Liquid quick-setting agent

Abstract

This liquid quick-setting agent contains (A) smectite, (B) sulfate ions, (C) aluminum ions, and (D) water, and the mass ratio (A) / (B) of the content of the component (A) and the content of the component (B) is 3 or less.

Description

Liquid fastening agent

[0001] The present 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.

[0002] Background Technology: 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] Japanese Patent Publication No. 2021-70611 discloses an additive for a sprayable hydraulic composition comprising (A) a clay mineral with a swelling degree of 15 mL / 2 g or more and 50 mL / 2 g or less, and (B) one or more rapid setting agents selected from cement mineral-based rapid setting agents and aluminum-based rapid setting agents. Japanese Patent Publication No. 2024-67807 discloses a wet spraying method in which (b) clay minerals are added to a hydraulic composition containing hydraulic powder, (a) a polymer thickener, and water, and mixed at a stirring work of 150 J or less, and the hydraulic composition containing the (b) component is sprayed onto the target object. Japanese Patent Publication No. 2024-47946 discloses an additive for a hydraulic composition in which aluminum is Al ２ O ３ Converted to 9.0-15.0% by mass, sulfur is SO ３ A liquid rapid setting agent is disclosed that contains 22.0 to 35.0% by mass of clay minerals, 0.5 to 2.0% by mass of clay minerals, and 0.5 to 5.0% by mass of amine compounds, with a Heywood mean diameter of dispersed particles of 3 to 30 μm as observed with an optical microscope using transmitted light. Furthermore, Chinese Patent Application Publication No. 106966625 discloses a cement additive for 3D printing, which is a mixture of modified bentonite, surfactant, coagulant, water-reducing agent, and water in specific ratios.

[0004] Summary of the Invention: Smectite and aluminum sulfate are used in sprayed hydraulic compositions to improve strength development and reduce dust, but the rapid setting properties of hydraulic compositions are relatively poor, and there is a need for improved shape retention immediately after application. Furthermore, in order to ensure stable application, the rapid setting agent needs to minimize fluctuations in shape retention performance due to differences in application conditions. The present invention provides a liquid rapid setting agent, a hydraulic composition, a method for producing the hydraulic composition, a spraying method, and use as a liquid rapid setting agent that exhibits excellent shape retention of hydraulic compositions and stable shape retention regardless of application conditions.

[0005] 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.

[0006] Furthermore, in other embodiments, the present invention provides a hydraulic composition comprising the liquid rapid setting agent.

[0007] 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.

[0008] 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.

[0009] 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.

[0010] 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.

[0011] 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, scatter and adsorb onto the cement surface. As a result, it is presumed that the hydraulic composition is crosslinked and aggregated, improving the shape retention of the hydraulic composition. Furthermore, it is presumed that the sulfate ions and aluminum ions held on the smectite at the aggregation points efficiently act on the cement, preventing the formation of aggregates of aluminum ions with other agents, making it less susceptible to the influence of other agents, and thus improving not only shape retention but also the stability of shape retention against differences in construction conditions, resulting in stable shape retention regardless of construction conditions. Furthermore, the liquid rapid setting agent, hydraulic composition, method for producing the hydraulic composition, spraying method, and use as a liquid rapid setting agent of the present invention are not limited to those described above based on the mechanism of action. In addition, in this specification, "excellent shape retention of the hydraulic composition" may mean either or both of the following: that the hydraulic composition has excellent moldability 4 minutes after mixing the rapid setting agent with the hydraulic composition and stirring, and that it is resistant to deformation even after molding.

[0012] <Liquid Rapid Setter> In exemplary embodiments, the liquid rapid setter of the present invention contains (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. The liquid rapid setter of the present invention may be, for example, a liquid rapid setter for hydraulic compositions, and furthermore, a liquid rapid setter for hydraulic compositions for spraying. In this specification, (A) smectite may be referred to as component (A), (B) sulfate ions as component (B), (C) aluminum ions as component (C), and (D) water as component (D).

[0013] <(A) component> The (A) component is smectite. One or more than one kind of the (A) component can be used. The type of smectite as the (A) component is not particularly limited, and it may be natural smectite or synthetic smectite. The clay mineral containing smectite as the (A) component includes, for example, one or more than one kind selected from montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, and stevensite. Smectite forms a layered structure in which thin plate-like crystals with a thickness of about 1 nm are stacked, and cations such as alkali metals and alkaline earth metals generally exist between the crystals. There is no particular limitation on the cations present between the crystal layers of smectite. For example, one or more than one kind selected from smectites of Na (sodium) type, Li (lithium) type, K (potassium) type, NH ４ (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.

[0014] The (A) component is not particularly limited, but for example, a clay mineral represented by the following general formula (a1) is preferable. [Si ８ (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 kind of Na, K, Li, Ca, Mg, and NH ４ and preferably at least one kind of Na and Ca.]

[0015] From the viewpoint of improving the shape retention of the hydraulic composition and enhancing the stability against variations in the manufacturing conditions of the shape retention, one or more than one kind selected from montmorillonite, saponite, hectorite, and stevensite are preferable as the (A) component.

[0016] ​Component (A) may be a clay mineral containing smectite in component (A) at a rate of preferably 10% by mass or more, more preferably 20% by mass or more, even 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, even more preferably 95% by mass or less, even more preferably 90% by mass or less, and even more preferably 80% by mass 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, component (A) may be a clay mineral containing smectite in component (A) at a rate of preferably 10% by mass or more and 100% by mass or less, more preferably 20% by mass or more and 98% by mass or less, even more preferably 30% by mass or more and 98% by mass or less, even more preferably 40% by mass or more and 95% by mass or less, even more preferably 50% by mass or more and 95% by mass or less, even more preferably 50% by mass or more and 80% by mass 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. The content of component (A) will be measured using the method described later in detail in <Method for measuring the smectite content of component (A)>.

[0017] (A) Component 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.

[0018] If component (A) contains the inorganic powder, component (A) contains the inorganic powder in an amount of 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 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, from the same viewpoint.

[0019] 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 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 (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, from the same viewpoint.

[0020] (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.

[0021] 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 increasing the stability of shape retention against fluctuations in manufacturing conditions. 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, 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, from the same viewpoint. If component (A) contains multiple types of clay minerals, this degree of swelling is the degree of swelling of a mixture of multiple types of component (A).

[0022] <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 after swelling is read from the scale of the graduated cylinder and displayed as the degree of swelling (mL / 2g).

[0023] 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.

[0024] Examples of commercially available products containing saponite include BeeGum T, BeeGum HV, BeeGum F, and BeeGum K manufactured by Vanderbilt, and Smecton SA manufactured by Kunimine Industries Co., Ltd.

[0025] 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.

[0026] Examples of commercially available products containing stevensite include Smecton ST manufactured by Kunimine Industries Co., Ltd.

[0027] Various synthetic smectites are also commercially available, such as Ionite H from Mizusawa Chemical Industries, Ltd., SWN and SAN from Coop Chemical Co., Ltd., Laponite from Laporte Industry Co., Ltd., and Laponite XLS and Laponite XLG from Lockwood Co., Ltd.

[0028] (A) Component may be a clay mineral having a smectite content of preferably 30% by mass or more and 100% by mass or less. (A) Examples of ingredients 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 Shiratsuchi Kogyo Co., Ltd., "Round Rosil DGA212", "Round Rosil PR414", "Round Rosil DG214", "Round Rosil DGA Powder", and "Furasoft-1 Powder" from Süd Chemi, and Pure Bentonite, Standard Bentonite, and Premium Bentonite from CSM.

[0029] <(B) component> The (B) component is sulfate ion. The sulfate ion may be a sulfate or a sulfate ion derived from sulfuric acid. The sulfate may be, for example, one or more selected from sodium sulfate, potassium sulfate, magnesium sulfate, zinc sulfate, iron sulfate, and aluminum sulfate. The counter ion of the sulfate ion may be, for example, one or more selected from monovalent cations, divalent cations, and trivalent cations. The monovalent cation may be, for example, one or more selected from hydrogen ion, sodium ion, potassium ion, ammonium ion, and organic amine ion. The divalent cation may be, for example, one or more selected from magnesium ion and calcium ion. The trivalent cation may be, for example, aluminum ion and iron ion.

[0030] <(C) component> The (C) component is aluminum ion. The aluminum ion may be an aluminum ion derived from an aluminum salt. The aluminum salt may be, for example, one or more selected from aluminum chloride, aluminum sulfate, aluminum fluoride, aluminum lactate, alum, aluminum hydroxide, and aluminum nitrate. The counter ion of the aluminum ion may be, for example, one or more selected from monovalent anions, divalent anions, and trivalent anions, and one or more selected from monovalent anions and divalent anions are preferred. The monovalent anion may be, for example, one or more selected from chloride ion, fluoride ion, hydroxide ion, nitrate ion, carboxylate ion, and sulfonate ion. The divalent anion may be, for example, sulfate ion. The trivalent anion may be, for example, phosphate ion.

[0031] <(D) component> The (D) component is water. The water is not particularly limited, and examples include tap water, well water, deionized water, and distilled water. The (D) component is preferably used in the amount of the remainder of the liquid quick-freezing agent (the amount that makes the total 100% by mass).

[0032] <Composition, etc.> The liquid rapid setting agent of the present invention contains component (A) in an amount of preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 5% by mass or more, and from the same viewpoint, 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 rapid setting agent of the present invention contains component (A) in an amount of preferably 1% by mass or more and 40% by mass or less, more preferably 2% by mass or more and 30% by mass or less, and even more preferably 5% by mass or more and 20% by mass or less, from the same viewpoint.

[0033] The regulations regarding the mass of component (A) are as follows: If component (A) is a synthetic smectite 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 regulations regarding the mass of component (A) below unless otherwise specified. The measurement of smectite content is performed on the dried component (A) after pretreatment, which involves drying component (A) in a hot air dryer at 105°C for 1 hour.

[0034] <Method for measuring the smectite content of component (A)> (1) Measurement of methylene blue adsorption amount 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) Sodium pyrophosphate (Na ４ P ２ O ７An aqueous solution of 0.2% by mass of ( ) <Operation method> Put about 0.4 g of component (A) into a 100 mL screw tube, and add 40 g of an aqueous solution of 0.2% by mass of sodium pyrophosphate thereto. Disperse this mixture with an ultrasonic cleaner (ASU CLEANER, ASU-3, manufactured by AS ONE Corporation) for 30 minutes, and then heat it with warm water at 80 °C for 30 minutes. While stirring the dispersed mixture with a magnetic stirrer, a 10 mmol / L methylene blue aqueous solution is dropped. Every time a predetermined amount is dropped, a part of the mixture is sucked up from the supernatant with a glass Pasteur pipette and dropped onto filter paper. The supernatant is dropped so that spots with a diameter of about 10 mm are formed on the filter paper. Repeat this operation until a halo is confirmed around the spot. When a halo is confirmed, the end point of the titration is taken when the width of the halo exceeds 2 mm. The calculation of the methylene blue adsorption amount (mmol) is to convert the product of the titration amount (L) and the methylene blue aqueous solution concentration (10 mmol / L) per 100 g of component (A). (2) Calculation of the smectite content The calculation of the smectite content of component (A) is based on "A proposed method for the determination of small amounts of smectites in clay mineral mixtures, Proceedings of British Ceramics Society 28 137-145, 1979" and "Evaluation of the montmorillonite content of bentonite considering the measurement accuracy of the methylene blue adsorption test, Journal of the Japan Society of Civil Engineers, Series C (Geotechnical Engineering), Vol. 76, No. 1, 26-39, 2020". Specifically, 140 mmol / 100 g is adopted as the methylene blue saturation adsorption amount of smectite, and 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. When the methylene blue adsorption amount exceeds 140 mmol / 100 g, the smectite content is set to 100%.

[0035] The liquid rapid setting agent of the present invention contains component (B) in the liquid rapid setting agent in an amount 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 increasing 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 in an amount preferably 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, 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.

[0036] 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 K 0102. 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.

[0037] The liquid rapid setting agent of the present invention contains component (C) in the liquid rapid setting agent, preferably in an amount of 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 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 rapid setting agent of the present invention contains component (C) in the liquid rapid setting agent, preferably in an amount of 1% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less, even more preferably 4% by mass or more and 13% by mass or less, and even more preferably 4% by mass or more and 11% by mass or less, from the same viewpoint.

[0038] 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, the 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 by the ECR method of the Digital Pack Test (model LR-Al).

[0039] 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 rapid setting agent of the present invention contains component (D) in an amount of preferably 30% by mass or more and 90% by mass or less, more preferably 40% by mass or more and 85% by mass or less, and even more preferably 48% by mass or more and 80% 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.

[0040] 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, even more preferably 0.04 or more, 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 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 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 or more and 3 or less, more preferably 0.03 or more and 2 or less, even more preferably 0.04 or more and 1 or less, even more preferably 0.04 or more and 0.6 or less, and even more preferably 0.04 or more and 0.3 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.

[0041] In the liquid rapid setting agent of the present invention, the mass ratio [(A) / (C)] of the content of component (A) to the content of component (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.

[0042] 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, 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 25 or less, more preferably 10 or less, 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, even more preferably 1.5 or more and 7 or less.

[0043] In the liquid rapid setting agent of the present invention, the mass ratio [(A) / (D)] of the content of component (A) to the content of component (D) is preferably 0.01 or more, more preferably 0.02 or more, and even more preferably 0.025 or more, 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 preferably 0.5 or less, more preferably 0.3 or less, and even more preferably 0.2 or less, from the viewpoint of increasing the stability of 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, from the same viewpoint.

[0044] <Component (E)> 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 one or more forms. "Insoluble" of component (E) means that 0.5 g or less dissolves in 100 g of water at 40°C.

[0045] 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, component (E) is preferably one or more selected from iron oxide, calcium sulfate, silicon dioxide, and lead sulfate.

[0046] 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.

[0047] 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.

[0048] 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, in the liquid rapid setting agent of the present invention. 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 an amount of preferably 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, in the liquid rapid setting agent of the present invention. In the provisions regarding the mass of component (E), insoluble components other than those corresponding to smectite contained in component (A) are included in the content of component (E).

[0049] The liquid rapid setting agent of the present invention may optionally contain one or more selected from fluorine components, alkanolamines, complex-forming agents, and alkaline earth metals. 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.

[0050] <Fluorine Components> 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, siliceous 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 siliceous fluoride salts include one or more selected from ammonium siliceous fluoride, sodium siliceous fluoride, potassium siliceous fluoride, and magnesium siliceous fluoride. 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 the fluorine component is preferably one or more selected from fluoride salts and siliceous fluoride salts due to its high safety, low manufacturing cost, and excellent coagulation properties.

[0051] <Alkanolamines> Alkanolamines are organic compounds having an N-R-OH structure in their structural formula, and 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 part 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.

[0052] <Complex Forming 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. The complex-forming 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 of complex-forming agents include (8) aminopolycarboxylic acids such as CyDTA, (9) phosphonic acids such as ethylenediaminetetra(methylenephosphonic acid) [EDTPO], ethylenediaminedi(methylenephosphonic acid) [EDDPO], nitrilotris(methylenephosphonic acid) [NTPO], and 1-hydroxyethylidene-1,1'-diphosphonic acid [HEDPO], (10) condensed phosphoric acids such as phosphoric acid, tripolyphosphate, and hexametaphosphate, and (11) diketones such as acetylacetone and hexafluoroacetylacetone. In the present invention, one or more of these complex-forming agents can be used. Preferably, the complex-forming agent is at least one selected from the group consisting of oxalic acid, malonic acid, succinic acid, and condensed phosphoric acids.

[0053] <Alkaline Earth Metal Carbonates> Alkaline earth metals can be 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 quick-setting agent 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 pipes, and it is even more preferable to use calcium carbonate in combination with sodium carbonate.

[0054] 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 in the liquid rapid setting agent, 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.

[0055] 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 replacing the preferred content in the above-mentioned liquid rapid setting agent of the present invention with the amounts. 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 formulated such that the content of component (B) or component (C) in the liquid rapid setting agent of the present invention is the preferred content of component (B) or component (C) in the above-mentioned liquid rapid setting agent of the present invention. Furthermore, in the liquid rapid setting agent of the present invention, the mass ratio of the amounts of each component can be applied by replacing the mass ratio of the preferred content in the above-mentioned liquid rapid setting agent of the present invention with the mass ratio of the amounts.

[0056] <Method for producing a liquid rapid 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) aluminum ions (D) water, in a mass ratio [(A) / (B)] of the amount of component (A) to the amount of component (B) being 3 or less. In another exemplary embodiment, the present invention provides a method for producing a liquid rapid setting agent by 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.

[0057] 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 arbitrarily mixed.

[0058] 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 an 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 for the mixing amounts or mixing ratios. Furthermore, in the liquid rapid setting agent of the present invention, the preferred content and mass ratio of component (B) and component (C) can be applied by applying the preferred content and mass ratio of each component in the liquid rapid setting agent of the present invention.

[0059] <Hydraulic Composition> In exemplary embodiments, the present invention provides a hydraulic composition comprising a liquid rapid 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 exemplary embodiments, the hydraulic composition of the present invention may be a hydraulic composition containing the liquid rapid setting agent of the present invention and a hydraulic powder. The hydraulic composition of the present invention may be a hydraulic composition for spraying.

[0060] 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 in the liquid rapid setting agent of the present invention. In the hydraulic composition of the present invention, preferred embodiments of the content of components (A) to (D) and other optional components contained in the liquid rapid setting agent, and the mass ratio of their content, are the same as preferred embodiments of the content of components (A) to (D) and optional components and the mass ratio of their content in the liquid rapid setting agent of the present invention.

[0061] <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 R 5214). 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. Furthermore, the hydraulic powder may contain blast furnace slag, fly ash, silica fume, anhydrous gypsum, etc., and may also contain non-hydraulic limestone fine powder, etc. The hydraulic powder may be blast furnace cement, fly ash cement, or silica fume cement, which are mixtures of cement with blast furnace slag, fly ash, silica fume, etc.

[0062] <Aggregate> The hydraulic composition of the present invention may optionally contain aggregate. The aggregate may be selected from fine aggregate and coarse aggregate. Fine aggregate may be those specified in JIS A 0203-2014, number 2311. For example, fine aggregate may be 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. Coarse aggregate may be those specified in JIS A 0203-2014, number 2312. For example, coarse aggregate may be river gravel, land gravel, mountain gravel, sea gravel, lime gravel, crushed stone thereof, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural), and recycled coarse aggregate. Fine aggregate and coarse aggregate may be mixed together or used as a single type.

[0063] The hydraulic composition of the present invention may contain fine aggregate. The amount of fine aggregate used in the hydraulic composition of the present invention is preferably 500 kg / m³. ３ More preferably 600 kg / m ３ In addition, preferably 2,000 kg / m ３ More preferably, 1,700 kg / m ３ The following applies to the hydraulic composition of the present invention. The fine aggregate ratio is preferably 35% or more, more preferably 45% or more, preferably 100% or less, more preferably 70% or less, and even more preferably 65% ​​or less. Here, the fine aggregate ratio is the volume content of fine aggregate in the total aggregate.

[0064] <Water> The hydraulic composition of the present invention may contain water. Examples of water include tap water, groundwater, lake water, and river water.

[0065] 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 increasing 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, 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 hydraulic composition of the present invention contains water in amounts of 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. This water / hydraulic powder ratio (W / C) is expressed as the ratio of water to hydraulic powder in the hydraulic composition as a mass percentage (mass%), and is calculated as (water / hydraulic powder) × 100. Furthermore, if the hydraulic powder includes powders that have properties of hardening by hydration reaction, such as cement, as well as powders selected from powders with pozzolanic properties, powders with latent hydraulic properties, and stone powder (calcium carbonate powder), the amounts of these are also included in the amount of hydraulic powder in the present invention. Furthermore, if the powder that has properties of hardening by hydration reaction 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.

[0066] 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 rapid setting agent in an amount of 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, relative to the hydraulic powder in the hydraulic composition, from the same viewpoint.

[0067] <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.

[0068] 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.

[0069] 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 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, per 100 parts by mass of hydraulic powder contained in the hydraulic composition, 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, 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 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, from the same viewpoint. In the hydraulic composition of the present invention, the preferred content of the active ingredient of the dispersant may be within the above range.

[0070] 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.

[0071] 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 or embankment, underground spaces, and concrete structures that are subject to repair by spraying methods.

[0072] In exemplary embodiments, the hydraulic composition of the present invention may be a hydraulic composition comprising a liquid rapid 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 a liquid rapid setting agent, a hydraulic powder, and water. The hydraulic composition of the present invention may further optionally contain any of the optional components described in the hydraulic composition of the present invention described above. Furthermore, in the hydraulic composition of the present invention, the preferred amounts of the liquid rapid setting agent, hydraulic powder water, and optional components can be applied by substituting the preferred content amounts in the hydraulic composition of the present invention described above.

[0073] <Method for producing a hydraulic composition> In an exemplary embodiment, the present invention provides a method for producing a hydraulic composition, comprising mixing a liquid rapid 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.

[0074] In exemplary embodiments, a method for producing a hydraulic composition of the present invention may be a method for producing a hydraulic composition by mixing the liquid rapid setting agent of the present invention with hydraulic powder and water. Alternatively, a method for producing a hydraulic composition of the present invention may be a method for producing a hydraulic composition by mixing a hydraulic composition obtained by mixing hydraulic powder and water with the liquid rapid setting agent of the present invention. A method for producing a hydraulic composition of the present invention may be a method for producing a hydraulic composition for spraying.

[0075] 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. 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. In addition, 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.

[0076] 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 rapid 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 mixture. The same applies to the spraying method, which will be described in detail later.

[0077] <Spraying Method> In exemplary embodiments, the present invention provides a spraying method in which a hydraulic composition containing hydraulic powder and water is mixed with a liquid rapid-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. In further exemplary embodiments, 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 is one of the objects described in the hydraulic composition of the present invention. Furthermore, the liquid rapid-setting agent may be the liquid rapid-setting agent of the present invention.

[0078] 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. A wet spraying method includes, for example, a method in which hydraulic powder, aggregate, and water are mixed and kneaded, then pumped under air pressure, and the liquid quick-setting agent is added and mixed before spraying. The spraying method of the present invention preferably involves separately pumping and mixing the liquid quick-setting agent of the present invention and a hydraulic composition containing water, hydraulic powder, and aggregate under air pressure, and then spraying the resulting hydraulic composition onto the target object. The liquid quick-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 quick-setting agent with a mixer; or, the liquid quick-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 and then combine and mix the liquid quick-setting agent and the hydraulic composition.

[0079] 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 more, more preferably 0.3 MPa or more, even more preferably 0.4 MPa or more, and from the same viewpoint, preferably 1.2 MPa or less, more preferably 1.0 MPa or less, even more preferably 0.8 MPa or less, and even more preferably 0.6 MPa or less. 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 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-pump the hydraulic composition of the present invention is within the above range.

[0080] 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, first, a hydraulic composition is produced by mixing hydraulic powder, aggregate, and water. The 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 (mass%)] which 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, from the same viewpoint.

[0081] 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.

[0082] 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.

[0083] 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, 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.

[0084] Furthermore, the spraying method of the present invention may optionally use the 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 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 hydraulic powder in the hydraulic composition in an amount of 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, from the same viewpoint. In the spraying method of the present invention, the preferred content of the active ingredient in the dispersant may be within the above range.

[0085] 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 carried out 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 an Arriba product, trade name "Arriba 280," etc., manufactured by Arriba Corporation, for pumping the hydraulic composition, and a Chiyoda Seisakusho product, trade name "Natomcrete," etc., for pumping the liquid quick-setting agent of the present invention, mix the two to prepare a hydraulic composition for spraying, and then spray it.

[0086] <Use as a liquid quick-setting agent> 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.

[0087] In using the present invention, the provisions described in the Liquid Rapid Setting Agent and its Manufacturing Method, the Hydraulic Composition and its Manufacturing Method, and the Spraying Method of the present invention can be appropriately applied. In using 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. In addition, in using 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 using the present invention, preferred embodiments of the content and mass ratio of components (A) to (D) and other optional components contained in the mixture are the same as preferred embodiments of the content and mass ratio of components (A) to (D) and optional components 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 Rapid Setting Agent, for example, 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.

[0088] The following are examples of embodiments of the present invention. The matters described in the sections on the liquid rapid setting agent, hydraulic composition, method for producing the hydraulic composition, spray application method, and use as a liquid rapid setting agent can be appropriately applied to these embodiments.

[0089] <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.

[0090] <2> The liquid rapid setting agent according to <1> above, 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.

[0091] <3> The liquid rapid setting agent according to <1> or <2> above, wherein component (A) is one or more selected from montmorillonite, saponite, hectorite, and stevensite.

[0092] <4> The liquid quick-setting agent according to any one of <1> to <3> above, wherein component (A) comprises one or more inorganic powders selected from crystalline silica, calcium carbonate, aluminosilicate, and talc.

[0093] <5> A liquid fastener according to any one of <1> to <4> above, wherein the average particle size of component (A) is 0.10 μm or more and 500 μm or less.

[0094] <6> A liquid quick-setting agent according to any of <1> to <5> above, further containing (E) insoluble matter [excluding those corresponding to component (A)], wherein the average particle size of component (E) is 0.01 μm or more and 500 μm or less.

[0095] <7> The liquid rapid setting agent according to <6> above, wherein the (E) insoluble substance is one or more selected from iron oxide, calcium sulfate, silicon dioxide, carbon, and lead sulfate.

[0096] <8> A liquid fastener according to any one of <1> to <7> above, wherein the content of component (A) is 1% by mass or more and 40% by mass or less.

[0097] <9> A liquid fastener according to any one of <1> to <8> above, wherein the content of component (B) is 5% by mass or more and 50% by mass or less.

[0098] <10> A liquid fastener according to any one of <1> to <9> above, wherein the content of component (C) is 1% by mass or more and 20% by mass or less.

[0099] <11> A liquid fastener according to any one of <1> to <10> above, wherein the content of component (D) is 30% by mass or more and 90% by mass or less.

[0100] <12> A liquid rapid setting agent according to any one of <1> to <11> above, wherein the mass ratio of the content of component (A) to the content of component (B) [(A) / (B)] is 0.02 or more and 3 or less.

[0101] <13> A liquid fastener according to any one of <1> to <12> above, wherein the mass ratio of the content of component (A) to the content of component (C) [(A) / (C)] is 0.05 or more and 10 or less.

[0102] <14> A liquid rapid setting agent according to any one of <1> to <13> above, wherein the mass ratio of the content of component (B) to the content of component (C) [(B) / (C)] is 0.5 or more and 25 or less.

[0103] <15> A liquid fastener according to any one of <1> to <14> above, wherein the mass ratio of the content of component (A) to the content of component (D) [(A) / (D)] is 0.5 or less.

[0104] <16> A liquid rapid setting agent according to any of <1> to <15> above, for use in a sprayable hydraulic composition.

[0105] <17> A hydraulic composition comprising a liquid rapid setting agent as described in any of <1> to <16> above.

[0106] <18> A hydraulic composition comprising a liquid rapid setting agent as described in any of <1> to <16> above, a hydraulic powder, and water, wherein the water / hydraulic powder ratio (W / C) is 30% by mass or more and 80% by mass or less.

[0107] <19> The hydraulic composition according to <17> or <18> above, comprising a polycarboxylic acid-based dispersant.

[0108] <20> A hydraulic composition according to any of <17> to <19> above, for spray application.

[0109] <21> A method for producing a hydraulic composition, comprising mixing a liquid rapid setting agent described in any of <1> to <16> above with a hydraulic powder.

[0110] <22> A spraying method comprising mixing a hydraulic composition containing hydraulic powder and water with a liquid rapid setting agent described in any of <1> to <16> above and spraying the mixture onto an object.

[0111] <23> 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.

[0112] Examples 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 the hydraulic compositions was then evaluated. The results are shown in Tables 4 to 7.

[0113] <(A) Components> 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 the 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.

[0114] (Components of Bentonite A) - Purified montmorillonite: Kunipia F, manufactured by Kunimine Industries Co., Ltd., smectite content 99% by mass - Quartz: manufactured by Sigma-Aldrich, average particle size 63.6 μm, crystallinity 100% - Aluminum silicate: Synthetic aluminum silicate (82% by mass SiO ２ , 9.5% by mass Al ２ O ３ , 8% by mass Na ２O) Sigma-Aldrich, swelling degree 7 mL / 2 g, average particle size 17.9 μm Kaolin: Kaolin, Hayashi Pure Chemical Industries, Ltd., average particle size 6.3 μm Zeolite K: Synthetic zeolite, HS-500, powder, potassium L, Fujifilm Wako Chemical Co., Ltd., swelling degree 3 mL / 2 g, average particle size 25.9 μm Synthetic mica: Synthetic mica, non-swelling, Fujifilm Wako Pure Chemical Corporation, swelling degree 3 mL / 2 g, average particle size 6.5 μm Calcium carbonate: Calcium carbonate CP, Sigma-Aldrich, average particle size 58.4 μm Talc: Fujifilm Wako Pure Chemical Corporation, average particle size 55.8 μm, average aspect ratio 1.33

[0115] (Method for preparing Bentonite A) 60 g of purified montmorillonite, 20 g of quartz, 3.75 g of aluminum silicate, 3.75 g of kaolin, 3.75 g of zeolite K, 3.75 g of synthetic mica, 3 g of calcium carbonate, and 2 g of talc were placed in a 250 mL bottle. The bottle was sealed with a lid and shaken for 10 minutes to prepare Bentonite A.

[0116] <Component (B), Component (C)> - Aluminum sulfate: Aluminum sulfate 1,4-1,8-hydrate (manufactured by Kanto Chemical Co., Ltd.) Aluminum sulfate is an inorganic salt from which the sulfate ions in component (B) and the aluminum ions in component (C) are derived. In Tables 1 to 3, the content of component (B) and component (C) calculated from the amount of aluminum sulfate is indicated in parentheses. <Component (C)> - 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) Ingredients> ・Water: Wakayama City tap water <Dispersant> ・Polycarboxylic acid-based dispersant: Mighty 21HF, active ingredient 24% by mass, manufactured by Kao Corporation <(E) Ingredients> ・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.

[0117] <Measurement of Swelling Degree> The swelling degree 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 8.0% by mass moisture content, 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 after the previous additive 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 swelling degree (mL / 2 g).

[0118] <Method for measuring the smectite content of component (A)> (i) Drying Component (A) was placed in a hot air dryer and dried at 105°C for 1 hour. (ii) Measurement of methylene blue adsorption The amount of methylene blue adsorbed by the clay mineral of component (A) 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) Sodium pyrophosphate (Na ４ P ２ O ７) 0.2% by mass aqueous solution <Procedure> Approximately 0.4 g of component (A) was placed in a 100 mL screw 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, and after each drop, a portion of the mixture was drawn up from the supernatant using a glass Pasteur pipette and dropped onto filter paper. The supernatant was added dropwise enough to form a spot with a diameter of approximately 10 mm on the filter paper. This operation was repeated until a halo was observed around the spot. Once a halo was observed, the titration was terminated when the width of the halo exceeded 2 mm. Then, the amount of methylene blue adsorbed per 100 g of component (A) was calculated based on the mass of component (A) and the total amount of 10 mmol / L methylene blue aqueous solution added dropwise to the endpoint. Specifically, the product of the titration volume (L) and the concentration of the methylene blue aqueous solution (10 mmol / L) was converted to the amount per 100 g of component (A) to calculate the total amount of methylene blue adsorbed (molecule). (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 amount of methylene blue adsorbed by component (A) by this saturation adsorption amount and multiplying by 100. If the amount of methylene blue adsorbed exceeds 140 mmol / 100 g, the smectite content was set to 100% by mass.

[0119] <Method for measuring average particle diameter> For each component (A), the arithmetic mean particle diameter 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.

[0120] <Preparation Method of Liquid Rapid Setting Agent> Liquid rapid setting agent B shown in Table 1 was prepared by the following method (1). (1) Liquid rapid 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 stirred at 100 rpm (EUROSTAR200 control, 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 Co., Ltd.) 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 to L, and R to T were prepared in the same manner as liquid rapid setting agent B using the components listed in Table 1 or Table 2.

[0121] The liquid rapid setting agents M, O to Q and the powder rapid setting agent N in Table 3 were prepared according to the preparation methods (2) to (4) below. (2) Preparation method for liquid rapid setting agent M 500 g of aluminum sulfate 14-18 hydrate was placed in a 2 L cup, water was added until the total volume was 1,000 g, and the mixture was mixed and dissolved to prepare liquid rapid setting agent M containing 27% by mass of aluminum sulfate. (3) Preparation method for powder rapid setting agent N Knigel GS, which is component (A), and anhydrous aluminum sulfate were placed in a 250 mL sealed bottle container so that the ratio of component (A) to aluminum sulfate was as shown in Table 3, and the bottle was manually shaken for 60 seconds while repeatedly inverting it to mix the contents and prepare powder rapid setting agent N. (4) Method for preparing liquid rapid setting agent O 500 g of aluminum sulfate 14-18 hydrate was placed in a 2 L cup, 400 g of water was added and mixed for 10 minutes, 100 g 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.

[0122]

[0123]

[0124]

[0125] <Notes> *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 hydrate water content (mass%) of aluminum sulfate 14-18 hydrate. *3: In Tables 1 to 3, the numbers in parentheses for component (B) indicate the sulfate ion content (mass%) derived from aluminum sulfate. *4: In Tables 1 to 3, the numbers in parentheses for component (C) indicate the aluminum ion content (mass%) derived from aluminum sulfate or aluminum hydroxide.

[0126] <Method for Evaluating Shape Retention> (1) Preparation of Hydraulic Composition A mortar mixer 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 to prepare 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)

[0127] 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 the mixture was stirred at low speed (stirring speed: orbital 62 rpm, rotational 141 rpm) for 2 minutes. The polycarboxylic acid-based dispersant was used after being mixed with water beforehand.

[0128] (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.), 7.76 g of each liquid rapid setting agent or powder rapid setting agent was added to 530 g of the hydraulic composition prepared in (1), and the time at which mixing began was set as 0 seconds, and the vane shear resistance value of the hydraulic composition after 4 minutes was measured. 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 higher the shape retention of the hydraulic composition, meaning that the shape is less likely to collapse after molding, and it is a liquid rapid setting agent with 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 construction conditions.

[0129]

[0130]

[0131]

[0132]

[0133] <Notes> 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 amount of active ingredient 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 any one of claims 1 to 3, 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 any one of claims 1 to 4, 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 any one of claims 1 to 5, 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 any one of claims 1 to 6, wherein the content of component (D) is 30% by mass or more and 90% by mass or less.

8. A liquid quick-setting agent according to any one of claims 1 to 7, 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. The liquid quick-setting agent according to any one of claims 1 to 8, wherein component (A) comprises one or more inorganic powders selected from crystalline silica, calcium carbonate, aluminosilicate, and talc.

10. A liquid rapid setting agent according to any one of claims 1 to 9, for use in a sprayable hydraulic composition.

11. A hydraulic composition comprising a liquid rapid setting agent according to any one of claims 1 to 10.

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

13. The hydraulic composition according to claim 11 or 12, comprising a polycarboxylic acid-based dispersant.

14. A method for producing a hydraulic composition, comprising mixing a liquid rapid setting agent according to any one of claims 1 to 10 with a hydraulic powder.

15. A spraying method comprising mixing a hydraulic composition containing hydraulic powder and water with a liquid rapid setting agent according to any one of claims 1 to 10 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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