Admixture for hydraulic compositions

Abstract

The present invention provides an admixture for hydraulic compositions that can suppress the increase in viscosity of a hydraulic composition slurry over time, even when the hydraulic composition contains an alternative powder, and a hydraulic composition in which the increase in viscosity of a hydraulic composition slurry over time is suppressed, even when the hydraulic composition contains an alternative powder. [Solution] An admixture for hydraulic compositions containing the following component (A) and component (B), wherein the mass ratio (B) / [(A)+(B)] of the content of component (B) to the total content of components (A) and (B) is 0.05 or more and 0.40 or less. (A) Component: A copolymer containing a specific constituent monomer (A1) represented by general formula (A1) and a specific constituent monomer (A2) represented by general formula (A2) as constituent monomers, wherein the proportion of constituent monomer (A1) in the total amount of constituent monomer (A1) and constituent monomer (A2) is 15% by mass or more and 30% by mass or less. (B) Components: One or more selected from specific phosphate monoesters having a group represented by general formula (B1), specific phosphate diesters having a group represented by general formula (B1), and salts thereof.

Description

[Technical Field]

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

[0002] In recent years, from the perspective of reducing CO2 emissions, there has been a growing trend to partially replace cement in hydraulic compositions such as concrete with alternative powders that have pozzolanic and / or latent hydraulic properties, such as blast furnace slag, fly ash, anhydrous gypsum, and silica fume, or with alternative powders such as calcium carbonate powder. However, using these alternative powders presents the challenge of reduced strength development in the hardened hydraulic compositions. To address this problem, it is common to improve the strength development of the hardened hydraulic composition by finely adjusting the Blaine value of the alternative powder or by lowering the water / cement ratio in the hydraulic composition. However, both methods increase the viscosity of the hydraulic composition slurry, which presents challenges in terms of workability.

[0003] Patent Document 1 discloses an additive for hydraulic compositions that exhibits an excellent viscosity reduction effect on hydraulic compositions, such as a slurry of water and hydraulic powder, and also has good workability when used as an aqueous solution. This additive contains a monoester or salt thereof (monoester) having a specific group such as an alkyl ether group, and a diester or salt thereof (diester) having a specific group such as an alkyl ether group, in a weight ratio of monoester / (monoester + diester) = 0.4 to 0.95 (the diester includes pyro-isomers). Patent Document 2 discloses a method for producing products efficiently and with good workability, even when centrifugal molding is performed with hydraulic compositions, particularly hydraulic compositions with a low W / P ratio. This method involves compacting centrifugal-molded concrete containing a centrifugal-molded concrete additive in a specific ratio, which includes a phosphate monoester or salt thereof (monoester) having a specific group such as an alkyl ether group, and a phosphate diester or salt thereof (diester) having a specific group such as an alkyl ether group, in a weight ratio of monoester / (monoester + diester) = 0.4 to 0.95 (the diester includes pyro-forms), with a centrifugal force of 0.5G or more. Patent Document 3 discloses a dispersant for hydraulic compositions in which shrinkage reduction performance is significantly improved while maintaining the dispersion performance of the hydraulic composition. This dispersant contains one or more (A) selected from the group consisting of an alkyl phosphate ester or salt thereof in which the proportion of the monoester is 45% by weight or less, and a polyoxyalkylene alkyl ether phosphate ester or salt thereof in which the proportion of the monoester is 45% by weight or less, and a polymer or copolymer or salt thereof obtained by polymerizing a monomer mixture containing an ethylenically unsaturated monomer having an average number of added moles of 2 to 300 polyoxyalkylene groups. Patent Document 4 discloses an admixture for hydraulic compositions that provides a hydraulic composition that satisfies a good balance of fluidity, viscosity, flow retention, and retardation by polymerizing a monomer mixture containing (A) a compound having at least one phosphonic acid group (a1) and a polyoxyalkylene group (a2), and (B) an ethylenically unsaturated monomer having an average degree of polymerization of 20 to 300. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2005-35872 [Patent Document 2] Japanese Patent Publication No. 2005-22906 [Patent Document 3] Japanese Patent Publication No. 2004-02172 [Patent Document 4] Japanese Patent Publication No. 2002-121058 [Overview of the project] [Problems that the invention aims to solve]

[0005] According to the aforementioned patent document, an approach using additives to reduce the viscosity of hydraulic composition slurry is disclosed. However, while this can improve the viscosity of the slurry at the initial stage of contact between cement and water during slurry preparation, it has not solved the problem of the viscosity of the hydraulic composition slurry increasing over time. Furthermore, with the recent increase in alternative powders, there is a need to improve its effectiveness.

[0006] The present invention provides an admixture for hydraulic compositions that can suppress the increase in viscosity of a hydraulic composition slurry over time, even when the hydraulic composition contains an alternative powder, and a hydraulic composition in which the increase in viscosity of a hydraulic composition slurry over time is suppressed, even when the hydraulic composition contains an alternative powder. [Means for solving the problem]

[0007] The present invention relates to an admixture for hydraulic compositions, comprising the following component (A) and component (B), wherein the mass ratio (B) / [(A)+(B)] of the content of component (B) to the total content of components (A) and (B) is 0.05 or more and 0.40 or less. (A) Component: A copolymer containing a constituent monomer (A1) represented by the following general formula (A1) and a constituent monomer (A2) represented by the following general formula (A2) as constituent monomers, wherein the proportion of constituent monomer (A1) in the total amount of constituent monomer (A1) and constituent monomer (A2) is 15% by mass or more and 30% by mass or less.

[0008] [ka]

[0009] [During the ceremony, R 1a , R 2a , R3a : Independently the same or different, a hydrogen atom, a methyl group or (CH2) r COOM 2a wherein (CH2) r COOM 2a is COOM 1a or another (CH2) r COOM 2a When forming an anhydride with them, M of those groups 1a , M 2a does not exist. M 1a , M 2a : Independently the same or different, a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroxyalkyl group or an alkenyl group r: A number from 0 to 2 inclusive is shown. ]

[0010]

Chemical formula

[0011] 〔In the formula, R 4a , R 5a : Independently the same or different, a hydrogen atom or a methyl group R 6a : A hydrogen atom, a methyl group, (CH2) r COOM 3a , or (CH2) q1 (CO) p1 O(AO) n1 R 7a R 7a : A hydrogen atom or an alkyl group having 1 to 4 carbon atoms AO: An alkyleneoxy group having 2 to 4 carbon atoms n1: The average number of moles of addition of AO, a number from 5 to 25 inclusive q1: A number from 0 to 6 inclusive p1: 0 or 1 M 3a: Hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group or alkenyl group r: A number between 0 and 2 (inclusive) This indicates... (B) Components: One or more selected from phosphate monoesters having a group represented by the following general formula (B1), phosphate diesters having a group represented by the following general formula (B1), and salts thereof. R 1b -O(AO) m - (B1) [In the formula, R 1b [where is a hydrocarbon group with 4 to 15 carbon atoms, AO is an alkylene oxy group with 2 to 4 carbon atoms, and m is the average number of moles of AO added, which is between 0 and 5.]

[0012] The present invention also relates to a hydraulic composition containing component (A), component (B), cement, and water, wherein the mass ratio (B) / [(A)+(B)] of the content of component (B) to the total content of components (A) and (B) is 0.05 or more and 0.40 or less. [Effects of the Invention]

[0013] According to the present invention, an admixture for hydraulic compositions is provided that can suppress the increase in viscosity of a hydraulic composition slurry over time, even when the hydraulic composition contains an alternative powder, and a hydraulic composition is provided in which the increase in viscosity of a hydraulic composition slurry over time is suppressed, even when the hydraulic composition contains an alternative powder. [Brief explanation of the drawing]

[0014] [Figure 1] A schematic diagram showing the apparatus used to measure the flow time in the example. [Modes for carrying out the invention]

[0015] The admixture for hydraulic compositions of the present invention can suppress the increase in viscosity of the hydraulic composition slurry over time, even when the hydraulic composition contains alternative powders. The reason why the increase in viscosity of the hydraulic composition slurry over time is suppressed even when the hydraulic composition contains alternative powders is not entirely clear, but is presumed to be as follows. In hydraulic composition slurries, the amount of trapped water in cement aggregates is released as the amount of dispersant adsorbed onto the cement particles increases, reducing the viscosity of the hydraulic composition slurry. However, highly adsorbent dispersants lose their ability to adsorb onto cement over time, making it difficult to maintain fluidity, which in turn increases the viscosity of the hydraulic composition slurry over time. Furthermore, increasing the amount of dispersant can cause the fluidity to exceed control limits at the initial stage of contact with water, potentially leading to separation of cement and water. In recent years, there has been an increase in the use of alternative powders such as fly ash, slag, and calcium carbonate to reduce CO2 emissions from cement. However, using these materials results in lower strength compared to cement, so this is addressed by reducing the water-to-powder ratio or by finer grinding of the alternative powder particles. This, however, leads to the problem of increased viscosity in the powder slurry. Therefore, the hydraulic composition admixture of the present invention tends to reduce the initial fluidity of cement without increasing viscosity. By combining a specific polycarboxylic acid-based dispersant (component A) with a specific phosphate ester (component B), component (A) acts like an accelerator and component (B) acts like a brake, making it possible to increase the amount of dispersant required to obtain a predetermined fluidity. As a result, even when the hydraulic composition contains alternative powders, the hydraulic composition admixture of the present invention not only maintains fluidity over time, but is also presumed to significantly improve viscosity over time due to its high cement adsorption capacity. However, the present invention is not limited to the above mechanism of action.

[0016] [Admixture for hydraulic compositions] <(A) component> The hydraulic composition admixture of the present invention contains a copolymer as component (A), comprising a constituent monomer (A1) represented by the following general formula (A1) and a constituent monomer (A2) represented by the following general formula (A2), wherein the proportion of constituent monomer (A1) in the total amount of constituent monomer (A1) and constituent monomer (A2) is 15% by mass or more and 30% by mass or less.

[0017] [ka]

[0018] [During the ceremony, R 1a , R 2a , R 3a : Identical or different, hydrogen atom, methyl group or (CH2) r COOM 2a (CH2) r COOM 2a COOM 1a or other (CH2) r COOM 2a When forming anhydrous compounds, the M of those groups 1a M 2a It does not exist. M 1a M 2a : Same or different hydrogen atoms, alkali metals, alkaline earth metals (1 / 2 atom), ammonium groups, alkylammonium groups, substituted alkylammonium groups, alkyl groups, hydroxyalkyl groups, or alkenyl groups r: A number between 0 and 2 (inclusive) This indicates...

[0019] [ka]

[0020] [During the ceremony, R 4a , R 5a : The same or different hydrogen atom or methyl group R 6a : Hydrogen atom, methyl group, (CH2) r COOM 3a, or (CH2) q1 (CO) p1 O(AO) n1 R 7a R 7a : 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 5 and 25 (inclusive). q1: A number between 0 and 6 (inclusive) p1:0 or 1 M 3a : Hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group or alkenyl group r: A number between 0 and 2 (inclusive) This indicates...

[0021] In general formula (A1), from the standpoint of availability, R 1a A hydrogen atom is preferred. In general formula (A1), R 2a The atom is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. In general formula (A1), from the standpoint of availability, R 3a A hydrogen atom is preferred. (CH2) r COOM 2a Regarding COOM 1a or other (CH2) r COOM 2a They may also form anhydrous compounds, in which case the M of those groups 1a M 2a It does not exist. M 1a and M 2a These are identical or different hydrogen atoms, alkali metals, alkaline earth metals (1 / 2 atom), ammonium groups, alkylammonium groups, substituted alkylammonium groups, alkyl groups, hydroxyalkyl groups, or alkenyl groups. M 1a and M 2aThe alkyl group, hydroxyalkyl group, and alkenyl group each preferably have 1 to 4 carbon atoms. M 1a and M 2a Preferably, the same or different components are 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 still more preferably, a hydrogen atom or alkali metal. (CH2) in general formula (A1) r COOM 2a r is preferably 0.

[0022] In general formula (A2), R 4a From the standpoint of availability, hydrogen atoms are preferred. In general formula (A2), R 5a From the viewpoint of availability and copolymerizability with constituent monomer (A1), a hydrogen atom or a methyl group is preferred, and a methyl group is more preferred. In general formula (A2), R 6a From the standpoint of availability, hydrogen atoms are preferred. In general formula (A2), R 7a 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 (A2), AO is preferably a group selected from an ethyleneoxy group and a propyleneoxy group, with an ethyleneoxy group being more preferred, from the viewpoint of availability and cost. It is preferable that AO contains an ethyleneoxy group. In general formula (A2), n1 is the average number of moles of AO added, and from the viewpoint of imparting dispersibility to the hydraulic composition, it is 5 or more, preferably 6 or more, more preferably 7 or more, and 25 or less, preferably 20 or less, more preferably 15 or less, even more preferably 13 or less, and even more preferably 11 or less. Furthermore, if the AO contains alkylene oxy groups with different numbers of carbon atoms in an average of n1 repeating units, these alkylene oxy groups with different numbers of carbon atoms may include random addition, block addition, or a mixture thereof. In the total AO, ethylene oxy groups are preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more, and it is preferable that the entire AO consists of ethylene oxy groups. For example, AO may also contain propylene oxy groups, butylene oxy groups, etc., in addition to ethylene oxy groups. In general formula (A2), 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 (A2), from the standpoint of availability, p1 is preferably 1. (CH2) in general formula (A2) r COOM 3a M 3a A preferred embodiment is M 1a M 2a This is the same as, and r is preferably 0.

[0023] In the total constituent monomers of component (A), the proportion of constituent monomer (A1) in the total amount of constituent monomer (A1) and constituent monomer (A2) is preferably 15% by mass or more, more preferably 17% by mass or more, even more preferably 19% by mass or more, and 30% by mass or less, preferably 25% by mass or less, and more preferably 22% by mass or less, from the viewpoint of improving the viscosity of the hydraulic composition.

[0024] In the total constituent monomers of component (A), the proportion of constituent monomer (A1) in the total amount of constituent monomer (A1) and constituent monomer (A2) is preferably 50 mol% or more, more preferably 55 mol% or more, even more preferably 57 mol% or more, and preferably 90 mol% or less, more preferably 85 mol% or less, even more preferably 82 mol% or less, even more preferably 75 mol% or less, and even more preferably 65 mol% or less.

[0025] In the total constituent monomers of component (A), the proportion of constituent monomer (A2) in the total amount of constituent monomer (A1) and constituent monomer (A2) is preferably 76% by mass or more, more preferably 77% by mass or more, even more preferably 78% by mass or more, and preferably 86% by mass or less, preferably 84% by mass or less, and more preferably 82% by mass or less, from the viewpoint of balancing the dispersibility of the hydraulic composition and its adsorption to cement.

[0026] In the total constituent monomers of component (A), the proportion of constituent monomer (A2) in the total amount of constituent monomer (A1) and constituent monomer (A2) is preferably 15 mol% or more, more preferably 20 mol% or more, even more preferably 25 mol% or more, even more preferably 30 mol% or more, even more preferably 35 mol% or more, and preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less.

[0027] (A) Of the total constituent monomers of component (A), the total amount of constituent monomer (A1) and constituent monomer (A2) is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and preferably 100% by mass or less, from the viewpoint of improving the dispersibility and viscosity of the hydraulic composition. This total amount may be 100% by mass. (A) Of the total constituent monomers of component (A), the total amount of constituent monomer (A1) and constituent monomer (A2) 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 improving the dispersibility and viscosity of the hydraulic composition. This total amount may be 100 mol%.

[0028] The copolymer of component (A) may contain constituent monomers other than constituent monomer (A1) and constituent monomer (A2) (hereinafter also referred to as constituent monomer (A3)). Examples of constituent monomer (A3) include hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-(methacryloyloxy)ethyl phosphate (HEMA-P), 2-hydroxyethyl acrylate (HEA), methyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate (HEMA), allyl sulfonic acid, methallyl sulfonic acid, and salts thereof, such as alkali metal salts, alkaline earth metal salts, ammonium salts, or amine salts. Furthermore, constituent units can be made using one or more monomers selected from (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, 2-(meth)acrylamide-2-methasulfonic acid, 2-(meth)acrylamide-2-ethanesulfonic acid, 2-(meth)acrylamide-2-propanesulfonic acid, styrene, styrenesulfonic acid, etc. (Meth)acrylic means acrylic or methacrylic.

[0029] The weight-average molecular weight (Mw) of component (A) is preferably 10,000 or more, more preferably 20,000 or more, even more preferably 25,000 or more, even more preferably 30,000 or more, even more preferably 35,000 or more, and preferably 70,000 or less, more preferably 60,000 or less, even more preferably 50,000 or less, and even more preferably 45,000 or less, from the viewpoint of improving the dispersibility and viscosity of the hydraulic composition.

[0030] (A) The ratio Mw / Mn of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of component (A) is preferably 1.0 or higher, more preferably 1.1 or higher, even more preferably 1.2 or higher, and preferably 2.0 or lower, more preferably 1.8 or lower, and even more preferably 1.5 or lower, from the viewpoint of improving the dispersibility and viscosity of the hydraulic composition.

[0031] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of component (A) were 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)

[0032] The content of component (A) in the admixture for hydraulic compositions of the present invention is preferably 60% by mass or more, more preferably 65% ​​by mass or more, even more preferably 70% by mass or more, even more preferably 92% by mass or less, and preferably 88% by mass or less, more preferably 84% by mass or less, and even more preferably 80% by mass or less, from the viewpoint of improving the dispersibility and viscosity of the hydraulic composition.

[0033] <(B) component> The admixture for hydraulic compositions of the present invention contains, as component (B), one or more selected from a phosphate monoester having a group represented by the following general formula (B1), a phosphate diester having a group represented by the following general formula (B1), and salts thereof. R 1b -O(AO) m - (B1) [In the formula, R 1b [where is a hydrocarbon group with 4 to 15 carbon atoms, AO is an alkylene oxy group with 2 to 4 carbon atoms, and m is the average number of moles of AO added, which is between 0 and 5.]

[0034] In general formula (B1), R 1b From the viewpoint of improving the viscosity of the hydraulic composition, the hydrocarbon group having 4 or more carbon atoms, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, and 15 or fewer carbon atoms, preferably 14 or fewer, more preferably 13 or fewer, is preferably an alkyl group or alkenyl group, more preferably an alkyl group. 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 ease of manufacture. It is preferable that AO contains an ethyleneoxy group. In general formula (B1), m is the average number of moles of AO added, and from the viewpoint of improving the viscosity of the hydraulic composition, it is 0 or more, preferably 1 or more, more preferably 2 or more, and 5 or less, preferably 4 or less.

[0035] (B) The salt of component (B) can be one or more selected from alkali metal salts, alkaline earth metal salts, ammonium salts, and amine salts, preferably one or more selected from potassium salts, sodium salts, calcium salts, and ammonium salts, more preferably one or more selected from potassium salts and sodium salts, and even more preferably potassium salts.

[0036] One or more of component (B), selected from phosphate monoesters, phosphate diesters, and salts thereof, are preferably those with a structure represented by the general formula (B1-1).

[0037] [ka]

[0038] [In the formula, R 1bis a hydrocarbon group having 4 to 15 carbon atoms, AO is an alkylene oxy group having 2 to 4 carbon atoms, m is the average number of moles of AO added, and is a number between 0 and 5. k is 1 or 2, and M represents a hydrogen atom, alkali metal, alkaline earth metal, ammonium group, alkylammonium group, or hydroxyl-substituted alkylammonium group.

[0039] In general formula (B1-1), R 1b , AO, and m are the same as the ranges described in general formula (B1). In the general formula (B1-1), there are two Ms when k is 1 and two Rs when k is 2. 1b m and m can be different. In general formula (B1-1), M is preferably a hydrogen atom or an alkali metal, more preferably a hydrogen atom, a potassium atom, or a sodium atom, and even more preferably a potassium atom.

[0040] Component (B) can be obtained, for example, by adding an alkylene oxide to an alcohol and then esterifying it with phosphoric acid. When adding an alkylene oxide to an alcohol with a low boiling point, it is desirable to select a catalyst that can minimize the generation of water. Alternatively, it can be obtained by esterifying a commercially available alcohol alkylene oxide adduct as a raw material. Natural alcohols or synthetic alcohols can be used as the alcohol. The alkylene oxide has 2 to 4 carbon atoms and includes ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter referred to as PO), and butylene oxide (hereinafter referred to as BO), with EO being preferred, or a combination of EO and PO being preferred, and EO being particularly preferred.

[0041] A general method can be used for the phosphate esterification reaction. For example, in addition to the method using anhydrous phosphoric acid, component (A) can also be produced by methods using anhydrous phosphoric acid and an aqueous phosphoric acid solution, anhydrous phosphoric acid and water, phosphorus oxychloride, or polyphosphate. In the present invention, to adjust the ratio of monoester compounds in component (A), the ratio of polyoxyalkylene alkyl ether to phosphorylating agent and the reaction time can be adjusted in the above-mentioned production method, or a hydrolysis reaction can be performed, or the product can be adjusted by purification such as crystallization or distillation, or by using the attached materials.

[0042] The content of component (B) in the admixture for hydraulic compositions of the present invention is preferably 7% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less, from the viewpoint of improving the viscosity of the hydraulic composition. In this invention, the mass of component (B) shall be the value converted to the potassium salt.

[0043] In the admixture for hydraulic compositions of the present invention, the mass ratio (B) / [(A)+(B)] of the content of component (B) to the total content of components (A) and (B) is 0.05 or more, preferably 0.10 or more, more preferably 0.15 or more, even more preferably 0.20 or more, even more preferably 0.23 or more, and 0.40 or less, preferably 0.35 or less, and even more preferably 0.30 or less.

[0044] The admixture for hydraulic compositions of the present invention may contain water. When the admixture for hydraulic compositions of the present invention contains water, the water content is preferably 30% by mass or more, preferably 35% by mass or more, more preferably 37% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0045] The admixture for hydraulic compositions of the present invention may optionally contain thickeners, chelating agents, heavy metal scavengers, rust inhibitors, preservatives, colorants, fragrances, defoamers, solvents, flocculants, water-soluble polymers, etc. (except those corresponding to components (A) and (B)).

[0046] The hydraulic composition admixture of the present invention can suppress the increase in viscosity of the hydraulic composition slurry over time, even when the hydraulic composition contains, in addition to cement, one or more alternative powders selected from powders having pozzolanic properties, powders having latent hydraulic properties, and calcium carbonate. In other words, the hydraulic composition admixture of the present invention can be suitably used as an admixture for hydraulic compositions that contain, in addition to cement, one or more alternative powders selected from a pozzolanic powder, a latent hydraulic powder, and calcium carbonate. In particular, the admixture for hydraulic compositions of the present invention contains cement and the substitute powder, and the mass ratio of the content of the substitute powder to the total content of cement and the substitute powder [substitute powder / (cement + substitute powder)] is preferably 0.40 or more, preferably 0.45 or more, preferably 1.0 or less, more preferably 0.8 or less, even more preferably 0.7 or less, even more preferably 0.6 or less, and even more preferably 0.55 or less, from the viewpoint of enjoying the effects of the present invention, and can be suitably used as an admixture for hydraulic compositions. The aforementioned substitute powders and cements can be appropriately adapted to the embodiments described in the hydraulic compositions of the present invention, which will be discussed later.

[0047] [Method for producing admixtures for hydraulic compositions] The present invention relates to a method for producing an admixture for hydraulic compositions, wherein component (A) and component (B) are mixed in such a mass ratio (B) / [(A)+(B)] of the amount of component (B) mixed to the total amount of components (A) and (B) mixed is 0.05 or more and 0.40 or less. The method for producing the admixture for hydraulic compositions of the present invention may further involve mixing in water. Components (A) and (B) are the same as those described in the admixture for hydraulic compositions of the present invention. The method for producing the admixture for hydraulic compositions of the present invention can be appropriately applied to the embodiments described in the description of the admixture for hydraulic compositions of the present invention. In the method for producing the admixture for hydraulic compositions of the present invention, the amount of component (A) mixed, the amount of component (B) mixed, the amount of water mixed, and the mass ratio (B) / [(A)+(B)] of the amount of component (B) mixed to the total amount of components (A) and (B) mixed can be appropriately applied by replacing the content of each component with the amount of mixing in the content and mass ratio of each component described in the admixture for hydraulic compositions of the present invention.

[0048] [Hydraulic composition] The present invention relates to a hydraulic composition containing component (A), component (B), cement, and water, wherein the mass ratio (B) / [(A)+(B)] of the content of component (B) to the total content of components (A) and (B) is 0.05 or more and 0.40 or less. The hydraulic composition of the present invention can be appropriately adapted to the embodiments described in the admixture for hydraulic composition and the method for producing the same of the present invention. Components (A) and (B) are the same as those described in the admixture for hydraulic compositions of the present invention.

[0049] Examples of cement include one or more selected from 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.

[0050] Even when the hydraulic composition of the present invention contains, in addition to cement, one or more substitute powders selected from powders having pozzolanic properties, powders having latent hydraulic properties, and calcium carbonate, the increase in viscosity of the hydraulic composition slurry over time is suppressed. Examples of the substitute powder include one or more selected from blast furnace slag, fly ash, anhydrous gypsum, silica fume, calcium carbonate, and calcined clay. From the viewpoint of enjoying the effects of the present invention, one or more selected from calcium carbonate, blast furnace slag, and fly ash is preferred, and one or more selected from calcium carbonate and blast furnace slag is more preferred.

[0051] 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.

[0052] In the hydraulic composition of the present invention, the content of component (A) is preferably 0.10 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 0.35 parts by mass or more, and preferably 1.0 part by mass or less, more preferably 0.80 parts by mass or less, even more preferably 0.60 parts by mass or less, even more preferably 0.50 parts by mass or less, and even more preferably 0.40 parts by mass or less, per 100 parts by mass of cement, from the viewpoint of dispersibility and viscosity improvement.

[0053] In the hydraulic composition of the present invention, the content of component (B) is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, even more preferably 0.05 parts by mass or more, even more preferably 0.10 parts by mass or more, and preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass or less, even more preferably 1.2 parts by mass or less, even more preferably 0.90 parts by mass or less, even more preferably 0.60 parts by mass or less, even more preferably 0.30 parts by mass or less, and even more preferably 0.20 parts by mass or less, per 100 parts by mass of cement, from the viewpoint of improving viscosity.

[0054] In the hydraulic composition of the present invention, the total content of component (A) and component (B) is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, even more preferably 0.3 parts by mass or more, and preferably 1.0 part by mass or less, more preferably 0.8 parts by mass or less, and even more preferably 0.6 parts by mass or less, per 100 parts by mass of cement, from the viewpoint of improving viscosity.

[0055] In the hydraulic composition of the present invention, the mass ratio (B) / [(A)+(B)] of the content of component (B) to the total content of components (A) and (B) is 0.05 or more, preferably 0.10 or more, more preferably 0.15 or more, even more preferably 0.20 or more, even more preferably 0.23 or more, and 0.40 or less, preferably 0.35 or less, and even more preferably 0.30 or less, from the viewpoint of dispersibility and viscosity improvement.

[0056] In the hydraulic composition of the present invention, the mass percentage of water content to cement content (water / cement ratio (W / C)) is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 75% by mass or less, and preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 65% ​​by mass or more, from the viewpoint of ensuring strength and improving viscosity. Here, the water / cement ratio (W / C) is the mass percentage (mass%) of the water content to the cement content in the hydraulic composition, and is calculated as water / cement × 100.

[0057] In the hydraulic composition of the present invention, when the alternative powder is contained, the mass ratio of the content of the alternative powder to the total content of cement and the alternative powder [alternative powder / (cement + alternative powder)] is preferably 0.40 or more, preferably 0.45 or more, and preferably 1.0 or less, more preferably 0.8 or less, still more preferably 0.7 or less, even more preferably 0.6 or less, even more preferably 0.55 or less, from the viewpoint of enjoying the effects of the present invention.

[0058] In the hydraulic composition of the present invention, when the alternative powder is contained, the mass percentage of the content of water (W) to the total content of cement (C) and the alternative powder (P) (water / (cement + alternative powder) ratio W / (C + P)) is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, even more preferably 40% by mass or less, and preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, even more preferably 30% by mass or more, from the viewpoints of ensuring strength and improving viscosity. Here, the water / (cement + alternative powder) ratio (W / (C + P)) is the mass percentage of the content of water (W) to the total content of cement (C) and the alternative powder (P), and is calculated by water / (cement + alternative powder) × 100.

[0059] When the hydraulic composition of the present invention is concrete, the amount of coarse aggregate used, from the viewpoints of developing the strength of the hydraulic composition and reducing the amount of hydraulic powder such as cement and improving the filling property into a formwork or the like, the bulk volume is preferably 50% or more, more preferably 55% or more, still more preferably 60% or more, and preferably 100% or less, more preferably 90% or less, still more preferably 80% or less. The bulk volume is the ratio of the volume (including voids) of the coarse aggregate in 1 m of concrete. 3 It is the ratio of the volume of the coarse aggregate (including voids) in the concrete. Also, when the hydraulic composition of the present invention is concrete, the amount of fine aggregate used, from the viewpoint of improving the filling property into a formwork or the like, is preferably 500 kg / m 3 or more, more preferably 600 kg / m 3 or more, still more preferably 700 kg / m 3Above, and preferably 1000 kg / m 3 or less, more preferably 900 kg / m 3 or less. When the hydraulic composition of the present invention is mortar, the amount of fine aggregate used is preferably 800 kg / m 3 or more, more preferably 900 kg / m 3 or more, still more preferably 1000 kg / m 3 or more, and preferably 2000 kg / m 3 or less, more preferably 1800 kg / m 3 or less, still more preferably 1700 kg / m 3 or less.

[0060] The hydraulic composition of the present invention can contain components such as a water-soluble polymer compound, a cement wetting agent, an expansion agent, a waterproof agent, a retarder, a quick-setting agent, a foaming agent, a foaming agent, a waterproof agent, a fluidizing agent, a thickening agent, a flocculant, a drying shrinkage reducing agent, a strength enhancer, a curing accelerator, a preservative, an antifoaming agent (however, excluding those corresponding to component (A) and component (B)).

[0061] Examples of the hydraulic composition of the present invention include concrete and the like. Among them, concrete using cement is preferred. The hydraulic composition of the present invention is useful in any field such as for centrifugal molding, self-leveling, refractories, plaster, lightweight or heavyweight concrete, AE, repair, prepacked, tremie, ground improvement, grout, cold weather use, etc. )]]

[0062] 〔Method for producing hydraulic composition〕 The present invention provides a method for producing a hydraulic composition, in which component (A), component (B), cement, and water are mixed such that the mass ratio (B) / [(A)+(B)] of the mixing amount of component (B) to the total mixing amount of component (A) and component (B) is 0.05 or more and 0.40 or less. By this production method, a hydraulic composition of the present invention containing component (A), component (B), cement, and water, and having a mass ratio (B) / [(A)+(B)] of the content of component (B) to the total content of component (A) and component (B) of 0.05 or more and 0.40 or less is produced. The method for producing the hydraulic composition of the present invention may further involve mixing in the aforementioned alternative powder. The method for producing the hydraulic composition of the present invention may further involve mixing in aggregate. The components (A) and (B) 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 the cement, the substitute powder, and the 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, cement is mixed such that the W / C ratio is within the range described in the hydraulic composition of the present invention. Furthermore, it is preferable that the substitute powder is mixed such that the mass ratio of the amount of substitute powder mixed to the total amount of cement and substitute powder mixed [substitute powder / (cement + substitute powder)] and W / (C+P) are 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 amount of component (A) mixed, the amount of component (B) mixed, the total amount of component (A) and component (B) mixed, and the mass ratio (B) / [(A)+(B)] of the amount of component (B) mixed to the total amount of component (A) and component (B) mixed can be appropriately applied by replacing the content of each component with the amount of mixing in the content and mass ratio of each component described in the hydraulic composition of the present invention. 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.

[0063] 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), and water, and then mix them with a mixture of cement, any alternative powder, and any aggregate. Furthermore, in the method for producing the hydraulic composition of the present invention, it is preferable to add components (A) and (B) using the admixture for hydraulic compositions of the present invention, and it is even more preferable to pre-mix the admixture for hydraulic compositions of the present invention with water and then mix it with a mixture of cement, any alternative powder and any aggregate.

[0064] The mixing of component (A), component (B), cement, any alternative powder, any aggregate, water, and 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 5 minutes or less, more preferably for 3 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. [Examples]

[0065] Table 1 shows the components (A) and (A') (comparative components of (A)) used in the examples and comparative examples, and component (B) is shown below.

[0066] [Table 1]

[0067] The constituent monomers used in Table 1 are as follows: MEPEG(9): Methoxypolyethylene glycol(9) monomethacrylate (the number in parentheses represents the average number of moles of ethylene oxide added.) MEPEG(23): Methoxypolyethylene glycol(23) monomethacrylate (the number in parentheses represents the average number of moles of ethylene oxide added.)

[0068] <Manufacturing of Copolymer A-1> 497.04 g of water was placed in a glass reaction vessel equipped with a stirrer, and while stirring, the vessel was purged with nitrogen and heated to 80°C in a nitrogen atmosphere. Two solutions were added dropwise to the vessel over 1.5 hours: one was a mixture of 411.11 g of an aqueous solution containing MEPEG(9) and methacrylic acid (349.64 g of MEPEG(9) and 61.47 g of methacrylic acid) and 5.81 g of 2-mercaptoethanol; the other was a solution of 7.07 g of ammonium persulfate dissolved in 30 g of water. Next, a solution of 1.41 g of ammonium persulfate dissolved in 10 g of water was added dropwise over 30 minutes, and the mixture was then aged at the same temperature (80°C) for 1 hour. After aging, the mixture was neutralized with 37.18 g of a 48% aqueous sodium hydroxide solution to obtain a reaction product containing copolymer A-1 with a weight-average molecular weight of 40,000 and water. Other copolymers in Table 1 were also manufactured in the same manner as described above, by changing the type and amount of constituent monomers used.

[0069] In Table 1, the weight-average molecular weight (Mw) and the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn), Mw / Mn, for each copolymer were 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)

[0070] <(B) component> ·Polyethylene glycol(3) lauryl ether phosphatepotassium salt: In general formula (B1-1), R 1bA compound in which C12 is an alkyl group, AO is an ethyleneoxy group, m is 3, k is 1, and M is potassium. Phosphanol RS-410 (C12-15) Pales-3phosphate: In general formula (B1-1), R 1b A compound in which C12-C15 alkyl group, AO is an ethylene oxy group, m is 3, k is 1, and M is a hydrogen atom. Manufactured by Toho Chemical Industry Co., Ltd. Phosphoric acid, isotridecyl ester: In general formula (B1-1), R 1b A compound where is an alkyl group with 13 carbon atoms, AO is none, m is 0, k is 1, and M is potassium. ·Polyethylene glycol(2) butyl etherphosphate potassium salt: In general formula (B1-1), R 1b A compound in which C4 is an alkyl group, AO is an ethyleneoxy group, m is 2, k is 1, and M is potassium.

[0071] [Mortar Test] (1) Mortar mix Table 2 shows the mortar mixes. W / C is the mass percentage of water content to cement content in the mortar mix (W / C × 100), W / (C+P) is the mass percentage of water content to the total content of cement and the substitute powder calcium carbonate in the mortar mix (W / (C+P) × 100), and P / (C+P) is the mass ratio of calcium carbonate content to the total content of cement and calcium carbonate [P / (C+P)].

[0072] [Table 2]

[0073] *Mortar mixture The following mortar materials were used, as shown in Table 2. Cement (C): Ordinary Portland cement (two-component mixture: manufactured by Taiheiyo Cement / manufactured by Sumitomo Osaka Cement = 1 / 1 (mass ratio)) Density 3.16 g / cm³ 3 • Calcium carbonate (P): NeoFlow 150, manufactured by Shimizu Kogyo Co., Ltd., density 2.71 g / cm³ 3 • Water (W): Tap water (containing component (A) or component (A'), and component (B)), density 1.00 g / cm³ 3 • Fine aggregate (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'), and (B) in the tap water were trace amounts relative to the mortar mixture, they were included in the calculation of W / C and W / (C+P) by including them in the amount of tap water.

[0074] (2) Preparation of mortar (hydraulic composition) The mortar mixture was prepared by adding the components (A) or (A') and (B) in the mortar (hydraulic composition) to tap water (W) and stirring, so that their content relative to 100 parts by mass of cement was as shown in Table 3. Using a mortar mixer (a multi-purpose mixing and stirring machine manufactured by Nishinihon Shikenki Co., Ltd., model: C-210, small mortar mixer), fine aggregate (S) was added and dry mixing was performed for 10 seconds at low speed (63 rpm) of the mortar mixer. Then, 100 g of tap water (part of the water (W) in Table 2) was added and mixed for 1 minute. Next, cement (C) and calcium carbonate (P) were added and mixed for 1 minute, and the mixed water (W) containing the prepared admixture for hydraulic composition was added. Finally, the mixture was thoroughly mixed for 120 seconds at low speed (63 rpm) of the mortar mixer to prepare the mortar. The content of component (A) or (A') and component (B) was determined such that the initial flow value of the hydraulic composition immediately after kneading was 220 mm ± 10 mm, as measured by the JIS R 5201 test method (flow test) using a conical container with a diameter of 100 mm.

[0075] (3) Evaluation of mortar viscosity Immediately after preparation, the mortar was filled into a device shaped like Figure 1, made by processing stainless steel (SUS304), with the lower discharge opening (2) closed. After scraping the mortar off the surface of the upper input opening (1), the lower discharge opening (2) was opened to allow the mortar to flow naturally. The time until holes could be seen in at least a portion of the mortar when observed visually from the upper input opening (1) (flow time) was measured and used to evaluate viscosity. A shorter flow time indicates lower mortar viscosity. Furthermore, the prepared mortar was stirred with a shovel for 10 seconds 30 minutes and 60 minutes after contact with the cement, and its viscosity was measured using the same method as above. The results are shown in Table 3.

[0076] [Table 3]

[0077] In Table 3, the content of component (A) and the content of component (B) are the respective contents per 100 parts by mass of cement, and are based on the effective content. The total content of (A) + (B) is the total content of component (A) and component (B) per 100 parts by mass of cement, and (B) / [(A) + (B)] (mass ratio) is the mass ratio of the content of component (B) in the hydraulic composition to the total content of component (A) and component (B). In Table 3, the notation "blocked" in the mortar viscosity evaluation indicates that the lower discharge opening (2) was blocked, making it impossible to measure the flow time.

[0078] In the mortar preparation method of (2), the fine aggregate (S) is deliberately thoroughly moistened with water before mixing with cement (C) and calcium carbonate (P) to create an aggregated state. Since the viscosity of the aggregated hydraulic composition slurry increases and its workability deteriorates, the evaluation was conducted under harsh conditions. However, even under these harsh conditions, it can be seen that the embodiment of the present invention is able to suppress the increase in viscosity of the hydraulic composition slurry over time, even when the hydraulic composition contains substitute powders. [Explanation of symbols]

[0079] 1...Top loading opening 2. Lower discharge opening

Claims

1. An admixture for hydraulic compositions, comprising the following components (A) and (B), wherein the mass ratio (B) / [(A)+(B)] of the content of component (B) to the total content of components (A) and (B) is 0.05 or more and 0.40 or less. (A) Component: A copolymer containing a constituent monomer (A1) represented by the following general formula (A1) and a constituent monomer (A2) represented by the following general formula (A2) as constituent monomers, wherein the proportion of constituent monomer (A1) in the total amount of constituent monomer (A1) and constituent monomer (A2) is 15% by mass or more and 30% by mass or less. 【Chemistry 1】 [During the ceremony, R １ａ 、 R ２ａ 、 R ３ａ : The same or different, a hydrogen atom, a methyl group or (CH ２ ) ｒ COOM ２ａ wherein, when (CH ２ ) ｒ COOM ２ａ forms an anhydride with COOM １ａ or another (CH ２ ) ｒ COOM ２ａ there is no M １ａ 、 M ２ａ for those groups. M １ａ M ２ａ : The same or different hydrogen atom, alkali metal, alkaline earth metal (half atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group or alkenyl group r: A number between 0 and 2 (inclusive) This indicates... 【Chemistry 2】 [During the ceremony, R ４ａ , R ５ａ : The same or different hydrogen atom or methyl group R ６ａ : Hydrogen atom, methyl group, (CH ２ ) ｒ COOM ３ａ , or (CH ２ ) ｑ１ (CO) ｐ１ O (AO) ｎ１ R ７a R ７ａ : 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 5 and 25. q1: A number between 0 and 6 (inclusive) p1: 0 or 1 M ３ａ : Hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group or alkenyl group r: A number between 0 and 2 (inclusive) This indicates... (B) Component: One or more selected from phosphate monoesters having a group represented by the following general formula (B1), phosphate diesters having a group represented by the following general formula (B1), and salts thereof. R １ｂ -O(AO) ｍ - (B1) [In the formula, R １ｂ [where is a hydrocarbon group with 4 to 15 carbon atoms, AO is an alkylene oxy group with 2 to 4 carbon atoms, and m is the average number of moles of AO added, which is between 0 and 5.]

2. The admixture for a hydraulic composition according to claim 1, which is for a hydraulic composition comprising a powder having pozzolanic activity, a powder having latent hydraulic properties, and one or more substitute powders selected from calcium carbonate.

3. A hydraulic composition containing the following component (A), component (B), cement, and water, wherein the mass ratio (B) / [(A)+(B)] of the content of component (B) to the total content of components (A) and (B) is 0.05 or more and 0.40 or less. (A) Component: A copolymer containing a constituent monomer (A1) represented by the following general formula (A1) and a constituent monomer (A2) represented by the following general formula (A2) as constituent monomers, wherein the proportion of constituent monomer (A1) in the total amount of constituent monomer (A1) and constituent monomer (A2) is 15% by mass or more and 30% by mass or less. 【Transformation 3】 [During the ceremony, R １ａ , R ２ａ , R ３ａ : The same or different, hydrogen atom, methyl group or (CH ２ ) ｒ COOM ２ａ (CH ２ ) ｒ COOM ２ａ COOM １ａ or other (CH ２ ) ｒ COOM ２ａ When forming anhydrous substances, the M of those groups １ａ M ２ａ It does not exist. M １ａ M ２ａ : The same or different hydrogen atom, alkali metal, alkaline earth metal (half atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group or alkenyl group r: A number between 0 and 2 (inclusive) This indicates... 【Chemistry 4】 [During the ceremony, R ４ａ , R ５ａ : The same or different hydrogen atom or methyl group R ６ａ : Hydrogen atom, methyl group, (CH ２ ) ｒ COOM ３ａ , or (CH ２ ) ｑ１ (CO) ｐ１ O (AO) ｎ１ R ７a R ７ａ : 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 5 and 25. q1: A number between 0 and 6 (inclusive) p1: 0 or 1 M ３ａ : Hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group or alkenyl group r: A number between 0 and 2 (inclusive) This indicates... (B) Component: One or more selected from phosphate monoesters having a group represented by the following general formula (B1), phosphate diesters having a group represented by the following general formula (B1), and salts thereof. R １ｂ -O(AO) ｍ - (B1) [In the formula, R １ｂ [where is a hydrocarbon group with 4 to 15 carbon atoms, AO is an alkylene oxy group with 2 to 4 carbon atoms, and m is the average number of moles of AO added, which is between 0 and 5.]

4. The hydraulic composition according to claim 3, further comprising a powder having pozzolanic properties, a powder having latent hydraulic properties, and one or more alternative powders selected from calcium carbonate.

5. The hydraulic composition according to claim 4, wherein the mass ratio of the content of the substitute powder to the total content of cement and the substitute powder [substitute powder / (cement + substitute powder)] is 0.4 or more.

Images