alkanolamines, and one or more of these can be used. Further, as the liquid quick-setting admixture used in the present invention, a known water-soluble hydration accelerator can be used. Examples of the hydration accelerator include organic hydration accelerators such as formic acid or a salt thereof, acetic acid or a salt thereof, and lactic acid or a salt thereof, water glass, nitrate, nitrite, thiosulfate, and thiocyanate. It is possible to use an inorganic hydration accelerator such as a salt. Examples of the powder quick-setting admixture include those containing calcium aluminates, sulfates, alkali metal aluminates, alkali metal carbonates, and oxycarboxylic acids, and one or two of these. The above can be used.
前記消泡剤としては、公知の消泡剤であれば良く特に限定されない。例えば、燈油、流動パラフィン等の鉱油系消泡剤；動植物油、ごま油、ひまし油、これらのアルキレンオキシド付加物等の油脂系消泡剤；オレイン酸、ステアリン酸、これらのアルキレンオキシド付加物等の脂肪酸系消泡剤；ジエチレングリコールモノラウレート、グリセリンモノリシノレート、アルケニルコハク酸誘導体、ソルビトールモノラウレート、ソルビトールトリオレエート、ポリオキシエチレンモノラウレート、ポリオキシエチレンソルビトールモノラウレート、天然ワックス等の脂肪酸エステル系消泡剤；オクチルアルコール、ヘキサデシルアルコール、アセチレンアルコール、グリコール類、ポリオキシアルキレングリコール等のアルコール系消泡剤；ポリオキシアルキレンアミド、アクリレートポリアミン等のアミド系消泡剤；リン酸トリブチル、ナトリウムオクチルホスフェート等のリン酸エステル系消泡剤；アルミニウムステアレート、カルシウムオレエート等の金属石鹸系消泡剤；シリコーン油、シリコーンペースト、シリコーンエマルジョン、有機変成ポリシロキサン、フルオロシリコーン油等のシリコーン系消泡剤；ポリオキシエチレンポリオキシプロピレン付加物等のオキシアルキレン系消泡剤；等が挙げられ、これらの１種または２種以上を用いることができる。上記例示の消泡剤の中でも特に、オキシアルキレン系消泡剤が最も好ましい。本発明のセメント混和剤用共重合体とオキシアルキレン系消泡剤とを組み合わせて用いると、消泡剤使用量が少なくて済み、さらに消泡剤と共重合体との相溶性にも優れるからである。オキシアルキレン系消泡剤としては、分子内にオキシアルキレン基を有しかつ水性液体中の気泡を減少させる作用を有する化合物であれば特に制限はないが、その中でも下記式（２）で表わされる特定のオキシアルキレン系消泡剤が好ましい。
Ｒ１｛−Ｔ−（Ｒ２Ｏ）ｔ−Ｒ３ ｝ｎ （２）
上記式（２）中、Ｒ１、Ｒ３は、同一又は異なって、水素原子、炭素数１〜２２のアルキル基、炭素数１〜２２のアルケニル基、炭素数１〜２２のアルキニル基、フェニル基またはアルキルフェニル基（アルキルフェニル基中のアルキル基の炭素数は１〜２２である）を表わす。Ｒ２Ｏは、炭素数２〜４のオキシアルキレン基の１種または２種以上の混合物を表わし、２種以上の場合はブロック状に付加していてもランダム状に付加していてもよい。ｔは、オキシアルキレン基の平均付加モル数であり、０〜３００の数を表わす。ｔが０のとき、Ｒ１、Ｒ３が同時に水素原子であることはなく、Ｔは−Ｏ−、−ＣＯ２−、−ＳＯ４−、−ＰＯ４−又は−ＮＨ−の基を表わす。ｎは、１又は２の整数を表わし、Ｒ１が水素原子のとき、ｎは１である。The defoaming agent is not particularly limited as long as it is a known defoaming agent. For example, mineral oil defoamers such as kerosene and liquid paraffin; oil and fat defoamers such as animal and vegetable oils, sesame oil, castor oil and these alkylene oxide adducts; fatty acids such as oleic acid, stearic acid and these alkylene oxide adducts. Defoamer; fatty acid esters such as diethylene glycol monolaurate, glycerin monolithinolate, alkenyl succinolate derivative, sorbitol monolaurate, sorbitol trioleate, polyoxyethylene monolaurate, polyoxyethylene sorbitol monolaurate, natural wax, etc. Defoamers; alcohol-based defoamers such as octyl alcohol, hexadecyl alcohol, acetylene alcohol, glycols, polyoxyalkylene glycol; amide defoamers such as polyoxyalkyleneamide and acrylate polyamine; tributyl phosphate, sodium Phosphate defoamers such as octyl phosphate; Metal soap defoamers such as aluminum stearate and calcium oleate; Silicone defoamers such as silicone oil, silicone paste, silicone emulsion, organically modified polysiloxane, fluorosilicone oil, etc. Foaming agents; oxyalkylene-based defoaming agents such as polyoxyethylene polyoxypropylene adducts; and the like, and one or more of these can be used. Among the above-exemplified defoaming agents, the oxyalkylene-based defoaming agent is most preferable. When the copolymer for cement admixture of the present invention is used in combination with an oxyalkylene defoaming agent, the amount of the defoaming agent used can be reduced, and the compatibility between the defoaming agent and the copolymer is also excellent. Is. The oxyalkylene defoaming agent is not particularly limited as long as it is a compound having an oxyalkylene group in the molecule and having an action of reducing bubbles in an aqueous liquid, but among them, it is represented by the following formula (2). Specific oxyalkylene defoamers are preferred.
R 1 {-T- (R 2 O) t-R 3 } n (2)
In the above formula (2), R 1 and R 3 are the same or different, and have a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 1 to 22 carbon atoms, an alkynyl group having 1 to 22 carbon atoms, and phenyl. Represents a group or an alkylphenyl group (the alkyl group in the alkylphenyl group has 1 to 22 carbon atoms). R 2 O represents one or more mixtures of oxyalkylene group having 2 to 4 carbon atoms, in the case of two or more may also be added in a block form are added to the random form. t is the average number of moles of oxyalkylene group added, and represents a number from 0 to 300. When t is zero, never R 1, R 3 are not hydrogen atoms at the same time, T is -O -, - CO 2 -, - SO 4 -, - represent or -NH- groups - PO 4. n represents an integer of 1 or 2, and when R 1 is a hydrogen atom, n is 1.
上記式（２）で表されるオキシアルキレン系消泡剤の例としては、（ポリ）オキシエチレン（ポリ）オキシプロピレン付加物等のポリオキシアルキレン類；ジエチレングリコールヘプチルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシプロピレンブチルエーテル、ポリオキシエチレンポリオキシプロピレン−２−エチルヘキシルエーテル、炭素数１２〜１４の高級アルコールへのオキシエチレンオキシプロピレン付加物等の（ポリ）オキシアルキレンアルキルエーテル類；ポリオキシプロピレンフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等の（ポリ）オキシアルキレン（アルキル）アリールエーテル類；２，４，７，９−テトラメチル−５−デシン−４，７−ジオール、２，５−ジメチル−３−ヘキシン−２，５−ジオール、３−メチル−１−ブチン−３−オール等のアセチレンアルコールにアルキレンオキシドを付加重合させたアセチレンエーテル類；ジエチレングリコールオレイン酸エステル、ジエチレングリコールラウリル酸エステル、エチレングリコールジステアリン酸エステル等の（ポリ）オキシアルキレン脂肪酸エステル類；ポリオキシエチレンソルビタンモノラウリン酸エステル、ポリオキシエチレンソルビタントリオレイン酸エステル等の（ポリ）オキシアルキレンソルビタン脂肪酸エステル類；ポリオキシプロピレンメチルエーテル硫酸ナトリウム、ポリオキシエチレンドデシルフェノールエーテル硫酸ナトリウム等の（ポリ）オキシアルキレンアルキル（アリール）エーテル硫酸エステル塩類；（ポリ）オキシエチレンステアリルリン酸エステル等の（ポリ）オキシアルキレンアルキルリン酸エステル類；ポリオキシエチレンラウリルアミン等の（ポリ）オキシアルキレンアルキルアミン類；等が挙げられ、これらの１種または２種以上を用いることができる。 Examples of the oxyalkylene-based defoaming agent represented by the above formula (2) include polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adduct; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, and poly. (Poly) oxyalkylene alkyl ethers such as oxypropylene butyl ether, polyoxyethylene polyoxypropylene-2-ethylhexyl ether, oxyethylene oxypropylene adduct to higher alcohols having 12 to 14 carbon atoms; polyoxypropylene phenyl ether, poly (Poly) oxyalkylene (alkyl) aryl ethers such as oxyethylene nonylphenyl ether; 2,4,7,9-tetramethyl-5-decine-4,7-diol, 2,5-dimethyl-3-hexin- Acetylene ethers obtained by addition-polymerizing an alkylene oxide to an acetylene alcohol such as 2,5-diol and 3-methyl-1-butin-3-ol; such as diethylene glycol oleic acid ester, diethylene glycol lauryl acid ester, and ethylene glycol distearate ester. (Poly) oxyalkylene fatty acid esters; (poly) oxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolauric acid ester and polyoxyethylene sorbitan trioleic acid ester; polyoxypropylene methyl ether sodium sulfate, polyoxyethylene dodecylphenol (Poly) oxyalkylene alkyl (aryl) ether sulfate esters such as sodium ether sulfate; (poly) oxyalkylene alkyl phosphates such as (poly) oxyethylene stearyl phosphate; (poly) such as polyoxyethylene laurylamine ) Oxyalkylene alkylamines; etc., and one or more of these can be used.
上記水硬性材料組成物において、上記減水剤の配合割合としては、固形分換算で、水硬性材料の全量１００質量％に対して、０．０１〜１質量％であることが好ましい。より好ましくは０．０３〜０．５質量％であり、更に好ましくは０．０５〜０．３質量％であり、一層好ましくは０．０７〜０．２質量％であり、特に好ましくは０．０７〜０．１５質量％である。 In the hydraulic material composition, the blending ratio of the water reducing agent is preferably 0.01 to 1% by mass with respect to 100% by mass of the total amount of the hydraulic material in terms of solid content. It is more preferably 0.03 to 0.5% by mass, further preferably 0.05 to 0.3% by mass, still more preferably 0.07 to 0.2% by mass, and particularly preferably 0. It is 07 to 0.15% by mass.
上記水硬性材料組成物においては、その１ｍ３あたりの単位水量、水硬性材料使用量及び水／水硬性材料比は特に限定されず、例えば、単位水量１００〜３００ｋｇ／ｍ３、使用水硬性材料量３００〜５００ｋｇ／ｍ３、水／水硬性材料量比（重量比）＝０．３５〜０．６であることが好ましい。より好ましくは、単位水量１４０〜２４０ｋｇ／ｍ３、使用水硬性材料量３５０〜４８０ｋｇ／ｍ３、水／水硬性材料比（重量比）＝０．４〜０．５である。In the above hydraulic material composition, the unit water amount per 1 m 3 and the amount of the hydraulic material used and the water / hydraulic material ratio are not particularly limited. For example, the unit water amount of 100 to 300 kg / m 3 and the hydraulic material used are not particularly limited. The amount is preferably 300 to 500 kg / m 3 , and the water / hydraulic material amount ratio (weight ratio) is preferably 0.35 to 0.6. More preferably, the unit water amount is 140 to 240 kg / m 3 , the amount of hydraulic material used is 350 to 480 kg / m 3 , and the water / hydraulic material ratio (weight ratio) is 0.4 to 0.5.
本発明の水硬性材料用添加剤は、水硬性材料組成物に用いられる限り特に制限されず、レディーミクストコンクリート、吹付けコンクリート等に用いることができる。好ましくは吹付けコンクリート用途に用いることである。本発明の水硬性材料用添加剤の吹付けコンクリートへの使用方法もまた、本発明の１つである。本発明は更に、本発明の水硬性材料用添加剤を水硬性材料とともに施工面に吹き付けて使用する方法でもある。
上記使用方法は、本発明の水硬性材料用添加剤を水硬性材料とともに施工面に吹き付ける限り特に制限されないが、水硬性材料用添加剤と水硬性材料とを混合したものを施工面に吹き付けることが好ましい。上記使用方法としては、水硬性材料用添加剤と水硬性材料とを混合する工程と、混合工程により得られた水硬性材料組成物を圧縮空気又はポンプ等で圧送する工程と、水硬性材料組成物と急結剤を混合する工程、圧送された水硬性材料組成物を吹き付ける工程とを含むことがより好ましい。
上記水硬性材料組成物の好ましい形態等は、上述のとおりである。The additive for a hydraulic material of the present invention is not particularly limited as long as it is used in a hydraulic material composition, and can be used for ready-mixed concrete, sprayed concrete, and the like. It is preferably used for sprayed concrete applications. The method of using the additive for hydraulic materials of the present invention in sprayed concrete is also one of the present inventions. The present invention is also a method in which the additive for a hydraulic material of the present invention is sprayed onto a construction surface together with a hydraulic material.
The above-mentioned usage method is not particularly limited as long as the additive for hydraulic material of the present invention is sprayed on the construction surface together with the hydraulic material, but a mixture of the additive for hydraulic material and the hydraulic material is sprayed on the construction surface. Is preferable. The above-mentioned usage methods include a step of mixing an additive for a water-hard material and a water-hard material, a step of pumping the water-hard material composition obtained by the mixing step with compressed air or a pump, and a water-hard material composition. It is more preferable to include a step of mixing the product and the quick-setting admixture and a step of spraying the pumped water-hard material composition.
Preferred forms and the like of the hydraulic material composition are as described above.
以下に実施例を掲げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「部」は「質量部」を、「％」は「質量％」を意味するものとする。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".
＜粒子径＞
動的光散乱法による粒子径測定装置（ Ｍａｌｖｅｒｎ社製Ｚｅｔａｓｉｚｅｒ Ｎａｎｏ） を用い、散乱強度平均粒子径を測定した。<Particle size>
The average particle size of the scattering intensity was measured using a particle size measuring device (Zetasizer Nano manufactured by Malvern) by a dynamic light scattering method.
＜実施例１＞水硬性材料用添加剤の製造
滴下ロート、攪拌機、窒素導入管、温度計および還流冷却管を備えたフラスコに、脱イオン水３６７．７ｇを仕込んだ。他方、滴下ロートに、ポリオキシエチレンアルキルアリールスルフォネート塩（第一工業製薬（株）製「ハイテノール１８Ｅ」）の２０％水溶液８２．５ｇ、脱イオン水２５８．１ｇ、ブチルアクリレート２９８．７ｇ、２−エチルヘキシルアクリレート２９８．７ｇ、メチルメタクリレート４８０．７ｇ、およびアクリル酸２２．０ｇからなるプレエマルションを調製して仕込んだ。次に、前記プレエマルション７．２ｇ（プレエマルション全量の０．５％に相当）をフラスコ内に添加し、ゆるやかに窒素ガスを吹き込みながら攪拌下で８０℃まで昇温した。昇温後、フラスコ内に、３．５％過硫酸カリウム水溶液１４．３ｇと２．５％二亜硫酸ナトリウム水溶液２．８ｇとを添加して重合を開始させた。添加後に反応系内を８０℃で２０分間維持した。ここまでを初期反応とする。初期反応終了後、反応系内を８０℃に維持したまま、残りのプレエマルション１４３３．４ｇ（プレエマルション全量の９９．５％に相当）と、３．５％過硫酸カリウム水溶液７３．７ｇとを２４０分間かけて均一に滴下した。滴下後、脱イオン水１８ｇで滴下ロートを洗浄し、洗浄液をフラスコ内に添加した。その後、８０℃で６０分間維持したのち、室温まで冷却した。得られた反応液に２５％アンモニア水溶液８．２ｇを添加し、３０分間攪拌したのち、１００メッシュの金網でろ過して、エマルション樹脂組成物を得た。得られたエマルション樹脂組成物を分析したところ、固形分５１．６％、粒子径２７０ｎｍであった。<Example 1> Production of additive for water-hard material 367.7 g of deionized water was charged into a flask provided with a dropping funnel, a stirrer, a nitrogen introduction pipe, a thermometer and a reflux condenser. On the other hand, 82.5 g of a 20% aqueous solution of polyoxyethylene alkylaryl sulfonate salt (“High Tenol 18E” manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), 258.1 g of deionized water, and 298.7 g of butyl acrylate were added to the dropping funnel. , 298.7 g of 2-ethylhexyl acrylate, 480.7 g of methyl methacrylate, and 22.0 g of acrylic acid were prepared and charged. Next, 7.2 g of the pre-emulsion (corresponding to 0.5% of the total amount of the pre-emulsion) was added into the flask, and the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas. After the temperature was raised, 14.3 g of a 3.5% potassium persulfate aqueous solution and 2.8 g of a 2.5% sodium sulfite aqueous solution were added to the flask to initiate polymerization. After the addition, the inside of the reaction system was maintained at 80 ° C. for 20 minutes. This is the initial reaction. After completion of the initial reaction, the remaining preemulsion 1433.4 g (corresponding to 99.5% of the total amount of the preemulsion) and 73.7 g of a 3.5% potassium persulfate aqueous solution were added while maintaining the inside of the reaction system at 80 ° C. The mixture was uniformly added dropwise over 240 minutes. After the dropping, the dropping funnel was washed with 18 g of deionized water, and the washing liquid was added into the flask. Then, after maintaining at 80 degreeC for 60 minutes, it cooled to room temperature. 8.2 g of a 25% aqueous ammonia solution was added to the obtained reaction solution, the mixture was stirred for 30 minutes, and then filtered through a 100-mesh wire mesh to obtain an emulsion resin composition. When the obtained emulsion resin composition was analyzed, the solid content was 51.6% and the particle size was 270 nm.
＜実施例２＞
滴下ロート、攪拌機、窒素導入管、温度計および還流冷却管を備えたフラスコに、脱イオン水３６７．７ｇを仕込んだ。他方、滴下ロートに、ポリオキシエチレンアルキルアリールスルフォネート塩（第一工業製薬（株）製「ハイテノール１８Ｅ」）の２０％水溶液８２．５ｇ、脱イオン水２５８．１ｇ、ブチルアクリレート３３７．７ｇ、２−エチルヘキシルアクリレート３３７．７ｇ、メチルメタクリレート４０２．６ｇ、およびアクリル酸２２．０ｇからなるプレエマルションを調製して仕込んだ。次に、前記プレエマルション７．２ｇ（プレエマルション全量の０．５％に相当）をフラスコ内に添加し、ゆるやかに窒素ガスを吹き込みながら攪拌下で８０℃まで昇温した。昇温後、フラスコ内に、３．５％過硫酸カリウム水溶液１４．３ｇと２．５％二亜硫酸ナトリウム水溶液２．８ｇとを添加して重合を開始させた。添加後に反応系内を８０℃で２０分間維持した。ここまでを初期反応とする。初期反応終了後、反応系内を８０℃に維持したまま、残りのプレエマルション１４３３．４ｇ（プレエマルション全量の９９．５％に相当）と、３．５％過硫酸カリウム水溶液７３．７ｇとを２４０分間かけて均一に滴下した。滴下後、脱イオン水１８ｇで滴下ロートを洗浄し、洗浄液をフラスコ内に添加した。その後、８０℃で６０分間維持したのち、室温まで冷却した。得られた反応液に２５％アンモニア水溶液８．２ｇを添加し、３０分間攪拌したのち、１００メッシュの金網でろ過して、エマルション樹脂組成物を得た。得られたエマルション樹脂組成物を分析したところ、固形分５１．７％、粒子径２９３ｎｍであった。<Example 2>
367.7 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser. On the other hand, 82.5 g of a 20% aqueous solution of polyoxyethylene alkylaryl sulfonate salt (“High Tenol 18E” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 258.1 g of deionized water, and 337.7 g of butyl acrylate were added to the dropping funnel. , 32-Ethylhexyl acrylate (337.7 g), methyl methacrylate (402.6 g), and acrylic acid (22.0 g) were prepared and charged. Next, 7.2 g of the pre-emulsion (corresponding to 0.5% of the total amount of the pre-emulsion) was added into the flask, and the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas. After the temperature was raised, 14.3 g of a 3.5% potassium persulfate aqueous solution and 2.8 g of a 2.5% sodium sulfite aqueous solution were added to the flask to initiate polymerization. After the addition, the inside of the reaction system was maintained at 80 ° C. for 20 minutes. This is the initial reaction. After completion of the initial reaction, the remaining preemulsion 1433.4 g (corresponding to 99.5% of the total amount of the preemulsion) and 73.7 g of a 3.5% potassium persulfate aqueous solution were added while maintaining the inside of the reaction system at 80 ° C. The mixture was uniformly added dropwise over 240 minutes. After the dropping, the dropping funnel was washed with 18 g of deionized water, and the washing liquid was added into the flask. Then, after maintaining at 80 degreeC for 60 minutes, it cooled to room temperature. 8.2 g of a 25% aqueous ammonia solution was added to the obtained reaction solution, the mixture was stirred for 30 minutes, and then filtered through a 100-mesh wire mesh to obtain an emulsion resin composition. When the obtained emulsion resin composition was analyzed, the solid content was 51.7% and the particle size was 293 nm.
＜実施例３＞
滴下ロート、攪拌機、窒素導入管、温度計および還流冷却管を備えたフラスコに、脱イオン水３３０．９ｇを仕込んだ。他方、滴下ロートに、ポリオキシエチレンアルキルアリールスルフォネート塩（第一工業製薬（株）製「ハイテノール１８Ｅ」）の２０％水溶液６６．８ｇ、脱イオン水２３２．３ｇ、ブチルアクリレート３０７．８ｇ、２−エチルヘキシルアクリレート３０７．８ｇ、メチルメタクリレート２５７．７ｇ、およびアクリル酸１７．８ｇからなるプレエマルションを調製して仕込んだ。次に、前記プレエマルション６．０ｇ（プレエマルション全量の０．５％に相当）をフラスコ内に添加し、ゆるやかに窒素ガスを吹き込みながら攪拌下で８０℃まで昇温した。昇温後、フラスコ内に、３．５％過硫酸カリウム水溶液１４．３ｇと２．５％二亜硫酸ナトリウム水溶液２．５ｇとを添加して重合を開始させた。添加後に反応系内を８０℃で２０分間維持した。ここまでを初期反応とする。初期反応終了後、反応系内を８０℃に維持したまま、残りのプレエマルション１１８４．２ｇ（プレエマルション全量の９９．５％に相当）と、３．５％過硫酸カリウム水溶液６４．９ｇとを２４０分間かけて均一に滴下した。滴下後、脱イオン水１６．２ｇで滴下ロートを洗浄し、洗浄液をフラスコ内に添加した。その後、８０℃で６０分間維持したのち、室温まで冷却した。得られた反応液に２５％アンモニア水溶液７．４ｇを添加し、３０分間攪拌したのち、１００メッシュの金網でろ過して、エマルション樹脂組成物を得た。得られたエマルション樹脂組成物を分析したところ、固形分４９．８％、粒子径２７５ｎｍであった。<Example 3>
330.9 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser. On the other hand, 66.8 g of a 20% aqueous solution of polyoxyethylene alkylaryl sulfonate salt (“Hitenol 18E” manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), 232.3 g of deionized water, and 307.8 g of butyl acrylate were added to the dropping funnel. , 2-Ethylhexyl acrylate 307.8 g, methyl methacrylate 257.7 g, and acrylic acid 17.8 g were prepared and charged. Next, 6.0 g of the pre-emulsion (corresponding to 0.5% of the total amount of the pre-emulsion) was added into the flask, and the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas. After the temperature was raised, 14.3 g of a 3.5% potassium persulfate aqueous solution and 2.5 g of a 2.5% sodium sulfite aqueous solution were added to the flask to initiate polymerization. After the addition, the inside of the reaction system was maintained at 80 ° C. for 20 minutes. This is the initial reaction. After completion of the initial reaction, while maintaining the inside of the reaction system at 80 ° C., the remaining preemulsion 1184.2 g (corresponding to 99.5% of the total amount of the preemulsion) and 64.9 g of a 3.5% potassium persulfate aqueous solution were added. The mixture was uniformly added dropwise over 240 minutes. After the dropping, the dropping funnel was washed with 16.2 g of deionized water, and the washing liquid was added into the flask. Then, after maintaining at 80 degreeC for 60 minutes, it cooled to room temperature. 7.4 g of a 25% aqueous ammonia solution was added to the obtained reaction solution, and the mixture was stirred for 30 minutes and then filtered through a 100-mesh wire mesh to obtain an emulsion resin composition. When the obtained emulsion resin composition was analyzed, the solid content was 49.8% and the particle size was 275 nm.
＜実施例４＞
滴下ロート、攪拌機、窒素導入管、温度計および還流冷却管を備えたフラスコに、脱イオン水５１１．７ｇを仕込んだ。他方、滴下ロートに、ポリオキシエチレンアルキルアリールスルフォネート塩（第一工業製薬（株）製「ハイテノール１８Ｅ」）の２０％水溶液６６．０ｇ、脱イオン水２０６．５ｇ、ブチルアクリレート３０１．８ｇ、２−エチルヘキシルアクリレート３０１．８ｇ、スチレン２５８．７ｇ、およびアクリル酸１７．６ｇからなるプレエマルションを調製して仕込んだ。次に、前記プレエマルション５．８ｇ（プレエマルション全量の０．５％に相当）をフラスコ内に添加し、ゆるやかに窒素ガスを吹き込みながら攪拌下で８０℃まで昇温した。昇温後、フラスコ内に、３．５％過硫酸カリウム水溶液１４．３ｇと２．５％二亜硫酸ナトリウム水溶液２．２ｇとを添加して重合を開始させた。添加後に反応系内を８０℃で２０分間維持した。ここまでを初期反応とする。初期反応終了後、反応系内を８０℃に維持したまま、残りのプレエマルション１１４６．７ｇ（プレエマルション全量の９９．５％に相当）と、３．５％過硫酸カリウム水溶液５６．１ｇとを２４０分間かけて均一に滴下した。滴下後、脱イオン水１４．４ｇで滴下ロートを洗浄し、洗浄液をフラスコ内に添加した。その後、８０℃で６０分間維持したのち、室温まで冷却した。得られた反応液に２５％アンモニア水溶液６．６ｇを添加し、３０分間攪拌したのち、１００メッシュの金網でろ過して、エマルション樹脂組成物を得た。得られたエマルション樹脂組成物を分析したところ、固形分４５．７％、粒子径２４８ｎｍであった。<Example 4>
511.7 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser. On the other hand, 66.0 g of a 20% aqueous solution of polyoxyethylene alkylaryl sulfide salt (“High Tenol 18E” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 206.5 g of deionized water, and 301.8 g of butyl acrylate were added to the dropping funnel. , 301.8 g of 2-ethylhexyl acrylate, 258.7 g of styrene, and 17.6 g of acrylic acid were prepared and charged. Next, 5.8 g of the pre-emulsion (corresponding to 0.5% of the total amount of the pre-emulsion) was added into the flask, and the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas. After the temperature was raised, 14.3 g of a 3.5% potassium persulfate aqueous solution and 2.2 g of a 2.5% sodium sulfite aqueous solution were added to the flask to initiate polymerization. After the addition, the inside of the reaction system was maintained at 80 ° C. for 20 minutes. This is the initial reaction. After completion of the initial reaction, the remaining preemulsion 1146.7 g (corresponding to 99.5% of the total amount of the preemulsion) and 56.1 g of a 3.5% potassium persulfate aqueous solution were added while maintaining the inside of the reaction system at 80 ° C. The mixture was uniformly added dropwise over 240 minutes. After the dropping, the dropping funnel was washed with 14.4 g of deionized water, and the washing liquid was added into the flask. Then, after maintaining at 80 degreeC for 60 minutes, it cooled to room temperature. 6.6 g of a 25% aqueous ammonia solution was added to the obtained reaction solution, and the mixture was stirred for 30 minutes and then filtered through a 100-mesh wire mesh to obtain an emulsion resin composition. When the obtained emulsion resin composition was analyzed, the solid content was 45.7% and the particle size was 248 nm.
＜実施例５＞
滴下ロート、攪拌機、窒素導入管、温度計および還流冷却管を備えたフラスコに、脱イオン水５１１．７ｇを仕込んだ。他方、滴下ロートに、ポリオキシエチレンアルキルアリールスルフォネート塩（第一工業製薬（株）製「ハイテノール１８Ｅ」）の２０％水溶液６６．０ｇ、脱イオン水２０６．５ｇ、ブチルアクリレート２６７．５ｇ、２−エチルヘキシルアクリレート２６７．５ｇ、スチレン３２７．４ｇ、およびアクリル酸１７．６ｇからなるプレエマルションを調製して仕込んだ。次に、前記プレエマルション５．８ｇ（プレエマルション全量の０．５％に相当）をフラスコ内に添加し、ゆるやかに窒素ガスを吹き込みながら攪拌下で８０℃まで昇温した。昇温後、フラスコ内に、３．５％過硫酸カリウム水溶液１４．３ｇと２．５％二亜硫酸ナトリウム水溶液２．２ｇとを添加して重合を開始させた。添加後に反応系内を８０℃で２０分間維持した。ここまでを初期反応とする。初期反応終了後、反応系内を８０℃に維持したまま、残りのプレエマルション１１４６．７ｇ（プレエマルション全量の９９．５％に相当）と、３．５％過硫酸カリウム水溶液５６．１ｇとを２４０分間かけて均一に滴下した。滴下後、脱イオン水１４．４ｇで滴下ロートを洗浄し、洗浄液をフラスコ内に添加した。その後、８０℃で６０分間維持したのち、室温まで冷却した。得られた反応液に２５％アンモニア水溶液６．６ｇを添加し、３０分間攪拌したのち、１００メッシュの金網でろ過して、エマルション樹脂組成物を得た。得られたエマルション樹脂組成物を分析したところ、固形分４６．３％、粒子径２５５ｎｍであった。<Example 5>
511.7 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser. On the other hand, 66.0 g of a 20% aqueous solution of polyoxyethylene alkylaryl sulfonate salt (“High Tenol 18E” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 206.5 g of deionized water, and 267.5 g of butyl acrylate were added to the dropping funnel. , 2-Ethylhexyl acrylate 267.5 g, styrene 327.4 g, and acrylic acid 17.6 g were prepared and charged. Next, 5.8 g of the pre-emulsion (corresponding to 0.5% of the total amount of the pre-emulsion) was added into the flask, and the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas. After the temperature was raised, 14.3 g of a 3.5% potassium persulfate aqueous solution and 2.2 g of a 2.5% sodium sulfite aqueous solution were added to the flask to initiate polymerization. After the addition, the inside of the reaction system was maintained at 80 ° C. for 20 minutes. This is the initial reaction. After completion of the initial reaction, the remaining preemulsion 1146.7 g (corresponding to 99.5% of the total amount of the preemulsion) and 56.1 g of a 3.5% potassium persulfate aqueous solution were added while maintaining the inside of the reaction system at 80 ° C. The mixture was uniformly added dropwise over 240 minutes. After the dropping, the dropping funnel was washed with 14.4 g of deionized water, and the washing liquid was added into the flask. Then, after maintaining at 80 degreeC for 60 minutes, it cooled to room temperature. 6.6 g of a 25% aqueous ammonia solution was added to the obtained reaction solution, and the mixture was stirred for 30 minutes and then filtered through a 100-mesh wire mesh to obtain an emulsion resin composition. When the obtained emulsion resin composition was analyzed, the solid content was 46.3% and the particle size was 255 nm.
＜比較例１＞
滴下ロート、攪拌機、窒素導入管、温度計および還流冷却管を備えたフラスコに、脱イオン水３６７．７ｇを仕込んだ。他方、滴下ロートに、ポリオキシエチレンアルキルアリールスルフォネート塩（第一工業製薬（株）製「ハイテノール１８Ｅ」）の２０％水溶液８２．５ｇ、脱イオン水２５８．１ｇ、ブチルアクリレート５３９．０ｇ、２−エチルヘキシルアクリレート５３９．０ｇ、およびアクリル酸２２．０ｇからなるプレエマルションを調製して仕込んだ。次に、前記プレエマルション７．２ｇ（プレエマルション全量の０．５％に相当）をフラスコ内に添加し、ゆるやかに窒素ガスを吹き込みながら攪拌下で８０℃まで昇温した。昇温後、フラスコ内に、３．５％過硫酸カリウム水溶液１４．３ｇと２．５％二亜硫酸ナトリウム水溶液２．８ｇとを添加して重合を開始させた。添加後に反応系内を８０℃で２０分間維持した。ここまでを初期反応とする。初期反応終了後、反応系内を８０℃に維持したまま、残りのプレエマルション１４３３．４ｇ（プレエマルション全量の９９．５％に相当）と、３．５％過硫酸カリウム水溶液７３．７ｇとを２４０分間かけて均一に滴下した。滴下後、脱イオン水１８ｇで滴下ロートを洗浄し、洗浄液をフラスコ内に添加した。その後、８０℃で６０分間維持したのち、室温まで冷却した。得られた反応液に２５％アンモニア水溶液１６．４ｇを添加し、３０分間攪拌したのち、１００メッシュの金網でろ過して、エマルション樹脂組成物を得た。得られたエマルション樹脂組成物を分析したところ、固形分５４．８％、粒子径２６９ｎｍであった。<Comparative example 1>
367.7 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser. On the other hand, 82.5 g of a 20% aqueous solution of polyoxyethylene alkylaryl sulfonate salt (“High Tenol 18E” manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), 258.1 g of deionized water, and 539.0 g of butyl acrylate were added to the dropping funnel. , 539.0 g of 2-ethylhexyl acrylate, and 22.0 g of acrylic acid were prepared and charged. Next, 7.2 g of the pre-emulsion (corresponding to 0.5% of the total amount of the pre-emulsion) was added into the flask, and the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas. After the temperature was raised, 14.3 g of a 3.5% potassium persulfate aqueous solution and 2.8 g of a 2.5% sodium sulfite aqueous solution were added to the flask to initiate polymerization. After the addition, the inside of the reaction system was maintained at 80 ° C. for 20 minutes. This is the initial reaction. After completion of the initial reaction, the remaining preemulsion 1433.4 g (corresponding to 99.5% of the total amount of the preemulsion) and 73.7 g of a 3.5% potassium persulfate aqueous solution were added while maintaining the inside of the reaction system at 80 ° C. The mixture was uniformly added dropwise over 240 minutes. After the dropping, the dropping funnel was washed with 18 g of deionized water, and the washing liquid was added into the flask. Then, after maintaining at 80 degreeC for 60 minutes, it cooled to room temperature. 16.4 g of a 25% aqueous ammonia solution was added to the obtained reaction solution, and the mixture was stirred for 30 minutes and then filtered through a 100-mesh wire mesh to obtain an emulsion resin composition. When the obtained emulsion resin composition was analyzed, the solid content was 54.8% and the particle size was 269 nm.
＜比較例２＞
滴下ロート、攪拌機、窒素導入管、温度計および還流冷却管を備えたフラスコに、脱イオン水３６７．７ｇを仕込んだ。他方、滴下ロートに、ポリオキシエチレンアルキルアリールスルフォネート塩（第一工業製薬（株）製「ハイテノール１８Ｅ」）の２０％水溶液８２．５ｇ、脱イオン水２５８．１ｇ、ブチルアクリレート２２９．４ｇ、２−エチルヘキシルアクリレート２２９．４ｇ、メチルメタクリレート６１９．３ｇ、およびアクリル酸２２．０ｇからなるプレエマルションを調製して仕込んだ。次に、前記プレエマルション７．２ｇ（プレエマルション全量の０．５％に相当）をフラスコ内に添加し、ゆるやかに窒素ガスを吹き込みながら攪拌下で８０℃まで昇温した。昇温後、フラスコ内に、３．５％過硫酸カリウム水溶液１４．３ｇと２．５％二亜硫酸ナトリウム水溶液２．８ｇとを添加して重合を開始させた。添加後に反応系内を８０℃で２０分間維持した。ここまでを初期反応とする。初期反応終了後、反応系内を８０℃に維持したまま、残りのプレエマルション１４３３．４ｇ（プレエマルション全量の９９．５％に相当）と、３．５％過硫酸カリウム水溶液７３．７ｇとを２４０分間かけて均一に滴下した。滴下後、脱イオン水１８ｇで滴下ロートを洗浄し、洗浄液をフラスコ内に添加した。その後、８０℃で６０分間維持したのち、室温まで冷却した。得られた反応液に２５％アンモニア水溶液８．２ｇを添加し、３０分間攪拌したのち、１００メッシュの金網でろ過して、エマルション樹脂組成物を得た。得られたエマルション樹脂組成物を分析したところ、固形分５７．０％、粒子径２５８ｎｍであった。<Comparative example 2>
367.7 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser. On the other hand, 82.5 g of a 20% aqueous solution of polyoxyethylene alkylaryl sulfonate salt (“High Tenol 18E” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 258.1 g of deionized water, and 229.4 g of butyl acrylate were added to the dropping funnel. , 229.4 g of 2-ethylhexyl acrylate, 619.3 g of methyl methacrylate, and 22.0 g of acrylic acid were prepared and charged. Next, 7.2 g of the pre-emulsion (corresponding to 0.5% of the total amount of the pre-emulsion) was added into the flask, and the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas. After the temperature was raised, 14.3 g of a 3.5% potassium persulfate aqueous solution and 2.8 g of a 2.5% sodium sulfite aqueous solution were added to the flask to initiate polymerization. After the addition, the inside of the reaction system was maintained at 80 ° C. for 20 minutes. This is the initial reaction. After completion of the initial reaction, the remaining preemulsion 1433.4 g (corresponding to 99.5% of the total amount of the preemulsion) and 73.7 g of a 3.5% potassium persulfate aqueous solution were added while maintaining the inside of the reaction system at 80 ° C. The mixture was uniformly added dropwise over 240 minutes. After the dropping, the dropping funnel was washed with 18 g of deionized water, and the washing liquid was added into the flask. Then, after maintaining at 80 degreeC for 60 minutes, it cooled to room temperature. 8.2 g of a 25% aqueous ammonia solution was added to the obtained reaction solution, the mixture was stirred for 30 minutes, and then filtered through a 100-mesh wire mesh to obtain an emulsion resin composition. When the obtained emulsion resin composition was analyzed, the solid content was 57.0% and the particle size was 258 nm.
＜製造例１＞減水剤（ポリカルボン酸共重合体）の製造
温度計、攪拌機、滴下ロート、環流冷却器を備えたガラス製反応容器にイオン交換水７２．２６部、３−メチル−３−ブテン−１−オールにエチレンオキサイドを５０モル付加した不飽和アルコール１２７．７４部を仕込み、６５℃に昇温した後、そこへ過酸化水素３０％水溶液０．７１部を添加し、アクリル酸４０％水溶液４６．５８部を３時間、３−メルカプトプロピオン酸２．４％水溶液３１．２７部を３時間、Ｌ−アスコルビン酸２．１％水溶液１２．９７部を３．５時間かけて滴下した。その後６０分引き続いて６５℃に温度を維持して重合反応を完結させ、温度を５０℃以下に降温し水酸化ナトリウム１２．２％水溶液７６．０７部でｐＨ４からｐＨ７になるように中和し、重量平均分子量２９，０００の重合体水溶液からなる本発明のポリカルボン酸共重合体を得た。尚、重合時に使用する原料の全量に対する全単量体の使用量は、５６．２重量％であった。<Production Example 1> Production of water reducing agent (polycarboxylic acid copolymer) 72.26 parts of ion-exchanged water, 3-methyl-3-3 in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a recirculation cooler. 127.74 parts of unsaturated alcohol obtained by adding 50 mol of ethylene oxide to butene-1-ol was charged, the temperature was raised to 65 ° C., 0.71 part of a 30% aqueous hydrogen solution solution was added thereto, and the acrylic acid 40 was added. 46.58 parts of a% aqueous solution was added dropwise over 3 hours, 31.27 parts of a 2.4% aqueous solution of 3-mercaptopropionic acid was added dropwise over 3 hours, and 12.97 parts of a 2.1% aqueous solution of L-ascorbic acid was added dropwise over 3.5 hours. .. After that, the temperature was maintained at 65 ° C. for 60 minutes to complete the polymerization reaction, the temperature was lowered to 50 ° C. or lower, and neutralized with 76.07 parts of a 12.2% sodium hydroxide aqueous solution from pH 4 to pH 7. , A polycarboxylic acid copolymer of the present invention consisting of a polymer aqueous solution having a weight average molecular weight of 29,000 was obtained. The amount of all monomers used was 56.2% by weight based on the total amount of raw materials used during polymerization.
＜テクスチャーアナライザーによる粘着性評価＞
（１）装置：英光精機株式会社製 テクスチャーアナライザーＴＡ．ＸＴ Ｐｌｕｓ
（２）装置の概要：プローブ、試料台、応力検出器からなり、一定荷重を一定時間与えることができる機構、及び、モルタルとプローブとの接触及び引き剥がしを一定速度で行えるように当該速度を制御できる機構を有する。
粘着性試験用プローブ：つきさし、圧縮用円柱プローブ Ｐ／３５（材質：アルミニウム、直径３５ｍｍ）
（３）評価方法：下記のとおり調製した（練り上げた）モルタル試料を２００ｍＬデスカップに移し試料台に置いた。次に毎秒１ｍｍの速度でプローブを試料の表面から２０ｍｍの深さまで貫入させ、その後直ちに１ｍｍ／ｓｅｃ．の速度でプローブを引き抜き、プローブがモルタルから剥がれる際に要する最大荷重を求め、プローブタック試験の値とした。単位はＮ／ｃｍ２で表記した。エマルション未添加の系の最大荷重を１００％としたときの各々の系の最大荷重比を、粘着性と定義した。最大荷重比が１００％以上である場合に、粘着性が高いとみなした。
（４）モルタル試料の調製：
モルタル試験は、温度が２０℃±１℃、相対湿度が６０％±１５％の環境下で行った。モルタル配合は、Ｃ／Ｓ／Ｗ＝６９０／１６００／３０４（ｇ）とした。
ただし、
Ｃ：セメント（普通ポルトランドセメント、太平洋セメント社製）
Ｓ：細骨材（大井川産陸砂）
Ｗ：試料と消泡剤のイオン交換水溶液
とし、Ｗについては上記実施例、比較例で得られた水硬性材料用添加剤、製造例で得られた減水剤及び消泡剤を含み、イオン交換水中充分に均一溶解させた。
モルタルミキサー（ホバート社製ミキサー、型番：Ｎ−５０）を用い、混練容器へＣおよびＳを投入し、１速で１０秒間混練した。さらに１速で混練しながら、Ｗを１０秒かけて投入した。混練を始めてから９０秒後にミキサーを停止し、３０秒間モルタルの掻き落としを行った。その後、さらに２速で６０秒間混練を行い、モルタルを調製した。上記のようにして得られたモルタルを、フロー測定板（６０ｃｍ×６０ｃｍ）に置かれたミニスランプコーン（ＪＩＳマイクロコンクリートスランプコーン、上端内径５０ｍｍ、下端内径１００ｍｍ、高さ１５０ｍｍ）に半量詰めて１５回突き棒で突き、さらにモルタルをミニスランプコーンのすりきりいっぱいまで詰めて１５回突き棒で突いた後、ミニスランプコーンの表面をならした。その後、最初にミキサーを始動させてから７分後にミニスランプコーンを垂直に引き上げ、広がったモルタルの直径（最も長い部分の直径（長径）および該長径に対して９０度をなす部分の直径）を２箇所測定し、その平均値をモルタルフロー値とした。このとき、フロー値が２５０ｍｍとなるように、製造例１で得られたポリカルボン酸共重合体の添加量を調整した。なお、空気量は消泡剤であるオキシアルキレン系消泡剤を添加して３．０％未満となるように調整した。<Adhesiveness evaluation by texture analyzer>
(1) Equipment: Texture Analyzer TA., manufactured by Eiko Seiki Co., Ltd. XT Plus
(2) Outline of the device: A mechanism consisting of a probe, a sample table, and a stress detector that can apply a constant load for a certain period of time, and the speed at which the mortar can be contacted and peeled off at a constant speed. It has a controllable mechanism.
Adhesive test probe: Tsukisashi, cylindrical probe for compression P / 35 (material: aluminum, diameter 35 mm)
(3) Evaluation method: The mortar sample prepared (kneaded) as follows was transferred to a 200 mL descup and placed on a sample table. The probe was then penetrated to a depth of 20 mm from the surface of the sample at a rate of 1 mm per second, followed immediately by 1 mm / sec. The probe was pulled out at the speed of, and the maximum load required for the probe to peel off from the mortar was calculated and used as the value of the probe tack test. The unit is N / cm 2 . The maximum load ratio of each system when the maximum load of the emulsion-free system was 100% was defined as adhesiveness. When the maximum load ratio was 100% or more, the adhesiveness was considered to be high.
(4) Preparation of mortar sample:
The mortar test was conducted in an environment where the temperature was 20 ° C. ± 1 ° C. and the relative humidity was 60% ± 15%. The mortar composition was C / S / W = 690/1600/304 (g).
However,
C: Cement (ordinary Portland cement, manufactured by Taiheiyo Cement)
S: Fine aggregate (land sand from Oi River)
W: An ion-exchange aqueous solution of a sample and a defoaming agent, and W contains an additive for a water-hard material obtained in the above Examples and Comparative Examples, a water-reducing agent and a defoaming agent obtained in a production example, and ion-exchanged. It was sufficiently uniformly dissolved in water.
Using a mortar mixer (Mixer manufactured by Hobart, model number: N-50), C and S were put into a kneading container and kneaded at 1st speed for 10 seconds. Further, while kneading at the 1st speed, W was added over 10 seconds. The mixer was stopped 90 seconds after the start of kneading, and the mortar was scraped off for 30 seconds. Then, kneading was further carried out at 2nd speed for 60 seconds to prepare a mortar. Half of the mortar obtained as described above is packed in a mini slump cone (JIS microconcrete slump cone, upper end inner diameter 50 mm, lower end inner diameter 100 mm, height 150 mm) placed on a flow measuring plate (60 cm × 60 cm). The surface of the mini slump cone was smoothed after piercing with a piercing rod, filling the mortar to the full extent of the mini slump cone, and piercing with the piercing rod 15 times. Then, 7 minutes after starting the mixer for the first time, the mini slump cone is pulled up vertically to measure the diameter of the expanded mortar (the diameter of the longest part (major diameter) and the diameter of the part that makes 90 degrees to the long diameter). Two points were measured, and the average value was used as the mortar flow value. At this time, the amount of the polycarboxylic acid copolymer obtained in Production Example 1 was adjusted so that the flow value was 250 mm. The amount of air was adjusted to less than 3.0% by adding an oxyalkylene defoaming agent as a defoaming agent.
＜混練時間の評価＞
モルタル試料調整時に、Ｃ・Ｓ・Ｗが均一に混ざりモルタルの流動性が出た状態を目視で判断し、Ｗ投入時から流動性が出るまでにかかった時間を混練時間とした。<Evaluation of kneading time>
At the time of preparing the mortar sample, the state in which C, S, and W were uniformly mixed and the mortar became fluid was visually determined, and the time taken from the time when W was added until the fluidity was obtained was defined as the kneading time.
＜結果＞
結果を表１に示した。表１における単量体は、以下のとおりである。なお、上記のＦｏｘの式（１）により重合性単量体成分のガラス転移温度（Ｔｇ）を算出するのに使用したそれぞれのホモポリマーのＴｇ値を下記に（ ）で示した。
ＢＡ：ブチルアクリレート（−５６℃）
２ＥＨＡ：２−エチルヘキシルアクリレート（−７０℃）
ＡＡ：アクリル酸（９５℃）
ＭＭＡ：メチルメタクリレート（１０５℃）
Ｓｔ：スチレン（１００℃）<Result>
The results are shown in Table 1. The monomers in Table 1 are as follows. The Tg value of each homopolymer used to calculate the glass transition temperature (Tg) of the polymerizable monomer component according to the Fox formula (1) is shown in () below.
BA: Butyl acrylate (-56 ° C)
2EHA: 2-ethylhexyl acrylate (-70 ° C)
AA: Acrylic acid (95 ° C)
MMA: Methyl methacrylate (105 ° C)
St: Styrene (100 ° C)
Claims (17)
該共重合体エマルション粒子は、全構造単位１００質量％に対して、炭素数が１〜２０であるアルキル基を有するアルキル（メタ）アクリレート（Ａ）由来の構造単位（ａ）を４０〜９９．９質量％有し、
（メタ）アクリル酸（塩）（Ｂ）由来の構造単位（ｂ）を０．１〜１０質量％有し、
芳香族ビニル化合物（Ｃ）由来の構造単位（ｃ）の含有割合が０〜５９．９質量％であり、
該アルキル（メタ）アクリレート（Ａ）、（メタ）アクリル酸（塩）（Ｂ）及び芳香族ビニル化合物（Ｃ）以外のその他の単量体（Ｄ）由来の構造単位（ｄ）の含有割合が０〜１０質量％であり、
該共重合体エマルション粒子のガラス転移温度が−５０〜５℃であり、
該共重合体エマルション粒子の平均粒子径が１３０ｎｍ以上であることを特徴とする水硬性材料用添加剤。An additive for hydraulic materials containing (meth) acrylate-based copolymer emulsion particles.
The copolymer emulsion particles contain 40 to 99. Of the structural unit (a) derived from the alkyl (meth) acrylate (A) having an alkyl group having 1 to 20 carbon atoms with respect to 100% by mass of the total structural unit. Has 9% by mass
It has 0.1 to 10% by mass of the structural unit (b) derived from (meth) acrylic acid (salt) (B).
The content ratio of the structural unit (c) derived from the aromatic vinyl compound (C) is 0 to 59.9% by mass.
The content ratio of the structural unit (d) derived from the monomer (D) other than the alkyl (meth) acrylate (A), (meth) acrylic acid (salt) (B) and the aromatic vinyl compound (C) is 0 to 10% by mass,
The copolymer emulsion particles have a glass transition temperature of −50 to 5 ° C.
An additive for hydraulic materials, wherein the copolymer emulsion particles have an average particle size of 130 nm or more.
該構造単位（ａ１）の割合が、構造単位（ａ２）１００質量％に対して０〜１４５質量％であることを特徴とする請求項１に記載の水硬性材料用添加剤。The (meth) acrylate-based copolymer emulsion particles have a structural unit (a2) derived from an alkyl (meth) acrylate (A2) having an alkyl group having 3 to 20 carbon atoms, and have 1 or 2 carbon atoms. It may have a structural unit (a1) derived from an alkyl (meth) acrylate (A1) having an alkyl group which is.
The additive for a hydraulic material according to claim 1, wherein the ratio of the structural unit (a1) is 0 to 145% by mass with respect to 100% by mass of the structural unit (a2).
A method in which the additive for a hydraulic material according to any one of claims 1 to 12 is sprayed onto a construction surface together with the hydraulic material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019056856 | 2019-03-25 | ||
| JP2019056856 | 2019-03-25 | ||
| PCT/JP2020/011749 WO2020196102A1 (en) | 2019-03-25 | 2020-03-17 | Additive for hydraulic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2020196102A1 true JPWO2020196102A1 (en) | 2021-10-28 |
| JP7228029B2 JP7228029B2 (en) | 2023-02-22 |
Family
ID=72609391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021509127A Active JP7228029B2 (en) | 2019-03-25 | 2020-03-17 | Additives for hydraulic materials |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP7228029B2 (en) |
| WO (1) | WO2020196102A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113173728B (en) * | 2021-05-08 | 2023-08-22 | 四川铁科新型建材有限公司 | Alkali-free accelerator for resisting aggregate alkali activity reaction and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09221350A (en) * | 1996-02-16 | 1997-08-26 | Mitsubishi Chem Basf Co Ltd | Cement composition |
| JP2000086372A (en) * | 1998-09-08 | 2000-03-28 | Lion Corp | Concrete surface reinforcing agent |
| JP2000509359A (en) * | 1995-10-25 | 2000-07-25 | ダブリユ・アール・グレイス・アンド・カンパニー・コネテイカツト | Nitrogen-containing strength enhancer for Portland cement |
| JP2003525190A (en) * | 2000-03-02 | 2003-08-26 | ダブリュ・アール・グレイス・アンド・カンパニー・コネテイカット | Air management in cementitious mixtures with plasticizers and clay active modifiers |
| JP2011046545A (en) * | 2009-08-25 | 2011-03-10 | Nippon Synthetic Chem Ind Co Ltd:The | Emulsion composition and coating film waterproofing material using the same |
| JP2017119737A (en) * | 2015-12-28 | 2017-07-06 | 日本合成化学工業株式会社 | Method for producing synthetic resin emulsion, polymer cement composition using synthetic resin emulsion obtained by production method, and coated film waterproof material obtained by using the polymer cement composition |
| JP2017521519A (en) * | 2014-07-01 | 2017-08-03 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Dispersion of (meth) acrylate copolymer containing hydroxyalkyl (meth) acrylate functional monomer units for flexible cement waterproofing |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2029635A1 (en) * | 1989-11-22 | 1991-05-23 | Rohm And Haas Company | Foamed hydraulic composition containing copolymeric foam stabilizer |
| JPH08183642A (en) * | 1994-12-27 | 1996-07-16 | Mitsui Toatsu Chem Inc | Emulsion resin for cement mortar |
-
2020
- 2020-03-17 WO PCT/JP2020/011749 patent/WO2020196102A1/en active Application Filing
- 2020-03-17 JP JP2021509127A patent/JP7228029B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000509359A (en) * | 1995-10-25 | 2000-07-25 | ダブリユ・アール・グレイス・アンド・カンパニー・コネテイカツト | Nitrogen-containing strength enhancer for Portland cement |
| JPH09221350A (en) * | 1996-02-16 | 1997-08-26 | Mitsubishi Chem Basf Co Ltd | Cement composition |
| JP2000086372A (en) * | 1998-09-08 | 2000-03-28 | Lion Corp | Concrete surface reinforcing agent |
| JP2003525190A (en) * | 2000-03-02 | 2003-08-26 | ダブリュ・アール・グレイス・アンド・カンパニー・コネテイカット | Air management in cementitious mixtures with plasticizers and clay active modifiers |
| JP2011046545A (en) * | 2009-08-25 | 2011-03-10 | Nippon Synthetic Chem Ind Co Ltd:The | Emulsion composition and coating film waterproofing material using the same |
| JP2017521519A (en) * | 2014-07-01 | 2017-08-03 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Dispersion of (meth) acrylate copolymer containing hydroxyalkyl (meth) acrylate functional monomer units for flexible cement waterproofing |
| JP2017119737A (en) * | 2015-12-28 | 2017-07-06 | 日本合成化学工業株式会社 | Method for producing synthetic resin emulsion, polymer cement composition using synthetic resin emulsion obtained by production method, and coated film waterproof material obtained by using the polymer cement composition |
Non-Patent Citations (1)
| Title |
|---|
| 川口春馬: "解説 乳化重合", 日本画像学会誌, vol. 44, no. 5, JPN6022038405, 2005, pages 369 - 374, ISSN: 0004873700 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7228029B2 (en) | 2023-02-22 |
| WO2020196102A1 (en) | 2020-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4727940B2 (en) | Redispersed powder stabilized with polyvinyl alcohol having fluidizing properties, process for its production and use | |
| JP2013517133A5 (en) | ||
| CN105801773A (en) | Comb-type polymer and its preparation method and use as water reducer | |
| KR101115054B1 (en) | Water Soluble Acrylic Polymer and Cement Mortar Quick Strength Admixture Using the Same | |
| JP4620085B2 (en) | Method for producing cement dispersant | |
| JP7228029B2 (en) | Additives for hydraulic materials | |
| JP6946101B2 (en) | Resin emulsion for cement additives | |
| JP2009023901A (en) | Cement admixture and cement composition | |
| JP5037144B2 (en) | Dispersant for hydraulic composition | |
| WO2020045515A1 (en) | Additive for hydraulic material | |
| JP7090166B2 (en) | Additives for hydraulic materials | |
| JP2001302307A (en) | Cement additive and concrete composition produced by using the same | |
| JP2011136880A (en) | Cement admixture and cement composition | |
| TW202021928A (en) | Additive for hydraulic compositions, and hydraulic composition | |
| JP4425775B2 (en) | Hydraulic powder dispersion copolymer | |
| JPH0952749A (en) | Admixture for high flowability concrete and concrete material containing the same | |
| JP7241643B2 (en) | Additive for cement, cement composition, method for improving cement strength | |
| JP4087042B2 (en) | Cement dispersant | |
| JP4562964B2 (en) | Cement dispersant | |
| CN105189401B (en) | The powder composition that can quickly suspend | |
| TWI778186B (en) | Additive for hydraulic composition and hydraulic composition | |
| JP5705423B2 (en) | Cement additive and cement composition | |
| JP7285737B2 (en) | Dispersant for ground improvement cement composition, ground improvement cement composition, ground improvement body and ground improvement method | |
| JPS641425B2 (en) | ||
| JP7075683B2 (en) | Additives for hydraulic compositions and hydraulic compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20210423 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220426 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20220623 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220708 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220913 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20221108 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20230207 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20230210 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7228029 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |