JP2023028708A - Dispersant composition for hydraulic composition - Google Patents

Abstract

To provide a dispersant composition for a fly ash-containing hydraulic composition having excellent uniformity of strength of a cured body of a hydraulic composition even when a hydraulic powder containing fly ash is used and to provide a fly ash-containing hydraulic composition.SOLUTION: There is provided a dispersant composition for a fly ash-containing hydraulic composition which comprises cement and fly ash as a hydraulic powder in which the content of fly ash in the hydraulic powder is 5 mass% or more and 40 mass% or less, wherein the dispersant composition comprises a component (A) and a component (B) composed of specific copolymers which differ from each other and the ratio of the content of the component (B) to the total content of the component (A) and the component (B) is 30 mass% or more and 70 mass% or less.SELECTED DRAWING: None

Description

The present invention relates to dispersant compositions for fly ash-containing hydraulic compositions.

Admixtures such as naphthalene-based, melamine-based, aminosulfonic acid-based and polycarboxylic acid-based admixtures are used to impart fluidity to hydraulic compositions such as concrete. Admixtures such as dispersants are required to have various performances such as imparting fluidity to hydraulic compositions, fluidity retention (fluidity retention), prevention of curing delay, etc. Polycarboxylic acid-based admixtures ( Dispersants) have also been proposed to be improved from this point of view.

For example, it has been proposed to use a combination of a plurality of polycarboxylic acid-based polymers in consideration of fluidity, fluid retention, and the like.
In Patent Document 1, a specific monomer (A) such as (meth)acrylic acid and a specific monomer (B) such as an ethylenically unsaturated carboxylic acid derivative having a polyoxyalkylene group are mixed in a specific weight A cement dispersant efficacy enhancer comprising a copolymer obtained by copolymerizing so as to satisfy both the ratio and a specific molar ratio, and the cement dispersant efficacy enhancer and the cement dispersant are combined into a predetermined Disclosed are cement dispersant compositions containing on a weight basis.

Blast-furnace slag and fly ash used to be discarded as industrial waste, but mortar and concrete made from cement containing blast-furnace slag and fly ash are generally more expensive than mortar and concrete made from Portland cement. Since it excels in long-term strength for months or more and has excellent durability, it has been used in large quantities year by year as a partial substitute for cement.
The annual amount of _CO2 generated from cement (from energy sources) is a huge amount equivalent to approximately 3% of the annual amount of _CO2 generated in Japan (1.3 billion tons).
By using cement obtained by mixing blast furnace slag or fly ash with Portland cement, it is possible to reduce the CO ₂ intensity required for manufacturing Portland cement. Ground granulated blast furnace slag and ground fly ash will contribute to the reduction of cement CO ₂ by the amount that Portland cement is replaced with. As a result, it becomes possible to reduce the CO ₂ unit consumption for manufacturing Portland cement, and furthermore it becomes possible to reduce the CO ₂ unit consumption of concrete compositions and their hardened bodies such as buildings and civil engineering structures.

JP-A-2001-316151

A formulation containing fly ash as a substitute powder for cement under high strength conditions where the mass percentage of water and hydraulic powder in the hydraulic composition (water/hydraulic powder ratio) is 50% by mass or less. However, depending on the composition of the polycarboxylic acid-based dispersant composition, the viscosity of the hydraulic composition increases and the kneading property is slow, so kneading becomes insufficient. The inventors have found that the intensity of .

The present invention provides a dispersant composition for a fly ash-containing hydraulic composition, and a fly ash-containing dispersant composition, which exhibits excellent uniformity in the strength of the cured product of the hydraulic composition even when hydraulic powder containing fly ash is used. A hydraulic composition is provided.

The present invention provides a dispersion for a fly ash-containing hydraulic composition, which contains cement and fly ash as hydraulic powder, and the content of fly ash in the hydraulic powder is 5% by mass or more and 40% by mass or less. agent composition,
It contains the following components (A) and (B), and the ratio of the content of component (B) to the total content of components (A) and (B) is 30% by mass or more and 70% by mass or less. Dispersant compositions for fly ash-containing hydraulic compositions.
<(A) Component>
A structural unit (A1) represented by the following formula (A1), a structural unit (A2) represented by the following formula (A2), and optionally a structural unit (A3) represented by the following formula (A3) A copolymer in which the ratio of the structural unit (A1) to the total of the structural unit (A1), the structural unit (A2), and the structural unit (A3) is 5% by mass or more and less than 9% by mass.

[Wherein, R ^1a , R ^2a and R ^4a are the same or different and each represent a hydrogen atom or a methyl group; R ^3a represents ^a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; represents a hydrogen atom or a salt counterion, X ¹ represents a divalent alkylene group having 1 to 6 carbon atoms, a direct bond or a carbonyl group, and na represents the average number of moles of ethylene oxide added. is a number of 20 or more and 130 or less, and R ^5a represents an alkyl group having 1 or more and 4 or less carbon atoms or a hydroxyalkyl group having 1 or more and 4 or less carbon atoms. ]
<(B) Component>
A copolymer having a structural unit (B1) represented by the following formula (B1) and a structural unit (B2) represented by the following formula (B2), wherein the structural unit (B1) and the structural unit (B2) A copolymer having a ratio of the structural unit (B1) to the total of 20% by mass or more and 28% by mass or less and a weight average molecular weight of 30,000 or more and 60,000 or less

[Wherein, R ^1b and R ^2b are the same or different and each represent a hydrogen atom or a methyl group, R ^3b represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and M ² represents a hydrogen represents an atom or a counter ion to be a salt, X ² represents a divalent alkylene group having 1 to 6 carbon atoms, a direct bond or a carbonyl group, nb represents the average number of added moles of ethylene oxide, 70 The number is greater than or equal to 170 and less than or equal to 170. ]

The present invention also provides a fly ash-containing hydraulic composition containing hydraulic powder containing cement and fly ash, water, the component (A), and the component (B),
The content of fly ash in the hydraulic powder is 5% by mass or more and 40% by mass or less, and the ratio of the content of component (B) to the total content of components (A) and (B) is 30% by mass. The present invention relates to a fly ash-containing hydraulic composition having a content of 70% by mass or less.

According to the present invention, a dispersant composition for a fly ash-containing hydraulic composition, which exhibits excellent uniformity in the strength of the cured product of the hydraulic composition even when hydraulic powder containing fly ash is used, and a fly An ash-containing hydraulic composition is provided.

The reason why the dispersant composition for the fly ash-containing hydraulic composition and the fly ash-containing hydraulic composition of the present invention is excellent in the uniformity of the strength of the hardened body of the hydraulic composition containing fly ash is not necessarily clear. is estimated as follows. When fly ash is contained, the viscosity of the slurry of the hydraulic composition increases, and when the kneading time is short, the kneading property becomes insufficient and the cement, fly ash, and sand that are the materials become uneven, and the test piece It is surmised that unevenness occurs in the filling property when packed into a container, and as a result, a difference in the uniformity of strength occurs. However, in the present invention, component (A) and component (B), which are specific copolymers, are used in a specific mass ratio, so that even a hydraulic composition containing fly ash has component (B) The copolymer of is adsorbed on cement and fly ash to release the aggregated state in which the slurry thickens, and the dispersion component of component (A) acts efficiently, so that it can be kneaded uniformly. , it is presumed that the strength of the hardened body of the hydraulic composition could be finished uniformly.

<Dispersant Composition for Fly Ash-Containing Hydraulic Composition>
The dispersant composition for a fly ash-containing hydraulic composition of the present invention contains components (A) and (B), and the ratio of component (B) to the total content of components (A) and (B) is The content ratio is 30% by mass or more and 70% by mass or less.

Component (A) includes a structural unit (A1) represented by the following formula (A1), a structural unit (A2) represented by the following formula (A2), and optionally a structural unit represented by the following formula (A3). A copolymer having (A3), wherein the ratio of the structural unit (A1) to the total of the structural unit (A1), the structural unit (A2) and the structural unit (A3) is 5% by mass or more and less than 9% by mass. , is a copolymer.

[Wherein, R ^1a , R ^2a and R ^4a are the same or different and each represent a hydrogen atom or a methyl group; R ^3a represents ^a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; represents a hydrogen atom or a salt counterion, X ¹ represents a divalent alkylene group having 1 to 6 carbon atoms, a direct bond or a carbonyl group, and na represents the average number of moles of ethylene oxide added. is a number of 20 or more and 130 or less, and R ^5a represents an alkyl group having 1 or more and 4 or less carbon atoms or a hydroxyalkyl group having 1 or more and 4 or less carbon atoms. ]

In formula (A1), R ^1a is preferably a hydrogen atom or a methyl group.
In formula (A1), M ¹ is preferably a hydrogen atom or sodium.

The structural unit (A1) can be obtained using a monomer selected from acrylic acid, methacrylic acid, and salts thereof. Salts include, for example, alkali metal salts, alkaline earth metal salts, ammonium salts, mono-, di-, and trialkyl (for example, having 2 or more and 8 or less carbon atoms) ammonium salts in which a hydroxyl group may be substituted.

In formula (A2), R ^2a is preferably a methyl group.
In formula (A2), R ^3a is preferably a hydrogen atom or a methyl group.
In formula (A2), X ¹ is preferably a direct bond or a carbonyl group.
In formula (A2), na is the average number of added moles of ethylene oxide, and from the viewpoint of dispersibility and strength development, na is 20 or more, preferably 30 or more, more preferably 40 or more, and 130 or less, preferably It is 130 or less, more preferably 125 or less.

Structural unit (A2) is a corresponding monomer, for example, (1) monoester of polyethylene glycol and acrylic acid or methacrylic acid, (2) one-terminal alkyl-blocked polyethylene glycol such as methoxypolyethylene glycol and acrylic acid or methacrylic acid (3) monoethers of polyethylene glycol with vinyl alcohol, allyl alcohol, methallyl alcohol, or isoprenyl alcohol; It can be obtained using a monomer selected from ethers with allyl alcohol and (5) ethylene oxide adducts with acrylic acid, methacrylic acid, maleic acid, allyl alcohol or methallyl alcohol.

In formula (A3), R ^4a is preferably a hydrogen atom or a methyl group.
In formula (A3), R ^5a is preferably one or more selected from a methyl group, an ethyl group, a hydroxyethyl group and a hydroxymethyl group.

The structural unit (A3) is one or more selected from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylic acid, hydroxymethyl acrylic acid, hydroxyethyl methacrylic acid, and hydroxymethyl methacrylic acid. It can be obtained using a monomer.

The polymer of component (A) has a ratio of the structural unit (A1) to the total of the structural unit (A1), the structural unit (A2) and the structural unit (A3), and the copolymer of the component (B) is cement or fly 5% by mass or more, preferably 6% by mass or more, and It is less than 9% by mass, preferably 8% by mass or less. This ratio is obtained by [% by mass of structural unit (A1)/[% by mass of structural unit (A1)+% by mass of structural unit (A2)+% by mass of structural unit (A3)]]×100.

In the polymer of component (A), the ratio of the structural unit (A2) to the total of the structural unit (A1), the structural unit (A2), and the structural unit (A3) is dispersibility at a low addition amount in the hydraulic composition. From the viewpoint of, preferably 70% by mass or more, more preferably 75% by mass or more, still more preferably 80% by mass or more, and preferably less than 98% by mass, more preferably 96% by mass or less, still more preferably 94% by mass 92% by mass or less, and more preferably 92% by mass or less. This ratio is obtained by [% by mass of structural unit (A2)/[% by mass of structural unit (A1)+% by mass of structural unit (A2)+% by mass of structural unit (A3)]]×100.

When the polymer of component (A) contains the structural unit (A3), the ratio of the structural unit (A3) to the total of the structural unit (A1), the structural unit (A2) and the structural unit (A3) is the hydraulic composition From the viewpoint of dispersibility, setting retardation, and flow retention at low addition amounts in products, it is preferably 2% by mass or more, more preferably 3% by mass or more, and preferably less than 15% by mass, preferably 12% by mass. It is below. This ratio is obtained by [% by mass of structural unit (A3)/[% by mass of structural unit (A1)+% by mass of structural unit (A2)+% by mass of structural unit (A3)]]×100.

The copolymer of component (A) may have a structural unit other than the structural unit (A1), the structural unit (A2), and the structural unit (A3) (hereinafter also referred to as the structural unit (A4)). Examples of the structural unit (A4) include 2-(methacryloyloxy)ethyl phosphate (HEMA-P), allylsulfonic acid, methallylsulfonic acid, and salts thereof such as alkali metal salts and alkaline earth metal salts. , ammonium salts, or amine salts. Further, (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, 2-(meth)acrylamide-2-methasulfonic acid, 2-(meth)acrylamide-2-ethanesulfonic acid, Structural units using monomers such as 2-(meth)acrylamido-2-propanesulfonic acid, styrene, and styrenesulfonic acid are included. (Meth)acrylic means acrylic or methacrylic.

When the copolymer of component (A) does not contain the structural unit (A3), the proportion of the structural unit (A1) and the structural unit (A2) in all structural units is preferably 80 from the viewpoint of improving dispersibility. % by mass or more, more preferably 90% by mass or more, and preferably 100% by mass or less.
Further, when the copolymer of the component (A) contains the structural unit (A3), the ratio of the structural unit (A1), the structural unit (A2), and the structural unit (A3) in the total structural units is the hydraulic composition From the viewpoint of dispersibility, setting retardation, and fluidity retention at a low addition amount in a product, the content is preferably 80% by mass or more, more preferably 90% by mass or more, and preferably 100% by mass or less.

From the viewpoint of dispersibility, the copolymer of component (A) has a weight average molecular weight of preferably 20,000 or more, more preferably 30,000 or more, still more preferably 40,000 or more, and preferably 100,000 or less, more preferably 80,000 or less. , and more preferably 70,000 or less. This weight average molecular weight is determined by high-speed GPC (HLC-8320GPC) Tosoh Corporation, detector: RI, column: G4000PWXL+G2500PWXL (anion), mobile phase: 0.2M phosphate buffer/acetonitrile = 9/1, flow rate: 1. 0 ml/min, column temperature: 40°C, standard substance: polyethylene glycol).

Component (B) is a copolymer having a structural unit (B1) represented by the following formula (B1) and a structural unit (B2) represented by the following formula (B2), wherein the structural unit (B1) and It is a copolymer in which the ratio of the structural unit (B1) to the total of the structural units (B2) is 20% by mass or more and 28% by mass or less, and the weight average molecular weight is 30,000 or more and 60,000 or less.

[Wherein, R ^1b and R ^2b are the same or different and each represent a hydrogen atom or a methyl group, R ^3b represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and M ² represents a hydrogen represents an atom or a counter ion to be a salt, X ² represents a divalent alkylene group having 1 to 6 carbon atoms, a direct bond or a carbonyl group, nb represents the average number of added moles of ethylene oxide, 70 The number is greater than or equal to 170 and less than or equal to 170. ]

In formula (B1), R ^1b is preferably a hydrogen atom or a methyl group.
In formula (B1), ^M2 is preferably a hydrogen atom or sodium.

The structural unit (B1) can be obtained using a monomer selected from acrylic acid, methacrylic acid, and salts thereof. Salts include, for example, alkali metal salts, alkaline earth metal salts, ammonium salts, mono-, di-, and trialkyl (for example, having 2 or more and 8 or less carbon atoms) ammonium salts in which a hydroxyl group may be substituted.

In formula (B2), R ^2b is preferably a hydrogen atom or a methyl group.
In formula (B2), R ^3b is preferably a hydrogen atom or a methyl group.
In formula (B2), X ² is preferably a direct bond or a carbonyl group.
In formula (B2), nb is the average number of added moles of ethylene oxide, and from the viewpoint of imparting dispersibility at a low addition amount, nb is 70 or more, preferably 80 or more, more preferably 90 or more, and still more preferably 100 or more. , more preferably 105 or more, and 170 or less, preferably 160 or less, more preferably 150 or less, still more preferably 140 or less, still more preferably 130 or less, still more preferably 125 or less.

Structural unit (B2) is a corresponding monomer, for example, (1) monoester of polyethylene glycol and acrylic acid or methacrylic acid, (2) one-end alkyl-blocked polyethylene glycol such as methoxypolyethylene glycol and acrylic acid or methacrylic acid (3) monoethers of polyethylene glycol with vinyl alcohol, allyl alcohol, methallyl alcohol, or isoprenyl alcohol; It can be obtained using a monomer selected from ethers with allyl alcohol and (5) ethylene oxide adducts with acrylic acid, methacrylic acid, maleic acid, allyl alcohol or methallyl alcohol.

In the copolymer of component (B), the ratio of the structural unit (B1) to the total of the structural unit (B1) and the structural unit (B2) is, from the viewpoint of imparting kneading properties to the hydraulic composition, on a mass basis: 20% by mass or more, preferably 22% by mass or more, and 28% by mass or less, preferably 26% by mass or less. This ratio is determined by [% by mass of structural unit (B1)/[% by mass of structural unit (B1)+% by mass of structural unit (B2)]]×100.

In the copolymer of component (B), the ratio of the structural unit (B2) to the total of the structural unit (B1) and the structural unit (B2) is preferably 70% by mass or more on a mass basis from the viewpoint of improving dispersibility. , more preferably 72% by mass or more, still more preferably 74% by mass or more, and preferably 80% by mass or less, more preferably 78% by mass or less. This ratio is determined by [% by mass of structural unit (B2)/[% by mass of structural unit (B1)+% by mass of structural unit (B2)]]×100.

The copolymer of component (B) may have a structural unit other than the structural unit (B1) and the structural unit (B2) [hereinafter also referred to as structural unit (B3)]. Examples of the structural unit (B3) include 2-(methacryloyloxy)ethyl phosphate (HEMA-P), 2-hydroxyethyl acrylate (HEA), methyl acrylate, methyl methacrylate, and 2-hydroxyethyl methacrylate (HEMA). , allylsulfonic acid, methallylsulfonic acid, and salts thereof such as alkali metal salts, alkaline earth metal salts, ammonium salts, or amine salts. Further, (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, 2-(meth)acrylamide-2-methasulfonic acid, 2-(meth)acrylamide-2-ethanesulfonic acid, Structural units using monomers such as 2-(meth)acrylamido-2-propanesulfonic acid, styrene, and styrenesulfonic acid are included. (Meth)acrylic means acrylic or methacrylic.

In the copolymer of component (B), the ratio of the structural unit (B1) and the structural unit (B2) in all structural units is preferably 80% by mass or more, from the viewpoint of imparting dispersibility to the hydraulic composition. It is preferably 90% by mass or more, and preferably 100% by mass or less.

The copolymer of component (B) has a weight average molecular weight of 30,000 or more, preferably 35,000 or more, more preferably 40,000 or more and 60,000 or less, from the viewpoint of imparting dispersibility to the hydraulic composition. It is more preferably 55,000 or less, still more preferably 50,000 or less. This weight average molecular weight is measured in the same manner as for the component (A).

The dispersant composition for a fly ash-containing hydraulic composition of the present invention preferably contains component (A) in an amount of 0.01% by mass or more, more preferably 0.01% by mass or more, from the viewpoint of imparting dispersibility to the hydraulic composition. 04% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.3% by mass or less, and even more preferably 0.1% by mass or less.

In the dispersant composition for fly ash-containing hydraulic composition of the present invention, the component (B) is preferably 0.015% by mass or more, more preferably 0% by mass, from the viewpoint of improving the kneading property of the hydraulic composition. 0.03% by mass or more, and preferably 0.3% by mass or less, more preferably 0.15% by mass or less, and even more preferably 0.1% by mass or less.

In the dispersant composition for the fly ash-containing hydraulic composition of the present invention, the ratio of the content of component (B) to the total content of components (A) and (B) is determined by kneading the hydraulic composition. From the viewpoint of improving properties, it is 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, and 70% by mass or less, preferably 65% by mass or less, more preferably 60% by mass or less. This ratio is obtained by [content of component (B)/[total content of component (A) and component (B)]]×100.

The dispersant composition for the fly ash-containing hydraulic composition of the present invention contains, as optional components, a retarder, a curing accelerator, an AE agent, a swelling agent, a foaming agent, a thickener, a fluidizing agent, a foaming agent, Components such as a waterproofing agent and an antifoaming agent [excluding those corresponding to components (A) and (B)] can be contained.

The dispersant composition for the fly ash-containing hydraulic composition of the present invention can contain water. The dispersant composition for the fly ash-containing hydraulic composition of the present invention may be a liquid composition.

The dispersant composition for a fly ash-containing hydraulic composition of the present invention contains cement and fly ash as hydraulic powder, and the content of fly ash in the hydraulic powder is 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and 40% by mass or less, preferably 30% by mass or less.

As the fly ash, for example, when pulverized coal is burned in a coal-fired power plant, a by-product obtained by collecting spherical fine particles obtained by cooling molten ash with an electric dust collector or the like can be used.
The main components of fly ash are silica (SiO ₂ ) and alumina (Al ₂ O ₃ ), and these two inorganic components account for, for example, 70 to 80% by mass of the total. In addition, it typically contains small amounts of ferric oxide (Fe ₂ O ₃ ), magnesium oxide (MgO), calcium oxide (CaO), and the like.
The chemical composition of the fly ash is preferably 50-70% by weight of SiO ₂ , 16-20% by weight of Al ₂ O ₃ , 5-6% by weight of Fe ₂ O ₃ , based on the total weight of the fly ash. CaO is 1 to 3% by mass. The quality of the fly ash may be, for example, a quality corresponding to any of fly ash types I, II, III, and IV defined in JIS A6201-2008 (fly ash for concrete). In addition, from the viewpoint of cost, fly ash with a SiO ₂ proportion of less than 50% by mass can also be used.
The ignition loss of fly ash is not particularly limited, but is preferably 5% or less, more preferably 3% or less. The ignition loss of fly ash is determined by, for example, the ignition loss test method (JIS A6201 (heat fly ash at a high temperature of 950 to 1000 ° C., determine the ignition loss from the mass reduction rate, dry at 105 ° C. for 3 hours, Moisture content is obtained from the mass reduction rate at constant temperature, and the amount of unburned carbon is calculated by subtracting the moisture content from the ignition loss of fly ash).
Although the average particle size of fly ash is not particularly limited, it is preferably 15 to 25 μm. The average particle size of fly ash means the average particle size at an integrated value of 50% in the particle size distribution obtained by the laser diffraction/scattering method, that is, the median diameter (D ₅₀ ).

<Hydraulic composition containing fly ash>
The present invention provides a fly ash-containing hydraulic composition containing hydraulic powder containing cement and fly ash, water, the component (A), and the component (B),
The content of fly ash in the hydraulic powder is 5% by mass or more and 40% by mass or less, and the ratio of the content of component (B) to the total content of components (A) and (B) is 30% by mass. Provided is a fly ash-containing hydraulic composition having a content of at least 70% by mass.

To the fly ash-containing hydraulic composition of the present invention, the matters described for the dispersant composition for the fly ash-containing hydraulic composition of the present invention can be appropriately applied. For example, specific examples and preferred embodiments of components (A) and (B) in the fly ash-containing hydraulic composition of the present invention are the same as those of the fly ash-containing hydraulic composition of the present invention. is.

Hydraulic powders are powders having physical properties that harden by hydration reaction, and include cement, gypsum, and the like. Cement such as ordinary portland cement, belite cement, moderate heat cement, high-early-strength cement, ultra-high-early-strength cement, and sulfate-resistant cement are preferred, and these are added with posolan action and/or Powder having latent hydraulicity, blast furnace slag cement, fly ash cement, silica fume cement, etc., to which stone powder (calcium carbonate powder) or the like is added may also be used. Here, the hydraulic powder is selected from powder having physical properties such as cement that hardens due to hydration reaction, powder having pozzolanic action, powder having latent hydraulic property, and stone powder (calcium carbonate powder). In the present invention, the amounts thereof are also included in the amount of hydraulic powder. Moreover, when the powder having the property of hardening by hydration 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 parts by mass and mass ratios related to the mass of the hydraulic powder.

The fly ash-containing hydraulic composition of the present invention contains cement and fly ash as hydraulic powder. In the fly ash-containing hydraulic composition of the present invention, the content of fly ash in the hydraulic powder is 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and 40% by mass. Below, preferably 30% by mass or less. As the fly ash, those described in the dispersant composition for the fly ash-containing hydraulic composition of the present invention can be used.
The Blaine value of fly ash is preferably less than 5000 cm ² /g, more preferably 4500 cm ² /g or less. The Blaine value is a specific surface area measured by the Blaine specific surface area measurement method. Specifically, the Blaine value of fly ash is measured using a Blaine air permeation apparatus defined in the cement physical test method (JIS R5201).

The fly ash-containing hydraulic composition of the present invention can contain aggregate. The aggregates include aggregates selected from fine aggregates and coarse aggregates. Examples of fine aggregates include those specified by No. 2311 in JISA0203-2014. 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 Fine aggregate etc. are mentioned. In addition, coarse aggregates include those specified by No. 2312 in JISA0203-2014. For example, coarse aggregates include river gravel, land gravel, mountain gravel, sea gravel, lime gravel, crushed stones thereof, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural) and recycled. Coarse aggregate etc. are mentioned. Different types of fine aggregates and coarse aggregates may be mixed and used, or a single type may be used.

In the fly ash-containing hydraulic composition of the present invention, from the viewpoint of imparting dispersibility to the hydraulic composition, component (A) is preferably added in an amount of 0.01 parts by mass or more based on 100 parts by mass of the hydraulic powder. More preferably 0.04 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, still more preferably 0.3 parts by mass or less, and even more preferably 0.15 parts by mass or less do.

In the fly ash-containing hydraulic composition of the present invention, component (B) is preferably added in an amount of 0.01 parts by mass or more per 100 parts by mass of the hydraulic powder, from the viewpoint of improving kneading properties of the hydraulic composition. , more preferably 0.02 parts by mass or more, more preferably 0.04 parts by mass or more, and preferably 0.2 parts by mass or less, more preferably 0.15 parts by mass or less, still more preferably 0.1 parts by mass Contains:

In the fly ash-containing hydraulic composition of the present invention, the ratio of the content of component (B) to the total content of components (A) and (B) is, from the viewpoint of improving kneading properties of the hydraulic composition, 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, and 70% by mass or less, preferably 65% by mass or less, more preferably 60% by mass or less. This ratio is obtained by [content of component (B)/[total content of component (A) and component (B)]]×100.

The mass percentage of water and hydraulic powder (water/hydraulic powder ratio) (abbreviated as W/P) in the fly ash-containing hydraulic composition of the present invention is the workability of the hydraulic composition. From the viewpoint of , it is preferably 25% by mass or more, more preferably 30% by mass or more, and from the viewpoint of strength development, it is preferably 50% by mass or less, more preferably 40% by mass.
The mass percentage of water and cement (water/cement ratio) (abbreviated as W/C) in the fly ash-containing hydraulic composition of the present invention is preferably 35% by mass or more from the viewpoint of workability. More preferably 45% by mass or more, preferably 70% by mass or less, and more preferably 60% by mass.

When the fly ash-containing hydraulic composition is concrete, the amount of coarse aggregate used reduces the strength of the hydraulic composition and the amount of hydraulic powder such as cement used, and improves the filling of the formwork. From the viewpoint of improving the 80% or less. Bulk volume is the ratio of the volume of coarse aggregate (including voids) in 1 m ³ of concrete.
Further, when the fly ash-containing hydraulic composition is concrete, the amount of fine aggregate used is preferably 500 kg/m ³ or more, more preferably 600 kg/m ³ , from the viewpoint of improving the fillability of the formwork or the like. Above, more preferably 700 kg/m ³ or more, preferably 1,000 kg/m ³ or less, more preferably 900 kg/m ³ or less.
When the fly ash-containing hydraulic composition is mortar, the amount of fine aggregate used is preferably 800 kg/m ³ or more, more preferably 900 kg/m ³ or more, and still more preferably 1,000 kg/m ³ or more, And it is preferably 2,000 kg/m ³ or less, more preferably 1,800 kg/m ³ or less, still more preferably 1,700 kg/m ³ or less.

The fly ash-containing hydraulic composition of the present invention may contain, as optional components, a retarder, a curing accelerator, an AE agent, an expanding agent, a foaming agent, a thickener, a fluidizing agent, a foaming agent, a waterproofing agent, and an antifoaming agent. [excluding those corresponding to components (A) and (B)] such as.

A cured body can be obtained by curing the fly ash-containing hydraulic composition of the present invention by a known method. Curing of the hydraulic composition can be carried out in consideration of the use, shape, etc. of the cured body.

<Method for producing hydraulic composition containing fly ash>
The present invention is a method for producing a fly ash-containing hydraulic composition, which comprises mixing cement, fly ash, water, the component (A), and the component (B) as hydraulic powders. ,
The amount of fly ash mixed in the hydraulic powder is 5% by mass or more and 40% by mass or less,
The ratio of the mixed amount of component (B) to the total mixed amount of component (A) and component (B) is 30% by mass or more and 70% by mass or less.
A method for producing a fly ash-containing hydraulic composition is provided.

To the method for producing the fly ash-containing hydraulic composition of the present invention, the dispersant composition for the fly ash-containing hydraulic composition and the fly ash-containing hydraulic composition of the present invention can be appropriately applied. can. Specific examples and preferred embodiments of the hydraulic powder, component (A), component (B), and optional components used in the method for producing the fly ash-containing hydraulic composition of the present invention are described in the fly ash-containing hydraulic composition of the present invention. The same is true for dispersant compositions for products, and fly ash-containing hydraulic compositions. In the fly ash-containing hydraulic composition of the present invention, the dispersant composition for the fly ash-containing hydraulic composition and the fly ash-containing hydraulic composition of the present invention, the content of each component is replaced by the mixing amount, and the preferred range is the fly ash-containing water of the present invention. It can be applied to a method for producing a hard composition.

In the method for producing a fly ash-containing hydraulic composition of the present invention, the ratio of the mixing amount of component (B) to the total mixing amount of components (A) and (B) is effective for improving kneading properties of the hydraulic composition. From the viewpoint, it is 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, and 70% by mass or less, preferably 65% by mass or less, more preferably 60% by mass or less. This ratio is obtained by [mixed amount of component (B)/[total mixed amount of component (A) and component (B)]]×100.

The method for producing the fly ash-containing hydraulic composition of the present invention is not limited to the order in which the components are mixed. and optionally aggregates, and then mixing a kneading liquid containing components (A), (B) and water. For example, cement, fly ash, coarse aggregate, and fine aggregate are mixed for a predetermined time, for example, 5 seconds or more and 60 seconds or less, and a kneading liquid containing (A) component, (B) component, and water is mixed. is mentioned. Mixing can be performed with a known mixer. The kneading liquid may be an aqueous solution or a water suspension.

In the method for producing the fly ash-containing hydraulic composition of the present invention, the component (A) and the component (B) are each added to the hydraulic powder in the range described for the fly ash-containing hydraulic composition of the present invention. can be mixed so that

In the method for producing a lyash-containing hydraulic composition of the present invention, optional components include a retarder, a curing accelerator, an AE agent, a swelling agent, a foaming agent, a thickener, a fluidizing agent, a foaming agent, a waterproofing agent, Components such as antifoaming agents [excluding those corresponding to components (A) and (B)] can be mixed.

In the method for producing a fly ash-containing hydraulic composition of the present invention, water and hydraulic powder are abbreviated as the mass percentage of water and hydraulic powder (water/hydraulic powder ratio) (W/P). ) is preferably 25% by mass or more, more preferably 30% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass, from the viewpoint of workability of the hydraulic composition. do.
In the method for producing a fly ash-containing hydraulic composition of the present invention, water and cement are mixed, and the mass percentage of water and cement (water/cement ratio) (abbreviated as W/C) is From the viewpoint of workability, it is preferably 35 mass % or more, more preferably 45 mass % or more, and from the viewpoint of strength development, it is preferably 70 mass % or less, more preferably 60 mass %.

The following were used as (A) component and (B) component.

<(A) Component>
A-1: methacrylic acid / MEPEG (120) ester = 6.0/94.0 (mass%) = 80/20 (mol%) copolymer, sodium salt, weight average molecular weight 53000
· A-2: Copolymer of methacrylic acid / MEPEG (23) ester = 8.8/91.2 (mass%) = 55.5/44.5 (mol%), sodium salt, weight average molecular weight 53000
· A-3: methacrylic acid / MEPEG (120) ester / ME (9) ester = 7.3 / 37.7 / 55.0 (mass%) = 49.5 / 6.0 / 44.5 (mol%) ) copolymer, sodium salt, weight average molecular weight 70000
A-4: Copolymer of methacrylic acid/MEPEG (120) ester/methyl acrylate = 6.0/90.4/3.7 (mass%) = 20/10/70 (mol%), sodium salt , weight average molecular weight 63000
A-5: Copolymer of methacrylic acid/MEPEG (120) ester/methyl acrylate = 6.0/82.6/11.4 (mass%) = 32/7/61 (mol%), sodium salt , weight average molecular weight 62000
A-6: Copolymer of methacrylic acid/MEPEG (120) ester/hydroxyethyl acrylic acid = 6.0/90.4/3.7 (mass%) = 59/14/27 (mol%), sodium Salt, weight average molecular weight 49000

<(B) Component>
B-1: methacrylic acid / MEPEG (120) ester = 23.1/76.9 (mass%) = 95/5 (mol%) copolymer, sodium salt, weight average molecular weight 44000
· B-2: methacrylic acid / MEPEG (120) ester = 20/80 (mass%) = 94/6 (mol%) copolymer, sodium salt, weight average molecular weight 43000
B-3: methacrylic acid / MEPEG (120) ester = 28/72 (mass%) = 96/4 (mol%) copolymer, sodium salt, weight average molecular weight 49000
<(B') Component (comparative component of (B) component>
· B'-1: methacrylic acid / MEPEG (120) ester = 34/66 (mass%) = 97/3 (mol%) copolymer, sodium salt, weight average molecular weight 66000
· B'-2: methacrylic acid / MEPEG (120) ester = 12.5/87.5 (mass%) = 90/10 (mol%) copolymer, sodium salt, weight average molecular weight 53000

The monomers of each of the above copolymers are as follows.
- MEPEG (120) ester: methoxypolyethylene glycol (120) monomethacrylate (the number in parentheses is the average number of added moles of ethylene oxide; the same shall apply hereinafter)
- MEPEG (23) ester: methoxypolyethylene glycol (23) monomethacrylate - ME (9) ester: methoxypolyethylene glycol (9) monomethacrylate

<Production Example 1: Production of copolymer A-1>
Copolymer A-1 was produced as follows.
A glass reactor equipped with a stirrer was charged with 301.8 g of water, the contents were replaced with nitrogen while stirring, and the temperature was raised to 80° C. in a nitrogen atmosphere. After that, 12.74 g of methacrylic acid, 1.80 g of 2-mercaptoethanol, 3.48 g of 75% phosphoric acid and 0.45 g of 25% Dequest 2066, MEPEG (120) ester (active content 59.35%, methacrylic acid 2.25%) and 3.5 g of ammonium persulfate dissolved in 19.85 g of water were dropped into the container over 1.5 hours. Thereafter, a solution obtained by dissolving 1.4 g of ammonium persulfate in 7.94 g of water was added dropwise at the same temperature (80° C.) over 0.5 hours, and then aged at the same temperature for 1 hour. After completion of aging, the product was neutralized with 18.61 g of a 48% aqueous sodium hydroxide solution to obtain a reaction product containing copolymer A-1 having a weight average molecular weight of 53,000 and water.

Other copolymers in Table 1 were also produced in the same manner as above, except that the types and amounts of monomers used were changed. Table 1 shows the monomer composition and weight average molecular weight of components (A) and (B).

(1-1) Preparation of dispersant composition for fly ash-containing hydraulic composition A dispersant composition for a fly ash-containing hydraulic composition was prepared by mixing so that the proportions of the amounts were as shown in Tables 3 to 5. The total content of components (A) and (B) in the dispersant composition for fly ash-containing hydraulic composition is 0.14% by mass.

(2-1) Preparation of mortar Cement (C), fly ash (FA ), the fine aggregate (S) is charged, and dry kneading is performed for 10 seconds at a low speed rotation (63 rpm) of a mortar mixer, and kneading water (W) containing a dispersant composition for a fly ash-containing hydraulic composition is prepared. was added. Then, main kneading was performed for 120 seconds at a low speed rotation (63 rpm) of a mortar mixer to prepare mortar. The mixing conditions of the mortar are as follows. On the other hand, it was added to the kneading water so that the amounts shown in Tables 3 to 5 were obtained.

The ingredients used for the preparation of the mortar are as follows.
- Water (W): Tap water was used.
・ Cement (C): Ordinary Portland cement (mixed of two types: Taiheiyo cement / Sumitomo Osaka cement = 1/1, mass ratio) Density 3.16 g / cm ³
Fly ash (FA): Fly ash (mixture of two types: Miike/Hibikinada = 1/1 (mass ratio)), Blaine value 4026 cm ² /g, chemical composition of fly ash, SiO ₂ is 70.3 mass %, Al ₂ O ₃ is 16.6 mass %, Fe ₂ O ₃ is 6.4 mass %, CaO is 1.7 mass %, the ignition loss of fly ash is 4.7%, the average of fly ash The particle size (median diameter ( _D50 )) is 20 μm.
・Fine aggregate (S): mountain sand from Joyo, density 2.55 g/cm ³

(2-2) Evaluation of strength of hardened mortar after 24 hours The strength of the hardened mortar after 24 hours was evaluated for the prepared mortar according to the test method shown below. The results are shown in Tables 3-5.
Based on JIS A 1132, three plastic concrete specimen molding molds (trade name Plamold, Marui Co., Ltd., cylinder type, bottom diameter 5 cm, height 10 cm), each with a double-layer packing method The mortar was filled with mortar, cured in the air (20°C) in a room at 20°C, and hardened to prepare three specimens. Twenty-four hours after the mortar was prepared, three hardened specimens were demoulded from the formwork.
Compressive strength was measured based on JIS A 1108 for three specimens. Tables 3 to 5 show the measured strength values of the specimens, their average values, and the deviation of the measured values. The time from mortar preparation was based on the time when water and cement first came into contact with each other during mortar preparation.

Claims (8)

A dispersant composition for a fly ash-containing hydraulic composition, which contains cement and fly ash as hydraulic powder, and the content of fly ash in the hydraulic powder is 5% by mass or more and 40% by mass or less. There is
It contains the following components (A) and (B), and the ratio of the content of component (B) to the total content of components (A) and (B) is 30% by mass or more and 70% by mass or less. A dispersant composition for fly ash-containing hydraulic compositions.
<(A) Component>
A structural unit (A1) represented by the following formula (A1), a structural unit (A2) represented by the following formula (A2), and optionally a structural unit (A3) represented by the following formula (A3) A copolymer in which the ratio of the structural unit (A1) to the total of the structural unit (A1), the structural unit (A2), and the structural unit (A3) is 5% by mass or more and less than 9% by mass.

[Wherein, R ^1a , R ^2a and R ^4a are the same or different and each represent a hydrogen atom or a methyl group; R ^3a represents ^a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; represents a hydrogen atom or a salt counter ion, X ¹ represents a divalent alkylene group having 1 to 6 carbon atoms, a direct bond or a carbonyl group, and na represents the average number of added moles of ethylene oxide. is a number of 20 or more and 130 or less, and R ^5a represents an alkyl group having 1 or more and 4 or less carbon atoms or a hydroxyalkyl group having 1 or more and 4 or less carbon atoms. ]
<(B) Component>
A copolymer having a structural unit (B1) represented by the following formula (B1) and a structural unit (B2) represented by the following formula (B2), wherein the structural unit (B1) and the structural unit (B2) A copolymer having a ratio of the structural unit (B1) to the total of 20% by mass or more and 28% by mass or less and a weight average molecular weight of 30,000 or more and 60,000 or less

[Wherein, R ^1b and R ^2b are the same or different and each represents a hydrogen atom or a methyl group, R ^3b represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and M ² represents a hydrogen represents an atom or a counter ion to be a salt, X ² represents a divalent alkylene group having 1 to 6 carbon atoms, a direct bond or a carbonyl group, nb represents the average number of added moles of ethylene oxide, 70 The number is greater than or equal to 170 and less than or equal to 170. ] The dispersant composition for a fly ash-containing hydraulic composition according to claim 1, containing 0.01% by mass or more and 1% by mass or less of component (A). 3. The dispersant composition for a fly ash-containing hydraulic composition according to claim 1 or 2, wherein component (A) has a weight average molecular weight of 20,000 or more and 100,000 or less. A fly ash-containing hydraulic composition containing hydraulic powder containing cement and fly ash, water, the following component (A), and the following component (B),
The content of fly ash in the hydraulic powder is 5% by mass or more and 40% by mass or less, and the ratio of the content of component (B) to the total content of components (A) and (B) is 30% by mass. A fly ash-containing hydraulic composition having a content of 70% by mass or more.
<(A) Component>
A structural unit (A1) represented by the following formula (A1), a structural unit (A2) represented by the following formula (A2), and optionally a structural unit (A3) represented by the following formula (A3) A copolymer in which the ratio of the structural unit (A1) to the total of the structural unit (A1), the structural unit (A2), and the structural unit (A3) is 5% by mass or more and less than 9% by mass.

[Wherein, R ^1a , R ^2a and R ^4a are the same or different and each represent a hydrogen atom or a methyl group; R ^3a represents ^a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; represents a hydrogen atom or a salt counterion, X ¹ represents a divalent alkylene group having 1 to 6 carbon atoms, a direct bond or a carbonyl group, and na represents the average number of moles of ethylene oxide added. is a number of 20 or more and 130 or less, and R ^5a represents an alkyl group having 1 or more and 4 or less carbon atoms or a hydroxyalkyl group having 1 or more and 4 or less carbon atoms. ]
<(B) Component>
A copolymer having a structural unit (B1) represented by the following formula (B1) and a structural unit (B2) represented by the following formula (B2), wherein the structural unit (B1) and the structural unit (B2) A copolymer having a ratio of the structural unit (B1) to the total of 20% by mass or more and 28% by mass or less and a weight average molecular weight of 30,000 or more and 60,000 or less

[Wherein, R ^1b and R ^2b are the same or different and each represents a hydrogen atom or a methyl group, R ^3b represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and M ² represents a hydrogen represents an atom or a counter ion to be a salt, X ² represents a divalent alkylene group having 1 to 6 carbon atoms, a direct bond or a carbonyl group, nb represents the average number of added moles of ethylene oxide, 70 The number is greater than or equal to 170 and less than or equal to 170. ] 5. The fly ash-containing hydraulic composition according to claim 4, wherein the component (A) is contained in an amount of 0.01 parts by mass or more and 1 part by mass or less per 100 parts by mass of the hydraulic powder. The fly ash-containing hydraulic composition according to claim 4 or 5, wherein component (A) has a weight average molecular weight of 20,000 or more and 100,000 or less. Any one of claims 4 to 6, wherein the mass percentage of water and hydraulic powder (water/hydraulic powder ratio) in the fly ash-containing hydraulic composition is 25% by mass or more and 50% by mass or less. The fly ash-containing hydraulic composition according to . The fly ash-containing hydraulic composition according to any one of claims 4 to 7, wherein the fly ash has a Blaine value of less than 5000 cm ² /g.