Additives for water hardening components

Abstract

The present invention provides an additive for hydraulic compositions that exhibits good shape retention and excellent pumpability regardless of changes in conditions. [Solution] (A) An additive for hydraulic compositions containing a polyalkylene oxide having a polydispersity (Mw / Mn) of 1.00 or more and 2.55 or less.

Description

[Technical Field]

[0001] This invention relates to an additive for hydraulic compositions, a hydraulic composition, a method for producing a hydraulic composition, a spraying method, and its use as an additive for hydraulic compositions. [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 a wet spraying method in which cement, water, aggregate, and solid polyethylene oxide with a weight-average molecular weight of 200,000 to 10,000,000 are mixed under specific conditions to produce a hydraulic composition, a solid quick-setting agent is mixed with the hydraulic composition to produce a hydraulic composition for spraying, and the hydraulic composition for spraying is sprayed onto the target object. Furthermore, Patent Document 2 discloses a hydraulic composition for spraying, which contains hydraulic powder, fine aggregate, (A) polyethylene oxide, optionally (B) clay mineral, and water, wherein the total adsorption amount of methylene blue measured in accordance with JIS Z 2451:2019 is 0.37 mmol or more per 100 g of the total content of the fine aggregate and (B). Furthermore, Patent Document 3 discloses a pumpability modifier containing polyethylene oxide that exhibits specific dynamic viscoelasticity. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2019-64909 [Patent Document 2] Japanese Patent Publication No. 2024-67808 [Patent Document 3] International Publication No. 2022-230388 [Overview of the project] [Problems that the invention aims to solve]

[0005] Polyalkylene oxides are known to reduce dust and improve pumpability. However, while polyalkylene oxides can increase the fluidity of hydraulic compositions, there is a need to improve the shape retention of the molded hydraulic composition and maintain excellent pumpability regardless of changes in conditions. The present invention provides an additive for hydraulic compositions that can maintain the shape of the hydraulic composition and provide excellent pumpability regardless of changes in conditions, a hydraulic composition, a method for producing a hydraulic composition, a spraying method, and use as an additive for hydraulic compositions. [Means for solving the problem]

[0006] In one embodiment, the present invention provides an additive for hydraulic compositions containing (A) a polyalkylene oxide having a polydispersity (Mw / Mn) of 1.00 or more and 2.55 or less.

[0007] Furthermore, in other embodiments, the present invention provides a hydraulic composition containing the additive for the hydraulic composition.

[0008] Furthermore, in another embodiment, the present invention provides a method for producing a hydraulic composition, which involves mixing the additive for the hydraulic composition with a hydraulic powder.

[0009] Furthermore, in another embodiment, the present invention provides a spraying method in which the additive for the hydraulic composition, hydraulic powder, and water are mixed and sprayed onto an object.

[0010] Furthermore, in another embodiment, the present invention provides the use of (A) a polyalkylene oxide having a polydispersity of 1.00 or more and 2.55 or less as an additive for hydraulic compositions. [Effects of the Invention]

[0011] The present invention provides an additive for hydraulic compositions, a hydraulic composition, a method for producing a hydraulic composition, a spraying method, and a method for using the additive for hydraulic compositions, all of which provide good shape retention and excellent pumpability regardless of changes in conditions. [Modes for carrying out the invention]

[0012] The mechanism by which a hydraulic composition containing the additive for hydraulic compositions of the present invention can maintain its shape well and provide excellent pumpability regardless of changes in conditions is not yet clear, but it is presumed to be as follows. (A) By designing the molecular weight distribution of the polyalkylene oxide component to a specific range, the entanglement density of polymers in the hydraulic composition slurry can be made uniform, reducing the amount of low molecular weight particles that act on particle dispersion and high molecular weight particles that act on particle crosslinking and aggregation, thereby reducing local inconsistencies in aggregation and dispersion. In this way, by maintaining a uniform local rheology in the rigid composition slurry, it is presumed that the hydraulic composition can be given a sense of unity, such as uniform fluidity and shape retention. Furthermore, by mixing the antioxidant component (B) with the additive for hydraulic compositions of the present invention, the decomposition of the polyalkylene oxide component (A) is suppressed, thereby obtaining the same effect even after long-term storage. Furthermore, the use of the present invention as an additive for hydraulic compositions, hydraulic compositions, methods for producing hydraulic compositions, spraying methods, and as an additive for hydraulic compositions is not limited to the above-described mechanism. Furthermore, in this specification, the shape retention of a hydraulic composition may mean either or both of the following: that the hydraulic composition has excellent moldability one minute or four minutes after mixing it with a quick-setting agent and stirring, and that it is resistant to deformation even after molding.

[0013] <Additive for hydraulic composition> In an exemplary embodiment, the additive for a hydraulic composition of the present invention contains a polyalkylene oxide having a polydispersity (Mw / Mn) of 1.00 or more and 2.55 or less [hereinafter referred to as component (A)]. In an exemplary embodiment, the additive for a hydraulic composition of the present invention may be an additive for a sprayable hydraulic composition. Further, in an exemplary embodiment, the additive for a hydraulic composition of the present invention may be a shape retention improver for a hydraulic composition and may also be a pumping property improver for a hydraulic composition.

[0014] <Component (A)> Component (A) is a polyalkylene oxide having a polydispersity (Mw / Mn) of 1.00 or more and 2.55 or less. One or more kinds of component (A) can be used. Component (A) includes one or more selected from polyoxyalkylene oxides having an alkyleneoxy group with 2 to 3 carbon atoms. From the viewpoint of imparting fluidity, shape retention, and pumping property independent of condition changes to the hydraulic composition, polyethylene oxide is preferred.

[0015] From the viewpoint of imparting fluidity, shape retention, and pumping property independent of condition changes to the hydraulic composition, the weight average molecular weight (Mw) of component (A) is preferably 200,000 or more, more preferably 300,000 or more, and from the same viewpoint, preferably 2,000,000 or less, more preferably 1,000,000 or less, still more preferably 9,00,000 or less, even more preferably 850,000 or less, and even more preferably 800,000 or less. Alternatively, from the same viewpoint, the weight average molecular weight (Mw) of component (A) is preferably 200,000 or more and 2,000,000 or less, more preferably 300,000 or more and 1,000,000 or less, still more preferably 300,000 or more and 900,000 or less, even more preferably 300,000 or more and 850,000 or less, and even more preferably 300,000 or more and 800,000 or less.

[0016] The weight-average molecular weight (Mw) of component (A) was measured by GPC using a high-speed GPC instrument (HLC-8320GPC, Tosoh Corporation), detector: RI, column: G4000PWXL+G2500PWXL (anion), mobile phase: 0.2M phosphate buffer / acetonitrile = 9 / 1, flow rate: 1.0 mL / min., column temperature: 40°C, standard substance: polyethylene glycol, sample concentration: 1% (0.5% for high viscosity). The first peak with a large area and retention time of 10 to 17.5 minutes was identified as the peak of component (A). The conditions for the gel permeation chromatography (GPC) used to measure the number-average molecular weight (Mn) of component (A) and the full width at half maximum of the first peak of the GPC of component (A) are the same as those for the GPC method described above.

[0017] (A) The number-average molecular weight (Mn) of component (A) is preferably 50,000 or more, more preferably 80,000 or more, from the viewpoint of providing fluidity, shape retention, and pumpability independent of changes in conditions for the hydraulic composition, and from the same viewpoint, preferably 800,000 or less, more preferably 500,000 or less, even more preferably 400,000 or less, even more preferably 350,000 or less, and even more preferably 300,000 or less. (A) The number-average molecular weight (Mn) of component (A) is preferably 50,000 to 800,000, more preferably 80,000 to 500,000, even more preferably 80,000 to 400,000, even more preferably 80,000 to 350,000, and even more preferably 80,000 to 300,000. The number-average molecular weight (Mn) of component (A) is calculated based on the first peak of component (A) obtained by the GPC method described above. Mw and Mn are also determined using a conversion standard substance.

[0018] (A) The polydispersity (Mw / Mn) of component (A) is 1.00 or higher, preferably 1.50 or higher, more preferably 1.70 or higher, even more preferably 1.80 or higher, even more preferably 1.90 or higher, and from the viewpoint of providing fluidity, shape retention, and pumpability independent of changes in conditions for the hydraulic composition, and is 2.55 or lower, preferably 2.52 or lower, more preferably 2.49 or lower, and even more preferably 2.46 or lower. Alternatively, the polydispersity (Mw / Mn) of component (A) is, from the same viewpoint, 1.00 or more and 2.55 or less, preferably 1.50 or more and 2.52 or less, more preferably 1.70 or more and 2.49 or less, even more preferably 1.80 or more and 2.46 or less, and even more preferably 1.90 or more and 2.46 or less. The polydispersity (Mw / Mn) of component (A) is calculated as the ratio (Mw / Mn) of the weight-average molecular weight (Mw) and the number-average average molecular weight of component (A).

[0019] (A) The full width at half maximum of the first peak of the GPC is preferably 100 seconds or more, more preferably 115 seconds or more, and from the viewpoint of providing fluidity, shape retention, and pumpability independent of changes in conditions of the hydraulic composition, preferably 300 seconds or less, more preferably 250 seconds or less, and even more preferably 210 seconds or less. Alternatively, from the same viewpoint, the full width at half maximum of the first peak of the GPC of component (A) is preferably 100 seconds or more and 300 seconds or less, more preferably 115 seconds or more and 250 seconds or less, and even more preferably 115 seconds or more and 210 seconds or less. The full width at half maximum of the first peak of the GPC of component (A) is calculated based on the first peak of component (A) obtained by the GPC method described above.

[0020] (A) Component is preferably a polyalkylene oxide having a polydispersity (Mw / Mn) within the above preferred range, or a polyalkylene oxide having a full width at half maximum (FWHM) of the first peak of the GPC within the above preferred range, from the viewpoint of providing fluidity, shape retention, and pumpability independent of changes in conditions for the hydraulic composition, and more preferably a polyalkylene oxide having a polydispersity (Mw / Mn) within the above preferred range and a full width at half maximum (FWHM) of the first peak of the GPC within the above preferred range.

[0021] Component (A) may be in the form of an aqueous solution, an aqueous dispersion, or a solid. (A) Component is preferably in solid form, particulate, and more preferably in powder or granular form. Granules are usually particles with a relatively larger particle size than powder. The shape of the solid component (A) is not limited and may be spherical, plate-shaped, etc. Furthermore, the shape of the solid component (A) may be fixed or amorphous.

[0022] When component (A) is in solid form, the average particle size of component (A) is preferably 1 μm or more, more preferably 10 μm or more, even more preferably 50 μm or more, from the viewpoint of providing fluidity, shape retention, and pumpability independent of changes in conditions of the hydraulic composition, and from the same viewpoint, preferably 5,000 μm or less, more preferably 1,000 μm or less, and even more preferably 500 μm or less. Alternatively, if component (A) is in solid form, the average particle size of component (A) is preferably 1 μm or more and 5,000 μm or less, more preferably 10 μm or more and 1,000 μm or less, and even more preferably 50 μm or more and 500 μm or less, from the same viewpoint.

[0023] The average particle size of component (A) is determined by measuring the solid and even powdered form of component (A) onto a glass slide and photographing it with a digital microscope (DSX1000, manufactured by OLYMPUS Corporation, 42x magnification). From the obtained image, the diameters of several dozen (e.g., 30-50) powder particles of any (A) component are measured, and the average particle diameter is calculated from the arithmetic mean of these values. Furthermore, when measuring the diameter of the powder particles of component (A), if the powder particles are circular, the diameter shall be used; if the powder particles of component (A) are elliptical, irregularly shaped, or have a high aspect ratio, the diameter shall be taken from the longest part.

[0024] The viscosity of a 2% by mass aqueous solution of component (A) at 25°C is preferably 10 mPa·s or more, more preferably 15 mPa·s or more, even more preferably 20 mPa·s or more, from the viewpoint of providing fluidity, shape retention, and pumpability independent of changes in conditions for the hydraulic composition, and from the same viewpoint, preferably 10,000 mPa·s or less, more preferably 6,000 mPa·s or less, and even more preferably 4,000 mPa·s or less. Alternatively, the viscosity of a 2% by mass aqueous solution of component (A) at 25°C is, from the same viewpoint, preferably 10 mPa·s or more and 10,000 mPa·s or less, more preferably 15 mPa·s or more and 6,000 mPa·s or less, and even more preferably 20 mPa·s or more and 4,000 mPa·s or less. The viscosity of a 2% by mass aqueous solution of component (A) at 25°C is measured using a B-type viscometer under the following conditions: 25°C, No. 2 rotor, 30 rpm, and after 1 minute.

[0025] <Composition, etc.> The additive for hydraulic compositions of the present invention contains component (A) in an amount of preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and from the same viewpoint, preferably 99.9999% by mass or less, more preferably 99.99% by mass or less, and even more preferably 99.9% by mass or less. Alternatively, the hydraulic composition additive of the present invention contains component (A) in an amount of preferably 85% by mass or more and 99.9999% by mass or less, more preferably 90% by mass or more and 99.99% by mass or less, and even more preferably 95% by mass or more and 99.9% by mass or less, in the hydraulic composition additive of the present invention.

[0026] <(B) component> The additive for hydraulic compositions of the present invention may optionally contain (B) an antioxidant [hereinafter referred to as component (B)]. Component (B) may be one or more types.

[0027] The inventors found that even if products containing component (A) have the same model number, the polydispersity (Mw / Mn) of component (A) differs depending on the lot. This is presumed to be because the polydispersity (Mw / Mn) changes depending on the manufacturing method and storage conditions such as oxygen and temperature (for example, Melt Extrusion: Materials, Technology and Drug Product Design, AAPS Advances in the Pharmaceutical Sciences Series 9, August 23, 2016, pp. 153, 158). As described above, the additive for hydraulic compositions of the present invention, by using component (A) having a specific polydispersity (Mw / Mn), can provide good shape retention and excellent pumpability of the hydraulic composition regardless of changes in conditions. Furthermore, by including component (B), the storage stability of component (A) is improved, and the shape retention and excellent pumpability of the hydraulic composition can be maintained even after long-term storage.

[0028] Component (B) is not particularly limited as long as it is an antioxidant, but from the viewpoint of radical scavenging, for example, at least one selected from the group consisting of phenolic antioxidants, amine antioxidants, organic sulfur antioxidants, and phosphorus antioxidants is preferred. Examples of phenolic antioxidants include dibutylhydroxytoluene (BHT), dibutylhydroxyanisole (BHA), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, and 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl Examples include one or more selected from phenylacrylate, 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, and 3,9-bis[2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5·5]undecane. Examples of amine antioxidants include one or more selected from phenyl-α-naphthylamine, phenyl-β-naphthylamine, diphenylamine, and p-hydroxyphenyl-β-naphthylamine. Examples of organosulfur antioxidants include one or more selected from dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythrityltetrakis(3-laurylthiopropionate), ditridecyl-3,3'-thiodipropionate, and 2-mercaptobenzimidazole. Examples of phosphorus antioxidants include one or more selected from triphenylphosphite and tris(2,4-di-tert-butylphenyl)phosphite.Among these antioxidants, phenolic antioxidants are preferred from the viewpoint of radical scavenging ability, and dibutylhydroxytoluene (BHT) is more preferred.

[0029] If the additive for hydraulic compositions of the present invention contains component (B), the additive for hydraulic compositions of the present invention contains component (B) in an amount of preferably 0.0001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.05% by mass or more, and from the same viewpoint, preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less. Alternatively, if the additive for hydraulic compositions of the present invention contains component (B), the additive for hydraulic compositions of the present invention contains component (B) in the same amount, preferably 0.0001% by mass or more and 5% by mass or less, more preferably 0.005% by mass or more and 1% by mass or less, and even more preferably 0.05% by mass or more and 0.5% by mass or less.

[0030] When the additive for hydraulic compositions of the present invention contains component (B), the mass ratio of the content of component (B) to the content of component (A) [(B) / (A)] in the additive for hydraulic compositions of the present invention is preferably 0.0001 or more, more preferably 0.0002 or more, even more preferably 0.0005 or more, and from the same viewpoint, preferably 0.05 or less, more preferably 0.02 or less, and even more preferably 0.01 or less. Alternatively, if the additive for the hydraulic composition of the present invention contains component (B), the mass ratio of the content of component (B) to the content of component (A) [(B) / (A)] in the additive for the hydraulic composition of the present invention is, from the same viewpoint, preferably 0.0001 or more and 0.05 or less, more preferably 0.0001 or more and 0.02 or less, even more preferably 0.0001 or more and 0.01 or less, even more preferably 0.0002 or more and 0.0005 or more and 0.01 or less.

[0031] <(C) component> The additive for hydraulic compositions of the present invention may optionally contain (C) water. The water is not particularly limited, but examples include tap water, deionized water, and distilled water. It is preferable that component (C) is used in an amount that makes up the remainder of the additive for hydraulic compositions (an amount that totals 100% by mass).

[0032] If the additive for hydraulic compositions of the present invention contains component (C), the additive for hydraulic compositions of the present invention contains component (C) in an amount of preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.0015% by mass or more, and from the same viewpoint, preferably 4% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. Alternatively, if the additive for hydraulic compositions of the present invention contains component (C), the additive for hydraulic compositions of the present invention contains component (C) in the same amount, preferably 0.0005% by mass or more and 4% by mass or less, more preferably 0.001% by mass or more and 2% by mass or less, and even more preferably 0.0015% by mass or more and 1% by mass or less.

[0033] The additive for hydraulic compositions of the present invention may optionally contain one or more selected from surfactants, water-soluble polymers (excluding those corresponding to component (A)), foaming agents, dispersants, thickeners, and inorganic salts, to the extent that it does not impair the effects of the present invention. The additive for hydraulic compositions of the present invention may contain these optional components in total at, for example, 0% by mass or more and 80% by mass or less, preferably 0% by mass or more and 60% by mass or less.

[0034] In exemplary embodiments, the additive for hydraulic compositions of the present invention may be an additive for hydraulic compositions comprising component (A). The hydraulic additive of the present invention may be a hydraulic additive comprising any of the optional components described in the hydraulic additive of the present invention. In the hydraulic composition additive of the present invention, the preferred blending amounts of component (A), component (B), and other optional components can be applied by substituting the preferred content in the hydraulic composition additive of the present invention with the blending amounts.

[0035] <Method for producing additives for hydraulic compositions> In an exemplary embodiment, the present invention provides a method for producing an additive for a hydraulic composition, comprising mixing (A) a polyalkylene oxide [component (A)] having a polydispersity (Mw / Mn) of 1.00 or more and 2.55 or less, and (B) an antioxidant [component (B)]. In the method for producing the additive for hydraulic compositions of the present invention, any of the components listed in the additive for hydraulic compositions of the present invention can be mixed as desired.

[0036] In the method for producing the additive for hydraulic compositions of the present invention, preferred embodiments of component (A), component (B), and optional components are the same as preferred embodiments of component (A), component (B), and other optional components of the additive for hydraulic compositions of the present invention described above. Furthermore, in the method for producing the additive for hydraulic compositions of the present invention, the preferred mixing amounts of component (A), component (B), and other optional components can be applied by substituting the preferred content of each component in the additive for hydraulic compositions of the present invention with the mixing amounts.

[0037] In the method for producing the additive for hydraulic compositions of the present invention, the temperature at which the mixture of component (A) and component (B) is mixed is preferably 0°C or higher, more preferably 5°C or higher, even more preferably 10°C or higher, and from the viewpoint of providing the fluidity, shape retention, and pumpability independent of changes in conditions of the hydraulic composition, and preferably 200°C or lower, more preferably 100°C or lower, and even more preferably 80°C or lower. Alternatively, from the same viewpoint, the temperature at which the mixture of component (A) and component (B) is mixed is preferably 0°C to 200°C, more preferably 5°C to 100°C, and even more preferably 10°C to 80°C.

[0038] The mixture of component (A) and component (B) can be made using a mixing mixer such as a pan-type forced mixer, twin-axis forced mixer, tiltable mixer, Hobart mixer, rotary mixer, W-type mixer, V-type mixer, drum-type mixer, conical screw-type mixer, ribbon mixer, tumbler mixer, double-cone mixer, mill mixer, juicer mixer, hand mixer, or Nauta mixer.

[0039] In the method for producing the additive for hydraulic compositions of the present invention, the mixing speed of the mixture of component (A) and component (B) is preferably 5 rpm or more, more preferably 10 rpm or more, even more preferably 50 rpm or more, and from the viewpoint of providing the fluidity, shape retention, and pumpability independent of changes in conditions of the hydraulic composition, preferably 2,000 rpm or less, more preferably 1,000 rpm or less, and even more preferably 800 rpm or less. Alternatively, from the same viewpoint, the mixing speed of the mixture of component (A) and component (B) is preferably 5 rpm to 2,000 rpm, more preferably 10 rpm to 1,000 rpm, and even more preferably 50 rpm to 800 rpm.

[0040] In the method for producing an additive for hydraulic compositions of the present invention, the mixing time of the mixture of component (A) and component (B) is preferably 5 minutes or more, more preferably 10 minutes or more, even more preferably 15 minutes or more, and from the viewpoint of providing the fluidity, shape retention, and pumpability independent of changes in conditions of the hydraulic composition, and from the same viewpoint, preferably 180 minutes or less, more preferably 120 minutes or less, and even more preferably 60 minutes or less. Alternatively, from the same viewpoint, the mixing time of the mixture of component (A) and component (B) is preferably 5 minutes or more and 180 minutes or less, more preferably 10 minutes or more and 120 minutes or less, and even more preferably 15 minutes or more and 60 minutes or less.

[0041] <Hydraulic composition> In an exemplary embodiment, the present invention provides a hydraulic composition containing an additive for hydraulic compositions which contains (A) a polyalkylene oxide having a polydispersity (Mw / Mn) of 1.00 or more and 2.55 or less. Furthermore, in exemplary embodiments, the hydraulic composition of the present invention may be a hydraulic composition containing the additive for hydraulic compositions of the present invention. In an exemplary embodiment, the hydraulic composition of the present invention may be a hydraulic composition containing the additive for hydraulic compositions of the present invention and a hydraulic powder. The hydraulic composition of the present invention may be a hydraulic composition for spraying.

[0042] The hydraulic composition of the present invention, or the additive for the hydraulic composition, may optionally contain any of the components listed in the additive for the hydraulic composition of the present invention. In the hydraulic composition of the present invention, preferred embodiments of component (A), component (B), other optional components, and additives for the hydraulic composition are the same as preferred embodiments of component (A), component (B), other optional components, and additives for the hydraulic composition in the additives for the hydraulic composition of the present invention described above. In the hydraulic composition of the present invention, the preferred configuration of the content of component (A), component (B), and other optional components contained in the additive for the hydraulic composition is the same as the preferred configuration of the content of component (A), component (B), and other optional components in the additive for the hydraulic composition of the present invention.

[0043] <Hydraulic powder> The hydraulic composition of the present invention may contain hydraulic powder. Hydraulic powder 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.

[0044] 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.

[0045] <Aggregates> The hydraulic composition of the present invention may optionally contain aggregate. The aggregate may be selected from fine aggregate and coarse aggregate. Examples of fine aggregate include those specified in JIS A 0203-2014, number 2311. Examples of fine aggregate include river sand, land sand, mountain sand, sea sand, lime sand, silica sand and their crushed sand, blast furnace slag fine aggregate, ferronickel slag fine aggregate, lightweight fine aggregate (artificial and natural), and recycled fine aggregate. Furthermore, coarse aggregates include those specified in JIS A 0203-2014, number 2312. For example, coarse aggregates include river gravel, land gravel, mountain gravel, sea gravel, lime gravel, crushed stone of these, 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.

[0046] 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 Above, a comfortable 600 kg / m 3 In addition, preferably 2,000 kg / m 3 More preferably, 1,700 kg / m 3 The following applies: In 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.

[0047] <Water> The hydraulic composition of the present invention may contain water. Examples of water include tap water, groundwater, lake water, and river water.

[0048] 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 providing the hydraulic composition with fluidity, shape retention, and pumpability that is independent of changes in 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, from the same viewpoint, 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, as well as 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.

[0049] The hydraulic composition of the present invention contains, from the viewpoint of providing the hydraulic composition with fluidity, shape retention, and pumpability independent of changes in conditions, preferably 0.0008% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, even more preferably 0.02% by mass or more, and from the same viewpoint, preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.5% by mass or less, relative to the hydraulic powder in the hydraulic composition. Alternatively, the hydraulic composition of the present invention contains, from the same viewpoint, the additive for the hydraulic composition of the present invention in an amount of 0.0008% by mass or more and 2.0% by mass or less, more preferably 0.0008% by mass or more and 1.0% by mass or less, even more preferably 0.0008% by mass or more and 0.5% by mass or less, even more preferably 0.005% by mass or more and 1.0% by mass or less, even more preferably 0.01% by mass or more and 0.5% by mass or less, and even more preferably 0.02% by mass or more and 0.5% by mass or less, relative to the hydraulic powder in the hydraulic composition.

[0050] In the hydraulic composition of the present invention, the content of the additive for the hydraulic composition of the present invention is preferably 0.0008% by mass or more, more preferably 0.0016% by mass or more, even more preferably 0.003% by mass or more, and from the same viewpoint, preferably 0.5% by mass or less, more preferably 0.25% by mass or less, and even more preferably 0.15% by mass or less. Alternatively, from the same viewpoint, the content of the additive for the hydraulic composition of the present invention in the hydraulic composition of the present invention is preferably 0.0008% by mass or more and 0.5% by mass or less, more preferably 0.0016% by mass or more and 0.25% by mass or less, and even more preferably 0.003% by mass or more and 0.15% by mass or less.

[0051] <Accelerating agent> The hydraulic composition of the present invention may optionally contain a rapid-setting agent. The rapid-setting agent can be used in any form, such as powder, liquid, or a combination thereof. Examples of rapid-setting agents include one or more rapid-setting agents selected from cement mineral-based rapid-setting agents and aluminum-based rapid-setting agents.

[0052] Examples of cement mineral-based rapid setting agents include one or more selected from calcium aluminate, calcium sulfoaluminate, and calcium aluminate. Examples of aluminum-based rapid setting agents include one or more selected from aluminum salts containing aluminum hydroxide, sodium aluminate, potassium aluminate, aluminum sulfate, aluminum chloride, potassium aluminum sulfate, potassium alum, iron alum, and ammonium iron alum. From the viewpoint of strength development, the rapid setting agent is preferably one or more selected from calcium aluminate, calcium sulfoaluminate, calcium aluminate, aluminum sulfate, sodium aluminate, and aluminum sulfate; more preferably one or more selected from calcium aluminate, calcium sulfoaluminate, and aluminum sulfate; and even more preferably one or more selected from calcium aluminate and aluminum sulfate. The quick-setting agent may include gypsum, alkali carbonates such as sodium carbonate, potassium carbonate, and sodium bicarbonate, sodium sulfate, hydroxide salts, fluorine components, alkanolamines, complex-forming agents, and alkaline earth metal carbonates.

[0053] More specifically, the rapid setting agents include Denka Co., Ltd.'s Denkanatomic series, Denkanatomic US-32, Denkanatomic US-50, Denkanatomic TYPE-5, Denkanatomic TYPE-10, Denkanatomic Z, Natomic L, Natomic LSA, Natomic USS, Natomic HSS, Denka Σ Shot V, and Taiheiyo Material Co., Ltd.'s Taiheiyo Shot Master series, Taiheiyo Shot Master A, Taiheiyo Shot Master A (for high strength), Taiheiyo Shot Master H, and Pozzolith Solution. You can use the Master Lock series from Shons Co., Ltd., including Master Lock SA160, Master Lock SA161, Master Lock SA167, Master Lock SA170, Master Lock SA178, Master Lock SA143, and Master Lock SA446, or the Cygnit series from Sika Japan Co., Ltd., including Cygnit P10AF, Cygnit L53AF, Cygnit U, Cygnit SA161, Cygnit SA167, Cygnit SA178, Cygnit SA143, and Cygnit SA446.

[0054] <Calcium Aluminate> Calcium aluminates (hereinafter referred to as CAs) are a general term for compounds that have hydration activity and are mainly composed of CaO and Al2O3. They are compounds in which part of CaO and / or Al2O3 is substituted with alkali metal oxides, alkaline earth metal oxides, silicon dioxide, titanium dioxide, iron oxide, alkali metal halides, alkaline earth metal halides, alkali metal sulfates, and alkaline earth metal sulfates, or substances in which small amounts of these are solid-dissolved in a substance mainly composed of CaO and Al2O3. CAs may be crystalline or amorphous.

[0055] Specific examples of crystalline calcium aluminates include C3A, C14A5 (where CaO is C and Al2O3 is A), C12A7, C11A7·CaF2, C4A·Fe2O3, and C3A3·CaSO4 (where alkali metals are dissolved in C3A). They may also contain, for example, Na2O, K2O, and Li2O. Amorphous calcium aluminates are preferred due to their good rapid setting properties.

[0056] Note that the calcium aluminate used in this embodiment may be contaminated with trace amounts of alkali metals and / or alkaline earth metals from industrial raw materials, and there is a possibility that CAs containing these alkali metals and / or alkaline earth metals are partially generated. However, the presence of these small amounts of alkali metals and / or alkaline earth metals does not impose any restrictions.

[0057] The CaO / Al2O3 molar ratio of the calcium aluminate is not particularly limited. However, considering the early strength development property, the molar ratio is preferably 2.0 or more and 3.0 or less, and more preferably 2.2 or more and 2.8 or less. When the molar ratio is 2.0 or more, the initial setting property can be improved. When the molar ratio is 3.0 or less, good long-term strength development property can be easily obtained.

[0058] The Blaine specific surface area of the calcium aluminate (hereinafter sometimes simply referred to as "Blaine") is preferably 4,000 cm 2 / g or more and 8,000 cm 2 / g or less, and more preferably 5,000 cm 2 / g or more and 7,000 cm 2 / g or less. When the specific surface area is 4,000 cm 2 / g or more and 8,000 cm 2 / g or less, early strength development property can be easily obtained, and the handling property of the mortar and / or concrete during spraying can be improved.

[0059] <Gypsum> Gypsum is effective for promoting the loss of fluidity immediately after the preparation of cement mortar or cement concrete and for promoting the strength development property for about one day. Gypsum is not particularly limited. For example, any gypsum such as potassium gypsum, chrome gypsum, iron gypsum, ammonium gypsum, sodium gypsum, natural gypsum, etc. can be used alone or in combination. Particularly, as a material that promotes the loss of fluidity of cement mortar or cement concrete, it is preferable to contain at least one selected from the group consisting of potassium gypsum, sodium gypsum, and ammonium gypsum.

[0060] <Gypsum> Any type of gypsum can be used: anhydrous, hemihydrate, or dihydrate. Of these, anhydrous gypsum is preferred from the viewpoint of good strength development. From the perspective of initial strength development, the particle size of gypsum should be 2,000 cm² in Blaine specific surface area. 2 Preferably 3,000 cm² or more 2 / g or more 6,000cm 2 A value of less than / g is more preferable. The Blaine specific surface area value used herein can be determined in accordance with JIS R5201 (Physical Testing Methods for Cement).

[0061] <Hydroxide salts> Hydroxide salts include hydroxide salts of alkali metals or alkaline earth metals. Examples of hydroxide salts include one or more selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, and calcium hydroxide. Among these, calcium hydroxide is preferred in terms of economy and strength development. Calcium hydroxide is an effective material for ensuring initial fluidity reduction and long-term strength development. While not specifically limited, calcium hydroxide can include slaked lime produced when quicklime is hydrated, and carbide slag produced when carbide is hydrated. Commercially available calcium hydroxide can also be used, and any combination of the above is possible.

[0062] The Blaine specific surface area of ​​calcium hydroxide is 5,000 cm². 2 / g or more 15,000cm 2 It is preferable that the amount be less than or equal to 7,000 cm². 2 / g or more 13,000cm 2 It is more preferable that the specific surface area is 5,000 cm² or less. 2 / g or more 15,000cm 2 By keeping the amount below / g, rapid hardening properties and long-term strength development can be ensured, making it easier to obtain good initial strength development.

[0063] <Alkaline Carbonate> Alkali carbonate is an alkali metal carbonate salt that can significantly improve the setting properties and initial strength development of powdered rapid setting agents. While not particularly limited, examples of alkali carbonate include one or more selected from lithium carbonate, sodium carbonate, sodium sesquicarbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, and sodium bicarbonate. Sodium carbonate, potassium carbonate, sodium sesquicarbonate, sodium bicarbonate, and sodium bicarbonate are particularly effective in setting and initial strength development, and these can be combined one or more of these. Preferably, it is at least one selected from the group consisting of sodium carbonate, sodium sesquicarbonate, sodium bicarbonate, and potassium carbonate.

[0064] <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. The fluoride salts mentioned above include, for example, 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.

[0065] <Alkanolamine> Alkanolamines are organic compounds having an NR-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 the nitrogen atom in two or more places, 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.

[0066] <Complexing agent> The complex-forming agent stabilizes metal ions in the 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 used. The complex-forming agent may also be one to three hydroxyl groups and / or one to three amino groups. 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.

[0067] <Alkaline earth metal carbonates> Alkaline earth metal carbonates are carbonates of alkaline earth metals that prevent the adhesion of fasteners to pipes and blockages in 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 pipe blockages, and it is even more preferable to use calcium carbonate in combination with sodium carbonate.

[0068] If the hydraulic composition of the present invention contains the above-mentioned rapid setting agent, the hydraulic composition of the present invention contains the 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 5.0% by mass or less, and even more preferably 3.0% 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, if the hydraulic composition of the present invention contains the above-mentioned rapid setting agent, the rapid setting agent is preferably contained in an amount of 0.1% to 10% by mass, more preferably 0.2% to 5.0% by mass, and even more preferably 0.5% to 3.0% by mass, relative to the hydraulic powder in the hydraulic composition, from the same viewpoint.

[0069] <(A) Water-soluble polymers other than component> The hydraulic composition of the present invention may optionally contain (C) a water-soluble polymer [excluding those corresponding to component (A)] [hereinafter referred to as component (C)], from the viewpoint of providing the hydraulic composition with fluidity, shape retention, and pumpability independent of changes in conditions. Component (C) may be used in the form of one or more types. Here, the water solubility of component (C) means that 0.01 g or more dissolves in 100 g of water at 20°C.

[0070] The weight-average molecular weight of component (C) is preferably 5,000 or more, more preferably 25,000 or more, even more preferably 50,000 or more, even more preferably 100,000 or more, and preferably 10,000,000 or less, more preferably 8,000,000 or less, even more preferably 5,000,000 or less, and even more preferably 1,000,000 or less, from the viewpoint of providing the hydraulic composition with fluidity, shape retention, and pumpability independent of changes in conditions. Alternatively, the weight-average molecular weight of component (C) is preferably 5,000 to 10,000,000, more preferably 25,000 to 8,000,000, even more preferably 50,000 to 5,000,000, and even more preferably 100,000 to 1,000,000.

[0071] The weight-average molecular weight of component (C) can be determined, for example, by gel permeation chromatography under the following conditions. • Equipment: HLC-8320 GPC (manufactured by Tosoh Corporation, with integrated detector) • Column: Manufactured by Tosoh Corporation, Product name: TSK-GEL guardcolumn PWXL Manufactured by Tosoh Corporation, Product name: TSK-GEL GMPWXL Manufactured by Tosoh Corporation, Product name: TSK-GEL GMPWXL Mobile phase: 0.2 mol / L phosphate buffer (potassium dihydrogen phosphate, disodium hydrogen phosphate aqueous solution, pH=7) / acetonitrile = 90 / 10 (volume ratio) • Detector: Differential refractive index detector Column temperature: 40°C ·Flow rate: 0.5mL / min • Conversion reference material: Polyethylene oxide [manufactured by Tosoh Corporation] • Sample: An aqueous polymer solution containing 5 mg of solids is mixed with ultrapure water to prepare a total volume of 10 mL. 100 μL of this prepared solution is then taken and injected into the column.

[0072] Component (C) is preferably one or more selected from polymers containing monomer-derived structural units containing carboxyl groups or salts thereof [excluding those corresponding to dispersants for hydraulic compositions as described in detail later] [hereinafter referred to as component (C1)] and cellulose-based polymers [hereinafter referred to as component (C2)], from the viewpoint of providing the hydraulic composition with fluidity, shape retention, and pumpability independent of changes in conditions.

[0073] Polymers containing constituent units derived from monomers including a carboxyl group of component (C1) or a salt thereof are preferred from the viewpoint of providing the fluidity, shape retention, and pumpability independent of changes in conditions of the hydraulic composition, and polymers containing constituent units derived from one or more monomers selected from acrylic acid, methacrylic acid, and their salts [hereinafter referred to as monomer (c1-1)]. Salts of acrylic acid and methacrylic acid include one or more selected from sodium salts, potassium salts, ammonium salts, aminium salts, and calcium salts. The monomer (c1-1) is preferably one or more selected from acrylic acid and its salts.

[0074] The (C1) component may include constituent units derived from monomers other than monomer (c1-1) [hereinafter referred to as monomer (c1-2)]. Monomers (c1-2) include, for example, unsaturated carboxylic acids such as itaconic acid, maleic acid, fumaric acid, citraconic acid, aconitic acid, and crotonic acid; unsaturated carboxylic acid anhydrides such as maleic anhydride and citraconic anhydride; unsaturated carboxylates such as monomethyl itaconic acid, monobutyl itaconic acid, and monoethyl maleate; unsaturated sulfonic acids such as vinyl sulfonic acid, methallyl sulfonic acid, and 2-(meth)acrylamide-2-methylpropanesulfonic acid; unsaturated phosphoric acids such as 2-(meth)acryloyloxy)ethyl phosphate and bis[2-(meth)acryloyloxy)ethyl hydrogen phosphate; unsaturated phenols such as vinylphenol; and acrylonitrile. Examples include vinyl esters of aliphatic carboxylic acids having 3 to 18 carbon atoms, such as cyanovinyl methacrylonitrile, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl octylate, and vinyl neodecanoate esters, vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and phenyl vinyl ether, polyfunctional vinyl monomers such as allyl methacrylate, unsaturated hydrocarbons such as ethylene, styrene, and butadiene, and unsaturated amide compounds such as methacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, and N-vinylpyrrolidone. One or more of these can be used.

[0075] The proportion of monomer (c1-1) among all monomers constituting component (C1) is preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and preferably 100 mol% or less, and may be 100 mol%. Alternatively, the proportion of monomer (c1-1) among all monomers constituting component (C1) is preferably 60 mol% or more and 100 mol% or less, more preferably 70 mol% or more and 100 mol% or less, and even more preferably 80 mol% or more and 100 mol% or less.

[0076] (C1) Component is preferably one or more selected from polyacrylic acid, polymethacrylic acid, and salts thereof, and more preferably one or more selected from polyacrylic acid and salts thereof, from the viewpoint of providing the fluidity, shape retention, and pumpability independent of changes in conditions of the hydraulic composition.

[0077] The weight-average molecular weight of component (C1) is preferably 10,000 or more, more preferably 15,000 or more, even more preferably 20,000 or more, even more preferably 25,000 or more, and preferably 6,500,000 or less, more preferably 5,000,000 or less, even more preferably 3,500,000 or less, even more preferably 2,500,000 or less, even more preferably 2,000,000 or less, even more preferably 1,000,000 or less, even more preferably 500,000 or less, even more preferably 100,000 or less, even more preferably 50,000 or less, and even more preferably 30,000 or less, from the viewpoint of providing the hydraulic composition with fluidity, shape retention, and pumpability independent of changes in conditions. Alternatively, the weight-average molecular weight of component (C1) is preferably 10,000 to 6,500,000, more preferably 15,000 to 5,000,000, even more preferably 20,000 to 3,500,000, even more preferably 25,000 to 2,500,000, even more preferably 25,000 to 2,000,000, even more preferably 25,000 to 1,000,000, even more preferably 25,000 to 500,000, even more preferably 25,000 to 100,000, even more preferably 25,000 to 50,000, and even more preferably 25,000 to 30,000.

[0078] The weight-average molecular weight of component (C1) can also be determined by gel permeation chromatography under the following conditions. Column: GMPWXL-GMPWXL (anion) manufactured by Tosoh Corporation Detector: Differential refractometer Eluent: 0.2M phosphate buffer / acetonitrile = 9 / 1 Standard: Polyethylene glycol equivalent (monodisperse polyethylene glycol with known molecular weights: 21,000, 44,200, 101,000, 185,000, 580,000, 977,000) Conditions: Column temperature: 40°C, Flow rate: 0.5 mL / min, Concentration: 2 mg / mL

[0079] The cellulosic polymer of component (C2) includes modified cellulose, such as carboxyalkyl, alkyl, or hydroxyalkyl modified cellulose, represented by carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, or hydroxypropylmethylcellulose.

[0080] The viscosity of a 1% by mass aqueous solution or dispersion of component (C2) at 25°C is preferably 10 mPa·s or more, more preferably 30 mPa·s or more, even more preferably 60 mPa·s or more, even more preferably 300 mPa·s or more, even more preferably 2,000 mPa·s or more, and from the viewpoint of providing the fluidity, shape retention, and pumpability independent of changes in conditions of the hydraulic composition, and also preferably 7,000 mPa·s or less, more preferably 6,000 mPa·s or less, and even more preferably 5,000 mPa·s or less. Alternatively, the viscosity of an aqueous solution or dispersion of component (C2) at 25°C at a concentration of 1% by mass is preferably 10 mPa·s or more and 7,000 mPa·s or less, more preferably 30 mPa·s or more and 6,000 mPa·s or less, even more preferably 60 mPa·s or more and 5,000 mPa·s or less, even more preferably 300 mPa·s or more and 5,000 mPa·s or less, and even more preferably 2,000 mPa·s or more and 5,000 mPa·s or less. The above viscosity is measured using a Type B viscometer (VISCOMETER, MODEL BM, manufactured by Tokyo Keiki Co., Ltd., rotor No. 2) at a rotation speed of 60 rpm.

[0081] The weight-average molecular weight of component (C2) is preferably 10,000 or more, more preferably 100,000 or more, even more preferably 400,000 or more, even more preferably 800,000 or more, even more preferably 1,500,000 or more, and preferably 20,000,000 or less, even more preferably 10,000,000 or less, and even more preferably 6,000,000 or less, from the viewpoint of providing the hydraulic composition with fluidity, shape retention, and pumpability independent of changes in conditions. Alternatively, the weight-average molecular weight of component (C2) is preferably 10,000 to 20,000,000, more preferably 100,000 to 10,000,000, even more preferably 400,000 to 6,000,000, even more preferably 800,000 to 6,000,000, and even more preferably 1,500,000 to 6,000,000. The weight-average molecular weight mentioned above was measured by gel permeation chromatography under the following measurement conditions.

[0082] <Method for measuring weight-average molecular weight> The weight-average molecular weight of component (C2) can be measured by GPC (gel permeation chromatography), and the weight-average molecular weight (Mw) can be determined using a conversion standard. The GPC measurement conditions are shown below. • Equipment: HLC-8320 GPC (manufactured by Tosoh Corporation, with integrated detector) • Column: Manufactured by Tosoh Corporation, Product name: TSK-GEL guardcolumn PWXL Manufactured by Tosoh Corporation, Product name: TSK-GEL GMPWXL Manufactured by Tosoh Corporation, Product name: TSK-GEL GMPWXL Mobile phase: 0.2 mol / L phosphate buffer (potassium dihydrogen phosphate, disodium hydrogen phosphate aqueous solution, pH=7) / acetonitrile = 90 / 10 (volume ratio) • Detector: Differential refractive index detector Column temperature: 40°C ·Flow rate: 0.5mL / min • Conversion reference material: Polyethylene oxide [manufactured by Tosoh Corporation] • Sample: An aqueous polymer solution containing 5 mg of solids is mixed with ultrapure water to prepare a total volume of 10 mL. 100 μL of this prepared solution is then taken and injected into the column.

[0083] (C2) Component is preferably one or more selected from carboxymethylcellulose and its salts, hydroxyethylcellulose, and hydroxypropylmethylcellulose, from the viewpoint of providing the fluidity, shape retention, and pumpability independent of changes in conditions of the hydraulic composition, and carboxymethylcellulose or its salts are more preferred. Examples of carboxymethylcellulose salts include alkali metal salts such as sodium salt and potassium salt, and ammonium salt. From the viewpoint of availability and other factors, alkali metal salts are preferred as carboxymethylcellulose salts, and sodium salts are more preferred.

[0084] The degree of etherification of the carboxymethylcellulose or salt thereof of component (C2) is preferably 0.5 or higher, more preferably 0.55 or higher, even more preferably 0.6 or higher, and from the same viewpoint, preferably 1.5 or lower, more preferably 1.3 or lower, and even more preferably 1.0 or lower. Alternatively, from the same viewpoint, the degree of etherification is preferably 0.5 to 1.5, more preferably 0.55 to 1.3, and even more preferably 0.6 to 1.0. The degree of etherification of carboxymethylcellulose or its salt (C2) refers to the degree of substitution of carboxymethyl groups per glucose unit in carboxymethylcellulose or its salt (C2). When carboxymethylcellulose sodium is (C2) component, its degree of etherification is measured by the following method, for example, according to the CMC Industry Association analytical method (ashing method). The degree of etherification of (C2) component can also be measured by the same method when carboxymethylcellulose is a salt other than sodium.

[0085] <Measurement of the degree of etherification of sodium carboxymethylcellulose> By accurately weighing 1 g of sodium carboxymethylcellulose, placing it in a magnetic crucible, and ashing it at 600°C, the sodium oxide produced by ashing is titrated with N / 10 sulfuric acid using phenolphthalein as an indicator. The titration volume Y mL per 1 g of sodium carboxymethylcellulose can be calculated using the following formula, and the resulting degree of etherification can be shown. Degree of etherification = (162 × Y) / (10,000 - 80 × Y)

[0086] (C2) The carboxymethylcellulose or salt thereof of component (C2) is preferably one or more selected from the group consisting of carboxymethylcellulose and sodium carboxymethylcellulose, with sodium carboxymethylcellulose being more preferred, from the viewpoint of providing the fluidity, shape retention, and pumpability independent of changes in conditions of the hydraulic composition. Examples of commercially available sodium carboxymethylcellulose include the CMC Daicel series from Daicel Corporation, the Sunrose series from Nippon Paper Industries Ltd., and the Selogen series from Daiichi Kogyo Seiyaku Co., Ltd.

[0087] Component (C) is preferably one or more selected from carboxymethylcellulose and its salts, hydroxyethylcellulose, hydroxypropylmethylcellulose, polyacrylic acid and its salts, polymethacrylic acid and its salts, and polyacrylamide, from the viewpoint of providing the hydraulic composition with fluidity, shape retention, and pumpability independent of changes in conditions. More preferably, one or more selected from polyacrylic acid, carboxymethylcellulose, and their salts is preferred, and carboxymethylcellulose or its salt is even more preferred.

[0088] If the hydraulic composition of the present invention contains component (C), the hydraulic composition of the present invention contains component (C) in an amount of 0.005% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.015% by mass or more, even more preferably 0.019% by mass or more, and from the same viewpoint, preferably 0.5% by mass or less, more preferably 0.2% by mass or less, and even more preferably 0.1% by mass or less. Alternatively, if the hydraulic composition of the present invention contains component (C), the hydraulic composition of the present invention contains component (C) in an amount of 0.005% by mass or more and 0.5% by mass or less, more preferably 0.01% by mass or more and 0.2% by mass or less, even more preferably 0.015% by mass or more and 0.1% by mass or less, and even more preferably 0.019% by mass or more and 0.1% by mass or less, relative to the hydraulic powder in the hydraulic composition.

[0089] If the hydraulic composition of the present invention contains component (C), the content of component (C) in the hydraulic composition of the present invention is preferably 0.001% by mass or more, more preferably 0.004% by mass or more, even more preferably 0.01% by mass or more, even more preferably 0.02% by mass or more, even more preferably 0.05% by mass or more, and from the same viewpoint, preferably 2% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1.0% by mass or less. Alternatively, if the hydraulic composition of the present invention contains component (C), the content of component (C) in the hydraulic composition of the present invention is preferably 0.001% by mass or more and 2% by mass or less, more preferably 0.004% by mass or more and 1.5% by mass or less, even more preferably 0.01% by mass or more and 1.0% by mass or less, even more preferably 0.02% by mass or more and 1.0% by mass or less, and even more preferably 0.05% by mass or more and 1.0% by mass or less.

[0090] <Aluminosilicate> The hydraulic composition of the present invention may optionally contain (D) aluminosilicate [hereinafter referred to as component (D)] from the viewpoint of providing the hydraulic composition with fluidity, shape retention, and pumpability independent of changes in conditions.

[0091] (D) Component aluminosilicate is a general term for compounds mainly composed of SiO2 and Al2O3, and includes clay minerals [hereinafter referred to as (D1) component], metakaolin, calcined clay, fly ash, incinerator ash [including but not limited to rice husks, sugarcane leaf ash, palm oil, boiler ash, paper waste sludge ash, municipal solid waste ash, and furnace bottom ash], natural pozzolanes, volcanic ash, blast furnace slag [from steel or iron], other industrial crushed slag [including but not limited to phosphorus, ferronickel, ferrochrome magnesia-iron, copper, nickel, and titan-iron], mine tailings or waste [including but not limited to coal gang and red mud]. Examples include one or more selected from ], zeolite, feldspar, framework aluminosilicate, and synthetic glass precursor [a mixture of silicate and aluminate], and preferably one or more selected from component (D1), metakaolin, incinerator ash, volcanic ash, natural pozzolanic acid, fly ash, and blast furnace slag.

[0092] The degree of swelling of component (D) is preferably 4 mL / 2 g or more, more preferably 10 mL / 2 g or more, even more preferably 15 mL / 2 g or more, and preferably 50 mL / 2 g or less, more preferably 48 mL / 2 g or less, even more preferably 42 mL / 2 g or less, and even more preferably 36 mL / 2 g or less, from the viewpoint of providing fluidity, shape retention, and pumpability that is independent of changes in conditions for the hydraulic composition. Alternatively, from the same viewpoint, the degree of swelling of component (D) is preferably 4 mL / 2 g or more and 50 mL / 2 g or less, more preferably 10 mL / 2 g or more and 48 mL / 2 g or less, even more preferably 15 mL / 2 g or more and 42 mL / 2 g or less, and even more preferably 15 mL / 2 g or more and 36 mL / 2 g or less. 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 8.0% by mass moisture content, 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).

[0093] The clay mineral of component (D1) may include, for example, one or more selected from layered silicates, and more specifically, one or more selected from bentonite, kaolinite, synthetic mica, smectite, clay, talc, montmorillonite, illite, gluconite, chlorite, hectorite, saponite, stevensite, nontronite, and sericite. Among these, the clay mineral of component (D1) is preferably one or more clay minerals selected from bentonite, kaolinite, montmorillonite, and smectite, from the viewpoint of providing the fluidity, shape retention, and pumpability independent of changes in conditions of the hydraulic composition, more preferably one or more clay minerals selected from bentonite and kaolinite, and even more preferably bentonite.

[0094] If the hydraulic composition of the present invention contains component (D), the hydraulic composition of the present invention contains component (D) in an amount of 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.15% by mass or more, even more preferably 0.2% by mass or more, and from the same viewpoint, preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. Alternatively, if the hydraulic composition of the present invention contains component (D), the hydraulic composition of the present invention contains component (D) in an amount of 0.05% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 2% by mass or less, even more preferably 0.15% by mass or more and 1% by mass or less, and even more preferably 0.2% by mass or more and 1% by mass or less, relative to the hydraulic powder in the hydraulic composition.

[0095] If the hydraulic composition of the present invention contains component (D), the content of component (D) in the hydraulic composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, even more preferably 0.12% by mass or more, and from the same viewpoint, preferably 2% by mass or less, even more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and even more preferably 0.25% by mass or less. Alternatively, if the hydraulic composition of the present invention contains component (D), the content of component (D) in the hydraulic composition of the present invention is preferably 0.01% by mass or more and 2% by mass or less, more preferably 0.05% by mass or more and 1% by mass or less, even more preferably 0.1% by mass or more and 0.5% by mass or less, and even more preferably 0.12% by mass or more and 0.25% by mass or less.

[0096] <Dispersant for hydraulic compositions> The hydraulic composition of the present invention may optionally contain a dispersant for hydraulic compositions. From the viewpoint of dispensing workability, a polycarboxylic acid-based dispersant is preferred.

[0097] 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.

[0098] When the hydraulic composition of the present invention contains a dispersant for hydraulic compositions, 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, 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 discharge workability and slag suppression. Alternatively, if the hydraulic composition of the present invention contains a dispersant for hydraulic compositions, 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.

[0099] 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 (excluding those corresponding to component (A), component (C), and a dispersant for hydraulic compositions), 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, a foaming agent, etc.

[0100] 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.

[0101] In an exemplary embodiment, the hydraulic composition of the present invention may be a hydraulic composition comprising the hydraulic composition additive 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 additive for hydraulic composition, hydraulic powder, water, and optional components can be applied by substituting the preferred content in the hydraulic composition of the present invention described above.

[0102] <Method for producing a hydraulic composition> In an exemplary embodiment, the present invention provides a method for producing a hydraulic composition, comprising mixing (A) an additive for hydraulic compositions containing a polyalkylene oxide having a polydispersity (Mw / Mn) of 1.00 or more and 2.55 or less, a hydraulic powder, and water.

[0103] In an exemplary embodiment, the method for producing the hydraulic composition of the present invention may be a method for producing a hydraulic composition in which an additive for the hydraulic composition of the present invention, a hydraulic powder, and water are mixed. Furthermore, the method for producing the hydraulic composition of the present invention may be a method for producing a hydraulic composition in which the additive for the hydraulic composition of the present invention and a hydraulic powder are mixed, and the resulting mixture is mixed with water. The method for producing the hydraulic composition of the present invention may be a method for producing a hydraulic composition for spraying.

[0104] The present invention may provide a method for producing a hydraulic composition, which includes a step of confirming the polydispersity of component (A) contained in the additive before mixing the additive for the hydraulic composition. This step may be a step to confirm that the polydispersity of component (A) contained in the additive is 1.00 or more and 2.55 or less.

[0105] In the method for producing the hydraulic composition of the present invention, preferred embodiments of component (A), component (B), other optional components, and additives for the hydraulic composition are the same as preferred embodiments of component (A), component (B), other optional components, and additives for the hydraulic composition in the additives for the hydraulic composition 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 additive for the hydraulic composition may optionally contain any of the additives for the hydraulic composition of the present invention or any of the components listed in the hydraulic composition of the present invention.

[0106] In the method for producing the hydraulic composition of the present invention, the preferred content of component (A), component (B), and other optional components contained in the additive for the hydraulic composition is the same as the preferred content of component (A), component (B), and other optional components in the additive for the hydraulic composition of the present invention. Furthermore, in the method for producing the hydraulic composition of the present invention, the amount or ratio of the additive for the hydraulic composition, the hydraulic powder, and the 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.

[0107] <Spray application method> In an exemplary embodiment, the present invention provides a spraying method comprising mixing (A) an additive for a hydraulic composition containing a polyalkylene oxide having a polydispersity (Mw / Mn) of 1.00 or more and 2.55 or less, a hydraulic powder, and water. The spraying method of the present invention may be a spraying method in which the additive for the hydraulic composition of the present invention, hydraulic powder, and water are mixed and sprayed onto the target 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.

[0108] The spraying method of the present invention may include a step of confirming the polydispersity of component (A) contained in the additive for the hydraulic composition before mixing the additive. This step may be a step to confirm that the polydispersity of component (A) contained in the additive is 1.00 or more and 2.55 or less.

[0109] The spraying method of the present invention is preferably a wet spraying method. Examples of the wet spraying method include mixing and kneading hydraulic powder, aggregate, additives for the hydraulic composition, and water, pumping the mixture under air pressure, and optionally adding and mixing the rapid-setting agent before spraying. In the spraying method of the present invention, for example, the additive for the hydraulic composition of the present invention can be mixed with hydraulic powder, and the resulting mixture can be mixed with water and sprayed onto the target object.

[0110] 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.

[0111] 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 powder, aggregate, and an additive for the hydraulic composition of the present invention are mixed, and then the mixture is mixed with water to produce a hydraulic composition.

[0112] 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.

[0113] In the present invention, the mixing of the additive for the hydraulic composition of the present invention, hydraulic powder, aggregate, water, and other optional components can be carried out by known methods. For example, one method is to simultaneously mix the additive for the hydraulic composition of the present invention, hydraulic powder, water, and aggregate. A mixing mixer such as a pan-type forced mixer, a twin-screw forced mixer, or a tiltable mixer can be used to mix these components.

[0114] In this invention, a hydraulic composition for spraying can be manufactured by mixing hydraulic powder, aggregate, and water to obtain a hydraulic composition, and optionally adding a dispersant for hydraulic compositions and a quick-setting agent. The dispersant for hydraulic compositions can be mixed with water beforehand. Furthermore, the mixing of the hydraulic composition and the quick-setting agent can be carried out, for example, by a general spraying method in which the hydraulic composition and the quick-setting agent are pneumatically fed and mixed together.

[0115] In the spraying method of the present invention, the additive for the hydraulic composition of the present invention can be used by mixing it with the hydraulic powder in advance during the process of preparing the hydraulic composition. In the spraying method of the present invention, the additive for the hydraulic composition of the present invention is mixed with the hydraulic powder in the hydraulic composition in an amount that is preferably 0.0008% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, even more preferably 0.02% by mass or more, and from the same viewpoint, preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.5% by mass or less. Alternatively, in the spraying method of the present invention, the additive for the hydraulic composition of the present invention is mixed with the hydraulic powder in the hydraulic composition in an amount that is, from the same viewpoint, preferably 0.0008% by mass or more and 2.0% by mass or less, more preferably 0.0008% by mass or more and 1.0% by mass or less, even more preferably 0.0008% by mass or more and 0.5% by mass or less, even more preferably 0.005% by mass or more and 1.0% by mass or less, even more preferably 0.01% by mass or more and 0.5% by mass or less, and even more preferably 0.02% by mass or more and 0.5% by mass or less.

[0116] In the spraying method of the present invention, if the hydraulic composition contains a rapid setting agent, the rapid setting agent is mixed with respect to the hydraulic powder in the hydraulic composition in an amount preferably of 0.1% by mass or more, more preferably of 0.2% by mass or more, even more preferably of 0.5% by mass or more, and preferably of 10% by mass or less, more preferably of 5.0% by mass or less, and even more preferably of 3.0% by mass or less, from the viewpoint of maintaining the shape of the hydraulic composition. Alternatively, in the spraying method of the present invention, if the hydraulic composition contains a rapid setting agent, the rapid setting agent is mixed with the hydraulic powder in the hydraulic composition in an amount of preferably 0.1% to 10% by mass, more preferably 0.2% to 5.0% by mass, and even more preferably 0.5% to 3.0% by mass, from the same viewpoint.

[0117] 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 quick-setting agent, mix the two to prepare the hydraulic composition, and then spray it.

[0118] <Use as an additive for hydraulic compositions> In exemplary embodiments, the present invention provides the use of a polyalkylene oxide [component (A)] having a polydispersity (Mw / Mn) of 1.00 to 2.55 as an additive for hydraulic compositions.

[0119] The matters described in the sections on additives for hydraulic compositions and their manufacturing methods, hydraulic compositions and their manufacturing methods of the present invention, and spraying methods can be appropriately applied to the use of the present invention. In the use of the present invention, a preferred embodiment of component (A) is the same as a preferred embodiment of component (A) in the additive for hydraulic compositions of the present invention described above. In use of the present invention, component (A) can be used in combination with any component such as component (B) described in the above-mentioned additive for hydraulic compositions of the present invention. Furthermore, preferred embodiments of the hydraulic composition in which component (A) is used as an additive for the hydraulic composition, such as 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 component (A) is to use a hydraulic composition additive containing component (A) in the amount described in the hydraulic composition additive of the present invention, in the amount described in the hydraulic composition of the present invention. The same applies to the use of optional components such as component (B) described in the hydraulic composition additive of the present invention. [Examples]

[0120] In the examples and comparative examples, the hydraulic composition additives listed in Tables 1 to 4 were prepared using component (A) below, and the shape retention and fluidity of the hydraulic composition containing the hydraulic composition additive were evaluated. The results are shown in Tables 1 to 4.

[0121] <(A) component> A-1: Polyethylene oxide, Alcox E-45, manufactured by Meisei Chemical Industry Co., Ltd., Lot. 53744, average particle size: 260 μm A-2: Polyethylene oxide, PEO-3, manufactured by Sumitomo Seika Co., Ltd., Lot. 0380204, average particle size: 272 μm A-3: Polyethylene oxide, Alcox E-30, manufactured by Meisei Chemical Industry Co., Ltd., Lot. 51728, average particle size: 415 μm A-4: Polyethylene oxide, Alcox E-30, manufactured by Meisei Chemical Industry Co., Ltd., Lot. 51882, average particle size: 248 μm A-5: Polyethylene oxide, Alcox E-60, manufactured by Meisei Chemical Industry Co., Ltd., Lot. 54298, average particle size: 132 μm <(A') component> A'-1: Polyethylene oxide, Alcox E-45, manufactured by Meisei Chemical Industry Co., Ltd., Lot. 53670, average particle size: 356 μm A'-2: Polyethylene oxide, Alcox E-45, manufactured by Meisei Chemical Industry Co., Ltd., average particle size: 91 μm A'-3: Polyethylene oxide, PEO-2, manufactured by Sumitomo Seika Co., Ltd., Lot. 0280102, average particle size: 216 μm A'-4: Polyethylene oxide, Alcox E-240, manufactured by Meisei Chemical Industry Co., Ltd., Lot. 67145, average particle size: 111 μm A'-5: Polyethylene oxide, Alcox E-30, manufactured by Meisei Chemical Industry Co., Ltd., Lot. 51882, 10g in a 200mL container, stored for 1 month at 60°C in a well-ventilated environment.

[0122] <(B) component> • B-1: Phenolic antioxidant, dibutylhydroxytoluene, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0123] <(C) component> • C-1: Sodium carboxymethylcellulose (degree of etherification 0.68, average particle size 89 μm, weight-average molecular weight 1,096,000, viscosity of 1% aqueous solution (25℃) 200 mPa·s, manufactured by Daicel Mirise Co., Ltd., product number 1160) • C-2: Hydroxypropyl methylcellulose (Asukaclean D, manufactured by Shin-Etsu Chemical Co., Ltd.) <Dispersant for hydraulic compositions> • Mighty 21HPR: Polycarboxylic acid-based dispersant, 25% by mass of active ingredient, manufactured by Kao Corporation.

[0124] <Method for measuring full width at half maximum and polydispersity> The full width at half maximum (FWHM), the weight-average molecular weight (Mw), and the number-average molecular weight (Mn) used to calculate the polydispersity (Mw / Mn) were calculated based on the GPC measurement results under the following conditions. Measurements were performed using the GPC method under the following conditions: high-speed GPC instrument (HLC-8320GPC, Tosoh Corporation), detector: RI, column: G4000PWXL+G2500PWXL (anion), mobile phase: 0.2M phosphate buffer / acetonitrile = 9 / 1, flow rate: 1.0 mL / min, column temperature: 40°C, standard substance: polyethylene glycol, sample concentration: 1% by mass (0.5% by mass for high viscosity). The first peak with a retention time of 10 to 17.5 minutes was considered to be the peak of component (A). In addition, only A'-4 was measured at a concentration of 0.5% by mass, while the other components of (A) were measured at a concentration of 1% by mass.

[0125] <Method for measuring average particle size> The average particle size of component (A) was determined by measuring solid and powdered components of (A) onto a glass slide and photographing them with a digital microscope (DSX1000, OLYMPUS Corporation, 42x magnification). From the obtained images, the diameters of 50 powder particles of component (A) were measured, and the average particle size was calculated from the arithmetic mean of these values. For the measurement of the diameter of powder particles of component (A), if the powder particles were circular, the diameter was used; if the powder particles of component (A) were elliptical, irregularly shaped, or had a high aspect ratio, the longest part was used as the diameter.

[0126] <Method for preparing additives for hydraulic compositions> For additives for hydraulic compositions containing component (A), component (A) was used as is as an additive for hydraulic compositions. The additive for the hydraulic composition containing components (A) and (B) was prepared by placing 9.99 g of (A) polyethylene oxide and 0.01 g of (B) dibutylhydroxytoluene into a 300 mL disposable cup, stirring 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) to prepare the additive for the hydraulic composition.

[0127] <Components of Bentonite A [Component (D)]> • Refined montmorillonite: Kunipia F, manufactured by Kunimine Industries Co., Ltd. • 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

[0128] <Method for preparing Bentonite A [Component (D)]> 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.

[0129] <Method for preparing a fast-setting agent> (1) Fastening agent A 500g of aluminum sulfate-14-18 hydrate (manufactured by Kanto Chemical Co., Ltd.) was added to a 2L cup, and then water was added until the total volume reached 1,000g. The mixture was then mixed and dissolved to prepare a rapid setting agent A containing 27% by mass of aluminum sulfate. (2) Fastening agent B 59.13 g of aluminum sulfate-14-18 hydrate (manufactured by Kanto Chemical Co., Ltd.) and 27.67 g of water were placed in a 300 mL disposable cup, and the mixture was stirred at 100 rpm (EUROSTAR200 control, manufactured by 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 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 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 the rapid setting agent B.

[0130] <Method for evaluating shape retention> Tables 1-3 show the evaluation results of the additives for hydraulic compositions of the present invention and the shape retention properties of the hydraulic compositions of the present invention. (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. In addition, the following water, cement, fine aggregate, and (C) water-soluble polymer were used in the preparation of the hydraulic composition. Water (W): Wakayama City 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

[0131] In the mixing bowl of a mortar mixer (Hobart type mixer, KC-8 manufactured by Kansai Kiki Seisakusho Co., Ltd.), 400g of cement, 1050g of fine aggregate, 0.40g of the hydraulic composition additives listed in Tables 1-3, and 4.40g of the hydraulic composition dispersant Mighty 21HPR were added 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.

[0132] (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 every minute, starting 30 seconds after mixing began with the addition of 7.76 g of quick-setting agent A to 530 g of the hydraulic composition prepared in (1). The results are shown in Table 1. Vanes measuring 20 mm x 40 mm were used. Similarly, the hydraulic composition prepared in (1) was to be combined with either the rapid setting agent A or the rapid setting agent B in the amounts shown in Table 2, and the vane shear resistance of the hydraulic composition was measured at 1 minute, with 30 seconds after the start of mixing as the reference point. The results are shown in Table 2. Furthermore, the results when (C) water-soluble polymer was used are shown in Table 3. When (C) water-soluble polymer was used, the rapid setting agent B was added to the hydraulic composition prepared in (1) in the amount shown in Table 3, and the vane shear resistance value of the hydraulic composition was measured at 1 minute, with 30 seconds after the start of mixing as the reference point. The results are shown in Table 3. The (C) water-soluble polymer was added and mixed together with cement and fine aggregate at the time of preparation of the hydraulic composition in (1) in the amount shown in Table 3.

[0133] Table 1 shows the vane shear resistance values ​​for each hydraulic composition after 1 to 4 minutes. A higher vane shear resistance value indicates better shape retention of the hydraulic composition, meaning that the hydraulic composition is less likely to deform after molding and has good moldability. Furthermore, hydraulic compositions with a high vane shear resistance value four minutes after mixing with a rapid setting agent tend to have better moldability immediately after spraying when used as a sprayable hydraulic composition, and are less prone to deformation after molding.

[0134] [Table 1]

[0135] Furthermore, as shown in Table 2, the inclusion of bentonite A (corresponding to the aluminosilicate of component (D)) in the hydraulic composition further improved the shape retention of the hydraulic composition. From these results, it can be said that the hydraulic composition containing component (D) has better moldability immediately after spraying when used as a hydraulic composition for spraying, and is less prone to deformation after molding.

[0136] [Table 2]

[0137] Furthermore, as shown in Table 3, the inclusion of the water-soluble polymer component (C) in the hydraulic composition further improved its shape retention. Based on these results, the hydraulic composition containing components (C) and (D) exhibits better moldability immediately after spraying when used as a sprayable hydraulic composition, and is less prone to shape deformation after molding.

[0138] [Table 3]

[0139] <Method for evaluating pumpability> Table 4 shows the evaluation results of the pumpability of the additives for the hydraulic composition of the present invention and the hydraulic composition of the present invention. The pumpability was evaluated based on the flow time of the hydraulic composition (funnel test). Specifically, under the conditions 1 to 3 below, hydraulic compositions prepared in the same manner as in (1) of the <Method for Evaluating Shape Retention> were filled into a conical hydraulic composition flow time measuring device having openings at the top and bottom. The hydraulic composition flow time measuring device is a 300 mm long cylinder with a tapered shape, having an upper input opening with a diameter of 100 mm and a lower discharge opening with a diameter of 20 mm. The discharge port of the hydraulic composition flow time measuring device was sealed with a rubber stopper, the hydraulic composition sample was filled up to the surface of the input opening (a certain amount), the rubber stopper on the discharge port was removed, and the time until all of the hydraulic composition was discharged was measured. <Condition> Condition 1: A dispersant for hydraulic compositions (Mighty 21HPR) was mixed with cement (C) at a ratio of 1.5% (% × C). The hydraulic composition was then filled into a hydraulic composition flow time measuring device, and the flow time was measured after a waiting time of 0 minutes. Condition 2: A dispersant for hydraulic compositions (Mighty 21HPR) was mixed with cement (C) at a ratio of 1.5% (C), and the hydraulic composition was filled into a hydraulic composition flow time measuring device. After a waiting time of 3 minutes, the flow time was measured. Condition 3: A dispersant for hydraulic compositions (Mighty 21HPR) was mixed with cement (C) at a ratio of 1.1 (% × C). The hydraulic composition was then filled into a hydraulic composition flow time measuring device, and the flow time was measured after a waiting time of 0 minutes.

[0140] The shorter the time it takes for the hydraulic composition to be completely discharged, the better the pumpability of the hydraulic composition additive. For example, if the time it takes for the hydraulic composition to be discharged is 40 seconds or less, it can be said to be a hydraulic composition additive with superior pumpability. Furthermore, for the time (s) required for all hydraulic compositions in each example and comparative example to be discharged, the maximum difference between conditions (%) was calculated based on the ratio of the difference between the maximum and minimum values ​​of the time measured under each condition. The smaller the maximum difference between conditions, the more likely it is that the additive for hydraulic compositions provides a hydraulic composition with excellent pumpability regardless of changes in conditions. For example, if the maximum difference between conditions 1 and 2 is small, the desirable fluidity of the hydraulic composition is maintained regardless of the elapsed spraying time or waiting time, and therefore it can be said that the additive for hydraulic compositions provides a hydraulic composition with excellent pumpability.

[0141] [Table 4]

[0142] Note 1: In Tables 1-4, the content (% × C) of additives for hydraulic compositions and dispersants for hydraulic compositions represents the actual content (mass %) relative to the cement (C) contained in the hydraulic composition.

[0143] <Changes in polydispersity over time> For component (A), polyethylene oxide (E-30, weight-average molecular weight 400,000-550,000, Lot. 51882), an accelerated storage test was conducted using a constant-temperature dryer (10g stored in a 200mL container at 60°C, stored for 1 month in a ventilated environment without sealing). The results are shown in Table 5, A'-5. Table 5, A-4 shows the same Lot number (Lot. 51882) polyethylene oxide (E-30, weight-average molecular weight 400,000-550,000) stored at room temperature for 1 month.

[0144] [Table 5]

[0145] The results in Table 5 show that the polydispersity of component (A) changes over time, indicating that the polydispersity of component (A) can vary depending on storage conditions, even for samples with the same manufacturing lot number.

Claims

1. (A) An additive for hydraulic compositions containing a polyalkylene oxide having a polydispersity (Mw / Mn) of 1.00 or more and 2.55 or less.

2. (B) Additive for hydraulic composition according to claim 1, comprising an antioxidant.

3. The additive for hydraulic compositions according to claim 2, wherein the mass ratio of the content of component (B) to the content of component (A) [(B) / (A)] is 0.0001 or more and 0.01 or less.

4. The additive for hydraulic compositions according to claim 1 or 2, wherein the weight-average molecular weight of component (A) is 200,000 or more and 2,000,000 or less.

5. The additive for hydraulic compositions according to claim 1 or 2, wherein component (A) is in powder or granular form.

6. An additive for a hydraulic composition according to claim 1 or 2, which is for spray application.

7. A hydraulic composition containing the additive for hydraulic compositions described in claim 1 or 2.

8. The hydraulic composition according to claim 7, wherein the hydraulic composition contains 0.0008% by mass or more and 0.5% by mass or less of the additive for the hydraulic composition.

9. The hydraulic composition according to claim 7, comprising an aluminosilicate.

10. (C) A water-soluble polymer [excluding those corresponding to component (A)], the hydraulic composition according to claim 7.

11. The hydraulic composition according to claim 7, for use in spraying.

12. A method for producing a hydraulic composition, comprising mixing the additive for hydraulic compositions described in claim 1 or 2 with a hydraulic powder.

13. A method for producing a hydraulic composition according to claim 12, comprising the step of confirming the polydispersity of component (A) contained in the additive before mixing the additive for the hydraulic composition.

14. A spraying method comprising mixing the additive for hydraulic composition according to claim 1 or 2, hydraulic powder, and water, and spraying the mixture onto an object.

15. (A) Use as an additive for hydraulic compositions of polyalkylene oxide having a polydispersity (Mw / Mn) of 1.00 or more and 2.55 or less.

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