Hydraulic composition

Abstract

To provide a hydraulic composition superior in workability.SOLUTION: A hydraulic composition includes a component A: polycarboxylic acid-based copolymer and a component B: cement having an angle of repose of 46-51°.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a hydraulic composition. [Background technology]

[0002] In order to improve the workability and durability of concrete, it is effective to reduce the unit water content in concrete. However, it is known that reducing the unit water content reduces the fluidity of concrete and impairs workability. Therefore, in order to ensure efficient workability of concrete even when the unit water content is reduced, various dispersants for hydraulic compositions that function to disperse cement particles are used.

[0003] In recent years, ultra-high strength concrete with a significantly reduced water-binder ratio has been put into practical use. Ultra-high strength concrete requires high dispersibility at a low water-binder ratio, reduced concrete viscosity, and a fast setting time. In the ultra-high strength range, there is a problem that dispersibility plateaus even when the amount of dispersant added is increased, so it is necessary to increase the limit at which dispersibility can be achieved.

[0004] On the other hand, there is a demand for dispersants that can be used in a wide range of concrete mixes, not only for ultra-high strength concrete with a significantly reduced water-binder ratio, but also for concrete with a high water-binder ratio, demonstrating dispersibility and reducing concrete viscosity. As dispersants for hydraulic compositions, various polycarboxylic acid-based dispersants have been reported so far (see, for example, Patent Documents 1 to 3). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 09-86990 [Patent Document 2] Japanese Patent Application Publication No. 09-286645 [Patent Document 3] Japanese Patent Application Laid-Open No. 2005-281022 Summary of the Invention [Problem to be solved by the invention]

[0006] In the polycarboxylic acid-based dispersants of Patent Documents 1 to 3, the chemical composition of the dispersant is set to a wide range so as to be compatible with a wide variety of fine aggregates, coarse aggregates, and cements in hydraulic compositions. However, the constituent units such as fine aggregate used in hydraulic compositions are inorganic compositions with various physical properties depending on their production area and production method. It has not yet been possible to obtain a polycarboxylic acid-based dispersant that works efficiently on all of these inorganic compositions, and there is a problem in that it is difficult to obtain the expected effects of the dispersant.

[0007] An object of the present invention is to provide a hydraulic composition that is excellent in workability. [Means for solving the problem]

[0008] The present inventors provide the following [1] to [4]. [1] A hydraulic composition containing the following component (A) and the following component (B): Component (A): A copolymer having at least two or more types of structural units selected from the group consisting of structural unit (I) derived from a monomer represented by the following general formula (1), structural unit (II) derived from a monomer represented by the following general formula (2), and structural unit (III) derived from a monomer represented by the following general formula (3): [ka] (In the general formula (1), R 1 , R 2 and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, p represents an integer of 0 to 2, and q represents an integer of 0 to 1. A 1 O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. n represents an integer of 40 to 150. R 4represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. [ka] (In the general formula (2), R 5 , R 6 and R 7 are each independently a hydrogen atom, -CH3 or -(CH2) r COOM 2 However, -(CH2) r COOM 2 If -COOM 1 or other -(CH2) r COOM 2 When an anhydride is formed, the M 1 , M 2 does not exist. M 1 and M 2 may be the same or different and represent a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, or a substituted alkylammonium group; and r represents an integer of 0 to 2. [ka] (In the general formula (3), R 8 , R 9 and R 10 R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 11 represents a hydrocarbon group having 1 to 4 carbon atoms which may contain a heteroatom; and s represents an integer of 0 to 2. Component (B): Cement with an angle of repose of 46 to 51 degrees. [2] The hydraulic composition according to the above [1], wherein the component (A) is a copolymer having at least the structural unit (I). [3] The structural unit (I) is R 2 The hydraulic composition according to the above [1] or [2], which contains at least a structural unit (IA) derived from a monomer in which is a methyl group. [4] The hydraulic composition according to [3], wherein the structural unit (IA) is a structural unit (IA') derived from polyoxyethylene glycol monomethallyl ether represented by the following general formula (4): [ka] (In the general formula (4), A 1 O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. n represents an integer of 40 to 150. [Effects of the Invention]

[0009] According to the present invention, a hydraulic composition having excellent workability can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below with reference to preferred embodiments thereof. In this specification, the notation "AA to BB" (where A and B represent numbers) means AA or more and BB or less.

[0011] The hydraulic composition contains component (A): a polycarboxylic acid copolymer and component (B): cement. Components (A), (B), other optional components, and a method for producing the composition will be described below in this order.

[0012] [1. Component (A): Polycarboxylic acid copolymer] The polycarboxylic acid copolymer of component (A) is a copolymer having at least two or more structural units selected from the group consisting of structural units (I) to (III). The copolymer may have two or more structural units selected from the group consisting of structural units (I) to (III), or may have all three structural units.

[0013] [1-1. Constituent Unit (I)] The structural unit (I) is a structural unit derived from a monomer represented by general formula (1).

[0014] [ka]

[0015] R in general formula (1) 1 , R 2 and R 3 R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. The alkyl group having 1 to 3 carbon atoms may have a substituent, but the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkyl group. 1 is preferably a hydrogen atom. 2 R is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. 2 It is presumed that when R is an alkyl group having 1 to 3 carbon atoms, it will have excellent adsorption properties to component (B). 3 is preferably a hydrogen atom.

[0016] In the general formula (1), p represents an integer of 0 to 2, and q represents an integer of 0 to 1.

[0017] A in general formula (1) 1 Each O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. Examples of the oxyalkylene group (alkylene glycol unit) include an oxyethylene group (ethylene glycol unit), an oxypropylene group (propylene glycol unit), and an oxybutylene group (butylene glycol unit), with an oxyethylene group and an oxypropylene group being preferred.

[0018] The above-mentioned "may be the same or different" means that A 1 If multiple Os are included (n is 2 or more), each A 1 This means that the O's may be the same oxyalkylene group or may be different (two or more types) oxyalkylene groups. 1When a plurality of O's are contained, an embodiment in which two or more oxyalkylene groups selected from the group consisting of oxyethylene, oxypropylene, and oxybutylene groups are present in a mixed state can be mentioned. Preferably, an embodiment in which an oxyethylene group and an oxypropylene group are present in a mixed state, or an embodiment in which an oxyethylene group and an oxybutylene group are present in a mixed state, and more preferably, an embodiment in which an oxyethylene group and an oxypropylene group are present in a mixed state. In an embodiment in which different oxyalkylene groups are present in a mixed state, the addition of two or more types of oxyalkylene groups may be in a block form or a random form. In the general formula (1), when q is 0, an alkylene group having a carbon atom number p and A 1 It bonds to O via an oxygen atom.

[0019] In general formula (1), n ​​is the average number of moles of oxyalkylene groups added, and represents an integer of 40 to 150. n is preferably 40 to 100, more preferably 45 to 100, even more preferably 50 to 100, and even more preferably more than 50 but not more than 100. The average number of moles added means the average value of the number of moles of oxyalkylene groups added to 1 mole of monomer.

[0020] R in general formula (1) 4 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. 4 is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and even more preferably a hydrogen atom or a methyl group. Within this range, the number of carbon atoms does not become too large, which can improve the dispersibility of the hydraulic composition.

[0021] The monomer represented by general formula (1) can be produced, for example, by adding 40 to 150 moles of alkylene oxide to an unsaturated alcohol such as allyl alcohol, methallyl alcohol, or 3-methyl-3-buten-1-ol. Monomers that can be produced by this method include, for example, (poly)ethylene glycol allyl ether, (poly)ethylene glycol methallyl ether, (poly)ethylene glycol 3-methyl-3-butenyl ether, (poly)ethylene (poly)propylene glycol allyl ether, (poly)ethylene (poly)propylene glycol methallyl ether, (poly)ethylene (poly)propylene glycol 3-methyl-3-butenyl ether, (poly)ethylene (poly)butylene glycol allyl ether, (poly)ethylene (poly)butylene glycol methallyl ether, (poly)ethylene (poly)butylene glycol 3-methyl-3-butenyl ether, methoxy(poly)ethylene ethylene glycol allyl ether, methoxy(poly)ethylene glycol methallyl ether, methoxy(poly)ethylene glycol 3-methyl-3-butenyl ether, methoxy(poly)ethylene (poly)propylene glycol allyl ether, methoxy(poly)ethylene (poly)propylene glycol methallyl ether, methoxy(poly)ethylene (poly)propylene glycol 3-methyl-3-butenyl ether, methoxy(poly)ethylene (poly)butylene glycol allyl ether, methoxy(poly)ethylene (poly)butylene glycol methallyl ether, methoxy(poly)ethylene (poly)butylene glycol 3-methyl-3-butenyl ether. Among these, (poly)ethylene glycol (meth)allyl ether, (poly)ethylene (poly)propylene glycol (meth)allyl ether, (poly)ethylene glycol 3-methyl-3-butenyl ether, and (poly)ethylene (poly)propylene glycol 3-methyl-3-butenyl ether are preferred in terms of the balance between hydrophilicity and hydrophobicity.

[0022] In this specification, the notation "(poly)" means that the constituent element or raw material described thereafter is bonded in multiple numbers or in only one number. "(Meth)allyl" means methallyl and / or allyl, "(meth)acrylate" means methacrylate and / or acrylate, and "(meth)acrylic acid" means methacrylic acid and / or acrylic acid.

[0023] Another method for producing the monomer represented by general formula (1) includes esterifying an unsaturated monocarboxylic acid such as acrylate or methacrylate with a (poly)alkylene glycol such as (poly)ethylene glycol, (poly)ethylene (poly)propylene glycol, (poly)ethylene (poly)butylene glycol, methoxy(poly)ethylene glycol, methoxy(poly)ethylene (poly)propylene glycol, or methoxy(poly)ethylene (poly)butylene glycol. Monomers that can be produced by this method include, for example, (poly)alkylene glycol (meth)acrylates such as (poly)ethylene glycol (meth)acrylate, (poly)ethylene (poly)propylene glycol (meth)acrylate, (poly)ethylene (poly)butylene glycol (meth)acrylate, methoxy(poly)ethylene glycol (meth)acrylate, methoxy(poly)ethylene (poly)propylene glycol (meth)acrylate, and methoxy(poly)ethylene (poly)butylene glycol (meth)acrylate. Among these, (poly)alkylene glycol (meth)acrylate and methoxy(poly)alkylene glycol (meth)acrylate are preferred, and methoxy(poly)ethylene glycol (meth)acrylate is more preferred.

[0024] The structural unit (I) may be of one type, or may be of two or more types derived from different monomers. 2 It is preferable that the structural unit (IA) contains at least a structural unit (IA) derived from a monomer in which R is a methyl group. The structural unit (IA) is preferably the following structural unit (IA'), i.e., a structural unit derived from polyoxyethylene glycol monomethallyl ether represented by the following general formula (4): [ka] This can further improve the dispersibility of component (B). The reason why this effect can be achieved is presumably because the compound exhibits good adsorption properties for component (B) and has a molecular chain length of at least a certain level, resulting in a structure of a constituent unit derived from polyoxyethylene glycol monomethallyl ether represented by the following general formula (4):

[0025] In general formula (4), A 1 O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. n represents an integer of 40 to 150.

[0026] The content of the structural unit (IA) (preferably (IA')) in the structural unit (I) is preferably 50% by weight or more, more preferably 70% by weight or more, even more preferably 80% by weight or more, even more preferably 90% by weight or more, and particularly preferably 100% by weight.

[0027] [1-2. Structural Unit (II)] The structural unit (II) is a structural unit derived from a monomer represented by general formula (2).

[0028] [ka] R in general formula (2) 5 , R 6 and R 7 are each independently a hydrogen atom, -CH3 or -(CH2)rCOOM 2 where (CH2) r COOM 2 If -COOM 1 or other -(CH2) r COOM 2 When an anhydride is formed, the M 1 , M 2 does not exist. R 5 is preferably a hydrogen atom. 6 is preferably a hydrogen atom or —CH3. 7 is preferably a hydrogen atom.

[0029] M 1 and M 2 M may be the same or different and represent a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, or a substituted alkylammonium group. 1 and M 2 are preferably a hydrogen atom, an alkali metal, or an alkaline earth metal.

[0030] r represents an integer of 0 to 2, with 0 being preferred.

[0031] Examples of the monomer represented by general formula (2) include unsaturated monocarboxylic acid monomers and unsaturated dicarboxylic acid monomers. Examples of the unsaturated monocarboxylic acid monomers include acrylic acid, methacrylic acid, and crotonic acid; their monovalent metal salts, ammonium salts, and organic amine salts. Examples of the unsaturated dicarboxylic acid include maleic acid, itaconic acid, citraconic acid, and fumaric acid; their monovalent metal salts, ammonium salts, and organic amine salts; and their anhydrides. Preferred examples of the monomer represented by general formula (2) include acrylic acid, methacrylic acid, and maleic acid.

[0032] The structural unit (II) may be of only one type, or may be of two or more types derived from different monomers.

[0033] [1-3. Structural Unit (III)] The structural unit (III) is a structural unit derived from a monomer represented by general formula (3).

[0034] [ka] In general formula (3), R 8 , R 9 and R 10 Each of the groups independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of alkyl groups having 1 to 3 carbon atoms include R 1 , R 2 and R 3 Similar to the example in R8 is preferably a hydrogen atom. 9 is preferably a hydrogen atom. 10 is preferably a hydrogen atom.

[0035] In general formula (3), R 11 represents a hydrocarbon group having 1 to 4 carbon atoms which may contain a heteroatom. The number of carbon atoms in the hydrocarbon group is preferably 1 to 3, more preferably 2 to 3, and even more preferably 3. Examples of heteroatoms include an oxygen atom, a nitrogen atom, a phosphorus atom, and a silicon atom, with an oxygen atom being preferred. Examples of hydrocarbon groups having 1 to 4 carbon atoms which may contain a heteroatom include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, and a glyceryl group. R 11 The number of heteroatoms contained in may be 1 or 2 or more. When two or more heteroatoms are contained, the heteroatoms may be the same or different from each other.

[0036] R 11 is preferably a hydrocarbon group containing a hetero atom and having 1 to 4 carbon atoms, more preferably a hydrocarbon group containing an oxygen atom and having 1 to 4 carbon atoms. Examples of such groups include a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, and a glyceryl group, of which a 2-hydroxypropyl group is preferred.

[0037] In the general formula (3), s represents an integer of 0 to 2, with 0 being preferred.

[0038] Examples of the monomer represented by general formula (3) include monoesters of unsaturated monocarboxylic acids, such as methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glyceryl (meth)acrylate.

[0039] Component (A) may have only one type of structural unit (III), or may have two or more types of structural unit (III) derived from different monomers.

[0040] [1-4. Building Block (IV)] Component (A) may further include a structural unit (IV). The structural unit (IV) is a structural unit derived from a monomer copolymerizable with the monomers represented by general formulas (1) to (3). The monomers copolymerizable with the monomers represented by general formulas (1) to (3) are structurally distinct from the monomers represented by general formulas (1) to (3). The monomer that constitutes the structural unit (IV) is not particularly limited, but examples include the following monomers, which can be used alone or in combination of two or more:

[0041] Diallyl bisphenols (e.g., 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylsulfone) represented by the following general formula (IV-1) substituted with allyl at the 3- and 3'-positions;

[0042] [ka]

[0043] Monoallyl bisphenols represented by general formula (IV-2) (e.g., 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylsulfone) substituted with an allyl group at the 3-position;

[0044] [ka]

[0045] Allylphenol represented by the following general formula (IV-3):

[0046] [ka]

[0047] Half esters and diesters of unsaturated dicarboxylic acids, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, and citraconic acid, with alcohols having 1 to 30 carbon atoms; half amides and diamides of such unsaturated dicarboxylic acids with amines having 1 to 30 carbon atoms;

[0048] half esters and diesters of alkyl (poly) alkylene glycols obtained by adding 1 to 500 moles of alkylene oxide having 2 to 18 carbon atoms to the above alcohols or amines, and the above unsaturated dicarboxylic acids;

[0049] half esters and diesters of the above unsaturated dicarboxylic acids with glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 moles of addition of such glycols;

[0050] half amides of maleamic acid with glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 moles of such glycols added;

[0051] Esters of alkoxy (poly)alkylene glycols obtained by adding 1 to 500 moles of alkylene oxide having 2 to 18 carbon atoms to alcohol having 1 to 30 carbon atoms, and unsaturated monocarboxylic acids such as (meth)acrylic acid;

[0052] adducts of alkylene oxides having 2 to 18 carbon atoms with unsaturated monocarboxylic acids such as (meth)acrylic acid by 1 to 500 moles, such as (poly)ethylene glycol monomethacrylate, (poly)propylene glycol monomethacrylate, and (poly)butylene glycol monomethacrylate (excluding monomers represented by general formulas (1) to (3));

[0053] (poly)alkylene glycol di(meth)acrylates such as triethylene glycol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and (poly)ethylene glycol (poly)propylene glycol di(meth)acrylate;

[0054] polyfunctional (meth)acrylates such as hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trimethylolpropane di(meth)acrylate;

[0055] (Poly)alkylene glycol dimaleates such as triethylene glycol dimaleate and polyethylene glycol dimaleate;

[0056] unsaturated sulfonic acids such as vinyl sulfonate, (meth)allyl sulfonate, 2-(meth)acryloxyethyl sulfonate, 3-(meth)acryloxypropyl sulfonate, 3-(meth)acryloxy-2-hydroxypropyl sulfonate, 3-(meth)acryloxy-2-hydroxypropyl sulfophenyl ether, 3-(meth)acryloxy-2-hydroxypropyloxysulfobenzoate, 4-(meth)acryloxybutyl sulfonate, (meth)acrylamidomethyl sulfonic acid, (meth)acrylamidoethyl sulfonic acid, 2-methylpropanesulfonic acid (meth)acrylamide, and styrenesulfonic acid, as well as their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts;

[0057] amides of unsaturated monocarboxylic acids and amines having 1 to 30 carbon atoms, such as methyl (meth)acrylamide;

[0058] vinyl aromatics such as styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene;

[0059] Alkanediol mono(meth)acrylates such as 1,5-pentanediol mono(meth)acrylate and 1,6-hexanediol mono(meth)acrylate (excluding monomers represented by general formula (3));

[0060] Dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, and 2-chloro-1,3-butadiene;

[0061] unsaturated amides such as (meth)acrylamide, (meth)acrylalkylamide, N-methylol(meth)acrylamide, and N,N-dimethyl(meth)acrylamide;

[0062] Unsaturated cyanides such as (meth)acrylonitrile and α-chloroacrylonitrile;

[0063] unsaturated esters such as vinyl acetate and vinyl propionate;

[0064] Unsaturated amines such as aminoethyl (meth)acrylate, methylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, and vinylpyridine (excluding monomers represented by general formula (3));

[0065] Divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate;

[0066] Allyl compounds such as (meth)allyl alcohol and glycidyl (meth)allyl ether; Vinyl ethers or allyl ethers such as methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono(meth)allyl ether, polyethylene glycol mono(meth)allyl ether (excluding the monomer represented by general formula (1)); and

[0067] Siloxane derivatives such as polydimethylsiloxane propylaminomaleic acid, polydimethylsiloxane aminopropylene aminomaleic acid, polydimethylsiloxane-bis-(propylaminomaleic acid), polydimethylsiloxane-bis-(dipropyleneaminomaleic acid), polydimethylsiloxane-(1-propyl-3-acrylate), polydimethylsiloxane-(1-propyl-3-methacrylate), polydimethylsiloxane-bis-(1-propyl-3-acrylate), and polydimethylsiloxane-bis-(1-propyl-3-methacrylate) (however, excluding the monomer represented by general formula (3)).

[0068] The structural unit (IV) may be of only one type, or may be of two or more types derived from different monomers.

[0069] [1-5.Copolymer (A-1)~(A-4)] Examples of copolymers of component (A) include the following copolymers (A-1) to (A-4), of which copolymer (A-1) is preferred.

[0070] -Copolymer (A-1)- Copolymer (A-1) has structural units (I) and (II). The content ratio of each structural unit (when there are two or more types, it is the total of the structural units; the same applies to the content ratios of the copolymers described below) is preferably structural unit (I) / structural unit (II)=1 to 99% by weight / 1 to 99% by weight, more preferably 10 to 98% by weight / 2 to 90% by weight, and even more preferably 50 to 98% by weight / 2 to 50% by weight.

[0071] -Copolymer (A-2)- Copolymer (A-2) has structural units (I) and (III). The content ratio of the structural units is preferably structural unit (I) / structural unit (III)=1 to 99% by weight / 1 to 99% by weight, more preferably 10 to 90% by weight / 10 to 90% by weight, and even more preferably 10 to 80% by weight / 20 to 90% by weight.

[0072] -Copolymer (A-3)- Copolymer (A-3) has structural units (II) and (III). The content ratio of the respective structural units is preferably structural unit (II) / structural unit (III)=1 to 99% by weight / 1 to 99% by weight, more preferably 1 to 90% by weight / 10 to 99% by weight, and even more preferably 1 to 80% by weight / 20 to 99% by weight.

[0073] -Copolymer (A-4)- Copolymer (A-4) has structural units (I), (II), and (III). The content ratio of each structural unit is preferably structural unit (I) / structural unit (II) / structural unit (III)=1 to 98% by weight / 1 to 98% by weight / 1 to 98% by weight, more preferably 10 to 89% by weight / 1 to 80% by weight / 10 to 89% by weight, and even more preferably 15 to 79% by weight / 1 to 75% by weight / 20 to 84% by weight.

[0074] [1-6. Method for producing copolymer] The polycarboxylic acid copolymer, component (A), can be produced by copolymerizing the respective predetermined monomers by known methods, such as polymerization in a solvent or bulk polymerization.

[0075] -Reaction solvent- Examples of solvents used in polymerization in a solvent include water, lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as cyclohexane and n-hexane, esters such as ethyl acetate, and ketones such as acetone and methyl ethyl ketone. From the viewpoint of the solubility of the raw material monomers and the resulting copolymer, it is preferable to use at least one of water and a lower alcohol, and it is more preferable to use water.

[0076] When copolymerization is carried out in a solvent, each monomer and the polymerization initiator may be continuously added dropwise to a reaction vessel, or a mixture of each monomer and the polymerization initiator may be continuously added dropwise to a reaction vessel. Alternatively, a solvent may be charged into a reaction vessel, and a mixture of the monomers and the solvent and a polymerization initiator solution may be continuously added dropwise to the reaction vessel, or a part or all of the monomers may be charged into a reaction vessel, and the polymerization initiator may be continuously added dropwise.

[0077] -Initiator- The polymerization initiator that can be used for copolymerization is not particularly limited. Examples of polymerization initiators that can be used when copolymerizing in an aqueous solvent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; and water-soluble peroxides such as t-butyl hydroperoxide and hydrogen peroxide. In this case, an accelerator such as L-ascorbic acid, sodium hydrogen sulfite, or Mohr's salt may be used in combination. Examples of polymerization initiators that can be used when copolymerizing in a solvent such as a lower alcohol, an aromatic hydrocarbon, an aliphatic hydrocarbon, an ester, or a ketone include peroxides such as benzoyl peroxide and lauryl peroxide, hydroperoxides such as cumene peroxide, and aromatic azo compounds such as azobisisobutyronitrile. In this case, an accelerator such as an amine compound may be used in combination. The polymerization initiator that can be used when copolymerizing in a water-lower alcohol mixed solvent may be appropriately selected from the above-mentioned polymerization initiators or combinations of polymerization initiators and accelerators. The polymerization temperature varies depending on the polymerization conditions such as the type of solvent and polymerization initiator used, but is usually 50 to 120°C.

[0078] - Chain transfer agent - In the copolymerization, molecular weight can be adjusted, if necessary, using a chain transfer agent. Examples of chain transfer agents that can be used include known thiol compounds such as mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, and 2-mercaptoethanesulfonic acid; and lower oxides and salts thereof, such as phosphorous acid, hypophosphorous acid, and salts thereof (e.g., sodium hypophosphite, potassium hypophosphite), sulfurous acid, hydrogen sulfite, dithionous acid, metabisulfite, and salts thereof (e.g., sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite). These may be used alone or in combination of two or more. In order to adjust the molecular weight of the copolymer, a monomer (V) with high chain transfer properties other than the monomers constituting the structural units (I) to (IV) may be used. Examples of the monomer (V) with high chain transfer properties include (meth)allylsulfonic acid (salt)-based monomers. The blending ratio of the monomer (V) in the copolymer is usually 20% by weight or less, and preferably 10% by weight or less. The blending ratio is the blending ratio when the total blending ratio of the monomers constituting the structural units (I) to (IV) when producing the copolymer is taken as 100% by weight.

[0079] -Neutralization- When copolymerization is performed in an aqueous solvent to obtain a copolymer, the pH during polymerization is usually strongly acidic due to the influence of the monomer having an unsaturated bond, but this can be adjusted to an appropriate pH. If pH adjustment is necessary during polymerization, the pH can be adjusted using an acidic substance such as phosphoric acid, sulfuric acid, nitric acid, alkyl phosphoric acid, alkyl sulfuric acid, alkyl sulfonic acid, or (alkyl)benzenesulfonic acid. Among these acidic substances, phosphoric acid is preferred because of its pH buffering effect. The polymerization reaction is preferably carried out at a pH of 2 to 7 to eliminate the instability of the ester bond of the ester-based monomer. There are no particular limitations on the alkaline substance that can be used to adjust the pH, but alkaline substances such as NaOH and Ca(OH)2 are common. The pH adjustment may be performed on the monomer before polymerization, or on the copolymer solution after polymerization. After polymerization is carried out by adding a portion of the alkaline substance before polymerization, the pH of the copolymer may be further adjusted.

[0080] [1-7. Physical properties of copolymers] -Weight average molecular weight- The weight-average molecular weight of the copolymer is preferably 5,000 or more, more preferably 6,000 or more, and even more preferably 6,500 or more. This allows the hydraulic composition to fully exhibit its dispersibility, achieving a water reduction rate that exceeds that of AE water reducers such as lignosulfonic acid-based or oxycarboxylic acid-based water reducers, thereby improving fluidity and workability. The upper limit of the weight-average molecular weight is preferably 60,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. This inhibits the aggregation of particles in the hydraulic composition, improving workability. The weight-average molecular weight is preferably 5,000 to 60,000, more preferably 6,000 to 50,000, and even more preferably 6,500 to 30,000.

[0081] -Mw / Mn- The molecular weight distribution (dispersity: Mw / Mn) of the copolymer is preferably 1.0 or more, more preferably 1.2 or more. The upper limit is preferably 3.0 or less, more preferably 2.5 or less. The molecular weight distribution is preferably in the range of 1.0 to 3.0, more preferably 1.2 to 2.5.

[0082] The weight-average molecular weight and number-average molecular weight can be measured by a known method using gel permeation chromatography (GPC) in terms of polyethylene glycol. The molecular weight distribution can be calculated by dividing the measured value of the weight-average molecular weight by the measured value of the number-average molecular weight. The GPC measurement conditions are as follows: The weight average molecular weights in the examples below are values ​​measured under these conditions.

[0083] The component (A) may be a single copolymer or a combination of two or more copolymers.

[0084] [2. Component (B): Cement] The cement of component (B) has an angle of repose of 46 to 51° and a specific surface area of ​​2500 to 3600 cm 2 / g.

[0085] -Angle of repose- The angle of repose of the cement is 46° or more, preferably 47° or more, and more preferably 48° or more. The upper limit is 51° or less, preferably 50.5° or less, and more preferably 50° or less. When the angle of repose is within the above range, the composition can fully exhibit the dispersing function derived from component (A).

[0086] -Specific surface area- The specific surface area of ​​cement is 2500 cm 2 / g or more is preferable, and 2700 cm 2 / g or more, more preferably 2900m 2 / g or more. This ensures that component (B) has a sufficient specific surface area and can adequately adsorb component (A). The upper limit is 3600 cm 2 / g or less, and more preferably 3550 cm 2 / g or less, more preferably 3500 cm 2 / g or less.

[0087] -density- The density of the cement is preferably 3.0 or more, more preferably 3.05 or more, and even more preferably 3.1 or more. The upper limit is preferably 3.3 or less, more preferably 3.25 or less. When the density is within the above range, the balance between the settling property and dispersibility of the cement when adsorbed with component (A) is excellent, and the effects of the present invention can be effectively exhibited.

[0088] -Types of cement- The cement may be any hydraulic material, and its type is not particularly limited. Examples include Portland cement (e.g., normal, early-strength, ultra-early-strength, moderate-heat, sulfate-resistant, and low-alkali forms of each), various blended cements (e.g., blast-furnace cement, silica cement, fly ash cement), white Portland cement, alumina cement, ultra-rapid-hardening cement (e.g., 1-clinker rapid-hardening cement, 2-clinker rapid-hardening cement, magnesium phosphate cement), grout cement, oil well cement, low-heat cement (e.g., low-heat blast-furnace cement, low-heat blast-furnace cement mixed with fly ash, high-belite cement), ultra-high-strength cement, cement-based solidification material, and ecocement (e.g., cement produced using one or more of municipal waste incineration ash and sewage sludge incineration ash as raw materials). Gypsum (e.g., gypsum hemihydrate, gypsum dihydrate, etc.) and dolomite are also suitable. The cement may contain added fine powders such as blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, and limestone powder.

[0089] Component (B) may be one type of cement alone or a combination of two or more types. In the case of a combination of two or more types, it is preferable that the mixture of the combined cements has a predetermined angle of repose.

[0090] [3. Content] The content of component (A) in the hydraulic composition is preferably 0.01% by weight or more, more preferably 0.02% by weight or more, and even more preferably 0.05% by weight or more, based on the total weight of the cement including component (B). This allows the cement composition to exhibit the effects expected of it. The upper limit is preferably 5.0% by weight or less, more preferably 2.0% by weight or less, and even more preferably 1.0% by weight or less. This allows the effect to be commensurate with the amount added, which is economical. Therefore, the content is preferably 0.01 to 5.0% by weight, more preferably 0.02 to 2.0% by weight, and even more preferably 0.05 to 1.0% by weight, which allows the effects of reducing the unit water content, increasing strength, improving durability, etc. to be efficiently obtained.

[0091] [4.Optional ingredients] The hydraulic composition may contain optional components other than components (A) and (B), such as aggregates (fine aggregate, coarse aggregate), cement additives other than component (A), and cements other than component (B).

[0092] -Fine aggregate- Examples of fine aggregate include sand, gravel, crushed stone; granulated slag; recycled aggregate; silica, clay, zircon, high alumina, silicon carbide, graphite, chromium, chromium-magnesium, and magnesia.

[0093] -Coarse aggregate- Examples of coarse aggregate include sand, gravel, crushed stone; granulated slag; recycled aggregate; and refractory aggregate such as silica, clay, zircon, high alumina, silicon carbide, graphite, chromium, chromium-magnesium, and magnesia.

[0094] - Cement additives (other than component (A)) - Examples of cement additives other than component (A) include, but are not limited to, water-soluble polymers, polymer emulsions, air-entraining agents, cement wetting agents, expansion agents, waterproofing agents, retarders, thickeners, flocculants, drying shrinkage-reducing agents, strength enhancers, cure accelerators, antifoaming agents, air-entraining agents, surfactants, other cement additives (e.g., carboxyl group- and / or salt-containing compounds (CA agents), sulfonic acid group- and / or salt-containing compounds (SA agents)), and combinations of two or more selected from these. Examples of CA agents include sodium polyacrylate and sodium gluconate. Examples of SA agents include sodium lignosulfonate and naphthalenesulfonic acid.

[0095] Examples of weight ratios when component (A) is used in combination with a CA agent and / or SA agent are as follows: When two components are used in combination, component (A) / CA agent or SA agent=0.1-99.9% by weight / 0.1-99.9% by weight is preferred. When three components are used in combination, component (A) / total of CA agent and SA agent=0.1-99.8% by weight / 0.1-99.8% by weight / 0.1-99.8% by weight is preferred.

[0096] -Cement (other than component (B))- Examples of cements other than component (B) include the above-mentioned cements (those with a specific surface area or angle of repose outside the range of component (B)).

[0097] The hydraulic composition is useful as concrete, for example, ready-mixed concrete, concrete for secondary concrete products (precast concrete), concrete for centrifugal molding, concrete for vibration compaction, steam-cured concrete, shotcrete, etc. Furthermore, it is also useful as mortar or concrete that requires high fluidity, such as medium-fluidity concrete (concrete with a slump value in the range of 22 to 25 cm), high-fluidity concrete (concrete with a slump value of 25 cm or more and a slump flow value in the range of 50 to 70 cm), underwater non-segregating concrete, self-compacting concrete, and self-leveling material.

[0098] [5. Manufacturing method of hydraulic composition] There are no particular limitations on the method for producing the hydraulic composition, and it can be produced by adding and mixing the components together with water in accordance with a conventional method. [Example]

[0099] The present invention will be described in detail below with reference to examples. The following examples are provided to better illustrate the present invention and are not intended to limit the present invention. Measurement methods for physical properties and the like are the same as those described above unless otherwise specified. "Parts" means parts by weight unless otherwise specified.

[0100] [Measurement conditions for copolymers] -Weight average molecular weight (Mw) and number average molecular weight (Mn)- The measurement was carried out by gel permeation chromatography (GPC) using polyethylene glycol as the standard. The GPC measurement conditions were as follows: Measuring device: Tosoh Columns used: Shodex Column OH-pak SB-806HQ, SB-804HQ, SB-802.5HQ Eluent: 0.05 mM sodium nitrate / acetonitrile 8 / 2 (v / v) Standard material: polyethylene glycol (Tosoh, GL Science) Detector: Differential refractometer (manufactured by Tosoh) Calibration curve: polyethylene glycol standard

[0101] -Dispersity (Mw / Mn)- It was calculated from the measured values ​​of weight average molecular weight (Mw) and number average molecular weight (Mn).

[0102] (Production Example 1: Production Example of Copolymer (1)) A glass reactor equipped with a thermometer, stirrer, reflux device, and dropping device was charged with 193 parts of water and 64 parts of an ethylene oxide adduct of methallyl alcohol (average number of ethylene oxide adducts: 40). 2.4 parts of L-ascorbic acid was added and the temperature was raised to 40°C. Then, an aqueous monomer solution containing 14 parts of acrylic acid, 1 part of 3-mercaptopropionic acid, and 200 parts of water, and a mixture of 0.4 parts of hydrogen peroxide and 25 parts of water, were added dropwise over 2 hours to the reactor, which was maintained at 40°C. After the addition, the mixture was allowed to react for another hour while maintaining the temperature, yielding an aqueous copolymer solution. The copolymer in the solution was copolymer (1) (weight average molecular weight: 16,600, Mw / Mn: 1.41).

[0103] (Production Example 2: Production Example of Copolymer (2)) A glass reactor equipped with a thermometer, stirrer, reflux device, and dropping apparatus was charged with 193 parts of water and 64 parts of an ethylene oxide adduct of methallyl alcohol (average number of ethylene oxide moles: 53). 0.6 parts of L-ascorbic acid was added and the temperature was raised to 40°C. Then, a monomer aqueous solution containing 14 parts of acrylic acid, 1 part of 3-mercaptopropionic acid, and 200 parts of water, and a mixture of 0.4 parts of hydrogen peroxide and 25 parts of water, were added dropwise over 2 hours to the reactor, which was maintained at 40°C. After the addition, the mixture was allowed to react for another hour while maintaining the temperature, yielding an aqueous copolymer solution. The copolymer in the solution was copolymer (2) (weight average molecular weight: 19,000, Mw / Mn: 1.46).

[0104] (Production Example 3: Production Example of Copolymer (3)) A glass reactor equipped with a thermometer, stirrer, reflux device, and dropping device was charged with 130 parts of water, 192 parts of an ethylene oxide adduct of methallyl alcohol (average number of moles of ethylene oxide added: 53), and 2.4 parts of L-ascorbic acid. The temperature was raised to 40°C. An aqueous monomer solution containing 14 parts of acrylic acid, 2 parts of 3-mercaptopropionic acid, and 126 parts of water, and a mixture of 1 part of hydrogen peroxide and 34 parts of water, were then added dropwise over 2 hours to the reactor, which was maintained at 40°C. After the addition, the mixture was allowed to react for an additional hour while maintaining the temperature, yielding an aqueous copolymer solution. The copolymer in the solution was copolymer (3) (weight average molecular weight: 16,100, Mw / Mn: 1.47).

[0105] (Production Example 4: Production Example of Copolymer (4)) A glass reactor equipped with a thermometer, stirrer, reflux device, and dropping apparatus was charged with 193 parts of water and 64 parts of an ethylene oxide adduct of methallyl alcohol (average number of ethylene oxide adducts: 10). 0.6 parts of L-ascorbic acid was added and the temperature was raised to 40°C. Then, a monomer aqueous solution containing 14 parts of acrylic acid, 1 part of 3-mercaptopropionic acid, and 200 parts of water, and a mixture of 0.4 parts of hydrogen peroxide and 25 parts of water, were added dropwise over 2 hours to the reactor, which was maintained at 40°C. After the addition, the mixture was allowed to react for another hour while maintaining the temperature, yielding an aqueous copolymer solution. The copolymer in the solution was copolymer (4) (weight average molecular weight: 14,500, Mw / Mn: 1.83).

[0106] (Production Example 5: Production Example of Copolymer (5)) A glass reactor equipped with a thermometer, stirrer, reflux device, and dropping device was charged with 134 parts of water and 201 parts of an ethylene oxide adduct of methallyl alcohol (average number of moles of ethylene oxide added: 25). 2 parts of L-ascorbic acid was added and the temperature was raised to 40°C. Then, an aqueous monomer solution containing 40 parts of acrylic acid, 2 parts of 3-mercaptopropionic acid, and 48 parts of water, and a mixture of 0.7 parts of hydrogen peroxide and 34 parts of water, were added dropwise over 2 hours to the reactor, which was maintained at 40°C. After the addition, the mixture was allowed to react for another hour while maintaining the temperature, yielding an aqueous copolymer solution. The copolymer in the solution was copolymer (5) (weight average molecular weight: 27,000, Mw / Mn: 1.66).

[0107] (Production Example 6: Production Example of Copolymer (6)) A glass reactor equipped with a thermometer, stirrer, reflux device, and dropping device was charged with 192 parts of water, 192 parts of an ethylene oxide adduct of methallyl alcohol (average number of moles of ethylene oxide added: 35), and 2.0 parts of L-ascorbic acid. The temperature was raised to 40°C. An aqueous monomer solution containing 12 parts of acrylic acid, 1 part of 3-mercaptopropionic acid, and 27 parts of water, and a mixture of 0.8 parts of hydrogen peroxide and 34 parts of water, were then added dropwise over 2 hours to the reactor, which was maintained at 40°C. After the addition, the mixture was allowed to react for another hour while maintaining the temperature, yielding an aqueous copolymer solution. The copolymer in the solution was copolymer (6) (weight average molecular weight: 14,800, Mw / Mn: 1.52).

[0108] The proportions of the structural units of the copolymers of Production Examples 1 to 6 and the physical properties thereof are listed in Table 1 below.

[0109] [Table 1]

[0110] [Footnotes to Table 1] n: Number of moles of EO added

[0111] The cements used as component (B) are as follows, each having a specific surface area and density as shown in Table 2. Cement 1: Ordinary Portland cement manufactured by Taiheiyo Cement Corporation Cement 2: Ordinary Portland cement manufactured by Ube Mitsubishi Cement Co., Ltd. Cement 3: Low-heat Portland cement manufactured by Taiheiyo Cement Corporation Cement 4: Nippon Steel Blast Furnace Cement Co., Ltd., Blast Furnace Cement Type B Fly ash 5: Electric Power Development Co., Ltd., Fly ash type II

[0112] [Measurement conditions for cement] -Specific surface area and density- The specific surface area and density of cements were obtained according to JIS R5201:2015.

[0113] -Angle of repose- A fixed stand was set up and a funnel (glass, small hole outer diameter 1.5 cm, inner diameter 1.2 cm) was clamped at a height of 18±0.5 cm from the ground to the entrance. An aluminum tray was placed under the funnel, and 50 g of sample was allowed to fall naturally through the funnel. When the powder was deposited on a horizontal surface, the angles made by the powder were measured in all directions. A digital goniometer (manufactured by Sogo Rikagaku Glass Manufacturing Co., Ltd.) was used to measure the angles.

[0114] [Table 2]

[0115] Example 1 Cement compositions were prepared by mixing cements 1 and 2, fine aggregate, water, antifoaming agent, and copolymer (1) under the following conditions and mechanically mixing them in a mortar mixer. The amount of copolymer (1) added is shown in Table 3. The angle of repose of the mixture of cements 1 and 2 was measured in the same manner as described above.

[0116] [Mixing and mixing conditions for cement composition (ordinary cement) (initial dispersion type)] -Combination conditions- Composition: W / C=30% W:308, C:1026, S:1434 Cement: Mix equal amounts of cement 1 and 2 (angle of repose of the mixture: 49.8°) Fine aggregate: Kakegawa land sand (density: 2.58, surface water: 0.1%) Antifoaming agent: Pronal 753 (manufactured by Toho Chemical Industry Co., Ltd.) (0.0005% of cement = 1T) 20T -Kneading conditions- 1 / 2S+C+1 / 2S → Low speed 10s → W → Low speed 30s → High speed 90s → Stand still for 3 minutes → Low speed 30s → Measurement

[0117] Example 2 The same procedure as in Example 1 was carried out except that copolymer (1) was changed to copolymer (2) (see Table 3).

[0118] Example 3 The same procedures as in Example 1 were carried out except that copolymer (1) was changed to copolymer (3) (see Table 3) and the kneading and measurement conditions were as follows.

[0119] [Regular cement mix and mixing conditions (retention type)] -Combination conditions- Composition: W / C=30% W:308, C:1026, S:1434 Cement: Mix equal amounts of cement 1 and 2 (angle of repose of the mixture: 49.8°) Fine aggregate: Kakegawa land sand (density: 2.58, surface water: 0.1%) Antifoaming agent: Pronal 753 (manufactured by Toho Chemical Industry Co., Ltd.) (0.0005% of cement = 1T) 20T -Kneading conditions- 1 / 2S+C+1 / 2S → Low speed 10s → W → Low speed 30s → High speed 90s → Measurement

[0120] Example 4 The same procedures as in Example 2 were carried out except that the blending amount of copolymer (2) was changed (see Table 3) and the kneading and measurement conditions were as follows.

[0121] [Mixing and measurement conditions for low-heat cement] -Test conditions- Composition: W / C=23.4% W:312, C:1333, S:1217 Cement: Cement 3 Fine aggregate: Kakegawa land sand (density: 2.58, surface water: 0.1%) Antifoaming agent: Pronal 753 (manufactured by Toho Chemical Industry Co., Ltd.) (0.0005% of cement = 1T) 20T -Kneading conditions- 1 / 2S+C+1 / 2S → Low speed 10s → W → Low speed 60s → High speed 60s → Stand still for 5 minutes → Low speed 30s → Measurement

[0122] Comparative Example 1 The same procedure as in Example 1 was carried out except that copolymer (1) was changed to copolymer (4) (see Table 3).

[0123] Comparative Example 2 The same procedure as in Example 4 was carried out, except that copolymer (2) was changed to copolymer (5) (see Table 3).

[0124] Comparative Example 3 The same procedure as in Example 3 was carried out, except that copolymer (3) was changed to copolymer (6) (see Table 3).

[0125] Comparative Example 4 The same procedure as in Example 1 was carried out, except that the cement composition was prepared under the following conditions. -Combination conditions- Composition: W / C=30% W:308, C:1026, S:1434 Cement: Cement 4 Fine aggregate: Kakegawa land sand (density: 2.58, surface water: 0.1%) Antifoaming agent: Pronal 753 (manufactured by Toho Chemical Industry Co., Ltd.) (0.0005% of cement = 1T) 20T -Kneading conditions- 1 / 2S+C+1 / 2S → Low speed 10s → W → Low speed 30s → High speed 90s → Stand still for 3 minutes → Low speed 30s → Measurement

[0126] Comparative Example 5 The same procedure as in Example 1 was carried out, except that the cement composition was prepared under the following conditions. -Combination conditions- Composition: W / C=30% W:308, C:1026, S:1434 Cement: Equal amounts of cement 1 and fly ash mixed (angle of repose of the mixture: 52.6°) Fine aggregate: Kakegawa land sand (density: 2.58, surface water: 0.1%) Antifoaming agent: Pronal 753 (manufactured by Toho Chemical Industry Co., Ltd.) (0.0005% of cement = 1T) 20T -Kneading conditions- 1 / 2S+C+1 / 2S → Low speed 10s → W → Low speed 30s → High speed 90s → Stand still for 3 minutes → Low speed 30s → Measurement

[0127] Using the hydraulic compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 5, the flow values ​​were measured by the following slump test.

[0128] [Measurement conditions for hydraulic composition] -Slump test- Measurements were made in accordance with JIS-A-1101 (measurement of the spread of a fresh cement composition when it falls from the top as a flow value). Measurements were made using samples immediately after they were discharged from the forced twin-shaft mixer (immediately after mixing) and 60 minutes later.

[0129] [Table 3]

[0130] The compositions of Comparative Examples 1 to 3, which were combinations of component (A') derived from a monomer with a low number of EO added moles instead of component (A) and component (B), had low flow values ​​immediately after mixing and after 60 minutes, whereas the compositions of the Examples, which were combinations of components (A) and (B), had high flow values ​​and good workability. In Comparative Example 4, in which the component (B) was outside the range of the present invention, the flow value was too high, which raised concerns about material separation. In Comparative Example 5, the flow value was low, which resulted in poor workability. This indicates that the hydraulic composition of the present invention can exhibit good workability.

Claims

1. Contains the following components (A) and (B): A hydraulic composition (excluding hydraulic compositions containing a lignin derivative) in which the content of component (A) relative to component (B) is 0.05 to 1.0% by weight. Component (A): At least a structural unit (I) derived from a monomer represented by the following general formula (1), and The polymer further comprises a structural unit (II) derived from a monomer represented by the following general formula (2), or further comprises at least one structural unit selected from the group consisting of the structural unit (II) and a structural unit (III) derived from a monomer represented by the following general formula (3): The structural unit (I) includes at least a structural unit (IA') derived from a polyoxyethylene glycol monomethallyl ether represented by the following general formula (4): The structural unit (II) derived from the monomer represented by general formula (2) is acrylic acid, A copolymer having a weight average molecular weight of 30,000 or less (excluding copolymers containing structural units derived from unsaturated dicarboxylic acid monomers). 【Chemical 1】 (In the general formula (1), R １ , R ２ and R ３ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, p represents an integer of 0 to 2, and q represents an integer of 0 to 1. A １ O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. n represents an integer of 40 to 100. R ４ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. 【Chemistry 2】 (In the general formula (2), R ５ , R ６ and R ７ are each independently a hydrogen atom, —CH ３ or -(CH ２ ) ｒ COOM ２ However, -(CH ２ ) ｒ COOM ２ If １ or other -(CH ２ ) ｒ COOM ２ When an anhydride is formed, the M １ , M ２ does not exist. １ and M ２ may be the same or different and represent a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, or a substituted alkylammonium group; and r represents an integer of 0 to 2. 【Chemistry 3】 (In the general formula (3), R ８ , R ９ and R １０ R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. １１ represents a hydrocarbon group having 1 to 4 carbon atoms which may contain a heteroatom; and s represents an integer of 0 to 2. 【Chemistry 4】 (In the general formula (4), A 1 O may be the same or different and represent an oxyalkylene group having 2 to 18 carbon atoms. n represents an integer of 40 to 53. Component (B): Angle of repose of 46 to 51°, density of 3.0 to 3.3 g / cm ３ That is, cement

2. 2. The hydraulic composition according to claim 1, wherein the molecular weight distribution of the copolymer of component (A) is 1.0 to 3.0.

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