JP2017160076A - Additive for hydraulic composition, and concrete composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an additive for hydraulic composition which can sufficiently exhibit a long-term curability improvement effect of a hydraulic composition containing hydraulic cement and can reduce an addition amount of a cement admixture such as a polycarboxylic-based copolymer, and to provide a concrete composition containing the additive for hydraulic composition.SOLUTION: An additive for hydraulic composition being an additive for hydraulic composition containing hydraulic cement contains a hydraulic material dispersant containing a polycarboxylic-based copolymer containing a structural unit (I) derived from a specific unsaturated polyalkylene glycol-based monomer (a) and a structural unit (II) derived from a specific unsaturated carboxylic-based monomer (b), and a strength improving agent containing a polyacrylic acid (salt).SELECTED DRAWING: None

Description

  The present invention relates to an additive for a hydraulic composition and a concrete composition.

  The hydraulic composition gives a cured product having excellent strength and durability. Therefore, hydraulic compositions are widely used as components of cement compositions such as cement paste, mortar, and concrete. The hydraulic composition is indispensable for constructing civil engineering and building structures (for example, Patent Document 1).

  Cement compositions such as cement paste, mortar, and concrete are required to improve long-term curability in many situations in various constructions using the same. In addition, a cement admixture such as a polycarboxylic acid-based copolymer is generally added to cement compositions such as cement paste, mortar, and concrete for the purpose of improving curability. There is a demand for improvement in economic efficiency by reducing the amount added.

JP2013-133241A

  An object of the present invention is to sufficiently exhibit the long-term curability improvement effect of a hydraulic composition containing hydraulic cement, and to reduce the amount of cement admixture such as a polycarboxylic acid copolymer. It is in providing the additive for hydraulic compositions. Moreover, it is providing the concrete composition containing such an additive for hydraulic compositions.

（一般式（２）中、Ｒ^３〜Ｒ^５は、同一または異なって、水素原子、メチル基、または−（ＣＨ_２）_ｚＣＯＯＭ基を表し、−（ＣＨ_２）_ｚＣＯＯＭ基は−ＣＯＯＸ基または他の−（ＣＨ_２）_ｚＣＯＯＭ基と無水物を形成していても良く、ｚは０〜２の整数であり、Ｍは、水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、有機アンモニウム基、または有機アミン基を表し、Ｘは、水素原子、メチル基、エチル基、アルカリ金属、アルカリ土類金属、アンモニウム基、有機アンモニウム基、または有機アミン基を表す。） The additive for hydraulic composition of the present invention is:
An additive for a hydraulic composition containing hydraulic cement,
Derived from the structural unit (I) derived from the unsaturated polyalkylene glycol monomer (a) represented by the general formula (1) and the unsaturated carboxylic acid monomer (b) represented by the general formula (2) A hydraulic material dispersant containing a polycarboxylic acid-based copolymer containing the structural unit (II), and a strength improver containing polyacrylic acid (salt).
YO— (R ¹ O) _n —R ² (1)
(In General Formula (1), Y represents an alkenyl group having 2 to 8 carbon atoms, R ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms, and n represents R ¹ O. The average addition mole number of the oxyalkylene group represented by the formula (1), n is 1 to 500, and R ² represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.)

(In General Formula (2), R ^{3 to} R ⁵ are the same or different and each represents a hydrogen atom, a methyl group, or — (CH ₂ ) _z COOM group, and — (CH ₂ ) _z COOM group represents a —COOX group. Or other — (CH ₂ ) _z COOM group may form an anhydride, z is an integer of 0 to 2, M is a hydrogen atom, alkali metal, alkaline earth metal, ammonium group, organic An ammonium group or an organic amine group is represented, and X represents a hydrogen atom, a methyl group, an ethyl group, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.)

  In one embodiment, Y in the general formula (1) is a 2-methyl-2-propenyl group, a 3-methyl-3-butenyl group, a 3-methyl-2-butenyl group, or 2-methyl-2. -It is either a butenyl group or a 2-methyl-3-butenyl group.

  In one embodiment, the hydraulic composition includes a pozzolanic substance.

  In one embodiment, the content ratio of the pozzolanic substance is larger than 30% by mass with respect to the total amount of the hydraulic cement and the pozzolanic substance in the hydraulic composition.

  In one embodiment, the pozzolanic material includes fly ash.

  The concrete composition of this invention contains the hydraulic composition containing a hydraulic cement, and the additive for hydraulic compositions of this invention.

  In one embodiment, the hydraulic composition includes a pozzolanic substance.

  In one embodiment, the content ratio of the pozzolanic substance is larger than 30% by mass with respect to the total amount of the hydraulic cement and the pozzolanic substance in the hydraulic composition.

  In one embodiment, the pozzolanic material includes fly ash.

  ADVANTAGE OF THE INVENTION According to this invention, while being able to fully express the long-term curability improvement effect of the hydraulic composition containing hydraulic cement, the addition amount of cement admixtures, such as a polycarboxylic acid-type copolymer, can be reduced. The strength additive for hydraulic compositions can be provided. Moreover, the concrete composition containing such an additive for hydraulic compositions can be provided.

  In the present specification, the expression “(meth) acryl” means “acryl and / or methacryl”, and the expression “(meth) acrylate” means “acrylate and / or methacrylate”. Means “allyl and / or methallyl”, and “(meth) acrolein” means “acrolein and / or methacrole”. It means "rain". Further, in the present specification, the expression “acid (salt)” means “acid and / or salt thereof”. In addition, when there is an expression “mass” in the present specification, it may be read as “weight” conventionally used as a unit of weight in general, and conversely, “weight” in the present specification. May be read as “mass”, which is commonly used as an SI system unit indicating weight.

  In this specification, when calculating the content ratio of the structural unit, the content ratio of the monomer, etc., the unsaturated carboxylic acid monomer (b) is in the form of a salt (ie, carboxylate) Is calculated assuming that the salt form is not taken. For example, in the case of sodium acrylate, it is calculated as acrylic acid.

  In the present invention, the hydraulic composition contains hydraulic cement. The content ratio of the hydraulic cement in the hydraulic composition is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and further preferably 90% by mass to 100% by mass. Yes, particularly preferably 95% by mass to 100% by mass, and most preferably substantially 100% by mass.

  In the present invention, the hydraulic composition may contain a pozzolanic substance.

  In recent years, for the purpose of reducing the cost of hydraulic cement and reducing environmental impact, a part of hydraulic cement has been changed to pozzolanic substances such as fly ash, silica fume, and blast furnace slag, which are by-products in the production of various industrial materials. Alternative substituted pozzolanic material-containing hydraulic compositions have attracted attention. When a pozzolanic substance is used as a partial substitute for hydraulic cement, the initial curability improvement effect may be expressed, but the long-term curability improvement effect cannot be fully expressed. When the amount increases, the degree of expression of the long-term curability improving effect becomes extremely insufficient.

  In the present specification, the “pozzolanic substance” does not have hydraulic properties by itself, but has the property of producing a hydrate by reacting with calcium hydroxide or calcium ions generated by the hydration reaction of hydraulic cement. It is a substance that has. Examples of such “pozzolanic substances” include natural pozzolans, blast furnace slag, fly ash, silica fume, and amorphous silica. Among these, as the “pozzolanic substance” in the present specification, blast furnace slag, fly ash, and silica fume are preferable, and fly ash is more preferable because the effects of the present invention can be more manifested. Fly ash is a type of coal incineration ash and is a by-product of thermal power generation, etc. If this fly ash can be effectively used as a partial substitute for hydraulic cement, it will greatly reduce the cost and environmental impact of hydraulic cement. Can be achieved.

  In the present invention, when the hydraulic composition contains a pozzolanic substance, the content ratio of the pozzolanic substance to the total amount of the hydraulic cement and the pozzolanic substance is preferably greater than 30% by mass, more preferably 31% by mass. It is -90 mass%, More preferably, it is 33 mass%-80 mass%, Most preferably, it is 35 mass%-70 mass%. When the hydraulic composition contains a pozzolanic substance, if the content ratio of the pozzolanic substance to the total amount of the hydraulic cement and the pozzolanic substance is within the above range, the cost reduction of the hydraulic cement and a more satisfactory environment are achieved. A load reduction can be achieved.

  When the hydraulic composition contains a pozzolanic substance, the content ratio of the total amount of the hydraulic cement and the pozzolanic substance in the hydraulic composition is preferably 50% by mass to 100% by mass, more preferably 70%. % By mass to 100% by mass, more preferably 90% by mass to 100% by mass, particularly preferably 95% by mass to 100% by mass, and most preferably substantially 100% by mass.

≪Additive for hydraulic composition≫
The additive for hydraulic composition of the present invention includes a hydraulic material dispersant containing a specific polycarboxylic acid copolymer and a strength improver containing polyacrylic acid (salt). The additive for a hydraulic composition of the present invention includes a hydraulic material dispersant containing a specific polycarboxylic acid-based copolymer and a strength improver containing polyacrylic acid (salt). The effect of improving the long-term curability of the hydraulic composition containing cement can be sufficiently exhibited, and the amount of cement admixture such as a polycarboxylic acid copolymer can be reduced.

  The polycarboxylic acid-based copolymer in the hydraulic material dispersant contained in the hydraulic composition additive of the present invention may be one type or two or more types.

  The content ratio of the polycarboxylic acid copolymer in the hydraulic material dispersant contained in the hydraulic composition additive of the present invention is preferably 50% by mass to 100% by mass, more preferably 70% by mass. It is -100 mass%, More preferably, it is 90 mass%-100 mass%, Especially preferably, it is 95 mass%-100 mass%, Most preferably, it is substantially 100 mass%.

  1 type may be sufficient as the polyacrylic acid (salt) in the strength improver contained in the additive for hydraulic compositions of this invention, and 2 or more types may be sufficient as it.

  The strength improver contained in the hydraulic composition additive of the present invention exhibits a compressive strength improving effect of 3% or more, more preferably 4% or more in the evaluation of <strength improvement rate> described later. It shows a compressive strength improving effect, and more preferably shows a compressive strength improving effect of 5% or more.

  The content of polyacrylic acid (salt) in the strength improver contained in the hydraulic composition additive of the present invention is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass. %, More preferably 90% by mass to 100% by mass, particularly preferably 95% by mass to 100% by mass, and most preferably substantially 100% by mass.

  The polyacrylic acid (salt) typically has a structural unit derived from acrylic acid and / or a salt thereof of 90% by mass or more, preferably 93% by mass or more, more preferably 95% by mass or more, and still more preferably 98% by mass. % Or more, particularly preferably 99% by mass or more, most preferably substantially 100% by mass. Examples of the salt include sodium salt, potassium salt, calcium salt and the like.

  In the additive for hydraulic composition of the present invention, the amount of the polycarboxylic acid copolymer used is preferably 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the hydraulic composition, and more. Preferably they are 0.02 mass parts-5 mass parts, More preferably, they are 0.05 mass parts-3 mass parts. If the content ratio of the polycarboxylic acid copolymer in the additive for a pozzolanic substance-containing hydraulic composition of the present invention is within the above range, the long-term hydraulic composition containing the hydraulic cement and the pozzolanic substance is used. The effect of improving the curability can be fully exhibited, and the amount of cement admixture such as a polycarboxylic acid copolymer can be further reduced.

  In the hydraulic composition additive of the present invention, the amount of polyacrylic acid (salt) used is preferably 0.001 to 5 parts by mass, more preferably 100 parts by mass with respect to the hydraulic composition. Is 0.005 to 3 parts by mass, more preferably 0.01 to 1 part by mass. If the content ratio of the polyacrylic acid (salt) in the hydraulic composition additive of the present invention is within the above range, the effect of improving the long-term curability of the hydraulic composition containing hydraulic cement is more fully expressed. And the amount of cement admixture such as polycarboxylic acid copolymer added can be further reduced.

<Polycarboxylic acid copolymer>
The polycarboxylic acid copolymer includes an unsaturated carboxylic acid represented by the structural unit (I) derived from the unsaturated polyalkylene glycol monomer (a) represented by the general formula (1) and the general formula (2). And a structural unit (II) derived from the acid monomer (b).
YO— (R ¹ O) _n —R ² (1)

  The structural unit (I) derived from the unsaturated polyalkylene glycol monomer (a) represented by the general formula (1) means that the unsaturated double bond of Y in the general formula (1) is cleaved by polymerization. Is a structural unit formed. Note that a structural unit formed by cleavage of an unsaturated double bond by polymerization means a structure of “RpRqC = CRrRs” (Rp, Rq, Rr, Rs is any suitable bond bonded to a carbon atom through a single bond). Is a structural unit of “—RpRqC—CRrRs—” formed by cleavage of the unsaturated double bond “C═C” of the group) by polymerization.

The structural unit (II) derived from the unsaturated carboxylic acid monomer (b) represented by the general formula (2) is specifically represented by the following formula.

  In the general formula (1) and the structural unit (I), Y represents an alkenyl group having 2 to 8 carbon atoms, preferably 2-methyl-2propenyl group, 3-methyl-butenyl group, 3-methyl-2 -Butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group.

In general formula (1) and structural unit (I), R ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms, preferably an oxyalkylene group having 2 to 8 carbon atoms. And more preferably an oxyalkylene group having 2 to 4 carbon atoms. When R ¹ O is any two or more selected from oxyethylene group, oxypropylene group, oxybutylene group, oxystyrene group, etc., the addition form of R ⁷ O is random addition or block addition. Any form such as alternate addition may be used. In order to secure a balance between hydrophilicity and hydrophobicity, it is preferable that the oxyalkylene group contains an oxyethylene group as an essential component, and more than 50 mol% of the entire oxyalkylene group is an oxyethylene group. Preferably, 90 mol% or more of the entire oxyalkylene group is more preferably an oxyethylene group, and 100 mol% of the entire oxyalkylene group is particularly preferably an oxyethylene group.

  In general formula (1) and structural unit (I), n represents the average added mole number of the oxyalkylene group represented by AO, and is 1 to 500, preferably 2 to 500, more preferably 5 It is -500, More preferably, it is 10-500, Most preferably, it is 15-500, Most preferably, it is 20-300.

In the general formula (1) and the structural unit (I), R ² represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. Examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms (an aliphatic alkyl group and an alicyclic alkyl group), an alkenyl group having 1 to 30 carbon atoms, and the number of carbon atoms. Examples thereof include an alkynyl group having 1 to 30 carbon atoms and an aromatic group having 6 to 30 carbon atoms. R ⁸ is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom or a carbon atom having 1 to 12 carbon atoms in that the effects of the present invention can be further exhibited. It is a hydrogen group, more preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In General Formula (2) and Structural Unit (II), R ^{3 to} R ⁵ are the same or different and each represents a hydrogen atom, a methyl group, or a — (CH ₂ ) _z COOM group. The — (CH ₂ ) _z COOM group may form an anhydride with the —COOX group or other — (CH ₂ ) _z COOM groups. z is an integer of 0-2.

  M represents a hydrogen atom, a monovalent metal atom, a divalent metal atom, an ammonium group, or an organic ammonium group.

  X represents a hydrogen atom, a methyl group, an ethyl group, a monovalent metal atom, a divalent metal atom, an ammonium group, or an organic ammonium group.

  Examples of the unsaturated carboxylic acid monomer (b) represented by the general formula (2) include monocarboxylic acid monomers such as (meth) acrylic acid and crotonic acid or salts thereof; maleic acid, And dicarboxylic acid monomers such as itaconic acid and fumaric acid or salts thereof; anhydrides of dicarboxylic acid monomers such as maleic acid, itaconic acid and fumaric acid or salts thereof; and the like. Examples of the salt herein include alkali metal salts, alkaline earth metal salts, ammonium salts, organic ammonium salts, and organic amine salts. Examples of the alkali metal salt include lithium salt, sodium salt, potassium salt and the like. Examples of alkaline earth metal salts include calcium salts and magnesium salts. Examples of the organic ammonium salt include methyl ammonium salt, ethyl ammonium salt, dimethyl ammonium salt, diethyl ammonium salt, trimethyl ammonium salt, and triethyl ammonium salt. Examples of organic amine salts include alkanolamine salts such as ethanolamine salts, diethanolamine salts, and triethanolamine salts.

  The unsaturated carboxylic acid monomer (b) represented by the general formula (2) is preferably (meth) acrylic acid, maleic acid, maleic anhydride in that the effects of the present invention can be further exhibited. More preferred are acrylic acid and methacrylic acid.

  The structural unit (II) derived from the unsaturated carboxylic acid monomer (b) represented by the general formula (2) and the unsaturated carboxylic acid monomer (b) represented by the general formula (2) There may be only 1 type, and 2 or more types may be sufficient as it.

  The total content of the structural unit (I) and the structural unit (II) in the polycarboxylic acid copolymer is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass. %, More preferably 80% by mass to 100% by mass, particularly preferably 90% by mass to 100% by mass, and most preferably 95% by mass to 100% by mass. If the total content of the structural unit (I) and the structural unit (II) in the polycarboxylic acid copolymer is within the above range, the long-term curability improvement effect of the hydraulic composition containing hydraulic cement As well as the amount of cement admixture such as polycarboxylic acid copolymer added can be further reduced.

  In the polycarboxylic acid copolymer, the content ratio of the structural unit (I), the content ratio of the structural unit (II), the total content ratio of the structural unit (I) and the structural unit (II), etc., for example, It can be known by various structural analyzes (for example, NMR) of the polycarboxylic acid copolymer. In addition, structural units derived from the various monomers calculated based on the amounts of the various monomers used when producing the polycarboxylic acid-based copolymer without performing the various structural analyzes as described above. In the polycarboxylic acid copolymer, the content ratio of the structural unit (I), the content ratio of the structural unit (II), and the total content ratio of the structural unit (I) and the structural unit (II) And so on. That is, the content ratio of the unsaturated polyalkylene glycol monomer (a) in all the monomer components used when producing the polycarboxylic acid copolymer, the unsaturated carboxylic acid monomer (b) The proportion of the total mass of the unsaturated polyalkylene glycol monomer (a) and the unsaturated carboxylic acid monomer (b) is the structural unit in the polycarboxylic acid copolymer. You may treat as the content rate of (I), the content rate of structural unit (II), the total content rate of structural unit (I), and structural unit (II).

  The polycarboxylic acid copolymer may contain a structural unit (III) derived from another monomer (c) in addition to the structural unit (I) and the structural unit (II).

  The monomer (c) is a monomer copolymerizable with the monomer (a) and the monomer (b). Only one type of monomer (c) may be used, or two or more types may be used.

  As the monomer (c), for example, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; unsaturated monomethyl such as methyl (meth) acrylate and glycidyl (meth) acrylate Esters of carboxylic acids and alcohols having 1 to 30 carbon atoms; various (alkoxy) (poly) alkylene glycol mono (meth) such as polyethylene glycol mono (meth) acrylate and methoxy (poly) ethylene glycol mono (meth) acrylate Acrylates; (anhydrous) half esters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and alcohols having 1 to 30 carbon atoms; (anhydrous) unsaturated such as maleic acid, fumaric acid and itaconic acid Dicarboxylic acids and carbon atoms 1 Diesters with 0 alcohol; half amides of the above unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms; diamides of the above unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms; Half esters of alkyl (poly) alkylene glycols obtained by adding 1 to 500 moles of alkylene oxides having 2 to 18 carbon atoms to amines and the above unsaturated dicarboxylic acids; Diesters of alkyl (poly) alkylene glycols having 1 to 500 moles of alkylene oxide added thereto and the above unsaturated dicarboxylic acids; the above unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or the number of moles of these glycols added Half esthetic with 2 to 500 polyalkylene glycols Diesters of the above unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or polyalkylene glycols having an addition mole number of these glycols of 2 to 500; maleamic acid and glycols having 2 to 18 carbon atoms or these Half-amides of polyalkylene glycols having an added mole number of glycol of 2 to 500; (poly) alkylene glycol di (meth) such as (poly) ethylene glycol di (meth) acrylate and (poly) propylene glycol di (meth) acrylate Acrylates; polyfunctional (meth) acrylates such as hexanediol di (meth) acrylate and trimethylolpropane tri (meth) acrylate; (poly) alkylene glycol dimaleates such as polyethylene glycol dimaleate; vinyl sulfonate, (meth T) Unsaturated sulfonic acids (salts) such as allyl sulfonate, 2-methylpropane sulfonic acid (meth) acrylamide, and styrene sulfonic acid; unsaturated monocarboxylic acids such as methyl (meth) acrylamide and those having 1 to 30 carbon atoms Amides with amines; Vinyl aromatics such as styrene, α-methylstyrene and vinyltoluene; Alkanediol mono (meth) acrylates such as 1,4-butanediol mono (meth) acrylate; Dienes such as butadiene and isoprene Unsaturated amides such as (meth) acrylic (alkyl) amide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide; Unsaturated cyanates such as (meth) acrylonitrile; Vinyl acetate Unsaturated esters; aminoethyl (meth) acrylate, (meth) acrylate Unsaturated amines such as dimethylaminoethyl and vinyl pyridine; divinyl aromatics such as divinylbenzene; allyls such as (meth) allyl alcohol and glycidyl (meth) allyl ether; (methoxy) polyethylene glycol monovinyl ether and the like Vinyl ethers; (meth) allyl ethers such as (methoxy) polyethylene glycol mono (meth) allyl ether; and the like.

  The content ratio of the structural unit (III) in the polycarboxylic acid copolymer can be known by, for example, various structural analyzes (for example, NMR) of the polycarboxylic acid copolymer. In addition, structural units derived from the various monomers calculated based on the amounts of the various monomers used when producing the polycarboxylic acid-based copolymer without performing the various structural analyzes as described above. The content ratio of the structural unit (III) in the polycarboxylic acid copolymer may be used as the content ratio. That is, the content ratio of the mass of the other monomer (c) in all the monomer components used when producing the polycarboxylic acid-based copolymer is changed to the structural unit (III in the polycarboxylic acid-based copolymer). ) Content ratio.

  The content ratio of the structural unit (I), the structural unit (II), and the structural unit (III) in the polycarboxylic acid-based copolymer is a mass ratio (% by mass), preferably (I) / (II). / (III) = 1 to 99/1 to 99/0 to 70, more preferably (I) / (II) / (III) = 50 to 99/1 to 50/0 to 49, Preferably, (I) / (II) / (III) = 55 to 98/2 to 45/0 to 40, and particularly preferably (I) / (II) / (III) = 60 to 97/3. -40 / 0-30.

  The mass average molecular weight (Mw) of the polycarboxylic acid copolymer is preferably 1000 to 500,000, and more preferably 5000 to 500,000 as the mass average molecular weight (Mw) in terms of polyethylene glycol by gel permeation chromatography (GPC). 300,000, more preferably 10,000 to 150,000. Since the mass average molecular weight (Mw) of the polycarboxylic acid copolymer is within the above range, the effect of improving the long-term curability of the hydraulic composition containing the hydraulic cement can be expressed more sufficiently. The amount of cement admixture such as polycarboxylic acid copolymer can be further reduced.

  The polycarboxylic acid copolymer can be produced by any appropriate method. The polycarboxylic acid copolymer is preferably a polymerization initiator for polymerizing a monomer component containing an unsaturated polyalkylene glycol monomer (a) and an unsaturated carboxylic acid monomer (b). It can be made in the presence.

  Unsaturated polyalkylene glycol monomer (a), unsaturated carboxylic acid monomer (b) that can be used in the production of the polycarboxylic acid copolymer, and other monomers (if necessary) The amount of c) used may be appropriately adjusted so that the proportion of structural units derived from each monomer in all structural units constituting the polycarboxylic acid copolymer is as described above. Preferably, as the polymerization reaction proceeds quantitatively, each monomer is added in the same proportion as the proportion of structural units derived from each monomer in all the structural units constituting the polycarboxylic acid copolymer described above. Use it.

  The unsaturated polyalkylene glycol monomer (a) can be synthesized by any appropriate method. For example, it can be synthesized by adding an alkylene oxide to an unsaturated alcohol such as allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol (isoprenol), hydroxyethyl vinyl ether, hydroxybutyl vinyl ether or the like.

  The polymerization of the monomer component can be performed by any appropriate method. Examples thereof include solution polymerization and bulk polymerization. Examples of the solution polymerization method include a batch method and a continuous method. Solvents that can be used for solution polymerization include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-hexane; esters such as ethyl acetate. Compounds; ketone compounds such as acetone and methyl ethyl ketone; cyclic ether compounds such as tetrahydrofuran and dioxane; and the like.

  When the monomer component is polymerized, a water-soluble polymerization initiator, for example, a persulfate such as ammonium persulfate, sodium persulfate, or potassium persulfate; hydrogen peroxide; 2,2′- Azoamidine compounds such as azobis-2-methylpropionamidine hydrochloride, cyclic azoamidine compounds such as 2,2′-azobis-2- (2-imidazolin-2-yl) propane hydrochloride, 2-carbamoylazoisobutyronitrile, etc. Water-soluble azo initiators such as azonitrile compounds of These polymerization initiators include alkali metal sulfites such as sodium hydrogen sulfite, metabisulfites, sodium hypophosphite, Fe (II) salts such as molle salts, sodium hydroxymethanesulfinate dihydrate, hydroxylamine hydrochloride Accelerators such as salt, thiourea, L-ascorbic acid (salt), and erythorbic acid (salt) can also be used in combination. Among the polymerization initiators, persulfate and hydrogen peroxide are preferable. Among the accelerators, Fe (II) salts such as molle salt and L-ascorbic acid (salt) are preferable. Each of these polymerization initiators and accelerators may be only one kind or two or more kinds.

  When performing solution polymerization using a lower alcohol, aromatic hydrocarbon, aliphatic hydrocarbon, ester compound, or ketone compound as a solvent, or when performing bulk polymerization, benzoyl peroxide, lauroyl peroxide may be used as a polymerization initiator. Peroxides such as oxide and sodium peroxide; hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; azo compounds such as azobisisobutyronitrile; When such a polymerization initiator is used, an accelerator such as an amine compound can be used in combination. Furthermore, when a water-lower alcohol mixed solvent is used, it can be appropriately selected from the above-mentioned various polymerization initiators or combinations of polymerization initiators and accelerators.

  The reaction temperature for the polymerization of the monomer component is appropriately determined depending on the polymerization method, solvent, polymerization initiator, and chain transfer agent used. The reaction temperature is preferably 0 ° C. or higher, more preferably 30 ° C. or higher, further preferably 50 ° C. or higher, preferably 150 ° C. or lower, more preferably 120 ° C. or lower. More preferably, it is 100 ° C. or lower.

  Any appropriate method can be adopted as a method of charging the monomer component into the reaction vessel.

  In the polymerization of the monomer component, a chain transfer agent can be preferably used. When a chain transfer agent is used, the molecular weight of the resulting copolymer can be easily adjusted. Only one type of chain transfer agent may be used, or two or more types may be used.

  Any appropriate chain transfer agent can be adopted as the chain transfer agent. Examples of such chain transfer agents include thiol chain transfer agents such as mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, and 2-mercaptoethanesulfonic acid; Secondary alcohols such as isopropanol; phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite, And lower salts of salts thereof (sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.) and salts thereof, etc. Is mentioned.

  The produced additive for hydraulic composition can be used as it is as the additive for hydraulic composition of the present invention, but from the viewpoint of handleability, the reaction solution after production of the additive for hydraulic composition is used. It is preferable to adjust the pH to 5 or more. However, in order to improve the polymerization rate, it is preferable to perform the polymerization at a pH of less than 5 and adjust the pH to 5 or more after the polymerization. The pH can be adjusted, for example, using an alkaline substance such as an inorganic salt such as monovalent metal or divalent metal hydroxide or carbonate; ammonia; organic amine;

  The manufactured additive for hydraulic composition can also adjust a density | concentration as needed with respect to the solution obtained by manufacture.

  The produced additive for hydraulic composition may be used as it is in the form of a solution, or may be used after powdered.

≪Concrete composition≫
The concrete composition of this invention contains the hydraulic composition containing a hydraulic cement, and the additive for hydraulic compositions of this invention.

  The concrete composition of the present invention preferably further contains water and aggregate. In addition, when using sand as an aggregate, it may be called a mortar composition.

  Any appropriate aggregate such as fine aggregate (sand, etc.) or coarse aggregate (crushed stone, etc.) can be adopted as the aggregate. Examples of such aggregates include gravel, crushed stone, granulated slag, and recycled aggregate. Examples of such aggregates include refractory aggregates such as siliceous, clay, zircon, high alumina, silicon carbide, graphite, chromic, chromic, and magnesia.

  The concrete composition of the present invention may contain other components. Examples of other components include a cement admixture and a cement dispersant.

  The cement admixture preferably comprises a cement admixture polymer.

  The cement admixture may contain any appropriate other component in addition to the cement admixture polymer as long as the effects of the present invention are not impaired.

  Examples of other components include a cement dispersant. When cement dispersant is used, the blending ratio of polymer for cement admixture and cement dispersant (cement admixture polymer / cement dispersant) is different in the type of cement dispersant used, blending conditions, test conditions, etc. Can set any appropriate blending ratio. The cement dispersant may be one kind or two or more kinds.

  Examples of the cement dispersant include a sulfonic acid-based dispersant having a sulfonic acid group in the molecule, and a polycarboxylic acid-based dispersant other than the polycarboxylic acid-based copolymer contained in the hydraulic composition additive of the present invention. Etc.

  Examples of the sulfonic acid-based dispersant include polyalkylaryl sulfonate-based sulfonic acid-based dispersants such as naphthalene sulfonic acid formaldehyde condensate, methyl naphthalene sulfonic acid formaldehyde condensate, anthracene sulfonic acid formaldehyde condensate; melamine sulfonic acid Melamine formalin sulfonate-based sulfonic acid dispersants such as formaldehyde condensates; Aromatic amino sulfonate-based sulfonic acid dispersants such as aminoaryl sulfonic acid-phenol-formaldehyde condensates; lignin sulfonates, Examples thereof include lignin sulfonate sulfonic acid dispersants such as modified lignin sulfonate; polystyrene sulfonate sulfonic acid dispersants;

  The cement admixture can contain any appropriate other cement additive (material) as long as the effects of the present invention are not impaired. Examples of such other cement additives (materials) include other cement additives (materials) exemplified in the following (1) to (12). The mixing ratio of the polymer for cement admixture that can be included in the cement admixture and such other cement additives (materials) is arbitrarily appropriate depending on the type and purpose of the other cement additives (materials) to be used. Various mixing ratios can be employed.

(1) Water-soluble polymer substances: nonionic cellulose ethers such as methylcellulose, ethylcellulose, carboxymethylcellulose; polysaccharides produced by microbial fermentation such as yeast glucan, xanthan gum, β-1.3 glucans; polyethylene glycol, etc. Polyoxyalkylene glycols; polyacrylamide and the like.

(2) Polymer emulsion: Copolymers of various vinyl monomers such as alkyl (meth) acrylate.

(3) Curing retarder: oxycarboxylic acid or salt thereof such as gluconic acid, glucoheptonic acid, alabonic acid, malic acid, citric acid; sugar and sugar alcohol; polyhydric alcohol such as glycerin; aminotri (methylenephosphonic acid) Phosphonic acid and its derivatives.

(4) Early strengthening agents / accelerators: soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide and calcium iodide; chlorides such as iron chloride and magnesium chloride; sulfates; potassium hydroxide; Sodium hydroxide; carbonate; thiosulfate; formate such as formic acid and calcium formate; alkanolamine; alumina cement; calcium aluminate silicate.

(5) Oxyalkylene-based antifoaming agent: polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; polyoxyalkylene alkyl ethers such as diethylene glycol heptyl ether; polyoxyalkylene acetylene ethers; ) Oxyalkylene fatty acid esters; polyoxyalkylene sorbitan fatty acid esters; polyoxyalkylene alkyl (aryl) ether sulfate salts; polyoxyalkylene alkyl phosphate esters; polyoxypropylene polyoxyethylene laurylamine (propylene oxide 1-20) Mole additions, ethylene oxide 1-20 mol adducts, etc.), fatty acid-derived amines obtained from cured beef tallow added with alkylene oxide (propylene oxide 1-20 mol) Additionally, polyoxyalkylene alkyl amines ethylene oxide 20 mol adduct) or the like; polyoxyalkylene amide.

(6) Antifoaming agents other than oxyalkylene type: Mineral oil type, fat type, fatty acid type, fatty acid ester type, alcohol type, amide type, phosphate ester type, metal soap type, silicone type and the like.

(7) AE agent: resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, ABS (alkylbenzene sulfonic acid), alkane sulfonate, polyoxyethylene alkyl (phenyl) ether, polyoxyethylene alkyl (phenyl) ether Sulfate ester or a salt thereof, polyoxyethylene alkyl (phenyl) ether phosphate ester or a salt thereof, protein material, alkenyl sulfosuccinic acid, α-olefin sulfonate and the like.

(8) Other surfactants: various anionic surfactants; various cationic surfactants such as alkyltrimethylammonium chloride; various nonionic surfactants; various amphoteric surfactants.

(9) Waterproofing agent: fatty acid (salt), fatty acid ester, fats and oils, silicon, paraffin, asphalt, wax and the like.

(10) Rust inhibitor: nitrite, phosphate, zinc oxide and the like.

(11) Crack reducing agent: polyoxyalkyl ether and the like.

(12) Expansion material: Ettlingite, coal, etc.

  Other known cement additives (materials) include cement wetting agents, thickeners, separation reducing agents, flocculants, drying shrinkage reducing agents, strength enhancers, self-leveling agents, colorants, fungicides, and the like. be able to. These known cement additives (materials) may be one kind or two or more kinds.

In the concrete composition and the mortar composition, any appropriate value can be set as the unit water amount per 1 m ³ , the usage amount of the hydraulic composition, and the (water / hydraulic composition) ratio. Such values, preferably, unit water is ^{50kg / m 3 ~200kg / m 3} , the amount of the hydraulic composition is ^{200kg / m 3 ~800kg / m 3} , ( water / hydraulic Composition) ratio (mass ratio) = 0.1 to 0.7, more preferably, the unit water amount is 100 kg / m ^{3 to} 185 kg / m ³ , and the usage amount of the hydraulic composition is 250 kg / m ^3. ˜600 kg / m ³ , (water / hydraulic composition) ratio (mass ratio) = 0.15 to 0.6.

  What is necessary is just to mix | blend a structural component by arbitrary appropriate methods and to adjust a concrete composition and a mortar composition. For example, the method etc. which knead | mix a structural component in a mixer are mentioned.

  In addition, in order to express the effect of the strength improver for hydraulic compositions of the present invention more, the components of the concrete composition and the mortar composition (hydraulic cement, pozzolanic substance, water, aggregate, etc.) It is also effective to adjust the usage ratio and unit amount of

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. Unless otherwise specified, the term “part” means mass part, and the term “%” means mass%.

<GPC analysis method>
The mass average molecular weight was measured under the following measurement conditions.
Device: Waters Alliance (2695)
Analysis software: Made by Waters, Empor2 Professional + GPC option column: Tosoh Co., Ltd., TSK guardcolumns SWXL (inner diameter: 6.0 mm × 40 mm) + TSKgel G4000SWXL (inner diameter: 7.8 mm × 300 mm) + G3000SWXL (inner diameter: 7.8 mm × 300 mm) ) + G2000SWXL (inner diameter: 7.8 mm × 300 mm)
Detector: differential refractometer (RI) detector (Waters 2414)
Eluent: A solution prepared by dissolving 115.6 g of sodium acetate trihydrate in a mixed solvent of 10999 g of ion-exchanged water and 6001 g of acetonitrile, and adjusting the pH to 6.0 with acetic acid.
Flow rate: 1 mL / min Column temperature: 40 ° C
Measurement time: 45 minutes Sample solution injection amount: 100 μL (eluent solution having a polymer concentration of 0.5% by mass)
GPC standard sample: polyethylene glycol manufactured by Tosoh Corporation, Mp = 300000, 200000, 107000, 44900, 30000, 20000, 11840, 6450, 4020, 1470
Calibration curve: Prepared by a cubic equation using the Mp value of polyethylene glycol.

<Making concrete>
In a bread-type concrete mixer, water, cement (ordinary Portland cement, made by Taiheiyo Cement), fly ash (fly ash type II, manufactured by Chubu Electric Power), coarse aggregate (Ome hard crushed stone, table Dry specific gravity = 2.65 g / cm ³ ), fine aggregate (Oikawa land sand, surface dry specific gravity = 2.62 g / cm ³ ), and strength improvers for hydraulic compositions shown in Tables 2 to 5 The concrete was prepared by kneading for 90 seconds. The addition amount of the polycarboxylic acid copolymer was adjusted so that the flow value was 400 ± 20 mm.
The amount of air was adjusted to be less than 2.0% by adding Adecanol LG-299 (manufactured by Adeka) as an antifoaming agent.
The flow and 28-day compressive strength of the obtained concrete were measured according to JIS A 1150 and JIS A 1108, respectively.

<Strength improvement rate>
In the same concrete blend, the compressive strength of the specimen is not included in the strength improver contained in the hydraulic composition additive of the present invention (only the hydraulic material dispersant containing the polycarboxylic acid copolymer). As a reference, the strength improvement rate when the hydraulic composition additive containing the strength improver of the present invention was used was determined by the following formula.
Strength improvement rate (%) = [(compressive strength of specimen using additive containing strength improver) / (compressive strength of specimen using additive not containing strength improver)] × 100-100

[Production Example 1]
In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser, water 231.5 g, 3-methyl-3-buten-1-ol ethylene oxide 50 mol adduct 552.9 g Then, 4.7 g of acrylic acid was charged, the inside of the reaction vessel was purged with nitrogen under stirring, the temperature was raised to 58 ° C. in a nitrogen atmosphere, and 44.6 g of 2% aqueous hydrogen peroxide was added. After the temperature was stabilized at 58 ° C., an aqueous solution in which 42.4 g of acrylic acid was dissolved in 17.5 g of water was added dropwise over 3 hours. At the same time when the acrylic acid aqueous solution was started to be dropped, an aqueous solution prepared by dissolving 1.2 g of L-ascorbic acid and 2.0 g of 2-mercaptopropionic acid in 93.3 g of water was dropped over 3.5 hours. Thereafter, the temperature was continuously maintained at 58 ° C. for 1 hour to complete the polymerization reaction. After cooling, the pH was neutralized to 6 with a 30% aqueous NaOH solution.
When the GPC measurement of the obtained polycarboxylic acid-type copolymer (1) was performed, the mass mean molecular weight was 35000.

[Production Example 2]
In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser, 231.5 g of water, 575.0 g of an ethylene oxide 100 mol adduct of 2-methyl-2-propen-1-ol. Then, 2.5 g of acrylic acid was charged, the inside of the reaction vessel was purged with nitrogen under stirring, the temperature was raised to 58 ° C. in a nitrogen atmosphere, and then 44.6 g of 2% hydrogen peroxide water was added. After the temperature was stabilized at 58 ° C., an aqueous solution in which 22.5 g of acrylic acid was dissolved in 17.5 g of water was added dropwise over 3 hours. At the same time as the dropwise addition of the acrylic acid aqueous solution, an aqueous solution prepared by dissolving 1.2 g of L-ascorbic acid and 3.0 g of 2-mercaptopropionic acid in 93.3 g of water was dropped over 3.5 hours. Thereafter, the temperature was continuously maintained at 58 ° C. for 1 hour to complete the polymerization reaction. After cooling, the pH was neutralized to 6 with a 30% aqueous NaOH solution.
When the GPC measurement of the obtained polycarboxylic acid-type copolymer (2) was performed, the mass mean molecular weight was 47000.

[Production Example 3]
A glass reaction vessel equipped with a thermometer, a stirrer, a dripping device, a nitrogen inlet tube, and a reflux condenser was charged with 300 g of water, the inside of the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. .
Next, 204 g of methoxypolyethylene glycol monomethacrylate (NK ester M-450G, manufactured by Shin-Nakamura Chemical Co., Ltd.), 36 g of methacrylic acid, and 0.90 g of 3-mercaptopropionic acid were dissolved in 50.0 g of water.
The obtained aqueous monomer solution was added dropwise over 4 hours. At the same time as the dropping of the monomer aqueous solution, an aqueous solution in which 2.8 g of ammonium persulfate was dissolved in 50.0 g of water was dropped over 5 hours. Thereafter, the temperature was continuously maintained at 80 ° C. for 1 hour to complete the polymerization reaction. After cooling, the pH was neutralized to 6 with a 30% aqueous NaOH solution.
When the GPC measurement of the obtained polycarboxylic acid-type copolymer (3) was performed, the mass mean molecular weight was 29000.

[Production Example 4]
A glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube and a reflux condenser was charged with 150.0 g of water, and the inside of the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 58 ° C. under a nitrogen atmosphere After raising the temperature, 35.0 g of 5% hydrogen peroxide water was added.
After the temperature was stabilized at 58 ° C., an aqueous solution in which 200.0 g of acrylic acid was dissolved in 30.0 g of water was added dropwise over 3 hours. At the same time as the dropwise addition of the acrylic acid aqueous solution, an aqueous solution in which 2.0 g of L-ascorbic acid and 8.0 g of 2-mercaptopropionic acid were dissolved in 60.0 g of water was dropped over 3.5 hours. Thereafter, the temperature was continuously maintained at 58 ° C. for 1 hour to complete the polymerization reaction. After cooling, the pH was neutralized to 6 with a 30% aqueous NaOH solution.
When the GPC measurement of the obtained polyacrylic acid (1) was performed, the mass mean molecular weight was 11000.

[Production Examples 5 to 8]
Except having changed the quantity of 2-mercaptopropionic acid to be used into the quantity indicated in Table 2, operation similar to manufacture example 4 was performed, and polyacrylic acid (2)-(5) was obtained.

[Example 1]
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (1) obtained in Production Example 4 are blended, and an additive for hydraulic composition. (1) was obtained.
Various evaluation was performed using the additive (1) for hydraulic compositions. The results are shown in Table 3.

[Example 2]
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (1) obtained in Production Example 4 are blended, and an additive for hydraulic composition. (2) was obtained.
Various evaluations were performed using the additive for hydraulic composition (2). The results are shown in Table 3.

Example 3
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (2) obtained in Production Example 5 are blended, and an additive for hydraulic composition. (3) was obtained.
Various evaluation was performed using the additive (3) for hydraulic compositions. The results are shown in Table 3.

Example 4
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (3) obtained in Production Example 6 were blended, and an additive for hydraulic composition. (4) was obtained.
Various evaluation was performed using the additive (4) for hydraulic compositions. The results are shown in Table 3.

Example 5
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (4) obtained in Production Example 7 are blended, and an additive for hydraulic composition. (5) was obtained.
Various evaluation was performed using the additive (5) for hydraulic compositions. The results are shown in Table 3.

Example 6
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (4) obtained in Production Example 7 are blended, and an additive for hydraulic composition. (6) was obtained.
Various evaluation was performed using the additive (6) for hydraulic compositions. The results are shown in Table 3.

Example 7
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (5) obtained in Production Example 8 were blended, and an additive for hydraulic composition. (7) was obtained.
Various evaluation was performed using the additive (7) for hydraulic compositions. The results are shown in Table 3.

[Comparative Example 1]
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 was used as the additive for hydraulic composition (C1).
Various evaluation was performed using the additive for hydraulic compositions (C1). The results are shown in Table 3.

[Comparative Example 2]
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and calcium nitrite were blended to obtain an additive for hydraulic composition (C2).
Various evaluations were performed using the additive for hydraulic composition (C2). The results are shown in Table 3.

[Comparative Example 3]
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and triethanolamine were blended to obtain an additive for hydraulic composition (C3).
Various evaluation was performed using the additive for hydraulic compositions (C3). The results are shown in Table 3.

  As shown in Table 3, compared with Comparative Example 1 in which the polycarboxylic acid copolymer (1) was used as the hydraulic composition additive (C1), the polycarboxylic acid copolymer (1) was polyacrylic. In Example 1-7 which added the acid (salt), it turns out that the long-term curability improvement effect of the hydraulic composition containing a hydraulic cement can fully be expressed. On the other hand, in Comparative Example 2 in which calcium nitrite was added to the polycarboxylic acid copolymer (1), the long-term curability improvement effect of the hydraulic composition containing hydraulic cement was hardly expressed. In Comparative Example 3 in which triethanolamine was added to the carboxylic acid copolymer (1), the long-term curability improving effect of the hydraulic composition containing the hydraulic cement was lower than that in Comparative Example 1. Recognize.

Example 8
As shown in Table 4, the polycarboxylic acid copolymer (2) obtained in Production Example 2 and the polyacrylic acid (4) obtained in Production Example 7 are blended, and an additive for hydraulic composition. (8) was obtained.
Various evaluation was performed using the additive (8) for hydraulic compositions. The results are shown in Table 4.

Example 9
As shown in Table 4, the polycarboxylic acid copolymer (2) obtained in Production Example 2 and the polyacrylic acid (5) obtained in Production Example 8 were blended, and an additive for hydraulic composition. (9) was obtained.
Various evaluation was performed using the additive (9) for hydraulic compositions. The results are shown in Table 4.

[Comparative Example 4]
As shown in Table 4, the polycarboxylic acid copolymer (2) obtained in Production Example 2 was used as the additive for hydraulic composition (C4).
Various evaluations were performed using the additive for hydraulic composition (C4). The results are shown in Table 4.

  As shown in Table 4, compared to Comparative Example 4 in which the polycarboxylic acid copolymer (2) was used as the hydraulic composition additive (C4), the polycarboxylic acid copolymer (2) was polyacrylic. In Examples 8 and 9 to which an acid (salt) was added, it can be seen that the effect of improving the long-term curability of the hydraulic composition containing the hydraulic cement can be sufficiently exhibited.

Example 10
As shown in Table 5, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (1) obtained in Production Example 4 are blended, and an additive for hydraulic composition. (10) was obtained.
Various evaluation was performed using the additive (10) for hydraulic compositions. The results are shown in Table 5.

Example 11
As shown in Table 5, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (4) obtained in Production Example 7 are blended, and an additive for hydraulic composition. (11) was obtained.
Various evaluation was performed using the additive for hydraulic compositions (11). The results are shown in Table 5.

Example 12
As shown in Table 5, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (5) obtained in Production Example 8 are blended, and an additive for hydraulic composition. (12) was obtained.
Various evaluation was performed using the additive for hydraulic compositions (12). The results are shown in Table 5.

[Comparative Example 5]
As shown in Table 5, the polycarboxylic acid copolymer (1) obtained in Production Example 1 was used as an additive for hydraulic composition (C5).
Various evaluation was performed using the additive for hydraulic compositions (C5). The results are shown in Table 5.

  As shown in Table 5, the polycarboxylic acid copolymer (1) is added to the hydraulic composition additive (C5) even for the hydraulic composition in which the pozzolanic substance is reduced as in the case of the concrete composition 2. In Examples 10-12 in which polyacrylic acid (salt) was added to the polycarboxylic acid copolymer (1) as compared to Comparative Example 5 described above, the long-term curing of the hydraulic composition containing hydraulic cement It can be seen that the effect of improving the property can be sufficiently exhibited.

[Comparative Example 6]
As shown in Table 6, the polycarboxylic acid copolymer (3) obtained in Production Example 3 and the polyacrylic acid (4) obtained in Production Example 7 were blended, and an additive for hydraulic composition. (C6) was obtained.
Various evaluation was performed using the additive for hydraulic compositions (C6). The results are shown in Table 6.

[Comparative Example 7]
As shown in Table 6, the polycarboxylic acid copolymer (3) obtained in Production Example 3 and the polyacrylic acid (5) obtained in Production Example 8 were blended, and an additive for hydraulic composition. (C7) was obtained.
Various evaluation was performed using the additive for hydraulic compositions (C7). The results are shown in Table 6.

  As shown in Table 6, the structural unit (I) derived from the unsaturated polyalkylene glycol monomer (a) represented by the general formula (1) and the unsaturated carboxylic acid system represented by the general formula (2) In Comparative Examples 6 and 7 using the additive for a hydraulic composition not containing a polycarboxylic acid-based copolymer containing the structural unit (II) derived from the monomer (b), it is represented by the general formula (1). The structural unit (I) derived from the unsaturated polyalkylene glycol monomer (a) and the structural unit (II) derived from the unsaturated carboxylic acid monomer (b) represented by the general formula (2) Polycarboxylic acid having a flow value of 400 ± 20 mm as compared with Examples 5, 7, 8 and 9 using the corresponding additive for hydraulic composition containing polycarboxylic acid-based copolymer containing It can be seen that the amount of the copolymer added is large and the economy is poor.

The additive for hydraulic compositions of the present invention can be suitably used as a material for concrete compositions such as cement paste, mortar, and concrete.

Claims (9)

An additive for a hydraulic composition containing hydraulic cement,
Derived from the structural unit (I) derived from the unsaturated polyalkylene glycol monomer (a) represented by the general formula (1) and the unsaturated carboxylic acid monomer (b) represented by the general formula (2) A hydraulic material dispersant containing a polycarboxylic acid-based copolymer containing the structural unit (II), and a strength improver containing polyacrylic acid (salt).
Additive for hydraulic composition.
YO— (R ¹ O) _n —R ² (1)
(In General Formula (1), Y represents an alkenyl group having 2 to 8 carbon atoms, R ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms, and n represents R ¹ O. The average addition mole number of the oxyalkylene group represented by the formula (1), n is 1 to 500, and R ² represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.)

(In General Formula (2), R ^{3 to} R ⁵ are the same or different and each represents a hydrogen atom, a methyl group, or — (CH ₂ ) _z COOM group, and — (CH ₂ ) _z COOM group represents a —COOX group. Or other — (CH ₂ ) _z COOM group may form an anhydride, z is an integer of 0 to 2, M is a hydrogen atom, alkali metal, alkaline earth metal, ammonium group, organic An ammonium group or an organic amine group is represented, and X represents a hydrogen atom, a methyl group, an ethyl group, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.)   Y in the general formula (1) is 2-methyl-2-propenyl group, 3-methyl-3-butenyl group, 3-methyl-2-butenyl group, 2-methyl-2-butenyl group, 2-methyl The additive for hydraulic compositions according to claim 1, which is any one of -3-butenyl groups.   The additive for hydraulic compositions according to claim 1 or 2, wherein the hydraulic composition contains a pozzolanic substance.   The additive for a hydraulic composition according to claim 3, wherein a content ratio of the pozzolanic substance relative to a total amount of the hydraulic cement and the pozzolanic substance in the hydraulic composition is greater than 30% by mass.   The additive for hydraulic compositions according to claim 3 or 4, wherein the pozzolanic substance contains fly ash.   The concrete composition containing the hydraulic composition containing a hydraulic cement and the additive for hydraulic compositions in any one of Claim 1-5.   The concrete composition according to claim 6, wherein the hydraulic composition includes a pozzolanic substance.   The concrete composition according to claim 7, wherein a content ratio of the pozzolanic substance to a total amount of the hydraulic cement and the pozzolanic substance in the hydraulic composition is greater than 30% by mass. The concrete composition according to claim 7 or 8, wherein the pozzolanic substance includes fly ash.