WO2024154722A1 - Liquid quick setting agent, repair material, and cured body - Google Patents
Liquid quick setting agent, repair material, and cured body Download PDFInfo
- Publication number
- WO2024154722A1 WO2024154722A1 PCT/JP2024/000921 JP2024000921W WO2024154722A1 WO 2024154722 A1 WO2024154722 A1 WO 2024154722A1 JP 2024000921 W JP2024000921 W JP 2024000921W WO 2024154722 A1 WO2024154722 A1 WO 2024154722A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- liquid quick
- cement
- setting admixture
- ppm
- mass
- Prior art date
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title claims description 45
- 239000004568 cement Substances 0.000 claims abstract description 79
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011593 sulfur Substances 0.000 claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000001228 spectrum Methods 0.000 claims abstract description 11
- 238000005259 measurement Methods 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical group 0.000 claims description 3
- 238000004910 27Al NMR spectroscopy Methods 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000000835 fiber Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 238000003860 storage Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000004576 sand Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000004567 concrete Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- -1 various alums Chemical compound 0.000 description 6
- 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 5
- 239000002956 ash Substances 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- 235000012255 calcium oxide Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 238000009415 formwork Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000007665 sagging Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000010801 sewage sludge Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000004056 waste incineration Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 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
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229940044172 calcium formate Drugs 0.000 description 1
- 235000019255 calcium formate Nutrition 0.000 description 1
- 239000004281 calcium formate Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 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
- 238000007865 diluting Methods 0.000 description 1
- 239000004499 emulsifiable powder Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013031 physical testing Methods 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- KUKFKAPJCRZILJ-UHFFFAOYSA-N prop-2-enenitrile;prop-2-enoic acid Chemical compound C=CC#N.OC(=O)C=C KUKFKAPJCRZILJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
Definitions
- the present invention relates to a liquid quick-setting agent, a repair material, and a hardened body.
- a quick-setting agent is used together with the sprayed material.
- quick-setting admixtures There are mainly two types of quick-setting admixtures: powder and liquid. Liquid quick-setting admixtures generally have a lower quick-setting ability than powder quick-setting admixtures. To improve this, for example, measures have been taken to improve strength by increasing the sulfate ion concentration, as shown in Patent Document 1.
- liquid quick-setting agents when stored for long periods of time, they can cause precipitates to form in the liquid, the liquid to gel, or suspended particles to settle.
- the solubility of aluminum sulfate in water is 27% at 20°C, and this varies depending on the coexisting solutes and the liquid temperature.
- Liquid quick-setting agents that contain aluminum sulfate in excess of the solubility limit have poor storage stability, and when combined with cement compositions, adhesion can be an issue.
- the present invention aims to provide a liquid quick-setting agent that has excellent storage stability and provides good adhesion when used with a cement composition.
- a liquid quick-setting admixture used together with a cement composition containing cement, a polymer, and a fine aggregate the liquid quick-setting admixture containing an aluminum component and a sulfur component and having a chemical shift peak in the range of -1.0 ppm to 3.0 ppm in a spectrum obtained by 27Al -NMR measured under the following conditions.
- a repair material comprising a cement composition containing cement, a polymer and a fine aggregate, and the liquid quick-setting admixture according to any one of [1], [3] and [4] above.
- a repair material comprising a cement composition containing cement and fine aggregate, and the liquid quick-setting admixture according to any one of [2] to [4] above.
- the repair material according to [6] above, wherein the liquid quick-setting admixture further contains a polymer.
- the repair material according to any one of [5] to [7] above, wherein the content of the fine aggregate in the composition is 40 to 300 parts by mass per 100 parts by mass of the cement.
- a hardened body obtained by using the repair material according to any one of [5] to [8] above.
- the present invention provides a liquid quick-setting agent that has excellent storage stability and improves adhesion when used with a cement composition.
- a first aspect of the liquid quick-setting admixture according to this embodiment is a liquid quick-setting admixture used together with a cement composition containing cement, a polymer, and a fine aggregate, the liquid quick-setting admixture containing an aluminum component and a sulfur component and having a peak in a chemical shift range of -1.0 ppm or more and 3.0 ppm or less in a spectrum obtained by 27Al -NMR measured under the following conditions:
- the liquid quick-setting admixture of the present invention contains an aluminum component and a sulfur component and has a peak at a predetermined position in the spectrum obtained by 27Al -NMR, thereby having excellent storage stability, and when used together with a cement composition containing cement, a polymer, and a fine aggregate, the liquid quick-setting admixture suppresses sagging and improves adhesion strength, thereby improving adhesion. (conditions) Observed nucleus: 27Al Sample tube rotation speed: 12Hz
- a second aspect of the liquid quick-setting admixture according to this embodiment is a liquid quick-setting admixture for repair used together with a cement composition containing cement and fine aggregate, the liquid quick-setting admixture containing an aluminum component and a sulfur component and having a peak in the chemical shift range of -1.0 ppm to 3.0 ppm in the spectrum obtained by 27Al -NMR measured under the conditions described above.
- the liquid quick-setting admixture of the present invention contains an aluminum component and a sulfur component and has a peak at a predetermined position in the spectrum obtained by 27Al -NMR, thereby having excellent storage stability, and when used for repair together with a cement composition containing cement and fine aggregate, it suppresses sagging and improves adhesion strength, thereby improving adhesion.
- the liquid quick-setting admixture of the first and second embodiments has a peak in the chemical shift range of -1.0 ppm to 3.0 ppm in the spectrum obtained by 27 Al-NMR.
- the half-width of the peak is preferably 10.0 ppm or less, more preferably 9.0 ppm or less, and even more preferably 8.0 ppm or less, for example. This can improve the storage stability of the liquid quick-setting admixture.
- the half-width may be, for example, 0.1 ppm or more.
- the 27 Al-NMR measurement of the liquid quick-setting admixture can be performed using a commercially available measuring device, for example, a superconducting nuclear magnetic resonance device (ECX-400) manufactured by JEOL Ltd.
- ECX-400 superconducting nuclear magnetic resonance device manufactured by JEOL Ltd.
- the first and second embodiments may be collectively referred to simply as a liquid quick-setting admixture.
- the liquid quick-setting admixture contains an aluminum component and a sulfur component.
- aluminum sulfate, various alums, aluminum hydroxide, etc. can be used as the raw material for the aluminum component
- sulfuric acid, etc. can be used as the raw material for the sulfur component.
- the ratio of the aluminum raw material to the sulfur raw material if the ratio of the aluminum raw material is increased, the above chemical shift tends to fall within the desired range, and if the ratio of the sulfur raw material is increased, the half-width tends to become smaller.
- the aluminum component in the liquid quick-setting admixture is 3.0 to 20.0%, preferably 5.0 to 18.0%, and more preferably 7.0 to 15.0%, calculated as Al2O3 , when the mass of the liquid quick-setting admixture is taken as 100%.
- the content of the aluminum component in the liquid quick-setting admixture can be adjusted to be within the above range, calculated as Al2O3 , by adjusting the amount of raw material of the aluminum component used when preparing the liquid quick - setting admixture.
- the sulfur component in the liquid quick-setting admixture is 10.0 to 30.0%, preferably 15.0 to 29.0%, and more preferably 15.0 to 20.5%, calculated as SO3 , when the mass of the liquid quick-setting admixture is taken as 100%.
- the content of the sulfur component in the liquid quick-setting admixture can be adjusted to within the above range in terms of SO3 by adjusting the amount of raw material of the sulfur component used when preparing the liquid quick-setting admixture.
- the fluoride ion concentration of the liquid quick-setting admixture is preferably 500 ppm or less, more preferably 450 ppm or less, even more preferably 350 ppm or less, and may be 0 ppm.
- the fluoride ion concentration in the liquid quick-setting admixture can be measured by a commercially available analyzer, for example, an ion chromatograph (ICS2100) manufactured by Thermo Scientific. When analyzing, the measurement can be performed by diluting the liquid in advance so that the fluoride ions are within the calibration curve.
- the pH of the liquid quick-setting admixture is preferably 7 or less, and more preferably 5 or less. A pH of 7 or less can reduce the environmental impact and suppress adverse effects on the human body.
- the pH is preferably 2 or more.
- the pH of the liquid quick-setting admixture can be measured using a pH meter.
- the total alkali content R2O (R is an alkali metal) in the liquid quick-setting admixture is preferably 1.0% or less, more preferably 0.8% or less, and even more preferably 0.5% or less, from the viewpoint of worker safety. It may also be 0% or more.
- the total alkali content R2O in the liquid quick-setting admixture can be measured by atomic absorption spectrometry.
- Liquid quick-setting agents can be obtained by mixing raw materials such as aluminum sulfate, various alums, aluminum hydroxide, and sulfuric acid, and then heating and reacting them.
- the heating temperature is preferably 70 to 100°C, more preferably 85 to 100°C, and even more preferably 85 to 95°C.
- the reaction time is preferably 30 to 150 minutes, more preferably 60 to 150 minutes, and even more preferably 90 to 120 minutes.
- liquid quick-setting admixture can contain various additives as long as they do not impair the effects of the present invention, but from the standpoint of ease of handling, it is preferable that it does not contain sodium aluminate.
- the repair material according to the present embodiment contains a cement composition containing cement, a polymer, and fine aggregate, and the liquid quick-setting admixture of the present invention.
- the content of the liquid quick-setting admixture in the repair material is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of cement in the cement composition.
- the adhesion of the repair material can be improved.
- the cement is not particularly limited, and examples thereof include various cements such as normal, early strength, super early strength, low heat and medium heat, various mixed cements obtained by mixing these cements with blast furnace slag, fly ash, silica fume, etc., environmentally friendly cements (eco-cements) manufactured using municipal waste incineration ash and sewage sludge incineration ash as raw materials, commercially available fine particle cements, etc., and various cements and various mixed cements can be used in a fine powder form. Also, cements adjusted by increasing or decreasing the amount of components (e.g., gypsum) used in normal cements can be used. In the present invention, it is preferable to select ordinary Portland cement or high-early-strength Portland cement from the viewpoint of adhesion.
- various cements such as normal, early strength, super early strength, low heat and medium heat
- various mixed cements obtained by mixing these cements with blast furnace slag, fly ash, silica fume, etc.
- environmentally friendly cements
- the cement preferably has a Blaine specific surface area of 2,500 to 7,000 cm 2 /g, more preferably 2,750 cm 2 /g to 6,000 cm 2 /g, and even more preferably 3,000 cm 2 /g to 4,500 cm 2 /g.
- the Blaine specific surface area value is determined in accordance with JIS R 5201:2015 (physical testing method for cement).
- the fine aggregate is not particularly limited, and the same fine aggregates as those used in ordinary cement mortar and concrete can be used.
- river sand, crushed stone, crushed sand, lime sand, silica sand, colored sand, artificial lightweight aggregate, etc. can be used, and combinations of these are also possible.
- silica sand or lime sand which is a silica-based material, is preferable, and the grain size of the fine aggregate is preferably JIS No. 6 to 8.
- the content of fine aggregate in the cement composition is preferably 40 to 300 parts by mass, more preferably 45 to 275 parts by mass, and even more preferably 50 to 250 parts by mass, per 100 parts by mass of cement.
- the cement composition preferably further contains a polymer, which is not particularly limited, but examples thereof include rubber latexes such as acrylonitrile-butadiene rubber, styrene-butadiene rubber, chloroprene rubber, and natural rubber, resin emulsions such as ethylene-vinyl acetate copolymers, acrylic acid ester copolymers such as polyacrylic acid esters, styrene-acrylic acid ester copolymers, and acrylonitrile-acrylic acid ester copolymers, and vinyl acetate-vinyl versatate copolymers.
- the polymer is available in re-emulsifiable powder and liquid forms, and is used to improve adhesion and the durability of mortar.
- the polymer content in the cement composition is preferably 1 to 20 parts by mass, more preferably 2 to 18 parts by mass, and even more preferably 3 to 15 parts by mass, in terms of solid content per 100 parts by mass of cement.
- the cement composition preferably further contains fibers.
- the fibers are not particularly limited, but examples include polymer fibers such as vinylon fibers, propylene fibers, acrylic fibers, nylon fibers, and aramid fibers, as well as inorganic fibers such as steel fibers, glass fibers, carbon fibers, and fibers made by melt-spinning rocks such as basalt.
- the fiber content in the cement composition is preferably 0.02 to 3.0 parts by mass, more preferably 0.03 to 2.5 parts by mass, and even more preferably 0.05 to 2.0 parts by mass, per 100 parts by mass of cement.
- the fiber content is 0.02 parts by mass or more, the effect of improving adhesion can be fully exerted.
- the fiber content is 1.5 parts by mass or less, the fluidity can be increased.
- the length of the fiber is preferably 15 mm or less, more preferably 12 mm or less, and even more preferably 10 mm or less. There is no particular lower limit to the length of the fiber, and it may be, for example, 1 mm or more.
- the cement composition preferably further contains a water-reducing agent.
- a water-reducing agent there are no particular limitations on the water-reducing agent, and examples of the water-reducing agent include naphthalene-based water-reducing agents, melamine-based water-reducing agents, aminosulfonic acid-based water-reducing agents, polycarboxylic acid-based water-reducing agents, etc., and one or more of these water-reducing agents can be used in the present invention.
- the content of the water-reducing agent in the cement composition is preferably 0.1 to 2 parts by mass, more preferably 0.2 to 1.8 parts by mass, and even more preferably 0.3 to 1.0 parts by mass, calculated as solid content per 100 parts by mass of cement.
- the content of the water-reducing agent be equal to or greater than the above lower limit, sufficient fluidity can be obtained. Furthermore, by having the content of the water-reducing agent be equal to or less than the above upper limit, material separation can be suppressed.
- the cement composition may further contain a hardening agent.
- a hardening agent There are no particular limitations on the hardening agent, so long as it promotes setting and increases strength in a short period of time.
- hardening agents that promote setting include calcium salts of organic acids such as calcium formate, nitrates, sulfates, carbonates, thiocyanates, amines, maleic anhydride, silicates such as water glass, aluminum sulfate, aluminum salts such as alum, and aluminates such as calcium aluminate (calcium aluminate). Of these, aluminates are preferred from the viewpoint of strength development, and it is more preferable for them to contain calcium aluminate (CA).
- CA calcium aluminate
- Calcium aluminate is a general term for a substance having hydration activity and mainly composed of CaO and Al 2 O 3, which is obtained by mixing a calcia raw material and an alumina raw material, firing them in a kiln, or melting them in an electric furnace and cooling them, and can be used whether it is crystalline or amorphous. It is a material that has a fast hardening time and high initial strength development.
- a representative example of calcium aluminate is alumina cement, and commercially available products can usually be used. For example, alumina cement No. 1 and alumina cement No. 2 can be used.
- amorphous calcium aluminate that is melted and then rapidly cooled is preferred because it hardens in a shorter time than alumina cement and has a high initial strength development thereafter.
- the molar ratio of CaO to Al 2 O 3 is preferably 1.0 to 3.0, and more preferably 1.7 to 2.5.
- the content of the hardening agent used in the present invention is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, and even more preferably 5 to 20 parts by mass, per 100 parts by mass of cement. Furthermore, when calcium aluminate is contained as the hardening agent, the content of calcium aluminate is preferably 2 to 20 parts by mass, more preferably 3 to 18 parts by mass, and even more preferably 4 to 15 parts by mass, per 100 parts by mass of cement. By having the content of the hardening agent be equal to or greater than the above lower limit, it is easier to achieve good strength development.
- one or more of the following may be used to the extent that they do not adversely affect performance: setting regulators, air-enhancing agents, rust inhibitors, water repellents, antibacterial agents, colorants, antifreeze agents, fine limestone powder, finely cooled blast furnace slag powder, admixtures such as sewage sludge incineration ash and its molten slag, municipal waste incineration ash and its molten slag, and pulp sludge incineration ash; defoamers, thickeners, shrinkage reducing agents, clay minerals such as bentonite and sepiolite; and anion exchangers such as hydrotalcite.
- each material is not particularly limited, and each material may be mixed at the time of construction, or some or all of the materials may be mixed in advance.
- the materials of the cement composition can be mixed in advance, and the liquid quick-setting agent can be mixed at the time of spraying to spray the repair material.
- any existing device can be used, such as a tilting mixer, omni mixer, Henschel mixer, V-type mixer, and Nauta mixer.
- the hardened body according to the present embodiment is a hardened body obtained by using the repair material of the present invention.
- the repair material of the present invention is mixed with water, and the hardened body can be obtained by applying the mixture by a plastering trowel or by pumping the mixture to a work site by a squeeze mortar pump or the like and spraying the mixture from a spray nozzle.
- the amount of water to be mixed is not particularly limited as it varies depending on the purpose and application of use and the content ratio of each material, but is preferably 5 to 70 parts by mass, more preferably 8 to 65 parts by mass, and even more preferably 10 to 60 parts by mass per 100 parts by mass of repair material.
- the amount of water to be mixed equal to or above the lower limit, it is possible to prevent a decrease in fluidity and prevent the amount of heat generation from becoming extremely large.
- the amount of water to be mixed equal to or below the upper limit, it is possible to ensure strength expression.
- the method for mixing the repair material and water is not particularly limited, but it is preferable to use a hand mixer with a rotation speed of 900 rpm or more, a normal mortar mixer, or a twin-shaft forced mixer.
- a hand mixer or mortar mixer it is preferable to put a predetermined amount of water in a container such as a pail or a mixer in advance, then add the remaining repair material while rotating the mixer, and mix for at least 3 minutes.
- a forced mixer it is preferable to put the repair material in the mixer in advance, add a predetermined amount of water while rotating the mixer, and mix for at least 4 minutes.
- Aluminum component source Aluminum hydroxide, industrial grade Sulfur component source: Sulfuric acid, industrial grade Solvent: Pure water
- Storage test A storage test was carried out to evaluate the storage stability of the liquid quick-setting admixture. When the storage stability is reduced, precipitates are formed in the liquid quick-setting admixture, especially in a low-temperature environment. The liquid quick-setting admixture was left to stand in a 10°C environment for one month, and the precipitates were extracted with filter paper, and the amount of precipitates per 100 g of the liquid quick-setting admixture was calculated. The results are shown in Table 1 below.
- Example 1 ⁇ Preparation of repair material> A cement composition was prepared by mixing 200 parts by mass of fine aggregate, 0.1 parts by mass of fiber, 0.5 parts by mass of water reducing agent, and 14 parts by mass of water with respect to 100 parts by mass of cement. 6 parts by mass of the liquid quick-setting admixture of Examples 1 to 5 and 8 and Comparative Examples 1 to 2 were mixed with 100 parts by mass of cement in this cement composition to prepare a repair material.
- Compressive strength test Compressive strength: The concrete was sprayed onto a formwork in accordance with JSCE-G 561-2010, and the compressive strength was measured at 1 day and 28 days after application. The test results are shown in Table 2 below.
- ⁇ Thick coating test Presence or absence of dripping>
- the base was a concrete plate, and mortar was sprayed into a formwork measuring 10 mm thick x 150 mm long x 250 mm wide. After finishing with a trowel, the formwork was removed and the test specimen was immediately set up vertically and left to stand for one day, after which the presence or absence of sagging was confirmed.
- the test results are shown in Table 2 below.
- Adhesion strength test A test specimen was prepared by spraying 60 mm of the repair material onto a pavement board measuring 300 x 300 x 60 mm. After 28 days, the specimen was cored with a diameter of 55 mm and the adhesion strength was measured using a Kenken adhesive strength tester (manufactured by Oxjack Co., Ltd.). The test results are shown in Table 2 below.
- Example 2 ⁇ Preparation of repair material> A cement composition was prepared with 200 parts by mass of fine aggregate, 3.0 parts by mass of polymer (polyacrylic acid ester re-emulsified resin, commercially available product, moisture content 0.8%, density 0.5 g/mL), 0.1 parts by mass of fiber, 0.5 parts by mass of water reducing agent, and 14 parts by mass of water, per 100 parts by mass of cement in this cement composition.
- Six parts by mass of the liquid quick-setting admixture of Examples 1 to 5, 8 and Comparative Examples 1 to 2 were mixed with each other per 100 parts by mass of cement in this cement composition to prepare a repair material.
- the compressive strength, thick coating property, and adhesive strength of the obtained repair material were measured by the same method as in Experimental Example 1. The results are shown in Table 3 below.
- the liquid quick-setting agent of the present invention can be suitably used, for example, in tunnels such as roads, railways, and waterways, in cement concrete sprayed onto exposed natural ground surfaces such as slopes, and as a repair material for concrete structures.
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Abstract
A liquid quick setting agent used with a cement composition containing a cement, a polymer, and a fine aggregate, wherein said liquid quick setting agent contains an aluminum component and a sulfur component, and has a peak in a chemical shift -1.0 to 3.0 ppm range in a spectrum obtained via 27Al-NMR measured with the following conditions. Conditions: Observation nucleus: 27Al. Sample tube rotation speed: 12 Hz. Measurement temperature: 25°C. Pulse width: 5 μsec (45° pulse). Waiting time: 5 seconds. External standard: aluminum chloride aqueous solution.
Description
本発明は、液体急結剤、補修材料、及び硬化体に関する。
The present invention relates to a liquid quick-setting agent, a repair material, and a hardened body.
従来、トンネル工事やコンクリート構造物の補修工事等において吹付け材料の急結性がもとめられる場合、吹付け材料とともに急結剤が使用されている。
急結剤には、主に粉体及び液体の２種類があり、液体急結剤は一般的に、粉体急結剤と比較して急結性が低いため、改善策として、例えば、特許文献１に示されるような、硫酸イオン濃度を高めることによって強度を改善する対策がなされている。 Conventionally, when quick setting of a sprayed material is required in tunnel construction, repair work of concrete structures, etc., a quick-setting agent is used together with the sprayed material.
There are mainly two types of quick-setting admixtures: powder and liquid. Liquid quick-setting admixtures generally have a lower quick-setting ability than powder quick-setting admixtures. To improve this, for example, measures have been taken to improve strength by increasing the sulfate ion concentration, as shown in Patent Document 1.
急結剤には、主に粉体及び液体の２種類があり、液体急結剤は一般的に、粉体急結剤と比較して急結性が低いため、改善策として、例えば、特許文献１に示されるような、硫酸イオン濃度を高めることによって強度を改善する対策がなされている。 Conventionally, when quick setting of a sprayed material is required in tunnel construction, repair work of concrete structures, etc., a quick-setting agent is used together with the sprayed material.
There are mainly two types of quick-setting admixtures: powder and liquid. Liquid quick-setting admixtures generally have a lower quick-setting ability than powder quick-setting admixtures. To improve this, for example, measures have been taken to improve strength by increasing the sulfate ion concentration, as shown in Patent Document 1.
しかしながら、高濃度の液体急結剤は、長期間保存すると液中に析出物が生成したり、液がゲル化したり、懸濁粒子が沈降したりする場合があった。硫酸アルミニウムの水に対する溶解度は２０℃で２７％であり、共存する溶質や液温によって変動するが、溶解度以上の硫酸アルミニウムを含有する液体急結剤は、貯蔵安定性が悪く、また、セメント組成物と組み合わせた場合の付着性が課題となることがあった。
However, when high-concentration liquid quick-setting agents are stored for long periods of time, they can cause precipitates to form in the liquid, the liquid to gel, or suspended particles to settle. The solubility of aluminum sulfate in water is 27% at 20°C, and this varies depending on the coexisting solutes and the liquid temperature. Liquid quick-setting agents that contain aluminum sulfate in excess of the solubility limit have poor storage stability, and when combined with cement compositions, adhesion can be an issue.
以上より、本発明は、優れた貯蔵安定性を有し、セメント組成物とともに用いた際、付着性を良好にする液体急結剤を提供することを目的とする。
The present invention aims to provide a liquid quick-setting agent that has excellent storage stability and provides good adhesion when used with a cement composition.
本発明者らは、上記のような課題を踏まえて鋭意検討を行った結果、アルミニウム成分及び硫黄成分を含有し、２７Ａｌ－ＮＭＲによって得られるスペクトルおいて、特定の化学シフトにピークを有する液体急結剤が、上記の課題を解決できることを見出し、本発明を完成するに至った。すなわち、本発明は、下記の通りである。
As a result of intensive research conducted by the present inventors in light of the above problems, they found that a liquid quick-setting admixture that contains an aluminum component and a sulfur component and has a peak at a specific chemical shift in a spectrum obtained by 27Al -NMR can solve the above problems, and thus completed the present invention.
［１］ セメント、ポリマー及び細骨材を含有するセメント組成物とともに用いられる液体急結剤であって、アルミニウム成分及び硫黄成分を含有し、下記の条件で測定される２７Ａｌ－ＮＭＲによって得られるスペクトルにおいて、化学シフト－１．０ｐｐｍ以上３．０ｐｐｍ以下の範囲にピークを有する、液体急結剤。
（条件）
観測核：２７Ａｌ
試料管回転数：１２Ｈｚ
測定温度：２５℃
パルス幅：５μｓｅｃ（４５°パルス）
待ち時間：５秒
外部標準：塩化アルミニウム水溶液
［２］ セメント及び細骨材を含有するセメント組成物とともに用いられる補修用の液体急結剤であって、アルミニウム成分及び硫黄成分を含有し、下記の条件で測定される２７Ａｌ－ＮＭＲによって得られるスペクトルにおいて、化学シフト－１．０ｐｐｍ以上３．０ｐｐｍ以下の範囲にピークを有する、補修用の液体急結剤。
（条件）
観測核：２７Ａｌ
試料管回転数：１２Ｈｚ
測定温度：２５℃
パルス幅：５μｓｅｃ（４５°パルス）
待ち時間：５秒
外部標準：塩化アルミニウム水溶液
［３］ 前記化学シフト－１．０ｐｐｍ以上３．０ｐｐｍ以下の範囲のピークの半値幅が、１０．０ｐｐｍ以下である、上記［１］または［２］に記載の液体急結剤。
［４］ 前記液体急結剤中の全アルカリ量Ｒ２Ｏ（Ｒはアルカリ金属）が、１．０質量％以下である、上記［１］～［３］のいずれか１つに記載の液体急結剤。
［５］ セメント、ポリマー及び細骨材を含有するセメント組成物と、上記［１］、［３］または［４］のいずれか１つに記載の液体急結剤とを含有する、補修材料。
［６］ セメント及び細骨材を含有するセメント組成物と、上記［２］～［４］のいずれか１つに記載の液体急結剤とを含有する、補修材料。
［７］ 前記液体急結剤が、さらにポリマーを含有する、上記［６］に記載の補修材料。
［８］ 前記組成物中の細骨材の含有量が、前記セメント１００質量部に対して４０～３００質量部である、上記［５］～［７］のいずれか１つに記載の補修材料。
［９］ 上記［５］～［８］のいずれか１つに記載の補修材料を用いてなる、硬化体。 [1] A liquid quick-setting admixture used together with a cement composition containing cement, a polymer, and a fine aggregate, the liquid quick-setting admixture containing an aluminum component and a sulfur component and having a chemical shift peak in the range of -1.0 ppm to 3.0 ppm in a spectrum obtained by 27Al -NMR measured under the following conditions.
(conditions)
Observed nucleus: 27Al
Sample tube rotation speed: 12Hz
Measurement temperature: 25°C
Pulse width: 5 μsec (45° pulse)
Waiting time: 5 seconds External standard: aluminum chloride aqueous solution [2] A liquid quick-setting admixture for repair to be used together with a cement composition containing cement and fine aggregate, the liquid quick-setting admixture for repair containing an aluminum component and a sulfur component, and having a peak in the chemical shift range of -1.0 ppm or more and 3.0 ppm or less in a spectrum obtained by 27Al -NMR measured under the following conditions.
(conditions)
Observed nucleus: 27Al
Sample tube rotation speed: 12Hz
Measurement temperature: 25°C
Pulse width: 5 μsec (45° pulse)
Waiting time: 5 seconds External standard: aluminum chloride aqueous solution [3] The liquid quick-setting admixture according to the above [1] or [2], wherein the half-width of the peak in the chemical shift range of −1.0 ppm to 3.0 ppm is 10.0 ppm or less.
[4] The liquid quick-setting admixture according to any one of the above [1] to [3], wherein the total alkali content R 2 O (R is an alkali metal) in the liquid quick-setting admixture is 1.0 mass % or less.
[5] A repair material comprising a cement composition containing cement, a polymer and a fine aggregate, and the liquid quick-setting admixture according to any one of [1], [3] and [4] above.
[6] A repair material comprising a cement composition containing cement and fine aggregate, and the liquid quick-setting admixture according to any one of [2] to [4] above.
[7] The repair material according to [6] above, wherein the liquid quick-setting admixture further contains a polymer.
[8] The repair material according to any one of [5] to [7] above, wherein the content of the fine aggregate in the composition is 40 to 300 parts by mass per 100 parts by mass of the cement.
[9] A hardened body obtained by using the repair material according to any one of [5] to [8] above.
（条件）
観測核：２７Ａｌ
試料管回転数：１２Ｈｚ
測定温度：２５℃
パルス幅：５μｓｅｃ（４５°パルス）
待ち時間：５秒
外部標準：塩化アルミニウム水溶液
［２］ セメント及び細骨材を含有するセメント組成物とともに用いられる補修用の液体急結剤であって、アルミニウム成分及び硫黄成分を含有し、下記の条件で測定される２７Ａｌ－ＮＭＲによって得られるスペクトルにおいて、化学シフト－１．０ｐｐｍ以上３．０ｐｐｍ以下の範囲にピークを有する、補修用の液体急結剤。
（条件）
観測核：２７Ａｌ
試料管回転数：１２Ｈｚ
測定温度：２５℃
パルス幅：５μｓｅｃ（４５°パルス）
待ち時間：５秒
外部標準：塩化アルミニウム水溶液
［３］ 前記化学シフト－１．０ｐｐｍ以上３．０ｐｐｍ以下の範囲のピークの半値幅が、１０．０ｐｐｍ以下である、上記［１］または［２］に記載の液体急結剤。
［４］ 前記液体急結剤中の全アルカリ量Ｒ２Ｏ（Ｒはアルカリ金属）が、１．０質量％以下である、上記［１］～［３］のいずれか１つに記載の液体急結剤。
［５］ セメント、ポリマー及び細骨材を含有するセメント組成物と、上記［１］、［３］または［４］のいずれか１つに記載の液体急結剤とを含有する、補修材料。
［６］ セメント及び細骨材を含有するセメント組成物と、上記［２］～［４］のいずれか１つに記載の液体急結剤とを含有する、補修材料。
［７］ 前記液体急結剤が、さらにポリマーを含有する、上記［６］に記載の補修材料。
［８］ 前記組成物中の細骨材の含有量が、前記セメント１００質量部に対して４０～３００質量部である、上記［５］～［７］のいずれか１つに記載の補修材料。
［９］ 上記［５］～［８］のいずれか１つに記載の補修材料を用いてなる、硬化体。 [1] A liquid quick-setting admixture used together with a cement composition containing cement, a polymer, and a fine aggregate, the liquid quick-setting admixture containing an aluminum component and a sulfur component and having a chemical shift peak in the range of -1.0 ppm to 3.0 ppm in a spectrum obtained by 27Al -NMR measured under the following conditions.
(conditions)
Observed nucleus: 27Al
Sample tube rotation speed: 12Hz
Measurement temperature: 25°C
Pulse width: 5 μsec (45° pulse)
Waiting time: 5 seconds External standard: aluminum chloride aqueous solution [2] A liquid quick-setting admixture for repair to be used together with a cement composition containing cement and fine aggregate, the liquid quick-setting admixture for repair containing an aluminum component and a sulfur component, and having a peak in the chemical shift range of -1.0 ppm or more and 3.0 ppm or less in a spectrum obtained by 27Al -NMR measured under the following conditions.
(conditions)
Observed nucleus: 27Al
Sample tube rotation speed: 12Hz
Measurement temperature: 25°C
Pulse width: 5 μsec (45° pulse)
Waiting time: 5 seconds External standard: aluminum chloride aqueous solution [3] The liquid quick-setting admixture according to the above [1] or [2], wherein the half-width of the peak in the chemical shift range of −1.0 ppm to 3.0 ppm is 10.0 ppm or less.
[4] The liquid quick-setting admixture according to any one of the above [1] to [3], wherein the total alkali content R 2 O (R is an alkali metal) in the liquid quick-setting admixture is 1.0 mass % or less.
[5] A repair material comprising a cement composition containing cement, a polymer and a fine aggregate, and the liquid quick-setting admixture according to any one of [1], [3] and [4] above.
[6] A repair material comprising a cement composition containing cement and fine aggregate, and the liquid quick-setting admixture according to any one of [2] to [4] above.
[7] The repair material according to [6] above, wherein the liquid quick-setting admixture further contains a polymer.
[8] The repair material according to any one of [5] to [7] above, wherein the content of the fine aggregate in the composition is 40 to 300 parts by mass per 100 parts by mass of the cement.
[9] A hardened body obtained by using the repair material according to any one of [5] to [8] above.
本発明によれば、優れた貯蔵安定性を有し、セメント組成物とともに用いた際、付着性を良好にする液体急結剤を提供することが出来る。
The present invention provides a liquid quick-setting agent that has excellent storage stability and improves adhesion when used with a cement composition.
以下、本発明の実施形態（本実施形態）を詳細に説明するが、本発明は当該実施形態に限定されるものではない。なお、本明細書における「％」は特に規定しない限り質量基準とする。
Below, an embodiment of the present invention (the present embodiment) will be described in detail, but the present invention is not limited to this embodiment. Note that "%" in this specification is based on mass unless otherwise specified.
［１．液体急結剤］
本実施形態に係る液体急結剤の第一の態様は、セメント、ポリマー及び細骨材を含有するセメント組成物とともに用いられる液体急結剤であって、アルミニウム成分及び硫黄成分を含有し、下記の条件で測定される２７Ａｌ－ＮＭＲによって得られるスペクトルにおいて、化学シフト－１．０ｐｐｍ以上３．０ｐｐｍ以下の範囲にピークを有する液体急結剤である。本発明の液体急結剤は、アルミニウム成分及び硫黄成分を含有し、２７Ａｌ－ＮＭＲによって得られるスペクトルにおいて所定の位置にピークを有することにより、優れた貯蔵安定性を有し、セメント、ポリマー、及び細骨材を含有するセメント組成物とともに用いた際、だれを抑制し付着強度を向上させることにより付着性を良好にする。
（条件）
観測核：２７Ａｌ
試料管回転数：１２Ｈｚ
測定温度：２５℃
パルス幅：５μｓｅｃ（４５°パルス）
待ち時間：５秒
外部標準：塩化アルミニウム水溶液 [1. Liquid quick-setting agent]
A first aspect of the liquid quick-setting admixture according to this embodiment is a liquid quick-setting admixture used together with a cement composition containing cement, a polymer, and a fine aggregate, the liquid quick-setting admixture containing an aluminum component and a sulfur component and having a peak in a chemical shift range of -1.0 ppm or more and 3.0 ppm or less in a spectrum obtained by 27Al -NMR measured under the following conditions: The liquid quick-setting admixture of the present invention contains an aluminum component and a sulfur component and has a peak at a predetermined position in the spectrum obtained by 27Al -NMR, thereby having excellent storage stability, and when used together with a cement composition containing cement, a polymer, and a fine aggregate, the liquid quick-setting admixture suppresses sagging and improves adhesion strength, thereby improving adhesion.
(conditions)
Observed nucleus: 27Al
Sample tube rotation speed: 12Hz
Measurement temperature: 25°C
Pulse width: 5 μsec (45° pulse)
Waiting time: 5 seconds External standard: Aluminum chloride aqueous solution
本実施形態に係る液体急結剤の第一の態様は、セメント、ポリマー及び細骨材を含有するセメント組成物とともに用いられる液体急結剤であって、アルミニウム成分及び硫黄成分を含有し、下記の条件で測定される２７Ａｌ－ＮＭＲによって得られるスペクトルにおいて、化学シフト－１．０ｐｐｍ以上３．０ｐｐｍ以下の範囲にピークを有する液体急結剤である。本発明の液体急結剤は、アルミニウム成分及び硫黄成分を含有し、２７Ａｌ－ＮＭＲによって得られるスペクトルにおいて所定の位置にピークを有することにより、優れた貯蔵安定性を有し、セメント、ポリマー、及び細骨材を含有するセメント組成物とともに用いた際、だれを抑制し付着強度を向上させることにより付着性を良好にする。
（条件）
観測核：２７Ａｌ
試料管回転数：１２Ｈｚ
測定温度：２５℃
パルス幅：５μｓｅｃ（４５°パルス）
待ち時間：５秒
外部標準：塩化アルミニウム水溶液 [1. Liquid quick-setting agent]
A first aspect of the liquid quick-setting admixture according to this embodiment is a liquid quick-setting admixture used together with a cement composition containing cement, a polymer, and a fine aggregate, the liquid quick-setting admixture containing an aluminum component and a sulfur component and having a peak in a chemical shift range of -1.0 ppm or more and 3.0 ppm or less in a spectrum obtained by 27Al -NMR measured under the following conditions: The liquid quick-setting admixture of the present invention contains an aluminum component and a sulfur component and has a peak at a predetermined position in the spectrum obtained by 27Al -NMR, thereby having excellent storage stability, and when used together with a cement composition containing cement, a polymer, and a fine aggregate, the liquid quick-setting admixture suppresses sagging and improves adhesion strength, thereby improving adhesion.
(conditions)
Observed nucleus: 27Al
Sample tube rotation speed: 12Hz
Measurement temperature: 25°C
Pulse width: 5 μsec (45° pulse)
Waiting time: 5 seconds External standard: Aluminum chloride aqueous solution
また、本実施形態に係る液体急結剤の第二の態様は、セメント及び細骨材を含有するセメント組成物とともに用いられる補修用の液体急結剤であって、アルミニウム成分及び硫黄成分を含有し、既述の条件で測定される２７Ａｌ－ＮＭＲによって得られるスペクトルにおいて、化学シフト－１．０ｐｐｍ以上３．０ｐｐｍ以下の範囲にピークを有する補修用の液体急結剤である。本発明の液体急結剤は、アルミニウム成分及び硫黄成分を含有し、２７Ａｌ－ＮＭＲによって得られるスペクトルにおいて所定の位置にピークを有することにより、優れた貯蔵安定性を有し、セメント及び細骨材を含有するセメント組成物とともに補修用として用いた際、だれを抑制し付着強度を向上させることにより付着性を良好にする。
A second aspect of the liquid quick-setting admixture according to this embodiment is a liquid quick-setting admixture for repair used together with a cement composition containing cement and fine aggregate, the liquid quick-setting admixture containing an aluminum component and a sulfur component and having a peak in the chemical shift range of -1.0 ppm to 3.0 ppm in the spectrum obtained by 27Al -NMR measured under the conditions described above. The liquid quick-setting admixture of the present invention contains an aluminum component and a sulfur component and has a peak at a predetermined position in the spectrum obtained by 27Al -NMR, thereby having excellent storage stability, and when used for repair together with a cement composition containing cement and fine aggregate, it suppresses sagging and improves adhesion strength, thereby improving adhesion.
第一の態様及び第二の態様の液体急結剤は、２７Ａｌ－ＮＭＲによって得られるスペクトルにおいて、化学シフト－１．０ｐｐｍ以上３．０ｐｐｍ以下の範囲にピークを有する。また、当該ピークの半値幅は、例えば、１０．０ｐｐｍ以下が好ましく、９．０ｐｐｍ以下がより好ましく、８．０ｐｐｍ以下がさらに好ましい。これにより、液体急結剤の貯蔵安定性を向上することができる。なお、半値幅は、例えば、０．１ｐｐｍ以上でもよい。なお、液体急結剤の２７Ａｌ－ＮＭＲ測定は、市販の測定装置、例えば、日本電子製の超伝導核磁気共鳴装置（ＥＣＸ－４００）を用いて行うことができる。
以下、第一の態様及び第二の態様をまとめて単に液体急結剤ということがある。 The liquid quick-setting admixture of the first and second embodiments has a peak in the chemical shift range of -1.0 ppm to 3.0 ppm in the spectrum obtained by 27 Al-NMR. The half-width of the peak is preferably 10.0 ppm or less, more preferably 9.0 ppm or less, and even more preferably 8.0 ppm or less, for example. This can improve the storage stability of the liquid quick-setting admixture. The half-width may be, for example, 0.1 ppm or more. The 27 Al-NMR measurement of the liquid quick-setting admixture can be performed using a commercially available measuring device, for example, a superconducting nuclear magnetic resonance device (ECX-400) manufactured by JEOL Ltd.
Hereinafter, the first and second embodiments may be collectively referred to simply as a liquid quick-setting admixture.
以下、第一の態様及び第二の態様をまとめて単に液体急結剤ということがある。 The liquid quick-setting admixture of the first and second embodiments has a peak in the chemical shift range of -1.0 ppm to 3.0 ppm in the spectrum obtained by 27 Al-NMR. The half-width of the peak is preferably 10.0 ppm or less, more preferably 9.0 ppm or less, and even more preferably 8.0 ppm or less, for example. This can improve the storage stability of the liquid quick-setting admixture. The half-width may be, for example, 0.1 ppm or more. The 27 Al-NMR measurement of the liquid quick-setting admixture can be performed using a commercially available measuring device, for example, a superconducting nuclear magnetic resonance device (ECX-400) manufactured by JEOL Ltd.
Hereinafter, the first and second embodiments may be collectively referred to simply as a liquid quick-setting admixture.
液体急結剤は、アルミニウム成分及び硫黄成分を含有する。アルミニウム成分の原料としては、例えば、硫酸アルミニウム、各種ミョウバン、水酸化アルミニウム等を使用することができ、硫黄成分の原料としては、硫酸等を使用することができる。ここで、アルミニウム分の原料と硫黄分の原料との比率において、アルミニウム分の原料の比率を大きくすると、上記化学シフトが所望の範囲に入りやすく、硫黄分の原料の比率を大きくすると、半値幅が小さくなりやすい。
The liquid quick-setting admixture contains an aluminum component and a sulfur component. For example, aluminum sulfate, various alums, aluminum hydroxide, etc. can be used as the raw material for the aluminum component, and sulfuric acid, etc. can be used as the raw material for the sulfur component. Here, in the ratio of the aluminum raw material to the sulfur raw material, if the ratio of the aluminum raw material is increased, the above chemical shift tends to fall within the desired range, and if the ratio of the sulfur raw material is increased, the half-width tends to become smaller.
液体急結剤中のアルミニウム成分は、付着性及び貯蔵安定性の観点から、液体急結剤の質量を１００％とすると、Ａｌ２Ｏ３換算で３．０～２０．０％であり、５．０～１８．０％が好ましく、７．０～１５．０％がさらに好ましい。液体急結剤中のアルミニウム成分の含有量は、液体急結剤調製時に、アルミニウム成分の原料の使用量を調整することで、液体急結剤中のアルミニウム成分をＡｌ２Ｏ３換算で上記範囲内とすることができる。
From the viewpoints of adhesion and storage stability, the aluminum component in the liquid quick-setting admixture is 3.0 to 20.0%, preferably 5.0 to 18.0%, and more preferably 7.0 to 15.0%, calculated as Al2O3 , when the mass of the liquid quick-setting admixture is taken as 100%. The content of the aluminum component in the liquid quick-setting admixture can be adjusted to be within the above range, calculated as Al2O3 , by adjusting the amount of raw material of the aluminum component used when preparing the liquid quick - setting admixture.
液体急結剤部中の硫黄成分は、付着性及び貯蔵安定性の観点から、液体急結剤の質量を１００％とすると、ＳＯ３換算で１０．０～３０．０％であり、１５．０～２９．０％が好ましく、１５．０～２０．５％がさらに好ましい。液体急結剤中の硫黄成分の含有量は、液体急結剤調製時に、硫黄成分の原料の使用量を調整することで、液体急結剤中の硫黄成分をＳＯ３換算で上記範囲内とすることができる。
From the viewpoints of adhesion and storage stability, the sulfur component in the liquid quick-setting admixture is 10.0 to 30.0%, preferably 15.0 to 29.0%, and more preferably 15.0 to 20.5%, calculated as SO3 , when the mass of the liquid quick-setting admixture is taken as 100%. The content of the sulfur component in the liquid quick-setting admixture can be adjusted to within the above range in terms of SO3 by adjusting the amount of raw material of the sulfur component used when preparing the liquid quick-setting admixture.
液体急結剤は、環境保全の観点から、フッ化物イオン濃度が、５００ｐｐｍ以下であることが好ましく、４５０ｐｐｍ以下がより好ましく、３５０ｐｐｍ以下がさらに好ましく、０ｐｐｍであってもよい。なお、本発明において、液体急結剤中のフッ化物イオン濃度は、市販の分析装置、例えば、Ｔｈｅｒｍｏ Ｓｃｉｅｎｔｉｆｉｃ製のイオンクロマトグラフィー（ＩＣＳ２１００）によって測定することができる。分析に際しては、予めフッ化物イオンが検量線内となるように希釈することで、測定を実施することができる。
From the viewpoint of environmental conservation, the fluoride ion concentration of the liquid quick-setting admixture is preferably 500 ppm or less, more preferably 450 ppm or less, even more preferably 350 ppm or less, and may be 0 ppm. In the present invention, the fluoride ion concentration in the liquid quick-setting admixture can be measured by a commercially available analyzer, for example, an ion chromatograph (ICS2100) manufactured by Thermo Scientific. When analyzing, the measurement can be performed by diluting the liquid in advance so that the fluoride ions are within the calibration curve.
液体急結剤のｐＨは、７以下であることが好ましく、５以下であることがより好ましい。ｐＨが７以下であることで、環境負荷低減効果及び人体への悪影響を抑制させることができる。また、ｐＨは２以上であることが好ましい。なお、液体急結剤のｐＨは、ｐＨ計を用いて測定することができる。
The pH of the liquid quick-setting admixture is preferably 7 or less, and more preferably 5 or less. A pH of 7 or less can reduce the environmental impact and suppress adverse effects on the human body. The pH is preferably 2 or more. The pH of the liquid quick-setting admixture can be measured using a pH meter.
液体急結剤における全アルカリ量Ｒ２Ｏ（Ｒはアルカリ金属）は、作業者の安全性の観点から、１．０％以下が好ましく、０．８％以下がより好ましく、０．５％以下がさらに好ましい。また、０％以上であってもよい。なお、液体急結剤中の全アルカリ量Ｒ２Ｏは、原子吸光法により測定することができる。
The total alkali content R2O (R is an alkali metal) in the liquid quick-setting admixture is preferably 1.0% or less, more preferably 0.8% or less, and even more preferably 0.5% or less, from the viewpoint of worker safety. It may also be 0% or more. The total alkali content R2O in the liquid quick-setting admixture can be measured by atomic absorption spectrometry.
液体急結剤は、例えば、硫酸アルミニウム、各種ミョウバン、水酸化アルミニウム、硫酸等の原料を混合し、加熱して反応させることによって得ることが出来る。加熱温度としては、７０～１００℃が好ましく、８５～１００℃がより好ましく、８５～９５℃がさらに好ましい。反応時間としては、３０～１５０分が好ましく、６０～１５０分がより好ましく、９０～１２０分がさらに好ましい。
Liquid quick-setting agents can be obtained by mixing raw materials such as aluminum sulfate, various alums, aluminum hydroxide, and sulfuric acid, and then heating and reacting them. The heating temperature is preferably 70 to 100°C, more preferably 85 to 100°C, and even more preferably 85 to 95°C. The reaction time is preferably 30 to 150 minutes, more preferably 60 to 150 minutes, and even more preferably 90 to 120 minutes.
液体急結剤は、既述の成分以外に、本発明の効果を阻害しない範囲で種々の添加剤を含有させることができるが、取扱い性の観点から、アルミン酸ソーダは含有しないことが好ましい。
In addition to the components already mentioned, the liquid quick-setting admixture can contain various additives as long as they do not impair the effects of the present invention, but from the standpoint of ease of handling, it is preferable that it does not contain sodium aluminate.
［２．補修材料］
本実施形態に係る補修材料は、セメント、ポリマー及び細骨材を含有するセメント組成物と、本発明の液体急結剤とを含有する。補修材料中の液体急結剤の含有量は、セメント組成物中のセメント１００質量部に対して、０．０１～２０質量部が好ましく、０．０３～１０質量部がより好ましく、０．０５～５質量部がさらに好ましい。補修材料中の液体急結剤の含有量が上記範囲内であると、補修材料の付着性を向上させることができる。 [2. Repair Materials]
The repair material according to the present embodiment contains a cement composition containing cement, a polymer, and fine aggregate, and the liquid quick-setting admixture of the present invention. The content of the liquid quick-setting admixture in the repair material is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of cement in the cement composition. When the content of the liquid quick-setting admixture in the repair material is within the above range, the adhesion of the repair material can be improved.
本実施形態に係る補修材料は、セメント、ポリマー及び細骨材を含有するセメント組成物と、本発明の液体急結剤とを含有する。補修材料中の液体急結剤の含有量は、セメント組成物中のセメント１００質量部に対して、０．０１～２０質量部が好ましく、０．０３～１０質量部がより好ましく、０．０５～５質量部がさらに好ましい。補修材料中の液体急結剤の含有量が上記範囲内であると、補修材料の付着性を向上させることができる。 [2. Repair Materials]
The repair material according to the present embodiment contains a cement composition containing cement, a polymer, and fine aggregate, and the liquid quick-setting admixture of the present invention. The content of the liquid quick-setting admixture in the repair material is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of cement in the cement composition. When the content of the liquid quick-setting admixture in the repair material is within the above range, the adhesion of the repair material can be improved.
セメントは、特に限定されるものではなく、普通、早強、超早強、低熱及び中庸熱等の各種セメント、これらのセメントに、高炉スラグやフライアッシュやシリカフューム等を混合した各種混合セメント、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）、市販されている微粒子セメント等が挙げられ、各種セメントや各種混合セメントを微粉末化して使用することも可能である。また、通常セメントに使用されている成分（例えばセッコウ等）量を増減して調整されたものも使用可能である。
本発明では、付着性の観点から、普通ポルトランドセメントや早強ポルトランドセメントを選定することが好ましい。 The cement is not particularly limited, and examples thereof include various cements such as normal, early strength, super early strength, low heat and medium heat, various mixed cements obtained by mixing these cements with blast furnace slag, fly ash, silica fume, etc., environmentally friendly cements (eco-cements) manufactured using municipal waste incineration ash and sewage sludge incineration ash as raw materials, commercially available fine particle cements, etc., and various cements and various mixed cements can be used in a fine powder form. Also, cements adjusted by increasing or decreasing the amount of components (e.g., gypsum) used in normal cements can be used.
In the present invention, it is preferable to select ordinary Portland cement or high-early-strength Portland cement from the viewpoint of adhesion.
本発明では、付着性の観点から、普通ポルトランドセメントや早強ポルトランドセメントを選定することが好ましい。 The cement is not particularly limited, and examples thereof include various cements such as normal, early strength, super early strength, low heat and medium heat, various mixed cements obtained by mixing these cements with blast furnace slag, fly ash, silica fume, etc., environmentally friendly cements (eco-cements) manufactured using municipal waste incineration ash and sewage sludge incineration ash as raw materials, commercially available fine particle cements, etc., and various cements and various mixed cements can be used in a fine powder form. Also, cements adjusted by increasing or decreasing the amount of components (e.g., gypsum) used in normal cements can be used.
In the present invention, it is preferable to select ordinary Portland cement or high-early-strength Portland cement from the viewpoint of adhesion.
セメントは、製造コストや強度発現性の観点から、ブレーン比表面積値が、２，５００～７，０００ｃｍ２／ｇであることが好ましく、２，７５０ｃｍ２／ｇ～６，０００ｃｍ２／ｇであることがより好ましく、３，０００ｃｍ２／ｇ～４，５００ｃｍ２／ｇであることがさらに好ましい。
ブレーン比表面積値は、ＪＩＳ Ｒ ５２０１：２０１５（セメントの物理試験方法）に準拠して求められる。 From the viewpoints of production costs and strength development, the cement preferably has a Blaine specific surface area of 2,500 to 7,000 cm 2 /g, more preferably 2,750 cm 2 /g to 6,000 cm 2 /g, and even more preferably 3,000 cm 2 /g to 4,500 cm 2 /g.
The Blaine specific surface area value is determined in accordance with JIS R 5201:2015 (physical testing method for cement).
ブレーン比表面積値は、ＪＩＳ Ｒ ５２０１：２０１５（セメントの物理試験方法）に準拠して求められる。 From the viewpoints of production costs and strength development, the cement preferably has a Blaine specific surface area of 2,500 to 7,000 cm 2 /g, more preferably 2,750 cm 2 /g to 6,000 cm 2 /g, and even more preferably 3,000 cm 2 /g to 4,500 cm 2 /g.
The Blaine specific surface area value is determined in accordance with JIS R 5201:2015 (physical testing method for cement).
細骨材は、特に限定されるものではなく、通常のセメントモルタルやコンクリートに使用するものと同様の細骨材が使用可能である。すなわち、川砂、砕石、砕砂、石灰砂、けい砂、色砂、及び人工軽量骨材等が使用可能であり、これらを組み合わせることも可能である。特に、シリカ質のけい砂や石灰砂の使用が好ましく、細骨材の粒度は、ＪＩＳ６～８号が好ましい。
The fine aggregate is not particularly limited, and the same fine aggregates as those used in ordinary cement mortar and concrete can be used. In other words, river sand, crushed stone, crushed sand, lime sand, silica sand, colored sand, artificial lightweight aggregate, etc. can be used, and combinations of these are also possible. In particular, the use of silica sand or lime sand, which is a silica-based material, is preferable, and the grain size of the fine aggregate is preferably JIS No. 6 to 8.
セメント組成物中の細骨材の含有割合は、セメント１００質量部に対して、４０～３００質量部であることが好ましく、４５～２７５質量部であることがより好ましく、５０～２５０質量部であることがさらに好ましい。細骨材の含有割合が上記範囲内であることで、補修材料の付着性をより良好にすることができる。
The content of fine aggregate in the cement composition is preferably 40 to 300 parts by mass, more preferably 45 to 275 parts by mass, and even more preferably 50 to 250 parts by mass, per 100 parts by mass of cement. By keeping the content of fine aggregate within the above range, the adhesion of the repair material can be improved.
セメント組成物は、さらにポリマーを含有することが好ましい。ポリマーのとしては、特に限定されるものではないが、例えば、アクリロニトリル・ブタジエンゴム、スチレン・ブタジエンゴム、クロロプレンゴム、天然ゴム等のゴムラテックスや、エチレン・酢酸ビニル共重合体、ポリアクリル酸エステル、スチレン・アクリル酸エステル共重合体やアクリロニトリル・アクリル酸エステルに代表されるアクリル酸エステル系共重合体、酢酸ビニルビニルバーサテート系共重合体等の樹脂エマルジョン等が挙げられる。
ポリマーの形態としては、再乳化型粉末タイプや液体タイプがあり、付着性改善、さらに、モルタルの耐久性向上のために使用される。 The cement composition preferably further contains a polymer, which is not particularly limited, but examples thereof include rubber latexes such as acrylonitrile-butadiene rubber, styrene-butadiene rubber, chloroprene rubber, and natural rubber, resin emulsions such as ethylene-vinyl acetate copolymers, acrylic acid ester copolymers such as polyacrylic acid esters, styrene-acrylic acid ester copolymers, and acrylonitrile-acrylic acid ester copolymers, and vinyl acetate-vinyl versatate copolymers.
The polymer is available in re-emulsifiable powder and liquid forms, and is used to improve adhesion and the durability of mortar.
ポリマーの形態としては、再乳化型粉末タイプや液体タイプがあり、付着性改善、さらに、モルタルの耐久性向上のために使用される。 The cement composition preferably further contains a polymer, which is not particularly limited, but examples thereof include rubber latexes such as acrylonitrile-butadiene rubber, styrene-butadiene rubber, chloroprene rubber, and natural rubber, resin emulsions such as ethylene-vinyl acetate copolymers, acrylic acid ester copolymers such as polyacrylic acid esters, styrene-acrylic acid ester copolymers, and acrylonitrile-acrylic acid ester copolymers, and vinyl acetate-vinyl versatate copolymers.
The polymer is available in re-emulsifiable powder and liquid forms, and is used to improve adhesion and the durability of mortar.
セメント組成物中のポリマーの含有割合は、セメント１００質量部に対して、固形分量で１～２０質量部であることが好ましく、２～１８質量部であることがより好ましく、３～１５質量部であることがさらに好ましい。ポリマーの含有割合が上記範囲内であることで、補修材料の付着性を向上させることができる。
The polymer content in the cement composition is preferably 1 to 20 parts by mass, more preferably 2 to 18 parts by mass, and even more preferably 3 to 15 parts by mass, in terms of solid content per 100 parts by mass of cement. By keeping the polymer content within the above range, the adhesion of the repair material can be improved.
セメント組成物は、さらに繊維を含有することが好ましい。繊維としては、特に限定されるものではないが、例えば、ビニロン繊維、プロピレン繊維、アクリル繊維、ナイロン繊維、アラミド繊維等の高分子繊維類や、鋼繊維、ガラス繊維、炭素繊維、及び玄武岩等の岩石を溶融紡糸した繊維等の無機繊維類が挙げられる。
The cement composition preferably further contains fibers. The fibers are not particularly limited, but examples include polymer fibers such as vinylon fibers, propylene fibers, acrylic fibers, nylon fibers, and aramid fibers, as well as inorganic fibers such as steel fibers, glass fibers, carbon fibers, and fibers made by melt-spinning rocks such as basalt.
セメント組成物中の繊維の含有割合は、セメント１００質量部に対して、０．０２～３．０質量部であることが好ましく、０．０３～２．５質量部であることがより好ましく、０．０５～２．０質量部であることがさらに好ましい。繊維の含有割合が０．０２質量部以上であることで、付着性を改善する効果を十分に発揮することができる。また、繊維の含有割合が１．５質量部以下であることで、流動性を高めることができる。繊維の長さは、コテ仕上げ面の美観の観点から、１５ｍｍ以下であることが好ましく、１２ｍｍ以下であることがより好ましく、１０ｍｍ以下であることがさらに好ましい。繊維の長さの下限は特に限定されず、例えば、１ｍｍ以上であればよい。
The fiber content in the cement composition is preferably 0.02 to 3.0 parts by mass, more preferably 0.03 to 2.5 parts by mass, and even more preferably 0.05 to 2.0 parts by mass, per 100 parts by mass of cement. When the fiber content is 0.02 parts by mass or more, the effect of improving adhesion can be fully exerted. Furthermore, when the fiber content is 1.5 parts by mass or less, the fluidity can be increased. From the viewpoint of the aesthetics of the trowel-finished surface, the length of the fiber is preferably 15 mm or less, more preferably 12 mm or less, and even more preferably 10 mm or less. There is no particular lower limit to the length of the fiber, and it may be, for example, 1 mm or more.
セメント組成物は、さらに減水剤を含有することが好ましい。減水剤としては、特に限定されるものではなく、例えば、ナフタレン系減水剤、メラミン系減水剤、アミノスルホン酸系減水剤、ポリカルボン酸系減水剤等が挙げられ、本発明ではこれら減水剤のうちの一種又は二種以上が使用可能である。
The cement composition preferably further contains a water-reducing agent. There are no particular limitations on the water-reducing agent, and examples of the water-reducing agent include naphthalene-based water-reducing agents, melamine-based water-reducing agents, aminosulfonic acid-based water-reducing agents, polycarboxylic acid-based water-reducing agents, etc., and one or more of these water-reducing agents can be used in the present invention.
セメント組成物中の減水剤の含有割合は、セメント１００質量部に対して、固形分換算で０．１～２質量部が好ましく、０．２～１．８質量部がより好ましく、０．３～１．０質量部がさらに好ましい。減水剤の含有割合が上記下限値以上であることで、十分な流動性を得ることができる。また、減水剤の含有割合が上記上限値以下であることで、材料分離を抑制することができる。
The content of the water-reducing agent in the cement composition is preferably 0.1 to 2 parts by mass, more preferably 0.2 to 1.8 parts by mass, and even more preferably 0.3 to 1.0 parts by mass, calculated as solid content per 100 parts by mass of cement. By having the content of the water-reducing agent be equal to or greater than the above lower limit, sufficient fluidity can be obtained. Furthermore, by having the content of the water-reducing agent be equal to or less than the above upper limit, material separation can be suppressed.
セメント組成物は、さらに急硬材を含有してもよい。急硬材としては、凝結を促進し、短期での強度増進を図るものであれば、特に限定されるものではない。急硬材は、凝結を促進するものとして、ギ酸カルシウムに代表される有機酸のカルシウム塩、硝酸塩、硫酸塩、炭酸塩、チオシアン酸塩、アミン類、無水マレイン酸、水ガラスに代表される珪酸塩、硫酸アルミニウム、及び、ミョウバンに代表されるアルミニウム塩、カルシウムアルミネート（アルミン酸カルシウム）等のアルミン酸塩等が挙げられる。これらの中では、強度発現性の観点から、アルミン酸塩が好ましく、カルシウムアルミネート（ＣＡ）を含むことがより好ましい。
The cement composition may further contain a hardening agent. There are no particular limitations on the hardening agent, so long as it promotes setting and increases strength in a short period of time. Examples of hardening agents that promote setting include calcium salts of organic acids such as calcium formate, nitrates, sulfates, carbonates, thiocyanates, amines, maleic anhydride, silicates such as water glass, aluminum sulfate, aluminum salts such as alum, and aluminates such as calcium aluminate (calcium aluminate). Of these, aluminates are preferred from the viewpoint of strength development, and it is more preferable for them to contain calcium aluminate (CA).
カルシウムアルミネートは、カルシア原料とアルミナ原料等とを混合して、キルンで焼成し、あるいは、電気炉で溶融し冷却して得られるＣａＯとＡｌ２Ｏ３とを主成分とする水和活性を有する物質の総称であり、結晶質、又は非晶質のいずれであっても使用可能である。硬化時間が早く、初期強度発現性が高い材料である。カルシウムアルミネートの代表的なものとしてはアルミナセメントが挙げられ、通常、市販品が使用できる。例えば、アルミナセメント１号、アルミナセメント２号などが使用できる。なかでも、アルミナセメントよりも短時間で硬化し、その後の初期強度発現性が高い点から、溶融後に急冷した非晶質カルシウムアルミネートが好ましい。
カルシウムアルミネートのなかでも、ＣａＯとＡｌ２Ｏ３とのモル比（ＣａＯ／Ａｌ２Ｏ３モル比）は、１．０～３．０であることが好ましく、１．７～２．５であることがより好ましい。モル比が上記範囲内であることで、硬化時間をより短縮して初期強度発現性を高めることができる。 Calcium aluminate is a general term for a substance having hydration activity and mainly composed of CaO and Al 2 O 3, which is obtained by mixing a calcia raw material and an alumina raw material, firing them in a kiln, or melting them in an electric furnace and cooling them, and can be used whether it is crystalline or amorphous. It is a material that has a fast hardening time and high initial strength development. A representative example of calcium aluminate is alumina cement, and commercially available products can usually be used. For example, alumina cement No. 1 and alumina cement No. 2 can be used. Among them, amorphous calcium aluminate that is melted and then rapidly cooled is preferred because it hardens in a shorter time than alumina cement and has a high initial strength development thereafter.
Among calcium aluminates, the molar ratio of CaO to Al 2 O 3 (CaO/Al 2 O 3 molar ratio) is preferably 1.0 to 3.0, and more preferably 1.7 to 2.5. By having the molar ratio within the above range, the curing time can be further shortened and the early strength development can be improved.
カルシウムアルミネートのなかでも、ＣａＯとＡｌ２Ｏ３とのモル比（ＣａＯ／Ａｌ２Ｏ３モル比）は、１．０～３．０であることが好ましく、１．７～２．５であることがより好ましい。モル比が上記範囲内であることで、硬化時間をより短縮して初期強度発現性を高めることができる。 Calcium aluminate is a general term for a substance having hydration activity and mainly composed of CaO and Al 2 O 3, which is obtained by mixing a calcia raw material and an alumina raw material, firing them in a kiln, or melting them in an electric furnace and cooling them, and can be used whether it is crystalline or amorphous. It is a material that has a fast hardening time and high initial strength development. A representative example of calcium aluminate is alumina cement, and commercially available products can usually be used. For example, alumina cement No. 1 and alumina cement No. 2 can be used. Among them, amorphous calcium aluminate that is melted and then rapidly cooled is preferred because it hardens in a shorter time than alumina cement and has a high initial strength development thereafter.
Among calcium aluminates, the molar ratio of CaO to Al 2 O 3 (CaO/Al 2 O 3 molar ratio) is preferably 1.0 to 3.0, and more preferably 1.7 to 2.5. By having the molar ratio within the above range, the curing time can be further shortened and the early strength development can be improved.
本発明で使用する急硬材の含有割合は、セメント１００質量部に対して、１～３０質量部であることが好ましく、３～２５質量部であることがより好ましく、５～２０質量部であることがさらに好ましい。また、急硬材としてカルシウムアルミネートを含有する場合、カルシウムアルミネートの含有割合は、セメント１００質量部に対して、２～２０質量部であることが好ましく、３～１８質量部であることがより好ましく、４～１５質量部であることがさらに好ましい。急硬材の含有割合が上記下限値以上であることで、強度発現性を良好としやすい。
The content of the hardening agent used in the present invention is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, and even more preferably 5 to 20 parts by mass, per 100 parts by mass of cement. Furthermore, when calcium aluminate is contained as the hardening agent, the content of calcium aluminate is preferably 2 to 20 parts by mass, more preferably 3 to 18 parts by mass, and even more preferably 4 to 15 parts by mass, per 100 parts by mass of cement. By having the content of the hardening agent be equal to or greater than the above lower limit, it is easier to achieve good strength development.
本発明では、性能に悪影響を与えない範囲で、凝結調整剤、ＡＥ剤、防錆剤、撥水剤、抗菌剤、着色剤、防凍剤、石灰石微粉末、高炉徐冷スラグ微粉末、下水汚泥焼却灰やその溶融スラグ、都市ゴミ焼却灰やその溶融スラグ、及びパルプスラッジ焼却灰等の混和材料、消泡剤、増粘剤、収縮低減剤、ベントナイト、セピオライト等の粘土鉱物、並びに、ハイドロタルサイト等のアニオン交換体等のうちの一種又は二種以上を、本発明の目的を実質的に阻害しない範囲で使用することが可能である。
In the present invention, one or more of the following may be used to the extent that they do not adversely affect performance: setting regulators, air-enhancing agents, rust inhibitors, water repellents, antibacterial agents, colorants, antifreeze agents, fine limestone powder, finely cooled blast furnace slag powder, admixtures such as sewage sludge incineration ash and its molten slag, municipal waste incineration ash and its molten slag, and pulp sludge incineration ash; defoamers, thickeners, shrinkage reducing agents, clay minerals such as bentonite and sepiolite; and anion exchangers such as hydrotalcite.
本発明の補修材料において、各材料の混合方法は特に限定されるものではなく、それぞれの材料を施工時に混合しても良いし、あらかじめ一部を、あるいは全部を混合しておいても差し支えない。例えば、吹付け工法で用いる場合は、あらかじめセメント組成物の材料を混合し、液体急結剤を吹付け時に混合して補修材料を吹付けることができる。混合装置としては、既存のいかなる装置、例えば、傾胴ミキサ、オムニミキサ、ヘンシェルミキサ、Ｖ型ミキサ、及びナウタミキサ等の使用が可能である。
In the repair material of the present invention, the method of mixing each material is not particularly limited, and each material may be mixed at the time of construction, or some or all of the materials may be mixed in advance. For example, when using a spraying method, the materials of the cement composition can be mixed in advance, and the liquid quick-setting agent can be mixed at the time of spraying to spray the repair material. As a mixing device, any existing device can be used, such as a tilting mixer, omni mixer, Henschel mixer, V-type mixer, and Nauta mixer.
［３．硬化体］
本実施形態に係る硬化体は、本発明の補修材料を用いてなる硬化体である。本発明の補修材料と水とを混練し、通常、左官コテによる塗り付け方法や、スクイズ式等のモルタルポンプにより施工箇所まで圧送して吹付けノズルより吹付ける吹付け方法により、硬化体とすることができる。 [3. Hardened body]
The hardened body according to the present embodiment is a hardened body obtained by using the repair material of the present invention. The repair material of the present invention is mixed with water, and the hardened body can be obtained by applying the mixture by a plastering trowel or by pumping the mixture to a work site by a squeeze mortar pump or the like and spraying the mixture from a spray nozzle.
本実施形態に係る硬化体は、本発明の補修材料を用いてなる硬化体である。本発明の補修材料と水とを混練し、通常、左官コテによる塗り付け方法や、スクイズ式等のモルタルポンプにより施工箇所まで圧送して吹付けノズルより吹付ける吹付け方法により、硬化体とすることができる。 [3. Hardened body]
The hardened body according to the present embodiment is a hardened body obtained by using the repair material of the present invention. The repair material of the present invention is mixed with water, and the hardened body can be obtained by applying the mixture by a plastering trowel or by pumping the mixture to a work site by a squeeze mortar pump or the like and spraying the mixture from a spray nozzle.
練り混ぜ水量は、使用する目的・用途や各材料の含有割合によって変化するため特に限定されるものではないが、補修材料１００質量部に対して、５～７０質量部であることが好ましく、８～６５質量部であることがより好ましく、１０～６０質量部であることがさらに好ましい。練り混ぜ水量が上記下限値以上であることで、流動性の低下を抑制し、発熱量が極めて大きくなることを抑制することができる。また、練り混ぜ水量が上記上限値以下であることで、強度発現性を確保することができる。
The amount of water to be mixed is not particularly limited as it varies depending on the purpose and application of use and the content ratio of each material, but is preferably 5 to 70 parts by mass, more preferably 8 to 65 parts by mass, and even more preferably 10 to 60 parts by mass per 100 parts by mass of repair material. By having the amount of water to be mixed equal to or above the lower limit, it is possible to prevent a decrease in fluidity and prevent the amount of heat generation from becoming extremely large. Furthermore, by having the amount of water to be mixed equal to or below the upper limit, it is possible to ensure strength expression.
本発明において、補修材料と水との練り混ぜ方法は特に限定されるものではないが、回転数が９００ｒｐｍ以上のハンドミキサ、通常のモルタルミキサ、又は二軸型の強制ミキサを使用することが好ましい。
ハンドミキサやモルタルミキサでの練り混ぜは、例えば、ペール缶等の容器やミキサにあらかじめ所定量の水を入れ、その後ミキサを回転させながら残りの補修材料を投入し、３分以上練り混ぜることが好ましい。又、強制ミキサでの練り混ぜは、例えば、あらかじめ補修材料をミキサに投入し、ミキサを回転させながら所定量の水を投入し、少なくとも４分以上練り混ぜることが好ましい。 In the present invention, the method for mixing the repair material and water is not particularly limited, but it is preferable to use a hand mixer with a rotation speed of 900 rpm or more, a normal mortar mixer, or a twin-shaft forced mixer.
For mixing with a hand mixer or mortar mixer, it is preferable to put a predetermined amount of water in a container such as a pail or a mixer in advance, then add the remaining repair material while rotating the mixer, and mix for at least 3 minutes. For mixing with a forced mixer, it is preferable to put the repair material in the mixer in advance, add a predetermined amount of water while rotating the mixer, and mix for at least 4 minutes.
ハンドミキサやモルタルミキサでの練り混ぜは、例えば、ペール缶等の容器やミキサにあらかじめ所定量の水を入れ、その後ミキサを回転させながら残りの補修材料を投入し、３分以上練り混ぜることが好ましい。又、強制ミキサでの練り混ぜは、例えば、あらかじめ補修材料をミキサに投入し、ミキサを回転させながら所定量の水を投入し、少なくとも４分以上練り混ぜることが好ましい。 In the present invention, the method for mixing the repair material and water is not particularly limited, but it is preferable to use a hand mixer with a rotation speed of 900 rpm or more, a normal mortar mixer, or a twin-shaft forced mixer.
For mixing with a hand mixer or mortar mixer, it is preferable to put a predetermined amount of water in a container such as a pail or a mixer in advance, then add the remaining repair material while rotating the mixer, and mix for at least 3 minutes. For mixing with a forced mixer, it is preferable to put the repair material in the mixer in advance, add a predetermined amount of water while rotating the mixer, and mix for at least 4 minutes.
以下、実施例及び比較例を用いて本発明を更に具体的に説明するが、本発明はその要旨を逸脱しない限り、下記の実施例に限定されるものではない。
The present invention will be explained in more detail below using examples and comparative examples, but the present invention is not limited to the following examples as long as it does not deviate from the gist of the invention.
［実施例１～８］
＜液体急結剤の調製＞
アルミニウム成分及び硫黄成分を、それぞれＡｌ２Ｏ３換算及びＳＯ３換算で表１に示す量となるよう各種原料を調整、混合し、９０℃で２時間加熱することで液体急結剤を作製した。 [Examples 1 to 8]
<Preparation of liquid quick-setting admixture>
Various raw materials were adjusted and mixed so that the aluminum component and sulfur component were in the amounts shown in Table 1, calculated as Al 2 O 3 and SO 3 , respectively, and heated at 90° C. for 2 hours to produce a liquid quick-setting admixture.
＜液体急結剤の調製＞
アルミニウム成分及び硫黄成分を、それぞれＡｌ２Ｏ３換算及びＳＯ３換算で表１に示す量となるよう各種原料を調整、混合し、９０℃で２時間加熱することで液体急結剤を作製した。 [Examples 1 to 8]
<Preparation of liquid quick-setting admixture>
Various raw materials were adjusted and mixed so that the aluminum component and sulfur component were in the amounts shown in Table 1, calculated as Al 2 O 3 and SO 3 , respectively, and heated at 90° C. for 2 hours to produce a liquid quick-setting admixture.
＜使用材料＞
アルミニウム成分源：水酸化アルミニウム、工業用品用
硫黄成分源：硫酸、工業用品用
溶媒：純水 <Materials used>
Aluminum component source: Aluminum hydroxide, industrial grade Sulfur component source: Sulfuric acid, industrial grade Solvent: Pure water
アルミニウム成分源：水酸化アルミニウム、工業用品用
硫黄成分源：硫酸、工業用品用
溶媒：純水 <Materials used>
Aluminum component source: Aluminum hydroxide, industrial grade Sulfur component source: Sulfuric acid, industrial grade Solvent: Pure water
＜２７Ａｌ－ＮＭＲ測定＞
調製した液体急結剤は、超伝導核磁気共鳴装置（日本電子製、ＥＣＸ－４００）を用いて下記の条件で行い、ピークの化学シフト及び半値幅を測定した。結果を下記表１に示す。 < 27Al -NMR Measurement>
The prepared liquid quick-setting admixture was subjected to measurement of the chemical shift and half-width of the peak using a superconducting nuclear magnetic resonance spectrometer (manufactured by JEOL Ltd., ECX-400) under the following conditions. The results are shown in Table 1 below.
調製した液体急結剤は、超伝導核磁気共鳴装置（日本電子製、ＥＣＸ－４００）を用いて下記の条件で行い、ピークの化学シフト及び半値幅を測定した。結果を下記表１に示す。 < 27Al -NMR Measurement>
The prepared liquid quick-setting admixture was subjected to measurement of the chemical shift and half-width of the peak using a superconducting nuclear magnetic resonance spectrometer (manufactured by JEOL Ltd., ECX-400) under the following conditions. The results are shown in Table 1 below.
＜２７Ａｌ－ＮＭＲ測定条件＞
観測核：２７Ａｌ
試料管回転数：１２Ｈｚ
測定温度：２５℃
パルス幅：５μｓｅｃ（４５°パルス）
待ち時間：５秒
外部標準：塩化アルミニウム水溶液 < 27 Al-NMR measurement conditions>
Observed nucleus: 27Al
Sample tube rotation speed: 12Hz
Measurement temperature: 25°C
Pulse width: 5 μsec (45° pulse)
Waiting time: 5 seconds External standard: Aluminum chloride aqueous solution
観測核：２７Ａｌ
試料管回転数：１２Ｈｚ
測定温度：２５℃
パルス幅：５μｓｅｃ（４５°パルス）
待ち時間：５秒
外部標準：塩化アルミニウム水溶液 < 27 Al-NMR measurement conditions>
Observed nucleus: 27Al
Sample tube rotation speed: 12Hz
Measurement temperature: 25°C
Pulse width: 5 μsec (45° pulse)
Waiting time: 5 seconds External standard: Aluminum chloride aqueous solution
＜貯蔵試験＞
液体急結剤の貯蔵安定性を評価するために貯蔵試験を実施した。貯蔵性が低下すると特に低温環境において液体急結剤中に析出物が生成する。液体急結剤を１０℃環境１か月間静置し、その析出物をろ紙にて抽出し、液体急結剤１００ｇ当たりの析出物量を算出した。結果を下記表１に示す。 Storage test
A storage test was carried out to evaluate the storage stability of the liquid quick-setting admixture. When the storage stability is reduced, precipitates are formed in the liquid quick-setting admixture, especially in a low-temperature environment. The liquid quick-setting admixture was left to stand in a 10°C environment for one month, and the precipitates were extracted with filter paper, and the amount of precipitates per 100 g of the liquid quick-setting admixture was calculated. The results are shown in Table 1 below.
液体急結剤の貯蔵安定性を評価するために貯蔵試験を実施した。貯蔵性が低下すると特に低温環境において液体急結剤中に析出物が生成する。液体急結剤を１０℃環境１か月間静置し、その析出物をろ紙にて抽出し、液体急結剤１００ｇ当たりの析出物量を算出した。結果を下記表１に示す。 Storage test
A storage test was carried out to evaluate the storage stability of the liquid quick-setting admixture. When the storage stability is reduced, precipitates are formed in the liquid quick-setting admixture, especially in a low-temperature environment. The liquid quick-setting admixture was left to stand in a 10°C environment for one month, and the precipitates were extracted with filter paper, and the amount of precipitates per 100 g of the liquid quick-setting admixture was calculated. The results are shown in Table 1 below.
［比較例１～４］
実施例１～８と同様にして、液体急結剤を作製し、各試験により評価した。結果を表１に示す。 [Comparative Examples 1 to 4]
Liquid quick-setting admixtures were prepared and evaluated in the same manner as in Examples 1 to 8. The results are shown in Table 1.
実施例１～８と同様にして、液体急結剤を作製し、各試験により評価した。結果を表１に示す。 [Comparative Examples 1 to 4]
Liquid quick-setting admixtures were prepared and evaluated in the same manner as in Examples 1 to 8. The results are shown in Table 1.
（実験例１）
＜補修材料の調製＞
セメント１００質量部に対して、細骨材２００質量部、繊維０．１質量部、減水剤０．５質量部、水１４質量部とし、セメント組成物を調製した。このセメント組成物中のセメント１００質量部に対して、実施例１～５、８及び比較例１～２の液体急結剤を６質量部混合し、補修材料を調製した。 (Experimental Example 1)
<Preparation of repair material>
A cement composition was prepared by mixing 200 parts by mass of fine aggregate, 0.1 parts by mass of fiber, 0.5 parts by mass of water reducing agent, and 14 parts by mass of water with respect to 100 parts by mass of cement. 6 parts by mass of the liquid quick-setting admixture of Examples 1 to 5 and 8 and Comparative Examples 1 to 2 were mixed with 100 parts by mass of cement in this cement composition to prepare a repair material.
＜補修材料の調製＞
セメント１００質量部に対して、細骨材２００質量部、繊維０．１質量部、減水剤０．５質量部、水１４質量部とし、セメント組成物を調製した。このセメント組成物中のセメント１００質量部に対して、実施例１～５、８及び比較例１～２の液体急結剤を６質量部混合し、補修材料を調製した。 (Experimental Example 1)
<Preparation of repair material>
A cement composition was prepared by mixing 200 parts by mass of fine aggregate, 0.1 parts by mass of fiber, 0.5 parts by mass of water reducing agent, and 14 parts by mass of water with respect to 100 parts by mass of cement. 6 parts by mass of the liquid quick-setting admixture of Examples 1 to 5 and 8 and Comparative Examples 1 to 2 were mixed with 100 parts by mass of cement in this cement composition to prepare a repair material.
＜圧縮強度試験＞
圧縮強度：ＪＳＣＥ－Ｇ ５６１－２０１０に準じて型枠に吹付けて、材齢１日、２８日時点での圧縮強度を測定した。試験結果を下記表２に示す。 <Compressive strength test>
Compressive strength: The concrete was sprayed onto a formwork in accordance with JSCE-G 561-2010, and the compressive strength was measured at 1 day and 28 days after application. The test results are shown in Table 2 below.
圧縮強度：ＪＳＣＥ－Ｇ ５６１－２０１０に準じて型枠に吹付けて、材齢１日、２８日時点での圧縮強度を測定した。試験結果を下記表２に示す。 <Compressive strength test>
Compressive strength: The concrete was sprayed onto a formwork in accordance with JSCE-G 561-2010, and the compressive strength was measured at 1 day and 28 days after application. The test results are shown in Table 2 below.
＜厚塗り性試験（だれの有無）＞
下地をコンクリート製平板とし厚さ１０ｍｍ×縦１５０ｍｍ×横２５０ｍｍの型枠内にモルタルを吹き付け、コテ仕上げを行った後に、その枠を取りはずし、直ちに試験体を垂直に立て、１日静置し、だれの有無を確認した。試験結果を下記表２に示す。 <Thick coating test (presence or absence of dripping)>
The base was a concrete plate, and mortar was sprayed into a formwork measuring 10 mm thick x 150 mm long x 250 mm wide. After finishing with a trowel, the formwork was removed and the test specimen was immediately set up vertically and left to stand for one day, after which the presence or absence of sagging was confirmed. The test results are shown in Table 2 below.
下地をコンクリート製平板とし厚さ１０ｍｍ×縦１５０ｍｍ×横２５０ｍｍの型枠内にモルタルを吹き付け、コテ仕上げを行った後に、その枠を取りはずし、直ちに試験体を垂直に立て、１日静置し、だれの有無を確認した。試験結果を下記表２に示す。 <Thick coating test (presence or absence of dripping)>
The base was a concrete plate, and mortar was sprayed into a formwork measuring 10 mm thick x 150 mm long x 250 mm wide. After finishing with a trowel, the formwork was removed and the test specimen was immediately set up vertically and left to stand for one day, after which the presence or absence of sagging was confirmed. The test results are shown in Table 2 below.
＜付着強度試験＞
付着強度：３００×３００×６０ｍｍの舗道板に補修材料を６０ｍｍ吹付け、試験体を作製した。材齢２８日にφ５５ｍｍでコアリングし、建研式接着力試験器（オックスジャッキ株式会社製）を用いて付着強度を測定した。試験結果を下記表２に示す。 <Adhesion strength test>
Adhesion strength: A test specimen was prepared by spraying 60 mm of the repair material onto a pavement board measuring 300 x 300 x 60 mm. After 28 days, the specimen was cored with a diameter of 55 mm and the adhesion strength was measured using a Kenken adhesive strength tester (manufactured by Oxjack Co., Ltd.). The test results are shown in Table 2 below.
付着強度：３００×３００×６０ｍｍの舗道板に補修材料を６０ｍｍ吹付け、試験体を作製した。材齢２８日にφ５５ｍｍでコアリングし、建研式接着力試験器（オックスジャッキ株式会社製）を用いて付着強度を測定した。試験結果を下記表２に示す。 <Adhesion strength test>
Adhesion strength: A test specimen was prepared by spraying 60 mm of the repair material onto a pavement board measuring 300 x 300 x 60 mm. After 28 days, the specimen was cored with a diameter of 55 mm and the adhesion strength was measured using a Kenken adhesive strength tester (manufactured by Oxjack Co., Ltd.). The test results are shown in Table 2 below.
（実験例２）
＜補修材料の調製＞
セメント１００質量部に対して、細骨材２００質量部、ポリマー（ポリアクリル酸エステル再乳化樹脂、市販品、水分率０．８％、密度０．５ｇ/ｍＬ）３．０質量部、繊維０．１質量部、減水剤０．５質量部、水１４質量部とし、セメント組成物を調製した。このセメント組成物中のセメント１００質量部に対して、実施例１～５、８及び比較例１～２の液体急結剤を６質量部混合し、補修材料を調製した。得られた補修材料は、実験例１と同じ方法により、圧縮強度、厚塗り性及び付着強度を測定した。結果を下記表３に示す。 (Experimental Example 2)
<Preparation of repair material>
A cement composition was prepared with 200 parts by mass of fine aggregate, 3.0 parts by mass of polymer (polyacrylic acid ester re-emulsified resin, commercially available product, moisture content 0.8%, density 0.5 g/mL), 0.1 parts by mass of fiber, 0.5 parts by mass of water reducing agent, and 14 parts by mass of water, per 100 parts by mass of cement in this cement composition. Six parts by mass of the liquid quick-setting admixture of Examples 1 to 5, 8 and Comparative Examples 1 to 2 were mixed with each other per 100 parts by mass of cement in this cement composition to prepare a repair material. The compressive strength, thick coating property, and adhesive strength of the obtained repair material were measured by the same method as in Experimental Example 1. The results are shown in Table 3 below.
＜補修材料の調製＞
セメント１００質量部に対して、細骨材２００質量部、ポリマー（ポリアクリル酸エステル再乳化樹脂、市販品、水分率０．８％、密度０．５ｇ/ｍＬ）３．０質量部、繊維０．１質量部、減水剤０．５質量部、水１４質量部とし、セメント組成物を調製した。このセメント組成物中のセメント１００質量部に対して、実施例１～５、８及び比較例１～２の液体急結剤を６質量部混合し、補修材料を調製した。得られた補修材料は、実験例１と同じ方法により、圧縮強度、厚塗り性及び付着強度を測定した。結果を下記表３に示す。 (Experimental Example 2)
<Preparation of repair material>
A cement composition was prepared with 200 parts by mass of fine aggregate, 3.0 parts by mass of polymer (polyacrylic acid ester re-emulsified resin, commercially available product, moisture content 0.8%, density 0.5 g/mL), 0.1 parts by mass of fiber, 0.5 parts by mass of water reducing agent, and 14 parts by mass of water, per 100 parts by mass of cement in this cement composition. Six parts by mass of the liquid quick-setting admixture of Examples 1 to 5, 8 and Comparative Examples 1 to 2 were mixed with each other per 100 parts by mass of cement in this cement composition to prepare a repair material. The compressive strength, thick coating property, and adhesive strength of the obtained repair material were measured by the same method as in Experimental Example 1. The results are shown in Table 3 below.
本発明の液体急結剤は、例えば、道路、鉄道、及び導水路等のトンネルや、法面等において露出した地山面へ吹付けるセメントコンクリートや、コンクリート構造物の補修材料等に対して好適に使用できる。
The liquid quick-setting agent of the present invention can be suitably used, for example, in tunnels such as roads, railways, and waterways, in cement concrete sprayed onto exposed natural ground surfaces such as slopes, and as a repair material for concrete structures.
Claims (9)
- セメント、ポリマー及び細骨材を含有するセメント組成物とともに用いられる液体急結剤であって、
アルミニウム成分及び硫黄成分を含有し、
下記の条件で測定される２７Ａｌ－ＮＭＲによって得られるスペクトルにおいて、化学シフト－１．０ｐｐｍ以上３．０ｐｐｍ以下の範囲にピークを有する、液体急結剤。
（条件）
観測核：２７Ａｌ
試料管回転数：１２Ｈｚ
測定温度：２５℃
パルス幅：５μｓｅｃ（４５°パルス）
待ち時間：５秒
外部標準：塩化アルミニウム水溶液 A liquid quick-setting admixture for use with a cement composition containing cement, a polymer and a fine aggregate, comprising:
Contains an aluminum component and a sulfur component,
A liquid quick-setting admixture having a peak in the chemical shift range of -1.0 ppm to 3.0 ppm in a spectrum obtained by 27 Al-NMR measured under the following conditions.
(conditions)
Observed nucleus: 27Al
Sample tube rotation speed: 12Hz
Measurement temperature: 25°C
Pulse width: 5 μsec (45° pulse)
Waiting time: 5 seconds External standard: Aluminum chloride aqueous solution - セメント及び細骨材を含有するセメント組成物とともに用いられる補修用の液体急結剤であって、
アルミニウム成分及び硫黄成分を含有し、
下記の条件で測定される２７Ａｌ－ＮＭＲによって得られるスペクトルにおいて、化学シフト－１．０ｐｐｍ以上３．０ｐｐｍ以下の範囲にピークを有する、補修用の液体急結剤。
（条件）
観測核：２７Ａｌ
試料管回転数：１２Ｈｚ
測定温度：２５℃
パルス幅：５μｓｅｃ（４５°パルス）
待ち時間：５秒
外部標準：塩化アルミニウム水溶液 A liquid quick-setting admixture for repair use with a cement composition containing cement and fine aggregate,
Contains an aluminum component and a sulfur component,
A liquid quick-setting admixture for repair, which has a peak in the chemical shift range of -1.0 ppm to 3.0 ppm in a spectrum obtained by 27 Al-NMR measured under the following conditions.
(conditions)
Observed nucleus: 27Al
Sample tube rotation speed: 12Hz
Measurement temperature: 25°C
Pulse width: 5 μsec (45° pulse)
Waiting time: 5 seconds External standard: Aluminum chloride aqueous solution - 前記化学シフト－１．０ｐｐｍ以上３．０ｐｐｍ以下の範囲のピークの半値幅が、１０．０ｐｐｍ以下である、請求項１または２に記載の液体急結剤。 The liquid quick-setting admixture according to claim 1 or 2, in which the half-width of the peak in the chemical shift range of -1.0 ppm to 3.0 ppm is 10.0 ppm or less.
- 前記液体急結剤中の全アルカリ量Ｒ２Ｏ（Ｒはアルカリ金属）が、１．０質量％以下である、請求項１または２に記載の液体急結剤。 The liquid quick-setting admixture according to claim 1 or 2, wherein a total amount of alkali R 2 O (R is an alkali metal) in the liquid quick-setting admixture is 1.0 mass % or less.
- セメント、ポリマー及び細骨材を含有するセメント組成物と、請求項１に記載の液体急結剤とを含有する、補修材料。 A repair material comprising a cement composition containing cement, a polymer and fine aggregate, and the liquid quick-setting admixture according to claim 1.
- セメント及び細骨材を含有するセメント組成物と、請求項２に記載の液体急結剤とを含有する、補修材料。 A repair material comprising a cement composition containing cement and fine aggregate, and the liquid quick-setting agent described in claim 2.
- 前記セメント組成物が、さらにポリマーを含有する、請求項６に記載の補修材料。 The repair material according to claim 6, wherein the cement composition further contains a polymer.
- 前記セメント組成物中の細骨材の含有量が、前記セメント１００質量部に対して４０～３００質量部である、請求項５～７のいずれか１つに記載の補修材料。 The repair material according to any one of claims 5 to 7, wherein the content of fine aggregate in the cement composition is 40 to 300 parts by mass per 100 parts by mass of the cement.
- 請求項５～７のいずれか１つに記載の補修材料を用いてなる、硬化体。 A hardened body made using the repair material described in any one of claims 5 to 7.
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| JP2023-006358 | 2023-01-19 | ||
| JP2023006358A JP7355953B1 (en) | 2023-01-19 | 2023-01-19 | Liquid quick-setting agent, repair material, cured product |
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| JP2002047048A (en) * | 2000-05-25 | 2002-02-12 | Denki Kagaku Kogyo Kk | Liquid curing accelerator, rapid curing cement/concrete using the same and method of producing rapid curing cement/concrete |
| JP2005060201A (en) * | 2003-08-20 | 2005-03-10 | Denki Kagaku Kogyo Kk | Spray material and spraying method using the same |
| JP2018030731A (en) * | 2016-08-22 | 2018-03-01 | デンカ株式会社 | Liquid rapid hardening agent, spraying material, and spraying method using the same |
| CN112608065A (en) * | 2019-12-13 | 2021-04-06 | 科之杰新材料集团(贵州)有限公司 | Liquid alkali-free accelerator for sprayed concrete and preparation method thereof |
| JP2021143090A (en) * | 2020-03-12 | 2021-09-24 | デンカ株式会社 | Liquid rapid-hardening agent and rapid-hardening cement concrete |
| JP2021178751A (en) * | 2020-05-13 | 2021-11-18 | デンカ株式会社 | Rapid-hardening additive agent, and spray material |
| JP6989719B1 (en) * | 2021-03-02 | 2022-01-05 | デンカ株式会社 | Two-form quick-setting admixture, spraying material and spraying method |
| JP2022072727A (en) * | 2020-10-30 | 2022-05-17 | デンカ株式会社 | Expandable accelerator, spray concrete composition, sprayed concrete, and spray construction method |
| JP2022076297A (en) * | 2020-11-09 | 2022-05-19 | デンカ株式会社 | Quick setting admixture, and spraying material |
| JP7209878B1 (en) * | 2022-01-12 | 2023-01-20 | デンカ株式会社 | liquid quick-setting agent, shotcrete |
-
2023
- 2023-01-19 JP JP2023006358A patent/JP7355953B1/en active Active
- 2023-09-21 JP JP2023154126A patent/JP2024102798A/en active Pending
-
2024
- 2024-01-16 WO PCT/JP2024/000921 patent/WO2024154722A1/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002047048A (en) * | 2000-05-25 | 2002-02-12 | Denki Kagaku Kogyo Kk | Liquid curing accelerator, rapid curing cement/concrete using the same and method of producing rapid curing cement/concrete |
| JP2005060201A (en) * | 2003-08-20 | 2005-03-10 | Denki Kagaku Kogyo Kk | Spray material and spraying method using the same |
| JP2018030731A (en) * | 2016-08-22 | 2018-03-01 | デンカ株式会社 | Liquid rapid hardening agent, spraying material, and spraying method using the same |
| CN112608065A (en) * | 2019-12-13 | 2021-04-06 | 科之杰新材料集团(贵州)有限公司 | Liquid alkali-free accelerator for sprayed concrete and preparation method thereof |
| JP2021143090A (en) * | 2020-03-12 | 2021-09-24 | デンカ株式会社 | Liquid rapid-hardening agent and rapid-hardening cement concrete |
| JP2021178751A (en) * | 2020-05-13 | 2021-11-18 | デンカ株式会社 | Rapid-hardening additive agent, and spray material |
| JP2022072727A (en) * | 2020-10-30 | 2022-05-17 | デンカ株式会社 | Expandable accelerator, spray concrete composition, sprayed concrete, and spray construction method |
| JP2022076297A (en) * | 2020-11-09 | 2022-05-19 | デンカ株式会社 | Quick setting admixture, and spraying material |
| JP6989719B1 (en) * | 2021-03-02 | 2022-01-05 | デンカ株式会社 | Two-form quick-setting admixture, spraying material and spraying method |
| JP7209878B1 (en) * | 2022-01-12 | 2023-01-20 | デンカ株式会社 | liquid quick-setting agent, shotcrete |
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| JP7355953B1 (en) | 2023-10-03 |
| JP2024102466A (en) | 2024-07-31 |
| JP2024102798A (en) | 2024-07-31 |
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