Liquid fastening agent

Abstract

This invention provides a liquid rapid setting agent that exhibits excellent shape retention for hydraulic compositions and provides stable shape retention regardless of application conditions. [Solution] A liquid quick-setting agent containing (A) smectite, (B) sulfate ions, (C) aluminum ions, and (D) water, wherein the mass ratio of the content of component (A) to the content of component (B) [(A) / (B)] is 3 or less.

Description

[Technical Field]

[0001] This invention relates to a liquid rapid setting agent, a hydraulic composition, a method for producing a hydraulic composition, a spraying method, and its use as a liquid rapid setting agent. [Background technology]

[0002] To prevent the collapse of exposed ground during tunnel excavation, a spraying method is employed that uses rapid-setting concrete or rapid-setting mortar, which are concrete mixed with a rapid-setting agent. In this method, sprayed concrete is usually prepared at a cement, aggregate, and water metering and mixing plant installed at the excavation site, and then transported by agitator truck to the spraying machine. The sprayed concrete and rapid-setting agent are then mixed in two lines: one line that uses the spraying machine's pump to air-pressure the sprayed concrete to the discharge port, and another line that uses a confluence pipe installed along the way to air-pressure the rapid-setting agent from the other side. The resulting rapid-setting sprayed concrete is then sprayed onto the ground surface to a specific thickness.

[0003] Patent Document 1 discloses an additive for a sprayable hydraulic composition comprising (A) a clay mineral having a swelling degree of 15 mL / 2 g or more and 50 mL / 2 g or less, and (B) one or more fasteners selected from cement mineral-based fasteners and aluminum-based fasteners. Furthermore, Patent Document 2 discloses a wet spraying method in which (a) a hydraulic composition containing hydraulic powder and a polymer thickener and water is mixed with (b) clay minerals at a stirring work of 150 J or less, and the hydraulic composition containing the (b) component is sprayed onto the target object. Furthermore, Patent Document 3 discloses a liquid rapid-setting agent containing 9.0 to 15.0 mass% of aluminum (in Al2O3 equivalent), 22.0 to 35.0 mass% of sulfur (in SO3 equivalent), 0.5 to 2.0 mass% of clay minerals, and 0.5 to 5.0 mass% of amine compounds, wherein the Heywood mean diameter of the dispersed particles observed with an optical microscope using transmitted light is 3 to 30 μm. Furthermore, Patent Document 4 discloses a cement additive for 3D printing, which is a mixture of modified bentonite, a surfactant, a coagulant, a water-reducing agent, and water in specific ratios. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2021-70611 [Patent Document 2] Japanese Patent Publication No. 2024-67807 [Patent Document 3] Japanese Patent Publication No. 2024-47946 [Patent Document 4] Chinese Patent Application Publication No. 106966625 Specification [Overview of the project] [Problems that the invention aims to solve]

[0005] Smectite and aluminum sulfate are used in sprayed hydraulic compositions to improve strength development and reduce dust, but their rapid setting properties are relatively poor, and improved shape retention immediately after application is required. Furthermore, to ensure stable application, rapid setting agents need to minimize variations in shape retention performance due to differences in application conditions. The present invention provides a liquid quick-setting agent that exhibits excellent shape retention of hydraulic compositions and stable shape retention regardless of construction conditions, a hydraulic composition, a method for producing a hydraulic composition, a spraying method, and its use as a liquid quick-setting agent. [Means for solving the problem]

[0006] In one embodiment, the present invention provides a liquid quick-setting agent containing (A) smectite, (B) sulfate ions, (C) aluminum ions, and (D) water, wherein the mass ratio of the content of component (A) to the content of component (B) [(A) / (B)] is 3 or less.

[0007] Furthermore, in other embodiments, the present invention provides a hydraulic composition comprising the liquid rapid setting agent.

[0008] Furthermore, in another embodiment, the present invention provides a method for producing a hydraulic composition by mixing the liquid quick-setting agent with a hydraulic powder.

[0009] Furthermore, in another embodiment, the present invention provides a spraying method in which a hydraulic composition containing hydraulic powder and water is mixed with the liquid quick-setting agent and sprayed onto an object.

[0010] Furthermore, in another embodiment, the present invention provides for the use of a mixture containing (A) smectite, (B) sulfate ions, (C) aluminum ions, and (D) water, wherein the mass ratio of the content of component (A) to the content of component (B) [(A) / (B)] is 3 or less, as a liquid quick-setting agent. [Effects of the Invention]

[0011] The present invention provides a liquid quick-setting agent that exhibits excellent shape retention of hydraulic compositions and stable shape retention regardless of construction conditions, a hydraulic composition, a method for producing a hydraulic composition, a spraying method, and a method for using the liquid quick-setting agent. [Modes for carrying out the invention]

[0012] The mechanism by which the liquid rapid setting agent and the hydraulic composition containing the liquid rapid setting agent of the present invention exhibit excellent shape retention and stable shape retention regardless of construction conditions is not clear, but it is presumed to be as follows. By mixing (D) water containing (B) sulfate ions and (C) aluminum ions with (A) smectite, aggregates of smectite and aluminum ions are formed. It is presumed that this causes (A) smectite to disperse more and scatter and adsorb onto the cement surface. As a result, it is presumed that the hydraulic composition is crosslinked and aggregated, improving its shape retention. In addition, the sulfate ions and aluminum ions retained on the smectite at the agglomeration points act efficiently on the cement, preventing the formation of aggregates of other agents and aluminum ions, making it less susceptible to the influence of other agents, and it is presumed that not only the shape retention property is improved, but also the stability of the shape retention property against differences in construction conditions is enhanced, and a stable shape retention property is exhibited regardless of the construction conditions. Note that the liquid accelerating agent, hydraulic composition, method for producing a hydraulic composition, spraying method, and use as a liquid accelerating agent of the present invention are not limited based on the above mechanism of action. In addition, in this specification, excellent shape retention property of the hydraulic composition may mean either or both of excellent moldability of the hydraulic composition 4 minutes after mixing and stirring a setting accelerator into the hydraulic composition and the shape being difficult to collapse even after molding.

[0013] <Liquid accelerating agent> In an exemplary embodiment, the liquid accelerating agent of the present invention contains (A) smectite, (B) sulfate ions, (C) aluminum ions, and (D) water, and the mass ratio [(A) / (B)] of the content of component (A) to the content of component (B) is 3 or less. The liquid accelerating agent of the present invention may be, for example, a liquid accelerating agent for a hydraulic composition, and further may be a liquid accelerating agent for a sprayed hydraulic composition. In this specification, component (A) smectite may be referred to as component (A), component (B) sulfate ions as component (B), component (C) aluminum ions as component (C), and component (D) water as component (D).

[0014] <Component (A)> Component (A) is smectite. One or more types of component (A) can be used. The type of smectite of component (A) is not particularly limited, and it may be natural smectite or synthetic smectite. The clay minerals containing smectite as component (A) include, for example, one or more selected from montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, and stevensite. Smectite forms a layered structure composed of thin plate-like crystals with a thickness of about 1 nm, and cations such as alkali metals and alkaline earth metals generally exist in the interlayer space between the crystals. There is no particular limitation on the cations present in the crystal interlayer of smectite. For example, one or more selected from smectites of Na (sodium) type, Li (lithium) type, K (potassium) type, NH4 (ammonium) type, Ca (calcium) type, Mg (magnesium) type, Ba (barium) type, Al (aluminum) type, Fe (iron) type, Cu (copper) type, and Zn (zinc) type can be used.

[0015] (Component (A) is not particularly limited, but for example, a clay mineral represented by the following general formula (a1) is preferred.) [Si8(Mg a Al b )O 20 (OH)4] X- ·Me X+ (a1) [In the formula, 0 < a ≤ 6, 0 < b ≤ 4, x = 12 - 2a - 3b, and Me is at least one of Na, K, Li, Ca, Mg, and NH4, preferably at least one of Na and Ca.]

[0016] (From the viewpoint of improving the shape retention of the hydraulic composition and enhancing the stability against variations in the production conditions of the shape retention, one or more selected from montmorillonite, saponite, hectorite, and stevensite are preferred for component (A).)

[0017] (From the viewpoint of improving the shape retention of the hydraulic composition and enhancing the stability against variations in the production conditions of the shape retention, smectite may be a clay mineral contained in component (A), preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and preferably 100% by mass or less, more preferably 98% by mass or less, still more preferably 95% by mass or less, even more preferably 90% by mass or less, even more preferably 80% by mass or less.) Alternatively, component (A) may be a clay mineral containing smectite in component (A) at a rate of preferably 10% to 100% by mass, more preferably 20% to 98% by mass, even more preferably 30% to 98% by mass, even more preferably 40% to 95% by mass, even more preferably 50% to 95% by mass, even more preferably 50% to 90% by mass, and even more preferably 50% to 80% by mass. The content of component (A) is measured by the method described later in detail in <<Method for measuring the smectite content of component (A)>>.

[0018] Component (A) is preferably a clay mineral containing one or more inorganic powders selected from, for example, crystalline silica, calcium carbonate, aluminosilicate, and talc, from the viewpoint of improving the shape retention of the hydraulic composition and enhancing the stability of the shape retention against fluctuations in manufacturing conditions, and more preferably a clay mineral containing one or more inorganic powders selected from crystalline silica, calcium carbonate, and aluminosilicate.

[0019] If component (A) contains the inorganic powder, component (A) contains the inorganic powder in an amount of preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and from the same viewpoint, preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less. Alternatively, if component (A) contains the inorganic powder, component (A) contains the inorganic powder in an amount of preferably 2% by mass or more and 90% by mass or less, more preferably 5% by mass or more and 80% by mass or less, even more preferably 10% by mass or more and 70% by mass or less, even more preferably 10% by mass or more and 60% by mass or less, and even more preferably 10% by mass or more and 50% by mass or less in component (A).

[0020] (A) The average particle size of component (A) is preferably 0.10 μm or more, more preferably 1 μm or more, even more preferably 10 μm or more, and from the viewpoint of improving the shape retention of the hydraulic composition and increasing the stability of shape retention against fluctuations in manufacturing conditions, and from the same viewpoint, preferably 500 μm or less, more preferably 200 μm or less, and even more preferably 50 μm or less. Alternatively, from the same viewpoint, the average particle size of component (A) is preferably 0.10 μm or more and 500 μm or less, more preferably 1 μm or more and 200 μm or less, and even more preferably 10 μm or more and 50 μm or less.

[0021] (A) The average particle size of component (A) is the arithmetic mean particle size of particles measured using a laser diffraction / scattering particle size distribution analyzer (e.g., LA-920 (manufactured by Horiba, Ltd.)) with ethanol (purity 99.5%) as the dispersion medium and ultrasound applied for 1 minute.

[0022] (A) The degree of swelling of component (A) is preferably 5 mL / 2 g or more and 90 mL / 2 g or less, from the viewpoint of improving the shape retention of the hydraulic composition and enhancing the stability of shape retention against fluctuations in manufacturing conditions. (A) The degree of swelling of component (A) is preferably 5 mL / 2 g or more, more preferably 10 mL / 2 g or more, even more preferably 15 mL / 2 g or more, and preferably 90 mL / 2 g or less, more preferably 70 mL / 2 g or less, and even more preferably 50 mL / 2 g or less, from the viewpoint of improving the shape retention of the hydraulic composition and increasing the stability of shape retention against fluctuations in manufacturing conditions. Alternatively, from the same viewpoint, the degree of swelling of component (A) is preferably 5 mL / 2 g or more and 90 mL / 2 g or less, more preferably 10 mL / 2 g or more and 70 mL / 2 g or less, and even more preferably 15 mL / 2 g or more and 50 mL / 2 g or less. If component (A) contains multiple types of clay minerals, this swelling degree is the swelling degree of a mixture of multiple types of component (A).

[0023] <Method for measuring swelling degree> In this invention, the degree of swelling is measured according to the swelling test method for bentonite (powdered) specified in JBAS104:77 of the Japan Bentonite Industry Association. Specifically, 2.0 g of the sample, adjusted to a moisture content of 8.0% by mass, is added in approximately 10 portions to a 100 mL stoppered graduated cylinder containing 100 mL of distilled water. At this time, the next addition is made only after the previous addition has settled at the bottom of the graduated cylinder. After standing for 24 hours, the apparent volume of the sample mass at the bottom of the graduated cylinder, which has swollen, is read from the scale of the graduated cylinder and displayed as the degree of swelling (mL / 2g).

[0024] Examples of commercially available products containing montmorillonite include Bengel, Bengel HV, Bengel A, Bengel FW, Bengel 31, and Bengel W-100 from Hojun Co., Ltd., Kunipia G and Kunipia F from Kunimine Industries Co., Ltd., Western Bond from American Colloid Company, and Yellowstone from Dresser Minerals.

[0025] Examples of commercially available products containing saponite include BeeGum T, BeeGum HV, BeeGum F, and BeeGum K manufactured by Vanderbilt, as well as Smecton SA manufactured by Kunimine Industries Co., Ltd.

[0026] Examples of commercially available products containing hectorite include Smecton SWN and Smecton SWF manufactured by Kunimine Industries Co., Ltd., Hectabrite AW, Hectabrite 200 and Benton EW manufactured by American Colloid Corporation, and Macaloid manufactured by National Reed Corporation.

[0027] Examples of commercially available products containing stevensite include Smecton ST manufactured by Kunimine Industries Co., Ltd.

[0028] Various synthetic smectites are also commercially available, such as Ionite H from Mizusawa Chemical Industries, SWN and SAN from Coop Chemical Co., Ltd., Laponite from Laporte Industry, and Laponite XLS and Laponite XLG from Lockwood.

[0029] (A) Component may be a clay mineral having a smectite content of preferably 30% by mass or more and 100% by mass or less. Examples of (A) component include "Kunigel V1", "Kunigel V2", "Kunigel VO", "Kunigel FS", and "Kunigel GS" from Kunimine Industries Co., Ltd., "Neoclay", "Superclay", and "Neomad" from Hojun Co., Ltd., "TB-250", "TB-300S", and "TB-S" from Tachibana Material Co., Ltd., "Bentonite", "Detasoft GIS", "Detasoft GIB", and "Detasoft GISW" from Raviosa, "Odosolve K-400" from Kurosaki Hakudo Kogyo Co., Ltd., "Round Rhozil DGA212", "Round Rhozil PR414", "Round Rhozil DG214", "Round Rhozil DGA Powder", and "Furasoft-1 Powder" from Süd Chemi, and Pure Bentonite, Standard Bentonite, and Premium Bentonite from CSM.

[0030] <(B) component> (B) Component is a sulfate ion. The sulfate ion may be a sulfate salt or a sulfate ion derived from sulfuric acid. Examples of sulfate salts include one or more selected from sodium sulfate, potassium sulfate, magnesium sulfate, zinc sulfate, iron sulfate, and aluminum sulfate. The counterions of sulfate ions include, for example, one or more selected from monovalent cations, divalent cations, and trivalent cations. Examples of monovalent cations include, for example, one or more selected from hydrogen ions, sodium ions, potassium ions, ammonium ions, and organic amine ions. Examples of divalent cations include, for example, one or more selected from magnesium ions and calcium ions. Examples of trivalent cations include aluminum ions and iron ions.

[0031] <(C) component> Component (C) is an aluminum ion. The aluminum ion may be an aluminum ion derived from an aluminum salt. Examples of aluminum salts include one or more selected from aluminum chloride, aluminum sulfate, aluminum fluoride, aluminum lactate, alum, aluminum hydroxide, and aluminum nitrate. The counterions of aluminum ions include, for example, one or more selected from monovalent anions, divalent anions, and trivalent anions, with one or more selected from monovalent anions and divalent anions being preferred. Examples of monovalent anions include one or more selected from chloride ions, fluoride ions, hydroxide ions, nitrate ions, carboxylate ions, and sulfonate ions. Examples of divalent anions include sulfate ions. Examples of trivalent anions include phosphate ions.

[0032] <(D) component> Component (D) is water. The water is not particularly limited, but examples include tap water, well water, deionized water, and distilled water. It is preferable that component (D) is used in an amount equal to the remainder of the liquid fastener (an amount that totals 100% by mass).

[0033] <Composition, etc.> The liquid rapid setting agent of the present invention contains component (A) in an amount preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 5% by mass or more, and from the viewpoint of improving the shape retention of the hydraulic composition and enhancing the stability of shape retention against fluctuations in manufacturing conditions, preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. Alternatively, the liquid fastener of the present invention contains component (A) in the liquid fastener in an amount of preferably 1% to 40% by mass, more preferably 2% to 30% by mass, and even more preferably 5% to 20% by mass.

[0034] (A) The provision regarding the mass of component (A) is that if component (A) is a synthetic smectite or other substance with a smectite content of 100% by mass, the mass of component (A) may be used. On the other hand, when using a composition containing smectite, such as natural smectite, the smectite content shall be measured by the amount of methylene blue adsorbed according to the smectite content measurement method described below, and the measured smectite content shall be taken as the mass of component (A). The same applies to the definition of the mass of component (A) below unless otherwise specified. The measurement of the smectite content shall be performed on the dried component (A) after drying it in a hot air dryer at 105°C for 1 hour as a pretreatment.

[0035] <(A) Method for measuring the smectite content> (1) Measurement of methylene blue adsorption (A) The amount of methylene blue adsorbed by component (A) shall be measured by the following method in accordance with the Japanese Industrial Standard (JIS Z 2451:2019). <Reagents> 10 mmol / L aqueous solution of methylene blue (molecular weight 374) 0.2% by mass aqueous solution of sodium pyrophosphate (Na4P2O7) <How to operate> Place approximately 0.4 g of component (A) into a 100 mL screw-cap tube, and add 40 g of a 0.2% by mass aqueous solution of sodium pyrophosphate. Disperse this mixture in an ultrasonic cleaner (ASUCLEANER, ASU-3, manufactured by AS ONE Corporation) for 30 minutes, then heat in 80°C warm water for 30 minutes. Add 10 mmol / L methylene blue aqueous solution dropwise to the dispersed mixture while stirring with a magnetic stirrer. After each drop, use a glass Pasteur pipette to draw up a portion of the supernatant and drop it onto filter paper. Add the supernatant until a spot of approximately 10 mm in diameter is formed on the filter paper. Repeat this operation until a halo is observed around the spot. Once a halo is observed, the titration is terminated when the width of the halo exceeds 2 mm. The amount of methylene blue adsorbed (mmol) is calculated by multiplying the titration volume (L) by the concentration of the methylene blue aqueous solution (10 mmol / L) and converting this product to an amount per 100 g of component (A). (2) Calculation of smectite content The calculation of the smectite content of component (A) is performed with reference to "A proposed method for the determination of small amounts of smectites in clay mineral mixtures, Proceedings of British Ceramics Society 28137-145, 1979" and "Journal of the Japan Society of Civil Engineers, Series C (Geosphere Engineering), Vol. 76, No. 1, 26-39, 2020: Evaluation of montmorillonite content of bentonite considering the measurement accuracy of methylene blue adsorption tests." Specifically, 140 mmol / 100g is used as the saturation adsorption amount of methylene blue for smectite. The smectite content of component (A) is calculated by dividing this saturation adsorption amount by the measured methylene blue adsorption amount of component (A) and multiplying by 100. If the methylene blue adsorption amount exceeds 140 mmol / 100g, the smectite content is considered to be 100%.

[0036] The liquid rapid setting agent of the present invention contains component (B) in an amount of preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, and from the viewpoint of improving the shape retention of the hydraulic composition and enhancing the stability of the shape retention against fluctuations in manufacturing conditions, preferably 50% by mass or less, more preferably 45% by mass or less, even more preferably 40% by mass or less, even more preferably 35% by mass or less, and even more preferably 30% by mass or less. Alternatively, the liquid rapid setting agent of the present invention contains component (B) in the liquid rapid setting agent, preferably in an amount of 5% by mass or more and 50% by mass or less, more preferably 8% by mass or more and 45% by mass or less, even more preferably 10% by mass or more and 40% by mass or less, even more preferably 10% by mass or more and 35% by mass or less, and even more preferably 10% by mass or more and 30% by mass or less.

[0037] In this specification, the mass of component (B) is calculated from the amount of compound from which sulfate ions are derived. If the amount of compound from which sulfate ions are derived is unknown, the mass of component (B) is measured according to the method in accordance with JIS K0102. The same applies to the mass of component (B) hereafter. In addition, sulfate ions can be easily measured using, for example, Pack Test (registered trademark, manufactured by Kyoritsu Chemical Research Institute). If insoluble matter is present in the liquid quick-setting agent, measure after dissolving it by storing it at 40°C for 24 hours.

[0038] The liquid rapid setting agent of the present invention contains component (C) in an amount preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 4% by mass or more, and from the viewpoint of improving the shape retention of the hydraulic composition and enhancing the stability of the shape retention against fluctuations in manufacturing conditions, preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 13% by mass or less, and even more preferably 11% by mass or less. Alternatively, the liquid fastener of the present invention contains component (C) in the liquid fastener, preferably 1% to 20% by mass, more preferably 3% to 15% by mass, even more preferably 4% to 13% by mass, and even more preferably 4% to 11% by mass.

[0039] In this specification, the mass of component (C) is calculated from the amount of the compound from which the aluminum ions are derived. If the amount of the compound from which the aluminum ions are derived is unknown, the mass of component (C) is measured using, for example, a digital pack test manufactured by Kyoritsu Chemical Laboratory Co., Ltd. The same applies to the mass of component (C) hereafter. Specifically, trivalent aluminum ions can be measured using the ECR method of the Digital Pack Test (model LR-Al).

[0040] The liquid rapid setting agent of the present invention contains component (D) in an amount of preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 48% by mass or more, and from the viewpoint of improving the shape retention of the hydraulic composition and enhancing the stability of shape retention against fluctuations in manufacturing conditions, preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. Alternatively, the liquid fastener of the present invention contains component (D) in the liquid fastener in an amount of preferably 30% to 90% by mass, more preferably 40% to 85% by mass, and even more preferably 48% to 80% by mass, from the same viewpoint.

[0041] In the liquid rapid setting agent of the present invention, the mass ratio of the content of component (A) to the content of component (B) [(A) / (B)] is preferably 0.02 or more, more preferably 0.03 or more, and even more preferably 0.04 or more, from the viewpoint of improving the shape retention of the hydraulic composition and increasing the stability of the shape retention against fluctuations in manufacturing conditions, and is 3 or less, preferably 2 or less, more preferably 1 or less, even more preferably 0.6 or less, and even more preferably 0.3 or less, from the viewpoint of increasing the stability of the shape retention of the hydraulic composition against fluctuations in manufacturing conditions. Alternatively, in the liquid rapid setting agent of the present invention, the mass ratio [(A) / (B)] is preferably 0.02 to 3, more preferably 0.03 to 2, even more preferably 0.04 to 1, even more preferably 0.04 to 0.6, and even more preferably 0.04 to 0.3, from the viewpoint of improving the shape retention of the hydraulic composition and enhancing the stability of shape retention against fluctuations in manufacturing conditions.

[0042] In the liquid rapid setting agent of the present invention, the mass ratio of the content of component (A) to the content of component (C) [(A) / (C)] is preferably 0.05 or more, more preferably 0.10 or more, even more preferably 0.15 or more, even more preferably 0.3 or more, and from the viewpoint of improving the shape retention of the hydraulic composition and increasing the stability of shape retention against fluctuations in manufacturing conditions, preferably 10 or less, more preferably 3 or less, even more preferably 2 or less, and even more preferably 1 or less. Alternatively, in the liquid rapid setting agent of the present invention, the mass ratio [(A) / (C)] is preferably 0.05 or more and 10 or less, more preferably 0.10 or more and 3 or less, even more preferably 0.15 or more and 2 or less, and even more preferably 0.3 or more and 1 or less.

[0043] In the liquid rapid setting agent of the present invention, the mass ratio of the content of component (B) to the content of component (C) [(B) / (C)] is preferably 0.5 or more, more preferably 1.0 or more, even more preferably 1.5 or more, and from the viewpoint of improving the shape retention of the hydraulic composition and increasing the stability of shape retention against fluctuations in manufacturing conditions, preferably 25 or less, more preferably 10 or less, and even more preferably 7 or less. Alternatively, in the liquid rapid setting agent of the present invention, the mass ratio [(B) / (C)] is preferably 0.5 or more and 25 or less, more preferably 1.0 or more and 10 or less, and even more preferably 1.5 or more and 7 or less.

[0044] In the liquid rapid setting agent of the present invention, the mass ratio of the content of component (A) to the content of component (D) [(A) / (D)] is preferably 0.01 or higher, more preferably 0.02 or higher, and even more preferably 0.025 or higher, from the viewpoint of improving the shape retention of the hydraulic composition and increasing the stability of the shape retention against fluctuations in manufacturing conditions, and preferably 0.5 or lower, more preferably 0.3 or lower, and even more preferably 0.2 or lower, from the viewpoint of increasing the stability of the shape retention of the hydraulic composition against fluctuations in manufacturing conditions. Alternatively, in the liquid rapid setting agent of the present invention, the mass ratio [(A) / (D)] is preferably 0.01 or more and 0.5 or less, more preferably 0.02 or more and 0.3 or less, and even more preferably 0.025 or more and 0.2 or less.

[0045] <(E) component> The liquid rapid setting agent of the present invention may optionally contain (E) insoluble matter [excluding those corresponding to component (A)] [hereinafter referred to as component (E)] from the viewpoint of improving the shape retention of the hydraulic composition and enhancing the stability of shape retention against fluctuations in manufacturing conditions. Component (E) may be used in the form of one or more types. (E) The term "insoluble" for component (E) means that it dissolves at a rate of 0.5 g or less in 100 g of water at 40°C.

[0046] Component (E) may be one or more selected from iron oxide, calcium sulfate, silicon dioxide, carbon, and lead sulfate. From the viewpoint of improving the shape retention of the hydraulic composition and enhancing the stability of shape retention against fluctuations in manufacturing conditions, one or more selected from iron oxide, calcium sulfate, silicon dioxide, and lead sulfate are preferred for component (E).

[0047] The average particle size of component (E) is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 1 μm or more, even more preferably 10 μm or more, and from the same viewpoint, preferably 500 μm or less, more preferably 200 μm or less, and even more preferably 50 μm or less. Alternatively, the average particle size of component (E) is preferably 0.01 μm or more and 500 μm or less, more preferably 0.05 μm or more and 200 μm or less, even more preferably 1 μm or more and 50 μm or less, and even more preferably 10 μm or more and 50 μm or less.

[0048] The average particle size of component (E) is the arithmetic mean particle size of particles measured using a laser diffraction / scattering particle size distribution analyzer (e.g., LA-920 (manufactured by Horiba, Ltd.)) with ethanol (purity 99.5%) as the dispersion medium and ultrasound applied for 1 minute.

[0049] If the liquid rapid setting agent of the present invention contains component (E), the liquid rapid setting agent of the present invention contains component (E) in an amount of preferably 0.001% by mass or more, more preferably 0.002% by mass or more, even more preferably 0.005% by mass or more, and from the same viewpoint, preferably 10.0% by mass or less, more preferably 7.0% by mass or less, and even more preferably 5.0% by mass or less. Alternatively, if the liquid rapid setting agent of the present invention contains component (E), the liquid rapid setting agent of the present invention contains component (E) in the same manner, preferably in an amount of 0.001% by mass or more and 10.0% by mass or less, more preferably 0.002% by mass or more and 7.0% by mass or less, and even more preferably 0.005% by mass or more and 5.0% by mass or less. Furthermore, in the provisions concerning the mass of component (E), insoluble components other than those corresponding to smectite contained in component (A) shall be included in the content of component (E).

[0050] The liquid rapid setting agent of the present invention may optionally contain one or more selected from a fluorine component, an alkanolamine, a complex-forming agent, and an alkaline earth metal. The liquid rapid setting agent of the present invention may contain these optional components in total at, for example, 0% by mass or more and 10% by mass or less, preferably 0% by mass or more and 5% by mass or less, and more preferably 0% by mass or more and 3.5% by mass or less.

[0051] <Fluoride component> Examples of fluorine components include fluoride salts or hydrofluoric acid, which can significantly improve the setting properties and initial strength development of the rapid setting agent. The raw material compound containing the fluorine component is not particularly limited, and is not limited to any compound that contains fluorine and is soluble or dispersed in water. Examples of raw material compounds containing the fluorine component include one or more fluorine compounds selected from fluoride salts, silica fluoride salts, boron fluoride salts, organofluorine compounds, and hydrofluoric acid. Examples of fluoride salts include one or more selected from lithium fluoride, sodium fluoride, potassium fluoride, calcium fluoride, aluminum fluoride, and cryolite. Cryolite can be either natural or synthetic. Examples of fluorosilica salts include one or more selected from ammonium fluorosilica, sodium fluorosilica, potassium fluorosilica, and magnesium fluorosilica. Examples of boron fluoride salts include one or more selected from boron fluoride, boron trifluoride, boron trifluoride monoethylamine complex, boron trifluoride acetate complex, boron trifluoride triethanolamine, ammonium borofluoride, sodium borofluoride, potassium borofluoride, and ferrous borofluoride. The raw material compound containing fluorine is preferably one or more selected from fluoride salts and silica fluoride salts, due to its high safety, low manufacturing cost, and excellent coagulation properties.

[0052] <Alkanolamine> Alkanolamines are organic compounds with an NR-OH structure in their structural formula, and they can significantly improve the setting properties and initial strength development of rapid setting agents. Here, R is an atomic group called an alkylene group or arylene group. Examples of R include linear alkylene groups such as methylene groups, ethylene groups, and n-propylene groups, branched alkylene groups such as isopropylene groups, and arylene groups having aromatic rings such as phenylene groups and torylene groups. R may be bonded to a nitrogen atom at two or more locations, and some or all of R may have a cyclic structure. Furthermore, R may be bonded to multiple hydroxyl groups, and some of the alkyl groups may contain elements other than carbon and hydrogen, such as sulfur, fluorine, chlorine, and oxygen. Examples of alkanolamines include one or more selected from ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, N,N-dibutylethanolamine, N-(2-aminoethyl)ethanolamine, borontriethanolamine trifluoride, and derivatives thereof. Diethanolamine, N,N-dimethylethanolamine, or mixtures thereof are preferred, and a mixture of diethanolamine and N,N-dimethylethanolamine is more preferred.

[0053] <Complexing agent> The complex-forming agent stabilizes metal ions in the liquid rapid-setting agent, and is not particularly limited as long as it is a substance that can be used for this purpose. For example, organic acids having at least one carboxyl group, preferably one to three, and more preferably two to three, are available. Furthermore, substances having one to three hydroxyl groups and / or one to three amino groups can also be used. Complexing agents include, for example, (1) monocarboxylic acids such as formic acid, acetic acid, and propionic acid; (2) dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid, and phthalic acid; (3) tricarboxylic acids such as trimellitic acid and tricarbaryl acid; (4) oxymonocarboxylic acids such as hydroxybutyric acid, lactic acid, and salicylic acid; (5) oxydicarboxylic acids such as malic acid; (6) aminocarboxylic acids such as aspartic acid and glutamic acid; (7) ethylenediaminetetraacetic acid (EDTA) and trans-1,2-diaminocyclohexanetetraacetic acid. Examples include aminopolycarboxylic acids such as CyDTA, (8) phosphonic acids such as ethylenediaminetetra(methylenephosphonic acid) [EDTPO], ethylenediaminedi(methylenephosphonic acid) [EDDPO], nitrilotris(methylenephosphonic acid) [NTPO], and 1-hydroxyethylidene-1,1'-diphosphonic acid [HEDPO], (9) condensed phosphoric acids such as phosphoric acid, tripolyphosphate, and hexametaphosphate, and (10) diketones such as acetylacetone and hexafluoroacetylacetone. In the present invention, one or more of these complex-forming agents can be used. The complex-forming agent is preferably at least one selected from the group consisting of oxalic acid, malonic acid, succinic acid, and condensed phosphoric acids.

[0054] <Alkaline earth metal carbonates> Alkaline earth metals can be found in the form of alkaline earth metal salts, and even more specifically, alkaline earth metal carbonates. Alkaline earth metal carbonates are carbonates of alkaline earth metals that prevent the fastener from adhering to pipes and from clogging pipes. Examples of alkaline earth metal carbonates include one or more selected from calcium carbonate, magnesium carbonate, and barium carbonate, with one or more selected from calcium carbonate and magnesium carbonate being preferred. Calcium carbonate is particularly preferred for its effectiveness in preventing adhesion to pipes and clogging, and it is even more preferable to use calcium carbonate in combination with sodium carbonate.

[0055] The liquid rapid setting agent of the present invention may optionally contain, in addition to the surfactant and the above-mentioned optional components, at least one of a water-soluble polymer, a foaming agent, a dispersant, and a thickening agent, as long as it does not impair the effects of the present invention. The liquid rapid setting agent of the present invention may contain these optional components in total at, for example, 0% by mass or more and 10% by mass or less, preferably 0% by mass or more and 5% by mass or less, and more preferably 0% by mass or more and 3.5% by mass or less.

[0056] In exemplary embodiments, the liquid rapid setting agent of the present invention may be a liquid rapid setting agent comprising component (A), a compound that dissociates into a cation with component (B) in water, a compound that dissociates into an anion with component (C) in water, and component (D). In the liquid rapid setting agent of the present invention, the preferred amounts of component (A) and component (D) can be applied by substituting the preferred content in the liquid rapid setting agent of the present invention described above. Furthermore, the compound that dissociates into a cation with component (B) in water, and the compound that dissociates into an anion with component (C) in water, are blended such that the content of component (B) or component (C) in the liquid rapid setting agent of the present invention is equal to the preferred content of component (B) or component (C) in the liquid rapid setting agent of the present invention described above. Furthermore, in the liquid rapid setting agent of the present invention, the mass ratio of the amount of each component can be applied by replacing the mass ratio of the preferred content in the liquid rapid setting agent of the present invention with the mass ratio of the amount of each component.

[0057] <Manufacturing method for liquid fast-setting agent> In an exemplary embodiment, the present invention provides a method for producing a liquid rapid setting agent by mixing (A) smectite, (B) sulfate ions, and (C) water containing aluminum ions, in a mass ratio [(A) / (B)] of the amount of component (A) to the amount of component (B) being 3 or less. Furthermore, in exemplary embodiments, the present invention provides a method for producing a liquid rapid setting agent, comprising mixing (A) a clay mineral containing smectite, a compound that dissociates into a cation with component (B) in water, a compound that dissociates into an anion with component (C) in water, and (D) water, in a mass ratio [(A) / (B)] of the amount of component (A) to the amount of component (B) being 3 or less.

[0058] In the method for producing the liquid rapid setting agent of the present invention, preferred embodiments of component (A), component (B), component (C), and component (D) are the same as preferred embodiments of component (A), component (B), component (C), and component (D) of the liquid rapid setting agent of the present invention described above. Furthermore, in the method for producing the liquid rapid setting agent of the present invention, any of the components listed in the liquid rapid setting agent of the present invention may be mixed as desired.

[0059] In the method for producing the liquid rapid setting agent of the present invention, the preferred mixing amounts and mixing ratios of component (A), component (D), a compound that dissociates into a cation with component (B) in water, a compound that dissociates into an anion with component (C) in water, and any optional component can be applied by substituting the preferred content or mass ratio of each component in the liquid rapid setting agent of the present invention with the mixing amounts or mixing ratios. Furthermore, the preferred content and mass ratio of component (B) and component (C) in the liquid rapid setting agent of the present invention can be determined by applying the preferred content and mass ratio of each component in the liquid rapid setting agent of the present invention described above.

[0060] <Hydraulic composition> In an exemplary embodiment, the present invention provides a hydraulic composition comprising a liquid quick-setting agent containing (A) smectite, (B) sulfate ions, (C) aluminum ions, and (D) water, wherein the mass ratio of the content of component (A) to the content of component (B) [(A) / (B)] is 3 or less. In an exemplary embodiment, the hydraulic composition of the present invention may be a hydraulic composition containing the liquid quick-setting agent of the present invention and a hydraulic powder. The hydraulic composition of the present invention may be a hydraulic composition for spraying.

[0061] In the hydraulic composition of the present invention, preferred embodiments of components (A) to (D) and the liquid rapid setting agent are the same as preferred embodiments of components (A) to (D) and the liquid rapid setting agent in the liquid rapid setting agent of the present invention described above. Furthermore, the hydraulic composition of the present invention, or the liquid rapid setting agent described above, may optionally contain any of the components listed for the liquid rapid setting agent of the present invention. In the hydraulic composition of the present invention, the preferred embodiment of the content of components (A) to (D) and other optional components contained in the liquid rapid setting agent, and the mass ratio of these contents, is the same as the preferred embodiment of the content of components (A) to (D) and other optional components and the mass ratio of these contents in the liquid rapid setting agent of the present invention.

[0062] <Hydraulic powder> The hydraulic powder used in the hydraulic composition of the present invention is a powder that hardens when mixed with water, and examples include ordinary Portland cement, rapid-hardening Portland cement, ultra-rapid-hardening Portland cement, sulfate-resistant Portland cement, low-heat Portland cement, moderate-heat Portland cement, white Portland cement, alumina cement, calcined clay-containing cement, or eco-cement (e.g., JIS R5214). Among these, from the viewpoint of expanding the range of hydraulic compositions, cement selected from rapid-hardening Portland cement, ordinary Portland cement, sulfate-resistant Portland cement, and white Portland cement is preferred, and rapid-hardening Portland cement or ordinary Portland cement is more preferred. In addition, the hydraulic powder may include blast furnace slag, fly ash, silica fume, anhydrous gypsum, etc., and may also include non-hydraulic fine limestone powder, etc. The hydraulic powder may be blast furnace cement, fly ash cement, silica fume cement in which cement is mixed with blast furnace slag, fly ash, silica fume, etc.

[0063] <Aggregate> The hydraulic composition of the present invention can optionally contain an aggregate. Examples of the aggregate include aggregates selected from fine aggregates and coarse aggregates. Examples of the fine aggregate include those defined by No. 2311 in JIS A 0203-2014. For example, the fine aggregate includes river sand, land sand, mountain sand, sea sand, lime sand, silica sand, and crushed sand thereof, blast furnace slag fine aggregate, ferronickel slag fine aggregate, lightweight fine aggregate (artificial and natural), and recycled fine aggregate, etc. Examples of the coarse aggregate include those defined by No. 2312 in JIS A 0203-2014. For example, the coarse aggregate includes river gravel, land gravel, mountain gravel, sea gravel, lime gravel, crushed stones thereof, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural), and recycled coarse aggregate, etc. The fine aggregate and the coarse aggregate may be used by mixing those of different types, or a single type may be used.

[0064] The hydraulic composition of the present invention can contain a fine aggregate. The amount of the fine aggregate used in the hydraulic composition of the present invention is preferably 500 kg / m 3 or more, more preferably 600 kg / m 3 or more, and preferably 2,000 kg / m 3 or less, more preferably 1,700 kg / m 3 or less. In the hydraulic composition of the present invention, the fine aggregate ratio is preferably 35% or more, more preferably 45% or more, and preferably 100% or less, more preferably 70% or less, still more preferably 65% or less. Here, the fine aggregate ratio is the volume content ratio of the fine aggregate in all the aggregates.

[0065] <Water> The hydraulic composition of the present invention may contain water. Examples of water include tap water, groundwater, lake water, and river water.

[0066] The hydraulic composition of the present invention has a water / hydraulic powder ratio (W / C) that is preferably 30% by mass or more, more preferably 35% by mass or more, even more preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less, from the viewpoint of improving the shape retention of the hydraulic composition and enhancing the stability of shape retention against fluctuations in manufacturing conditions. Alternatively, the water / hydraulic powder ratio (W / C) is preferably 30% by mass or more and 80% by mass or less, more preferably 35% by mass or more and 70% by mass or less, and even more preferably 40% by mass or more and 65% by mass or less. In other words, the hydraulic composition of the present invention contains water in an amount of preferably 30 parts by mass or more, more preferably 35 parts by mass or more, even more preferably 40 parts by mass or more, and preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 65 parts by mass or less, per 100 parts by mass of hydraulic powder. Alternatively, from the same viewpoint, the hydraulic composition of the present invention contains water in the following proportions: preferably 30 to 80 parts by mass, more preferably 35 to 70 parts by mass, and even more preferably 40 to 65 parts by mass, per 100 parts by mass of hydraulic powder. The water / hydraulic powder ratio (W / C) represents the proportion of water to hydraulic powder in the hydraulic composition, expressed as a mass percentage (mass%), and is calculated as (water / hydraulic powder) × 100. Furthermore, if the hydraulic powder includes powders selected from those having properties that harden through hydration reactions such as cement, powders having pozzolanic properties, powders having latent hydraulic properties, and stone powder (calcium carbonate powder), the amounts of these powders are also included in the amount of hydraulic powder in this invention. In addition, if the powder having properties that harden through hydration reactions contains a high-strength admixture, the amount of the high-strength admixture is also included in the amount of hydraulic powder. This is also true for other parts of mass where the mass of the hydraulic powder is relevant.

[0067] The hydraulic composition of the present invention contains the above-mentioned liquid rapid setting agent in an amount of 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, and preferably 10% by mass or less, more preferably 9.0% by mass or less, and even more preferably 8.0% by mass or less, relative to the hydraulic powder in the hydraulic composition, from the viewpoint of maintaining the shape of the hydraulic composition. Alternatively, the hydraulic composition of the present invention contains the above-mentioned liquid quick-setting agent in an amount of 0.1% to 10% by mass, more preferably 0.2% to 9.0% by mass, and even more preferably 0.5% to 8.0% by mass, relative to the hydraulic powder in the hydraulic composition, from the same viewpoint.

[0068] <Dispersant> The hydraulic composition of the present invention may optionally contain a dispersant. One or more dispersants may be used in combination. From the viewpoint of dispensing workability, a polycarboxylic acid-based dispersant is preferred.

[0069] Polycarboxylic acid-based dispersants can include copolymers of a monoester of polyalkylene glycol and (meth)acrylic acid with a carboxylic acid such as (meth)acrylic acid (for example, the compound described in Japanese Patent Publication No. 8-12397), copolymers of an unsaturated alcohol having polyalkylene glycol with a carboxylic acid such as (meth)acrylic acid, and copolymers of an unsaturated alcohol having polyalkylene glycol with a dicarboxylic acid such as maleic acid. Here, (meth)acrylic acid refers to a carboxylic acid selected from acrylic acid and methacrylic acid.

[0070] If the hydraulic composition of the present invention contains a dispersant, the hydraulic composition of the present invention contains the dispersant in an amount of preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.07 parts by mass or more, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, and even more preferably 0.3 parts by mass or less, per 100 parts by mass of the hydraulic powder contained in the hydraulic composition, from the viewpoint of improving the shape retention of the hydraulic composition and enhancing the stability of the shape retention against fluctuations in manufacturing conditions. Alternatively, if the hydraulic composition of the present invention contains a dispersant, the hydraulic composition of the present invention contains, from the same viewpoint, preferably 0.01 parts by mass or more and 1 part by mass or less, more preferably 0.05 parts by mass or more and 0.5 parts by mass or less, and even more preferably 0.07 parts by mass or more and 0.3 parts by mass or less, per 100 parts by mass of hydraulic powder contained in the hydraulic composition. In the hydraulic composition of the present invention, the preferred content of the active ingredient of the dispersant may be within the range described above.

[0071] The hydraulic composition of the present invention may optionally contain one or more of the following: a high-performance water-reducing agent, a high-performance AE water-reducing agent, a water-reducing agent including an AE water-reducing agent and a fluidizing agent, an expanding agent, a hardening accelerator, a hardening retarder, a polymer for cement, a foaming agent, a waterproofing agent, a rust inhibitor, a shrinkage reducing agent, a pigment, a fiber, a water-repellent agent, an efflorescence inhibitor, a thickening agent, etc.

[0072] Examples of objects to which the hydraulic composition of the present invention is sprayed include tunnels such as roads, railways, and water conduits, slopes formed by excavation of natural ground, embankments, underground spaces, and concrete structures that are subject to repair by spraying methods.

[0073] In exemplary embodiments, the hydraulic composition of the present invention may be a hydraulic composition comprising a liquid quick-setting agent containing (A) smectite, (B) sulfate ions, (C) aluminum ions, and (D) water, a hydraulic powder, and water. In exemplary embodiments, the hydraulic composition of the present invention may be a hydraulic composition comprising the liquid rapid setting agent of the present invention, a hydraulic powder, and water. The hydraulic composition of the present invention may further contain any of the optional components described above in the hydraulic composition of the present invention. Furthermore, in the hydraulic composition of the present invention, the preferred amounts of the liquid quick-setting agent, hydraulic water powder, and optional components can be applied by substituting the preferred content in the hydraulic composition of the present invention described above.

[0074] <Method for producing a hydraulic composition> In an exemplary embodiment, the present invention provides a method for producing a hydraulic composition by mixing a liquid quick-setting agent containing (A) smectite, (B) sulfate ions, (C) aluminum ions, and (D) water, wherein the mass ratio of the content of component (A) to the content of component (B) [(A) / (B)] is 3 or less, a hydraulic powder, and water.

[0075] In an exemplary embodiment, the method for producing the hydraulic composition of the present invention may be a method for producing the hydraulic composition by mixing the liquid rapid setting agent of the present invention, a hydraulic powder, and water. Furthermore, the method for producing the hydraulic composition of the present invention may be a method for producing a hydraulic composition in which a hydraulic composition obtained by mixing hydraulic powder and water is mixed with the liquid rapid setting agent of the present invention. The method for producing the hydraulic composition of the present invention may be a method for producing a hydraulic composition for spraying.

[0076] In the method for producing the hydraulic composition of the present invention, preferred embodiments of components (A) to (D) and the liquid rapid setting agent are the same as preferred embodiments of components (A) to (D) and the liquid rapid setting agent in the liquid rapid setting agent of the present invention described above. Furthermore, preferred embodiments of the hydraulic powder and water are the same as preferred embodiments of the hydraulic powder and water in the hydraulic composition of the present invention. Furthermore, in the method for producing the hydraulic composition of the present invention, the hydraulic composition or the liquid rapid setting agent may optionally contain any of the components listed in the liquid rapid setting agent or the hydraulic composition of the present invention.

[0077] In the method for producing the hydraulic composition of the present invention, the preferred embodiment of the content and mass ratio of components (A) to (D) and other optional components contained in the liquid rapid setting agent is the same as the preferred embodiment of the content and mass ratio of components (A) to (D) and other optional components in the liquid rapid setting agent of the present invention. Furthermore, in the method for producing the hydraulic composition of the present invention, the amount or ratio of liquid quick-setting agent, hydraulic powder, and water can be applied by substituting the content or mass ratio of each component in the hydraulic composition of the present invention for the amount or ratio of the content. The same applies to the spray application method, which will be explained in detail later.

[0078] <Spray application method> In an exemplary embodiment, the present invention provides a spraying method in which a hydraulic composition containing hydraulic powder and water is mixed with a liquid quick-setting agent containing (A) smectite, (B) sulfate ions, (C) aluminum ions, and (D) water, and the mass ratio of the content of component (A) to the content of component (B) [(A) / (B)] is 3 or less, and the mixture is sprayed onto an object. Furthermore, in an exemplary embodiment, the present invention provides a spraying method in which a hydraulic composition containing hydraulic powder and water is mixed with the liquid rapid setting agent of the present invention and sprayed onto an object. Furthermore, the spraying method of the present invention may be a spraying method in which the hydraulic composition of the present invention is sprayed onto an object. Specifically, the object may be the object described in the hydraulic composition of the present invention. Furthermore, the liquid fastener may be the liquid fastener of the present invention.

[0079] The spraying method of the present invention preferably involves separately pumping the hydraulic composition and the liquid quick-setting agent and then combining and mixing them, with a wet spraying method being preferred. The wet spraying method includes, for example, a method in which hydraulic powder, aggregate, and water are mixed and kneaded, pumped under air pressure, and then combined and mixed with the liquid quick-setting agent before spraying. The spraying method of the present invention is preferably a method in which the liquid rapid setting agent of the present invention and a hydraulic composition containing water, hydraulic powder, and aggregate are each pumped under air pressure and mixed, and the resulting hydraulic composition for spraying is sprayed onto the target object. The liquid rapid setting agent of the present invention may be prepared by mixing water, hydraulic powder, and aggregate to produce a hydraulic composition, and then mixing the liquid rapid setting agent with the hydraulic composition using a mixer, or the liquid rapid setting agent and the hydraulic composition may be separately pumped and then combined and mixed. From the viewpoint of maintaining the shape of the hydraulic composition, it is preferable to separately pump the liquid rapid setting agent and the hydraulic composition and then combine and mix them.

[0080] In the spraying method of the present invention, when the hydraulic composition of the present invention is sprayed onto an object by air pressure, the air pressure used to spray the hydraulic composition onto the object is preferably 0.2 MPa or higher, more preferably 0.3 MPa or higher, even more preferably 0.4 MPa or higher, and from the same viewpoint, preferably 1.2 MPa or lower, more preferably 1.0 MPa or lower, even more preferably 0.8 MPa or lower, and even more preferably 0.6 MPa or lower. Alternatively, in the spraying method of the present invention, when the hydraulic composition of the present invention is sprayed onto an object by air pressure, the air pressure used to spray the hydraulic composition onto the object is, from the same viewpoint, preferably 0.2 MPa or more and 1.2 MPa or less, more preferably 0.3 MPa or more and 1.0 MPa or less, even more preferably 0.4 MPa or more and 0.8 MPa or less, and even more preferably 0.4 MPa or more and 0.6 MPa or less. It is preferable that the pressure used to air-feed the hydraulic composition of the present invention is within the above range.

[0081] The spraying method of the present invention will be described in detail with specific examples. However, the spraying method of the present invention is not limited in any way based on these specific examples. In the spraying method of the present invention, a hydraulic composition is first produced by mixing hydraulic powder, aggregate, and water. A hydraulic composition produced by mixing hydraulic powder, aggregate, and water, and furthermore, the hydraulic composition of the present invention, has a water / hydraulic powder ratio (W / C) [mass percentage of water and hydraulic powder in the hydraulic composition] which, from the viewpoint of shape retention of the hydraulic composition, is preferably 30% by mass or more, more preferably 35% by mass or more, even more preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less. Alternatively, the water / hydraulic powder ratio (W / C) is preferably 30% by mass or more and 80% by mass or less, more preferably 35% by mass or more and 70% by mass or less, and even more preferably 40% by mass or more and 65% by mass or less.

[0082] In the present invention, the mixing of hydraulic powder, aggregate, water, and other optional components can be carried out by known methods. For example, a method of simultaneously mixing hydraulic powder, water, and aggregate can be used. Mixing mixers such as pan-type forced mixers, twin-screw forced mixers, and tiltable mixers can be used to mix these components.

[0083] In the present invention, a hydraulic composition for spraying can be produced by mixing a hydraulic powder, aggregate, and water to obtain a hydraulic composition, and then mixing it with the liquid rapid setting agent of the present invention. The mixing of the hydraulic composition and the liquid rapid setting agent of the present invention can be carried out, for example, by a general spraying method in which the hydraulic composition and the liquid rapid setting agent of the present invention are pneumatically fed and mixed together.

[0084] In the present invention, the liquid rapid setting agent of the present invention is mixed with the hydraulic powder in the hydraulic composition in an amount preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, and preferably 10% by mass or less, more preferably 9.0% by mass or less, and even more preferably 8.0% by mass or less, from the viewpoint of maintaining the shape of the hydraulic composition. Alternatively, in the present invention, the liquid rapid setting agent of the present invention is mixed with the hydraulic powder in the hydraulic composition in an amount preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.2% by mass or more and 9.0% by mass or less, and even more preferably 0.5% by mass or more and 8.0% by mass or less, from the same viewpoint.

[0085] Furthermore, the spraying method of the present invention may optionally use the aforementioned dispersant. When a dispersant is used in the spraying method of the present invention, the dispersant may be mixed with water in advance during the process of preparing the hydraulic composition. In the present invention, when the dispersant is used, the dispersant is mixed with 100 parts by mass of hydraulic powder in the hydraulic composition in an amount of preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.07 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, and even more preferably 0.3 parts by mass or less, from the viewpoint of improving the shape retention of the hydraulic composition and increasing the stability of the shape retention against fluctuations in manufacturing conditions. Alternatively, in the present invention, when the dispersant is used, the dispersant is mixed with 100 parts by mass of the hydraulic powder in the hydraulic composition, preferably in an amount of 0.01 parts by mass or more and 1 part by mass or less, more preferably 0.05 parts by mass or more and 0.5 parts by mass or less, and even more preferably 0.07 parts by mass or more and 0.3 parts by mass or less. In the spraying method of the present invention, the preferred content of the active ingredient in the dispersant may be within the above range.

[0086] In the spraying method of the present invention, the hydraulic composition for spraying prepared in this manner is sprayed onto the target object. The spraying method of the present invention can be implemented using conventional spraying equipment. The spraying equipment only needs to be able to perform spraying without any problems. For example, it is possible to use Arriba Corporation's "Arriba 280" or the like for pumping the hydraulic composition, and Chiyoda Seisakusho Co., Ltd.'s "Natomcrete" or the like for pumping the liquid quick-setting agent of the present invention, mix the two to prepare a hydraulic composition for spraying, and then perform the spraying.

[0087] <Use as a liquid fastener> In exemplary embodiments, the present invention provides for the use of a mixture containing (A) smectite, (B) sulfate ions, (C) aluminum ions, and (D) water, wherein the mass ratio of the content of component (A) to the content of component (B) [(A) / (B)] is 3 or less, as a liquid quick-setting agent.

[0088] The present invention can be appropriately applied to the use of the liquid rapid setting agent and its manufacturing method, the hydraulic composition and its manufacturing method, and the spraying method of the present invention. In use of the present invention, preferred embodiments of components (A) to (D) are the same as preferred embodiments of components (A) to (D) in the liquid rapid setting agent of the present invention described above. Furthermore, in use of the present invention, preferred embodiments of the mixture can be applied by replacing the liquid rapid setting agent of the present invention with the mixture. Furthermore, the mixture of the present invention may optionally contain any of the components listed in the liquid rapid setting agent of the present invention. In the use of the present invention, preferred embodiments of the content of components (A) to (D) and other optional components contained in the mixture, and the mass ratio of these contents, are the same as preferred embodiments of the content of components (A) to (D) and other optional components and the mass ratio of these contents in the liquid rapid setting agent of the present invention. Furthermore, preferred embodiments of the hydraulic composition in which the mixture is used as a liquid quick-setting agent, such as preferred embodiments of hydraulic powder and water, are the same as preferred embodiments of hydraulic powder and water in the hydraulic composition of the present invention. Furthermore, in the use of the present invention, one possible use of the mixture is to use a mixture containing components (A) to (D) in the amounts described for the liquid rapid setting agent of the present invention, in the amounts described for the hydraulic composition of the present invention. [Examples]

[0089] In the examples and comparative examples, liquid or powdered rapid setting agents were prepared using components (A) to (D) listed below, and hydraulic compositions containing the prepared rapid setting agents and the dispersants listed below were prepared. The shape retention of these hydraulic compositions was then evaluated. The results are shown in Tables 4 to 7.

[0090] <(A) component> • Bentonite: Bentonite A, a mixture prepared by the following preparation method, with a swelling degree of 35 mL / 2 g, a smectite content of 59% by mass, and a total content of 40% by mass of one or more inorganic powders selected from crystalline silica, calcium carbonate, aluminosilicate, and talc. Synthetic hectorite: Smecton SWF, manufactured by Kunimine Industries Co., Ltd., swelling degree 52 mL / 2 g, smectite content 100% by mass Synthetic stevensite: Smecton ST, manufactured by Kunimine Industries Co., Ltd., swelling degree 45 mL / 2 g, smectite content 100% by mass • Synthetic saponite: Smecton SA, manufactured by Kunimine Industries Co., Ltd., swelling degree 46 mL / 2 g, smectite content 99% by mass Bentonite: Kunigel GS, manufactured by Kunimine Industries Co., Ltd., swelling degree 33 mL / 2 g, average particle size 39 μm, smectite content 54% by mass, and total content of one or more inorganic powders selected from crystalline silica, calcium carbonate, and aluminosilicate is 46% by mass. • Bentonite: TB-250, manufactured by Tachibana Material Co., Ltd., swelling degree 14 mL / 2 g, smectite content 38% by mass, and total content of one or more inorganic powders selected from crystalline silica, calcium carbonate, and aluminosilicate is 62% by mass. • Bentonite: Superclay, manufactured by Hojun Co., Ltd., swelling degree 24 mL / 2 g, smectite content 51% by mass, and total content of one or more inorganic powders selected from crystalline silica, calcium carbonate, aluminosilicate, and talc is 49% by mass.

[0091] (Components of Bentonite A) • Refined montmorillonite: Kunipia F, manufactured by Kunimine Industries Co., Ltd., smectite content 99% by mass • Quartz: Sigma-Aldrich, average particle size 63.6 μm, crystallinity 100% • Aluminum silicate: Synthetic aluminum silicate (82% SiO2, 9.5% Al2O3, 8% Na2O), manufactured by Sigma-Aldrich, swelling degree 7 mL / 2 g, average particle size 17.9 μm • Kaolin: Kaolin, manufactured by Hayashi Pure Chemical Industries, Ltd., average particle size 6.3 μm Zeolite K: Synthetic zeolite, HS-500, powder, potassium L, manufactured by Fujifilm Wako Chemical Co., Ltd., swelling degree 3 mL / 2 g, average particle size 25.9 μm • Synthetic mica: Synthetic mica, non-swelling, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., swelling degree 3 mL / 2 g, average particle size 6.5 μm • Calcium carbonate: Calcium carbonate CP, manufactured by Sigma-Aldrich, average particle size 58.4 μm • Talc: Manufactured by Fujifilm Wako Pure Chemical Corporation, average particle size 55.8 μm, average aspect ratio 1.33

[0092] (Method for preparing bentonite A) Bentonite A was prepared by placing 60g of purified montmorillonite, 20g of quartz, 3.75g of aluminum silicate, 3.75g of kaolin, 3.75g of zeolite K, 3.75g of synthetic mica, 3g of calcium carbonate, and 2g of talc into a 250mL bottle, sealing the bottle with the lid, and shaking it for 10 minutes.

[0093] <(B) component, (C) component> • Aluminum sulfate: Aluminum sulfate 14-18 hydrate (manufactured by Kanto Chemical Co., Ltd.) Aluminum sulfate is the inorganic salt from which the sulfate ions in component (B) and the aluminum ions in component (C) originate. In Tables 1 to 3, the content of components (B) and (C) calculated from the amount of aluminum sulfate are indicated in parentheses. <(C) component> • Aluminum hydroxide: Aluminum hydroxide, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Aluminum hydroxide is an inorganic salt from which the aluminum ions in component (C) are derived. <(D) component> • Water: Wakayama City tap water <Dispersant> • Polycarboxylic acid-based dispersant: Mighty 21HF, 24% by mass of active ingredient, manufactured by Kao Corporation. <(E) component> • Colloidal silica: Cataloid SI-80PW, manufactured by JGC Catalysts & Chemicals Co., Ltd., average particle size 80 nm <Other ingredients> • Sepiolite: Milcon MS-2, manufactured by Showa KDE Co., Ltd.

[0094] <Measurement of swelling degree> (A) The degree of swelling of component (A) was measured according to the swelling test method for bentonite (powder) specified in JBAS104:77 of the Japan Bentonite Industry Association. Specifically, 2.0 g of the sample, adjusted to a moisture content of 8.0% by mass, was added in approximately 10 portions to a 100 mL stoppered graduated cylinder containing 100 mL of distilled water. At this time, the next addition was made only after the previous addition had settled at the bottom of the graduated cylinder. After standing for 24 hours, the apparent volume of the sample mass at the bottom of the graduated cylinder that had swollen was read from the scale of the graduated cylinder and defined as the degree of swelling (mL / 2g).

[0095] <(A) Method for measuring the smectite content> (i)Drying (A) The component was placed in a hot air dryer and dried at 105°C for 1 hour. (ii) Measurement of methylene blue adsorption (A) The amount of methylene blue adsorbed by the clay mineral was measured according to the following method in accordance with the Japanese Industrial Standard (JIS Z2451:2019). 1.87 g of methylene blue (molecular weight 374, Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in 500 mL of deionized water to prepare a 10 mmol / L aqueous solution of methylene blue. In addition, 1.68 g of sodium pyrophosphate decahydrate (molecular weight 446, Sigma-Aldrich) was dissolved in 500 mL of deionized water to prepare a 0.2% by mass aqueous solution of sodium pyrophosphate. <Reagents> 10 mmol / L aqueous solution of methylene blue (molecular weight 374) 0.2% by mass aqueous solution of sodium pyrophosphate (Na4P2O7) <How to operate> Approximately 0.4 g of component (A) was placed in a 100 mL screw-top tube, and 40 g of a 0.2% by mass aqueous solution of sodium pyrophosphate was added to it. This mixture was dispersed in an ultrasonic cleaner (ASUCLEANER, ASU-3, manufactured by AS ONE Corporation) for 30 minutes, and then heated in 80°C hot water for 30 minutes. A 10 mmol / L methylene blue aqueous solution was added dropwise to the dispersed mixture while stirring with a magnetic stirrer. After each drop, a portion of the supernatant was drawn up using a glass Pasteur pipette and added to filter paper. The supernatant was added in an amount sufficient to form a spot approximately 10 mm in diameter on the filter paper. This procedure was repeated until a halo was observed around the spot. Once the halo was observed, the titration was terminated when the width of the halo exceeded 2 mm. Then, based on the mass of component (A) and the total amount of 10 mmol / L aqueous methylene blue solution added dropwise to the endpoint, the amount of methylene blue adsorbed per 100 g of component (A) was calculated. Specifically, the product of the titration volume (L) and the concentration of the methylene blue aqueous solution (10 mmol / L) was converted to a value per 100 g of component (A) to calculate the total amount of methylene blue adsorbed (mmol). (iii) Calculation of smectite content A saturation adsorption amount of methylene blue for smectite was set at 140 mmol / 100 g. The smectite content of component (A) was calculated by dividing the measured methylene blue adsorption amount of component (A) by this saturation adsorption amount and multiplying by 100. If the methylene blue adsorption amount exceeds 140 mmol / 100 g, the smectite content was assumed to be 100% by mass.

[0096] <Method for measuring average particle size> For each component (A), the arithmetic mean particle size was measured using a laser diffraction / scattering particle size distribution analyzer (LA-920 (manufactured by Horiba, Ltd.)) with ethanol (purity 99.5%) as the dispersion medium and ultrasound applied for 1 minute.

[0097] <Method for preparing liquid fastening agent> Liquid quick-setting agent B in Table 1 was prepared by the following method (1). (1) Liquid quick-setting agent B 59.13 g of aluminum sulfate-14-18 hydrate and 27.67 g of water were placed in a 300 mL disposable cup, and the mixture was stirred at 100 rpm (EUROSTAR200control, IKA Japan Co., Ltd.) at 20°C for 1 hour using a flat 6-blade paddle (FP-50, manufactured by AS ONE Corporation). Subsequently, 6 g of aluminum hydroxide, 3 g of bentonite A, 1.4 g of formic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.6 g of phosphoric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.5 g of diethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.5 g of 2,2'-methyliminodiethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.2 g of ammonium fluoride (manufactured by Sigma-Aldrich Corporation), and 1.0 g of colloidal silica (ASP-350, manufactured by JGC Catalysts & Chemicals Inc.) were added, and the mixture was stirred at 100 rpm at 20°C for 1 hour using a flat 6-blade paddle to prepare liquid rapid setting agent B. Liquid rapid setting agents A, C-L, and R-T were prepared in the same manner as liquid rapid setting agent B using the components listed in Table 1 or Table 2.

[0098] The liquid rapid setting agents M, O-Q and powder rapid setting agent N in Table 3 were prepared according to the preparation methods described in (2) to (4) below. (2) Method for preparing liquid fastening agent M A liquid rapid setting agent M containing 27% by mass of aluminum sulfate was prepared by adding 500g of aluminum sulfate-14-18 hydrate to a 2L cup, adding water until the total volume reached 1,000g, and mixing to dissolve. (3) Method for preparing powdered rapid setting agent N (A) The components Knigel GS and anhydrous aluminum sulfate were placed in a 250 mL sealed bottle container so that the ratio of components (A) to aluminum sulfate was as shown in Table 3. The mixture was then mixed by manually shaking the bottle while repeatedly inverting it for 60 seconds to prepare powdered quick-setting agent N. (4) Method for preparing liquid fastening agent O 500g of aluminum sulfate-14-18 hydrate was added to a 2L cup, 400g of water was added and mixed for 10 minutes, then 100g of bentonite (Kunigel GS, manufactured by Kunimine Industries Co., Ltd.), which is component (A), was added and mixed at 300 rpm for 1 hour using a flat 6-blade paddle to prepare liquid rapid setting agent O. Liquid rapid setting agents P and Q were prepared in the same manner as liquid rapid setting agent O, by replacing component (A) with bentonite (TB-250, manufactured by Tachibana Material Co., Ltd.) and bentonite (Superclay, manufactured by Hojun Co., Ltd.), respectively.

[0099] [Table 1]

[0100] [Table 2]

[0101] [Table 3]

[0102] <Note> *1: In Tables 1 to 3, the numbers in parentheses for component (A) indicate the smectite content (mass %). *2: In Tables 1 to 3, the numbers in parentheses for aluminum sulfate indicate the amount of water of hydration (mass%) of aluminum sulfate-14-18 hydrate. *3: In Tables 1 to 3, the values ​​in parentheses for component (B) indicate the content (mass %) of sulfate ions derived from aluminum sulfate. *4: In Tables 1 to 3, the values ​​in parentheses for component (C) indicate the content (mass%) of aluminum ions derived from aluminum sulfate or aluminum hydroxide.

[0103] <Method for evaluating shape retention> (1) Preparation of hydraulic composition A mortar mixer as specified in "JIS R 5201 Physical Testing Methods for Cement" was used to prepare the hydraulic composition. The following water, cement, fine aggregate, and dispersant were used in the preparation of the hydraulic composition. Water (W): Tap water Cement (C): Ordinary Portland cement (two-component mixture: Taiheiyo Cement / Sumitomo Osaka Cement = 1 / 1, mass ratio) Density 3.16 g / cm³ 3 Fine aggregate (S): Joyo mountain sand density 2.55g / cm 3 Dispersant: Mighty 21HF (manufactured by Kao Corporation)

[0104] In a mortar mixer (Hobart-type mixer, KC-8, manufactured by Kansai Kiki Seisakusho Co., Ltd.), 400g of cement and 1050g of fine aggregate were added to the mixing bowl and dry-mixed for 10 seconds. Then, 192g of water was added and mixed at low speed (mixing speed: orbital 62 rpm, rotational 141 rpm) for 2 minutes. The polycarboxylic acid-based dispersant was used after being mixed with water beforehand.

[0105] (2) Method for evaluating shape retention The shape retention of the hydraulic composition prepared in (1) was evaluated based on the vane shear resistance value of the hydraulic composition. Specifically, using a direct-reading torque driver (manufactured by Tohnichi Manufacturing Co., Ltd.), the vane shear resistance of the hydraulic composition was measured after 4 minutes, with the time at which mixing began (0 seconds) after adding 7.76 g of each liquid or powdered rapid setting agent to 530 g of the hydraulic composition prepared in (1) was used as the reference time. A vane measuring 20 mm x 40 mm was used. The results are shown in Tables 4 to 7. The higher the vane shear resistance value, the better the shape retention of the hydraulic composition, resulting in a liquid rapid setting agent that is less prone to deformation after molding and has good moldability. Furthermore, as shown in Examples 6-1 to 6-3 in Table 7, when liquid rapid setting agent O was used, stable shape retention was observed regardless of the application conditions.

[0106] [Table 4]

[0107] [Table 5]

[0108] [Table 6]

[0109] [Table 7]

[0110] <Note> Note 1: In Table 6, the content of the rapid setting agent (act% × C) is the amount of active ingredient relative to the cement (C) contained in the hydraulic composition. Note 2: In Tables 4 to 7, the content of the rapid setting agent (% × C) is the actual content relative to the cement (C) contained in the hydraulic composition. Also, the content of the dispersant (% × C) is the amount of active ingredient relative to the cement (C) contained in the hydraulic composition.

Claims

1. A liquid quick-setting agent containing (A) smectite, (B) sulfate ions, (C) aluminum ions, and (D) water, wherein the mass ratio of the content of component (A) to the content of component (B) [(A) / (B)] is 3 or less.

2. The liquid rapid setting agent according to claim 1, wherein component (A) is a clay mineral having a swelling degree of 5 mL / 2 g or more and 90 mL / 2 g or less.

3. The liquid quick-setting agent according to claim 1 or 2, wherein the mass ratio of the content of component (A) to the content of component (D) [(A) / (D)] is 0.5 or less.

4. The liquid quick-setting agent according to claim 1 or 2, wherein the content of component (A) is 1% by mass or more and 40% by mass or less.

5. The liquid quick-setting agent according to claim 1 or 2, wherein the content of component (B) is 5% by mass or more and 50% by mass or less.

6. The liquid quick-setting agent according to claim 1 or 2, wherein the content of component (C) is 1% by mass or more and 20% by mass or less.

7. The liquid quick-setting agent according to claim 1 or 2, wherein the content of component (D) is 30% by mass or more and 90% by mass or less.

8. Furthermore, the liquid quick-setting agent according to claim 1 or 2, further comprising (E) insoluble matter [excluding that which corresponds to component (A)], wherein the average particle size of component (E) is 0.01 μm or more and 500 μm or less.

9. (A) The liquid quick-setting agent according to claim 1 or 2, wherein component (A) comprises one or more inorganic powders selected from crystalline silica, calcium carbonate, aluminosilicate, and talc.

10. A liquid quick-setting agent according to claim 1 or 2, for use in a sprayable hydraulic composition.

11. A hydraulic composition comprising the liquid quick-setting agent described in claim 1 or 2.

12. The hydraulic composition according to claim 11, which is for spray application.

13. The hydraulic composition according to claim 11, comprising a polycarboxylic acid-based dispersant.

14. A method for producing a hydraulic composition, comprising mixing a liquid quick-setting agent according to claim 1 or 2 with a hydraulic powder.

15. A spraying method comprising mixing a hydraulic composition containing hydraulic powder and water with the liquid rapid setting agent described in claim 1 or 2 and spraying the mixture onto an object.

16. Use as a liquid quick-setting agent of a mixture containing (A) smectite, (B) sulfate ions, (C) aluminum ions, and (D) water, wherein the mass ratio of the content of component (A) to the content of component (B) [(A) / (B)] is 3 or less.

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