JP2008156152A - Method for preventing water absorption in polymer cement composition - Google Patents
Method for preventing water absorption in polymer cement composition Download PDFInfo
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- JP2008156152A JP2008156152A JP2006345729A JP2006345729A JP2008156152A JP 2008156152 A JP2008156152 A JP 2008156152A JP 2006345729 A JP2006345729 A JP 2006345729A JP 2006345729 A JP2006345729 A JP 2006345729A JP 2008156152 A JP2008156152 A JP 2008156152A
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- polymer
- polymer emulsion
- cement composition
- emulsion
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- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 239000011414 polymer cement Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 21
- 238000010521 absorption reaction Methods 0.000 title description 12
- 230000003405 preventing effect Effects 0.000 title description 10
- 239000000839 emulsion Substances 0.000 claims abstract description 83
- 229920000642 polymer Polymers 0.000 claims abstract description 56
- 239000004568 cement Substances 0.000 claims abstract description 34
- 239000004567 concrete Substances 0.000 claims abstract description 24
- 125000000129 anionic group Chemical group 0.000 claims abstract description 23
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000010276 construction Methods 0.000 claims description 12
- 239000008119 colloidal silica Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 239000010410 layer Substances 0.000 claims description 7
- 239000011247 coating layer Substances 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 230000007547 defect Effects 0.000 abstract description 3
- -1 polyethylene Polymers 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 239000004570 mortar (masonry) Substances 0.000 description 12
- 125000002091 cationic group Chemical group 0.000 description 11
- 239000007787 solid Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 125000003010 ionic group Chemical group 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 3
- 229910052912 lithium silicate Inorganic materials 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000008055 alkyl aryl sulfonates Chemical class 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
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 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
- 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
- HVYJSOSGTDINLW-UHFFFAOYSA-N 2-[dimethyl(octadecyl)azaniumyl]acetate Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CC([O-])=O HVYJSOSGTDINLW-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 1
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- PLUHAVSIMCXBEX-UHFFFAOYSA-N azane;dodecyl benzenesulfonate Chemical compound N.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 PLUHAVSIMCXBEX-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- VOOQRJIZEJHBGL-UHFFFAOYSA-N butyl 2-methylprop-2-enoate;2-methylprop-2-enoic acid Chemical class CC(=C)C(O)=O.CCCCOC(=O)C(C)=C VOOQRJIZEJHBGL-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- TWFQJFPTTMIETC-UHFFFAOYSA-N dodecan-1-amine;hydron;chloride Chemical compound [Cl-].CCCCCCCCCCCC[NH3+] TWFQJFPTTMIETC-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- QGVQVNIIRBPOAM-UHFFFAOYSA-N dodecyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCCCCCCCCCCCC)=CC=CC2=C1 QGVQVNIIRBPOAM-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RJUVPCYAOBNZAX-VOTSOKGWSA-N ethyl (e)-3-(dimethylamino)-2-methylprop-2-enoate Chemical compound CCOC(=O)C(\C)=C\N(C)C RJUVPCYAOBNZAX-VOTSOKGWSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000009477 glass transition Effects 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
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229940094506 lauryl betaine Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011433 polymer cement mortar Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
Abstract
Description
本発明は、モルタル・コンクリート表面に発生するドライアウトを防止できるポリマーセメント組成物の施工方法及び該施工により得られるセメント硬化体に関する。 The present invention relates to a method for applying a polymer cement composition capable of preventing dryout generated on a mortar / concrete surface, and a hardened cement obtained by the application.
コンクリート躯体にモルタルを薄層で施工する場合、コンクリート躯体にモルタルの水分が吸収されることにより、モルタルがドライアウトし、硬化不良、付着不良などの不具合を起こすことがある。こうした弊害を防ぐために、古くから、モルタル施工に先駆けて「ノロがけ」、「水湿し」などが行われている。
「ノロがけ」とは、セメントを水で溶いたセメントミルク（ノロ）を刷毛などで躯体に薄く塗布することにより、躯体の吸水を防ぐ方法であるが、ノロがドライアウトする前にモルタルを施工する必要があり、作業が煩雑となる。また、「水湿し」とは、躯体を事前に水浮きがない程度に湿らせてモルタルを施工する方法であるが、「ノロがけ」と同様、躯体が乾く前にモルタルを施工しなければならない。
これらの方法では、施工速度と下地処理の乾燥のバランスにより、均一性を欠いた施工となり易いのが問題とされていた。
When the mortar is applied to the concrete frame in a thin layer, the mortar is dried out by the moisture of the mortar being absorbed into the concrete frame, which may cause problems such as poor curing and poor adhesion. In order to prevent such harmful effects, “Norogake”, “Water dampening”, etc. have been performed for a long time before mortar construction.
“Norogake” is a method to prevent water absorption of the chassis by applying a thin coat of cement milk (noro) with cement in water with a brush or the like, but mortar is applied before Noro dries out. It is necessary to do this, and the work becomes complicated. “Water dampening” is a method of applying mortar by moistening the chassis in advance so that it does not float. However, as with “Noroke”, the mortar must be applied before the chassis is dry. Don't be.
In these methods, due to the balance between the construction speed and the drying of the ground treatment, it has been a problem that the construction tends to lack uniformity.
こうした不具合をなくすため、従来よりポリマーエマルションを吸水防止プライマーとして予め躯体に塗布・乾燥させ、皮膜化することにより、続いて施工するモルタルのドライアウトを防止することが行われている。一般に使用されているプライマーとしては、エチレン-酢酸ビニル系、スチレン-アクリル系、オールアクリル系などがある。
しかしながら、特に乾燥条件下、或いは高温条件下においては、水分蒸発が早いためドライアウトによる硬化不良や付着強度の低下が生じ易く、十分な耐久性を有するコンクリート構造物が得られないという問題があった。
In order to eliminate such problems, conventionally, a polymer emulsion is applied to a casing in advance as a water absorption preventing primer and dried to form a film, thereby preventing the mortar from being subsequently dried out. Commonly used primers include ethylene-vinyl acetate, styrene-acrylic, and all acrylic.
However, especially under dry or high-temperature conditions, moisture evaporation is fast, so that there is a problem that a hardened concrete due to dryout and a decrease in adhesion strength are likely to occur, and a concrete structure having sufficient durability cannot be obtained. It was.
本発明の目的は、厳しい環境下においてもセメント組成物の水分散逸を防止し、ドライアウトによる硬化不良や付着不良を生ずることのないポリマーセメント組成物の施工方法及び該施工により得られるセメント硬化体を提供することにある。 SUMMARY OF THE INVENTION An object of the present invention is to provide a method for applying a polymer cement composition that prevents water dispersion of the cement composition even under harsh environments and does not cause hardening failure or adhesion failure due to dryout, and a cement hardened body obtained by the construction. Is to provide.
本発明者は、コンクリート躯体とポリマーセメント組成物との接着に用いるプライマーについて種々検討したところ、主としてポリマーセメント組成物に含まれるポリマーエマルションと同じ樹脂成分のエマルションが、プライマーとして用いられていることが判明した。すなわち、プライマーに用いるエマルションとセメント組成物に用いるエマルションは、プライマー層とセメント組成物との接着性や硬化性、施工性等の点から同じイオン性基を有するものを用いるのが好ましいと考えられていた。そこでさらに検討したところ、全く意外にも、プライマーに用いるエマルションとして、セメント組成物に用いるエマルションと逆性のイオン性基を有するエマルションを用いれば、モルタルからの水分逸脱を防止し、ドライアウトによる硬化不良やひび割れを防止でき、かつ付着強度にも優れることを見出し、本発明を完成した。 The inventor conducted various studies on the primer used for adhesion between the concrete frame and the polymer cement composition. As a result, it was found that an emulsion of the same resin component as the polymer emulsion contained in the polymer cement composition was mainly used as the primer. found. That is, it is considered that the emulsion used for the primer and the emulsion used for the cement composition are preferably those having the same ionic group from the viewpoint of adhesion between the primer layer and the cement composition, curability, workability, etc. It was. Thus, further investigation revealed that, surprisingly, if an emulsion having an ionic group opposite to the emulsion used for the cement composition is used as the emulsion used for the primer, it prevents moisture from mortar and cures by dryout. It was found that defects and cracks can be prevented and adhesion strength is excellent, and the present invention has been completed.
すなわち、本発明は、カチオン性ポリマーエマルションからなる塗布層の表面に、アニオン性及び／又はノニオン性ポリマーエマルションを含有するポリマーセメント組成物の硬化層を設けてなることを特徴とするセメント硬化体を提供するものである。
また、本発明は、アニオン性及び／又はノニオン性ポリマーエマルションからなる塗布層の表面に、カチオン性ポリマーエマルションを含有するポリマーセメント組成物の硬化層を設けてなることを特徴とするセメント硬化体を提供するものである。
また、本発明は、コンクリート躯体に予めカチオン性ポリマーエマルションを塗布、乾燥した後、アニオン性及び／又はノニオン性ポリマーエマルションを含有するポリマーセメント組成物を施工することを特徴とするポリマーセメント組成物の施工方法を提供するものである。
さらにまた、本発明は、コンクリート躯体に予めアニオン性及び／又はノニオン性ポリマーエマルションを塗布、乾燥した後、カチオン性ポリマーエマルションを含有するポリマーセメント組成物を施工することを特徴とするポリマーセメント組成物の施工方法を提供するものである。
That is, the present invention provides a hardened cement body comprising a hardened layer of a polymer cement composition containing an anionic and / or nonionic polymer emulsion on the surface of a coating layer made of a cationic polymer emulsion. It is to provide.
The present invention also provides a hardened cement body comprising a hardened layer of a polymer cement composition containing a cationic polymer emulsion on the surface of a coating layer made of an anionic and / or nonionic polymer emulsion. It is to provide.
In addition, the present invention provides a polymer cement composition characterized by applying a polymer cement composition containing an anionic and / or nonionic polymer emulsion after applying a cationic polymer emulsion to a concrete body in advance and drying it. A construction method is provided.
Furthermore, the present invention relates to a polymer cement composition comprising applying a polymer cement composition containing a cationic polymer emulsion after applying an anionic and / or nonionic polymer emulsion to a concrete body in advance and then drying the emulsion. The construction method is provided.
本発明によれば、セメント組成物の水分がコンクリート躯体に吸収されるのを防止できるため、高温条件下等の厳しい環境下においても、ドライアウトによる硬化不良やひび割れを生ずることのない安定した付着性能（引張り強度）を有するセメント硬化体を得ることができる。 According to the present invention, the moisture of the cement composition can be prevented from being absorbed by the concrete frame, and therefore, stable adhesion without causing poor curing or cracking due to dry-out even under severe conditions such as high temperature conditions. A hardened cement body having performance (tensile strength) can be obtained.
本発明においては、先ずコンクリート躯体にポリマーエマルションからなる吸水防止プライマーを塗布する。該プライマーを塗布するコンクリート躯体としては、特に限定されず、土木用、建築用などのモルタル・コンクリート構造物を挙げることができる。 In the present invention, first, a water absorption preventing primer made of a polymer emulsion is applied to a concrete frame. The concrete frame to which the primer is applied is not particularly limited, and examples thereof include mortar / concrete structures for civil engineering and construction.
本発明で用いるポリマーエマルションは、有機高分子ポリマーが乳化して水系溶媒中に均一に分散した水溶液で、乾燥後ポリマー皮膜を形成し得るものである。ポリマーエマルションは、カチオン性、アニオン性、ノニオン性又は両性のいずれでもよい。
ポリマーエマルションとしては、例えばポリ酢酸ビニル、エチレン−酢酸ビニル共重合体、エチレン−酢酸ビニル−塩化ビニル共重合体、酢酸ビニル−アクリル酸エステル共重合体、変性酢酸ビニル、酢酸ビニル−ベオバ共重合体等の酢酸ビニル系樹脂；ポリアクリル酸エステル、ポリメタクリル酸エステル、アクリル酸エステル−スチレン共重合体等のアクリル系樹脂；ポリエチレン、及びポリプロピレン等のポリオレフィン系樹脂、不飽和ポリエステル系樹脂、ポリウレタン系樹脂、エポキシ系樹脂等の合成樹脂エマルション；天然ゴム、スチレン−ブタジエン共重合体、クロロプレンゴム、アクリロニトリル−ブタジエン共重合体、メチルメタクリレート−ブタジエン共重合体等のゴムラテックスのエマルション；アスファルト、ゴムアスファルト、パラフィン等の瀝青質等のエマルションが挙げられ、これらを併用してもよい。また、粉末状にした再乳化型粉末樹脂を用いてもよい。本発明において、ポリマーは得られるエマルションの性質に応じて選択される。
The polymer emulsion used in the present invention is an aqueous solution in which an organic polymer is emulsified and uniformly dispersed in an aqueous solvent, and can form a polymer film after drying. The polymer emulsion may be cationic, anionic, nonionic or amphoteric.
Examples of the polymer emulsion include polyvinyl acetate, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, vinyl acetate-acrylic ester copolymer, modified vinyl acetate, vinyl acetate-veova copolymer. Vinyl acetate resins such as: acrylic resins such as polyacrylates, polymethacrylates, acrylate-styrene copolymers; polyolefin resins such as polyethylene and polypropylene, unsaturated polyester resins, polyurethane resins Synthetic resin emulsions such as epoxy resins; emulsions of rubber latex such as natural rubber, styrene-butadiene copolymer, chloroprene rubber, acrylonitrile-butadiene copolymer, methyl methacrylate-butadiene copolymer; asphalt, rubber Asphalt, include emulsion bituminous such as paraffin or the like may be used in combination. Moreover, you may use the re-emulsification type powder resin made into the powder form. In the present invention, the polymer is selected according to the properties of the resulting emulsion.
これらのうち、アクリル系樹脂エマルションを用いるのが吸水防止性の点から好ましい。アクリル樹脂系エマルションとしては、例えばアクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、ヒドロキシエチルアクリレート、Ｎ，Ｎ’−ジメチルアミノエチルアクリレート等のアクリル酸エステル；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸２−エチルヘキシル、ヒドロキシエチルメタクリレート、Ｎ,Ｎ'−ジメチルアミノエチルメタクリレート等のメタクリル酸エステル；（メタ）アクリルアミド等のアミド系アクリレート等の（メタ）アクリル酸又はその誘導体より選択されるモノマーからなる重合体、共重合体が挙げられる。また、さらにこれらのモノマーと共重合可能なスチレン、酢酸ビニル、塩化ビニリデンなどのビニル化合物と共重合させたものを用いることもできる。 Of these, it is preferable to use an acrylic resin emulsion from the viewpoint of water absorption prevention. Examples of the acrylic resin emulsion include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, N, N′-dimethylaminoethyl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate Methacrylic acid esters such as 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, N, N′-dimethylaminoethyl methacrylate; monomers selected from (meth) acrylic acid such as amide acrylates such as (meth) acrylamide or derivatives thereof And polymers and copolymers. Further, those copolymerized with vinyl compounds such as styrene, vinyl acetate, vinylidene chloride and the like that can be copolymerized with these monomers can also be used.
エマルション中に含まれるポリマー成分のガラス転移温度は特に制限されないが、例えば−７０〜３０℃、好ましくは−５０〜１０℃である。また、吸水防止プライマーのエマルション中に含まれるポリマーの固形分は、５〜５０質量％が好ましく、特に５〜３５質量％が好ましい。
エマルションの保存濃度は、保存安定性の点から、ポリマー固形分として１０〜６０重量％が好ましく、特に２０〜５５質量％が好ましい。
The glass transition temperature of the polymer component contained in the emulsion is not particularly limited, but is, for example, −70 to 30 ° C., preferably −50 to 10 ° C. Moreover, 5-50 mass% is preferable and, as for the solid content of the polymer contained in the emulsion of a water absorption prevention primer, 5-35 mass% is especially preferable.
The storage concentration of the emulsion is preferably 10 to 60% by weight, particularly preferably 20 to 55% by weight as the polymer solid content from the viewpoint of storage stability.
ポリマーエマルションは、公知の製造方法により得られるものを用いることができ、例えば、乳化剤の存在下に、重合開始剤を用いて、水又は含水溶媒中で合成樹脂の原料となる重合性モノマーを乳化重合する方法などにより製造することができる。乳化剤としては、カチオン性、アニオン性、ノニオン性又は両性の界面活性剤、ポリビニルアルコールなどの保護コロイドが挙げられる。 As the polymer emulsion, one obtained by a known production method can be used. For example, in the presence of an emulsifier, a polymerization initiator is used to emulsify a polymerizable monomer that is a raw material for a synthetic resin in water or a hydrous solvent. It can be produced by a polymerization method or the like. Examples of emulsifiers include cationic, anionic, nonionic or amphoteric surfactants and protective colloids such as polyvinyl alcohol.
カチオン性界面活性剤としては、例えば、ドデシルアンモニウムクロライド、ココナットアミンアセテート、ステアリルアミンアセテート等のアルキルアミンの塩；ラウリルトリメチルアンモニウムクロライド、ステアリルトリメチルアンモニウムクロライド、セチルトリメチルアンモニウムクロライド等の第４級アンモニウム塩等が挙げられる。 Examples of the cationic surfactant include salts of alkylamines such as dodecyl ammonium chloride, coconut amine acetate and stearylamine acetate; quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and cetyltrimethylammonium chloride. Etc.
アニオン性界面活性剤としては、例えば、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム等のアルキル硫酸エステル塩類；ドデシルベンゼンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸アンモニウム、ドデシルナフタレンスルホン酸ナトリウム等のアルキルアリールスルホン酸塩類；ポリオキシエチレンアルキルスルホン酸塩、ポリオキシエチレンアルキルアリールスルホン酸塩、ジアルキルスルホコハク酸塩、アリールスルホン酸ホルマリン縮合物、ドデシル酸アンモニウム、ステアリン酸ナトリウム、オレイン酸カリウム、ヒマシ油カリ石ケン等の脂肪酸塩等が挙げられる。 Examples of the anionic surfactant include alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylaryl sulfonates such as sodium dodecylbenzenesulfonate, ammonium dodecylbenzenesulfonate, and sodium dodecylnaphthalenesulfonate; polyoxy Fatty acid salts such as ethylene alkyl sulfonate, polyoxyethylene alkyl aryl sulfonate, dialkyl sulfosuccinate, aryl sulfonate formalin condensate, ammonium dodecylate, sodium stearate, potassium oleate, castor oil potassium soap, etc. Can be mentioned.
ノニオン性界面活性剤としては、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、ポリエチレングリコールとポリプロピレングリコールの縮合物、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、脂肪酸モノグリセライド、ポリアミド、エチレンオキサイドと脂肪族アミンの縮合生成物等が挙げられる。 Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, condensate of polyethylene glycol and polypropylene glycol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, polyamide, and ethylene oxide. And a condensation product of an aliphatic amine and the like.
両性界面活性剤としては、例えば、ラウリルベタイン、ステアリルベタイン、ラウリルジメチルアミンオキサイド等のアルキルベタイン、アルキルアミンオキサイド型乳化剤等が挙げられる。 Examples of amphoteric surfactants include alkylbetaines such as lauryl betaine, stearyl betaine, lauryl dimethylamine oxide, and alkylamine oxide type emulsifiers.
ポリビニルアルコールとしては、完全けん化ポリビニルアルコール、部分けん化ポリビニルアルコール、ポリビニルアルコールの一部をカルボキシル基、スルフォニル基等で修飾したアニオン化ポリビニルアルコールなどが挙げられる。乳化力の点から、けん化率は ８５〜１００％、平均重合度は３００〜４０００が好ましい。 Examples of polyvinyl alcohol include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, and anionized polyvinyl alcohol obtained by modifying a part of polyvinyl alcohol with a carboxyl group, a sulfonyl group, or the like. From the viewpoint of emulsifying power, the saponification rate is preferably 85 to 100%, and the average degree of polymerization is preferably 300 to 4000.
重合開始剤としては、水又は含水溶媒中でラジカル重合できるものが好ましく、過酸化水素、過酢酸、過硫酸又はこれらのアンモニウム塩や硫酸塩等の水溶性の過酸化物やその塩などを挙げることができる。また、ベンゾイルパーオキサイド、ｔ−ブチルハイドロパーオキサイド、２，２'−アゾビスイソブチルニトリルなどの有機過酸化物、メタ亜硫酸ナトリウムやピロ亜硫酸ナトリウムなどの還元剤を併用することができる。
重合開始剤の使用量は、エマルションが製造できる範囲であれば適宜選択できる。
As the polymerization initiator, those capable of radical polymerization in water or a hydrous solvent are preferable, and examples thereof include hydrogen peroxide, peracetic acid, persulfuric acid, water-soluble peroxides such as ammonium salts and sulfates thereof, and salts thereof. be able to. Further, organic peroxides such as benzoyl peroxide, t-butyl hydroperoxide, 2,2′-azobisisobutylnitrile, and reducing agents such as sodium metasulfite and sodium pyrosulfite can be used in combination.
The amount of the polymerization initiator used can be appropriately selected as long as the emulsion can be produced.
ポリマーエマルションを塗布する方法としては、例えば刷毛塗り、ローラー塗り等の塗布手段や、噴霧、吹き付け等の散布等、通常の方法が挙げられる。また、ポリマーエマルションを塗布後、その塗布表面を鏝押えにより均すことで、塗膜の強度向上を図ることができる。鏝押えは、少量の水をかけながら行ってもよく、また水の代わりに塗膜養生材をかけながら行ってもよい。液体をかけながら鏝押さえをすることにより、鏝が滑り、表面にセメントペーストが浮き出て、きれいに表面を仕上げることができる。 Examples of the method for applying the polymer emulsion include usual methods such as application means such as brushing and roller coating, and spraying and spraying. Moreover, after apply | coating a polymer emulsion, the intensity | strength improvement of a coating film can be aimed at by equalizing the application | coating surface with a heel presser. The presser foot may be performed while applying a small amount of water, or may be performed while applying a film curing material instead of water. By holding the heel while applying the liquid, the heel slips and the cement paste rises to the surface, so that the surface can be finished cleanly.
ポリマーエマルションの塗布量は、固形分換算で５〜５０ｇ／ｍ2が好ましく、特に１０〜３０ｇ／ｍ2が好ましい。塗布量が少なすぎると十分な効果が得られず、他方塗布量が多すぎるとその上に施工するポリマーセメント組成物の剥離を生じ易い。 The coating amount of the polymer emulsion is preferably 5 to 50 g / m 2 , particularly 10 to 30 g / m 2 in terms of solid content. If the coating amount is too small, a sufficient effect cannot be obtained. On the other hand, if the coating amount is too large, peeling of the polymer cement composition applied thereon is likely to occur.
吸水防止プライマーは、珪酸塩及び／又はコロイダルシリカを配合することにより、さらに吸水防止性が向上する。
本発明で用いる珪酸塩としては、例えば珪酸リチウム、珪酸ナトリウム、珪酸カリウム等の珪酸アルカリ金属塩；珪酸マグネシウム、珪酸カルシウムなどの珪酸アルカリ土類金属塩等が挙げられ、特に珪酸アルカリ金属塩が好ましい。
吸水防止プライマーに珪酸塩を配合する場合、ポリマーエマルションとしてカチオン性以外のエマルションを用いるのが保存安定性の点から好ましい。
The water absorption preventing primer is further improved in water absorption preventing property by blending silicate and / or colloidal silica.
Examples of the silicate used in the present invention include alkali metal silicates such as lithium silicate, sodium silicate and potassium silicate; alkaline earth metal silicates such as magnesium silicate and calcium silicate, and alkali metal silicate is particularly preferable. .
When a silicate is blended in the water absorption preventing primer, it is preferable from the viewpoint of storage stability to use a non-cationic emulsion as the polymer emulsion.
コロイダルシリカは、平均粒子径１〜５０ｎｍ、好ましくは５〜３０ｎｍで、酸性又はアルカリ性の水分散液、あるいはアルコール、ケトン、エステル等の有機溶媒中に分散させたものを用いることができる。粒子径が小さすぎると反応性が高くエマルションとの混和性が悪くなり、他方大きすぎると十分な効果が得られにくい。
吸水防止プライマーにコロイダルシリカを配合する場合、ポリマーエマルションとしてカチオン性ポリマーエマルションを用いる場合は、例えばアルミナコーティングしたもの等、粒子の表面が正に荷電したものを用いるのが好ましく、ポリマーエマルションとしてアニオン性ポリマーエマルションを用いる場合は、負に荷電し、アルカリ性の水分散液に分散させたものを用いるのが好ましい。
Colloidal silica having an average particle diameter of 1 to 50 nm, preferably 5 to 30 nm, and dispersed in an acidic or alkaline aqueous dispersion or an organic solvent such as alcohol, ketone and ester can be used. When the particle size is too small, the reactivity is high and the miscibility with the emulsion is deteriorated. On the other hand, when the particle size is too large, a sufficient effect is hardly obtained.
When colloidal silica is blended in the water absorption preventing primer, when a cationic polymer emulsion is used as the polymer emulsion, it is preferable to use a positively charged particle surface such as an alumina coating, and an anionic polymer emulsion. In the case of using a polymer emulsion, it is preferable to use a negatively charged one dispersed in an alkaline aqueous dispersion.
プライマー中の珪酸塩の固形分含有量は、全固形分中５〜４０質量％が好ましく、コロイダルシリカの固形分含有量は、全固形分中５〜４０質量％が好ましい。珪酸塩及び／又はコロイダルシリカの配合量が少なすぎると十分な効果が得られず、他方配合量が多すぎると粘性が大きくなるため作業性に劣る。また、珪酸塩及び／又はコロイダルシリカの塗布量は、固形分換算でそれぞれ５〜５０ｇ／ｍ2とするのが好ましい。塗布量が少なすぎると十分な効果が得られず、他方塗布量が多すぎるとその上に施工するポリマーセメント組成物の剥離を生じ易い。 The solid content of the silicate in the primer is preferably 5 to 40% by mass in the total solid content, and the solid content of the colloidal silica is preferably 5 to 40% by mass in the total solid content. If the blending amount of silicate and / or colloidal silica is too small, a sufficient effect cannot be obtained. On the other hand, if the blending amount is too large, the viscosity increases, resulting in poor workability. Moreover, it is preferable that the application quantity of a silicate and / or colloidal silica shall be 5-50 g / m < 2 >, respectively in conversion of solid content. If the coating amount is too small, a sufficient effect cannot be obtained. On the other hand, if the coating amount is too large, peeling of the polymer cement composition applied thereon is likely to occur.
本発明においては、コンクリート躯体にポリマーエマルションからなるプライマーを塗布し、これを乾燥させた後、その塗布表面にポリマーセメント組成物を施工するが、ここで施工するポリマーセメント組成物は、塗布したポリマーエマルションと逆性のポリマーエマルションを有する組成物であることが必要である。すなわち、塗布するポリマーエマルションがカチオン性である場合、組成物中のポリマーエマルションはアニオン性及び／又はノニオン性であることが必要であり、他方塗布するポリマーエマルションがアニオン性及び／又はノニオン性である場合、組成物中のポリマーエマルションはカチオン性であることが必要である。
ポリマーエマルションがカチオン性であるとは、ポリマーエマルションがそのポリマー又は乳化剤の分子内に３級アミノ基、第４級アンモニウム塩基等のカチオン性基を有していることをいう。また、ポリマーエマルションがアニオン性であるとは、ポリマーエマルションがそのポリマー又は乳化剤の分子内にカルボキシル基、スルホ基、リン酸基又はそれらの塩等のアニオン性基を有していることをいい、ポリマーエマルションがノニオン性であるとは、ポリマーエマルションがそのポリマー又は乳化剤の分子内にイオン性基を有していないことをいう。ポリマーエマルションが有するカチオン性基、アニオン性基は、モノマー由来でもよく、界面活性剤（乳化剤）由来でもよい。
ポリマーエマルションの性質は、使用するモノマーの種類や界面活性剤の種類、それらの使用量により決めることができる。
In the present invention, a primer made of a polymer emulsion is applied to a concrete body, and after drying, a polymer cement composition is applied to the application surface. The polymer cement composition to be applied here is applied to the applied polymer. It is necessary that the composition has a polymer emulsion opposite to the emulsion. That is, when the polymer emulsion to be applied is cationic, the polymer emulsion in the composition needs to be anionic and / or nonionic, while the polymer emulsion to be applied is anionic and / or nonionic. In some cases, the polymer emulsion in the composition needs to be cationic.
The polymer emulsion being cationic means that the polymer emulsion has a cationic group such as a tertiary amino group or a quaternary ammonium base in the molecule of the polymer or emulsifier. In addition, the polymer emulsion being anionic means that the polymer emulsion has an anionic group such as a carboxyl group, a sulfo group, a phosphoric acid group or a salt thereof in the molecule of the polymer or emulsifier, The polymer emulsion being nonionic means that the polymer emulsion does not have an ionic group in the molecule of the polymer or emulsifier. The cationic group and the anionic group of the polymer emulsion may be derived from a monomer or a surfactant (emulsifier).
The properties of the polymer emulsion can be determined by the type of monomer used, the type of surfactant, and the amount used.
本発明において、ポリマーセメント組成物とは、基本的にはセメント、骨材及びポリマーエマルションを混合してなるものである。
本発明で用いるセメントは、水硬化性セメントであれば特に限定されず、例えば普通、早強、超早強、中庸熱、低熱、耐硫酸塩、白色等の各種ポルトランドセメント；高炉スラグ、フライアッシュ、シリカフューム等との混合セメント；アルミナセメント、半水石膏、ドロマイトプラスター等が挙げられ、これらを併用してもよい。
In the present invention, the polymer cement composition is basically a mixture of cement, aggregate and polymer emulsion.
The cement used in the present invention is not particularly limited as long as it is a water-curable cement. For example, various portland cements such as normal, early strength, very early strength, moderate heat, low heat, sulfate resistance, white, etc .; blast furnace slag, fly ash , Mixed cement with silica fume and the like; alumina cement, hemihydrate gypsum, dolomite plaster and the like may be used, and these may be used in combination.
本発明で用いる骨材としては、一般にモルタルやコンクリートに使用されている骨材であれば特に限定されず、例えば珪砂、砕砂、砕石、陸砂、陸砂利、川砂、川砂利、人工骨材、貝殻、スラグ骨材、石粉等が挙げられ、これらを併用してもよい。
ポリマーセメント組成物中の骨材の配合量は、セメント１００重量部に対し、０〜６００質量部が好ましく、特に１０〜５００質量部が好ましい。
The aggregate used in the present invention is not particularly limited as long as it is generally used in mortar and concrete, for example, silica sand, crushed sand, crushed stone, land sand, land gravel, river sand, river gravel, artificial aggregate, Shells, slag aggregates, stone powder and the like may be mentioned, and these may be used in combination.
The amount of aggregate in the polymer cement composition is preferably 0 to 600 parts by weight, particularly preferably 10 to 500 parts by weight, with respect to 100 parts by weight of cement.
ポリマーセメント組成物に用いるポリマーエマルションとしては、前記と同様のものを挙げることができる。エマルション中に含まれるポリマーの固形分は、接着性・中性化抑制性・乾燥収縮低下作用等への有効性、作業性、硬化時間、強度発現性などの点から５〜５０質量％、好ましくは１０〜４５質量％である。 Examples of the polymer emulsion used in the polymer cement composition include the same as those described above. The solid content of the polymer contained in the emulsion is preferably 5 to 50% by mass from the viewpoints of adhesiveness, neutralization suppression, drying shrinkage lowering effect, workability, curing time, strength development, etc. Is 10 to 45% by mass.
ポリマーセメント組成物には、セメント、骨材及びポリマーエマルションの他に、例えば消泡剤、収縮低減剤、膨張材、各種スラグ、各種ポゾラン、増粘剤、繊維、粘土鉱物、減水剤、流動化剤、硬化遅延剤、硬化促進剤等を混合してもよい。 In addition to cement, aggregate and polymer emulsion, polymer cement compositions include, for example, antifoaming agents, shrinkage reducing agents, expanding materials, various slags, various pozzolans, thickeners, fibers, clay minerals, water reducing agents, fluidization An agent, a curing retarder, a curing accelerator and the like may be mixed.
ポリマーセメント組成物をコンクリート躯体に施工する方法としては、例えば鏝塗り等の塗布や、吹き付け等の散布、流し込み、注入等の通常の方法が挙げられる。ポリマーセメント組成物を乾燥、硬化させた後、更に同じ操作を繰り返し複数の硬化層を形成させてもよい。 Examples of the method for applying the polymer cement composition to the concrete frame include normal methods such as coating such as plastering, spraying and spraying, pouring, and pouring. After the polymer cement composition is dried and cured, the same operation may be repeated to form a plurality of cured layers.
このように、コンクリート躯体にポリマーエマルションを塗布し、乾燥させた後、その塗布表面にポリマーセメント組成物を施工することによりセメント硬化体が得られる。ポリマーセメント組成物に含まれるエマルションと逆性のエマルションからなるプライマーを予め塗布することで、セメントからの吸水を防止できるため、該セメント硬化体は、強風条件下や高温乾燥条件下などの厳しい環境下においてもドライアウトが生じず、また付着強度に優れることから、これをコンクリート躯体に積層することにより、ひび割れのない耐久性に優れたコンクリート躯体を得ることができる。 Thus, after apply | coating a polymer emulsion to a concrete frame and making it dry, a cement hardened body is obtained by constructing the polymer cement composition on the application | coating surface. By applying a primer composed of an emulsion opposite to the emulsion contained in the polymer cement composition in advance, it is possible to prevent water absorption from the cement, so that the hardened cement body is used in severe environments such as strong wind conditions and high temperature drying conditions. Since no dry-out occurs at the bottom and the adhesion strength is excellent, by laminating it on the concrete frame, a concrete frame excellent in durability without cracking can be obtained.
以下、本発明について実施例をあげて具体的に説明するが、本発明はこれらによって何等限定されるものではない。
＜使用材料＞
ポリマーエマルション：ガンツ化成社 ウルトラゾール CMX-235（カチオン性、オールアクリル）、ニチゴー・モビニール社 モビニール7700（アニオン性、保護コロイドオールアクリル）、ニチゴー・モビニール社 モビニール7800（カチオン性、保護コロイドオールアクリル）、ニチゴー・モビニール社 モビニールDM765（アニオン性、スチレンアクリル）、旭化成ケミカルズ社 A1500（アニオン性、スチレンアクリル）、太平洋マテリアル社 CX-B（アニオン性、SBR）
粉末樹脂：日本NSC社 TITAN 8100（カチオン性、オールアクリル）、ワッカー社 LL512（アニオン性、スチレンアクリル）、ニチゴー・モビニール社 DM-2072P（アニオン性、酢酸ビニル・ベオバ・アクリル）、ニチゴー・モビニール社 LDM-7000P（ノニオン性、オールアクリル）
セメント：太平洋セメント社普通ポルトランドセメント
珪砂： 三河産珪砂FM 1.7
珪酸リチウム：日本化学工業社 珪酸リチウム35
珪酸ナトリウム：日本化学工業社 Ｊ珪酸ソーダ1号
コロイダルシリカ：デュポン社 ルドックスAM
デュポン社 ルドックスLS
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
<Materials used>
Polymer Emulsion: Gantz Kasei Ultrasol CMX-235 (cationic, all acrylic), Nichigo Mobile Co., Ltd. Movinyl 7700 (anionic, protective colloid all acrylic), Nichigo Mobile Co., Ltd. Mobile 7800 (cationic, protective colloid all acrylic) , Nichigo Movinyl, Inc. Movinyl DM765 (anionic, styrene acrylic), Asahi Kasei Chemicals A1500 (anionic, styrene acrylic), Pacific Materials CX-B (anionic, SBR)
Powder resin: Nippon NSC TITAN 8100 (cationic, all acrylic), Wacker LL512 (anionic, styrene acrylic), Nichigo Mobile, Inc. DM-2072P (anionic, vinyl acetate, veova, acrylic), Nichigo Mobile, Ltd. LDM-7000P (nonionic, all acrylic)
Cement: Taiheiyo Cement Normal Portland cement quartz sand: Mikawa quartz sand FM 1.7
Lithium silicate: Nippon Chemical Industry Co., Ltd. Lithium silicate 35
Sodium silicate: Nippon Chemical Industry Co., Ltd. J Sodium silicate No. 1 colloidal silica: DuPont Ludox AM
DuPont Ludox LS
＜乾燥条件下施工における付着試験＞
コンクリート歩道板（300×300×60mm）上に表１に示す吸水防止プライマーをそれぞれ塗布した後、35℃、相対湿度40％条件下で表１に示す各種ポリマーセメントモルタルを塗付けした。塗付け後、24時間同条件にて養生を行い、20℃相対湿度60％に移動し、試験材齢まで更に養生を行った。
試験前に剥落防止工施工面に40×40mmの正方形に、コンクリート歩道板表面に達するまでダイヤモンドカッターにて切込みを入れ、同サイズの鋼製アタッチメントをエポキシ接着材にて貼付け、硬化後、建研式接着力試験器で施工面に対し垂直方向に引張り、付着強度を測定した。付着強度1.8N/mm2以上を合格とした。また、「ひび割れ」の有無を目視により判定した。結果を表１〜表３に示す。
<Adhesion test in construction under dry conditions>
After applying the water absorption preventing primer shown in Table 1 on a concrete sidewalk board (300 × 300 × 60 mm), various polymer cement mortars shown in Table 1 were applied at 35 ° C. and a relative humidity of 40%. After the application, curing was carried out under the same conditions for 24 hours, the temperature was shifted to 20 ° C. and 60% relative humidity, and further curing was performed until the test material age.
Before the test, make a 40 x 40 mm square on the construction surface to prevent peeling, and cut with a diamond cutter until it reaches the surface of the concrete sidewalk board. Stick the steel attachment of the same size with epoxy adhesive, and after curing, Kenken The adhesion strength was measured by pulling in the direction perpendicular to the construction surface with a type adhesion tester. An adhesion strength of 1.8 N / mm 2 or higher was accepted. In addition, the presence or absence of “cracks” was visually determined. The results are shown in Tables 1 to 3.
表１及び３の結果から、ポリマーセメント組成物に含まれるエマルションと逆性のイオン性基を有するエマルションを予め塗布すれば、高温乾燥条件下においてもひび割れが生じず、また硬化不良を起こすことなく、付着強度も1.8N/mm2以上と優れたセメント硬化体が得られることが確認できた。また、表２の結果から、プライマーに珪酸塩及び／又はコロイダルシリカを配合することで、より安定した付着性能を有するセメント硬化体が得られることが確認できた。 From the results of Tables 1 and 3, if an emulsion having an ionic group that is opposite to the emulsion contained in the polymer cement composition is applied in advance, cracking does not occur even under high-temperature drying conditions, and curing does not occur. It was confirmed that an excellent cement cured body with an adhesion strength of 1.8 N / mm 2 or more was obtained. Moreover, it has confirmed from the result of Table 2 that the cement hardened body which has more stable adhesion performance is obtained by mix | blending a silicate and / or colloidal silica with a primer.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013217031A (en) * | 2012-04-05 | 2013-10-24 | Aica Kogyo Co Ltd | Substrate concrete surface adjustment method and substrate concrete floor construction method applying the same |
| JP2015078098A (en) * | 2013-10-18 | 2015-04-23 | 太平洋マテリアル株式会社 | Primer for water supply facility |
| US20170158570A1 (en) * | 2008-02-05 | 2017-06-08 | Arris Technologies, LLC | Methods for finishing concrete to provide a glossy surface |
| JP2020033509A (en) * | 2018-08-31 | 2020-03-05 | 株式会社エフコンサルタント | Aqueous coating material |
| JP2023149462A (en) * | 2022-03-31 | 2023-10-13 | デンカ株式会社 | Cross section repairing structure of reinforced concrete structure and cross section repairing method of reinforced concrete structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60865A (en) * | 1983-06-20 | 1985-01-05 | Toagosei Chem Ind Co Ltd | Waterproofing method |
| JPH0316980A (en) * | 1989-06-15 | 1991-01-24 | Sumitomo Cement Co Ltd | Concrete deterioration-preventive construction |
| JP2000016886A (en) * | 1998-06-30 | 2000-01-18 | Toagosei Co Ltd | Technique for protecting concrete structure |
-
2006
- 2006-12-22 JP JP2006345729A patent/JP5066359B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60865A (en) * | 1983-06-20 | 1985-01-05 | Toagosei Chem Ind Co Ltd | Waterproofing method |
| JPH0316980A (en) * | 1989-06-15 | 1991-01-24 | Sumitomo Cement Co Ltd | Concrete deterioration-preventive construction |
| JP2000016886A (en) * | 1998-06-30 | 2000-01-18 | Toagosei Co Ltd | Technique for protecting concrete structure |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170158570A1 (en) * | 2008-02-05 | 2017-06-08 | Arris Technologies, LLC | Methods for finishing concrete to provide a glossy surface |
| JP2013217031A (en) * | 2012-04-05 | 2013-10-24 | Aica Kogyo Co Ltd | Substrate concrete surface adjustment method and substrate concrete floor construction method applying the same |
| JP2015078098A (en) * | 2013-10-18 | 2015-04-23 | 太平洋マテリアル株式会社 | Primer for water supply facility |
| JP2020033509A (en) * | 2018-08-31 | 2020-03-05 | 株式会社エフコンサルタント | Aqueous coating material |
| JP7011990B2 (en) | 2018-08-31 | 2022-01-27 | 株式会社エフコンサルタント | Aqueous dressing |
| JP2023149462A (en) * | 2022-03-31 | 2023-10-13 | デンカ株式会社 | Cross section repairing structure of reinforced concrete structure and cross section repairing method of reinforced concrete structure |
| JP7443410B2 (en) | 2022-03-31 | 2024-03-05 | デンカ株式会社 | Cross-sectional repair structure of reinforced concrete structure and cross-sectional repair method of reinforced concrete structure |
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