Admixture for hydraulic compositions

Abstract

The present invention provides an admixture for hydraulic compositions that enables a reduction in the mixing time required to obtain a predetermined fluidity of the hydraulic composition, and a hydraulic composition that enables a reduction in the mixing time required to obtain a predetermined fluidity. [Solution] An admixture for hydraulic compositions containing the following components (A) and (B). (A) Component: A formaldehyde condensation polymer comprising a monomer unit (a1) having a polyalkylene oxy group on the aromatic ring, a monomer unit (a2) having a carboxylic acid group and / or a salt thereof on the aromatic ring, or a monomer unit (a3) ​​having a phosphate group and / or a salt thereof on the aromatic ring. (B) Components: One or more selected from the following components (B1) and (B2). (B1) Components: One or more selected from alkyl or alkenyl sulfates, polyoxyalkylene alkyl or alkenyl ether sulfates, and salts thereof. (B2) Ingredients: Rosin acid and / or its salt

Description

[Technical Field]

[0001] This invention relates to an admixture for hydraulic compositions and hydraulic compositions. [Background technology]

[0002] Centrifugal molding is a known method for manufacturing hollow cylindrical concrete molded products such as pipes, piles, and poles. In this method, mixed concrete material is poured into a mold, and the mold is rotated at high speed. The resulting centrifugal force compacts the concrete against the inner surface of the mold. Molded products manufactured by these methods are supported by the hard ground underground and play an important role in supporting buildings.

[0003] Patent Document 1 discloses a dispersant composition for hydraulic compositions, comprising (A) a polymer having monomer units having a group selected from a carboxylic acid group and a phosphate group, and monomer units having a polyalkylene oxy group, with a weight-average molecular weight of 1,000 to 1,000,000 (excluding component (B) below), and (B) a polymer having monomer units having a polyalkylene oxy group with an average number of added moles of alkylene oxy groups of 5 to 300, and an aromatic ring, and that a hydraulic composition with excellent initial fluidity can be obtained using the said dispersant composition for hydraulic compositions. Patent Document 2 discloses a polycondensate comprising the following (I) to (III): (I) at least one structural unit, the structural unit being an aromatic moiety having a polyether side chain having 9 to 41 alkylene glycol units; (II) at least one structural unit, the structural unit being an aromatic moiety having at least one phosphate ester group; and (III) at least one methylene unit (-CH2-). The use of the polycondensate as a building material mixture containing the polycondensate, and as a dispersant for inorganic binders, is also disclosed. Patent Document 3 discloses an admixture for centrifugal-molded concrete comprising a polycondensate having at least one structural unit (I), at least one structural unit (II), and at least one structural unit (III), wherein structural unit (I) is an aromatic moiety having a polyether side chain having a specific number and type of alkylene glycol units, and an aromatic moiety having at least one phosphate ester group and / or a salt thereof which is structural unit (II) in a specific ratio to structural unit (I), and structural unit (III) is at least one methylene unit (-CH2-), the methylene unit being bonded to two aromatic structural units, structural unit (I) and structural unit (II), and having a specific weight-average molecular weight, and discloses that by using the admixture for centrifugal-molded concrete, the reduction in strength of the inner portion of the concrete is suppressed, the molding time is reduced, and integral deformation is obtained. Patent Document 4 discloses a hydraulic composition for centrifugal molding, comprising (A) a dispersant for hydraulic powders consisting of a polymer compound containing an aromatic ring, and (B) one or more compounds selected from specific compounds represented by general formulas (B1) to (B4), hydraulic powder, aggregate, and water, wherein the water / hydraulic powder ratio is greater than 25% by mass and less than or equal to 35% by mass. It is also disclosed that by using the hydraulic composition for centrifugal molding, the hardened product produced by centrifugal molding has high strength and excellent moldability. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-75840 [Patent Document 2] Special Publication No. 2017-502140 [Patent Document 3] Japanese Patent Publication No. 2019-112251 [Patent Document 4] Japanese Patent Publication No. 2018-48068 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In recent years, there has been a trend towards increasing the strength of concrete piles due to the increasing height of buildings and the need for higher bearing capacity to shorten construction periods. To improve the strength of concrete, it is effective to reduce the ratio of water to hydraulic powder (water / hydraulic powder), but this results in a longer mixing time to obtain the required fluidity, so there is a demand for shortening the mixing time. To shorten the mixing time, it is effective to increase the amount of cement dispersant added to the aqueous composition, but this results in increased fluidity during centrifugal molding, causing slag and honeycombing, and resulting in an uneven distribution of materials such as cement, water, and aggregate. In addition, the compressive strength of the centrifugal-molded concrete fluctuates, and the smoothness of the inner surface of the pile may decrease due to the slag, which can result in resistance when installing it in the ground and reduce workability. Therefore, the inventors have found that it is necessary to investigate means that can shorten the mixing time without changing the fluidity of fresh concrete during centrifugal molding.

[0006] The present invention provides an admixture for hydraulic compositions that enables a reduction in the mixing time required to obtain a predetermined fluidity of the hydraulic composition, and a hydraulic composition that enables a reduction in the mixing time required to obtain a predetermined fluidity. [Means for solving the problem]

[0007] The present invention relates to an admixture for hydraulic compositions containing the following components (A) and (B). (A) Component: A formaldehyde condensation polymer comprising a monomer unit (a1) having a polyalkylene oxy group on the aromatic ring, a monomer unit (a2) having a carboxylic acid group and / or a salt thereof on the aromatic ring, or a monomer unit (a3) ​​having a phosphate group and / or a salt thereof on the aromatic ring. (B) Components: One or more selected from the following components (B1) and (B2). (B1) Components: One or more selected from alkyl or alkenyl sulfates, polyoxyalkylene alkyl or alkenyl ether sulfates, and salts thereof. (B2) Ingredients: Rosin acid and / or its salt

[0008] The present invention also relates to a hydraulic composition containing component (A), component (B), hydraulic powder, and water. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide an admixture for hydraulic compositions that enables a reduction in the mixing time required to obtain a predetermined fluidity of the hydraulic composition, and a hydraulic composition that enables a reduction in the mixing time required to obtain a predetermined fluidity.

[0010] The hydraulic composition admixture and hydraulic composition of the present invention allow for a reduction in mixing time (for example, from 6 minutes to 3 minutes), and exhibit excellent fluidity even with a reduced mixing time. This reduces the time required for mixing and molding, thereby improving productivity. Furthermore, after a certain period of time has elapsed since mixing, the hydraulic composition admixture and hydraulic composition of the present invention exhibit no change in fluidity compared to a hydraulic composition that does not contain the hydraulic composition admixture of the present invention. For example, during centrifugal molding after molding the hydraulic composition of the present invention into a mold, no slag is generated, and a hydraulic composition hardened body with a good finish can be obtained. Moreover, because the hydraulic composition admixture of the present invention exhibits excellent fluidity even with a reduced mixing time, a hydraulic composition hardened body with a good finish can be obtained without the occurrence of unfilled areas (honeycombs) in the hardened body molded by centrifugal force. [Modes for carrying out the invention]

[0011] The reason why the admixture for hydraulic compositions and hydraulic compositions of the present invention enable a reduction in mixing time is not entirely clear, but we surmise the following. When water is added to a hydraulic powder, the hydraulic powder forms secondary particles while retaining water internally. However, the presence of component (A) causes these secondary particles to become primary particles, releasing the internal water from the system, thus kneading the hydraulic composition and achieving a certain degree of fluidity. However, in the case of hydraulic compositions with a small water / hydraulic powder ratio, the initial unit amount of water is small, so it takes time for the internal water to be released from the system. Therefore, it is important to promote the spread of water on the surface of the secondary particles, and as a result, it is expected that the kneading time can be shortened. We believe that specific surfactants and resins of component (B) are effective in promoting the spread of water on the surface of secondary particles. This is because when component (B) dissolves in water at the solid-liquid interface, the surface tension of water and the interfacial tension of the solid-liquid decrease, promoting the wetting of the liquid on the solid surface. Therefore, in this invention, by using component (B) and component (A) in combination, component (B) promotes wetting on the surface of secondary particles, making it easier for water to spread. As a result, the adsorption rate of component (A) contained in water to the surface of secondary particles improves, and it is thought that the mixing time of the hydraulic composition can be shortened. However, the present invention is not limited to the estimation mechanism described above.

[0012] [Admixture for hydraulic compositions] <(A) component> The admixture for hydraulic compositions of the present invention contains the following component (A). (A) Component: A formaldehyde condensation polymer comprising a monomer unit (a1) having a polyalkylene oxy group on the aromatic ring, a monomer unit (a2) having a carboxylic acid group and / or a salt thereof on the aromatic ring, or a monomer unit (a3) ​​having a phosphate group and / or a salt thereof on the aromatic ring. Here, "monomer unit" refers to a "repeating unit" in a polymer.

[0013] Examples of monomer units (a1) include monomer units obtained from one or more compounds selected from benzene compounds having a polyalkylene oxy group and which may have substituents other than the polyalkylene oxy group, and naphthalene compounds having a polyalkylene oxide group and which may have substituents other than the polyalkylene oxy group. A monomer unit obtained from a benzene compound having a polyalkylene oxy group and which may have substituents other than the polyalkylene oxy group is preferred. Other substituents besides the polyalkylene oxy group include one or more selected from alkyl groups having 1 to 4 carbon atoms, alkenyl groups having 2 to 4 carbon atoms, hydroxyl groups, and halogeno groups.

[0014] In the monomer unit (a1), the alkylene oxy group is preferably an alkylene oxy group having 2 to 3 carbon atoms, and more preferably an ethylene oxy group. In monomer units (a1), the average number of added moles of alkylene oxy groups is preferably 5 or more, more preferably 8 or more, even more preferably 10 or more, even more preferably 15 or more, and preferably 300 or less, more preferably 200 or less, even more preferably 100 or less, even more preferably 75 or less, and even more preferably 50 or less, from the viewpoint of the dispersibility of the hydraulic composition.

[0015] From the viewpoint of the dispersibility of the hydraulic composition, monomer units (a1) are preferably monomer units obtained from compounds represented by the following general formula (a1).

[0016] [ka]

[0017] [In the formula, AO is an alkylene oxy group, and m is the average number of added moles of alkylene oxy groups, which is between 5 and 300. Y 1 is any substituent on the benzene ring, and is one or more selected from alkyl groups having 1 to 4 carbon atoms, alkenyl groups having 2 to 4 carbon atoms, hydroxyl groups, and halogeno groups.

[0018] In general formula (a1), AO is preferably an alkylene oxy group having 2 to 3 carbon atoms, and more preferably an ethylene oxy group. In general formula (a1), m is 5 or more, preferably 8 or more, more preferably 10 or more, even more preferably 15 or more, and 300 or less, preferably 200 or less, more preferably 100 or less, even more preferably 75 or less, and even more preferably 50 or less, from the viewpoint of the dispersibility of the hydraulic composition. In general formula (a1), Y 1 If Y 1 It is preferably one or more alkyl groups with 1 to 4 carbon atoms, and more preferably alkyl groups with 1 to 2 carbon atoms. 1 It is not necessary to have it.

[0019] Monomer unit (a1) can be obtained from one or more compounds selected from polyoxyalkylene phenyl ethers and polyoxyalkylene naphthyl ethers. Specifically, the raw material compounds for monomer unit (a1) are compounds obtained by adding an average of 5 to 300 moles of alkylene oxy groups to phenol, cresol, nonylphenol, naphthalene, methylnaphthalene, butylnaphthalene, bisphenol, etc.

[0020] Aromatic compounds having a carboxylic acid group and / or a salt thereof in a monomer unit (a2) include monomer units obtained from one or more compounds selected from benzene compounds having a carboxylic acid group and / or a salt thereof and which may have substituents other than a carboxylic acid group and / or a salt thereof, and naphthalene compounds having a carboxylic acid group and / or a salt thereof and which may have substituents other than a carboxylic acid group and / or a salt thereof, with monomer units obtained from benzene compounds having a carboxylic acid group and / or a salt thereof and which may have substituents other than a carboxylic acid group and / or a salt thereof being preferred. A carboxylate group and / or its salt is a group selected from carboxylate groups and carboxylate groups that are salts, and includes carboxylate groups that have formed an anhydride with other carboxylate groups. Examples of substituents other than a carboxylic acid group and / or its salt include one or more selected from an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a hydroxyl group, and a halogeno group.

[0021] From the viewpoint of the dispersibility of the hydraulic composition, the monomer unit (a2) is preferably a monomer unit obtained from a compound represented by the following general formula (a2).

[0022] [Chemical formula]

[0023] [In the formula, Z 1 is a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, an alkylammonium group or a substituted alkylammonium group. Y 2 is an arbitrary substituent of the benzene ring and is one or more selected from an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a hydroxyl group, and a halogeno group. ]

[0024] In the general formula (a2), Z 1 is preferably a hydrogen atom or an alkali metal, more preferably a hydrogen atom. In the general formula (a2), when Y 2 is present, Y 2 is preferably one or more selected from a hydroxyl group and an alkyl group having from 1 to 20 carbon atoms, more preferably a hydroxyl group. Also, Y 2 does not necessarily have to be present.

[0025] The monomer unit (a2) includes monomer units obtained from one or more compounds selected from benzene or naphthalene derivatives, specifically, hydroxybenzoic acid, benzoic acid, isophthalic acid, oxynaphthoic acid, isomers thereof, and salts thereof. From the viewpoint of the dispersibility of the hydraulic composition, monomer units obtained from one or more compounds selected from hydroxybenzoic acid, benzoic acid, and salts thereof are preferred, and monomer units obtained from hydroxybenzoic acid are more preferred.

[0026] Aromatic compounds having a phosphate group and / or a salt thereof in the monomer unit (a3) ​​include monomer units obtained from one or more compounds selected from benzene compounds having a phosphate group and / or a salt thereof and which may have substituents other than the phosphate group and / or a salt thereof, and naphthalene compounds having a phosphate group and / or a salt thereof and which may have substituents other than the phosphate group and / or a salt thereof, with monomer units obtained from benzene compounds having a phosphate group and / or a salt thereof and which may have substituents other than the phosphate group and / or a salt thereof being preferred. Phosphate groups and / or salts thereof include those formed by the dehydration condensation of phosphate groups with other phosphate groups. Other substituents besides phosphate groups and / or salts thereof include one or more selected from alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 4 carbon atoms, hydroxyl groups, and halogeno groups. The phosphate group and / or its salt may coordinate as a substituent to the aromatic compound, or it may be a phosphate ester or phosphate diester of an aromatic alcohol.

[0027] The monomer unit (a3) ​​is benzene or naphthalene derivatives, specifically phenylphosphonic acid, phenylphosphinic acid, naphthylphosphonic acid, naphthylphosphinic acid, phenyl phosphate (mono-, di-, or triesters, or mixtures thereof), phenoxyethanol phosphate (mono-, di-, or triesters, or mixtures thereof), phenoxydiglycol phosphate (mono-, di-, or triesters, or mixtures thereof), phenoxy(poly)alkylene glycol phosphate (mono-, di-, or triesters, Examples include monomer units obtained from one or more compounds selected from phenoxyethanol phosphate (mono-, di-, or triesters, or mixtures thereof), naphthol phosphate (mono-, di-, or triesters, or mixtures thereof), isomers thereof, and salts thereof. From the viewpoint of dispersibility of the hydraulic composition, monomer units obtained from one or more compounds selected from phenoxyethanol phosphate (mono-, di-, or triesters, or mixtures thereof) and salts thereof are preferred.

[0028] Component (A) may have other polymerizable monomers in addition to monomer units (a1), monomer units (a2), and monomer units (a3), as long as the effects of the present invention are not impaired. Examples of monomer units other than monomer units (a1), monomer units (a2), and monomer units (a3) ​​include monomer units obtained from alkylphenols such as phenol and cresol, benzene or naphthalene derivatives, specifically benzenesulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, alkylnaphthalenesulfonic acid, naphtholsulfonic acid, and monomer units obtained from compounds.

[0029] When component (A) contains monomer units (a1) and monomer units (a2), the molar ratio (a1) / (a2) of monomer units (a1) to monomer units (a2) in component (A) is preferably 5 / 95 or more, more preferably 10 / 90 or more, even more preferably 15 / 85 or more, and preferably 50 / 50 or less, more preferably 40 / 60 or less, and even more preferably 30 / 70 or less, from the viewpoint of the dispersibility of the hydraulic composition. The molar ratio (a1) / (a2) of monomer units (a1) in component (A) may be calculated from the charging ratio of the raw material compound that becomes monomer unit (a1) and the raw material compound that becomes monomer unit (a2) when producing component (A).

[0030] When component (A) contains monomer units (a1) and monomer units (a3), the molar ratio (a1) / (a3) of monomer units (a1) to monomer units (a3) ​​in component (A) is preferably 5 / 95 or more, more preferably 10 / 90 or more, even more preferably 20 / 80 or more, even more preferably 30 / 70 or more, even more preferably 40 / 60 or more, and preferably 65 / 35 or less, more preferably 60 / 40 or less, and even more preferably 55 / 45 or less. The molar ratio (a1) / (a3) of monomer units (a1) to monomer units (a3) ​​in component (A) may be calculated from the charging ratio of the raw material compound that becomes monomer unit (a1) and the raw material compound that becomes monomer unit (a3) ​​when producing component (A).

[0031] If component (A) contains monomer units (a1) and monomer units (a2), the total amount of monomer units (a1) and monomer units (a2) in the total constituent monomer units of component (A) is 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, and 100 mol% or less. This total amount may be 100 mol%. The total amount of monomer units (a1) and monomer units (a2) in the total constituent monomer units of component (A) shall be calculated assuming that the constituent monomer units of component (A) do not contain formaldehyde used in the condensation polymerization reaction.

[0032] If component (A) contains monomer units (a1) and monomer units (a3), the total amount of monomer units (a1) and monomer units (a3) ​​in the total constituent monomer units of component (A) is 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, and 100 mol% or less. This total amount may be 100 mol%. The total amount of monomer units (a1) and monomer units (a3) ​​in the total constituent monomer units of component (A) shall be calculated assuming that the constituent monomer units of component (A) do not contain formaldehyde used in the condensation polymerization reaction.

[0033] The weight-average molecular weight of component (A) is preferably 5,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, and preferably 150,000 or less, more preferably 100,000 or less, even more preferably 50,000 or less, even more preferably 30,000 or less, and even more preferably 20,000 or less, from the viewpoint of the dispersibility of the hydraulic composition. This weight-average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions. *GPC conditions Equipment: GPC (HLC-8320GPC), manufactured by Tosoh Corporation. Columns: G4000SWXL + G2000SWXL + Guard Column SWXL (manufactured by Tosoh Corporation) Eluent: 30mM CH3COONa / CH3CN=6 / 4 Flow rate: 0.7mL / min Column temperature: Room temperature Detection: RI Sample size: 0.2 mg / mL Standard substances: Polyethylene glycol equivalent (monodisperse polyethylene glycols with known molecular weights: 250,000, 145,000, 87,500, 46,000, 24,000)

[0034] <(B) component> The admixture for hydraulic compositions of the present invention contains the following component (B). (B) Components: One or more selected from the following components (B1) and (B2). (B1) Components: One or more selected from alkyl or alkenyl sulfates, polyoxyalkylene alkyl or alkenyl ether sulfates, and salts thereof. (B2) Ingredients: Rosin acid and / or its salt

[0035] From the viewpoint of shortening the mixing time of the hydraulic composition, component (B1) is preferably a compound represented by the following general formula (B1). R 1b -O-(AO) t -SO3 M 1b (B1) [In the formula, R 1b is a straight-chain aliphatic hydrocarbon group with 8 to 18 carbon atoms, AO is an alkylene oxy group with 2 to 4 carbon atoms, and t is the average number of moles of AO added, which is between 0 and 30. 1b This represents a hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), ammonium, or organic ammonium.

[0036] In general formula (B1), R 1b From the viewpoint of shortening the mixing time by improving fluidity after, for example, 3 to 6 minutes from the mixing of the hydraulic composition, the linear aliphatic hydrocarbon group, preferably a linear alkyl group, has 8 or more carbon atoms, preferably 10 or more, and 18 or less, preferably 16 or less, more preferably 14 or less, and even more preferably 12 or less. In general formula (B1), AO is preferably a group selected from an ethyleneoxy group and a propyleneoxy group, and more preferably an ethyleneoxy group, from the viewpoint of shortening the mixing time by improving fluidity after, for example, 3 to 6 minutes from the mixing of the hydraulic composition. In general formula (B1), t is a number that is 0 or greater, and 30 or less, preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, even more preferably 5 or less, and even more preferably 3 or less, from the viewpoint of shortening the mixing time by improving fluidity after, for example, 3 to 6 minutes from the mixing of the hydraulic composition. In general formula (B1), M 1bThe element is preferably a hydrogen atom, an alkali metal such as sodium or potassium, an alkaline earth metal (half an atom) such as magnesium or calcium, ammonium, or an organic ammonium. 1b The element is preferably an alkali metal such as sodium or potassium, or an alkanol ammonium such as monoethanolammonium, diethanolammonium, or triethanolamine, and more preferably sodium.

[0037] (B2) Examples of rosin acid in component (B2) include natural rosins such as gum rosin, tall oil rosin, and wood rosin; various modified rosins such as disproportionated rosin, hydrogenated rosin, dehydrogenated rosin, polymerized rosin, and α,β-ethylenically unsaturated carboxylic acid modified rosin; purified products of the aforementioned natural rosin; and purified products of the aforementioned modified rosin. One or more of these may be used. Natural rosin usually contains multiple resin acids, one or more of which are selected from pimaric acid, sandaracopimalic acid, palastric acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimalic acid, dihydroabietic acid, and tetrahydroabietic acid. Furthermore, examples of unsaturated carboxylic acids used in the preparation of the α,β-ethylenically unsaturated carboxylic acid-modified rosin include one or more selected from maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, acrylic acid, and methacrylic acid. The rosinate of component (B2) can be one or more selected from sodium rosinate, potassium rosinate, and magnesium rosinate. The rosinate of component (B2) is a reaction product of rosin acid and a metal compound, and component (B2) includes both a mixture of the rosinate and unreacted rosin acid, and a rosinate that does not contain unreacted rosin acid. Examples of metal compounds that react with rosin acid to form a salt include compounds that have metal elements such as sodium, potassium, and magnesium and that form a salt with rosin acid, and specifically include chlorides, nitrates, acetates, sulfates, carbonates, and hydroxides of the said metals.

[0038] Component (B2) is preferably one or more selected from pimaric acid, abietic acid, palastic acid, isopimaric acid, and salts thereof, from the viewpoint of shortening the mixing time by improving fluidity, for example, 3 to 6 minutes after mixing the hydraulic composition, and more preferably one or more selected from abietic acid, palastic acid, and salts thereof.

[0039] <Composition, etc.> In the admixture for hydraulic compositions of the present invention, the content of component (A) is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of the initial dispersibility of the hydraulic composition.

[0040] In the admixture for hydraulic compositions of the present invention, the content of component (B) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and even more preferably 1.0% by mass or less, from the viewpoint of shortening the mixing time by improving fluidity after, for example, 3 to 6 minutes from the mixing of the hydraulic composition. In the present invention, if component (B) includes component (B1), the mass of component (B1) shall be the value obtained by converting it to a sodium salt.

[0041] In the hydraulic composition admixture of the present invention, when component (B1) is included as component (B), the content of component (B1) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and even more preferably 1.0% by mass or less, from the viewpoint of shortening the mixing time by improving fluidity after, for example, 3 to 6 minutes from the mixing of the hydraulic composition.

[0042] In the admixture for hydraulic compositions of the present invention, when component (B2) is included as component (B), the content of component (B2) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and even more preferably 1.0% by mass or less, from the viewpoint of shortening the mixing time by improving fluidity after, for example, 3 to 6 minutes from the mixing of the hydraulic composition.

[0043] In the admixture for hydraulic compositions of the present invention, the mass ratio (B) / (A) of the content of component (A) to the content of component (B) is preferably 0.0005 or more, more preferably 0.001 or more, even more preferably 0.0015 or more, even more preferably 0.0030 or more, even more preferably 0.0045 or more, and preferably 0.0100 or less, more preferably 0.0095 or less, and even more preferably 0.0090 or less.

[0044] From the viewpoint of improving the fluidity of the hydraulic composition and reducing the amount of the hydraulic composition admixture used in the hydraulic composition, the admixture for hydraulic compositions of the present invention preferably further contains the following component (C). (C) Component: Polycarboxylic acid-based dispersant

[0045] Component (C) is preferably a copolymer containing monomer (c1) represented by the following general formula (c1) and monomer (c2) represented by the following general formula (c2) as constituent monomers, from the viewpoint of the dispersibility of the hydraulic composition.

[0046] [ka]

[0047] [During the ceremony, R 1c , R 2c , R 3c : They may be the same or different, and may be a hydrogen atom, a methyl group, or (CH2) r COOM2 (CH2) r COOM 2 COOM 1 or other (CH2) r COOM 2 They may also form anhydrous compounds, in which case the M of those groups 1 M 2 It does not exist. M 1 M 2 : They may be the same or different, and include hydrogen atoms, alkali metals, alkaline earth metals (1 / 2 atom), ammonium groups, alkylammonium groups, substituted alkylammonium groups, alkyl groups, hydroalkyl groups, or alkenyl groups. r: A number between 0 and 2 (inclusive) This indicates...

[0048] [ka]

[0049] [During the ceremony, R 4c , R 5c , R 6c : They may be the same or different, hydrogen atom, methyl group, (CH2) s COOM 3 , or (CH2) q1 (CO) p1 O(AO) n1 -R 7c R 7c : Hydrogen atom or alkyl group having 1 to 4 carbon atoms AO: Alkylene oxy group with 2 to 4 carbon atoms n1: The average number of moles added to AO, a number between 4 and 200. q1: A number between 0 and 2 (inclusive) p1:0 or 1 M 3 : Hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroalkyl group or alkenyl group s: A number between 0 and 2 (inclusive) This indicates...

[0050] In general formula (c1), from the standpoint of availability, R 1c A hydrogen atom is preferred. In general formula (c1), R 2c The atom is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. In general formula (c1), from the standpoint of availability, R 3c A hydrogen atom is preferred. (CH2) r COOM 2 Regarding COOM 1 or other (CH2) r COOM 2 They may also form anhydrous compounds, in which case the M of those groups 1 M 2 It does not exist. M 1 and M 2 These may be the same or different, and are a hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroalkyl group, or alkenyl group. M 1 M 2 The alkyl group, hydroalkyl group, and alkenyl group each preferably have 1 to 4 carbon atoms. M 1 and M 2 These may be the same or different, and are preferably a hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), ammonium group, or alkylammonium group; more preferably a hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), or ammonium group; even more preferably a hydrogen atom, alkali metal, or alkaline earth metal (1 / 2 atom); and even more preferably a hydrogen atom or alkali metal. (CH2) in general formula (c1) r COOM 2 r is preferably 0.

[0051] In general formula (c2), R 4cFrom the standpoint of availability, hydrogen atoms are preferred. In general formula (c2), R 5c From the viewpoint of availability and copolymerizability with monomer (c1), a hydrogen atom or a methyl group is preferred, and a methyl group is more preferred. In general formula (c2), R 6c From the standpoint of availability, hydrogen atoms are preferred. In general formula (c2), R 7c From the viewpoint of ease of manufacture and the quality stability of the product, a hydrogen atom or a methyl group is preferred, and a methyl group is more preferred. In general formula (c2), AO is preferably a group selected from ethyleneoxy and propyleneoxy groups, and more preferably an ethyleneoxy group, from the viewpoint of dispersibility of the hydraulic composition. AO preferably contains an ethyleneoxy group. In general formula (c2), n1 is the average number of moles of AO added, and from the viewpoint of the dispersibility of the hydraulic composition, it is preferably 4 or more, more preferably 20 or more, even more preferably 40 or more, even more preferably 50 or more, even more preferably 60 or more, and preferably 200 or less, more preferably 150 or less, even more preferably 120 or less, even more preferably 100 or less, and even more preferably 80 or less. In general formula (c2), from the viewpoint of availability, q1 is preferably 0, 1, or 2, more preferably 0 or 1, and even more preferably 0. In general formula (c2), from the viewpoint of the dispersibility of the hydraulic composition and copolymerizability with monomer (c1), p1 is preferably 0 or 1, and more preferably 1. In general formula (c2), M 3 These are a hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroalkyl group, or alkenyl group. M 3 The alkyl group, hydroalkyl group, and alkenyl group each preferably have 1 to 4 carbon atoms. M 3The component is preferably a hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), ammonium group, or alkylammonium group; more preferably a hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), or ammonium group; even more preferably a hydrogen atom, alkali metal, or alkaline earth metal (1 / 2 atom); and even more preferably a hydrogen atom or alkali metal. In the general formula (c2), of (CH2) s COOM 3 s is preferably 0.

[0052] In general formula (c2), when p1 is 1, n1 is 4 or more, more preferably 20 or more, and 60 or less, preferably 40 or less, and the monomer (c1) is preferably methacrylic acid. In general formula (c2), when p1 is 0, n1 is 20 or more, preferably 45 or more, and 100 or less, preferably 80 or less, and the monomer (c1) is preferably acrylic acid.

[0053] (C) In the total constituent monomers of component (C), the proportion of monomer (c1) in the total amount of monomer (c1) and monomer (c2) is preferably 60 mol% or more, more preferably 65 mol% or more, even more preferably 70 mol% or more, and preferably 95 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less. In the present invention, the proportion of these constituent monomers in the total constituent monomers of component (C) can be calculated from the amount (molar ratio) of the constituent monomers used as raw materials.

[0054] (C) Of the total constituent monomers of component (C), the proportion of monomer (c1) is preferably 60 mol% or more, more preferably 65 mol% or more, even more preferably 70 mol% or more, and preferably 95 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less.

[0055] (C) Of the total constituent monomers of component (C), the total amount of monomer (c1) and monomer (c2) is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and preferably 100 mol% or less, from the viewpoint of the dispersibility of the hydraulic composition. This total amount may be 100 mol%.

[0056] The copolymer of component (C) may optionally contain one or more monomers (c3) that are copolymerizable with monomer (c1) and / or monomer (c2), in addition to monomer (c1) and monomer (c2). Examples of monomer (c3) include acrylic acid esters. The copolymer of (c1) may have a total of 100 mol% of monomers (c1) and monomer (c2), or a total of monomers (c1), monomer (c2), and monomer (c3) in all constituent monomers.

[0057] (C) The weight-average molecular weight of component (C) is preferably 20,000 or more, more preferably 30,000 or more, even more preferably 40,000 or more, and preferably 100,000 or less, more preferably 80,000 or less, even more preferably 70,000 or less, and even more preferably 60,000 or less, from the viewpoint of the dispersibility of the hydraulic composition.

[0058] The weight-average molecular weight of component (C) was measured by gel permeation chromatography (GPC) under the following conditions. *GPC conditions Equipment: GPC (HLC-8320GPC), manufactured by Tosoh Corporation. Columns: G4000PWXL + G2500PWXL (manufactured by Tosoh Corporation) Eluent: 0.2M phosphate buffer / CH3CN=9 / 1 Flow rate: 1.0mL / min Column temperature: 40℃ Detection: RI Sample size: 0.2 mg / mL Standard substances: Polyethylene glycol equivalent (monodisperse polyethylene glycols with known molecular weights: 250,000, 145,000, 87,500, 46,000, 24,000)

[0059] Note that component (C) is a copolymer only and may be added directly to the admixture for aqueous compositions of the present invention, or it may be added together with a suitable solvent (or dispersion medium). Water is preferred as the solvent (or dispersion medium), and it is preferable for convenience to add component (C) together with water to the admixture for hydraulic compositions of the present invention. When adding as an aqueous solution (or aqueous dispersion), it is necessary to add these amounts of water to the water essential for the admixture for aqueous compositions of the present invention, but this can be ignored if the concentration of the aqueous solution (or aqueous dispersion) is high or the amount added is small.

[0060] In the present invention, when the admixture for hydraulic compositions contains component (C), the content of component (C) is preferably 2.5% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, from the viewpoint of the dispersibility of the hydraulic composition.

[0061] The admixture for hydraulic compositions of the present invention may contain water for ease of manufacture. In the present invention, when water is included in the admixture for hydraulic compositions, the water content is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less, from the viewpoint of ease of manufacture.

[0062] The admixture for hydraulic compositions of the present invention may contain components such as water-soluble polymer compounds, cement wetting agents, expansive agents, waterproofing agents, retarders, quick-setting agents, thickeners, flocculants, drying shrinkage reducing agents, strength enhancers, hardening accelerators, preservatives, and defoaming agents, to the extent that they do not impair the effects of the present invention (however, excluding those corresponding to components (A), (B), and (C)).

[0063] The hydraulic composition admixture of the present invention, when incorporated into a hydraulic composition, can shorten the mixing time (for example, from 6 minutes to 3 minutes), thereby reducing the time required for mixing and molding, and improving productivity. Furthermore, after a certain period of time has elapsed since mixing, the fluidity of the hydraulic composition remains unchanged compared to a hydraulic composition that does not contain the hydraulic composition admixture of the present invention. As a result, no slag is generated during centrifugal molding after the hydraulic composition is molded, and a hydraulic composition hardened body with a good finish can be obtained. Therefore, the hydraulic composition admixture of the present invention can be suitably used in hydraulic compositions for centrifugal molding. Furthermore, the admixture for hydraulic compositions of the present invention can also provide the above-mentioned effects in hydraulic compositions for solid mixing, where the proportion of water is low in order to obtain a high-strength hardened body. Therefore, the admixture for hydraulic compositions of the present invention can be suitably used in hydraulic compositions for solid mixing. In the present invention, a hydraulic composition for solid mixing is defined as a hydraulic composition having a slump of 0 cm or more and 6 cm or less using a slump cone as described in JIS A1171, and a mass % of the water (W) content relative to the hydraulic powder (P) content in the hydraulic composition (water / hydraulic powder ratio (W / P) × 100) of 15% by mass or more and 25% by mass or less.

[0064] [Method for producing admixtures for hydraulic compositions] The present invention provides a method for producing an admixture for hydraulic compositions, comprising mixing component (A) and component (B). By this method, an admixture for hydraulic compositions of the present invention containing component (A) and component (B) is produced. The method for producing the admixture for hydraulic compositions of the present invention may further involve mixing in component (C). The method for producing the admixture for hydraulic compositions of the present invention may further involve mixing in water. Specific examples and preferred embodiments of components (A), (B), and (C) used in the method for producing the hydraulic admixture of the present invention are the same as those described in the description of the hydraulic admixture of the present invention. The matters described in the present invention concerning the admixture for hydraulic compositions can be appropriately applied to the method for producing the admixture for hydraulic compositions of the present invention. In the method for producing the hydraulic admixture of the present invention, the content and mass ratio of each component described in the hydraulic admixture of the present invention can be appropriately applied by replacing the content of each component with the amount of mixture.

[0065] [Hydraulic composition] The present invention provides a hydraulic composition containing component (A), component (B), hydraulic powder, and water. From the viewpoint of the dispersibility of the hydraulic composition, the hydraulic composition of the present invention preferably further contains component (C). Specific examples and preferred embodiments of components (A) and (B) used in the hydraulic composition of the present invention are the same as those described in the admixture for hydraulic composition of the present invention. The matters described in the admixture for hydraulic compositions and the method for producing the same of the present invention can be appropriately applied to the hydraulic compositions of the present invention.

[0066] <Hydraulic powder> The hydraulic powder used in the hydraulic composition of the present invention is a powder that hardens when mixed with water, and examples include ordinary Portland cement, rapid-hardening Portland cement, ultra-rapid-hardening Portland cement, sulfate-resistant Portland cement, low-heat Portland cement, white Portland cement, and eco-cement (e.g., JIS R5214). Among these, from the viewpoint of strength development, one or more cements selected from rapid-hardening Portland cement, ordinary Portland cement, sulfate-resistant Portland cement, and white Portland cement are preferred, and one or more cements selected from rapid-hardening Portland cement and ordinary Portland cement are more preferred. Furthermore, the hydraulic powder may contain a high-strength admixture. Examples of high-strength admixtures include one or more powders having pozzolanic action and / or latent hydraulic properties such as blast furnace slag, fly ash, anhydrous gypsum, and silica fume, as well as stone powder (calcium carbonate powder) and powders that actively generate calcium silicate hydrate. Hydraulic powders preferably contain powders that actively generate calcium silicate hydrates. As hydraulic powders, blast furnace cement, fly ash cement, or silica fume cement, which are mixtures of cement with blast furnace slag, fly ash, silica fume, etc., may be used. Clay such as bentonite may also be included. The hydraulic compositions finally obtained by adding sand, sand and gravel as aggregates to these powders are generally called mortar, concrete, etc.

[0067] <Aggregates> The hydraulic composition of the present invention may contain aggregate. Examples of aggregate include one or more types of aggregate selected from fine aggregate and coarse aggregate. Examples of fine aggregate include those specified in JIS A0203-2014, number 2311. Examples of fine aggregate include river sand, land sand, mountain sand, sea sand, lime sand, silica sand and their crushed forms, blast furnace slag fine aggregate, ferronickel slag fine aggregate, lightweight fine aggregate (artificial and natural), and recycled fine aggregate. Examples of coarse aggregate include those specified in JIS A0203-2014, number 2312. For example, examples of coarse aggregate include river gravel, land gravel, mountain gravel, sea gravel, lime gravel, their crushed forms, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural), and recycled coarse aggregate. Different types of fine aggregate and coarse aggregate may be mixed, or a single type may be used.

[0068] <Composition, etc.> In the hydraulic composition of the present invention, the content of component (A) is preferably 0.15 parts by mass or more, more preferably 0.20 parts by mass or more, even more preferably 0.30 parts by mass or more, even more preferably 0.40 parts by mass or more, and preferably 3.00 parts by mass or less, more preferably 2.00 parts by mass or less, even more preferably 1.50 parts by mass or less, even more preferably 1.00 parts by mass or less, and even more preferably 0.75 parts by mass or less, per 100 parts by mass of hydraulic powder, from the viewpoint of improving initial dispersibility after, for example, 3 to 6 minutes from kneading and shortening the kneading time.

[0069] In the hydraulic composition of the present invention, the content of component (B) is preferably 0.00025 parts by mass or more, more preferably 0.0005 parts by mass or more, even more preferably 0.001 parts by mass or more, even more preferably 0.0015 parts by mass or more, even more preferably 0.0020 parts by mass or more, and preferably 0.00475 parts by mass or less, more preferably 0.004 parts by mass or less, even more preferably 0.0035 parts by mass or less, and even more preferably 0.0030 parts by mass or less, from the viewpoint of improving initial dispersibility after, for example, 3 to 6 minutes after kneading and shortening the kneading time, per 100 parts by mass of hydraulic powder.

[0070] In the hydraulic composition of the present invention, when component (B1) is included as component (B), the content of component (B1) is preferably 0.00025 parts by mass or more, more preferably 0.0005 parts by mass or more, even more preferably 0.001 parts by mass or more, even more preferably 0.0015 parts by mass or more, even more preferably 0.0020 parts by mass or more, and preferably 0.00475 parts by mass or less, more preferably 0.004 parts by mass or less, even more preferably 0.0035 parts by mass or less, and even more preferably 0.0030 parts by mass or less, from the viewpoint of improving initial dispersibility after, for example, 3 to 6 minutes from kneading and shortening the kneading time, per 100 parts by mass of hydraulic powder.

[0071] In the hydraulic composition of the present invention, when component (B) contains component (B2), the content of component (B2) is preferably 0.00025 parts by mass or more, more preferably 0.0005 parts by mass or more, even more preferably 0.001 parts by mass or more, even more preferably 0.0015 parts by mass or more, even more preferably 0.0020 parts by mass or more, and preferably 0.00475 parts by mass or less, more preferably 0.004 parts by mass or less, even more preferably 0.0035 parts by mass or less, and even more preferably 0.0030 parts by mass or less, from the viewpoint of improving initial dispersibility after, for example, 3 to 6 minutes from kneading and shortening the kneading time, per 100 parts by mass of hydraulic powder.

[0072] In the hydraulic composition of the present invention, the mass ratio (B) / (A) of the content of component (A) to the content of component (B) is preferably 0.0005 or more, more preferably 0.001 or more, even more preferably 0.0015 or more, even more preferably 0.0030 or more, even more preferably 0.0045 or more, and preferably 0.0100 or less, more preferably 0.0095 or less, and even more preferably 0.0090 or less.

[0073] In the hydraulic composition of the present invention, if component (C) is included, the content of component (C) is preferably 0.05 parts by mass or more, more preferably 0.075 parts by mass or more, even more preferably 0.10 parts by mass or more, and preferably 3.0 parts by mass or less, more preferably 2.0 parts by mass or less, even more preferably 1.0 part by mass or less, even more preferably 0.5 parts by mass or less, and even more preferably 0.3 parts by mass or less, from the viewpoint of improving initial dispersibility after, for example, 3 to 6 minutes from kneading and shortening the kneading time, per 100 parts by mass of hydraulic powder.

[0074] In the hydraulic composition of the present invention, the mass % of the water (W) content relative to the hydraulic powder (P) content (water / hydraulic powder ratio (W / P) × 100) is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and preferably 10% by mass or more, more preferably 12% by mass or more, and even more preferably 15% by mass or more, from the viewpoint of compressive strength. Here, the water / hydraulic powder ratio (W / P) is the mass percentage of water (W) relative to the hydraulic powder (P) content in the hydraulic composition, and is calculated as water / hydraulic powder × 100. The water / hydraulic powder ratio is calculated based on the amount of powder that has physical properties that harden through a hydration reaction. Also, if the hydraulic powder is cement, W / P may be expressed as W / C. Furthermore, if the hydraulic powder includes powders selected from those having properties that harden through hydration reactions such as cement, powders having pozzolanic properties, powders having latent hydraulic properties, and stone powder (calcium carbonate powder), then in this invention, the amounts of these powders are also included in the amount of hydraulic powder. In addition, if the powder having properties that harden through hydration reactions contains a high-strength admixture, then the amount of the high-strength admixture is also included in the amount of hydraulic powder. This also applies to other parts of mass related to the mass of the hydraulic powder.

[0075] When the hydraulic composition of the present invention is concrete, the amount of coarse aggregate used is preferably 50% or more, more preferably 55% or more, even more preferably 60% or more, preferably 100% or less, more preferably 90% or less, and even more preferably 80% or less, from the viewpoint of developing the strength of the hydraulic composition, reducing the amount of hydraulic powder such as cement used, and improving the ability to fill into formwork, etc. The bulk volume is 1 m³ of concrete. 3 This is the ratio of the volume of coarse aggregate (including voids) inside. Furthermore, when the hydraulic composition of the present invention is concrete, the amount of fine aggregate used is preferably 500 kg / m³ from the viewpoint of improving the ability to fill into formwork, etc. 3 Above, a comfortable 600 kg / m 3 More preferably 700 kg / m 3 In addition, preferably 1000 kg / m 3 Below, more comfortably 900 kg / m 3 The following applies: When the hydraulic composition of the present invention is mortar, the amount of fine aggregate used is preferably 800 kg / m³. 3 In summary, a comfortable 900 kg / m 3 More preferably 1000 kg / m 3 In addition, preferably 2000 kg / m 3 More preferably, 1800 kg / m 3 More preferably, 1700 kg / m 3 The following applies:

[0076] The hydraulic composition of the present invention may contain components such as water-soluble polymer compounds, cement wetting agents, expansive agents, waterproofing agents, retarders, quick-setting agents, foaming agents, foaming agents, waterproofing agents, fluidizing agents, thickeners, flocculants, drying shrinkage reducing agents, strength enhancers, hardening accelerators, preservatives, and defoaming agents [excluding those corresponding to components (A), (B), and (C)].

[0077] Examples of the hydraulic composition of the present invention include concrete, among others. Concrete using cement is preferred. The hydraulic composition of the present invention is useful in any of the following fields: centrifugal molding, self-leveling, refractories, plasters, lightweight or heavy concrete, AE (air-enhanced concrete), repair, pre-packed concrete, tremie, ground improvement, grouting, and cold weather applications. The hydraulic composition of the present invention allows for a reduction in mixing time (for example, from 6 minutes to 3 minutes), thereby shortening the mixing and molding time and improving productivity. Furthermore, after a certain period of time has elapsed since mixing, the fluidity of the hydraulic composition remains unchanged compared to hydraulic compositions that do not contain components (A) and (B) of the present invention. As a result, no slag or honeycombing occurs during centrifugal molding after the hydraulic composition is molded, and a hydraulic composition hardened body with a good finish can be obtained. Therefore, the hydraulic composition of the present invention can be suitably used for centrifugal molding. Furthermore, the hydraulic composition of the present invention can also provide the above-mentioned effects to the hydraulic composition for solid mixing described above, which has a low water content in order to obtain a high-strength hardened body. For this reason, the hydraulic composition of the present invention can be suitably used in hydraulic compositions for solid mixing.

[0078] [Method for producing hydraulic compositions] The present invention provides a method for producing a hydraulic composition by mixing component (A), component (B), hydraulic powder, and water. By this method, the hydraulic composition of the present invention, containing component (A), component (B), hydraulic powder, and water, is produced. The method for producing the hydraulic composition of the present invention may further involve mixing in component (C). The method for producing the hydraulic composition of the present invention may further involve mixing in aggregate. Specific examples and preferred embodiments of components (A), (B), and (C) used in the method for producing the hydraulic composition of the present invention are the same as those described in the admixture for the hydraulic composition of the present invention, and specific examples and preferred embodiments of the hydraulic powder and aggregate are the same as those described in the hydraulic composition of the present invention. In the method for producing the hydraulic composition of the present invention, the hydraulic powder is mixed such that the mass % of the amount of water (W) relative to the amount of hydraulic powder (P) (water / hydraulic powder ratio (W / P) × 100) falls within the range described in the hydraulic composition of the present invention. The amount of aggregate used (mixing amount) is also within the same range as described in the hydraulic composition of the present invention. In the method for producing the hydraulic composition of the present invention, the content and mass ratio of each component described in the hydraulic composition of the present invention can be appropriately applied by replacing the content of each component with the amount of mixture. The matters described in the present invention concerning the admixture for hydraulic compositions, the method for producing the same, and the hydraulic composition can be appropriately applied to the method for producing the hydraulic composition of the present invention.

[0079] In the method for producing the hydraulic composition of the present invention, from the viewpoint of productivity, it is preferable to pre-mix component (A), component (B), optionally component (C), and water, and then mix them with the hydraulic powder. Furthermore, in the method for producing the hydraulic composition of the present invention, the addition of component (A), component (B), and optionally component (C) is preferably done using the admixture for hydraulic compositions of the present invention, and it is more preferable to pre-mix the admixture for hydraulic compositions of the present invention with water and then mix it with the hydraulic powder.

[0080] The mixing of component (A), component (B), optional component (C), hydraulic powder, optional aggregate, water, and any other components used as needed can be carried out using a mixer such as a mortar mixer or a forced twin-shaft mixer. Furthermore, the mixture is preferably mixed for 1 minute or more, more preferably for 2 minutes or more, and preferably for 6 minutes or less, more preferably for 5 minutes or less. When preparing the hydraulic composition, the materials and agents and their amounts described in the section on hydraulic compositions can be used.

[0081] The hydraulic composition obtained by the above mixing can be further hardened by filling a mold with the hydraulic composition, centrifugal molding, and then curing. Examples of molds include those for buildings and those for concrete products. Methods for filling the mold include directly pouring the composition from a mixer and introducing the hydraulic composition into the mold by pumping it.

[0082] During the curing of hydraulic compositions, heat curing may be performed to accelerate hardening. Here, heat curing can accelerate hardening by holding the hydraulic composition at a temperature of 40°C to 90°C.

[0083] [Method for manufacturing a hardened body of a hydraulic composition] The present invention provides a method for producing a hardened body of a hydraulic composition, comprising the following steps. Step 1: A step in which component (A), component (B), an optional component (C), hydraulic powder, aggregate, and water are mixed to obtain a hydraulic composition, and the obtained hydraulic composition is filled into a mold. Step 2: A step in which the hydraulic composition filled into the mold obtained in Step 1 is clamped by applying centrifugal force. Step 3: A step to solidify the molded hydraulic composition obtained in Step 2 within the mold.

[0084] Specific examples and preferred embodiments of components (A), (B), and (C) used in the method for producing a hardened body of the hydraulic composition of the present invention are the same as those described in the admixture for hydraulic composition of the present invention. Furthermore, specific examples and preferred embodiments of the hydraulic powder and aggregate used in the method for producing the hardened body of the hydraulic composition of the present invention are the same as those described in the hydraulic composition of the present invention. The hydraulic powder is mixed so that the mass % of the amount of water (W) relative to the amount of hydraulic powder (P) (water / hydraulic powder ratio (W / P) × 100) is within the range described in the hydraulic composition of the present invention. The amount of aggregate used (mixing amount) is also within the range described in the hydraulic composition of the present invention. Furthermore, in step 1 of the method for producing a hardened body of the hydraulic composition of the present invention, the content and mass ratio of each component described in the hydraulic composition of the present invention can be appropriately applied by replacing the content of each component with the amount of mixture. The matters described in the admixture for hydraulic compositions and its manufacturing method, as well as the hydraulic composition and its manufacturing method of the present invention, can be appropriately applied to the method for manufacturing a hardened body of the hydraulic composition of the present invention.

[0085] The method for producing the cured product of the present invention preferably includes the following step 4 in addition to steps 1 to 3. Step 4: A step in which the hydraulic composition that has solidified in Step 3 is steam-cured in a mold.

[0086] The method for producing a cured product of the present invention may include the following step 5 in addition to steps 1 to 4. Step 5: After Step 4, the hydraulic composition is cooled and removed from the mold.

[0087] The method for producing a cured product of the present invention may include the following step 6 in addition to steps 1 to 5. Step 6: A step of curing the hardened body of the hydraulic composition obtained in Step 5 at room temperature and pressure.

[0088] In step 1, a method of adding a mixture containing water, component (A), component (B), and an optional component (C) to a mixture containing aggregate and hydraulic powder and mixing is preferred because it allows for easy and uniform mixing even when manufacturing the hydraulic composition. Furthermore, the addition of component (A), component (B), and an optional component (C) is preferably done using the hydraulic composition admixture of the present invention, and a method of adding a mixture containing the hydraulic composition admixture of the present invention and water to a mixture containing aggregate and hydraulic powder and mixing is preferred because it allows for easy and uniform mixing even when manufacturing the hydraulic composition.

[0089] A specific method for step 1 is to mix the hydraulic powder and aggregate, add a mixture containing water, component (A), component (B), and an arbitrary component (C) in the aforementioned amounts, and knead to prepare a hydraulic composition.

[0090] In step 1, components (A), (B), and an optional (C) can be added separately to water, hydraulic powder, and aggregate and then mixed.

[0091] One method for filling the mold with the hydraulic composition obtained in step 1 is to discharge the mixed hydraulic composition from the mixing means, pour it into the mold, and level it.

[0092] In step 2, the hydraulic composition filled into the mold is clamped by centrifugal force, and it is preferable to change the centrifugal force at least once. In step 2, the hydraulic composition can be clamped by applying a centrifugal force that changes in stages. That is, in step 2, the hydraulic composition can be clamped by changing the centrifugal force at least once, and furthermore, by applying a centrifugal force that changes in stages, or by applying a centrifugal force that increases continuously.

[0093] In step 2, it is preferable to clamp the hydraulic composition filled into the mold with a centrifugal force of 0.5G or more. The centrifugal force for centrifugal molding is preferably 0.5G or more, preferably 30G or less, and more preferably 25G or less. From the viewpoint of reducing energy costs and moldability, for example, if the process is 1 minute or longer, it is preferable to maintain the centrifugal force in the range of 15G or more, 30G or less, and even more preferably 25G or less (also called high centrifugal force).

[0094] The time for compaction by centrifugal force is preferably 5 minutes or more, more preferably 7 minutes or more, even more preferably 9 minutes or more, and preferably 40 minutes or less, with a centrifugal force of 0.5G or more and 30G or less. When compacting the molded body smoothly, compaction by maintaining a high centrifugal force, for example, 20G or more, is preferably 1 minute or more, more preferably 3 minutes or more, even more preferably 5 minutes or more, and preferably 15 minutes or less. In other words, in step 3, it is preferable to apply a centrifugal force of 0.5G or more and 30G for preferably 5 minutes or more, more preferably 7 minutes or more, even more preferably 9 minutes or more, and preferably 40 minutes or less. Also, in step 3, when compaction by maintaining a centrifugal force of 20G or more is performed, it is preferable to do so for preferably 1 minute or more, more preferably 3 minutes or more, even more preferably 5 minutes or more, and preferably 15 minutes or less.

[0095] Centrifugal compaction can be carried out in stages, and from the viewpoint of moldability, it is preferable to gradually increase the centrifugal force G. The process can be carried out under the stage conditions shown below until the desired centrifugal force is reached. For example, in the case of five stages, in step 3, it is preferable to compact the hydraulic composition under the following conditions: (1) the initial velocity, which is the first stage, is a centrifugal force of 0.5G or more and less than 2G for more than 0 minutes and 15 minutes or less; (2) the second velocity, which is the second stage, is a centrifugal force of 2G or more and less than 5G for more than 0 minutes and 15 minutes or less; (3) the third velocity, which is the third stage, is a centrifugal force of 5G or more and less than 10G for more than 0 minutes and 15 minutes or less; (4) the fourth velocity, which is the fourth stage, is a centrifugal force of 10G or more and less than 20G for more than 0 minutes and 15 minutes or less; (5) the fifth velocity, which is the fifth stage, is a centrifugal force of 20G or more and 30G or less for more than 0 minutes and 15 minutes or less.

[0096] In step 3, the hydraulic composition obtained in step 2 can be allowed to set. Specifically, it can be cured in the air for 3 to 4 hours after mixing.

[0097] In step 4, the hardened hydraulic composition in the mold obtained in step 3 can be steam-cured. Specifically, steam curing is preferably performed at a temperature of 40°C to 90°C, and more preferably at a temperature of 60°C to 90°C. Furthermore, in step 4, it is preferable to perform steam curing after pre-curing. For example, it is preferable to perform pre-curing by setting the temperature around the mold filled with the hydraulic composition (hereinafter sometimes referred to as ambient temperature) to room temperature, preferably 10°C to 40°C, and leaving it for 1 to 4 hours, and then performing steam curing by setting the ambient temperature to 40°C to 90°C, and further to 60°C to 90°C. In this case, pre-curing is preferably one hour or longer, from the viewpoint of suppressing the reduction in strength due to cracking of the hardened material. Furthermore, if the method for manufacturing the cured body of the present invention includes step 5, steps 4 and 5 can be carried out continuously under a series of temperature controls. Steam curing is performed by applying steam around a mold filled with a hydraulic composition and maintaining it at a predetermined temperature for a certain period of time. After applying steam, the steam curing period may include (1) the period during which the temperature rises until it reaches the predetermined temperature, (2) the period during which it is maintained at the predetermined temperature for a certain period of time, and (3) the period during which the temperature decreases after being maintained at the predetermined temperature for a certain period of time.

[0098] As specific steam curing conditions in the method for manufacturing a cured body of the present invention, in step 4, the ambient temperature around the mold is raised to 60°C to 85°C at a heating rate of 10°C to 30°C per hour, and the raised temperature is maintained for 2 hours to 8 hours. Then, in step 5, the ambient temperature is cooled to room temperature, for example, 20°C, at a cooling rate of 5°C to 20°C per hour, and the molded body is demolded. From the viewpoint of suppressing strength reduction due to cracking of the hardened material, the heating rate is preferably 20°C or less per hour. One example of preferred conditions is a method in which a mold filled with a hydraulic composition is left for 3 hours at an ambient temperature of room temperature, for example, 10°C to 30°C (pre-curing), the ambient temperature is raised to 70°C to 90°C at a rate of 20°C per hour, the temperature is maintained at 70°C to 90°C for 2 to 6 hours, the ambient temperature is then cooled to room temperature, for example, 20°C at a rate of 10°C per hour (step 4), and the molded body is demolded after being left at that temperature for 20 to 30 hours (step 5). Furthermore, it is also possible to perform autoclave curing at approximately 180°C.

[0099] In step 6, the hardened hydraulic composition obtained in step 5 can be cured at room temperature and atmospheric pressure. Specifically, it is stored at 20°C and atmospheric pressure.

[0100] The present invention provides a method for producing a hardened body of a hydraulic composition, comprising steps 1 to 5, wherein the time from the start of preparation of the hydraulic composition to demolding in step 5 is 8 hours or more and 30 hours or less. Here, the start of preparation of the hydraulic composition refers to the point in time when the hydraulic powder and water first come into contact.

[0101] The hardened hydraulic composition obtained by the manufacturing method of the present invention can be used as a centrifugal-molded concrete product, specifically, in the form of piles, poles, Hume pipes, etc. The manufacturing method of the hardened composition of the present invention allows for a reduction in mixing time (for example, from 6 minutes to 3 minutes), thereby shortening the mixing and molding time and improving productivity. Furthermore, after a certain period of time has elapsed since mixing, the resulting hydraulic composition exhibits no change in fluidity compared to a hydraulic composition that does not contain the admixture for hydraulic compositions of the present invention. Therefore, no slag is generated during centrifugal molding after the hydraulic composition is molded, and a hydraulic composition hardened body with good finish can be obtained. [Examples]

[0102] The components (A), (A') (comparative component of (A)), (B), and (C) used in the examples and comparative examples were as follows.

[0103] <(A) component> PAE: Formaldehyde condensation polymer containing monomer units (a1) and (a3), monomer unit (a1) / monomer unit (a2) = polyoxyethylene (20) phenyl ether (average number of added moles in parentheses) / phenoxyethanol phosphate = 50 moles / 50 moles (compounding ratio), total amount of monomer units (a1) and (a2) in the total monomer units 100 mol%, weight-average molecular weight 12,500 The PAE was synthesized by the following method: 0.5 moles of polyoxyethylene(20) phenyl ether, 0.5 moles of phenoxyethanol phosphate, 0.27 moles of water, and 0.4 moles of sulfuric acid were charged into a stirred reactor, and 1.1 moles of 37% formaldehyde were added dropwise. After addition, the mixture was reacted at 105°C for 14 hours, then cooled, 48% sodium hydroxide was added to adjust the pH to 10 or higher, and water was added to adjust the solid content, yielding a condensed polymer with a weight-average molecular weight of 12,500. PHG: A formaldehyde condensation polymer containing monomer units (a1) and (a2). Monomer unit (a1) / monomer unit (a2) = polyoxyethylene (40) phenyl ether (average number of added moles in parentheses) / p-hydroxybenzoic acid = 20 moles / 80 moles (compounding ratio). Total amount of monomer units (a1) and (a2) in the total monomer units: 100 mol%, weight-average molecular weight: 18,000. The synthesis of PHG was carried out by the following method: 0.2 moles of polyoxyethylene(40) phenyl ether, 0.8 moles of p-hydroxybenzoic acid, 0.5 moles of sulfuric acid, and 5 moles of water were charged into a stirring reactor, and 37% formalin was added dropwise. After dropwise addition, the reaction was carried out at 105°C for 9 hours, then cooled, 48% sodium hydroxide was added to adjust the pH to 10 or higher, and water was added to adjust the solid content to obtain a condensed polymer with a weight-average molecular weight of 18,000.

[0104] (A') component (comparative component of (A)) NSF: Sodium salt of naphthalene sulfonic acid formalin condensate, weight-average molecular weight 15,000

[0105] <(B) component> (B-1): In general formula (B1), R1b is a compound in which the linear alkyl group has 12 and 14 carbon atoms (the mass ratio (C12 / C14) of the linear alkyl group with 12 carbon atoms (C12) to the linear alkyl group with 14 carbon atoms (C14) is 75 / 25), AO is an ethyleneoxy group, t is 2, M 1b is sodium, component (B1) (B-2): In general formula (B1), R 1b is a linear alkyl group with 10 carbon atoms, t is 0, M 1b is sodium, component (B1) (B-3): In general formula (B1), R 1b is a linear alkenyl group with 18 carbon atoms, t is 0, M 1b is sodium, component (B1) (B-4): In general formula (B1), R 1b is a linear alkyl group with 8 carbon atoms, t is 0, M 1b is sodium, component (B1) (B-5): In general formula (B1), R 1b is a linear alkyl group with 12 carbon atoms, t is 0, M 1b is sodium, component (B1) (B-6): In general formula (B1), R 1b is a linear alkyl group with 12 carbon atoms, AO is an ethyleneoxy group, t is 3, M 1b is sodium, component (B1) (B-7): In general formula (B1), R 1b is a linear alkyl group with 16 carbon atoms, AO is an ethyleneoxy group, t is 2, M 1b is sodium, component (B1) (B-8): In general formula (B1), R 1b is a linear alkenyl group with 18 carbon atoms, AO is an ethyleneoxy group, t is 7, M 1b is sodium, component (B1) (B-9): A mixture of abietic acid salt and parastrophosphate, component (B2)

[0106] <(C) component> · Ether PCE: Acrylic acid / TPEG(66) = 80 mol% / 20 mol%, weight average molecular weight = 56,000 • Ester PCE: Methacrylic acid / MEPEG(23) = 73 mol% / 27 mol%, weight-average molecular weight = 45,000 The monomers of each of the above copolymers are as follows: • TPEG(66): Polyethylene glycol (66) isoprenyl ether (the number in parentheses represents the average number of moles of ethylene oxy groups added. The same applies below.) • MEPEG(23): Methoxypolyethylene glycol(23) monomethacrylate The method for producing the above-mentioned ether PCE is shown below. 220.7 parts of TPEG(66) and 141.3 parts of water were charged into a glass reactor (four-necked flask) equipped with a stirrer. The reactor was stirred while purging with nitrogen and heated to 80°C in a nitrogen atmosphere. Then, 0.7 parts of 35% hydrogen peroxide were added. Two aqueous solutions, one of 21.3 parts of acrylic acid dissolved in 31.9 parts of water and the other of 1.2 parts of 3-mercaptopropionic acid dissolved in 38.0 parts of water, were added dropwise to the same container over 3 hours each. An aqueous solution of 0.3 parts of L-ascorbic acid dissolved in 32.2 parts of water was added dropwise over 3.5 hours. The mixture was then aged at 80°C for 1 hour. After aging, the mixture was neutralized with 12.3 parts of 48% sodium hydroxide to obtain an aqueous solution containing a copolymer with a weight-average molecular weight of 56,000. The method for producing the above-mentioned ester PCE is shown below. 356 parts of deionized water were charged into a glass reactor (four-necked flask) equipped with a stirrer, and the mixture was heated to 80°C under nitrogen atmosphere while stirring and purging with nitrogen. Next, an aqueous monomer solution prepared by mixing 318 parts of MEPEG(23), 67 parts of methacrylic acid, and 176 parts of deionized water, an aqueous solution prepared by mixing 2.8 parts of 3-mercaptopropionic acid and 27.7 parts of deionized water, and an aqueous solution prepared by mixing 3.3 parts of ammonium persulfate and 18.6 parts of deionized water were added dropwise over 2 hours. After the dropwise addition was complete, an aqueous solution prepared by mixing 1.1 parts of ammonium persulfate and 6.2 parts of deionized water was added dropwise over 0.5 hours. After the dropwise addition was complete, the temperature was maintained at 80°C for 1 hour for maturation. Subsequently, the reaction vessel was neutralized with an aqueous sodium hydroxide solution at a temperature below 80°C to obtain an aqueous solution containing a copolymer with a weight-average molecular weight of 45,000.

[0107] The weight-average molecular weight (Mw) of components (A) and (C) was measured by gel permeation chromatography (GPC) under the following conditions. *GPC conditions Equipment: GPC (HLC-8320GPC), manufactured by Tosoh Corporation. Columns: G4000PWXL + G2500PWXL (manufactured by Tosoh Corporation) Eluent: 0.2M phosphate buffer / CH3CN=9 / 1 Flow rate: 1.0mL / min Column temperature: 40℃ Detection: RI Sample size: 0.2 mg / mL Standard substances: Polyethylene glycol equivalent (monodisperse polyethylene glycols with known molecular weights: 250,000, 145,000, 87,500, 46,000, 24,000)

[0108] [Mortar Test] (1) Mortar mix Table 1 shows the mortar mix designs. W / (C+P) is the mass % of the water content relative to the hydraulic powder content (total amount of cement (C) and high-strength admixture (P)) in the mortar mix (W / (C+P) × 100).

[0109] [Table 1]

[0110] *Mortar mixture The following mortar materials were used, as shown in Table 1. Cement (C): High-early-strength Portland cement, manufactured by Taiheiyo Cement Corporation, density 3.14 g / cm³ 3 • High-strength admixture (P): High-strength admixture, manufactured by Sumitomo Osaka Cement Co., Ltd., Super Nonclave, density 2.55 g / cm³ 3 • Tap water (W): Wakayama City tap water (containing component (A) or component (A'), component (B), and component (C)), density 1.00 g / cm³ 3 • Sand (S): Mountain sand, from Joyo, density 2.55 g / cm³ 3 All materials were adjusted to 20°C, and since the amounts of components (A), (A'), (B), and (C) in the tap water were trace amounts relative to the mortar mixture, they were included in the calculation of W / (C+P) by including them in the amount of tap water.

[0111] (2) Preparation of mortar (hydraulic composition) Mixing water was prepared by adding components (A) or (A'), (B) and (C) to tap water (W) of the mortar mixture so that the content of components (A) or (A'), (B) and (C) in the mortar (hydraulic composition) was as shown in Table 2, and stirring. Half of the sand (S) was put into a mortar pot, then cement (C), high-strength admixture (P), and the remaining sand (S) were added, and the mixture was stirred at low speed for 10 seconds using a mortar mixer (manufactured by Kansai Kiki Co., Ltd.), and the prepared mixing water was added and mixed for a predetermined time to obtain mortar (hydraulic composition).

[0112] (3) Evaluation of fluidity with respect to time elapsed since mixing The fluidity of each mortar (hydraulic composition) was measured from the time of mixing (meaning from the moment water first came into contact with the cement) to the time specified in Table 2. The fluidity was measured according to JIS R5201, Section 12, Flow Test. Specifically, the details are as follows: At each mixing time, the mortar (hydraulic composition) was filled into a flow cone (70 mm upper diameter x 100 mm lower diameter x 60 mm height) as described in JIS R5201, placed on a flow table. The flow cone was then removed vertically, and the fluidity was measured. The results are shown in Table 2.

[0113] [Table 2]

[0114] In Table 2, the content of component (A) or component (A'), component (B), and component (C) in each mortar (hydraulic composition) is the content (parts by mass) per 100 parts by mass of hydraulic powder, and represents the content of effective content (solids). (B) / (A) (mass ratio) is the mass ratio (B) / (A) of the content of component (B) to the content of component (A) in each mortar (hydraulic composition).

[0115] Table 2 shows that the examples containing component (A) and component (B) exhibit superior fluidity 3 minutes (180 seconds) after mixing compared to comparative examples that do not contain component (A) or component (B), or that contain these comparative components. On the other hand, it can be seen that the fluidity does not change significantly after 6 minutes (360 seconds) after mixing. Therefore, the admixture for hydraulic compositions and the hydraulic compositions of the present invention enable a reduction in mixing time (for example, from 6 minutes to 3 minutes), thereby shortening the time required for mixing and molding, and improving productivity.

[0116] [Table 3]

[0117] [Concrete Testing] (1) Concrete mix Table 3 shows the concrete mix designs. W / (C+P) is the mass % of the water content relative to the hydraulic powder content (total amount of cement (C) and high-strength admixture (P)) in the concrete mix (W / (C+P) × 100).

[0118] *Concrete mix The concrete materials used in Table 3 are as follows: Cement (C): High-early-strength Portland cement, manufactured by Taiheiyo Cement Corporation, density 3.14 g / cm³ 3 • High-strength admixture (P): High-strength admixture, manufactured by Sumitomo Osaka Cement Co., Ltd., Super Nonclave, density 2.55 g / cm³ 3 • Tap water (W): Wakayama City tap water (containing component (A) or component (A'), component (B), and component (C)), density 1.00 g / cm³ 3 • Sand (S): Mountain sand, from Joyo, density 2.55 g / cm³ 3 • Gravel (G): Crushed stone from the Ieshima Islands, density 2.63 g / cm³ 3 All materials were adjusted to 20°C, and since the amounts of components (A), (A'), (B), and (C) in the tap water were trace amounts relative to the concrete mix, they were included in the amount of tap water and W / (C+P) was calculated.

[0119] * Concrete preparation Mixing water was prepared by adding components (A), (B), and (C) to tap water (W) of the concrete mix material and stirring, so that the content of components (A), (B), and (C) in the concrete (hydraulic composition) would be as shown in Table 5. The entire amount of gravel (G) was put into a dicross mixer, then half of the sand (S) was added, followed by cement (C), high-strength admixture (P), and the remaining sand (S). The mixture was stirred for 30 seconds, the prepared mixing water was added, and the mixture was kneaded for the predetermined time shown in Table 5 to obtain concrete (hydraulic composition). Subsequently, the fluidity (slump) was evaluated, and piles were manufactured under the centrifugal molding conditions and steam curing conditions shown below, and the formability was evaluated. <Centrifugal molding conditions> 15.5 kg of prepared concrete was placed in a cylindrical centrifugal molding mold (φ20 cm × height 30 cm) for pile manufacturing, and centrifugal molding was performed in the following order: low speed, medium speed 1, medium speed 2, and high speed, under the conditions shown in Table 4.

[0120] [Table 4]

[0121] <Steam curing conditions> The steam curing conditions were as follows: 1. Preliminary steps: 20℃, 3 hours 2. Heating gradient: 20°C / hour 3. Maximum temperature: 80℃, 3 hours 4. Cooling gradient: 10°C / hour

[0122] (4) Evaluation of fluidity with respect to time elapsed since mixing The slump was measured for each concrete (hydraulic composition) after mixing for the specified time shown in Table 5, starting from the initial mixing stage (meaning from the point when water first came into contact with the cement). Slump was measured using a slump cone as specified in JIS A1150. The results are shown in Table 5.

[0123] *Evaluation of moldability in relation to the time elapsed since mixing. For each concrete (hydraulic composition) mixed for the specified time described in Table 5, from the initial mixing stage (meaning the moment when water first comes into contact with the cement), the concrete was filled into formwork, and the formwork was subjected to centrifugal molding and steam curing under the conditions described above. The formability of each concrete after hardening and demolding was evaluated. The evaluation of formability was determined by the occurrence of honeycombing on the end faces of each concrete after demolding, according to the following criteria. The end faces refer to both ends in the height direction of the concrete pile after demolding, and honeycombing here refers to unfilled areas that occur during centrifugal molding of fresh concrete after mixing for the specified time described in Table 5 due to insufficient mixing time. The results are shown in Table 5. ○: No honeycombing occurred, and both ends of the concrete pile exhibited a smooth and uniform surface. ×: Honeycombing has occurred.

[0124] [Table 5]

[0125] In Table 5, the content of components (A), (B), and (C) in each concrete (hydraulic composition) is the content (parts by mass) per 100 parts by mass of hydraulic powder, and represents the amount of effective content (solids). (B) / (A) (mass ratio) is the mass ratio (B) / (A) of the content of component (B) to the content of component (A) in each concrete (hydraulic composition).

[0126] Table 5 shows that the examples containing components (A) and (B) exhibit superior fluidity in concrete 2 minutes after mixing compared to the comparative example without component (B), but the fluidity does not change significantly after 6 minutes after mixing. Therefore, the admixture for hydraulic compositions and the hydraulic compositions of the present invention allow for a reduction in mixing time. As a result of verifying the moldability 2 minutes after mixing, the examples containing components (A) and (B) showed superior moldability compared to the comparative example without component (B), and furthermore, no slag was generated even 6 minutes after mixing. As shown in the examples of the present invention, the excellent moldability allows for a reduction in mixing and mold-filling work time, improving productivity and enabling the production of a hydraulic composition hardened body with a good finish.

Claims

1. An admixture for hydraulic compositions containing the following components (A) and (B). (A) Component: A formaldehyde condensation polymer comprising a monomer unit (a1) having a polyalkylene oxy group on the aromatic ring, a monomer unit (a2) having a carboxylic acid group and / or a salt thereof on the aromatic ring, or a monomer unit (a3) ​​having a phosphate group and / or a salt thereof on the aromatic ring. (B) Component: One or more selected from the following components (B1) and (B2). (B1) Components: One or more selected from alkyl or alkenyl sulfate esters, polyoxyalkylene alkyl or alkenyl ether sulfate esters, and salts thereof. (B2) Ingredients: Rosin acid and / or its salt

2. The admixture for hydraulic compositions according to claim 1, wherein component (B1) is a compound represented by the following general formula (B1). R １ｂ -O-(AO) ｔ -SO ３ M １ｂ (B1) [In the formula, R １ｂ is a straight-chain aliphatic hydrocarbon group with 8 to 18 carbon atoms, AO is an alkylene oxy group with 2 to 4 carbon atoms, and t is the average number of moles of AO added, which is between 0 and 30. １ｂ This represents a hydrogen atom, alkali metal, alkaline earth metal (half atom), ammonium, or organic ammonium.

3. The admixture for hydraulic compositions according to claim 1 or 2, wherein the mass ratio (B) / (A) of the content of component (A) to the content of component (B) is 0.0005 or more and 0.0100 or less.

4. Furthermore, the admixture for hydraulic compositions according to claim 1 or 2, further containing the following component (C). (C) Component: Polycarboxylic acid-based dispersant

5. The admixture for hydraulic compositions according to claim 4, wherein component (C) is a copolymer comprising a monomer (c1) represented by the following general formula (c1) and a monomer (c2) represented by the following general formula (c2) as constituent monomers. 【Chemistry 1】 [During the ceremony, R １ｃ 、R ２ｃ 、R ３ｃ : may be the same or different, and is a hydrogen atom, a methyl group or (CH ２ ) ｒ COOM ２ where (CH ２ ) ｒ COOM ２ may form an anhydride with COOM １ or another (CH ２ ) ｒ COOM ２ , and in that case, M １ , M ２ does not exist. M １ M ２ : They may be the same or different, and include hydrogen atoms, alkali metals, alkaline earth metals (half an atom), ammonium groups, alkylammonium groups, substituted alkylammonium groups, alkyl groups, hydroalkyl groups, or alkenyl groups. r: A number between 0 and 2 (inclusive) This indicates... 【Chemistry 2】 [During the ceremony, R ４ｃ , R ５ｃ , R ６ｃ : They may be the same or different, hydrogen atom, methyl group, (CH ２ ) ｓ COOM ３ , or (CH ２ ) ｑ1 (CO) ｐ１ O (AO) ｎ１ -R ７ｃ R ７ｃ : Hydrogen atom or alkyl group having 1 to 4 carbon atoms AO: Alkylene oxy group with 2 to 4 carbon atoms n1: The average number of moles of AO added, a number between 4 and 200. q1: A number between 0 and 2 (inclusive) p1: 0 or 1 M ３ : Hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroalkyl group or alkenyl group s: A number between 0 and 2 (inclusive) This indicates...

6. An admixture for a hydraulic composition according to claim 1 or 2, which is for solid mixing.

7. An admixture for a hydraulic composition according to claim 1 or 2, for use in centrifugal molding.

8. A hydraulic composition containing the following components (A), (B), hydraulic powder, and water. (A) Component: A formaldehyde condensation polymer comprising a monomer unit (a1) having a polyalkylene oxy group on the aromatic ring, a monomer unit (a2) having a carboxylic acid group and / or a salt thereof on the aromatic ring, or a monomer unit (a3) ​​having a phosphate group and / or a salt thereof on the aromatic ring. (B) Component: One or more selected from the following components (B1) and (B2). (B1) Components: One or more selected from alkyl or alkenyl sulfate esters, polyoxyalkylene alkyl or alkenyl ether sulfate esters, and salts thereof. (B2) Ingredients: Rosin acid and / or its salt

9. The hydraulic composition according to claim 8, wherein component (B1) is a compound represented by the following general formula (B1). R １ｂ -O-(AO) ｎ１ -SO ３ M １ｂ (B1) [In the formula, R １ｂ is a straight-chain aliphatic hydrocarbon group with 8 to 18 carbon atoms, AO is an alkylene oxy group with 2 to 4 carbon atoms, and n1 is the average number of moles of AO added, which is between 0 and 30. １ｂ This represents a hydrogen atom, alkali metal, alkaline earth metal (half atom), ammonium, or organic ammonium.

10. The admixture composition for hydraulic compositions according to claim 8 or 9, wherein the mass ratio (B) / (A) of the content of component (A) to the content of component (B) is 0.0005 or more and 0.0100 or less.

11. Furthermore, the hydraulic composition according to claim 8 or 9, further comprising the following component (C). (C) Component: Polycarboxylic acid-based dispersant

12. The hydraulic composition according to claim 11, wherein component (C) is a copolymer comprising a monomer (c1) represented by the following general formula (c1) and a monomer (c2) represented by the following general formula (c2) as constituent monomers. 【Transformation 3】 [During the ceremony, R １ｃ , R ２ｃ , R ３ｃ : They may be the same or different, and may be a hydrogen atom, a methyl group or (CH ２ ) ｒ COOM ２ (CH ２ ) ｒ COOM ２ COOM １ or other (CH ２ ) ｒ COOM ２ They may also form anhydrous compounds, in which case the M of those groups １ M ２ It does not exist. M １ M ２ : They may be the same or different, and include hydrogen atoms, alkali metals, alkaline earth metals (half an atom), ammonium groups, alkylammonium groups, substituted alkylammonium groups, alkyl groups, hydroalkyl groups, or alkenyl groups. r: A number between 0 and 2 (inclusive) This indicates... 【Chemistry 4】 [During the ceremony, R ４ｃ , R ５ｃ , R ６ｃ : They may be the same or different, hydrogen atom, methyl group, (CH ２ ) ｓ COOM ３ , or (CH ２ ) ｑ1 (CO) ｐ１ O (AO) ｎ１ -R ７ｃ R ７ｃ : Hydrogen atom or alkyl group having 1 to 4 carbon atoms AO: Alkylene oxy group with 2 to 4 carbon atoms n1: The average number of moles of AO added, a number between 4 and 200. q1: A number between 0 and 2 (inclusive) p1: 0 or 1 M ３ : Hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroalkyl group or alkenyl group s: A number between 0 and 2 (inclusive) This indicates...

13. The hydraulic composition according to claim 8 or 9, wherein the mass percentage of the water content relative to the hydraulic powder content (water / hydraulic powder × 100) is 10% by mass or more and 40% by mass or less.

14. A hydraulic composition according to claim 8 or 9, for use in centrifugal molding.

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