JP2011046574A - Spray material and spraying method using the same - Google Patents
Spray material and spraying method using the same Download PDFInfo
- Publication number
- JP2011046574A JP2011046574A JP2009198019A JP2009198019A JP2011046574A JP 2011046574 A JP2011046574 A JP 2011046574A JP 2009198019 A JP2009198019 A JP 2009198019A JP 2009198019 A JP2009198019 A JP 2009198019A JP 2011046574 A JP2011046574 A JP 2011046574A
- Authority
- JP
- Japan
- Prior art keywords
- alkali metal
- quaternary ammonium
- meth
- cement
- spray material
- 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
- 238000005507 spraying Methods 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 24
- 239000007921 spray Substances 0.000 title claims abstract description 15
- -1 quaternary ammonium salt compound Chemical class 0.000 claims abstract description 45
- 239000004568 cement Substances 0.000 claims abstract description 31
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000004567 concrete Substances 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 11
- 150000004760 silicates Chemical class 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 239000012615 aggregate Substances 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 28
- 239000000843 powder Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000011378 shotcrete Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 4
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 4
- 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 4
- 238000010276 construction Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 3
- 238000009415 formwork Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 238000009412 basement excavation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910052914 metal silicate Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- TVXNKQRAZONMHJ-UHFFFAOYSA-M (4-ethenylphenyl)methyl-trimethylazanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=C(C=C)C=C1 TVXNKQRAZONMHJ-UHFFFAOYSA-M 0.000 description 1
- JWTGRKUQJXIWCV-UHFFFAOYSA-N 1,2,3-trihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(O)C(O)CO JWTGRKUQJXIWCV-UHFFFAOYSA-N 0.000 description 1
- NQUXRXBRYDZZDL-UHFFFAOYSA-N 1-(2-prop-2-enoyloxyethyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCOC(=O)C=C)C(O)=O NQUXRXBRYDZZDL-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- NKVCQMYWYHDOOF-UHFFFAOYSA-N 1-phenoxyethane-1,2-diol Chemical compound OCC(O)OC1=CC=CC=C1 NKVCQMYWYHDOOF-UHFFFAOYSA-N 0.000 description 1
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-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
- SHJIJMBTDZCOFE-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-methoxyethanol Chemical compound COC(O)COCCOCCOCCO SHJIJMBTDZCOFE-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QENRKQYUEGJNNZ-UHFFFAOYSA-N 2-methyl-1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(C)C(S(O)(=O)=O)NC(=O)C=C QENRKQYUEGJNNZ-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- UXTGJIIBLZIQPK-UHFFFAOYSA-N 3-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(CCOC(=O)C=C)=C1C(O)=O UXTGJIIBLZIQPK-UHFFFAOYSA-N 0.000 description 1
- IITUOFIPZOFBRF-UHFFFAOYSA-M 4-ethenyl-1-methylpyridin-1-ium;bromide Chemical compound [Br-].C[N+]1=CC=C(C=C)C=C1 IITUOFIPZOFBRF-UHFFFAOYSA-M 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 1
- 235000019738 Limestone Nutrition 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 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
- 239000011707 mineral Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000004056 waste incineration Methods 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
- 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
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- Inorganic Chemistry (AREA)
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Abstract
Description
本発明は、主に、土木・建築業界で使用される吹付け材料及びそれを用いた吹付け工法に関する。 The present invention mainly relates to a spraying material used in the civil engineering and construction industry and a spraying method using the same.
トンネル掘削等の露出した地山の崩落を防止するために、急結剤をコンクリートに配合した急結コンクリートの吹付工法が行われている（特許文献１参照）。この工法は、通常、掘削工事現場に設置した、セメント、骨材、及び水の計量混合プラントで吹付コンクリートを調製し、アジテータ車で運搬し、コンクリートポンプで圧送し、途中に設けた合流管で、他方から圧送した急結剤と混合し、急結性吹付コンクリートとして地山面に所定の厚みになるまで吹付ける工法である。 In order to prevent collapse of exposed ground such as tunnel excavation, a rapid setting concrete spraying method in which a quick setting agent is mixed with concrete is performed (see Patent Document 1). This method usually involves preparing sprayed concrete at a cement, aggregate and water metering and mixing plant installed at the excavation site, transporting it with an agitator car, pumping it with a concrete pump, and using a confluence pipe installed in the middle. It is a method of mixing with a rapid setting agent fed by pressure from the other side and spraying it to the ground surface as a quick setting sprayed concrete until a predetermined thickness is reached.
急結剤としては、カルシウムアルミネート、アルカリ金属アルミン酸塩とアルカリ金属炭酸塩等との混合物、並びに、カルシウムアルミネート、アルカリ金属アルミン酸塩、及びアルカリ金属炭酸塩等の混合物や、カルシウムアルミネートと３ＣａＯ・ＳｉＯ２との混合物等が知られている（特許文献２〜５参照）。 Accelerating agents include calcium aluminate, a mixture of alkali metal aluminate and alkali metal carbonate, etc., and a mixture of calcium aluminate, alkali metal aluminate, alkali metal carbonate, and calcium aluminate. And 3CaO · SiO 2 are known (see Patent Documents 2 to 5).
近年、粉じんの発生量を抑制することができる吹付け技術も開発されており、その使用量が増加している（特許文献６〜８参照）。この吹付け技術では、液状の急結剤を使用することが特徴であり、液状の急結剤の主成分としては、硫酸アルミニウムなどの水溶性のアルミニウム塩を含有することが特徴である。水溶性アルミニウム塩を含有する液状急結剤は、凝結性状が粉体急結剤に比べ悪く、特に水セメント比が大きい場合（例えば６０％）やセメント量が少ない場合（例えば４５０kg／m3以下）は、地山に吹き付けてもはく落が発生する場合があり、厚付けできないといった課題がある。また、数時間レベルの強度発現性も従来の粉体急結剤に比べ小さいといった課題もある。 In recent years, spraying techniques that can suppress the generation amount of dust have been developed, and the amount of use has increased (see Patent Documents 6 to 8). This spraying technique is characterized by using a liquid quick-setting agent, and is characterized by containing a water-soluble aluminum salt such as aluminum sulfate as the main component of the liquid quick-setting agent. Liquid quick-setting agents containing water-soluble aluminum salts have poor setting properties compared to powder quick-setting agents, especially when the water-cement ratio is large (eg 60%) or when the amount of cement is small (eg 450 kg / m 3 or less) ) May cause peeling even when sprayed on natural ground, and there is a problem that it cannot be thickened. In addition, there is also a problem that the strength development property at the level of several hours is smaller than that of the conventional powder quick-setting agent.
液状急結剤で硫酸アルミニウム以外に使用可能なものとして、ケイ酸アルカリ金属塩の水溶液が挙げられる（特許文献９参照）。ケイ酸アルカリ金属塩は、単独で使用しても急結作用を示す。粉体急結剤に比べ混合直後の瞬間的な強ばりが弱く、コンクリートでの吹付けも実施できるが、１０ｃｍ以上の厚付けを必要としないモルタルの吹付け施工などに向いている。また、ケイ酸アルカリ金属塩を添加した硬化体は収縮が大きく、湧水などの影響で硬化体から金属イオンとして溶出しやすいという課題もある。 An aqueous solution of an alkali metal silicate salt that can be used in addition to aluminum sulfate as a liquid setting agent (see Patent Document 9). Alkali metal silicates exhibit rapid setting action even when used alone. Compared to a powder quick-set agent, the momentary strength immediately after mixing is weak and can be sprayed with concrete, but it is suitable for mortar spraying that does not require thickening of 10 cm or more. Moreover, the hardened | cured material which added the alkali metal silicate salt has a big shrinkage | contraction, and there also exists a subject that it is easy to elute from a hardened | cured material as a metal ion under the influence of spring water etc.
ケイ酸アルカリ塩と四級アンモニウム塩に関する従来の技術としては、抗菌性を有する素材としての利用に関するものが知られている（特許文献１０参照）。この文献には、予めケイ酸アルカリ塩と四級アンモニウム塩を混合し反応させて得られる生成物をセメント系材料と混合して使用する技術が開示されている。 As a conventional technique related to an alkali silicate salt and a quaternary ammonium salt, one relating to utilization as an antibacterial material is known (see Patent Document 10). This document discloses a technique in which a product obtained by mixing and reacting an alkali silicate salt and a quaternary ammonium salt in advance is mixed with a cement-based material and used.
本発明は、セメントコンクリート側に四級アンモニウム塩化合物を添加し、ある特定のケイ酸アルカリ塩水溶液を急結剤としてセメントコンクリートに適用することで、粉体急結剤に匹敵する凝結性状および初期強度発現性が得られ、硬化体の収縮量やイオンの溶出量も抑制でき、さらに、粉じん発生量も少ない吹付け材料およびそれを用いた吹付け工法を提供する。 In the present invention, a quaternary ammonium salt compound is added to the cement concrete side, and a specific alkali silicate aqueous solution is applied to the cement concrete as a rapid setting agent. A spraying material that can exhibit strength development, can suppress the amount of shrinkage of a cured product and the amount of ions eluted, and has a small amount of dust generation, and a spraying method using the same.
すなわち、本発明は、（１）セメント、骨材、四級アンモニウム塩化合物を含有するセメントコンクリートと、アルカリ金属（Ｒ：Ｌｉ、Ｎａ、Ｋ）と珪素（Ｓｉ）の酸化物換算のモル比であるＳｉＯ２／Ｒ２Ｏが３．３〜４．５のケイ酸アルカリ金属塩を含有する急結剤とからなる吹付け材料であり、（２）四級アンモニウム塩化合物の重量平均分子量が、３０００〜５０００００の重合体である（１）の吹付け材料であり、（３）アルカリ金属ケイ酸塩が水溶液である（１）または（２）の吹付け材料であり、（４）（１）〜（３）のうちのいずれかの吹付け材料を用いる吹付け工法である。 That is, the present invention is (1) a cement concrete containing cement, aggregate, quaternary ammonium salt compound, and a molar ratio in terms of oxides of alkali metal (R: Li, Na, K) and silicon (Si). A spray material comprising a rapid setting agent containing an alkali metal silicate having a SiO 2 / R 2 O of 3.3 to 4.5, and (2) the weight average molecular weight of the quaternary ammonium salt compound is (1) spray material of 3000 to 500,000 polymer, (3) (1) or (2) spray material in which the alkali metal silicate is an aqueous solution, (4) (1) It is a spraying construction method using the spraying material in any one of-(3).
本発明の吹付け材料を用いることで、粉体急結剤に匹敵する凝結性状および初期強度発現性が得られ、硬化体の収縮量やイオンの溶出量も抑制でき、さらに、粉じん発生量も少ない吹付け施工が可能となる。 By using the spray material of the present invention, it is possible to obtain a coagulation property and initial strength expression comparable to a powder accelerating agent, it is possible to suppress the amount of shrinkage of the cured body and the amount of ion elution, and also the amount of dust generated Less spray construction is possible.
なお、本発明で使用する部、％は、特に規定しない限り質量基準である。 The parts and% used in the present invention are based on mass unless otherwise specified.
本発明で使用するセメントとは、普通、早強、超早強、低熱、および中庸熱などの各種ポルトランドセメントや、これらポルトランドセメントに、高炉スラグ、フライアッシュ、またはシリカを混合した各種混合セメント、ブレーン比表面積で２０００ｃｍ２/ｇを超える石灰石粉末や高炉徐冷スラグ微粉末などを混合したフィラーセメント、ならびに、都市ゴミ焼却灰や下水汚泥焼却灰を原料として製造された環境調和型セメント（エコセメント）などのポルトランドセメントが挙げられ、これらのうちの１種または２種以上が使用可能である。 The cement used in the present invention is usually various Portland cements such as early strength, super early strength, low heat, and moderate heat, and various mixed cements obtained by mixing these Portland cements with blast furnace slag, fly ash, or silica, Eco-cement (eco-cement) made from filler cement mixed with limestone powder with a Blaine specific surface area exceeding 2000 cm 2 / g, blast furnace slow-cooled slag fine powder, etc., and municipal waste incineration ash and sewage sludge incineration ash Portland cement such as), and one or more of these can be used.
本発明で使用する四級アンモニウム塩化合物とは、四級アンモニウムイオンにおけるＲ１、Ｒ２、Ｒ３、Ｒ４が炭素数１〜３０のアルキル基（ベンゼン環、カルボニル基、ヒドロキシル基、不飽和結合を有するアルケニルなどを有してもよい）であり、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、オクタデシル、フェニル、ベンジル、アセチル、ビニル、アリル、ヒドロキシエチル、ヒドロキシプロピルなどが挙げられる。 The quaternary ammonium salt compound used in the present invention is a quaternary ammonium ion in which R1, R2, R3, and R4 are alkyl groups having 1 to 30 carbon atoms (benzene ring, carbonyl group, hydroxyl group, alkenyl having an unsaturated bond). For example, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, octadecyl, phenyl, benzyl Acetyl, vinyl, allyl, hydroxyethyl, hydroxypropyl and the like.
四級アンモニウムイオン重合体としては、ジメチルアミノエチル（メタ）アクリレートの四級化物、ジアリルジメチルアンモニウムクロライド、４−ビニルベンジルトリメチルアンモニウムクロライド、４−ビニル−１−メチルピリジニウムブロマイドなどのモノマーを重合してなるホモポリマーや、これらと以下に示すようなモノマーとの共重合体であっても構わない。
例えば、共重合に使用されるモノマーとしては、ビニルアルコール、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、グリセロールモノ（メタ）アクリレート、（メタ）アクリル酸及びそのアルカリ金属塩、イタコン酸およびそのアルカリ金属塩、２−（メタ）アクリロイルオキシエチルコハク酸およびそのアルカリ金属塩、２−（メタ）アクリロイルオキシエチルフタル酸およびそのアルカリ金属塩、２−（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸およびそのアルカリ金属塩、２−（メタ）アクリルアミド−２−メチルプロパンスルホン酸およびその塩、スチレンスルホン酸およびその塩、ビニルスルホン酸およびその塩、２−スルホエチル（メタ）アクリレート及びその塩、２−（メタ）アクリロイルオキシエチル燐酸およびその塩、（メタ）アクリルアミド、（メタ）アクリロイルモルホリン、ビニルピリジン、Ｎ−メチル（メタ）アクリルアミド、Ｎ，Ｎ′−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ′−ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ′−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ′−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ′−ジメチルアミノネオペンチル（メタ）アクリレート、Ｎ−ビニル−２ピロリドン、ダイアセトンアクリルアミド、Ｎ−メチロール（メタ）アクリルミド、メトキシトリエチレングリコール（メタ）アクリレート、メトキシテトラエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート（ポリエチレングリコールの数平均分子量４００）、メトキシポリエチレングリコール（メタ）アクリレート（ポリエチレングリコールの数平均分子量１０００）、ブトキシエチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、ノニルフェノキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソデシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、テトラフルフリル（メタ）アクリレート、ベンジル（メタ）アクリレート、メチル（メタ）アクリレート、エチル（メタ）アクリレート、スチレンなどが挙げられる。
四級アンモニウムイオンの対となる陰イオンとしては、塩素イオン、臭素イオン、フッ素イオン、ヨウ素イオン、硝酸イオン、ヒドロキシイオン、酢酸イオン、硫酸イオン、炭酸イオン、炭酸水素イオンなどが挙げられる。
これらの中で、ケイ酸アルカリ金属塩と混合したときの強ばりが強い点で、四級アンモニウム化合物の重合体の使用が好ましい。
四級アンモニウム化合物の重合体の重量平均分子量は、３０００〜５０００００が好ましい。３０００より小さいと、硬化収縮量が大きくなり、５０００００を越えるとゲル化の反応性が低下する場合がある。
As quaternary ammonium ion polymers, monomers such as quaternized dimethylaminoethyl (meth) acrylate, diallyldimethylammonium chloride, 4-vinylbenzyltrimethylammonium chloride, 4-vinyl-1-methylpyridinium bromide are polymerized. Or a copolymer of these with the following monomers.
For example, monomers used for copolymerization include vinyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, ( (Meth) acrylic acid and its alkali metal salt, itaconic acid and its alkali metal salt, 2- (meth) acryloyloxyethyl succinic acid and its alkali metal salt, 2- (meth) acryloyloxyethylphthalic acid and its alkali metal salt, 2- (meth) acryloyloxyethyl hexahydrophthalic acid and its alkali metal salt, 2- (meth) acrylamido-2-methylpropanesulfonic acid and its salt, styrenesulfonic acid and its salt, vinylsulfonic acid and its salt, 2 -Su Phoethyl (meth) acrylate and salts thereof, 2- (meth) acryloyloxyethyl phosphoric acid and salts thereof, (meth) acrylamide, (meth) acryloylmorpholine, vinylpyridine, N-methyl (meth) acrylamide, N, N′-dimethyl (Meth) acrylamide, N, N′-dimethylaminopropyl (meth) acrylamide, N, N′-dimethylaminoethyl (meth) acrylate, N, N′-diethylaminoethyl (meth) acrylate, N, N′-dimethylamino Neopentyl (meth) acrylate, N-vinyl-2pyrrolidone, diacetone acrylamide, N-methylol (meth) acrylimide, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxy Liethylene glycol (meth) acrylate (polyethylene glycol number average molecular weight 400), methoxypolyethylene glycol (meth) acrylate (polyethylene glycol number average molecular weight 1000), butoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol ( (Meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) Acrylate, isodecyl (meth) acrylate, cyclohexyl (meth) acrylate, tetraf Examples include rufuryl (meth) acrylate, benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and styrene.
Examples of anions that form pairs of quaternary ammonium ions include chlorine ions, bromine ions, fluorine ions, iodine ions, nitrate ions, hydroxy ions, acetate ions, sulfate ions, carbonate ions, and bicarbonate ions.
Among these, the use of a polymer of a quaternary ammonium compound is preferable in that it is strong when mixed with an alkali metal silicate.
As for the weight average molecular weight of the polymer of a quaternary ammonium compound, 3000-500000 are preferable. When it is less than 3000, the amount of cure shrinkage increases, and when it exceeds 500,000, the gelation reactivity may decrease.
四級アンモニウム化合物は、セメントコンクリート側に添加されるが、純品をそのまま添加してもよく、水溶液として添加してもよい。
四級アンモニウム化合物の使用量は、セメント１００部に対して、０．００１〜５０部が好ましく、０．０１〜３５部がより好ましい。０．００１部未満では、瞬時の強ばりを得ることが難しい場合があり、５０部を越えると強ばりが弱くなるおそれがある。
The quaternary ammonium compound is added to the cement concrete side, but a pure product may be added as it is or may be added as an aqueous solution.
The amount of the quaternary ammonium compound used is preferably 0.001 to 50 parts and more preferably 0.01 to 35 parts with respect to 100 parts of cement. If it is less than 0.001 part, it may be difficult to obtain an instantaneous strong flash, and if it exceeds 50 parts, the strong flash may be weakened.
本発明で使用するケイ酸アルカリ金属塩とは、四級アンモニウム化合物の窒素原子とケイ酸分子中の−ＯＮａ部が反応し架橋構造を作りゲル化を促進する作用を示す。
例えば、ＪＩＳ Ｋ １４０８に規定されている１号（ＳｉＯ２／Ｒ２Ｏ＝１．９〜２．３）、２号（ＳｉＯ２／Ｒ２Ｏ＝２．４〜２．７）、３号（ＳｉＯ２／Ｒ２Ｏ＝２．９〜３．４）の水ガラス、１種のメタケイ酸ナトリウム（ＳｉＯ２／Ｒ２Ｏ＝０．９５〜１．０５）、２種のメタケイ酸ナトリウム（ＳｉＯ２／Ｒ２Ｏ＝０．９〜１．１）、オルトケイ酸ナトリウム（ＳｉＯ２／Ｒ２Ｏ＝０．４８〜０．５２）が挙げられるが、これらは、瞬時にゲル化を起こす能力は小さい。
瞬時のゲル化を起こす能力としては、アルカリケイ酸塩の酸化物換算のモル比（ＳｉＯ２／Ｒ２Ｏ）で決まる。特に、四級アンモニウム化合物を混合したときのゲル化速度は、ＳｉＯ２／Ｒ２Ｏが３．３〜４．５のときが瞬間的な反応が起こりやすく、吹付け施工を行なう場合はその範囲が特に好ましい。
Ｒは入手が容易で安価な点でナトリウムが好ましいが、それ以外のアルカリ金属（リチウムやカリウム）のケイ酸塩も使用できる。
ＳｉＯ２／Ｒ２Ｏが４．５を越えるとコロイダルシリカの組成に近づくので溶解性が悪くなり、強ばり性が得られないおそれがある。
ケイ酸アルカリ金属塩の使用量は、セメント１００部に対して固形分で０．５〜１０部が好ましく、１〜７部がより好ましい。０．５部未満では、十分な急結力を付与することが難しい場合があり、１０部を越えると長期強度を阻害する場合がある。
ケイ酸アルカリ金属塩は、吹付け施工での粉じんを低減する目的で水溶液として使用するのが好ましい。
The alkali metal silicate used in the present invention has a function of promoting gelation by reacting a nitrogen atom of a quaternary ammonium compound with a -ONa portion in a silicate molecule to form a crosslinked structure.
For example, No. 1 (SiO 2 / R 2 O = 1.9 to 2.3), No. 2 (SiO 2 / R 2 O = 2.4 to 2.7), No. 3 specified in JIS K 1408 (SiO 2 / R 2 O = 2.9 to 3.4) water glass, one kind of sodium metasilicate (SiO 2 / R 2 O = 0.95 to 1.05), two kinds of sodium metasilicate ( SiO 2 / R 2 O = 0.9 to 1.1) and sodium orthosilicate (SiO 2 / R 2 O = 0.48 to 0.52) are mentioned, but these have the ability to cause gelation instantaneously. Is small.
The ability to cause instantaneous gelation is determined by the molar ratio of oxide of alkali silicate (SiO 2 / R 2 O). In particular, the gelation rate when a quaternary ammonium compound is mixed is likely to cause an instantaneous reaction when SiO 2 / R 2 O is 3.3 to 4.5, and the range when spraying is performed. Is particularly preferred.
R is sodium because it is easily available and inexpensive, but other alkali metal (lithium and potassium) silicates can also be used.
When SiO 2 / R 2 O exceeds 4.5, the composition becomes close to the composition of colloidal silica, so that the solubility is deteriorated, and there is a possibility that the strength is not obtained.
The amount of the alkali metal silicate used is preferably 0.5 to 10 parts, more preferably 1 to 7 parts in terms of solid content with respect to 100 parts of cement. If it is less than 0.5 part, it may be difficult to give sufficient rapid setting force, and if it exceeds 10 parts, long-term intensity | strength may be inhibited.
The alkali metal silicate is preferably used as an aqueous solution for the purpose of reducing dust during spraying.
本発明のセメントコンクリートは、吹付けが可能であれば特に配合は限定されるものではない。一般的な配合としては、スランプ１０ｃｍ程度、Ｗ／Ｃ=６０％程度、ｓ／ａ=６０％程度、セメント量３６０ｋｇ／ｍ３程度、砂利の最大寸法１３ｍｍで実施されている場合が多く、高強度タイプでは、スランプ２０ｃｍ程度、スランプフローで２５〜３５ｃｍ、Ｗ／Ｃ=４０〜５０％程度、ｓ／ａ=６０％程度、セメント量４００〜５００ｋｇ／ｍ３程度、砂利の最大寸法１３ｍｍで実施されている場合が多い。 The cement concrete of the present invention is not particularly limited as long as spraying is possible. As a general blending, the slump is about 10 cm, W / C = about 60%, s / a = about 60%, the cement amount is about 360 kg / m3, and the maximum gravel dimension is 13 mm, and the strength is high. In the type, the slump is about 20 cm, the slump flow is about 25 to 35 cm, W / C = about 40-50%, s / a = about 60%, the cement amount is about 400-500 kg / m3, and the maximum gravel dimension is 13 mm. There are many cases.
本発明で使用する骨材は、特に限定するものではなく、市販されているあらゆる骨材の使用が可能であり、吹付け施工に支障をきたさないものであれば問題ない。 The aggregate used in the present invention is not particularly limited, and any commercially available aggregate can be used, and there is no problem as long as it does not hinder spray construction.
本発明では、吹付け施工に支障をきたさない範囲で、減水剤、ＡＥ減水剤、高性能減水剤、高性能ＡＥ減水剤、セルロースエーテル類、ポリエチレンオキサイド類、多糖類などの増粘剤、消泡剤、防錆剤、防凍剤、収縮低減剤、高分子エマルジョン、凝結促進剤、凝結遅延剤、高分子凝集剤、ベントナイトなどの粘土鉱物やハイドロタルサイトなどのアニオン交換体などの各種添加剤、高炉水砕スラグ微粉末や高炉徐冷スラグ微粉末、フライアッシュやシリカフュームなどの混和材料、無水セッコウなどのセッコウ類、カルシウムアルミネート類からなる群のうちの１種又は２種以上を併用することが可能である。 In the present invention, a water reducing agent, AE water reducing agent, high performance water reducing agent, high performance AE water reducing agent, cellulose ether, polyethylene oxide, polysaccharide thickener, etc. Various additives such as foaming agents, antirust agents, antifreeze agents, shrinkage reducing agents, polymer emulsions, setting accelerators, setting retarders, polymer flocculants, clay minerals such as bentonite and anion exchangers such as hydrotalcite , Blast furnace granulated slag fine powder or blast furnace slow-cooled slag fine powder, admixtures such as fly ash and silica fume, gypsum such as anhydrous gypsum, one or more of the group consisting of calcium aluminates It is possible.
本発明の吹付け方法は、特に限定するものではないが、圧送されてくる水を加えて練り混ぜたセメントコンクリートに急結剤を合流させて吹き付ける湿式吹付け工法や、ドライな状態でコンクリートと急結剤を圧送し、ノズル手前で水を合流させて吹き付ける乾式吹付け工法が可能である。 The spraying method of the present invention is not particularly limited, but a wet spraying method in which a rapid setting agent is combined and sprayed to cement concrete mixed with water that is pumped and mixed, or in a dry state with concrete. It is possible to use a dry spraying method in which a rapid setting agent is pumped and water is combined and sprayed before the nozzle.
「実験例１」
各材料の単位量、セメント３６０ｋｇ／ｍ３、細骨材１０２１ｋｇ／ｍ３、粗骨材６９１ｋｇ／ｍ３、水２１６ｋｇ／ｍ３、セメント１００部に対して四級アンモニウム塩化合物（２）を０．５部加え吹付けコンクリートを調整した。この吹付けコンクリートを吹付け圧力０．４ＭＰａ、吹付け速度１０ｍ３／ｈの条件下で、コンクリート圧送機「ＭＫＷ−２５ＳＭＴ」によりポンプ圧送した。液体急結剤搬送装置で圧縮空気とともにケイ酸アルカリ金属の水溶液（固形分３０％に調整）を表し示すようにノズル先端から１ｍの位置で合流混合し吹き付けた。この急結性吹付けコンクリートについて厚付け性、コンクリート圧縮強度、硬化収縮量、ケイ酸イオンの溶出量を測定した。尚、比較のために、市販の硫酸アルミニウムを主成分とする液体急結剤と、粉体急結剤を用いて同じ試験を行った。結果を表１に示す。
"Experiment 1"
Unit amount of each material cement 360 kg / m 3, fine aggregate 1021kg / m 3, a coarse aggregate 691kg / m 3, water 216 kg / m 3, quaternary ammonium salt compound per 100 parts cement (2) 0 Add 5 parts and adjust the shotcrete. The sprayed concrete was pumped by a concrete pumping machine “MKW-25SMT” under conditions of a spraying pressure of 0.4 MPa and a spraying speed of 10 m 3 / h. In the liquid accelerating agent conveying device, the mixture was mixed and sprayed at a position of 1 m from the nozzle tip so as to represent an aqueous solution of alkali metal silicate (adjusted to a solid content of 30%) together with compressed air. Thickness, concrete compressive strength, hardening shrinkage, and silicate ion elution were measured for this quick setting shotcrete. For comparison, the same test was performed using a commercially available liquid accelerator mainly composed of aluminum sulfate and a powder accelerator. The results are shown in Table 1.
（使用材料）
粗骨材：新潟県糸魚川市姫川産川砂利、表乾状態、比重２．６６、最大寸法１３ｍｍ
細骨材：新潟県糸魚川市姫川産川砂利、表乾状態、比重２．６２、最大寸法５ｍｍ
セメント：普通ポルトランドセメント、市販品
四級アンモニウム塩化合物（２）：ジアリルジメチルアンモニウムクロライド重合体の３０％水溶液、重量平均分子量２０００００、市販品
ケイ酸アルカリ金属塩水溶液Ａ：２号水ガラス、ＳｉＯ２／Ｎａ２Ｏモル比２．５５、市販品
ケイ酸アルカリ金属塩水溶液Ｂ：３号水ガラス、ＳｉＯ２／Ｎａ２Ｏモル比３．３２、市販品
ケイ酸アルカリ金属塩水溶液Ｃ：ＳｉＯ２／Ｎａ２Ｏモル比３．７２、市販品
ケイ酸アルカリ金属塩水溶液Ｄ：ＳｉＯ２／Ｎａ２Ｏモル比４．４８、市販品
市販の液体急結剤（Ｌ）：主成分硫酸アルミニウム、固形分濃度４１％、懸濁状
市販の粉体急結剤（Ｐ）：セメント鉱物系粉体急結剤
(Materials used)
Coarse aggregate: Himekawa Sakegawa gravel, Itoigawa City, Niigata Prefecture, surface dry condition, specific gravity 2.66, maximum dimension 13mm
Fine aggregate: Himekawa Sakegawa gravel, Itoigawa City, Niigata Prefecture, surface dry condition, specific gravity 2.62, maximum dimension 5mm
Cement: ordinary Portland cement, commercially available quaternary ammonium salt compound (2): 30% aqueous solution of diallyldimethylammonium chloride polymer, weight average molecular weight 200000, commercially available alkaline metal silicate aqueous solution A: No. 2 water glass, SiO 2 / Na 2 O molar ratio 2.55, commercial product alkali metal silicate aqueous solution B: No. 3 water glass, SiO 2 / Na 2 O molar ratio 3.32, commercial product alkaline metal silicate aqueous solution C: SiO 2 / Na 2 O molar ratio 3.72, commercially available alkali metal silicate aqueous solution D: SiO 2 / Na 2 O molar ratio 4.48, commercially available liquid accelerator (L): main component aluminum sulfate, solid content 41% concentration, commercially available powder quick-setting agent (P): cement mineral powder quick-setting agent
（測定方法）
スランプ：ＪＩＳ Ａ １１０１に準拠して測定した。測定は練り上がり直後とした。
厚付け性：吹付けノズルを１ｍの範囲で繰り返し動かしながら吹付けコンクリートを天井面に吹き付け、はく落するまでの厚みを計測した。３０cm以上の厚みになったら良好な吹付け性と判断し試験を止めた。なお、試験を止めてから２４時間以内ではく落した場合は厚付け性が不良と判断した。吹き付けた下地は鉄板。
コンクリート圧縮強度：材齢１時間、２４時間の圧縮強度は、幅２５ｃｍ×長さ２５ｃｍのプルアウト型枠に設置したピンを、プルアウト型枠表面から急結性吹付けコンクリートで被覆し、型枠の裏側よりピンを引き抜き、その時の引き抜き強度を求め、（圧縮強度）＝（引き抜き強度）×４／（供試体接触面積）の式から圧縮強度を算出した。材齢２８日の圧縮強度は、幅５０ｃｍ×長さ５０ｃｍ×厚さ２０ｃｍの型枠に急結性吹付けコンクリートを吹付け、１日後にコアドリルで採取した直径５ｃｍ×長さ１０ｃｍの供試体を２０トン耐圧機で測定し、圧縮強度を求めた。測定までの養生は２０℃水中養生とした。
硬化収縮量：専用型枠（１０×１０×３６ｃｍ）に吹付けて供試体を作製した。材齢１日後脱型し基長を行い、温度２０℃、湿度６０％の室内で２８日間養生後、収縮量を測定した。測定はＪＩＳ Ｒ １１２９−３（ダイヤルゲージ法）に準拠した。
ケイ酸イオンの溶出量：圧縮強度と同様にコアドリルで試験体を採取し、ジョークラッシャーで粉砕した。その粉砕物１００ｇを１０００ｇの純粋に加え、１時間振動器を用いて攪拌した。その後、ろ過してろ液についてイオンクロマトグラフィーを用いてケイ酸イオンの溶出量を測定した。
(Measuring method)
Slump: Measured according to JIS A 1101. The measurement was performed immediately after kneading.
Thickness: Spray concrete was sprayed on the ceiling surface while repeatedly moving the spray nozzle in the range of 1 m, and the thickness until peeling was measured. When the thickness was 30 cm or more, it was judged that the sprayability was good and the test was stopped. In addition, when it peeled within 24 hours after stopping the test, it was judged that the thickness was poor. The sprayed ground is an iron plate.
Concrete compressive strength: The compressive strength of 1 hour and 24 hours of age is to cover the pin placed on the pullout formwork with 25cm width x 25cm length with the quick setting sprayed concrete from the surface of the pullout formwork. The pin was pulled out from the back side, the pulling strength at that time was determined, and the compressive strength was calculated from the formula of (compressive strength) = (pullout strength) × 4 / (test specimen contact area). The compressive strength at the age of 28 days was obtained by spraying quick setting sprayed concrete on a mold of width 50 cm x length 50 cm x thickness 20 cm, and a specimen 5 cm in diameter x 10 cm in length taken with a core drill one day later. The compressive strength was determined by measuring with a 20-ton pressure machine. Curing up to the measurement was water curing at 20 ° C.
Curing shrinkage: A specimen was prepared by spraying on a dedicated formwork (10 × 10 × 36 cm). After 1 day of age, the mold was removed and the base length was determined. After curing in a room at a temperature of 20 ° C. and a humidity of 60% for 28 days, the amount of shrinkage was measured. The measurement was based on JIS R 1129-3 (dial gauge method).
Silicate ion elution amount: A specimen was collected with a core drill in the same manner as the compressive strength, and pulverized with a jaw crusher. 100 g of the pulverized product was added to 1000 g of pure, and stirred for 1 hour using a vibrator. Then, it filtered and the elution amount of the silicate ion was measured about the filtrate using the ion chromatography.
「実験例２」
セメント１００部に対してケイ酸アルカリ金属塩Ｃを３．０部とし、種々の四級アンモニウム塩化合物を表に示すように加えた以外は実験例１と同様に行なった。結果を表２、３に示す。
"Experimental example 2"
The test was conducted in the same manner as in Experimental Example 1 except that the alkali metal silicate C was 3.0 parts with respect to 100 parts of cement and various quaternary ammonium salt compounds were added as shown in the table. The results are shown in Tables 2 and 3.
（使用材料）
四級アンモニウム塩化合物（１）：市販しているテトラメチルアンモニウムクロライドの５０％水溶液
四級アンモニウム塩化合物（３）：ジアリルジメチルアンモニウムヒドロキシド重合体の３０％水溶液、重量平均分子量９５０００、市販品
四級アンモニウム化合物（４）：ジアリルジメチルアンモニウムクロライド重合体の３０％水溶液、重量平均分子量３１００、市販品
四級アンモニウム化合物（５）：ジアリルジメチルアンモニウムクロライド重合体の３０％水溶液、重量平均分子量４８５０００、市販品
(Materials used)
Quaternary ammonium salt compound (1): Commercially available 50% aqueous solution of tetramethylammonium chloride Quaternary ammonium salt compound (3): 30% aqueous solution of diallyldimethylammonium hydroxide polymer, weight average molecular weight 95,000, commercially available product 4 Quaternary ammonium compound (4): 30% aqueous solution of diallyldimethylammonium chloride polymer, weight average molecular weight 3100, commercially available quaternary ammonium compound (5): 30% aqueous solution of diallyldimethylammonium chloride polymer, weight average molecular weight 485000, commercially available Goods
本発明の吹付け材料は、粉体急結剤に匹敵する凝結性状および初期強度発現性が得られ、硬化体の収縮量やイオンの溶出量も抑制でき、さらに、急結成分が液体であるため粉じん発生量も少ない吹付け施工への利用が可能となるため、土木分野などに好適である。 The spray material of the present invention has a coagulation property and initial strength expression comparable to those of a powder accelerating agent, can suppress the shrinkage amount of the cured body and the elution amount of ions, and the rapid setting component is liquid. Therefore, since it can be used for spraying with a small amount of dust generation, it is suitable for the civil engineering field.
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| JP2014509680A (en) * | 2011-03-31 | 2014-04-21 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | Cationic polymers for processing construction aggregates |
| JPWO2019176957A1 (en) * | 2018-03-14 | 2020-04-23 | デンカ株式会社 | Powdered quick-setting agent, quick-setting material, quick-setting material cured product, and spraying method |
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| JP2002249359A (en) * | 2001-02-22 | 2002-09-06 | Denki Kagaku Kogyo Kk | Spray material and spray technique using it |
| JP2003292359A (en) * | 2002-03-29 | 2003-10-15 | Taiheiyo Material Kk | Dust reduction agent |
| JP2006045010A (en) * | 2004-08-05 | 2006-02-16 | Kao Corp | Additive for hydraulic composition |
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| JP2002249359A (en) * | 2001-02-22 | 2002-09-06 | Denki Kagaku Kogyo Kk | Spray material and spray technique using it |
| JP2003292359A (en) * | 2002-03-29 | 2003-10-15 | Taiheiyo Material Kk | Dust reduction agent |
| JP2006045010A (en) * | 2004-08-05 | 2006-02-16 | Kao Corp | Additive for hydraulic composition |
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| JP2014509680A (en) * | 2011-03-31 | 2014-04-21 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | Cationic polymers for processing construction aggregates |
| JPWO2019176957A1 (en) * | 2018-03-14 | 2020-04-23 | デンカ株式会社 | Powdered quick-setting agent, quick-setting material, quick-setting material cured product, and spraying method |
| US11691919B2 (en) | 2018-03-14 | 2023-07-04 | Denka Company Limited | Powdered quick-setting agent, quick-setting material, quick-setting material cured product, and spraying method |
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