Additive composition for hydraulic compositions

Abstract

The present invention provides an additive composition for hydraulic compositions that improves the strength of a hardened hydraulic composition even in low-temperature environments (e.g., 0-10°C) simulating winter conditions, for example, 7-28 days after preparation, and a hydraulic composition that improves the strength of a hardened hydraulic composition even in low-temperature environments (e.g., 0-10°C) simulating winter conditions, for example, 7-28 days after preparation. [Solution] An additive composition for hydraulic compositions containing the following component (A) and component (B). (A) Ingredients: Calcite (B) Component: A specific alkanolamine compound represented by general formula (b)

Description

Technical Field

[0001] The present invention relates to an additive composition for a hydraulic composition and a hydraulic composition.

Background Art

[0002] In recent years, from the perspective of decarbonization, effective utilization of blended cement obtained by mixing alternative powders with Portland cement has been demanded. As alternative powders, powders having latent hydraulicity such as fine powder of blast furnace slag, powders having pozzolanic activity such as fly ash, metakaolin, and volcanic ash, and inorganic fillers such as fine powder of limestone are used. However, the reactivity of these alternative powders is significantly lower than that of Portland cement. Therefore, especially in winter when the reactivity decreases, there are many cases where the design strength of a structure cannot be achieved within a predetermined period. Also, even at sites where blended cement mixed with alternative powders is used from spring to autumn, there are many cases where Portland cement is used in winter to ensure strength. Furthermore, at sites where blended cement mixed with alternative powders is used in winter, measures such as extending the curing period and increasing the amount of binder per unit volume are taken to ensure strength, but problems such as prolongation of the construction period, increase in manufacturing cost, and deterioration of workability have occurred. From the above, when using blended cement mixed with alternative powders, it is required to obtain sufficient strength development even in a low-temperature environment assuming winter. On the other hand, from the perspective of realizing a low-carbon society, so-called carbon recycling, which captures carbon dioxide as a carbon resource, recovers it, and reuses it as various carbon compounds, has attracted attention. Calcium carbonate is cited as one of the materials that can reuse carbon dioxide, and technologies for increasing the added value of calcium carbonate are required.

[0003] Patent Document 1 discloses an accelerating agent for a hydraulic composition containing (a) calcite, (b) a specific polycarboxylic acid-based dispersant, and water. The accelerating agent for the hydraulic composition is excellent in workability during transportation and during the preparation of the hydraulic composition because of its low viscosity during shear, and it is disclosed that the strength of the hardened body of the hydraulic composition after, for example, 5 to 20 hours from the preparation is improved. Patent Document 2 discloses a cement setting accelerator composed of calcium carbonate adjusted to have an average particle size of less than 0.7 μm. The cement setting accelerator is disclosed to cause no phenomenon that adversely affects the durability of the hardened body, such as reinforcing bar corrosion or alkali-aggregate reaction, and moreover, to have an excellent setting acceleration effect.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] Generally, the strength of the hardened body of a hydraulic composition varies depending on the season. For example, in a low-temperature environment assumed in winter (for example, 0 to 10°C), the strength of the hardened body of the hydraulic composition decreases. Therefore, there is a strong demand for providing an additive composition for a hydraulic composition that improves the strength at low temperatures. Therefore, an object of the present invention is to provide an additive composition for a hydraulic composition that improves the strength of the hardened body of the hydraulic composition, for example, 7 to 28 days after preparation, even in a low-temperature environment assumed in winter (for example, 0 to 10°C), and a hydraulic composition in which the strength of the hardened body of the hydraulic composition, for example, 7 to 28 days after preparation, is improved even in a low-temperature environment assumed in winter (for example, 0 to 10°C).

Means for Solving the Problems

[0006] The present invention relates to an additive composition for a hydraulic composition containing the following component (A) and the following component (B). Component (A): Calcite Component (B): A compound represented by the following general formula (b)

[0007] [ka]

[0008] [In the formula, R 1b , R 2b : Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -AO-H, and a group selected from the following general formula (b1), where AO represents an alkylene oxy group having 2 to 4 carbon atoms.

[0009] [ka]

[0010] The present invention also relates to a hydraulic composition containing component (A), component (B), cement, and water. [Effects of the Invention]

[0011] The present invention provides an additive composition for hydraulic compositions that improves the strength of a hardened hydraulic composition even in low-temperature environments (e.g., 0 to 10°C) simulating winter conditions, for example, 7 to 28 days after preparation, and a hydraulic composition that improves the strength of a hardened hydraulic composition even in low-temperature environments (e.g., 0 to 10°C) simulating winter conditions, for example, 7 to 28 days after preparation. [Modes for carrying out the invention]

[0012] The reason why the additive composition for hydraulic compositions of the present invention improves the strength of the hardened hydraulic composition even in low-temperature environments (e.g., 0-10°C) simulating winter conditions, for example, 7-28 days after preparation, is not entirely clear, but it is presumed to be as follows. Component (A) of the present invention is presumed to function as an precipitation agent for the hydration reaction products of Portland cement, thereby contributing to the acceleration of the hydration reaction of the calcium silicate phase in Portland cement during the early stages of its age. Furthermore, component (B) of the present invention is presumed to contribute to the acceleration of the hydration reaction of the interstitial phase in Portland cement during the mid-to-long term of its age by promoting the dissolution of iron ions, aluminum ions, and gypsum contained in Portland cement through its chelating action. Normally, when component (A) is used alone, it is presumed that only the very early stages of the calcium silicate phase reaction are accelerated, but when component (B) is used in combination, the dissolution of iron ions and aluminum ions around the calcium silicate phase is accelerated, resulting in the acceleration of the hydration reaction of the calcium silicate phase during the mid-to-long term. Furthermore, while it is generally known that the hydration reaction rate of Portland cement is temperature-dependent, it is unexpectedly presumed that the combined use of components (A) and (B) stimulated the hydration reaction of the inactivated calcium silicate phase even at low temperatures, resulting in high strength development. However, the present invention is not limited to the mechanism of action described above.

[0013] [Additive composition for hydraulic compositions] The additive composition for hydraulic compositions of the present invention contains calcite as component (A). Calcite is calcium carbonate that has the crystalline structure of calcite. Calcite can be obtained from "heavy calcium carbonate" produced by crushing natural limestone, or from "synthetic calcium carbonate (or light calcium carbonate)" produced by synthesizing calcium carbonate in water using calcium, carbon dioxide, and alkali. From the viewpoint of strength development in hydraulic compositions, synthetic calcite is preferred. In addition, the additive composition for the hydraulic composition of the present invention may contain, as minerals other than calcite, calcium hydroxide, vaterite, aragonite, etc., which are contained in natural limestone or remain as unreacted components during the carbonation reaction of calcium, calcium carbonate hydrates such as ikaite, basic calcium carbonate, and other amorphous calcium carbonates. However, these calcium carbonates other than calcite are not included in the component (a) of the present invention. Vaterite is calcium carbonate having the crystal structure of fatterite (vaterite or vaterite). Aragonite is calcium carbonate having the crystal structure of arareite (aragonite). Ikaite is calcium carbonate hexahydrate having the crystal structure of ika stone (ikaite). Basic calcium carbonate is a crystalline mineral represented by the chemical composition of Ca3(OH)2(CO3)2·1.5H2O.

[0014] (A) From the viewpoint of the strength development property of the hydraulic composition at low temperatures, the BET specific surface area of calcite of the component is preferably 1 m 2 / g or more, more preferably 10 m 2 / g or more, still more preferably 20 m 2 / g or more, even more preferably 40 m 2 / g or more, and preferably 200 m 2 / g or less, more preferably 150 m 2 / g or less, still more preferably 120 m 2 / g or less, even more preferably 100 m 2 / g or less. BET specific surface area is a gas adsorption method in which gaseous particles such as nitrogen (N2) are adsorbed onto solid particles, and the surface area is measured from the amount of adsorbed particles. Specifically, the specific surface area is determined by measuring the amount of single-molecule adsorbed VM using the BET equation (Brunauer, Emmet, and Teller's equation) based on the relationship between pressure P and the amount of adsorption V. This measurement can be performed using a fully automatic specific surface area measuring device (for example, the fully automatic specific surface area measuring device Macsorb, manufactured by Mountec Co., Ltd.).

[0015] (A) The average primary particle size of the calcite in component (A) is preferably 5 nm or more, more preferably 10 nm or more, even more preferably 15 nm or more, and preferably 1000 nm or less, more preferably 500 nm or less, even more preferably 100 nm or less, and even more preferably 50 nm or less, from the viewpoint of the strength development of the hydraulic composition at low temperatures. (a) The average primary particle size of the calcite component can be calculated using the following formula, in addition to direct observation with a scanning electron microscope (SEM), transmission electron microscope (TEM), etc. d = 6 / (ρ × s) d: Average particle diameter (nm) ρ: Density of calcium carbonate s: Specific surface area The specific surface area in this invention can be measured by a gas adsorption method using nitrogen, water vapor, argon, krypton, etc., and it is preferable to use the BET specific surface area measured by the BET method using nitrogen gas as described above. In addition, the average primary particle diameter of calcium carbonate in this invention is calculated assuming a density of calcium carbonate of 2.71.

[0016] The calcite of component (A) has a crystallite size of the (10⁴) plane calculated by Scherrer's formula that is preferably 50 nm or less, more preferably 40 nm or less, even more preferably 30 nm or less, and preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 15 nm or more, from the viewpoint of the strength development of the hydraulic composition at low temperatures.

[0017] The crystallite size of the (10⁴) plane of calcite can be calculated using an X-ray structural diffractometer (for example, a desktop X-ray diffractometer MiniFlex600, manufactured by Rigaku Corporation) using the following Scherrer formula. D = Kλ / (βcosθ) D: Crystallite size (nm) K: Scherrer constant λ: Wavelength of the X-ray being measured β: Full width at half maximum of the X-ray peak being measured θ: Bragg angle of the X-ray peak of the target X-ray. In this invention, the crystallite size is preferably measured using CuKα X-rays. When using CuKα, the wavelength is λ = 1.5406 Å. The Scherrer constant is set to 0.9, and the Bragg angle of the (10⁴) plane of calcite is set to 14.657 degrees for calculation.

[0018] The additive composition for hydraulic compositions of the present invention may contain (A) calcite as aggregated secondary particles. In the present invention, "secondary particles" means particles that are isolated from other particles by aggregating primary calcite particles so as to share a portion of their outer circumference (grain boundary). The secondary particles of component (A), calcite, may exist as spherical or chain-like aggregated particles. Of these, spherical is preferred from the viewpoint of rapid strengthening of the hydraulic composition. Spherical does not mean only perfectly spherical, but may also be elliptical, nearly spherical, or have fine holes or irregularities on the surface, with a ratio of short axis to long axis of 1:1 to 1:2. Spherical does not include primary calcite particles linked together in a chain. The shape of the secondary calcite particles can be observed with a transmission electron microscope or scanning electron microscope.

[0019] (A) The following methods can be used to produce calcite, a component of this product. Calcium carbonate calcite is produced by mixing calcium hydroxide, a compound other than calcium hydroxide, and water to prepare an aqueous dispersion, and then introducing carbon dioxide into the aqueous dispersion under constant water temperature conditions until the pH reaches 7. Compounds other than calcium hydroxide include alkaline earth metal hydroxides such as magnesium hydroxide and barium hydroxide, sulfates such as lithium sulfate, sodium sulfate, potassium sulfate, calcium sulfate, magnesium sulfate, aluminum sulfate, zinc sulfate, and alum, magnesium salts such as magnesium chloride, magnesium nitrate, and magnesium acetate, zinc salts such as zinc chloride and zinc nitrate, organic acids and their salts such as acetic acid, citric acid, and gluconic acid, and high molecular weight organic acids and their salts such as polyacrylic acid. From the viewpoint of the crystallite size of the resulting calcite, one or more compounds selected from magnesium hydroxide, sodium sulfate, magnesium sulfate, and zinc sulfate are preferred, one or more compounds selected from zinc sulfate and magnesium hydroxide are more preferred, and magnesium hydroxide is even more preferred. Here, the mass ratio of the amount of calcium hydroxide mixed to the amount of compounds other than calcium hydroxide in the aqueous dispersion (calcium hydroxide / compounds other than calcium hydroxide) is preferably 10 or more, more preferably 30 or more, even more preferably 50 or more, and preferably 100 or less, and more preferably 80 or less, from the viewpoint of the crystallite size of the calcite produced.

[0020] The additive composition for hydraulic compositions of the present invention contains component (A) in the additive composition in an amount of preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more, from the viewpoint of the strength development of the hydraulic composition at low temperatures, and preferably 100% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, from the viewpoint of the ease of handling of the additive composition for hydraulic compositions.

[0021] The additive composition for hydraulic compositions of the present invention contains, as component (B), a compound represented by the following general formula (b).

[0022] [ka]

[0023] [In the formula, R 1b , R2b : Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -AO-H, and a group selected from the following general formula (b1), where AO represents an alkylene oxy group having 2 to 4 carbon atoms.

[0024] [ka]

[0025] In general formula (b), R 1b From the viewpoint of the strength development of the hydraulic composition at low temperatures, the group is preferably selected from a methyl group, a hydroxyethyl group, a hydroxypropyl group, and a group represented by general formula (b1), more preferably a group selected from a hydroxyethyl group and a hydroxypropyl group, and even more preferably a hydroxyethyl group. In general formula (b), R 2b From the viewpoint of the strength development of the hydraulic composition at low temperatures, the group is preferably selected from a methyl group, a hydroxyethyl group, and a hydroxypropyl group, more preferably selected from a hydroxyethyl group and a hydroxypropyl group, and even more preferably a hydroxyethyl group. In general formula (b), AO is an alkylene oxy group having 2 or more carbon atoms and 4 or fewer carbon atoms, preferably 3 or fewer carbon atoms.

[0026] (B) Specifically, component (B) is one or more selected from 2,2'-methyliminodiethanol, 2,2'-ethyliminodiethanol, 2,2'-propyliminodiethanol, 2,2'-butyliminodiethanol, 2,2'-[(2-hydroxypropyl)imino]bisethanol, 2,2',2''-nitrilotriethanol, 1,1',1''-nitrilotri-2-propanol, 2,2',2'',2'''-ethylenednitrilotetraethanol, 1,1'-[(2-hydroxyethyl)imino]bis(2-propanol), and 1,1',1'',1''''-(ethylenednitrilo)tetra-2-propanol, and the hydraulic composition is effective at low temperatures. From the viewpoint of strength expression, one or more selected from 2,2'-methyliminodiethanol, 2,2'-[(2-hydroxypropyl)imino]bisethanol, 1,1',1''-nitrilotri-2-propanol, 2,2',2'',2'''-ethylenednitrilotetraethanol, and 1,1'-[(2-hydroxyethyl)imino]bis(2-propanol) are preferred, one or more selected from 2,2'-methyliminodiethanol, 2,2'-[(2-hydroxypropyl)imino]bisethanol, and 1,1'-[(2-hydroxyethyl)imino]bis(2-propanol) are more preferred, and 2,2'-methyliminodiethanol is even more preferred.

[0027] The additive composition for hydraulic compositions of the present invention contains component (B) in an amount of preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, from the viewpoint of the strength development of the hydraulic composition at low temperatures, and preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, from the viewpoint of the ease of handling of the additive composition for hydraulic compositions.

[0028] In the additive composition for hydraulic compositions of the present invention, the mass ratio (A) / (B) of the content of component (A) to the content of component (B) is preferably 1 or more, more preferably 2 or more, even more preferably 5 or more, even more preferably 10 or more, and preferably 300 or less, more preferably 250 or less, even more preferably 200 or less, even more preferably 160 or less, even further 140 or less, even further 120 or less, even further 100 or less, even further 80 or less, even further 60 or less, and even further 40 or less.

[0029] The additive composition for hydraulic compositions of the present invention preferably contains a formaldehyde derivative as component (C) from the viewpoint of the strength development of the hydraulic composition at low temperatures. A formaldehyde derivative is a compound obtained by reaction with formaldehyde, or a compound that decomposes in the hydraulic composition and releases formaldehyde.

[0030] Component (C) specifically includes one or more selected from formaldehyde, 1,3,5-trioxane, sodium hydroxymethanesulfonate, methylolated urea, ureaform, methylolated thiourea, melamine formalin resin prepolymer, phenol formalin resin prepolymer, urea formalin resin prepolymer, and furfuryl alcohol formalin resin prepolymer. From the viewpoint of the strength development of the hydraulic composition at low temperatures, one or more selected from methylolated urea, sodium hydroxymethanesulfonate, and urea formalin resin prepolymer are more preferred, and methylolated urea and sodium hydroxymethanesulfonate are even more preferred.

[0031] The additive composition for hydraulic compositions of the present invention, when it contains component (C), contains component (C) in the additive composition in an amount of preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, from the viewpoint of the strength development of the hydraulic composition at low temperatures, and preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, from the viewpoint of the solubility of component (C) in the additive composition for hydraulic compositions.

[0032] From the viewpoint of the dispersibility of the hydraulic composition, the additive composition for hydraulic compositions of the present invention preferably contains a dispersant for hydraulic compositions as component (D).

[0033] The dispersant for the hydraulic composition of component (D) includes one or more compounds selected from naphthalene polymers, polycarboxylic acid polymers, ligninsulfonic acid polymers, melamine polymers, polymers containing phosphate groups in their structure, and polymers containing aromatics having polyalkylene oxy groups. From the viewpoint of dispersibility of the hydraulic composition, polycarboxylic acid polymers are preferred.

[0034] Polycarboxylic acid polymers can include copolymers of a monoester of polyalkylene glycol and (meth)acrylic acid with a carboxylic acid such as (meth)acrylic acid (for example, the compound described in Japanese Patent Publication No. 8-12397), copolymers of an unsaturated alcohol having polyalkylene glycol with a carboxylic acid such as (meth)acrylic acid, and copolymers of an unsaturated alcohol having polyalkylene glycol with a dicarboxylic acid such as maleic acid. Here, (meth)acrylic acid refers to a carboxylic acid selected from acrylic acid and methacrylic acid.

[0035] Examples of polycarboxylic acid polymers (hereinafter also referred to as (d1)) include copolymers containing a monomer (11d) represented by the following general formula (11d) and a monomer (12d) represented by the following general formula (12d) as constituent monomers.

[0036] [ka]

[0037] [During the ceremony, R 11d , R 12d , R 13d : They may be the same or different, and may be a hydrogen atom, a methyl group, or (CH2) r COOM 12 (CH2) rCOOM 12 COOM 11 or other (CH2) r COOM 12 They may also form anhydrous compounds, in which case the M of those groups 11 M 12 It does not exist. M 11 M 12 : 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...

[0038] [ka]

[0039] [During the ceremony, R 14d , R 15d , R 16d : They may be the same or different, hydrogen atom, methyl group, (CH2) s COOM 13 , or (CH2) q1 (CO) p1 O(AO) n1 -R 17d R 17d : 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 13 : 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...

[0040] In the general formula (11d), from the standpoint of availability, R 11d A hydrogen atom is preferred. In the general formula (11d), from the standpoint of availability, R 12d A hydrogen atom or a methyl group is preferred. In the general formula (11d), from the standpoint of availability, R 13d A hydrogen atom is preferred. (CH2) r COOM 12 Regarding COOM 11 or other (CH2) r COOM 12 They may also form anhydrous compounds, in which case the M of those groups 11 M 12 It does not exist. M 11 and M 12 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 11 and M 12 The alkyl group, hydroalkyl group, and alkenyl group each preferably have 1 to 4 carbon atoms. M 11 and M 12 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 (11d) r COOM 12 r is preferably 0.

[0041] In general formula (12d), R 14d From the standpoint of availability, hydrogen atoms are preferred. In general formula (12d), R 15dFrom the viewpoint of availability and dispersibility of the hydraulic composition, hydrogen atoms or methyl groups are preferred, and methyl groups are more preferred. In general formula (12d), R 16d From the standpoint of availability, hydrogen atoms are preferred. In general formula (12d), R 17d From the viewpoint of availability, a hydrogen atom or a methyl group is preferred, and a methyl group is more preferred. In general formula (12d), 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 the general formula (12d), 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 50 or more, even more preferably 80 or more, and preferably 150 or less, more preferably 130 or less, and even more preferably 120 or less. In general formula (12d), from the viewpoint of the dispersibility of the hydraulic composition, q1 is preferably 0, 1, or 2, more preferably 0 or 1, and even more preferably 0. In general formula (12d), from the viewpoint of the dispersibility of the hydraulic composition, p1 is preferably 1. In general formula (12d), M 13 These are hydrogen atoms, alkali metals, alkaline earth metals (1 / 2 atom), ammonium groups, alkylammonium groups, substituted alkylammonium groups, alkyl groups, hydroalkyl groups, or alkenyl groups. M 13 The alkyl group, hydroalkyl group, and alkenyl group each preferably have 1 to 4 carbon atoms. M 13 The 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 (12d), (CH2) sCOOM 13 s is preferably 0.

[0042] In the copolymer of (d1), the proportion of monomer (11d) in the total amount of monomer (11d) and monomer (12d) is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and even more preferably 20% by mass or less.

[0043] Of the total constituent monomers of the copolymer (d1), the proportion of monomer (11d) is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and even more preferably 20% by mass or less.

[0044] Of the total constituent monomers of copolymer (d1), the sum of monomer (11d) and monomer (12d) 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 the dispersibility of the hydraulic composition. This sum may be 100% by mass.

[0045] The weight-average molecular weight of copolymer (d1) is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 20,000 or more, even more preferably 30,000 or more, and preferably 100,000 or less, more preferably 80,000 or less, even more preferably 60,000 or less, and even more preferably 50,000 or less, from the viewpoint of the dispersibility of the hydraulic composition.

[0046] The weight-average molecular weight of the copolymer 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)

[0047] The copolymer of (d1) may optionally contain, in addition to monomer (11d) and monomer (12d), one or more monomers (13d) that are copolymerizable with monomer (11d) and / or monomer (12d). Examples of monomer (13d) include acrylic acid esters. The copolymer of (d1) may contain 100% by mass of monomer (11d) and monomer (12d) in total constituent units, or 100% by mass of monomer (11d), monomer (12d), and monomer (13d).

[0048] The additive composition for hydraulic compositions of the present invention, when it contains component (D), contains component (D) in the additive composition in an amount of preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, from the viewpoint of the dispersion stability of component (A) and the dispersibility of the hydraulic composition, and preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of the solubility of component (C) in the additive composition for hydraulic compositions.

[0049] From the viewpoint of the strength development of the hydraulic composition at low temperatures and the ease of handling of the additive composition, the additive composition of the present invention preferably contains, as component (E), one or more selected from polyols having 2 to 100 carbon atoms, sugars, and oxycarboxylic acids and their salts.

[0050] Examples of polyols having 2 to 100 carbon atoms include polyols with a valency of 2 to 6. Specifically, these include glycerin, alkylene oxide adducts of glycerin such as ethylene oxide adducts of glycerin, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, sorbitol, xylitol, erythritol, pentaerythritol, and ethylene oxide adducts thereof, and one or more of these can be used.

[0051] Examples of sugars include glucose, fructose, galactose, mannose, maltose, talose, ribose, erythrose, xylulose, cellulose, ribulose, lyxose, arabinose, sucrose, and dextrin, and one or more of these can be used.

[0052] The oxycarboxylic acid is a so-called hydroxycarboxylic acid having a hydroxyl group and a carboxyl group in its molecule. The number of carbon atoms in the oxycarboxylic acid is preferably 2 or more, more preferably 3 or more, preferably 18 or less, more preferably 12 or less, even more preferably 10 or less, and even more preferably 8 or less. The number of hydroxyl groups in the oxycarboxylic acid is preferably 1 or more, more preferably 2 or more, even more preferably 4 or more, preferably 18 or less, more preferably 12 or less, even more preferably 10 or less, and even more preferably 8 or less. The number of carboxyl groups in the oxycarboxylic acid is preferably 1 or more, preferably preferably 12 or less, more preferably 6 or less, and even more preferably 3 or less. Specifically, the oxycarboxylic acid is one or more selected from gluconic acid, citric acid, glucoheptonic acid, arabonic acid, malic acid, tartaric acid, tartonic acid, glyceric acid, glycolic acid, and salts thereof. Examples of oxycarboxylic acid salts include alkali metal salts such as sodium salts and alkaline earth metal salts such as magnesium salts.

[0053] Component (E) is preferably one or more selected from glycerin, diethylene glycol, sorbitol, glucose, dextrin, sucrose, and sodium gluconate, more preferably one or more selected from glycerin, sucrose, and sodium gluconate, and even more preferably glycerin, from the viewpoint of the strength development of the hydraulic composition at low temperatures and the ease of handling of the additive composition.

[0054] The additive composition for hydraulic compositions of the present invention, when it contains component (E), contains component (E) in the additive composition in an amount of preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, from the viewpoint of the strength development of the hydraulic composition at low temperatures and the ease of handling of the additive composition, and preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, from the viewpoint of the ease of handling of the additive composition.

[0055] The additive composition for hydraulic compositions of the present invention may contain water. That is, the additive composition for hydraulic compositions of the present invention may be a liquid composition containing water, preferably an aqueous dispersion. The additive composition for hydraulic compositions of the present invention, when it contains water, contains water in an amount of 0% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, from the viewpoint of ease of handling of the additive composition, and from the viewpoint of economy, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0056] The additive composition for hydraulic compositions of the present invention may further contain other components. Examples include AE ​​agents, retarders, foaming agents, thickeners, foaming agents, waterproofing agents, fluidizing agents, defoaming agents, etc. (excluding components corresponding to (A), (B), (C), (D), and (E)).

[0057] The additive composition for hydraulic compositions of the present invention can be used by adding it when preparing a hydraulic composition by mixing cement and water. Furthermore, from the viewpoint of the strength development of the hydraulic composition at low temperatures, it is preferable to use the additive composition for hydraulic compositions of the present invention in the form of an aqueous dispersion in which component (A) is dispersed by component (D) when preparing the hydraulic composition. Furthermore, from the viewpoint of improving the miscibility with cement, it is preferable to use the additive composition for hydraulic compositions of the present invention by mixing it with water beforehand when mixing cement and water.

[0058] [Method for producing additive compositions for hydraulic compositions] The additive composition for hydraulic compositions of the present invention can be produced by mixing component (A) and component (B). In other words, the present invention provides a method for producing an additive composition for hydraulic compositions by mixing component (A) and component (B). The method for producing the additive composition for hydraulic compositions of the present invention may further involve mixing in component (C). The method for producing the additive composition for hydraulic compositions of the present invention may further involve mixing in component (D). The method for producing the additive composition for hydraulic compositions of the present invention may further involve mixing in component (E). The method for producing the additive composition for hydraulic compositions of the present invention may further involve mixing in water. Specific examples and preferred embodiments of components (A), (B), (C), (D), and (E) are the same as those described in the additive composition for hydraulic compositions of the present invention. In the method for producing the additive composition for hydraulic compositions of the present invention, the amount of (A) mixed, the amount of (B) mixed, the amount of (C) mixed, the amount of (D) mixed, the amount of (E) mixed, the amount of water mixed, and the mass ratio (A) / (B) of the amount of (A) mixed to the amount of (B) mixed can be applied to the method for producing the additive composition for hydraulic compositions of the present invention by replacing the content of each component with the amount of mixing in each mass ratio of the additive composition for hydraulic compositions of the present invention. The method for producing the additive composition for hydraulic compositions of the present invention can be appropriately applied to the embodiments described in the description of the additive composition for hydraulic compositions of the present invention. In the method for producing the additive composition for hydraulic compositions of the present invention, from the viewpoint of the strength development of the hydraulic composition at low temperatures, it is preferable to obtain the composition in the form of an aqueous dispersion in which component (A) is dispersed with component (D) and water.

[0059] [Hydraulic composition] The present invention provides a hydraulic composition containing component (A), component (B), cement, and water. The hydraulic composition of the present invention may further contain component (C). The hydraulic composition of the present invention may further contain component (D). The hydraulic composition of the present invention may further contain component (E). Specific examples and preferred embodiments of components (A), (B), (C), (D), and (E) are the same as those described in the additive composition for hydraulic compositions of the present invention. Components (A), (B), (C), (D), and (E) can be incorporated into a hydraulic composition using the hydraulic composition additive composition of the present invention. In other words, the present invention provides a hydraulic composition containing the additive composition for hydraulic compositions of the present invention, cement, and water. The hydraulic composition of the present invention can be appropriately adapted to the embodiments described in the additive composition for the hydraulic composition of the present invention.

[0060] 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.

[0061] The hydraulic composition of the present invention may contain, in addition to cement, one or more alternative powders selected from powders having pozzolanic properties and powders having latent hydraulic properties. When a hydraulic composition contains the aforementioned substitute powder, the strength of the hardened hydraulic composition decreases after, for example, 7 to 28 days from preparation, under low-temperature conditions (e.g., 0 to 10°C) simulating winter conditions. However, with the additive composition for hydraulic compositions of the present invention, and the hydraulic composition of the present invention, even when the hydraulic composition contains the aforementioned substitute powder, the strength of the hardened hydraulic composition can be improved after, for example, 7 to 28 days from preparation, under low-temperature conditions (e.g., 0 to 10°C) simulating winter conditions. Examples of the substitute powder include one or more selected from blast furnace slag fine powder, fly ash, anhydrous gypsum, silica fume, calcined kaolinite, metakaolin, stone powder of natural ores such as limestone and silica, and volcanic ash. From the viewpoint of enjoying the effects of the present invention, one or more selected from blast furnace slag fine powder, fly ash, metakaolin, and volcanic ash are preferred, and one or more selected from blast furnace slag fine powder, fly ash, and metakaolin are more preferred. However, component (A) is excluded from the aforementioned substitute powder.

[0062] In the hydraulic composition of the present invention, the mass percentage of water and hydraulic powder (total content of cement and the substitute powder) in the hydraulic composition (water / hydraulic powder ratio (W / P)) is preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, even more preferably 35% by mass or more, even more preferably 45% by mass or more, and preferably 200% by mass or less, more preferably 100% by mass or less, even more preferably 80% by mass or less, even more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less. Here, the water / hydraulic powder ratio (W / P) is the mass percentage (mass%) of water and hydraulic powder in the hydraulic composition, and is calculated as water / hydraulic powder × 100. Furthermore, if the hydraulic powder includes powders that harden through hydration reactions such as cement, powders that exhibit pozzolanic properties, and one or more alternative powders selected from latent hydraulic properties, the amounts of these alternative powders are also included in the amount of hydraulic powder in this invention (however, the amount of calcium carbonate, which is component (A), is not included). This also applies to other parts by mass related to the mass of the hydraulic powder.

[0063] In the hydraulic composition of the present invention, if the substitute powder is included, 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 0.1 or more, more preferably 0.15 or more, even more preferably 0.2 or more, and preferably 0.9 or less, more preferably 0.8 or less, and even more preferably 0.7 or less, from the viewpoint of enjoying the effects of the present invention.

[0064] The hydraulic composition of the present invention contains, with respect to 100 parts by mass of hydraulic powder, component (A) preferably in an amount of 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, even more preferably 0.5 parts by mass or more, even more preferably 0.7 parts by mass or more, even more preferably 0.9 parts by mass or more, even more preferably 1.1 parts by mass or more, even more preferably 1.3 parts by mass or more, and from the viewpoint of economic efficiency, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or even more preferably 2 parts by mass or less.

[0065] The hydraulic composition of the present invention contains component (B) in an amount of 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, even more preferably 0.01 parts by mass or more, per 100 parts by mass of hydraulic powder, from the viewpoint of strength development of the hydraulic composition at low temperatures, and from the viewpoint of economic efficiency, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, even more preferably 0.3 parts by mass or less, even more preferably 0.2 parts by mass or less, and even more preferably 0.15 parts by mass or less.

[0066] In the hydraulic composition of the present invention, the mass ratio (A) / (B) of the content of component (A) to the content of component (B) is preferably 1 or more, more preferably 2 or more, even more preferably 5 or more, even more preferably 10 or more, and preferably 300 or less, more preferably 250 or less, even more preferably 200 or less, even more preferably 160 or less, even further 140 or less, even further 120 or less, even further 100 or less, even further 80 or less, even further 60 or less, and even further 40 or less.

[0067] The hydraulic composition of the present invention, when it contains component (C), contains component (C) in an amount of 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, even more preferably 0.01 parts by mass or more, per 100 parts by mass of hydraulic powder, from the viewpoint of strength development of the hydraulic composition at low temperatures, and from the viewpoint of economy, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, even more preferably 0.3 parts by mass or less, even more preferably 0.2 parts by mass or less, and even more preferably 0.1 parts by mass or less.

[0068] The hydraulic composition of the present invention, when it contains component (D), contains component (D) in an amount of preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass or more, even more preferably 0.15 parts by mass or more, and even more preferably 0.30 parts by mass or more, per 100 parts by mass of hydraulic powder, from the viewpoint of dispersibility of the hydraulic composition, and preferably 2 parts by mass or less, more preferably 1 part by mass or less, even more preferably 0.8 parts by mass or less, and even more preferably 0.6 parts by mass or less, from the viewpoint of economic efficiency.

[0069] The hydraulic composition of the present invention, when it contains component (E), contains component (E) in an amount of 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, even more preferably 0.01 parts by mass or more, per 100 parts by mass of hydraulic powder, from the viewpoint of strength development of the hydraulic composition at low temperatures, and from the viewpoint of economy, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, even more preferably 0.3 parts by mass or less, even more preferably 0.2 parts by mass or less, and even more preferably 0.1 parts by mass or less.

[0070] The hydraulic composition of the present invention may contain aggregate. Examples of aggregate include fine aggregate and coarse aggregate. Examples of fine aggregate include those specified in JIS A 0203-2014, number 2311. Examples of fine aggregate include river sand, land sand, mountain sand, sea sand, lime sand, silica sand and their crushed 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 A 0203-2014, 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.

[0071] When the hydraulic composition 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 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 More preferably 900 kg / m 3 The following applies: When the hydraulic composition 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 3More preferably, 1800 kg / m 3 More preferably, 1700 kg / m 3 The following applies:

[0072] In the hydraulic composition of the present invention, if aggregate is included, the mass ratio [aggregate / hydraulic powder] of the aggregate content to the hydraulic powder content (total content of cement and the substitute powder) is preferably 1.0 or more, more preferably 1.5 or more, even more preferably 2.0 or more, and preferably 10 or less, more preferably 7.5 or less, and even more preferably 5 or less, from the viewpoint of maintaining strength.

[0073] The hydraulic composition of the present invention may be concrete or mortar. The hydraulic composition of the present invention is useful in any field, such as self-leveling, refractory, plaster, lightweight or mass concrete, AE, repair, pre-packed, tremie, ground improvement, grouting, and cold weather applications. The hydraulic composition of the present invention can improve the strength of the hardened hydraulic composition even in low-temperature environments (e.g., 0-10°C) simulating winter conditions, for example, 7-28 days after preparation. Therefore, it is preferable to use it in concrete vibration products, centrifugal molded products, secondary tunnel linings, bridge piers, beams, box culverts, concrete pavements, etc.

[0074] The hydraulic composition of the present invention can be cured by air curing in a low-temperature environment (e.g., 0-10°C) simulating winter conditions. The hydraulic composition of the present invention can be obtained with improved strength in the cured hydraulic composition after, for example, 7-28 days from preparation, without curing under heating conditions of 40°C or higher, i.e., without so-called heat curing.

[0075] [Method for producing a hydraulic composition] The hydraulic composition of the present invention can be produced by mixing component (A), component (B), cement, and water. In other words, the present invention provides a method for producing a hydraulic composition by mixing component (A), component (B), cement, and water. 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 component (D). The method for producing the hydraulic composition of the present invention may further involve mixing in component (E). 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. Specific examples and preferred embodiments of components (A), (B), (C), (D), and (E) are the same as those described in the additive composition for hydraulic compositions of the present invention. Specific examples and preferred embodiments of cement, the substitute 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 amount of component (A), the amount of component (B), the amount of component (C), the amount of component (D), the amount of component (E), and the mass ratio (A) / (B) of the amount of component (A) to the amount of component (B) can be applied to the method for producing the hydraulic composition of the present invention by replacing the content of each component with the amount of each component in the content of each component and each mass ratio. In the method for producing the hydraulic composition of the present invention, the cement is mixed such that the W / P 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)] is within the range described in the hydraulic composition of the present invention. Furthermore, it is preferable that the mass ratio of the amount of aggregate mixed to the amount of hydraulic powder mixed (total amount of cement and substitute powder mixed) [aggregate / hydraulic powder] is also within the range described in the hydraulic composition of the present invention. The method for producing the hydraulic composition of the present invention can appropriately apply the embodiments described in the hydraulic composition additive composition and method for producing the same, as well as the hydraulic composition of the present invention. Components (A), (B), (C), (D), and (E) can be mixed into a hydraulic composition using the hydraulic composition additive composition of the present invention. In other words, the present invention provides a method for producing a hydraulic composition by mixing the additive composition for hydraulic compositions of the present invention, cement, and water. In the method for producing the hydraulic composition of the present invention, from the viewpoint of the strength development of the hydraulic composition at low temperatures, it is preferable to mix component (A) in an aqueous dispersion obtained by dispersing component (D) with water. [Examples]

[0076] The materials used in the examples and comparative examples are shown below. <(A) component> • Synthesis of a-1 In a glass reaction vessel (four-necked flask) equipped with a stirrer, 944 g of deionized water, 60 g of calcium hydroxide (reagent grade, manufactured by Fujifilm Wako Pure Chemical Industries), 1 g of magnesium hydroxide (reagent grade, manufactured by Fujifilm Wako Pure Chemical Industries), and 5 g of zinc sulfate aqueous solution (100 g of zinc sulfate (reagent grade, manufactured by Fujifilm Wako Pure Chemical Industries) dissolved in 100 g of deionized water) were charged. Under conditions of a water temperature of 15°C, carbon dioxide (100 vol%) was blown in at a flow rate of 1.0 L / min until the pH was 7 or less, to obtain a slurry of calcium carbonate (calcite) a-1. The obtained calcium carbonate slurry was filtered by suction using a Buchner funnel to prepare a dehydrated cake of calcium carbonate (calcite) a-1.

[0077] • Synthesis of a-2 949 g of deionized water, 60 g of calcium hydroxide (reagent grade, manufactured by Fujifilm Wako Pure Chemical Industries), and 1 g of magnesium hydroxide (reagent grade, manufactured by Fujifilm Wako Pure Chemical Industries) were charged into a glass reaction vessel (four-necked flask) equipped with a stirrer. Under conditions of a water temperature of 15°C, carbon dioxide (100 vol%) was blown in at a flow rate of 1.0 L / min until the pH was 7 or less, to obtain a slurry of calcium carbonate (calcite) a-2. The obtained calcium carbonate slurry was filtered by suction using a Buchner funnel to prepare a dehydrated cake of calcium carbonate (calcite) a-2.

[0078] Dehydrated cakes of synthesized a-1 and a-2 were dried at room temperature under a nitrogen environment, and the BET specific surface area, average primary particle diameter, and crystallite size of the (10⁴) plane were measured. The results are shown in Table 1.

[0079] The BET specific surface area of ​​each component (A) was measured using the BET method with nitrogen gas as the adsorbing gas, and a fully automatic specific surface area measuring device (Macsorb, manufactured by Mountec Co., Ltd.). Furthermore, the average primary particle diameter of component (a) was calculated using the BET specific surface area measured above, according to the following formula. d = 6 / (ρ × s) d: Average particle diameter (nm) ρ: Density of calcium carbonate (2.71) s:BET specific surface area

[0080] The crystallite size of the (10⁴) plane of component (A) was measured using an X-ray structural diffractometer (benchtop X-ray diffractometer MiniFlex600, manufactured by Rigaku Corporation) and calculated using the following Scherrer formula. D = Kλ / (βcosθ) D: Crystallite size (nm) K: Scherrer constant λ: Wavelength of the X-ray being measured β: Full width at half maximum of the X-ray peak being measured θ: Bragg angle of the X-ray peak of the target X-ray. Measurements were performed using CuKα X-rays, with a CuKα wavelength of λ = 1.5406 Å. The Scherrer constant was set to 0.9, and the Bragg angle of the (10⁴) plane of calcite was calculated to be 14.657 degrees. The X-ray structural diffraction apparatus was used with a high-speed one-dimensional detector, tube voltage of 40 kV, tube current of 15 mV, step width of 0.02 degrees, and step speed of 10 min / deg.

[0081] <(B) component> • 2,2'-Methyliminodiethanol: Manufactured by Tokyo Chemical Industry Co., Ltd. ·2,2'-[(2-hydroxypropyl)imino]bisethanol: Manufactured by Tokyo Chemical Industry Co., Ltd. ·2,2',2''-nitrilotriethanol: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. · 1,1',1''-nitrilotri-2-propanol: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ·2,2',2'',2'''-Ethylenednitrilotetraethanol: Manufactured by Tokyo Chemical Industry Co., Ltd. • 1,1'-[(2-hydroxyethyl)imino]bis(2-propanol): Manufactured by Sigma-Aldrich Japan LLC.

[0082] <(C) component> • Methylolate urea: Manufactured by Tokyo Chemical Industry Co., Ltd. • Sodium hydroxymethanesulfonate: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0083] <(D) component> • Synthesis of d-1 350.65 g of deionized water was placed in a glass reaction vessel equipped with a stirrer, and while stirring, nitrogen purging was performed and the temperature was raised to 80°C in a nitrogen atmosphere. Two solutions were added dropwise to the vessel over 1.5 hours each: (i) 512.49 g of an aqueous solution containing methacrylic acid as monomer (11d) and methacrylic acid (methoxypolyethylene glycol 120 moles (average number of moles added)) ester (hereinafter referred to as MEPEG(120) ester) as monomer (12d) (water content 39.15% by mass, methacrylic acid content 2.97% by mass, MEPEG(120) ester content 51.37% by mass), mixed with 64.38 g of methacrylic acid and 7.98 g of 2-mercaptoethanol; and (ii) 5.55 g of ammonium persulfate dissolved in 22.19 g of deionized water. Next, 4.44 g of ammonium persulfate was dissolved in 17.76 g of deionized water and added dropwise over 30 minutes, followed by aging at the same temperature (80°C) for 1 hour. After aging, the mixture was neutralized with 11.28 g of 48% sodium hydroxide aqueous solution to obtain a reaction product containing a copolymer with a weight-average molecular weight (Mw) of 44,000 (hereinafter referred to as copolymer d-1) and water. In this method, the ratio of monomer (11d) to the total of monomer (11d) and monomer (12d) was 23.0% by mass. Furthermore, the solid content concentration in the reaction medium from the time of dropwise addition of the total amount of monomer (11d) and monomer (12d) until the end of the reaction (end of aging) was 40% by mass.

[0084] d-2: Polycarboxylic acid polymer, manufactured by Kao Corporation, Mighty 21HP

[0085] <Other materials> • Ordinary Portland Cement: A mixture of ordinary Portland cement manufactured by Taiheiyo Cement Corporation and ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd. in a mass ratio of 50 / 50, with a specific gravity of 3.16. • Blast furnace cement type B: JIS R5211 standard product, manufactured by Sumitomo Osaka Cement Co., Ltd. • Blast furnace slag fine powder: Manufactured by Nippon Steel Blast Furnace Cement Co., Ltd., Esment 40G2 • Fly ash: Manufactured by Techno Chubu Co., Ltd. • Metakaolin: Manufactured by SKW East Asia Co., Ltd. • Water: Tap water (Wakayama City tap water, specific gravity 1.00) • Fine aggregate: Mountain sand (from Joyo, Kyoto City, surface-dry specific gravity 2.50)

[0086] (1) Preparation of hydraulic composition (mortar) After adding component (A), water, and component (D) d-1 in the amounts shown in Table 1 (the remainder being deionized water), the mixture was stirred at 2000 rpm for 2 minutes using a stirrer equipped with a disperser blade to prepare an aqueous dispersion of component (A). In a test chamber adjusted to 10℃±2℃, cement (C), substitute powder (P1), and fine aggregate (S) were added to a mortar mixer (Dalton Co., Ltd., universal mixing and stirring machine, model: 5DM-03-γ) to the amounts listed in Tables 2 and 3. Dry mixing was performed for 10 seconds at low speed (63 rpm) of the mortar mixer. Mixing water (W) containing each dispersion from Table 1, components (B), (C), and (D), which were prepared to the amounts listed in Tables 2 and 3, was then added. Finally, the mixture was thoroughly mixed for 120 seconds at low speed (63 rpm) of the mortar mixer to prepare a hydraulic composition (mortar).

[0087] [Table 1]

[0088] (2) Formwork filling and curing Based on JIS A1132, mortar was filled into cylindrical plastic molds (base diameter: 5 cm, height: 10 cm) using a two-layer filling method. The molds were then sealed and cured in a constant temperature chamber (ESPEC Corporation PR-3J) with an air temperature adjusted to 10°C to allow them to harden. Starting from the point when the mixing water first came into contact with the cement, specimens were demolded after 28 days to obtain specimens for strength testing. Three specimens were prepared for each type of mortar prepared.

[0089] (3) Evaluation of curing strength The compressive strength of each prepared specimen was measured according to JIS A1108, and the average value of three specimens was calculated. The results are shown in Tables 2 and 3.

[0090] [Table 2]

[0091] [Table 3]

[0092] In Tables 2 and 3, W / P is the mass percentage (W / P × 100) of the water (W) content in the hydraulic composition (mortar) to the hydraulic powder (P) content (total amount of cement and substitute powder), and P1 / (C+P1) is the mass ratio [P1 / (C+P1)] of the substitute powder (P1) content in the hydraulic composition (mortar) to the total content of cement (C) and substitute powder (P1). Also, S / (C+P1) is the mass ratio [S / (C+P1)] of the aggregate (S) content in the hydraulic composition (mortar) to the total content of cement (C) and substitute powder (P1). In Tables 2 and 3, the content of the dispersion in the hydraulic composition (mortar), the content of component (A), the content of d-1, the content of component (B), the content of component (C), and the content of component (D) are the content per 100 parts by mass of hydraulic powder (total of cement and substitute powder), and (A) / (B) (mass ratio) is the mass ratio of the content of component (A) to the content of component (B) in the hydraulic composition. In Table 2, the curing strengths for Examples 1-1 to 1-4 and Comparative Examples 1-2 to 1-3 are shown as relative ratios with Comparative Example 1-1 set to 100. Furthermore, in Table 3, in order to evaluate the cement and alternative powders used in a standardized manner, the curing strengths of Examples 2-1 to 2-6 are shown as relative ratios of the curing strengths with Comparative Example 2-1 set to 100, the curing strengths of Examples 2-7 to 2-9 are shown as relative ratios with Comparative Example 2-2 set to 100, the curing strength of Example 2-10 is shown as a relative ratio with Comparative Example 2-3 set to 100, and the curing strengths of Examples 2-11 to 2-13 are shown as relative ratios with Comparative Example 2-4 set to 100.

Claims

1. An additive composition for hydraulic compositions, comprising the following component (A) and component (B). (A) Ingredients: Calcite (B) Component: Compound represented by the following general formula (b) 【Chemistry 1】 [In the formula, R １ｂ , R ２ｂ : Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -AO-H, and a group represented by the following general formula (b1), which may be the same or different, where AO represents an alkylene oxy group having 2 to 4 carbon atoms. 【Chemistry 2】

2. (A) The additive composition for hydraulic compositions according to claim 1, wherein component (A) is synthetic calcite.

3. The additive composition for hydraulic compositions according to claim 1 or 2, wherein the mass ratio (A) / (B) of the content of component (A) to the content of component (B) is 1 or more and 300 or less.

4. The additive composition for hydraulic compositions according to claim 1 or 2, further containing the following component (C). (C) Component: Formaldehyde derivative

5. The additive composition for hydraulic compositions according to claim 1 or 2, further containing the following component (D). (D) Component: Dispersant for hydraulic compositions

6. The additive composition for hydraulic compositions according to claim 1 or 2, further containing the following component (E). (E) Component: One or more selected from polyols with 2 to 100 carbon atoms, sugars, and oxycarboxylic acids and their salts.

7. A hydraulic composition containing the following components (A), (B), cement, and water. (A) Ingredients: Calcite (B) Component: Compound represented by the following general formula (b) 【Transformation 3】 [In the formula, R １ｂ , R ２ｂ : Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -AO-H, and a group represented by the following general formula (b1), which may be the same or different, where AO represents an alkylene oxy group having 2 to 4 carbon atoms. 【Chemistry 4】

8. (A) The hydraulic composition according to claim 7, wherein component (A) is synthetic calcite.

9. The hydraulic composition according to claim 7 or 8, wherein the mass ratio (A) / (B) of the content of component (A) to the content of component (B) is 1 or more and 300 or less.

10. The hydraulic composition according to claim 7 or 8, further comprising the following component (C). (C) Component: Formaldehyde derivative

11. The hydraulic composition according to claim 7 or 8, further comprising the following component (D). (D) Component: Dispersant for hydraulic compositions

12. The hydraulic composition according to claim 7 or 8, further comprising the following component (E). (E) Component: One or more selected from polyols with 2 to 100 carbon atoms, sugars, and oxycarboxylic acids and their salts.

13. The hydraulic composition according to claim 7 or 8, further comprising one or more alternative powders selected from powders having pozzolanic properties and powders having latent hydraulic properties.

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