WO2021070699A1 - Dispersant composition for hydraulic compositions for centrifugal molding - Google Patents

Abstract

Provided are: a dispersant composition for hydraulic compositions for centrifugal molding, the dispersant composition enabling a hydraulic composition to exhibit better moldability for a predetermined time (e.g., 15 minutes to 60 minutes) from kneading; a method for producing same; a hydraulic composition for centrifugal molding which exhibits better moldability for a predetermined time (e.g., 15 minutes to 60 minutes) from kneading; and a method for producing a cured product of a hydraulic composition. This dispersant composition for hydraulic compositions for centrifugal molding contains the following component (A) and water. Component (A): a copolymer (A) containing a monomer (A1) represented by general formula (A1), a monomer (A2) represented by general formula (A2), and a monomer (A3) represented by general formula (A3) as constituent monomers and having a molecular weight of 10,000 to 70,000, the monomer (A1) being present in an amount of 30 mol% to 70 mol% of the constituent monomers of the copolymer, the monomer (A2) being present in an amount of 10 mol% to 50 mol%, the monomer (A3) being present in an amount of 20 mol% to 35 mol%.

Description

Dispersant composition for water-hard composition for centrifugation

The present invention relates to a dispersant composition for a water-hard composition for centrifugation and a method for producing the same, a water-hard composition for centrifugation, and a method for producing a cured product of the water-hard composition.

Background technology Centrifugal molding is known as a method for manufacturing hollow cylindrical concrete molded products such as pipes, piles, and poles. This centrifugal molding method is a method in which a kneaded concrete material is put into a mold and the concrete is compacted by pressing the concrete against the inner surface of the mold by the centrifugal force generated by rotating the mold at high speed.
Forming by the centrifugal molding method is carried out before the uncured concrete hardens, but in production lines where it takes time to prepare the formwork under high temperature or in a very tight production situation, from kneading to centrifugal molding. It is known that the fluidity of concrete is impaired over time due to the lengthening of the time required for the process, and the concrete does not reach every corner of the formwork, often causing molding defects and defects. There is. Therefore, a hydraulic composition for centrifugal molding is desired, in which the hydraulic composition exhibits more excellent moldability for a certain period of time (for example, 15 minutes or more and 60 minutes or less) after kneading.

Japanese Unexamined Patent Publication No. 2002-121055 describes the unsaturated (poly) alkylene glycol ether-based monomer represented by the general formula (1) and the unsaturated monocarboxylic acid-based monomer represented by the general formula (2). A cement dispersant containing a copolymer containing the constituent unit of the above as an essential component and containing at least a structure in which the constituent unit is derived from acrylic acid (salt) is disclosed.
Japanese Patent Application Laid-Open No. 2002-348161 describes a structural unit (III) derived from a specific unsaturated polyalkylene glycol ether-based monomer (a2) and a specific unsaturated monocarboxylic acid-based monomer (b). A cement dispersant containing a copolymer containing a constituent unit (II) as an essential component, wherein the constituent unit (III) accounts for 50 mol% or less of all the constituent units of the copolymer, and the above. The number of milliequivalents of carboxyl groups when the structural unit (II) contains at least a structure derived from methacrylic acid (salt) and all the carboxyl groups of the copolymer are converted to the unneutralized type is per 1 g of the copolymer. Cement dispersants of 3.30 meq or less are disclosed.
Japanese Unexamined Patent Publication No. 2009-96672 describes a monomer containing a specific monomer 1 represented by the general formula (1) and a specific monomer 2 represented by the general formula (2), and a general formula. A dispersant for a water-hard composition containing a copolymer obtained by polymerizing the specific monomer 3 represented by (3), and a single amount in the constituent monomers of the copolymer. Dispersants for water-hard compositions are disclosed in which the ratios of the body 1, the monomer 2 and the monomer 3 are each in a specific range.
In Japanese Unexamined Patent Publication No. 2009-22125, the specific monomer 1 represented by the general formula (1), the specific monomer 2 represented by the general formula (2), and the general formula (3) are represented. A dispersion-holding agent for a water-hard composition obtained by polymerizing a specific monomer 3 and having a weight average molecular weight of 30,000 to 60,000, the composition of the copolymer of the copolymer. Dispersion-retaining agents for water-hard compositions are disclosed, wherein the monomer 1 is 25 to 78% by weight and the monomer 3 is 0 to 18% by weight among the polymers.

Outline of the Invention In the present invention, a dispersant composition for a water-hard composition for centrifugation and a dispersant composition thereof, wherein the water-hard composition exhibits better moldability for a certain period of time (for example, 15 minutes or more and 60 minutes or less) after kneading. In the method and the water-hard composition for centrifugation, the water-hard composition for centrifugation and the water-hard composition for which the water-hard composition exhibits better moldability for a certain period of time (15 minutes or more and 60 minutes or less) after kneading. Provided is a method for producing a cured product.

The present invention relates to a dispersant composition for a water-hard composition for centrifugation, which contains the following component (A) and water.
Component (A): A monomer (A1) represented by the following general formula (A1), a monomer (A2) represented by the following general formula (A2), and a single amount represented by the following general formula (A3). A copolymer having a weight average molecular weight of 10,000 or more and 70,000 or less containing the body (A3) as a constituent monomer, and the monomer (A1) is contained in the constituent monomers of the copolymer. The copolymer (A) in which 30 mol% or more and 70 mol% or less, the monomer (A2) is 10 mol% or more and 50 mol% or less, and the monomer (A3) is 20 mol% or more and 35 mol% or less.

[In the formula,
R ^11a , R ^12a , R ^13a : may be the same or different and may be a hydrogen atom, a methyl group or (CH ₂ ) _r COM ^2a , where (CH ₂ ) _r COM ^2a is COM ^1a or another (CH _2). ) _R COMM ^2a may form an anhydride, in which case M ^1a , M ^2a of those groups are absent.
M ^1a , M ^2a : The same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group or substituted alkylammonium group r: Number of 0 or more and 2 or less Is shown. ]

[In the formula,
R ^21a , R ^22a : may be the same or different, hydrogen atom or methyl group R ^23a : hydrogen atom or -COO (AO) _n X ^1a
X ^1a : Alkyl group or hydrogen atom having 1 or more and 4 or less carbon atoms AO: Group selected from ethyleneoxy group and propyleneoxy group n: Average number of moles of AO, 5 or more and 70 or less p: 0 or more and 2 The following numbers q: Indicates the number of 0 or 1. ]

[In the formula,
R ^31a : Indicates a hydrocarbon group that may contain a heteroatom having 1 or more and 4 or less carbon atoms. ]

The present invention also relates to a method for producing a dispersant composition for a water-hard composition for centrifugation, which mixes the component (A) with water.

The present invention also relates to a hydraulic composition for centrifugation, which contains the component (A), a hydraulic powder, an aggregate and water.

The present invention also relates to a method for producing a cured product of a hydraulic composition, which comprises the following steps.
Step 1: A step of mixing the component (A), the hydraulic powder, the aggregate, and water to obtain a hydraulic composition, and filling the mold with the obtained hydraulic composition.
Step 2: A step of applying centrifugal force to mold the hydraulic composition filled in the mold obtained in Step 1.
Step 3: A step of condensing the mold-clamped hydraulic composition obtained in Step 2 in a mold.

According to the present invention, in a dispersant composition for a water-hard composition for centrifugation and a method for producing the same, and a water-hard composition for centrifugation, in which the water-hard composition exhibits more excellent moldability for a certain period of time from kneading. Provided are a water-hardening composition for centrifugal molding in which the water-hardening composition exhibits more excellent moldability for a certain period of time from kneading, and a method for producing a cured water-hardening composition. This fixed time is, for example, 15 minutes or more and 60 minutes or less from kneading (meaning from the time when water first comes into contact with the hydraulic powder; the same applies hereinafter).

Embodiment for carrying out the invention The present inventors include the monomer (A1), the monomer (A2), and the monomer (A3) as constituent monomers in a specific ratio. When the dispersant composition for a water-hard composition for centrifugation containing the component (A) which is a polymer is used for the water-hard composition for centrifugation, it takes a certain period of time from kneading (for example, 15 minutes or more and 60 minutes or less). During the period, it was found that the moldability of the water-hard composition was improved.
The reason for such an effect is not always clear, but it is presumed as follows.
The component (A), which is a copolymer containing the monomer (A1), the monomer (A2), and the monomer (A3) as constituent monomers in a specific ratio, is at the initial stage of kneading. Has low adsorptivity to cement particles, and more component (A) remains in bulk water than a general polycarboxylic acid-based dispersant. By gradually adsorbing the residual component (A) to the cement particles over time, the dispersed state of the cement particles is maintained, and the fluidity of the concrete is maintained, so that a certain period of time (for example, 15 minutes or more) from kneading is 60. It is considered that the hydraulic composition exhibits better moldability during the period (less than a minute).

[Dispersant composition]
The present invention provides a dispersant composition for a water-hard composition for centrifugation, which contains the component (A) and water.

<Ingredient (A)>
The components (A) are the monomer (A1) represented by the following general formula (A1), the monomer (A2) represented by the following general formula (A2), and the simple compound represented by the following general formula (A3). A copolymer having a weight average molecular weight of 10,000 or more and 70,000 or less containing a dimer (A3) as a constituent monomer, and among the constituent monomers of the copolymer, the monomer (A1) Is 30 mol% or more and 70 mol% or less, the monomer (A2) is 10 mol% or more and 50 mol% or less, and the monomer (A3) is 20 mol% or more and 35 mol% or less, the copolymer (A). Is.

[In the formula,
R ^11a , R ^12a , R ^13a : may be the same or different and may be a hydrogen atom, a methyl group or (CH ₂ ) _r COM ^2a , where (CH ₂ ) _r COM ^2a is COM ^1a or another (CH _2). ) _R COMM ^2a may form an anhydride, in which case M ^1a , M ^2a of those groups are absent.
M ^1a , M ^2a : The same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group or substituted alkylammonium group r: Number of 0 or more and 2 or less Is shown. ]

[In the formula,
R ^21a , R ^22a : may be the same or different, hydrogen atom or methyl group R ^23a : hydrogen atom or -COO (AO) _n X ^1a
X ^1a : Alkyl group or hydrogen atom having 1 or more and 4 or less carbon atoms AO: Group selected from ethyleneoxy group and propyleneoxy group n: Average number of moles of AO, 5 or more and 70 or less p: 0 or more and 2 The following numbers q: Indicates the number of 0 or 1. ]

[In the formula,
R ^31a : Indicates a hydrocarbon group that may contain a heteroatom having 1 or more and 4 or less carbon atoms. ]

In the general formula (A1), R ^11a is preferably a hydrogen atom from the viewpoint of stability of centrifugation over time.
In the general formula (A1), R ^12a is preferably a methyl group or a hydrogen atom, and more preferably a hydrogen atom, from the viewpoint of stability of centrifugation over time.
In the general formula (A1), R ^13a is preferably a hydrogen atom.
For (CH ₂ ) _r COMM ^2a , anhydrous may be formed with COOM ^1a or other (CH ₂ ) _r COMM ^{2a , in which case M 1a} and M ^2a of those groups are absent.
Regarding the copolymer (A), from the viewpoint of stability of centrifugal moldability over time, M ^1a and M ^{2a in} the general formula (A1) may be the same or different, and hydrogen atoms are preferable, respectively.
_{The r of (CH 2} ) r COMM ^{2a in} the general formula (A1) is preferably 1 from the viewpoint of stability of centrifugal moldability over time.

In the general formula (A2), R ^21a is preferably a hydrogen atom from the viewpoint of stability of centrifugation over time.
In the general formula (A2), R ^22a is preferably a methyl group from the viewpoint of stability of centrifugation over time.
In the general formula (A2), R ^23a is preferably a hydrogen atom from the viewpoint of stability of centrifugation over time.
In the general formula (A2), X ^1a is preferably a methyl group or a hydrogen atom from the viewpoint of stability of centrifugation over time.
In the general formula (A2), the AO is preferably an ethyleneoxy group from the viewpoint of stability of centrifugation over time. The AO preferably contains an ethyleneoxy group.

In the general formula (A2), n is the average number of moles added of AO, which is 5 or more and 70 or less. n is preferably 10 or more, more preferably 15 or more, still more preferably 20 or more, still more preferably 25 or more, still more preferably 25 or more, from the viewpoint of workability, dispersibility and stability of centrifugation over time. The number is 30, more preferably 35 or more, even more preferably 40 or more, even more preferably 45 or more, even more preferably 50 or more, and preferably 65 or less, more preferably 60 or less.

In the general formula (A2), p is preferably 1 or 2 from the viewpoint of stability of centrifugation over time.
In the general formula (A2), q is preferably 0 from the viewpoint of stability of centrifugation over time.

In the general formula (A3), R ^31a is a hydrocarbon group which may contain a heteroatom having 1 or more carbon atoms, preferably 2 or more carbon atoms, and 4 or less, preferably 3 or less carbon atoms. Heteroatoms are oxygen atoms, nitrogen atoms and the like.

Examples of the monomer (A3) include one or more selected from methyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, methoxyethyl acrylate, and n-butyl acrylate. From the viewpoint of stability of centrifugation over time, one or more selected from methyl acrylate, 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate is preferable.

In the constituent monomer of the copolymer (A),
From the viewpoint of fluidity immediately after kneading and stability of centrifugation over time, the monomer (A1) is 30 mol% or more, preferably 40 mol% or more, more preferably 50 mol% or more, and 70. Mol% or less, preferably 65 mol% or less, more preferably 60 mol% or less,
From the viewpoint of fluidity and stability of centrifugation over time, the monomer (A2) is 10 mol% or more, preferably 14 mol% or more, and 50 mol% or less, preferably 45 mol% or less. More preferably 40 mol% or less, still more preferably 30 mol% or less, even more preferably 25 mol% or less, still more preferably 20 mol% or less,
The monomer (A3) is 20 mol% or more, preferably 25 mol% or more, more preferably 30 mol% or more, and 35 mol% or less from the viewpoint of stability of centrifugal moldability over time.

The copolymer (A) is a monomer (A1), a monomer (A2), and a monomer (A3) in the constituent monomers from the viewpoint of fluidity and stability of centrifugation over time. The total amount of the above is 90 mol% or more, preferably 92 mol% or more, more preferably 95 mol% or more, and 100 mol% or less. This total amount may be 100 mol%.

The weight average molecular weight of the copolymer (A) is preferably 10,000 or more, more preferably 15,000 or more, still more preferably 20,000 or more, and preferably 100, from the viewpoint of fluidity and workability. It is 000 or less, more preferably 70,000 or less, still more preferably 50,000 or less. This weight average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions.
* GPC conditions Equipment: GPC (HLC-8320GPC) manufactured by Tosoh Corporation Column: G4000PWXL + G2500PWXL (manufactured by Tosoh Corporation)
Eluent: 0.2M phosphate buffer / CH ₃ CN = 9/1
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detection: RI
Sample size: 0.2 mg / mL
Standard substance: Polyethylene glycol equivalent (monodisperse polyethylene glycol: molecular weight 87,500, 250,000, 145,000, 46,000, 24,000)

In the dispersant composition for a water-hard composition for centrifugal molding of the present invention, the component (A) is preferably 1% by mass or more, more preferably 10% by mass or more, from the viewpoint of stability of centrifugal moldability over time. It is more preferably 20% by mass or more, preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less.

<Ingredient (B)>
The dispersant composition for a water-hard composition for centrifugation of the present invention preferably further contains the following component (B) from the viewpoint of fluidity and stability of centrifugation over time.
Component (B): A polymer (B1) represented by the following general formula (B1) and a monomer (B2) represented by the following general formula (B2) are contained as constituent monomers and have a molecular weight of 10,000. A copolymer of 70,000 or less, in which the monomer (B1) is 70 mol% or more and 99 mol% or less and the monomer (B2) is 1 mol% in the constituent monomers of the copolymer. Copolymer (B) of 30 mol% or more

[In the formula,
^{R 11b, R 12b, R 13b} : may be the same or different, a hydrogen atom, a methyl group or ^{_{(CH 2) r 'COOM 2b}} , (CH 2) r COOM 2b is, COOM ^1b or other (CH _{2) r 'COOM} ^2b and may form an anhydride, in which case, ^M 1b of those ^{groups, M 2b} is absent.
M ^1b , M ^2b : The same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group or substituted alkylammonium group r': 0 or more and 2 or less Show the number. ]

[In the formula,
R ^{21b, R 22b:} may be the same or different, a hydrogen atom or a methyl group R ^23b: a hydrogen atom or -COO (AO) _{n 'X} ^1b
X ^1b : Alkyl group or hydrogen atom having 1 or more and 4 or less carbon atoms AO: Group selected from ethyleneoxy group and propyleneoxy group n': Average number of moles of AO, 5 or more and 100 or less p': 0 Numbers greater than or equal to 2 and less than or equal to q': Indicates a number of 0 or 1. ]

In the general formula (B1), R ^11b is preferably a hydrogen atom from the viewpoint of stability of centrifugation over time.
In the general formula (B1), R ^12b is preferably a methyl group or a hydrogen atom from the viewpoint of stability of centrifugation over time.
In the general formula (B1), R ^13b is preferably a hydrogen atom from the viewpoint of stability of centrifugation over time.
_'For COOM ^{2b, COOM 1b} or other _{(CH 2) r' (CH} 2) r may also form COOM ^2b and anhydrides, in which case, ^M 1b of those ^{groups, M 2b} is absent ..
^{Regarding the copolymer (B), M 1b} and M ^2b may be the same or different in the general formula (B2) from the viewpoint of stability of centrifugation over time, and hydrogen atoms are preferable for each.
The _'r of COOM ^2b' formula (B1) in the _(CH 2) _r, from the viewpoint of the stability of a centrifugal molding property over time, 1 is preferable.

In the general formula (B2), R ^21b is preferably a hydrogen atom from the viewpoint of stability of centrifugation over time.
In the general formula (B2), R ^22b is preferably a methyl group from the viewpoint of stability of centrifugation over time.
In the general formula (B2), R ^23b is preferably a hydrogen atom from the viewpoint of stability of centrifugation over time.
In the general formula (B2), X ^1b is preferably a methyl group or a hydrogen atom from the viewpoint of stability of centrifugation over time.
In the general formula (B2), the AO is preferably an ethyleneoxy group from the viewpoint of stability of centrifugation over time. The AO preferably contains an ethyleneoxy group.

In the general formula (B2), n'is the average number of moles added of AO, which is 5 or more and 100 or less. n'is preferably 10 or more, more preferably 20 or more, and preferably 80 or less, more preferably 60 or less, from the viewpoint of fluidity, workability, and stability of centrifugation over time. ..

In the general formula (A2), p'is preferably 1 or 2 from the viewpoint of stability of centrifugation over time.
In the general formula (A2), q'is preferably 0 from the viewpoint of stability of centrifugation over time.

In the constituent monomer of the copolymer (B),
The monomer (B1) is 70 mol% or more, preferably more than 70 mol%, more preferably 72 mol% or more, still more preferably 72 mol% or more, from the viewpoint of fluidity, workability and stability of centrifugation over time. Is 75 mol% or more and 99 mol% or less, preferably 92 mol% or less, more preferably 85 mol% or less,
The monomer (B2) is 1 mol% or more, preferably 8 mol% or more, more preferably 15 mol% or more, and 30 from the viewpoint of fluidity, workability, and stability of centrifugation over time. It is mol% or less, preferably 28 mol% or less, and more preferably 25 mol% or less.

The total amount of the monomer (B1) and the monomer (B2) in the constituent monomer of the copolymer (B) is 90 mol from the viewpoint of fluidity and stability of centrifugation over time. % Or more, preferably 92 mol% or more, more preferably 95 mol% or more, and 100 mol% or less. This total amount may be 100 mol%.

The weight average molecular weight of the copolymer (B) is preferably 10,000 or more, more preferably 15,000 or more, still more preferably 20,000 or more, and preferably 100, from the viewpoint of fluidity and workability. It is 000 or less, more preferably 70,000 or less, still more preferably 50,000 or less. This weight average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions.
* GPC conditions Equipment: GPC (HLC-8320GPC) manufactured by Tosoh Corporation Column: G4000PWXL + G2500PWXL (manufactured by Tosoh Corporation)
Eluent: 0.2M phosphate buffer / CH ₃ CN = 9/1
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detection: RI
Sample size: 0.2 mg / mL
Standard substance: Polyethylene glycol equivalent (monodisperse polyethylene glycol: molecular weight 87,500, 250,000, 145,000, 46,000, 24,000)

In the dispersant composition for a water-hard composition for centrifugation of the present invention, the component (B) is preferably 1% by mass or more, more preferably, from the viewpoint of fluidity, workability and stability of centrifugation over time. Is contained in an amount of 10% by mass or more, more preferably 20% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less.

In the dispersant composition for a water-hard composition for centrifugal molding of the present invention, the total content of the component (A) and the component (B) is preferably 2% by mass or more from the viewpoint of the stability of the centrifugal moldability over time. , More preferably 10% by mass or more, further preferably 20% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less.

In the dispersant composition for a water-hard composition for centrifugation of the present invention, the mass ratio (B) / (A) of the content of the component (A) to the content of the component (B) is the fluidity and centrifugation with respect to the passage of time. From the viewpoint of moldability stability, it is preferably 0.02 or more, more preferably 0.1 or more, still more preferably 0.2 or more, still more preferably 0.5 or more, and preferably 10 or less, more preferably. It is 5 or less, more preferably 3 or less, still more preferably 2.5 or less, still more preferably 2 or less, still more preferably 1.5 or less, still more preferably 1 or less.

<Ingredient (C)>
The dispersant composition for a water-hard composition for centrifugation of the present invention preferably further contains the following component (C) from the viewpoint of strength development and stability of centrifugation over time.
Component (C): Hydroxycarboxylic acid

Examples of the hydroxycarboxylic acid of the component (C) include one or more selected from lactic acid, citric acid, tartrate acid, and gluconic acid, and lactic acid, from the viewpoint of strength development and stability of centrifugation over time. One or more selected from citric acid and gluconic acid are more preferable, and one or more selected from lactic acid and gluconic acid are further preferable.

In the dispersant composition for a water-hard composition for centrifugation of the present invention, the component (C) is preferably 0.0001% by mass or more, more preferably 0.0001% by mass or more, from the viewpoint of strength development and stability of centrifugation over time. Is contained in an amount of 0.001% by mass or more, more preferably 0.01% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less.

In the dispersant composition for a water-hard composition for centrifugation of the present invention, the total content of the component (A), the component (B) and the component (C) is determined from the viewpoint of fluidity and stability of centrifugation over time. Therefore, it is preferably contained in an amount of 2% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less. To do.

In the dispersant composition for a water-hard composition for centrifugation of the present invention, the mass ratio of the total content of the component (A) and the component (B) to the content of the component (C) [(A) + (B)]. / (C) is preferably 1 or more, more preferably 5 or more, still more preferably 10 or more, still more preferably 15 or more, and preferably 1 or more, from the viewpoint of fluidity and stability of centrifugation over time. It is 100 or less, more preferably 50 or less, still more preferably 25 or less.

The dispersant composition for a water-hard composition for centrifugal molding of the present invention contains water, preferably 10% by mass or more, more preferably 12% by mass or more, still more preferably 12% by mass or more, from the viewpoint of stability of centrifugal moldability over time. It is contained in an amount of 14% by mass or more, preferably 30% by mass or less, more preferably 28% by mass or less, still more preferably 25% by mass or less.

The dispersant composition for a water-hardening composition for centrifugation of the present invention is a conventional cement dispersant, a water-soluble polymer compound, an air entraining agent, a cement wetting agent, a swelling material, a waterproofing agent, a retarding agent, a quick-setting agent, and an increase. Ingredients such as thickeners, flocculants, drying shrinkage reducing agents, strength enhancers, curing accelerators, preservatives, antifoaming agents [However, those corresponding to (A) component, (B) component, and (C) component Excludes] can be contained.

[Method for producing dispersant composition]
The present invention provides a method for producing a dispersant composition for a water-hard composition for centrifugation, which mixes the component (A) with water. By this production method, the dispersant composition for a water-hard composition for centrifugation of the present invention containing the component (A) and water is produced.
In the method for producing a dispersant composition for a water-hard composition for centrifugation of the present invention, it is preferable to further mix the component (B). That is, the present invention provides a method for producing a dispersant composition for a water-hard composition for centrifugation, in which a component (A), a component (B) and water are mixed. By this production method, the dispersant composition for a water-hard composition for centrifugation of the present invention containing the component (A), the component (B), and water is produced.
In the method for producing a dispersant composition for a water-hard composition for centrifugation of the present invention, it is preferable to further mix the component (C). That is, the present invention provides a method for producing a dispersant composition for a water-hard composition for centrifugation, in which a component (A), a component (B), a component (C) and water are mixed. By this production method, the dispersant composition for a water-hard composition for centrifugation of the present invention containing the component (A), the component (B), the component (C), and water is produced.

Specific examples and preferred embodiments of the components (A), (B), and (C) used in the method for producing a dispersant composition for a water-hard composition for centrifugation of the present invention are the water for centrifugation of the present invention, respectively. It is the same as that described in the dispersant composition for a rigid composition.
The matters described in the dispersant composition for a water-hard composition for centrifugation of the present invention can be appropriately applied to the method for producing a dispersant composition for a water-hard composition for centrifugation of the present invention.
In the method for producing a dispersant composition for a water-hard composition for centrifugation of the present invention, the content of each component and the mass ratio thereof described in the dispersant composition for a water-hard composition for centrifugation of the present invention are each component. The content of can be replaced with a mixed amount and applied as appropriate.

[Hydraulic composition]
The present invention provides a hydraulic composition for centrifugation, which contains the component (A), a hydraulic powder, an aggregate and water.
The water-hardening composition for centrifugation of the present invention preferably further contains the component (B). That is, the present invention provides a hydraulic composition for centrifugation, which contains a component (A), a component (B), a hydraulic powder, an aggregate and water.
The water-hardening composition for centrifugation of the present invention preferably further contains the component (C). That is, the present invention provides a hydraulic composition for centrifugation, which contains a component (A), a component (B), a component (C), a hydraulic powder, an aggregate and water.

Specific examples and preferred embodiments of the component (A), the component (B), and the component (C) used in the water-hard composition for centrifugation of the present invention are the dispersant composition for the water-hard composition for centrifugation of the present invention, respectively. It is the same as that described in.
The matters described in the dispersant composition for a water-hard composition for centrifugation of the present invention and the method for producing the same can be appropriately applied to the water-hard composition for centrifugation of the present invention.

<Hydraulic powder>
The hydraulic powder used in the hydraulic composition for centrifugation of the present invention is a powder having a physical property that is cured by a hydration reaction, and examples thereof include cement and gypsum. Preferably, it is a cement such as ordinary Portoland cement, belite cement, moderate heat cement, early-strength cement, ultra-fast-strength cement, sulfate-resistant cement, and blast furnace slag, fly ash, silica fume, stone powder (calcium carbonate powder) and the like. May be used, such as blast furnace slag cement, fly ash cement, and silica fume cement to which is added. The hydraulic composition finally obtained by adding sand, sand and gravel as aggregates to these powders is generally called mortar, concrete or the like, respectively.

<Aggregate>
The water-hardening composition for centrifugation of the present invention contains an aggregate. Examples of the aggregate include aggregates selected from fine aggregates and coarse aggregates. Examples of the fine aggregate include those specified by No. 2311 in JIS A0203-2014. Fine aggregates include river sand, land sand, mountain sand, sea sand, lime sand, silica sand and their crushed sand, blast furnace slag fine aggregate, ferronickel slag fine aggregate, lightweight fine aggregate (artificial and natural) and recycled. Examples include fine aggregates. Further, as the coarse aggregate, those specified by No. 2312 in JIS A0203-2014 can be mentioned. For example, coarse aggregates include river gravel, land gravel, mountain gravel, sea gravel, lime gravel, crushed stones, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural) and recycled. Coarse aggregate and the like can be mentioned. As the fine aggregate and the coarse aggregate, different types may be mixed and used, or a single type may be used.

<Composition of hydraulic composition, etc.>
In the water-hard composition for centrifugation of the present invention, the content of the component (A) is preferably 0 with respect to 100 parts by mass of the water-hard powder from the viewpoint of fluidity and stability of centrifuge over time. .1 parts by mass or more, more preferably 0.2 parts by mass or more, further preferably 0.3 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less. , More preferably 3 parts by mass or less, still more preferably 1 part by mass or less, still more preferably 0.75 parts by mass or less, still more preferably 0.5 parts by mass or less.

In the water-hard composition for centrifugation of the present invention, the content of the component (B) is preferably 0 with respect to 100 parts by mass of the water-hard powder from the viewpoint of fluidity and stability of centrifuge over time. 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.2 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less. , More preferably 3 parts by mass or less, still more preferably 1 part by mass or less, still more preferably 0.75 parts by mass or less, still more preferably 0.5 parts by mass or less.

In the water-hard composition for centrifugation of the present invention, the total content of the component (A) and the component (B) is 100 parts by mass of the water-hard powder from the viewpoint of fluidity and stability of centrifuge over time. On the other hand, preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, further preferably 0.3 part by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, further. It is preferably 6 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less.

In the water-hard composition for centrifugation of the present invention, the mass ratio (B) / (A) of the content of the component (A) to the content of the component (B) is stable in fluidity and centrifuge property over time. From the viewpoint of sex, it is preferably 0.02 or more, more preferably 0.1 or more, still more preferably 0.2 or more, still more preferably 0.5 or more, and preferably 10 or less, more preferably 5 or less, further. It is preferably 3 or less, more preferably 2.5 or less, still more preferably 2 or less, still more preferably 1.5 or less, and even more preferably 1 or less.

In the water-hard composition for centrifugal molding of the present invention, the content of the component (C) is preferably 0.00001 mass with respect to 100 parts by mass of the water-hard powder from the viewpoint of stability of the centrifugal moldability over time. Parts or more, more preferably 0.0001 parts by mass or more, still more preferably 0.001 parts by mass or more, still more preferably 0.01 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.5 parts by mass. It is less than a part, more preferably 0.1 part by mass or less, still more preferably 0.05 part by mass or less.

In the water-hardening composition for centrifugation of the present invention, the total content of the components (A), (B) and (C) is determined from the viewpoint of fluidity and stability of centrifugation over time. With respect to 100 parts by mass of the body, preferably 0.1 part by mass or more, more preferably 0.2 parts by mass or more, further preferably 0.3 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass. It is less than or equal to parts by mass, more preferably 6 parts by mass or less, still more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less.

In the water-hardening composition for centrifugation of the present invention, the mass ratio [(A) + (B)] / (C) of the total content of the components (A) and (B) to the content of the component (C) is From the viewpoint of fluidity and stability of centrifugation over time, preferably 1 or more, more preferably 5 or more, still more preferably 10 or more, still more preferably 15 or more, and preferably 100 or less, more preferably. Is 50 or less, more preferably 25 or less.

In the water-hard composition for centrifugal molding of the present invention, the water / water-hard powder ratio (hereinafter, may be referred to as W / P) is preferably 10% by mass or more from the viewpoint of centrifugal moldability and strength, and 12 7% by mass or more is more preferable, 14% by mass or more is further preferable, 30% by mass or less is preferable, 25% by mass or less is more preferable, 24% by mass or less is further preferable, 23% by mass or less is further preferable, and 22. More preferably, it is by mass or less.
Here, the water / water-hard powder ratio is a mass percentage (mass%) of water and the water-hard powder in the water-hard composition, and is calculated by water / water-hard powder × 100. The water / hydraulic powder ratio is calculated based on the amount of powder having physical characteristics that hardens by a hydration reaction. When the powder having physical properties that are cured by the hydration reaction contains a high-strength admixture, the amount of the high-strength admixture is also included in the amount of the hydraulic powder. The same applies to other quantitative relationships of hydraulic compositions with respect to hydraulic powders.

When the hydraulic composition for centrifugation is concrete, the amount of coarse aggregate used reduces the development of the strength of the hydraulic composition and the amount of hydraulic powder such as cement, and improves the filling property into the mold and the like. From the viewpoint of improvement, the bulk volume is preferably 50% or more, more preferably 55% or more, further 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 3 of concrete.}
When the water-hard composition for centrifugation is concrete, the amount of fine aggregate used is preferably 500 kg / m ³ or more, more preferably 600 kg / m ³ or more, from the viewpoint of improving the filling property into a mold or the like. , More preferably 700 kg / m ³ or more, and preferably 1000 kg / m ³ or less, more preferably 900 kg / m ³ or less.
If centrifugal molding water hydraulic composition is mortar, the amount of fine aggregate is preferably from 800 kg / ^{m 3} or more, more preferably 900 kg / ^{m 3} or more, more preferably 1000 kg / ^{m 3} or more, and preferably Is 2000 kg / m ³ or less, more preferably 1800 kg / m ³ or less, still more preferably 1700 kg / m ³ or less.

Examples of the water-hardening composition for centrifugal molding include concrete and the like. Of these, concrete using cement is preferable. The hydraulic composition of the present invention can be used for self-leveling, refractory, plaster, lightweight or heavy concrete, AE, repair, prepacked, traymy, ground improvement, grout, cold weather, etc. It is also useful in the field of.

The water-hardening composition for centrifugation of the present invention may also contain a fast-strengthening agent such as glycerin and N-methyldiethanolamine and a chelating agent such as sodium ethylenediaminetetraacetate. The content of the chelating agent is preferably 0.1 part by mass or less with respect to 100 parts by mass in total of the hydraulic powder and the high-strength admixture containing silica from the viewpoint of developing strength after steam curing.

The water-hardening composition for centrifugation of the present invention is a conventional cement dispersant, water-soluble polymer compound, air entraining agent, cement wetting agent, swelling agent, waterproofing agent, retarding agent, quick-setting agent, foaming agent, foaming agent. , Waterproofing agent, fluidizing agent, thickener, flocculant, drying shrinkage reducing agent, strength enhancer, curing accelerator, preservative, antifoaming agent, etc. [However, (A) component, (B) component, (C) excluding those corresponding to the component] can be contained.

[Method for producing hydraulic composition]
The present invention provides a method for producing a hydraulic composition for centrifugation, which mixes a component (A), a hydraulic powder, an aggregate and water. By this production method, the hydraulic composition for centrifugation of the present invention containing the component (A), the hydraulic powder, the aggregate, and water is produced.
In the method for producing a water-hard composition for centrifugation of the present invention, it is preferable to further mix the component (B). That is, the present invention provides a method for producing a hydraulic composition for centrifugation, in which a component (A), a component (B), a hydraulic powder, an aggregate and water are mixed. By this production method, the hydraulic composition for centrifugation of the present invention containing the component (A), the component (B), the hydraulic powder, the aggregate, and water is produced.
In the method for producing a water-hard composition for centrifugation of the present invention, it is preferable to further mix the component (C). That is, the present invention provides a method for producing a water-hard composition for centrifugation, in which a component (A), a component (B), a component (C), a water-hard powder, an aggregate and water are mixed. By this production method, the hydraulic composition for centrifugation of the present invention containing the component (A), the component (B), the component (C), the hydraulic powder, the aggregate, and water is produced.

Specific examples and preferred embodiments of the component (A), the component (B), and the component (C) used in the method for producing the water-hard composition for centrifugation of the present invention are each dispersed for the water-hard composition for centrifugation of the present invention. It is the same as that described in the agent composition.
Further, specific examples and preferred embodiments of the water-hard powder and the aggregate used in the method for producing the water-hard composition for centrifugation of the present invention are the same as those described in the water-hard composition for centrifugation of the present invention. The hydraulic powder is used so that the W / P is within the range described in the hydraulic composition for centrifugation of the present invention. Further, the amount of aggregate used is also the same as that described in the water-hardening composition for centrifugation of the present invention.
In the method for producing a water-hard composition for centrifugation of the present invention, the content of each component and the mass ratio thereof described in the water-hard composition for centrifugation of the present invention are appropriately adjusted by substituting the content of each component with a mixed amount. Can be applied.
The dispersant composition for a water-hard composition for centrifugation of the present invention, a method for producing the same, and the matters described in the water-hard composition for centrifugation can be appropriately applied to the method for producing a water-hard composition for centrifugation of the present invention. it can.

In the method for producing a hydraulic composition of the present invention, from the viewpoint of productivity, a component (A), an arbitrary component (B), an arbitrary component (C), and water are mixed in advance to form a hydraulic powder. It is preferred to mix with the body.
Further, in the method for producing a water-hard composition of the present invention, the addition of the component (A), the optional component (B) and the optional component (C) is carried out by adding the dispersant composition for the water-hard composition for centrifugation of the present invention. It is preferable to add the mixture using, and it is more preferable to mix the dispersant composition for a water-hard composition for centrifugation of the present invention with water in advance and mix it with the water-hard powder.

Mixing the component (A), the component (B), the component (C), the hydraulic powder, the aggregate, the water, and the component used as needed is a mortar mixer. This can be done using a mixer such as a forced twin-screw mixer.
Further, the mixture is preferably mixed for 1 minute or longer, more preferably 2 minutes or longer, and preferably 5 minutes or shorter, more preferably 3 minutes or shorter. In preparing the hydraulic composition, the materials and chemicals described in the hydraulic composition and their amounts can be used.

The obtained hydraulic composition is further filled with a hydraulic composition in a mold, centrifuged, and then cured and cured. Examples of formwork include building formwork, formwork for concrete products, and the like. Examples of the filling method into the mold include a method of directly charging from a mixer, a method of pumping a hydraulic composition with a pump, and a method of introducing the hydraulic composition into the mold.

When curing the hydraulic composition, it may be heat-cured to promote curing to promote curing. Here, the heat curing can promote the curing by holding the hydraulic composition at a temperature of 40 ° C. or higher and 90 ° C. or lower.

[Method for producing a cured product of hydraulic composition]
The present invention provides a method for producing a cured product of a hydraulic composition, which comprises the following steps.
Step 1: A step of mixing the component (A), the hydraulic powder, the aggregate, and water to obtain a hydraulic composition, and filling the mold with the obtained hydraulic composition.
Step 2: A step of applying centrifugal force to mold the hydraulic composition filled in the mold obtained in Step 1.
Step 3: A step of condensing the mold-clamped hydraulic composition obtained in Step 2 in a mold.

In step 1, it is preferable to further mix the component (B). That is, step 1 is preferably a step of mixing the component (A), the component (B), the hydraulic powder, the aggregate, and water to obtain a hydraulic composition.
In step 1, it is preferable to further mix the component (C). That is, step 1 is preferably a step of mixing the component (A), the component (B), the component (C), the hydraulic powder, the aggregate, and water to obtain a hydraulic composition.

Specific examples and preferred embodiments of the components (A), (B) and (C) used in the method for producing a cured product of the water-hard composition of the present invention are for the water-hard composition for centrifugation of the present invention, respectively. It is the same as that described in the dispersant composition.
Further, specific examples and preferred embodiments of the water-hard powder and the aggregate used in the method for producing a cured product of the water-hard composition of the present invention are the same as those described in the water-hard composition for centrifugation of the present invention. .. The hydraulic powder is used so that the W / P is within the range described in the hydraulic composition for centrifugation of the present invention. Further, the amount of aggregate used is also the same as that described in the water-hardening composition for centrifugation of the present invention.
Further, in step 1 of the method for producing a cured product of the water-hard composition of the present invention, the content of each component and the mass ratio thereof described in the water-hard composition for centrifugal molding of the present invention are the contents of each component. It can be appropriately applied in place of a mixed amount.
The matters described in the dispersant composition for a water-hard composition for centrifugation of the present invention and a method for producing the same, the water-hard composition for centrifugation, and the method for producing a water-hard composition for centrifugation are the same as the water-hard composition of the present invention. It can be appropriately applied to a method for producing a cured product.

The method for producing a cured product of the present invention preferably includes the following steps 4 in addition to steps 1 to 3.
Step 4: A step of steam curing the hydraulic composition condensed in Step 3 in a mold.

The method for producing a cured product of the present invention can include the following steps 5 in addition to steps 1 to 4.
Step 5: After step 4, the step of cooling the hydraulic composition and removing it from the mold.

The method for producing a cured product of the present invention can include the following steps 6 in addition to steps 1 to 5.
Step 6: A step of curing the cured product of the hydraulic composition obtained in Step 5 at normal temperature and pressure.

In step 1, a method in which a mixture containing water, a component (A), an arbitrary component (B), and an arbitrary component (C) is added to a mixture containing an aggregate and a hydraulic powder and mixed is water. Even when producing a rigid composition, it is preferable because it can be easily and uniformly mixed. Further, the addition of the component (A), the arbitrary component (B) and the arbitrary component (C) is preferably added using the dispersant composition for a water-hard composition for centrifugation of the present invention, and the centrifugation of the present invention is used. A method of adding a mixture containing a dispersant composition for a water-hard composition for molding and water to a mixture containing an aggregate and a water-hard powder and mixing them is easily uniform even when producing a water-hard composition. It is preferable because it can be mixed with.

As a specific method of step 1, the hydraulic powder and the aggregate are mixed, and a mixture containing water, a component (A), an arbitrary component (B), and an arbitrary component (C) is obtained as described above. Examples thereof include a step of adding the mixture in such a mixed amount and kneading the mixture to prepare a hydraulic composition.

In step 1, the component (A), the optional component (B), and the optional component (C) can be separately added to water, hydraulic powder, and aggregate and mixed.

As a method of filling the mold with the obtained hydraulic composition in step 1, a method of discharging the hydraulic composition after kneading from the kneading means and manually putting it into the mold can be mentioned.

In step 2, the hydraulic composition filled in the mold is molded by applying centrifugal force, but at this time, it is preferable to change the centrifugal force at least once. In step 2, the hydraulic composition can be molded by applying a centrifugal force that changes stepwise. That is, in step 2, the hydraulic composition can be molded by changing the centrifugal force at least once, and further, by applying a centrifugal force that changes stepwise and becomes larger stepwise. ..

In step 2, it is preferable to mold the hydraulic composition filled in the mold with a centrifugal force of 0.5 G or more. The centrifugal force of centrifugal molding is preferably 0.5 G or more, preferably 30 G or less, and more preferably 25 G or less. From the viewpoint of energy cost reduction and moldability, it is preferable to keep the centrifugal force in the range of 15 G or more, 30 G or less, and 25 G or less (also referred to as high centrifugal force) for 1 minute or more.

The compaction by centrifugal force is carried out, for example, with a centrifugal force of 0.5 G or more and 30 G or less, preferably 5 minutes or more, more preferably 7 minutes or more, further preferably 9 minutes or more, and preferably 40 minutes or less. From the viewpoint of smooth compaction of the molded product, compaction by holding a high centrifugal force, for example, a centrifugal force of 20 G or more is preferably 1 minute or longer, more preferably 3 minutes or longer, still more preferably 5 minutes or longer, and preferably. Do it for 15 minutes or less. That is, in step 3, a centrifugal force of 0.5 G or more and 30 G or less is preferably applied over 5 minutes or more, more preferably 7 minutes or more, further preferably 9 minutes or more, and preferably 40 minutes or less to form a hydraulic composition. You can mold things. Further, in step 3, compaction by holding a centrifugal force of 20 G or more can be carried out preferably for 1 minute or more, more preferably 3 minutes or more, further preferably 5 minutes or more, and preferably 15 minutes or less.

The compaction by centrifugal force can be performed in stages, and from the viewpoint of moldability, a method of gradually increasing the centrifugal force G is preferable. It can be carried out under the following step conditions until the desired centrifugal force is obtained. For example, in the case of five stages, in step 3, (1) the first stage, the initial speed is 0.5 G or more and less than 2 G, and the centrifugal force is more than 0 minutes and 15 minutes or less, and (2) the second stage, the second speed, is 2 G. Centrifugal force of 5G or more and less than 5G for more than 0 minutes and 15 minutes or less, (3) Third stage of third speed is more than 5G and less than 10G of centrifugal force for more than 0 minutes and less than 15 minutes, (4) Fourth stage of fourth speed A water-hard composition according to the conditions of a centrifugal force of 10 G or more and less than 20 G for more than 0 minutes and 15 minutes or less, and (5) a centrifugal force of 20 G or more and 30 G or less for the fifth stage, which is more than 0 minutes and 15 minutes or less. It is preferable to perform mold clamping.

In step 3, the hydraulic composition obtained in step 2 is condensed. Specifically, aerial curing is performed for 3 to 4 hours after kneading.

In step 4, the cured hydraulic composition in the mold obtained in step 3 is steam-cured. In step 4, steam curing is preferably performed at 40 ° C. or higher and 90 ° C. or lower, and more preferably 60 ° C. or higher and 90 ° C. or lower.
Further, in step 4, it is preferable to perform steam curing after performing pre-curing. For example, the ambient temperature of the mold filled with the hydraulic composition (hereinafter, also referred to as ambient temperature) is set to room temperature, preferably 10 ° C. or higher and 40 ° C. or lower, and is left for 1 hour or more and 4 hours or less before curing. After that, steam curing can be performed by setting the ambient temperature to 40 ° C. or higher and 90 ° C. or lower, and further to 60 ° C. or higher and 90 ° C. or lower.
The pre-curing was carried out as a "preface" in the examples and comparative examples described later.
The pre-curing is preferably 1 hour or more from the viewpoint of suppressing a decrease in strength due to cracking of the cured product.
Further, when the method for producing a cured product of the present invention includes step 5, steps 4 and 5 can be continuously performed under a series of temperature controls.
The steam curing is carried out by holding the mold at a predetermined temperature for a certain period of time in a state where steam is applied around the mold filled with the hydraulic composition. After applying steam, (1) a temperature rise period until it reaches a predetermined temperature, (2) a period of holding it at a predetermined temperature for a certain period of time, and (3) a period of holding it at a predetermined temperature for a certain period of time, and then lowering the temperature. The period may be the period of steam curing.

As a specific steam curing condition in the method for producing a cured product of the present invention, as step 4, the ambient temperature of the mold is raised to 60 ° C. or higher and 85 ° C. or lower at a heating rate of 10 ° C. or higher and 30 ° C. or lower per hour. Then, the temperature raised is maintained for 2 hours or more and 8 hours or less, and then, as step 5, the ambient temperature is cooled to room temperature, for example, 20 ° C. at a temperature lowering rate of 5 ° C. or more and 20 ° C. or less per hour, and the molded product is formed. Demold.
The rate of temperature rise is preferably 20 ° C. or less per hour from the viewpoint of suppressing a decrease in strength due to cracks in the cured product.
To give an example of preferable conditions, a mold filled with a water-hard composition is left to stand at an ambient temperature of room temperature, for example, 10 ° C. or higher and 30 ° C. or lower for 3 hours (pre-curing), and the temperature rises by 20 ° C. per hour. The ambient temperature is raised to 70 ° C. or higher and 90 ° C. or lower at a temperature rate, and the temperature of 70 ° C. or higher and 90 ° C. or lower is maintained for 2 hours or longer and 6 hours or lower, and then at a temperature lowering rate of 10 ° C. Examples thereof include a method in which the ambient temperature is cooled to room temperature, for example, 20 ° C. (step 4), and the molded product is demolded after being left at that temperature for 20 hours or more and 30 hours or less (step 5).
Further, it is also possible to perform autoclave curing at about 180 ° C.

In step 6, the cured product of the hydraulic composition obtained in step 5 is cured at normal temperature and pressure. Specifically, it is stored at 20 ° C. and atmospheric pressure.

The production method of the present invention includes steps 1 to 5, and the time from the start of preparation of the hydraulic composition to the demolding in step 5 is 8 hours or more and 30 hours or less. Examples thereof include a method for producing a cured product. Here, the start of preparation of the hydraulic composition is the time when the hydraulic powder and water first come into contact with each other.

The cured product of the hydraulic composition obtained by the method for producing a cured product of the present invention can be used as a centrifugally molded concrete product, and specific examples thereof include piles, poles, and hume pipes. The cured product of the hydraulic composition obtained by the method for producing a cured product of the present invention is excellent in moldability of the hydraulic composition after a certain period of time (15 minutes or more and 60 minutes or less) has passed from kneading. In addition, there are few irregularities on the end face, the surface is excellent in appearance, and the inner surface of the product is finished smoothly, so that the obstacles of the cutting machine during pile driving and Nakabori method are improved.

Examples As the component (A), the component (A') (comparative component of the component (A)), the component (B) and the component (C) shown in Table 1, the following components were used.

(A) Component (a-1): Monomer (A1) / Monomer (A2) / Monomer (A3) = Acrylic acid / Isoprenyl polyethylene glycol (55) Ether / 2-Hydroxyethyl acrylate = 50 Mol% / 15 mol% / 35 mol%, weight average molecular weight = 50,000 (average number of added moles in parentheses)
(A-2): monomer (A1) / monomer (A2) / monomer (A3) = methacrylic acid / methoxypolyethylene glycol (45) methacrylate / 2-hydroxyethyl acrylate = 60 mol% / 20 mol % / 20 mol%, weight average molecular weight = 35,000 (average number of moles added in parentheses)
Each polymer obtained is a sodium salt.

(A') component (comparative component of (A) component)
(A'-1): Monomer (A1) / Monomer (A2) / Monomer (A3) = Acrylic acid / Metallyl polyethylene glycol (55) Ether / 2-Hydroxyethyl acrylate = 41 mol% / 14 mol% / 45 mol%, weight average molecular weight = 38,000 (average number of added moles in parentheses)
(A'-2): monomer (A1) / monomer (A2) / monomer (A3) = methacrylic acid / methoxypolyethylene glycol (100) methacrylate / 2-hydroxyethyl acrylate = 65 mol% / 15 Molar% / 20 mol%, weight average molecular weight = 52,000 (average number of moles added in parentheses)
(A'-3): monomer (A1) / monomer (A2) / monomer (A3) = methacrylic acid / methoxypolyethylene glycol (15) methacrylate / 2-hydroxyethyl acrylate = 56 mol% / 29 Mol% / 15 mol%, weight average molecular weight = 45,000 (average number of moles added in parentheses)
(A'-4): monomer (A1) / monomer (A2) / monomer (A3) = acrylic acid / isoprenyl polyethylene glycol (55) ether / 2-hydroxyethyl acrylate = 60 mol% / 25 mol% / 15 mol%, weight average molecular weight = 40,000 (average number of added moles in parentheses)
Each polymer obtained is a sodium salt.

(B) Component (b-1): Monomer (B1) / Monomer (B2) = Acrylic acid / Isoprenyl polyethylene glycol (55) Ether = 80 mol% / 20 mol%, Weight average molecular weight = 50, 000 (Average number of moles added in parentheses)
The obtained polymer is a sodium salt.

(C) Ingredient (c-1): 90% fermented lactic acid (PURAC ULTRAPURE90, manufactured by PURAC Thailand Ltd.)

<Example 1 and Comparative Example 1>
(1) Concrete composition The concrete composition 1 and 2 are shown below. W / P is the ratio (% by mass) of water / hydraulic powder, and the amount of hydraulic powder is the total amount of cement (P ₁ ) and inorganic early-strengthening agent (P ₂ ).

* Concrete formulation 1
Cement (P ₁ ): 13.4 kg (ordinary Portland cement manufactured by Taiheiyo Cement Co., Ltd., specific gravity 3.16)
Inorganic fast-strengthening agent (P ₂ ): 0.4 kg (Microsilica 920 manufactured by Elkem, specific gravity 2.2)
Tap water (W): 3.5 kg (including (A) component, (B) component, and (C) component)
W / P: 25% by mass
Sand 1 (S1): 11.2 kg (specific gravity 2.55 from Ibigawa, Gifu Prefecture)
Sand 2 (S2): 12.4 kg (specific gravity 2.58 from Koka, Shiga Prefecture)
Gravel (G): 31.6 kg (specific gravity 2.63 from Iejima, Hyogo Prefecture)
In addition, all the materials are adjusted to 30 ° C., and the components (A), (B) and (C) in tap water have a small amount of these components with respect to the concrete composition, so that the tap water has a small amount. W / P was calculated by including it in the quantity.

* Concrete formulation 2
Cement (P ₁ ): 12.9 kg (ordinary Portland cement manufactured by Taiheiyo Cement Co., Ltd., specific gravity 3.16)
Inorganic fast-strengthening agent (P ₂ ): 0.1 kg (manufactured by Denki Kagaku Kogyo Co., Ltd., specific gravity 2.45)
Tap water (W): 3.0 kg (including (A) component, (B) component, and (C) component)
W / P: 23% by mass
Sand 1 (S1): 9.4 kg (specific gravity 2.55 from Ibigawa, Gifu Prefecture)
Sand 2 (S2): 10.9 kg (specific gravity 2.58 from Koka, Shiga Prefecture)
Gravel (G): 25.6 kg (specific gravity 2.63 from Iejima, Hyogo Prefecture)
In addition, all the materials are adjusted to 30 ° C., and the components (A), (B) and (C) in tap water have a small amount of these components with respect to the concrete composition, so that the tap water has a small amount. W / P was calculated by including it in the quantity.

(2) Preparation of concrete A composition containing the component (A), the component (B), the component (C) and water was prepared so as to be added in the amount shown in Table 1, and the composition was added to tap water (W) of the concrete compounding material. The composition was added and stirred to prepare kneaded water. Concrete is put into a forced twin-screw mixer (manufactured by KYC) in the order of gravel, about half the amount of sand, a mixture of cement and an inorganic early-strengthening agent, and the remaining sand, and then dry-kneaded for 30 seconds, and then quickly described above. The prepared kneading water was added and kneaded for 240 seconds to obtain concrete.

(3) Evaluation of moldability with respect to the elapsed time from kneading 15 minutes, 30 minutes, 45 minutes, and 60 minutes after kneading (meaning from the time when water first comes into contact with cement. The same applies hereinafter). Put concrete in a centrifugal formwork (inner diameter 20 cm, outer diameter 25 cm, height 40 cm), initial speed is 1G for 2 minutes, 2nd speed is 3G for 2 minutes, 3rd speed is 7G for 2 minutes, 4th speed is 15G. Centrifugal compaction was carried out for 3 minutes at a 5th speed of 25 G for 3 minutes. The efferent formability was evaluated visually at each time point on the uncured molded product, and if cement sludge called sludge leaked onto the surface of the molded product, it was described as "sludge", and the molded product was tilted to sludge. Was discharged and collected, and the mass (g) thereof was also shown. In addition, those with reduced fluidity and insufficient filling and molding of concrete are described as "junkers", and those with no molding defects such as "sludge" and "junker" are described as "formability". "Good" was described. In addition, in order to quantitatively evaluate the moldability (flow retention) of the molded product judged to be "good moldability", a steel measure was penetrated into the uncured centrifugal test body surface after centrifugation. The penetration depth (mm) was recorded and listed together. The results are shown in Table 1. Further, among the molded bodies obtained by centrifugal compaction, the compression strength (7-day strength) of the centrifugal molded body having no molding defects at the age of 7 days was measured based on JIS A 1108. The results are shown in Table 1.

In Table 1, the addition amount of the component (A), the component (B), and the component (C) is the addition amount (parts by mass) with respect to 100 parts by mass of the hydraulic powder, and is the addition amount of the solid content (effective component). is there.

In Table 1, the examples containing the component (A) have better moldability for a longer period of time than the comparative examples containing the component (A') instead of the component (A) or the component (A). In addition, it can be seen that even when the component (A) and the component (B) are used in combination in the examples, better moldability is exhibited for a longer period of time as the ratio of the component (A) increases. It is considered that this is because the component (A) is intermittently adsorbed on the cement by the above mechanism, and the fluidity of the concrete is effectively maintained.

Further, in Table 1, the example containing the component (B) in addition to the component (A) tends to require a smaller amount of addition in order not to cause molding defects as compared with the example using the component (A) alone. It is in. This is because the component (B) is superior to the component (A) in the fluidity immediately after kneading, so that the fluidity of the concrete is effectively maintained by the component (A) while reducing the total amount of addition. it is conceivable that.

Further, in Table 1, the examples containing the component (C) in addition to the component (A) and the component (B) include the component (A) alone and the component (B) in addition to the component (A). Compared with the above, the compression strength (7-day strength) of the centrifuge molded product with a material age of 7 days tends to be excellent. It is considered that this is because the component (C) activates the hydration reaction of the hydraulic powder represented by cement and densifies the cured product structure.

Claims (26)

1. A dispersant composition for a water-hard composition for centrifugation, which contains the following component (A) and water.
   Component (A): A monomer (A1) represented by the following general formula (A1), a monomer (A2) represented by the following general formula (A2), and a single amount represented by the following general formula (A3). A copolymer having a weight average molecular weight of 10,000 or more and 70,000 or less containing the body (A3) as a constituent monomer, and the monomer (A1) is contained in the constituent monomers of the copolymer. The copolymer (A) in which 30 mol% or more and 70 mol% or less, the monomer (A2) is 10 mol% or more and 50 mol% or less, and the monomer (A3) is 20 mol% or more and 35 mol% or less.
   

   

   [In the formula,
   R ^11a , R ^12a , R ^13a : may be the same or different and may be a hydrogen atom, a methyl group or (CH ₂ ) _r COM ^2a , where (CH ₂ ) _r COM ^2a is COM ^1a or another (CH _2). ) _R COMM ^2a may form an anhydride, in which case M ^1a , M ^2a of those groups are absent.
   M ^1a , M ^2a : The same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group or substituted alkylammonium group r: Number of 0 or more and 2 or less Is shown. ]
   

   

   [In the formula,
   R ^21a , R ^22a : may be the same or different, hydrogen atom or methyl group R ^23a : hydrogen atom or -COO (AO) _n X ^1a
   X ^1a : Alkyl group or hydrogen atom having 1 or more and 4 or less carbon atoms AO: Group selected from ethyleneoxy group and propyleneoxy group n: Average number of moles of AO, 5 or more and 70 or less p: 0 or more and 2 The following numbers q: Indicates the number of 0 or 1. ]
   

   

   [In the formula,
   R ^31a : Indicates a hydrocarbon group that may contain a heteroatom having 1 or more and 4 or less carbon atoms. ]
2. The dispersant composition for a water-hard composition for centrifugal molding according to claim 1, wherein the content of the component (A) is 1% by mass or more and 60% by mass or less.
3. The dispersant composition for a water-hard composition for centrifugation according to claim 1 or 2, further containing the following component (B).
   Component (B): A polymer (B1) represented by the following general formula (B1) and a monomer (B2) represented by the following general formula (B2) are contained as constituent monomers and have a molecular weight of 10,000. A copolymer of 70,000 or less, in which the monomer (B1) is 70 mol% or more and 99 mol% or less and the monomer (B2) is 1 mol% in the constituent monomers of the copolymer. Copolymer (B) of 30 mol% or more
   

   

   [In the formula,
   ^{R 11b, R 12b, R 13b} : may be the same or different, a hydrogen atom, a methyl group or ^{_{(CH 2) r 'COOM 2b}} , (CH 2) r COOM 2b is, COOM ^1b or other (CH _{2) r 'COOM} ^2b and may form an anhydride, in which case, ^M 1b of those ^{groups, M 2b} is absent.
   M ^1b , M ^2b : The same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group or substituted alkylammonium group r': 0 or more and 2 or less Show the number. ]
   

   

   [In the formula,
   R ^{21b, R 22b:} may be the same or different, a hydrogen atom or a methyl group R ^23b: a hydrogen atom or -COO (AO) _{n 'X} ^1b
   X ^1b : Alkyl group or hydrogen atom having 1 or more and 4 or less carbon atoms AO: Group selected from ethyleneoxy group and propyleneoxy group n': Average number of moles of AO, 5 or more and 100 or less p': 0 Numbers greater than or equal to 2 and less than or equal to 2 q': Indicates a number of 0 or 1. ]
4. The dispersant composition for a water-hard composition for centrifugal molding according to claim 3, wherein the total content of the component (A) and the component (B) is 2% by mass or more and 60% by mass or less.
5. The dispersant composition for a water-hard composition for centrifugation according to any one of claims 1 to 4, further containing the following component (C).
   Component (C): Hydroxycarboxylic acid
6. The dispersant composition for a water-hard composition for centrifugal molding according to claim 5, wherein the total content of the component (A), the component (B) and the component (C) is 2% by mass or more and 60% by mass or less.
7. A method for producing a dispersant composition for a water-hard composition for centrifugation, which mixes the following component (A) with water. Component (A): A monomer (A1) represented by the following general formula (A1), a monomer (A2) represented by the following general formula (A2), and a single amount represented by the following general formula (A3). A copolymer having a weight average molecular weight of 10,000 or more and 70,000 or less containing the body (A3) as a constituent monomer, and the monomer (A1) is contained in the constituent monomers of the copolymer. The copolymer (A) in which 30 mol% or more and 70 mol% or less, the monomer (A2) is 10 mol% or more and 50 mol% or less, and the monomer (A3) is 20 mol% or more and 35 mol% or less.
   

   

   [In the formula,
   R ^11a , R ^12a , R ^13a : may be the same or different and may be a hydrogen atom, a methyl group or (CH ₂ ) _r COM ^2a , where (CH ₂ ) _r COM ^2a is COM ^1a or another (CH _2). ) _R COMM ^2a may form an anhydride, in which case M ^1a , M ^2a of those groups are absent.
   M ^1a , M ^2a : The same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group or substituted alkylammonium group r: Number of 0 or more and 2 or less Is shown. ]
   

   

   [In the formula,
   R ^21a , R ^22a : may be the same or different, hydrogen atom or methyl group R ^23a : hydrogen atom or -COO (AO) _n X ^1a
   X ^1a : Alkyl group or hydrogen atom having 1 or more and 4 or less carbon atoms AO: Group selected from ethyleneoxy group and propyleneoxy group n: Average number of moles of AO, 5 or more and 70 or less p: 0 or more and 2 The following numbers q: Indicates the number of 0 or 1. ]
   

   

   [In the formula,
   R ^31a : Indicates a hydrocarbon group that may contain a heteroatom having 1 or more and 4 or less carbon atoms. ]
8. The method for producing a dispersant composition for a water-hard composition for centrifugation according to claim 7, further mixing the following component (B).
   Component (B): A polymer (B1) represented by the following general formula (B1) and a monomer (B2) represented by the following general formula (B2) are contained as constituent monomers and have a molecular weight of 10,000. A copolymer of 70,000 or less, in which the monomer (B1) is 70 mol% or more and 99 mol% or less and the monomer (B2) is 1 mol% in the constituent monomers of the copolymer. Copolymer (B) of 30 mol% or more
   

   

   [In the formula,
   ^{R 11b, R 12b, R 13b} : may be the same or different, a hydrogen atom, a methyl group or ^{_{(CH 2) r 'COOM 2b}} , (CH 2) r COOM 2b is, COOM ^1b or other (CH _{2) r 'COOM} ^2b and may form an anhydride, in which case, ^M 1b of those ^{groups, M 2b} is absent.
   M ^1b , M ^2b : The same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group or substituted alkylammonium group r': 0 or more and 2 or less Show the number. ]
   

   

   [In the formula,
   R ^{21b, R 22b:} may be the same or different, a hydrogen atom or a methyl group R ^23b: a hydrogen atom or -COO (AO) _{n 'X} ^1b
   X ^1b : Alkyl group or hydrogen atom having 1 or more and 4 or less carbon atoms AO: Group selected from ethyleneoxy group and propyleneoxy group n': Average number of moles of AO, 5 or more and 100 or less p': 0 Numbers greater than or equal to 2 and less than or equal to 2 q': Indicates a number of 0 or 1. ]
9. The method for producing a dispersant composition for a water-hard composition for centrifugation according to claim 7 or 8, further mixing the following component (C).
   Component (C): Hydroxycarboxylic acid
10. A hydraulic composition for centrifugal molding containing the following component (A), hydraulic powder, aggregate and water.
    Component (A): A monomer (A1) represented by the following general formula (A1), a monomer (A2) represented by the following general formula (A2), and a single amount represented by the following general formula (A3). A copolymer having a weight average molecular weight of 10,000 or more and 70,000 or less containing the body (A3) as a constituent monomer, and the monomer (A1) is contained in the constituent monomers of the copolymer. The copolymer (A) in which 30 mol% or more and 70 mol% or less, the monomer (A2) is 10 mol% or more and 50 mol% or less, and the monomer (A3) is 20 mol% or more and 35 mol% or less.
    

    

    [In the formula,
    R ^11a , R ^12a , R ^13a : may be the same or different and may be a hydrogen atom, a methyl group or (CH ₂ ) _r COM ^2a , where (CH ₂ ) _r COM ^2a is COM ^1a or another (CH _2). ) _R COMM ^2a may form an anhydride, in which case M ^1a , M ^2a of those groups are absent.
    M ^1a , M ^2a : The same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group or substituted alkylammonium group r: Number of 0 or more and 2 or less Is shown. ]
    

    

    [In the formula,
    R ^21a , R ^22a : may be the same or different, hydrogen atom or methyl group R ^23a : hydrogen atom or -COO (AO) _n X ^1a
    X ^1a : Alkyl group or hydrogen atom having 1 or more and 4 or less carbon atoms AO: Group selected from ethyleneoxy group and propyleneoxy group n: Average number of moles of AO, 5 or more and 70 or less p: 0 or more and 2 The following numbers q: Indicates the number of 0 or 1. ]
    

    

    [In the formula,
    R ^31a : Indicates a hydrocarbon group that may contain a heteroatom having 1 or more and 4 or less carbon atoms. ]
11. The hydraulic composition for centrifugation according to claim 10, wherein the content of the component (A) is 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the hydraulic powder.
12. The water-hard composition for centrifugation according to claim 10 or 11, further containing the following component (B).
    Component (B): A polymer (B1) represented by the following general formula (B1) and a monomer (B2) represented by the following general formula (B2) are contained as constituent monomers and have a molecular weight of 10,000. A copolymer of 70,000 or less, in which the monomer (B1) is 70 mol% or more and 99 mol% or less and the monomer (B2) is 1 mol% in the constituent monomers of the copolymer. Copolymer (B) of 30 mol% or more
    

    

    ^{Wherein, R 11b, R 12b, R} 13b: may be the same or different, a hydrogen atom, a methyl group or ^{_{(CH 2) r 'COOM 2b}} , (CH 2) r COOM 2b is, COOM ^1b or other _(CH 2) may form a _{r 'COOM} ^2b and anhydrides, in which case, ^M 1b of those ^{groups, M 2b} is absent.
    M ^1b , M ^2b : The same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group or substituted alkylammonium group r': 0 or more and 2 or less Show the number. ]
    

    

    [In the formula,
    R ^{21b, R 22b:} may be the same or different, a hydrogen atom or a methyl group R ^23b: a hydrogen atom or -COO (AO) _{n 'X} ^1b
    X ^1b : Alkyl group or hydrogen atom having 1 or more and 4 or less carbon atoms AO: Group selected from ethyleneoxy group and propyleneoxy group n': Average number of moles of AO, 5 or more and 100 or less p': 0 Numbers greater than or equal to 2 and less than or equal to 2 q': Indicates a number of 0 or 1. ]
13. The water-hard composition for centrifugal molding according to claim 12, wherein the mass ratio (B) / (A) of the content of the component (A) to the content of the component (B) is 0.01 or more and 10 or less.
14. The water-hard composition for centrifugation according to any one of claims 10 to 13, further containing the following component (C).
    Component (C): Hydroxycarboxylic acid
15. The hydraulic composition for centrifugal molding according to any one of claims 10 to 14, wherein the ratio of water / hydraulic powder is 10% by mass or more and 30% by mass or less.
16. The hydraulic composition for centrifugal molding according to any one of claims 10 to 14, wherein the ratio of water / hydraulic powder is 10% by mass or more and 25% by mass or less.
17. A method for producing a cured product of a hydraulic composition, which comprises the following steps.
    Step 1: A step of mixing the following component (A), hydraulic powder, aggregate, and water to obtain a hydraulic composition, and filling the mold with the obtained hydraulic composition.
    Step 2: A step of applying centrifugal force to mold the hydraulic composition filled in the mold obtained in Step 1.
    Step 3: A step of condensing the mold-clamped hydraulic composition obtained in Step 2 in a mold.
    Component (A): A monomer (A1) represented by the following general formula (A1), a monomer (A2) represented by the following general formula (A2), and a single amount represented by the following general formula (A3). A copolymer having a weight average molecular weight of 10,000 or more and 70,000 or less containing the body (A3) as a constituent monomer, and the monomer (A1) is contained in the constituent monomers of the copolymer. The copolymer (A) in which 30 mol% or more and 70 mol% or less, the monomer (A2) is 10 mol% or more and 50 mol% or less, and the monomer (A3) is 20 mol% or more and 35 mol% or less.
    

    

    [In the formula,
    R ^11a , R ^12a , R ^13a : may be the same or different and may be a hydrogen atom, a methyl group or (CH ₂ ) _r COM ^2a , where (CH ₂ ) _r COM ^2a is COM ^1a or another (CH _2). ) _R COMM ^2a may form an anhydride, in which case M ^1a , M ^2a of those groups are absent.
    M ^1a , M ^2a : The same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group or substituted alkylammonium group r: Number of 0 or more and 2 or less Is shown. ]
    

    

    [In the formula,
    R ^21a , R ^22a : may be the same or different, hydrogen atom or methyl group R ^23a : hydrogen atom or -COO (AO) _n X ^1a
    X ^1a : Alkyl group or hydrogen atom having 1 or more and 4 or less carbon atoms AO: Group selected from ethyleneoxy group and propyleneoxy group n: Average number of moles of AO, 5 or more and 70 or less p: 0 or more and 2 The following numbers q: Indicates the number of 0 or 1. ]
    

    

    [In the formula,
    R ^31a : Indicates a hydrocarbon group that may contain a heteroatom having 1 or more and 4 or less carbon atoms. ]
18. The method for producing a cured water-hard composition according to claim 17, wherein in step 1, the component (A) is mixed in an amount of 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the water-hard powder.
19. The method for producing a cured hydraulic composition according to claim 17 or 18, wherein the following component (B) is further mixed in step 1.
    Component (B): A polymer (B1) represented by the following general formula (B1) and a monomer (B2) represented by the following general formula (B2) are contained as constituent monomers and have a molecular weight of 10,000. A copolymer of 70,000 or less, in which the monomer (B1) is 70 mol% or more and 99 mol% or less and the monomer (B2) is 1 mol% in the constituent monomers of the copolymer. Copolymer (B) of 30 mol% or more
    

    

    [In the formula,
    ^{R 11b, R 12b, R 13b} : may be the same or different, a hydrogen atom, a methyl group or ^{_{(CH 2) r 'COOM 2b}} , (CH 2) r COOM 2b is, COOM ^1b or other (CH _{2) r 'COOM} ^2b and may form an anhydride, in which case, ^M 1b of those ^{groups, M 2b} is absent.
    M ^1b , M ^2b : The same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group or substituted alkylammonium group r': 0 or more and 2 or less Show the number. ]
    

    

    [In the formula,
    R ^{21b, R 22b:} may be the same or different, a hydrogen atom or a methyl group R ^23b: a hydrogen atom or -COO (AO) _{n 'X} ^1b
    X ^1b : Alkyl group or hydrogen atom having 1 or more and 4 or less carbon atoms AO: Group selected from ethyleneoxy group and propyleneoxy group n': Average number of moles of AO, 5 or more and 100 or less p': 0 Numbers greater than or equal to 2 and less than or equal to 2 q': Indicates a number of 0 or 1. ]
20. The hydraulic composition according to claim 19, wherein in step 1, the components (A) and (B) are mixed in a total amount of 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the hydraulic powder. Manufacturing method of hardened material.
21. The method for producing a cured hydraulic composition according to any one of claims 17 to 20, wherein the following component (C) is further mixed in step 1.
    Component (C): Hydroxycarboxylic acid
22. In claim 21, in step 1, the component (A), the component (B) and the component (C) are mixed in a total amount of 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the hydraulic powder. The method for producing a cured product of a hydraulic composition according to the above.
23. The cured product of the hydraulic composition according to any one of claims 17 to 22, which prepares a hydraulic composition having a water / hydraulic powder ratio of 10% by mass or more and 30% by mass or less in step 1. Production method.
24. The cured product of the hydraulic composition according to any one of claims 17 to 22, which prepares a hydraulic composition having a water / hydraulic powder ratio of 10% by mass or more and 25% by mass or less in step 1. Production method.
25. The method for producing a cured hydraulic composition according to any one of claims 17 to 24, which comprises the following step 4 after the step 3.
    Step 4: A step of steam curing the condensed hydraulic composition obtained in Step 3 in a mold.
26. The method for producing a cured hydraulic composition according to claim 25, wherein the steam curing temperature is 40 ° C. or higher and 90 ° C. or lower in step 4.