Fluidity-retaining agent composition for hydraulic compositions

Abstract

To provide a fluidity-retaining agent composition for a hydraulic composition comprising blast furnace slag in which a hydraulic composition has good initial fluidity and excellent fluidity retention property even when a hydraulic powder containing blast furnace slag is used and to provide a hydraulic composition comprising blast furnace slag.SOLUTION: There is provided a fluidity-retaining agent composition for a hydraulic composition comprising blast furnace slag which comprises cement and blast furnace slag as a hydraulic powder in which the content of blast furnace slag in the hydraulic powder is 5 mass% or more and 60 mass% or less, wherein the fluidity-retaining agent 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 10 mass% or more and 50 mass% or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a fluidity retaining agent composition for a hydraulic composition containing blast furnace slag. [Background technology]

[0002] 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, retaining fluidity (fluidity retention), and preventing hardening delay, and improvements have been proposed for polycarboxylic acid-based admixtures (dispersants) from this perspective.

[0003] For example, in consideration of flowability and flow retention, it has been proposed to use a combination of multiple polycarboxylic acid polymers. Patent Document 1 discloses an effectiveness enhancer for cement dispersants, which comprises a copolymer obtained by copolymerizing a specific monomer (A) such as (meth)acrylic acid with a specific monomer (B) such as an ethylenically unsaturated carboxylic acid derivative having a polyoxyalkylene group so as to satisfy both a specific weight ratio and a specific molar ratio, and a cement dispersant composition containing the effectiveness enhancer for cement dispersants and a cement dispersant in a predetermined weight ratio. Patent Document 2 discloses a dispersion-retaining agent for hydraulic compositions, which comprises a copolymer obtained by polymerizing a specific monomer 1 represented by general formula (1) and a specific monomer 2 represented by general formula (2) whose corresponding alcohol compound satisfies specific physical properties, in which the ratio of monomer 1 among the constituent monomers of the copolymer is within a specific range, a specific monomer is used as at least a part of monomer 2, and the ratio of a monomer having an acid group or a neutralizing group thereof is 5% by weight or less. Patent Document 3 discloses an admixture for hydraulic compositions, which contains a copolymer A (excluding copolymer B) obtained by polymerizing a specific monomer A1 represented by general formula (A1) with a monomer having a carboxylic acid group and / or a phosphoric acid group, and a copolymer B having a weight average molecular weight of 6,000 to 27,000 obtained by polymerizing a specific monomer B1 represented by general formula (B1) with 2-hydroxyethyl acrylate in an amount of 95% by weight or more of the constituent monomers.

[0004] In addition, blast furnace slag and fly ash were once disposed of as industrial waste, but because mortar and concrete made from cement containing blast furnace slag or fly ash have superior long-term strength (lasting six months or more) and durability compared to mortar and concrete made from ordinary Portland cement, they are now being used in greater quantities each year as a partial substitute for cement. Annual CO from cement 2 The amount of CO generated (from energy sources) is equivalent to the total annual CO 2 This is a huge amount, equivalent to approximately 3% of the total amount generated (1.3 billion tons). By using cement made by mixing blast furnace slag and fly ash with Portland cement, the CO required for the production of Portland cement can be reduced. 2 The CO2 emissions from cement can be reduced by the amount of Portland cement replaced with ground granulated blast furnace slag or ground granulated fly ash. 2 This will contribute to reducing the CO2 emissions required to manufacture Portland cement. 2 It is possible to reduce the basic unit and further reduce the CO emissions from concrete compositions and their hardened bodies, such as buildings and civil engineering structures. 2 It is possible to reduce the basic unit. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2001-316151 A [Patent Document 2] JP 2009-1479 A [Patent Document 3] JP 2013-133241 A Summary of the Invention [Problem to be solved by the invention]

[0006] In a formulation in which the mass percentage of water and hydraulic powder in the hydraulic composition (water / hydraulic powder ratio) is 50 mass% or less and blast furnace slag is further included as a substitute powder for cement, the amount of polycarboxylic acid-based dispersant composition required for the hydration reaction tends to be small because the hydration activity of blast furnace slag is slower than that of cement, and fluidity retention is deteriorated. To solve this problem, a hydrolysis retention agent is used, but since it is hardly adsorbed to cement at the beginning of contact with water, a large amount needs to be added, which not only increases the manufacturing cost of the hardened body of the hydraulic composition, but also makes it difficult to control the fluidity of the hydraulic composition slurry, and in some cases, the fluidity of the hydraulic composition slurry increases over time, causing material separation, delayed setting, and reduced strength. The inventors have found that.

[0007] The present invention provides a fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition, which has good initial fluidity and excellent fluidity retention properties even when a hydraulic powder containing blast furnace slag is used, and a blast furnace slag-containing hydraulic composition. [Means for solving the problem]

[0008] The present invention provides a fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition, the fluidity retaining agent composition comprising cement and blast furnace slag as hydraulic powder, and the content of the blast furnace slag in the hydraulic powder is 5% by mass or more and 60% by mass or less, The present invention relates to a fluidity-retaining agent composition for a blast furnace slag-containing hydraulic composition, comprising the following components (A) and (B), in which the ratio of the content of component (B) to the total content of components (A) and (B) is 10 mass % or more and 50 mass % or less. <Component (A)> A copolymer having 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), wherein the proportion of the structural unit (A1) to the total of the structural units (A1), (A2), and (A3) is 70 mol % or more and 95 mol % or less, and the proportion of the structural unit (A3) is 20 mol % or less.

[0009] [ka]

[0010] [In the formula, R 1a , R 3a , and R 5a are the same or different and each represents a hydrogen atom or a methyl group; R 2a represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, R 4a represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; X 1 represents a divalent alkylene group having 1 to 6 carbon atoms, a direct bond, or a carbonyl group; na represents the average number of moles of ethylene oxide added, which is a number of 5 to 150; M 1 represents a hydrogen atom or a counter ion that forms a salt. <(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 proportion of the structural unit (B1) to the total of the structural units (B1) and (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.

[0011] [ka]

[0012] [In the formula, R 1b , and R 2b are the same or different and each represents a hydrogen atom or a methyl group; R 3brepresents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; M 2 represents a hydrogen atom or a counter ion which becomes a salt, and X 2 represents a divalent alkylene group having 1 to 6 carbon atoms, a direct bond, or a carbonyl group, and nb represents the average number of moles of ethylene oxide added and is a number of 700 to 170.

[0013] The present invention also provides a blast furnace slag-containing hydraulic composition comprising hydraulic powder containing cement and blast furnace slag, water, the component (A), and the component (B), The present invention relates to a blast furnace slag-containing hydraulic composition, in which the content of blast furnace slag in the hydraulic powder is 5% by mass or more and 60% by mass or less, and the ratio of the content of component (B) to the total content of components (A) and (B) is 10% by mass or more and 50% by mass or less. Effect of the Invention

[0014] According to the present invention, there are provided a fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition, and a blast furnace slag-containing hydraulic composition, which have good initial fluidity and excellent fluidity retention properties even when a hydraulic powder containing blast furnace slag is used. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The reason why the fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition and the blast furnace slag-containing hydraulic composition of the present invention have good initial fluidity and excellent fluidity retention is not necessarily clear, but it is presumed as follows. The fluidity retaining agent is slowly adsorbed to cement and slag, but it is presumed that the aggregation action caused by the progress of the hydration reaction creates an environment where fluidity is difficult to be expressed. In the present invention, by using the (A) component and the (B) component, which are copolymers with excellent kneading properties, in combination as the fluidity retaining agent, under conditions where the cement and slag are uniformly dispersed, the fluidity retaining agent effectively acts in an environment, so it is presumed that the fluidity retaining agent acts effectively even with a small amount added.

[0016] <Fluidity retaining agent composition for blast furnace slag-containing hydraulic composition> The fluidity-retaining agent composition for a blast furnace slag-containing hydraulic composition of the present invention contains component (A) and component (B), and the ratio of the content of component (B) to the total content of components (A) and (B) is 10 mass% or more and 50 mass% or less.

[0017] The component (A) is a copolymer having 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), in which the proportion of the structural unit (A1) to the total of the structural units (A1), (A2), and (A3) is 70 mol % or more and 95 mol % or less, and the proportion of the structural unit (A3) is 20 mol % or less.

[0018] [ka]

[0019] [In the formula, R 1a , R 3a , and R 5a are the same or different and each represents a hydrogen atom or a methyl group; R 2a represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, R 4a represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; X 1 represents a divalent alkylene group having 1 to 6 carbon atoms, a direct bond, or a carbonyl group; na represents the average number of moles of ethylene oxide added, which is a number of 5 to 150; M 1 represents a hydrogen atom or a counter ion that forms a salt.

[0020] In formula (A1), R 1a is preferably a hydrogen atom or a methyl group. In formula (A1), R 2a is preferably one or more selected from a methyl group, an ethyl group, a hydroxyethyl group, and a hydroxymethyl group.

[0021] The structural unit (A1) can be obtained using one or more monomers selected from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylic acid, hydroxymethyl acrylic acid, hydroxyethyl methacrylic acid, and hydroxymethyl methacrylic acid.

[0022] In formula (A2), R 3a is preferably a methyl group. In formula (A2), R 4a 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 moles of ethylene oxide added, and from the viewpoint of imparting dispersibility, it is 5 or more, preferably 10 or more, more preferably 15 or more, and 150 or less, preferably 140 or less, more preferably 130 or less.

[0023] The structural unit (A2) can be obtained using a corresponding monomer, for example, a monomer selected from the group consisting of (1) a monoester of polyethylene glycol and acrylic acid or methacrylic acid, (2) an ester of polyethylene glycol capped at one end with an alkyl group, such as methoxypolyethylene glycol, and acrylic acid or methacrylic acid, (3) a monoether of polyethylene glycol and vinyl alcohol, allyl alcohol, methallyl alcohol, or isoprenyl alcohol, (4) an ether of polyethylene glycol capped at one end with an alkyl group, such as methoxypolyethylene glycol, and allyl alcohol or methallyl alcohol, and (5) an ethylene oxide adduct to acrylic acid, methacrylic acid, maleic acid, allyl alcohol, or methallyl alcohol.

[0024] In formula (A3), R 5a is preferably a hydrogen atom or a methyl group. In formula (A3), M 1 is preferably a hydrogen atom or sodium.

[0025] The structural unit (A3) can be obtained using a monomer selected from acrylic acid, methacrylic acid, and salts thereof. Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, and mono-, di-, or trialkyl (e.g., having 2 to 8 carbon atoms) ammonium salts that may be substituted with a hydroxyl group.

[0026] In the polymer of component (A), the ratio of the structural unit (A1) to the total of the structural units (A1), (A2) and (A3) is 70 mol % or more, preferably 75 mol % or more, and preferably 95 mol % or less, more preferably 90 mol % or less, and even more preferably 85 mol % or less, from the viewpoint of fluidity retention of the hydraulic composition. This ratio is calculated by [mol % of structural unit (A1) / [mol % of structural unit (A1)+mol % of structural unit (A2)+mol % of structural unit (A3)]]×100.

[0027] In the polymer of component (A), the ratio of the structural unit (A2) to the total of the structural units (A1), (A2) and (A3) is preferably 5 mol % or more, more preferably 10 mol % or more, and preferably 30 mol % or less, more preferably 25 mol % or less, from the viewpoint of imparting steric repulsion and increasing the dispersibility of the hydraulic composition. This ratio is calculated by [mol % of structural unit (A2) / [mol % of structural unit (A1)+mol % of structural unit (A2)+mol % of structural unit (A3)]]×100.

[0028] In the polymer of component (A), the ratio of the structural unit (A3) to the total of the structural units (A1), (A2) and (A3) is 0 mol % or more, preferably 5 mol % or more, from the viewpoint of imparting dispersibility to the hydraulic composition, and 20 mol % or less, preferably 15 mol % or less, from the viewpoint of imparting fluidity retention to the hydraulic composition. This ratio is calculated by [mol % of structural unit (A3) / [mol % of structural unit (A1)+mol % of structural unit (A2)+mol % of structural unit (A3)]]×100.

[0029] 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 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, alkaline earth metal salts, ammonium salts, or amine salts. Further examples include structural units using monomers such as (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, 2-(meth)acrylamide-2-methasulfonic acid, 2-(meth)acrylamide-2-ethanesulfonic acid, 2-(meth)acrylamide-2-propanesulfonic acid, styrene, and styrenesulfonic acid. (Meth)acryl means acrylic or methacrylic.

[0030] When the copolymer of component (A) does not contain the structural unit (A3), the proportion of the structural units (A1) and (A2) in all structural units is preferably 80 mol % or more, more preferably 90 mol % or more, and preferably 100 mol % or less, from the viewpoint of the fluidity retention of the hydraulic composition. Furthermore, when the copolymer of component (A) contains the structural unit (A3), the proportions of the structural units (A1), (A2), and (A3) in all structural units are, from the viewpoint of the fluidity retention of the hydraulic composition, preferably 60 mol % or more, more preferably 70 mol % or more, even more preferably 80 mol % or more, and preferably 100 mol % or less.

[0031] From the viewpoint of imparting fluidity to the hydraulic composition, the copolymer of component (A) has a weight average molecular weight of preferably 15,000 or more, more preferably 20,000 or more, and preferably 100,000 or less, more preferably 80,000 or less, even more preferably 60,000 or less, and even more preferably 55,000 or less. This weight average molecular weight was measured using a 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).

[0032] 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), in which the proportion of structural unit (B1) to the total of structural units (B1) and (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.

[0033] [ka]

[0034] [In the formula, 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; M 2 represents a hydrogen atom or a counter ion which becomes a salt, and X 2 represents a divalent alkylene group having 1 to 6 carbon atoms, a direct bond, or a carbonyl group, and nb represents the average number of moles of ethylene oxide added and is a number of 100 to 150.

[0035] In formula (B1), R 1b is preferably a hydrogen atom or a methyl group. In formula (B1), M 2 is preferably a hydrogen atom or sodium.

[0036] The structural unit (B1) can be obtained using a monomer selected from acrylic acid, methacrylic acid, and salts thereof. Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, and mono-, di-, or trialkyl (e.g., having 2 to 8 carbon atoms) ammonium salts that may be substituted with a hydroxyl group.

[0037] 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 moles of ethylene oxide added, and from the viewpoint of imparting dispersibility in a hydraulic composition with a small amount added, it is 70 or more, preferably 80 or more, more preferably 90 or more, even more preferably 100 or more, still more preferably 105 or more, and is 170 or less, preferably 160 or less, more preferably 150 or less, still more preferably 140 or less, still more preferably 130 or less, and still more preferably 125 or less.

[0038] The structural unit (B2) can be obtained using a corresponding monomer, for example, a monomer selected from the group consisting of (1) a monoester of polyethylene glycol and acrylic acid or methacrylic acid, (2) an ester of polyethylene glycol capped at one end with an alkyl group, such as methoxypolyethylene glycol, and acrylic acid or methacrylic acid, (3) a monoether of polyethylene glycol and vinyl alcohol, allyl alcohol, methallyl alcohol, or isoprenyl alcohol, (4) an ether of polyethylene glycol capped at one end with an alkyl group, such as methoxypolyethylene glycol, and allyl alcohol or methallyl alcohol, and (5) an ethylene oxide adduct to acrylic acid, methacrylic acid, maleic acid, allyl alcohol, or methallyl alcohol.

[0039] In the copolymer of component (B), the ratio of the structural unit (B1) to the total of the structural units (B1) and (B2) is, on a mass basis, 20 mass% or more, preferably 22 mass% or more, and 28 mass% or less, preferably 26 mass% or less, from the viewpoint of imparting kneading properties to the hydraulic composition. This ratio is calculated by [mass% of structural unit (B1) / [mass% of structural unit (B1)+mass% of structural unit (B2)]]×100.

[0040] In the copolymer of component (B), the proportion of the structural unit (B2) to the total of the structural units (B1) and (B2) is, from the viewpoint of imparting dispersibility, preferably 70% by mass or more, more preferably 72% by mass or more, and preferably 80% by mass or less, more preferably 78% by mass or less, based on the mass. This proportion is calculated by [mass% of structural unit (B2) / [mass% of structural unit (B1)+mass% of structural unit (B2)]]×100.

[0041] 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, 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 examples include structural units using monomers such as (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, 2-(meth)acrylamide-2-methasulfonic acid, 2-(meth)acrylamide-2-ethanesulfonic acid, 2-(meth)acrylamide-2-propanesulfonic acid, styrene, and styrenesulfonic acid. (Meth)acryl means acrylic or methacrylic.

[0042] In the copolymer of component (B), the proportion of the structural units (B1) and (B2) in all structural units is preferably 80 mass% or more, more preferably 90 mass% or more, and preferably 100 mass% or less, from the viewpoint of imparting dispersibility to the hydraulic composition.

[0043] From the viewpoint of imparting dispersibility to the hydraulic composition, 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, more preferably 55,000 or less, and even more preferably 50,000 or less. This weight average molecular weight is measured in the same manner as for component (A).

[0044] The fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition of the present invention contains component (A) in an amount of preferably 0.01 mass % or more, more preferably 0.03 mass % or more, and preferably 0.2 mass % or less, more preferably 0.15 mass % or less, from the viewpoint of imparting dispersibility to the hydraulic composition.

[0045] The fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition of the present invention contains the (B) component in an amount of preferably 0.005 mass % or more, more preferably 0.01 mass % or more, and preferably 0.05 mass % or less, more preferably 0.03 mass % or less, from the viewpoint of improving the kneading properties of the hydraulic composition.

[0046] In the fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition of the present invention, the ratio of the content of the (B) component to the total content of the (A) component and the (B) component is 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and 50% by mass or less, preferably 45% by mass or less, more preferably 40% by mass or less, from the viewpoint of improving the kneading property of the hydraulic composition. This ratio is calculated by [the content of the (B) component / [the total content of the (A) component and the (B) component]]×100.

[0047] From the viewpoint of imparting dispersibility to the hydraulic composition, the fluidity retaining agent composition of the present invention for a blast furnace slag-containing hydraulic composition preferably further contains a polycarboxylic acid-based dispersant (excluding components (A) and (B)) as component (C).

[0048] Examples of polycarboxylic acid-based dispersants that can be used include copolymers of monoesters of polyalkylene glycol and (meth)acrylic acid and carboxylic acids such as (meth)acrylic acid (e.g., compounds described in JP-A-8-12397), copolymers of unsaturated alcohols having polyalkylene glycol and carboxylic acids such as (meth)acrylic acid, and copolymers of unsaturated alcohols having polyalkylene glycol and dicarboxylic acids such as maleic acid. Here, (meth)acrylic acid is a carboxylic acid selected from acrylic acid and methacrylic acid. This means:

[0049] The polycarboxylic acid dispersant is preferably a copolymer (hereinafter referred to as component (C1)) having a structural unit (C1) represented by the following formula (C1) and a structural unit (C2) represented by the following formula (C2).

[0050] [ka]

[0051] [In the formula, R 1c , and R 2c are the same or different and each represents a hydrogen atom or a methyl group; R 3c represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; M 3 represents a hydrogen atom or a counter ion which becomes a salt, and X 3 represents a divalent alkylene group having 1 to 6 carbon atoms, a direct bond, or a carbonyl group, AO represents an alkylene oxide, and nc represents the average number of moles of alkylene oxide added, which is a number of 5 to 150.

[0052] In formula (C1), R 1c is preferably a hydrogen atom or a methyl group. In formula (C1), M 3 is preferably a hydrogen atom or sodium.

[0053] The structural unit (C1) can be obtained using a monomer selected from acrylic acid, methacrylic acid, and salts thereof. Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, and mono-, di-, or trialkyl (e.g., having 2 to 8 carbon atoms) ammonium salts that may be substituted with a hydroxyl group.

[0054] In formula (C2), R 2c is preferably a hydrogen atom or a methyl group. In formula (C2), R 3c is preferably a hydrogen atom or a methyl group. In formula (C2), X 3 is preferably a direct bond or a carbonyl group. In formula (C2), AO is preferably ethylene oxide or propylene oxide, more preferably ethylene oxide. In formula (C2), nc is the average number of moles of alkylene oxide added, and from the viewpoint of imparting dispersibility to the hydraulic composition, it is preferably 5 or more, more preferably 7 or more, and preferably 150 or less, more preferably 130 or less, even more preferably 110 or less, still more preferably 90 or less, still more preferably 70 or less, and still more preferably 50 or less.

[0055] The structural unit (C2) can be obtained using a corresponding monomer, for example, a monomer selected from the group consisting of (1) a monoester of polyethylene glycol and acrylic acid or methacrylic acid, (2) an ester of polyethylene glycol capped at one end with an alkyl group, such as methoxypolyethylene glycol, and acrylic acid or methacrylic acid, (3) a monoether of polyethylene glycol and vinyl alcohol, allyl alcohol, methallyl alcohol, or isoprenyl alcohol, (4) an ether of polyethylene glycol capped at one end with an alkyl group, such as methoxypolyethylene glycol, and allyl alcohol or methallyl alcohol, and (5) an ethylene oxide adduct to acrylic acid, methacrylic acid, maleic acid, allyl alcohol, or methallyl alcohol.

[0056] In the copolymer of component (C1), the ratio of the structural unit (C1) to the total of the structural units (C1) and (C2) is, in terms of dispersibility in the hydraulic composition, preferably 9 mass% or more, more preferably 10 mass% or more, and preferably 19 mass% or less, more preferably 18 mass% or less. This ratio is calculated by [mass% of structural unit (C1) / [mass% of structural unit (C1)+mass% of structural unit (C2)]]×100.

[0057] In the copolymer of component (C1), the proportion of the structural unit (C2) to the total of the structural units (C1) and (C2) is, from the viewpoint of imparting dispersibility, preferably 71 mass% or more, more preferably 72 mass% or more, and preferably 91 mass% or less, more preferably 90 mass% or less. This proportion is calculated by [mass% of structural unit (C2) / [mass% of structural unit (C1)+mass% of structural unit (C2)]×100.

[0058] The copolymer of component (C1) may have a structural unit other than the structural unit (C1) and the structural unit (C2) [hereinafter, also referred to as structural unit (C3)]. Examples of structural unit (C3) include 2-(methacryloyloxy)ethyl phosphate (HEMA-P), 2-hydroxyethyl acrylate (HEA), methyl acrylate, methyl methacrylate, 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. In addition, structural units using monomers such as (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, 2-(meth)acrylamide-2-methasulfonic acid, 2-(meth)acrylamide-2-ethanesulfonic acid, 2-(meth)acrylamide-2-propanesulfonic acid, styrene, and styrenesulfonic acid may be mentioned. (Meth)acryl means acrylic or methacrylic.

[0059] In the copolymer of component (C1), the proportion of the structural units (C1) and (C2) in all structural units is preferably 80 mass% or more, more preferably 90 mass% or more, and preferably 100 mass% or less, from the viewpoint of imparting dispersibility to the hydraulic composition.

[0060] From the viewpoint of imparting dispersibility to the hydraulic composition, the copolymer of component (C1) has a weight average molecular weight of preferably at least 20,000, more preferably at least 30,000, even more preferably at least 40,000, and preferably at most 100,000, more preferably at most 80,000, even more preferably at most 60,000. This weight average molecular weight is measured in the same manner as for component (A).

[0061] In the fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition of the present invention, when the fluidity retaining agent composition contains the (C) component, the content ratio of the (C) component to the total content of the (A), (B) and (C) components is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, even more preferably 70% by mass or less, and even more preferably 60% by mass or less, from the viewpoint of imparting dispersibility to the hydraulic composition. This ratio is calculated by [content of the (C) component / [total content of the (A), (B) and (C) components]]×100.

[0062] The fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition of the present invention may contain, as optional components, components such as retarders, hardening accelerators, AE agents, expansion agents, foaming agents, thickeners, fluidizing agents, foaming agents, waterproofing agents, and defoamers (excluding those corresponding to components (A) to (C)).

[0063] The fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition of the present invention may contain water. The fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition of the present invention may be a liquid composition.

[0064] The fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition of the present invention contains cement and blast furnace slag as hydraulic powder, and is used for a hydraulic composition in which the content of blast furnace slag in the hydraulic powder is 5% by mass or more, preferably 15% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and 60% by mass or less, preferably 50% by mass or less. Blast furnace slag is a by-product obtained when producing pig iron in a blast furnace, and examples of the blast furnace slag include slowly cooled slag that is slowly cooled in air and rapidly cooled slag that is rapidly cooled in water.

[0065] <Hydraulic composition containing blast furnace slag> The present invention relates to a blast furnace slag-containing hydraulic composition comprising a hydraulic powder containing cement and blast furnace slag, water, the component (A), and the following component (B): The present invention provides a blast furnace slag-containing hydraulic composition, in which the content of blast furnace slag in the hydraulic powder is from 5% by mass to 60% by mass, and the ratio of the content of component (B) to the total content of components (A) and (B) is from 10% by mass to 50% by mass.

[0066] The matters described in the fluidity retaining agent composition for the blast furnace slag-containing hydraulic composition of the present invention can be appropriately applied to the blast furnace slag-containing hydraulic composition of the present invention. For example, specific examples and preferred embodiments of the (A) component and the (B) component in the blast furnace slag-containing hydraulic composition of the present invention are the same as those in the fluidity retaining agent composition for the blast furnace slag-containing hydraulic composition of the present invention.

[0067] The hydraulic powder is a powder having a physical property of being hardened by a hydration reaction, and examples thereof include cement and gypsum. Preferred are ordinary portland cement, belite cement, moderate heat cement, early strength cement, ultra-early strength cement, and sulfate-resistant cement. In addition, powders having pozzolanic action and / or latent hydraulic properties, such as blast furnace slag, fly ash, and silica fume, and powders having stone powder (calcium carbonate powder) or the like may be added to these, such as blast furnace slag cement, fly ash cement, and silica fume cement. Here, when the hydraulic powder includes powders selected from powders having pozzolanic action, powders having latent hydraulic properties, and stone powder (calcium carbonate powder) in addition to powders having physical properties of being hardened by a hydration reaction, such as cement, the amount of these powders is also included in the amount of the hydraulic powder in the present invention. In addition, when the powder having physical properties of being hardened by a 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 parts by mass and mass ratios that involve the mass of the hydraulic powder.

[0068] The blast furnace slag-containing hydraulic composition of the present invention contains cement and blast furnace slag as hydraulic powder. In the blast furnace slag-containing hydraulic composition of the present invention, the content of blast furnace slag in the hydraulic powder is 5 mass% or more, preferably 15 mass% or more, more preferably 30 mass% or more, even more preferably 40 mass% or more, and 60 mass% or less, preferably 50 mass% or less. The blast furnace slag may be the one described in the fluidity retaining agent composition for the blast furnace slag-containing hydraulic composition of the present invention. The Blaine value of the blast furnace slag is preferably 3000 cm 2 / g or more, more preferably 3500cm 2 / g or more, and preferably 5000 cm 2 / g, more preferably less than 4500 cm 2 / g or less. The Blaine value is the specific surface area measured by the Blaine specific surface area measurement method.

[0069] The blast furnace slag-containing hydraulic composition of the present invention may contain aggregate. Examples of aggregates include aggregates selected from fine aggregates and coarse aggregates. Examples of fine aggregates include those specified by number 2311 in JISA0203-2014. Examples of fine aggregates include river sand, land sand, mountain sand, sea sand, lime sand, silica sand and crushed sands thereof, blast furnace slag fine aggregate, ferronickel slag fine aggregate, lightweight fine aggregate (artificial and natural), and recycled fine aggregate. Examples of coarse aggregates include those specified by number 2312 in JISA0203-2014. For example, examples of 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. The fine aggregate and the coarse aggregate may be used in a mixture of different types, or a single type may be used.

[0070] From the viewpoint of fluidity retention of the hydraulic composition, the blast furnace slag-containing hydraulic composition of the present invention contains, relative to 100 parts by mass of hydraulic powder, preferably 0.01 parts by mass or more of component (A), more preferably 0.03 parts by mass or more, even more preferably 0.04 parts by mass or more, still more preferably 0.05 parts by mass or more, and preferably 0.5 parts by mass or less, more preferably 0.4 parts by mass or less, even more preferably 0.3 parts by mass or less, still more preferably 0.2 parts by mass or less, still more preferably 0.1 parts by mass or less, and still more preferably 0.08 parts by mass or less.

[0071] From the viewpoint of improving the kneadability of the hydraulic composition, the blast furnace slag-containing hydraulic composition of the present invention contains, per 100 parts by mass of hydraulic powder, preferably 0.005 parts by mass or more of (B) component, more preferably 0.008 parts by mass or more, even more preferably 0.01 parts by mass or more, and preferably 0.1 parts by mass or less, more preferably 0.08 parts by mass or less, even more preferably 0.05 parts by mass or less, and even more preferably 0.03 parts by mass or less.

[0072] In the blast furnace slag-containing hydraulic composition of the present invention, the ratio of the content of the (B) component to the total content of the (A) component and the (B) component is 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and 50% by mass or less, preferably 45% by mass or less, more preferably 40% by mass or less, from the viewpoint of improving the kneading property of the hydraulic composition. This ratio is calculated by [content of the (B) component / [total content of the (A) component and the (B) component]]×100.

[0073] The blast furnace slag-containing hydraulic composition of the present invention preferably contains the above-mentioned component (C) from the viewpoint of imparting dispersibility to the hydraulic composition. Specific examples and preferred embodiments of the component (C) in the blast furnace slag-containing hydraulic composition of the present invention are the same as those of the fluidity retaining agent composition for the blast furnace slag-containing hydraulic composition of the present invention. When the blast furnace slag-containing hydraulic composition of the present invention contains component (C), from the viewpoint of imparting dispersibility to the hydraulic composition, the hydraulic composition contains, per 100 parts by mass of hydraulic powder, preferably 0.03 parts by mass or more, more preferably 0.04 parts by mass or more, even more preferably 0.05 parts by mass or more, and preferably 0.5 parts by mass or less, more preferably 0.4 parts by mass or less, even more preferably 0.3 parts by mass or less, still more preferably 0.2 parts by mass or less, still more preferably 0.1 parts by mass or less, and even more preferably 0.09 parts by mass or less of component (C).

[0074] In the blast furnace slag-containing hydraulic composition of the present invention, the ratio of the content of the (C) component to the total content of the (A), (B) and (C) components is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, still more preferably 70% by mass or less, and even more preferably 60% by mass or less, from the viewpoint of imparting dispersibility to the hydraulic composition. This ratio is calculated by [the content of the (C) component / [the total content of the (A), (B) and (C) components]]×100.

[0075] The mass percentage of water to hydraulic powder (water / hydraulic powder ratio) (abbreviated as W / P) in the blast furnace slag-containing hydraulic composition of the present invention is preferably 30 mass% or more, more preferably 35 mass% or more, from the viewpoint of workability, and is preferably 50 mass% or less, more preferably 45 mass% or less, from the viewpoint of strength expression of the hydraulic composition. The mass percentage of water and cement (water / cement ratio) (abbreviated as W / C) in the blast furnace slag-containing hydraulic composition of the present invention is, from the viewpoint of workability, preferably 75 mass% or more, more preferably 85 mass% or more, even more preferably 95 mass% or more, and preferably 125 mass% or less, more preferably 115 mass% or less.

[0076] When the blast furnace slag-containing hydraulic composition is concrete, the amount of coarse aggregate used is preferably 50% or more, more preferably 55% or more, even more preferably 60% or more, and preferably 100% or less, more preferably 90% or less, even more preferably 80% or less, from the viewpoints of exerting the strength of the hydraulic composition, reducing the amount of hydraulic powder such as cement used, and improving the filling property into a formwork, etc. 3 It is the ratio of the volume of coarse aggregate (including voids) in the concrete. In addition, when the blast furnace slag-containing hydraulic composition is concrete, the amount of fine aggregate used is preferably 500 kg / m from the viewpoint of improving the filling property into a formwork or the like. 3 More preferably, 600 kg / m 3 More preferably, 700 kg / m 3 and preferably 1,000 kg / m 3 Less than or equal to 900 kg / m 3 The following is the result. When the blast furnace slag-containing hydraulic composition is a mortar, the amount of fine aggregate used is preferably 800 kg / m 3 More preferably, 900kg / m 3 More preferably, 1,000 kg / m 3 and preferably 2,000 kg / m 3 Less than or equal to 1,800 kg / m 3 or less, more preferably 1,700 kg / m 3 The following is the result.

[0077] The blast furnace slag-containing hydraulic composition of the present invention may contain, as optional components, components such as retarders, hardening accelerators, AE agents, expansion agents, foaming agents, thickeners, fluidizing agents, foaming agents, waterproofing agents, and defoamers (excluding those corresponding to components (A) to (C)).

[0078] The blast furnace slag-containing hydraulic composition of the present invention can be hardened by a known method to obtain a hardened product. The hardening of the hydraulic composition can be carried out taking into consideration the application, shape, etc. of the hardened product.

[0079] <Method for producing hydraulic composition containing blast furnace slag> The present invention relates to a method for producing a blast furnace slag-containing hydraulic composition, which comprises mixing, as hydraulic powder, cement, blast furnace slag, water, the (A) component, and the (B) component, The amount of blast furnace slag mixed in the hydraulic powder is 5% by mass or more and 60% by mass or less, The ratio of the amount of the component (B) to the total amount of the components (A) and (B) is 30% by mass or more and 70% by mass or less. A method for producing a blast furnace slag-containing hydraulic composition is provided. In the method for producing a blast furnace slag-containing hydraulic composition of the present invention, it is preferable to further mix the component (C) from the viewpoint of imparting dispersibility to the hydraulic composition.

[0080] The description of the fluidity retaining agent composition for blast furnace slag-containing hydraulic composition and the blast furnace slag-containing hydraulic composition of the present invention can be appropriately applied to the method for producing the blast furnace slag-containing hydraulic composition of the present invention. Specific examples and preferred aspects of the hydraulic powder, (A) component, (B) component, and optional (C) component used in the method for producing the blast furnace slag-containing hydraulic composition of the present invention are the same as those of the fluidity retaining agent composition for blast furnace slag-containing hydraulic composition and the blast furnace slag-containing hydraulic composition of the present invention. In addition, the content of each component in the fluidity retaining agent composition for blast furnace slag-containing hydraulic composition and the blast furnace slag-containing hydraulic composition of the present invention can be replaced with the mixed amount, and the preferred range can be applied to the method for producing the blast furnace slag-containing hydraulic composition of the present invention.

[0081] In the method for producing a blast furnace slag-containing hydraulic composition of the present invention, the ratio of the amount of component (B) mixed to the total amount of components (A) and (B) mixed is 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and 50% by mass or less, preferably 45% by mass or less, and more preferably 40% by mass or less, from the viewpoint of improving the kneading properties of the hydraulic composition. This ratio is calculated by [amount of component (B) mixed / [total amount of component (A) and component (B) mixed]]×100.

[0082] In the method for producing a blast furnace slag-containing hydraulic composition of the present invention, when the (C) component is mixed, the ratio of the amount of the (C) component mixed to the total amount of the (A), (B) and (C) components mixed is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, still more preferably 70% by mass or less, and even more preferably 60% by mass or less, from the viewpoint of imparting dispersibility to the hydraulic composition. This ratio is calculated by [amount of the (C) component mixed / [total amount of the (A), (B) and (C) components mixed]]×100.

[0083] The method for producing the blast furnace slag-containing hydraulic composition of the present invention is not limited to the order of mixing the components, but as a method for more easily obtaining a high effect, for example, a method of mixing cement, blast furnace slag, and optionally aggregate as hydraulic powder, and then mixing a kneading liquid containing component (A), component (B), and water can be mentioned. For example, a method of mixing cement, blast furnace slag, coarse aggregate, and fine aggregate for a predetermined time, for example, from 5 seconds to 60 seconds, and mixing the kneading liquid containing component (A), component (B), and water can be mentioned. Mixing can be performed with a known mixer. The kneading liquid may be an aqueous solution or an aqueous suspension.

[0084] In the manufacturing method of the blast furnace slag-containing hydraulic composition of the present invention, the (A) component, the (B) component, and the optional (C) component can be mixed with the hydraulic powder so that each of them falls within the ranges described for the blast furnace slag-containing hydraulic composition of the present invention.

[0085] In the manufacturing method of the blast furnace slag-containing hydraulic composition of the present invention, optional components such as retarders, hardening accelerators, AE agents, expansion agents, foaming agents, thickeners, fluidizing agents, foaming agents, waterproofing agents, and defoamers (excluding those corresponding to components (A) to (C)) can be mixed.

[0086] In the manufacturing method of the blast furnace slag-containing hydraulic composition of the present invention, water and hydraulic powder are mixed so that the mass percentage of water to hydraulic powder (water / hydraulic powder ratio) (abbreviated as W / P) is preferably 30 mass% or more, more preferably 35 mass% or more, and preferably 50 mass% or less, more preferably 45 mass% or less, from the viewpoint of workability. In the manufacturing method of the blast furnace slag-containing hydraulic composition of the present invention, water and cement are mixed so that the mass percentage of water to cement (water / cement ratio) (abbreviated as W / C) is, from the viewpoint of workability, preferably 75 mass% or more, more preferably 85 mass% or more, even more preferably 95 mass% or more, and preferably 125 mass% or less, more preferably 115 mass% or less. EXAMPLES

[0087] The following were used as components (A), (B), and (C).

[0088] <Component (A)> A-1: Hydroxyethyl acrylic acid / MEPEG(9) ester = 85 / 15 (mol%) = 57 / 43 (mass%) copolymer, weight average molecular weight 23000 A-2: copolymer of hydroxyethyl acrylic acid / MEPEG(23) ester=85 / 15 (mol%)=37.1 / 62.9 (mass%), weight average molecular weight 40,000 A-3: copolymer of methyl acrylate / MEPEG(120) ester / methacrylic acid=70 / 10 / 20 (mol%)=9.7 / 87.5 / 2.8 (mass%), weight average molecular weight 53000

[0089] <(B) component> B-1: Methacrylic acid / MEPEG(120) ester = 23.2 / 76.8 (mass%) = 95 / 5 (mol%) copolymer, sodium salt, weight average molecular weight 44000

[0090] <(C) component> C-1: Polycarboxylic acid dispersant, FC900, manufactured by Nippon Shokubai Co., Ltd.

[0091] The monomers of the above copolymers are as follows. MEPEG (9) ester: Methoxypolyethylene glycol (9) monomethacrylate (The number in parentheses is the average number of moles of ethylene oxide added. The same applies below.) MEPEG (23) Ester: Methoxypolyethylene glycol (23) monomethacrylate MEPEG(120) ester: Methoxypolyethyleneglycol(120) monomethacrylate

[0092] <Production Example 1: Production of Copolymer A-1> Copolymer A-1 was prepared as follows. 463.19g of water was charged into a glass reaction vessel (four-neck flask) equipped with a stirrer, and the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 70°C in a nitrogen atmosphere. A monomer mixture of 188.26g of ω-methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 9, water content: 10%, purity: 93.6%) and 210.19g of 2-hydroxyethyl acrylate (referred to as HEA in the table), an aqueous solution of 5.65g of 3-mercaptopropionic acid (Sigma-Aldrich Japan Co., Ltd., reagent) dissolved in 30g of water, and an aqueous solution of ammonium persulfate (I) [8.74g of ammonium persulfate (Wako Pure Chemical Industries, Ltd., reagent) dissolved in 40g of water] were simultaneously added dropwise, and each was added dropwise over 5 hours, and then an aqueous solution of ammonium persulfate (II) [1.46g of ammonium persulfate dissolved in 20g of water] was added dropwise over 0.5 hours. Thereafter, the mixture was aged for 1 hour at 70° C. After completion of the aging, the mixture was neutralized with a 20% aqueous sodium hydroxide solution to obtain an aqueous solution (solid content 40% by weight) containing copolymer A-1 (weight average molecular weight 23,000).

[0093] The other copolymers in Table 1 were produced in the same manner as above, except that the types and amounts of monomers used were changed. Table 1 shows the monomer compositions and weight average molecular weights of components (A) and (B).

[0094] [Table 1]

[0095] (1-1) Preparation of fluidity retaining agent composition for blast furnace slag-containing hydraulic composition A fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition was prepared by mixing the (A) and (B) components such that the ratio of the content of the (B) component to the total content of the (A) and (B) components, and the ratio of the content of the (C) component to the total content of the (A), (B) and (C) components were as shown in Table 3. The total content of the (A), (B) and (C) components in the fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition was 0.12 to 0.18 mass%.

[0096] (2-1) Preparation of mortar Using a mortar mixer (Dalton Co., Ltd., universal mixer, model: 5DM-03-γ), cement (C), blast furnace slag, and fine aggregate (S) were added in the amounts shown in Table 2, and dry mixing was performed for 10 seconds at a low rotation speed (63 rpm) of the mortar mixer, and mixing water (W) containing the prepared fluidity retainer composition for blast furnace slag-containing hydraulic composition was added. Then, main mixing was performed for 120 seconds at a low rotation speed (63 rpm) of the mortar mixer to prepare mortar. As for the mixing conditions of the mortar, for all mortar temperatures, the fluidity retainer composition for blast furnace slag-containing hydraulic composition was added to the mixing water so that the contents of the (A), (B), and (C) components were in the amounts shown in Table 3 relative to 100 parts by mass of hydraulic powder.

[0097] [Table 2]

[0098] The ingredients used in preparing the mortar were as follows: Water (W): Tap water was used. Cement (C): Ordinary Portland cement (two-type mixture: Taiheiyo Cement / Sumitomo Osaka Cement = 1 / 1, mass ratio) Density 3.16g / cm 3 Blast furnace slag: Finely ground blast furnace slag, manufactured by Esment Kanto Co., Ltd., Blaine value 3800 cm 2 / g ·Fine aggregate (S): Joyo mountain sand density 2.55g / cm 3

[0099] (2-2) Evaluation of mortar fluidity According to the test method (flow test) of JIS R 5201, the fluidity was evaluated immediately after mixing (2 minutes after the start of mixing), 30 minutes after mixing, 60 minutes after mixing, and 90 minutes after mixing. The results are shown in Table 3. The start of mixing was the point when mixing water (W) was added to the mortar mixer and the cement and mixing water first came into contact with each other.

[0100] [Table 3]

[0101] In Table 3, in the comparative examples in which the result of mortar flow is described as "separation", separation of the mortar material was confirmed, so that the fluidity was not evaluated.

[0102] In Table 3, the examples of the present invention have good initial fluidity and excellent fluidity retention from immediately after kneading until 90 minutes later, in comparison with the comparative examples, and therefore have excellent workability. In addition, in Table 3, Comparative Examples 2, 5, and 8 are not preferable because the fluidity of the mortar increases with time, causing material separation and delayed setting.

Claims

1. A fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition, comprising cement and blast furnace slag as hydraulic powder, the content of the blast furnace slag in the hydraulic powder being 5% by mass or more and 60% by mass or less, A fluidity-retaining agent composition for a blast furnace slag-containing hydraulic composition, comprising the following components (A) and (B), wherein the ratio of the content of component (B) to the total content of components (A) and (B) is 10 mass% or more and 50 mass% or less. <Component (A)> A copolymer having 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), wherein the proportion of the structural unit (A1) to the total of the structural units (A1), (A2), and (A3) is 70 mol % or more and 95 mol % or less, and the proportion of the structural unit (A3) is 20 mol % or less. 【Chemistry 1】 [In the formula, R １ａ , R ３ａ , and R ５ａ are the same or different and each represents a hydrogen atom or a methyl group; R ２ａ represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms; R ４ａ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; X １ represents a divalent alkylene group having 1 to 6 carbon atoms, a direct bond, or a carbonyl group; na represents the average number of moles of ethylene oxide added, which is a number of 5 to 150; M １ represents a hydrogen atom or a counter ion that forms a salt. <(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 proportion of the structural unit (B1) to the total of the structural units (B1) and (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. 【Chemistry 2】 [In the formula, 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; M ２ represents a hydrogen atom or a counter ion which becomes a salt, and X ２ represents a divalent alkylene group having 1 to 6 carbon atoms, a direct bond, or a carbonyl group, and nb represents the average number of moles of ethylene oxide added and is a number of 70 to 170.

2. The fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition according to claim 1, comprising 0.01 mass % or more and 0.2 mass % or less of the (A) component.

3. 3. The fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition according to claim 1 or 2, wherein the weight average molecular weight of the (A) component is 15,000 or more and 100,000 or less.

4. The fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition according to any one of claims 1 to 3, further comprising (C) a polycarboxylic acid-based dispersant (excluding components (A) and (B)) (hereinafter referred to as component (C)).

5. A fluidity retaining agent composition for a blast furnace slag-containing hydraulic composition according to claim 4, wherein the ratio of the content of the (C) component to the total content of the (A) component, the (B) component, and the (C) component is 30 mass% or more and 90 mass% or less.

6. A blast furnace slag-containing hydraulic composition comprising a hydraulic powder containing cement and blast furnace slag, water, the following component (A), and the following component (B): A blast furnace slag-containing hydraulic composition, in which the content of blast furnace slag in the hydraulic powder is 5% by mass or more and 60% by mass or less, and the ratio of the content of component (B) to the total content of components (A) and (B) is 10% by mass or more and 50% by mass or less. <Component (A)> A copolymer having 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), wherein the proportion of the structural unit (A1) to the total of the structural units (A1), (A2), and (A3) is 70 mol % or more and 95 mol % or less, and the proportion of the structural unit (A3) is 20 mol % or less. 【Chemistry 3】 [In the formula, R １ａ , R ３ａ , and R ５ａ are the same or different and each represents a hydrogen atom or a methyl group; R ２ａ represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms; R ４ａ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; X １ represents a divalent alkylene group having 1 to 6 carbon atoms, a direct bond, or a carbonyl group; na represents the average number of moles of ethylene oxide added, which is a number of 5 to 150; M １ represents a hydrogen atom or a counter ion that forms a salt. <(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 proportion of the structural unit (B1) to the total of the structural units (B1) and (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. 【Chemistry 4】 [In the formula, 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; M ２ represents a hydrogen atom or a counter ion which becomes a salt, and X ２ represents a divalent alkylene group having 1 to 6 carbon atoms, a direct bond, or a carbonyl group, and nb represents the average number of moles of ethylene oxide added and is a number of 70 to 170.

7. 7. The blast furnace slag-containing hydraulic composition according to claim 6, comprising 0.01 to 0.2 parts by mass of component (A) per 100 parts by mass of the hydraulic powder.

8. The blast furnace slag-containing hydraulic composition according to claim 6 or 7, wherein the weight average molecular weight of component (A) is 15,000 or more and 100,000 or less.

9. The blast furnace slag-containing hydraulic composition according to any one of claims 6 to 8, further comprising (C) a polycarboxylic acid-based dispersant (excluding components (A) and (B)) (hereinafter referred to as component (C)).

10. The blast furnace slag-containing hydraulic composition according to claim 9, wherein the ratio of the content of the (C) component to the total content of the (A) component, the (B) component, and the (C) component is 30 mass% or more and 90 mass% or less.

11. The blast furnace slag-containing hydraulic composition according to any one of claims 6 to 10, wherein the mass percentage of water and hydraulic powder in the blast furnace slag-containing hydraulic composition (water / hydraulic powder ratio) is 35 mass% or more and 50 mass% or less.

12. The Blaine value of blast furnace slag is 5000 cm ２ The blast furnace slag-containing hydraulic composition according to any one of claims 6 to 11, wherein the slag content is less than 1 / g.

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