JP2017160075A - Strength improving agent for pozzolan substance-containing hydraulic composition, additive for pozzolan substance-containing hydraulic composition, and concrete composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a strength improving agent for pozzolan substance-containing hydraulic composition and an additive for pozzolan substance-containing hydraulic composition which can sufficiently exhibit a long-term curability improvement effect of a hydraulic composition containing hydraulic cement and a pozzolan substance, and to provide a concrete composition containing the strength improving agent for pozzolan substance-containing hydraulic composition and the additive for pozzolan substance-containing hydraulic composition.SOLUTION: There is provided a strength improving agent for pozzolan substance-containing hydraulic composition being a strength improving agent for hydraulic composition containing hydraulic cement and a pozzolan substance, the composition containing at least one selected from a polyacrylic acid (salt), a polyphosphoric acid (salt) and a phosphoric acid-containing copolymer (salt). An additive for pozzolan substance-containing hydraulic composition being an additive for hydraulic composition containing hydraulic cement and a pozzolan substance contains a hydraulic material dispersant containing at least one selected from a sulfonic acid-based dispersant and a polycarboxylic-based copolymer, and a strength improving agent for pozzolan substance-containing hydraulic composition contains at least one selected from a polyacrylic acid (salt), a polyphosphoric acid (salt) and a phosphoric acid-containing copolymer (salt).SELECTED DRAWING: None

Description

  The present invention relates to a strength improving agent for a pozzolanic substance-containing hydraulic composition, an additive for a pozzolanic substance-containing 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.

  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. Substitutionally substituted pozzolanic substance-containing hydraulic compositions have attracted attention (for example, Patent Documents 1 and 2).

  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.

JP 2002-226245 A JP 2010-132547 A

  An object of the present invention is to provide a strength improving agent for a pozzolanic substance-containing hydraulic composition and a pozzolanic substance capable of sufficiently expressing the long-term curability improving effect of the hydraulic composition containing the hydraulic cement and the pozzolanic substance. It is providing the additive for containing hydraulic compositions. Another object of the present invention is to provide a concrete composition containing such a pozzolanic substance-containing hydraulic composition strength improver and a pozzolanic substance-containing hydraulic composition additive.

The strength improver for a pozzolanic substance-containing hydraulic composition of the present invention is:
A strength improving agent for a hydraulic composition containing a hydraulic cement and a pozzolanic substance,
It contains at least one selected from polyacrylic acid (salt), polyphosphoric acid (salt), and phosphoric acid group-containing copolymer (salt).

  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 additive for the pozzolanic substance-containing hydraulic composition of the present invention,
An additive for a hydraulic composition containing a hydraulic cement and a pozzolanic substance,
A hydraulic material dispersant containing at least one selected from a sulfonic acid-based dispersant and a polycarboxylic acid-based copolymer;
A strength improving agent for a pozzolanic substance-containing hydraulic composition containing at least one selected from polyacrylic acid (salt), polyphosphoric acid (salt), and a phosphoric acid group-containing copolymer (salt);
including.

（一般式（１）中、Ｒ^１およびＲ^２は、同一または異なって、水素原子またはメチル基を表し、Ｒ^３は、水素原子または炭素原子数１〜３０の炭化水素基を表し、ＡＯは、炭素原子数２〜１８のオキシアルキレン基を表し、ｎは、ＡＯで表されるオキシアルキレン基の平均付加モル数を表し、ｎは１〜５００の数であり、ｘは０〜２の整数であり、ｙは０または１である。）

（一般式（２）中、Ｒ^４〜Ｒ^６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。） In one embodiment, the hydraulic material dispersant is 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). It is a polycarboxylic acid type copolymer containing the structural unit (II) derived from the unsaturated carboxylic acid type monomer (b) represented.

(In General Formula (1), R ¹ and R ² are the same or different and each represents a hydrogen atom or a methyl group; R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms; Represents an oxyalkylene group having 2 to 18 carbon atoms, n represents the average number of added moles of the oxyalkylene group represented by AO, n is a number from 1 to 500, and x is an integer from 0 to 2 And y is 0 or 1.)

(In general formula (2), R ^{4 to} R ⁶ 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, the unsaturated polyalkylene glycol monomer (a) represented by the general formula (1) is an unsaturated polyalkylene glycol monomer (a) represented by the general formula (3). c).
YO— (R ⁷ O) _n —R ⁸ (3)
(In General Formula (3), Y represents an alkenyl group having 2 to 8 carbon atoms, R ⁷ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms, and n represents R ⁷ O. The average addition mole number of the oxyalkylene group represented by the formula (1), n is 1 to 500, and R ⁸ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.)

  In one embodiment, Y in the general formula (3) 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 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 the present invention comprises:
A hydraulic composition containing a hydraulic cement and a pozzolanic substance, and a strength improving agent for a pozzolanic substance-containing hydraulic composition of the present invention are included.

  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 the present invention comprises:
The hydraulic composition containing a hydraulic cement and a pozzolanic substance and the additive for the pozzolanic substance-containing hydraulic composition of the present invention are included.

  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.

  According to the present invention, a strength improving agent for a pozzolanic substance-containing hydraulic composition and a pozzolanic substance capable of sufficiently expressing the long-term curability improving effect of the hydraulic composition containing the hydraulic cement and the pozzolanic substance. An additive for containing hydraulic composition can be provided. Moreover, the concrete composition containing the strength improvement agent for such pozzolanic substance-containing hydraulic compositions and the additive for pozzolanic substance-containing 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., when the salt form is employed (for example, carboxylate), the calculation is performed assuming that the salt form is not employed. I decided to. For example, in the case of sodium acrylate, it is calculated as acrylic acid.

  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, the pozzolanic substance-containing hydraulic composition is a hydraulic composition containing hydraulic cement and a pozzolanic substance, and the content ratio of the pozzolanic substance to the total amount of the hydraulic cement and the pozzolanic substance is It is preferably greater than 30% by mass, more preferably 31% by mass to 90% by mass, even more preferably 33% by mass to 80% by mass, and particularly preferably 35% by mass to 70% by mass. 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, it is possible to achieve a greater cost reduction and a more sufficient environmental load reduction of the hydraulic cement.

  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, and still more preferably. It is 90% by mass to 100% by mass, particularly preferably 95% by mass to 100% by mass, and most preferably substantially 100% by mass.

≪Strength improver for hydraulic composition containing pozzolanic substances≫
The strength improving agent for a pozzolanic substance-containing hydraulic composition of the present invention contains at least one selected from polyacrylic acid (salt), polyphosphoric acid (salt), and phosphoric acid group-containing copolymer (salt).

  The strength improving agent for a pozzolanic substance-containing hydraulic composition of the present invention exhibits a compressive strength improving effect of 3% or more in evaluation of <strength improvement rate> described later, more preferably 4% or more. It shows a strength improvement effect, and more preferably shows a compression strength improvement effect of 5% or more.

  The content ratio of at least one selected from polyacrylic acid (salt), polyphosphoric acid (salt), and phosphoric acid group-containing copolymer (salt) in the strength improving agent for a pozzolanic substance-containing hydraulic composition of the present invention. Is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, still more preferably 90% by mass to 100% by mass, and particularly preferably 95% by mass to 100% by mass. And most preferably substantially 100% by weight.

  By including at least one selected from the group consisting of polyacrylic acid (salt), polyphosphoric acid (salt), and phosphoric acid group-containing copolymer (salt), the strength improving agent for a pozzolanic substance-containing hydraulic composition of the present invention. The long-term curability improving effect of the hydraulic composition containing the hydraulic cement and the pozzolanic substance can be sufficiently expressed.

  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.

  Only one type of polyacrylic acid (salt) may be used, or two or more types may be used.

  The polyphosphoric acid (salt) is a polymer having a structural unit derived from polyphosphoric acid and / or a salt thereof, and is typically a polymer having a structure in which phosphoric acid is bound by condensation. Arbitrary appropriate structure can be employ | adopted for the structure of polyphosphoric acid (salt), for example, a linear form, a branched form may be sufficient, and a cyclic | annular form may be sufficient. Examples of polyphosphoric acid include pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, pentapolyphosphoric acid, hexametaphosphoric acid, cyclic metaphosphoric acid, and ultraphosphoric acid. Examples of the salt include sodium salt, potassium salt, calcium salt and the like.

  Only 1 type may be sufficient as polyphosphoric acid (salt), and 2 or more types may be sufficient as it.

  The phosphate group-containing copolymer (salt) is a copolymer having a structural unit derived from a monomer having a phosphate group and / or a salt thereof, and a monomer having a phosphate group and / or a salt thereof. Is a copolymer obtained by copolymerizing a monomer component containing as an essential component.

  Only one type of phosphate group-containing copolymer (salt) may be used, or two or more types may be used.

  Monomers having a phosphate group and / or a salt thereof include phosphoric acid mono- (2-hydroxyethyl) acrylate, phosphoric acid mono- (2-hydroxyethyl) methacrylate, and phosphoric acid di- (2-hydroxyethyl). Acrylate, phosphoric acid di- (2-hydroxyethyl) methacrylate, phosphoric acid mono- (polyalkylene glycol) acrylate, phosphoric acid mono- (polyalkylene glycol) methacrylate, phosphoric acid di- (polyalkylene glycol) ) Acrylate, di- (polyalkylene glycol) methacrylate, vinyl phosphonic acid, and salts thereof. The monomer having a phosphate group and / or a salt thereof may be only one type or two or more types.

  In the phosphoric acid group-containing copolymer (salt), the content ratio of the monomer having a phosphoric acid group and / or a salt thereof is preferably 1 mol% to 100 mol%, more preferably 5 mol% to 90 mol%. It is mol%, More preferably, it is 10 mol%-80 mol%, Most preferably, it is 20 mol%-70 mol%.

  In the strength improving agent for a pozzolanic substance-containing hydraulic composition of the present invention, the amount used is at least one selected from polyacrylic acid (salt), polyphosphoric acid (salt), and phosphoric acid group-containing copolymer (salt). The amount is preferably 0.001 parts by mass to 5 parts by mass, more preferably 0.005 parts by mass to 3 parts by mass, and still more preferably 0.01 parts by mass to 100 parts by mass of the hydraulic composition. 1 part by mass. The use amount of at least one selected from polyacrylic acid (salt), polyphosphoric acid (salt), and phosphoric acid group-containing copolymer (salt) in the strength improving agent for a pozzolanic substance-containing hydraulic composition of the present invention is If it exists in the said range, the long-term curability improvement effect of the hydraulic composition containing a hydraulic cement and a pozzolanic substance can fully be expressed.

  The strength improving agent for a pozzolanic substance-containing hydraulic composition can be used as it is as the strength improving agent for a pozzolanic substance-containing hydraulic composition of the present invention, but from the viewpoint of handleability, the pozzolanic substance-containing hydraulic property It is preferable to adjust the pH of the composition strength improver solution 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 strength improver for a pozzolanic substance-containing hydraulic composition can be subjected to concentration adjustment, if necessary, with respect to the solution obtained by production.

  The strength improving agent for a pozzolanic substance-containing hydraulic composition may be used as it is in the form of a solution, or may be used in the form of powder.

≪Additive for hydraulic composition containing pozzolanic substances≫
The additive for a pozzolanic substance-containing hydraulic composition of the present invention includes a hydraulic material dispersant containing at least one selected from a sulfonic acid-based dispersant and a polycarboxylic acid-based copolymer, and polyacrylic acid (salt). And a strength improving agent for a pozzolanic substance-containing hydraulic composition containing at least one selected from polyphosphoric acid (salt) and a phosphoric acid group-containing copolymer (salt).

  The strength improving agent for a pozzolanic substance-containing hydraulic composition containing at least one selected from polyacrylic acid (salt), polyphosphoric acid (salt), and a phosphoric acid group-containing copolymer (salt) has been described above. Street.

  The content ratio of at least one selected from a sulfonic acid-based dispersant and a polycarboxylic acid-based copolymer in the hydraulic material dispersant contained in the additive for a pozzolanic substance-containing hydraulic composition of the present invention is preferably Is 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, still more preferably 90% by mass to 100% by mass, and particularly preferably 95% by mass to 100% by mass, Most preferably, it is substantially 100% by mass.

  In the additive for a pozzolanic substance-containing hydraulic composition of the present invention, at least one amount selected from a sulfonic acid-based dispersant and a polycarboxylic acid-based copolymer is used with respect to 100 parts by mass of the hydraulic composition. Preferably, it is 0.01 mass part-10 mass parts, More preferably, it is 0.02 mass part-5 mass parts, More preferably, it is 0.05 mass part-3 mass parts. If the use amount of at least one selected from a sulfonic acid-based dispersant and a polycarboxylic acid-based copolymer in the additive for a pozzolanic substance-containing hydraulic composition of the present invention is within the above range, the hydraulic cement and The effect of improving the long-term curability of the hydraulic composition containing the pozzolanic substance can be expressed more sufficiently.

<Sulphonic acid-based dispersant>
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 and 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;

  Only one type of sulfonic acid dispersant may be used, or two or more types may be used.

<Polycarboxylic acid copolymer>
The polycarboxylic acid copolymer is preferably 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 an unsaturated carboxylic acid monomer (b).

The structural unit (I) derived from the unsaturated polyalkylene glycol monomer (a) represented by the general formula (1) is specifically represented by the following formula.

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 general formula (1) and structural unit (I), R ¹ and R ² are the same or different and each represents a hydrogen atom or a methyl group.

In the general formula (1) and the structural unit (I), R ³ 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 ³ 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 (1) and structural unit (I), AO is the same or different and is an oxyalkylene group having 2 to 18 carbon atoms, preferably an oxyalkylene group having 2 to 8 carbon atoms, and more An oxyalkylene group having 2 to 4 carbon atoms is preferred. When AO is any two or more selected from oxyethylene group, oxypropylene group, oxybutylene group, oxystyrene group, etc., the addition form of AO is random addition, block addition, alternating addition, etc. Either form may be sufficient. 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 general formula (1) and structural unit (I), x is an integer of 0-2.

  In the general formula (1) and the structural unit (I), y is 0 or 1.

  As the unsaturated polyalkylene glycol monomer (a) represented by the general formula (1), for example, an alkylene oxide having 2 to 18 carbon atoms is added to a saturated aliphatic alcohol having 1 to 20 carbon atoms. Obtained by polymerizing an alkylene oxide having 2 to 18 carbon atoms with an ester of an alkoxypolyalkylene glycol obtained by this method and (meth) acrylic acid or crotonic acid; a saturated aliphatic alcohol having 1 to 20 carbon atoms Esterified products of polyalkylene glycols and (meth) acrylic acid or crotonic acid; C 3-20 unsaturated aliphatic alcohols such as (meth) allyl alcohol, crotyl alcohol, oleyl alcohol, etc. Alkoxypolyalkylene glycos obtained by adding 2 to 8 alkylene oxides And an esterified product of (meth) acrylic acid or crotonic acid; unsaturated aliphatic alcohols having 3 to 20 carbon atoms such as (meth) allyl alcohol, crotyl alcohol and oleyl alcohol; Esterified product of polyalkylene glycols obtained by polymerizing alkylene oxide and (meth) acrylic acid or crotonic acid; alicyclic alcohols having 3 to 20 carbon atoms such as cyclohexanol; An esterified product of an alkoxypolyalkylene glycol obtained by adding an alkylene oxide and (meth) acrylic acid or crotonic acid; an alicyclic alcohol having 3 to 20 carbon atoms such as cyclohexanol; Polyalkylene glycols obtained by polymerizing 18 alkylene oxides , Esterified products with (meth) acrylic acid or crotonic acid; alkoxypolyalkylene glycols obtained by adding alkylene oxides having 2 to 18 carbon atoms to aromatic alcohols having 6 to 20 carbon atoms; ) Esterified product of acrylic acid or crotonic acid; polyalkylene glycol obtained by polymerizing alkylene oxide having 2 to 18 carbon atoms to aromatic alcohol having 6 to 20 carbon atoms, and (meth) acrylic acid or croton Esterified products with acids; and the like.

  Specific examples of the unsaturated polyalkylene glycol ether monomer (a) include methoxy polyethylene glycol monoallyl ether, polyethylene glycol monomethallyl ether, polyethylene glycol mono (3-methyl-3-butenyl) ether, Polyethylene glycol mono (3-methyl-2-butenyl) ether, polyethylene glycol mono (2-methyl-3-butenyl) ether, polyethylene glycol mono (2-methyl-2-butenyl) ether, polyethylene glycol mono (1,1- Dimethyl-2-propenyl) ether, polyethylene polypropylene glycol mono (3-methyl-3-butenyl) ether, methoxypolyethylene glycol mono (3-methyl-3-butenyl) ether, ethoxypoly Tylene glycol mono (3-methyl-3-butenyl) ether, 1-propoxypolyethylene glycol mono (3-methyl-3-butenyl) ether, cyclohexyloxypolyethylene glycol mono (3-methyl-3-butenyl) ether, 1-octyl Oxypolyethylene glycol mono (3-methyl-3-butenyl) ether, nonylalkoxypolyethyleneglycol mono (3-methyl-3-butenyl) ether, laurylalkoxypolyethyleneglycolmono (3-methyl-3-butenyl) ether, stearylalkoxypolyethyleneglycol Mono (3-methyl-3-butenyl) ether, phenoxypolyethylene glycol mono (3-methyl-3-butenyl) ether, naphthoxypolyethylene glycol mono (3-methyl Le-3-butenyl) such as ether.

  The unsaturated polyalkylene glycol monomer (a) is preferably an ester of an alkoxy polyalkylene glycol of (meth) acrylic acid; vinyl alcohol, (meth), because the effects of the present invention can be further exhibited. Allyl alcohol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-2-buten-1-ol And a compound obtained by adding 1 to 500 mol of alkylene oxide to any one of 2-methyl-3-buten-1-ol, and more preferably, alkylene oxide is added to 3-methyl-3-buten-1-ol. It is a compound added with 1 mol to 500 mol.

  Unsaturated polyalkylene glycol monomer (a) represented by general formula (1), structural unit (I) derived from unsaturated polyalkylene glycol monomer (a) represented by general formula (1) 1 type may be sufficient and 2 or more types may be sufficient.

The unsaturated polyalkylene glycol monomer (a) represented by the general formula (1) is preferably an unsaturated polyalkylene glycol monomer (c) represented by the general formula (3).
YO— (R ⁷ O) _n —R ⁸ (3)

  In the general formula (3), Y represents an alkenyl group having 2 to 8 carbon atoms, preferably a 2-methyl-2-propenyl group, a 3-methyl-3-butenyl group, or a 3-methyl-2-butenyl group. 2-methyl-2-butenyl group and 2-methyl-3-butenyl group.

In the general formula (3), R ⁷ 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, more preferably a carbon atom. It is an oxyalkylene group of formula 2-4. When R ⁷ 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 (3), n represents the average addition mole number of the oxyalkylene group represented by R < ⁷ > O, is 1-500, Preferably it is 2-500, More preferably, it is 5-500. More preferably, it is 10-500, Most preferably, it is 15-500, Most preferably, it is 20-300.

In General Formula (3), R ⁸ 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 ^{4 to} R ⁶ 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-based copolymer is within the above range, the long-term hydraulic composition containing the hydraulic cement and the pozzolanic substance can be used. The effect of improving curability can be more sufficiently exhibited.

  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-based copolymer is within the above range, the effect of improving the long-term curability of the hydraulic composition containing the hydraulic cement and the pozzolanic substance is more fully expressed. Can do.

  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 a pozzolanic substance-containing hydraulic composition can be used as it is as an additive for a pozzolanic substance-containing hydraulic composition of the present invention. It is preferable to adjust the pH of the reaction solution after the production of the additive for a hard composition 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 produced additive for a pozzolanic substance-containing hydraulic composition can be subjected to concentration adjustment as necessary with respect to the solution obtained by the production.

  The produced additive for pozzolanic substance-containing hydraulic composition may be used as it is in the form of a solution, or may be used in the form of powder.

≪Concrete composition≫
The concrete composition of the present invention includes a hydraulic composition containing a hydraulic cement and a pozzolanic substance, a strength improving agent for a pozzolanic substance-containing hydraulic composition of the present invention, or a pozzolanic substance-containing hydraulic composition of the present invention. And additives for physical use.

  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 polycarboxylic acid-based dispersants other than the polycarboxylic acid-based copolymer contained in the additive for the pozzolanic substance-containing hydraulic composition of the present invention.

  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 order to develop the effect of the strength improver for a pozzolanic substance-containing hydraulic composition of the present invention, the components of the concrete composition and the mortar composition (hydraulic cement, pozzolanic substance, water) It is also effective to adjust the usage ratio and unit amount of the aggregate.

  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.

<Mortar creation>
Cement (ordinary Portland cement, made by Taiheiyo Cement), fly ash (fly ash type II, manufactured by Chubu Electric Power Co., Ltd.), sand (Oikawa land sand, surface dryness) in a mortar mixer in a mortar mixer in an atmosphere of 20 ° C. Specific gravity = 2.62 g / cm ³ ), water in which a predetermined amount of polycarboxylic acid copolymer is dissolved, and an antifoaming agent (Adecanol LG-299, manufactured by Adeka) are added, and in accordance with JIS-R-5201. To make mortar. The amount of antifoaming agent was adjusted so that the amount of air was 2.0% or less.

<Flow value>
In accordance with JIS-R-5201, a zero hit flow value was measured. The addition amount of the polycarboxylic acid copolymer was adjusted so that the flow value became a numerical value within the range of 200 ± 20 mm.

<Compressive strength>
The obtained mortar was filled into a cylindrical shape having a diameter of 50 mm and a height of 100 mm, left at 30 ° C. for 24 hours, demolded, and cured in water at 30 ° C. for 28 days.
The specimen after curing was measured for compressive strength using a compression tester in accordance with Japan Society of Civil Engineers JSCE-G 505-1999.

<Strength improvement rate>
Based on the compressive strength of the specimen to which the strength improver of the present invention was not added in the same mortar formulation, the strength improvement rate when the strength improver of the present invention was added was determined by the following formula.
Strength improvement rate (%) = [(compressive strength of specimen added with strength improver) / (compressive strength of specimen not added with 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, 295 g of methoxypolyethylene glycol monomethacrylate (NK ester M-450G, manufactured by Shin-Nakamura Chemical Co., Ltd.), 26 g of methacrylic acid, and 0.66 g of 3-mercaptopropionic acid were dissolved in 75 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 1.2 g of 2,2′-azobis (2-methylpropionamidine) dihydrochloride was dissolved in 98.8 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 42000.

[Example 1]
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 polyacrylic acid (1) which is the intensity | strength improving agent for pozzolanic substance containing hydraulic compositions was performed, the mass mean molecular weight was 11000.

[Examples 2 to 5]
Except that the amount of 2-mercaptopropionic acid to be used was changed to the amount described in Table 2, the same operation as in Example 1 was carried out, and polyacrylic acid (2 which is a strength improving agent for pozzolanic substance-containing hydraulic compositions (2 ) To (5) were obtained.

〔実施例６〕
温度計、撹拌機、滴下装置、窒素導入管、還流冷却器を備えたガラス製反応容器に水２００．０ｇを仕込み、撹拌下に反応容器内を窒素置換し、窒素雰囲気下で８０℃に昇温した。
次にメトキシポリエチレングリコールモノメタクリレート（ＮＫエステルＭ−２３０Ｇ、新中村化学工業社製）６５．９ｇ、リン酸モノ−（２−ヒドロキシエチル）メタクリレート／リン酸ジ−（２−ヒドロキシエチル）メタクリレート＝８８．８／１１．２モル％の混合物（ライトエステルＰ−１Ｍ、共栄社化学社製）４０．６ｇ、３−メルカプトプロピオン酸１．７ｇを水９７．０ｇに溶解させた。
このモノマー水溶液を１．５時間かけて滴下した。モノマー水溶液を滴下し始めると同時に、過硫酸アンモニウム４．７ｇを水４５．０ｇに溶解させた水溶液を１．５時間かけて滴下した。
滴下終了後、過硫酸アンモニウム２．４ｇを水１５ｇに溶解させた水溶液を０．５時間かけて滴下し、その後引き続き０．５時間８０℃で内温を維持し、重合反応を完結させた。
冷却後、３０％ＮａＯＨ水溶液でｐＨを６まで中和し、６９モル％のリン酸基を有するポゾラン性物質含有水硬性組成物用強度向上剤であるリン酸基含有共重合体（１）を得た。得られたポゾラン性物質含有水硬性組成物用強度向上剤であるリン酸基含有共重合体（１）のＧＰＣ測定を行ったところ、質量平均分子量は２２０００であった。

Example 6
200.0 g of water was charged into a glass reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser, the inside of the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 80 ° C. under a nitrogen atmosphere. Warm up.
Next, 65.9 g of methoxypolyethylene glycol monomethacrylate (NK ester M-230G, manufactured by Shin-Nakamura Chemical Co., Ltd.), phosphoric acid mono- (2-hydroxyethyl) methacrylate / phosphoric acid di- (2-hydroxyethyl) methacrylate = 88 40.6 g of a 8 / 11.2 mol% mixture (Light Ester P-1M, manufactured by Kyoeisha Chemical Co., Ltd.) and 1.7 g of 3-mercaptopropionic acid were dissolved in 97.0 g of water.
This monomer aqueous solution was added dropwise over 1.5 hours. At the same time as the dropping of the monomer aqueous solution, an aqueous solution in which 4.7 g of ammonium persulfate was dissolved in 45.0 g of water was dropped over 1.5 hours.
After completion of the dropwise addition, an aqueous solution in which 2.4 g of ammonium persulfate was dissolved in 15 g of water was dropped over 0.5 hours, and then the internal temperature was maintained at 80 ° C. for 0.5 hours to complete the polymerization reaction.
After cooling, the phosphoric acid group-containing copolymer (1), which is a strength improving agent for a pozzolanic substance-containing hydraulic composition having a phosphate group of 69 mol%, is neutralized to pH 6 with a 30% NaOH aqueous solution. Obtained. When the GPC measurement of the obtained phosphate group-containing copolymer (1) which is the strength improver for a pozzolanic substance-containing hydraulic composition was performed, the mass average molecular weight was 22,000.

Example 7
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and sodium polyacrylate (manufactured by Aldrich, mass average molecular weight = 2100) are blended, and a pozzolanic substance-containing hydraulic property An additive for composition (1) was obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (1). The results are shown in Table 3.

Example 8
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (1) obtained in Example 1 were blended to form a pozzolanic substance-containing hydraulic composition. A product additive (2) was obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (2). The results are shown in Table 3.

Example 9
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (2) obtained in Example 2 were blended to form a pozzolanic substance-containing hydraulic composition. A product additive (3) was obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (3). The results are shown in Table 3.

Example 10
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (3) obtained in Example 3 were blended to form a pozzolanic substance-containing hydraulic composition. A product additive (4) was obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (4). The results are shown in Table 3.

Example 11
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (4) obtained in Example 4 were blended to form a pozzolanic substance-containing hydraulic composition. A product additive (5) was obtained.
Various evaluations were performed using an additive (5) for a pozzolanic substance-containing hydraulic composition. The results are shown in Table 3.

Example 12
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (4) obtained in Example 4 were blended to form a pozzolanic substance-containing hydraulic composition. A product additive (6) was obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (6). The results are shown in Table 3.

Example 13
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (4) obtained in Example 4 were blended to form a pozzolanic substance-containing hydraulic composition. A product additive (7) was obtained.
Various evaluations were performed using an additive (7) for a pozzolanic substance-containing hydraulic composition. The results are shown in Table 3.

Example 14
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (5) obtained in Example 5 were blended, and a pozzolanic substance-containing hydraulic composition. A product additive (8) was obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (8). The results are shown in Table 3.

Example 15
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and sodium tripolyphosphate (manufactured by Taihei Chemical Sangyo) are blended, and an additive for a pozzolanic substance-containing hydraulic composition (9) was obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (9). The results are shown in Table 3.

Example 16
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and sodium tripolyphosphate (manufactured by Taihei Chemical Sangyo) are blended, and an additive for a pozzolanic substance-containing hydraulic composition (10) was obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (10). The results are shown in Table 3.

Example 17
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and sodium tetrapolyphosphate (manufactured by Taihei Chemical Sangyo) are blended and added for a pozzolanic substance-containing hydraulic composition. Agent (11) was obtained.
Various evaluations were performed using an additive (11) for a pozzolanic substance-containing hydraulic composition. The results are shown in Table 3.

Example 18
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and sodium hexametaphosphate (produced by Taihei Chemical Sangyo Co., Ltd.) are blended to add a pozzolanic substance-containing hydraulic composition. (12) was obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (12). The results are shown in Table 3.

Example 19
As shown in Table 3, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the phosphoric acid group-containing copolymer (1) obtained in Example 6 were blended to produce pozzolanic properties. An additive (13) for a substance-containing hydraulic composition was obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (13). The results are shown in Table 3.

[Comparative Example 1]
As shown in Table 3, without using a strength improver, only the polycarboxylic acid copolymer (1) obtained in Production Example 1 was used as an additive (C1) for a pozzolanic substance-containing hydraulic composition.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (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 a pozzolanic substance-containing hydraulic composition additive (C2). .
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (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 a pozzolanic substance-containing hydraulic composition additive (C3). .
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (C3). The results are shown in Table 3.

  As shown in Table 3, compared to Comparative Example 1 in which only the polycarboxylic acid copolymer (1) was used as an additive for a pozzolanic substance-containing hydraulic composition (C1), a polycarboxylic acid copolymer ( In Example 7-19, in which polyacrylic acid (salt), polyphosphoric acid (salt), or a phosphate group-containing copolymer (salt) was added as a strength improver to 1), a hydraulic cement and a pozzolanic substance were contained. It can be seen that the effect of improving the long-term curability of the hydraulic composition is sufficient. On the other hand, in Comparative Example 2 in which calcium nitrite was added to the polycarboxylic acid copolymer (1), the effect of improving the long-term curability of the hydraulic composition containing hydraulic cement and pozzolanic material could be manifested. In Comparative Example 3 in which triethanolamine was added to the polycarboxylic acid copolymer (1), the long-term curability improvement effect of the hydraulic composition containing hydraulic cement and pozzolanic material was Comparative Example 1. It turns out that it is falling.

Example 20
As shown in Table 4, the polycarboxylic acid copolymer (2) obtained in Production Example 2 and the polyacrylic acid (4) obtained in Example 4 were blended to form a pozzolanic substance-containing hydraulic composition. A product additive (14) was obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (14). The results are shown in Table 4.

Example 21
As shown in Table 4, the polycarboxylic acid copolymer (2) obtained in Production Example 2 and sodium tripolyphosphate (manufactured by Taihei Chemical Sangyo) are blended, and an additive for a pozzolanic substance-containing hydraulic composition (15) was obtained.
Various evaluations were performed using an additive (15) for a pozzolanic substance-containing hydraulic composition. The results are shown in Table 4.

[Comparative Example 4]
As shown in Table 4, without using a strength improver, only the polycarboxylic acid copolymer (2) obtained in Production Example 2 was used as an additive for a pozzolanic substance-containing hydraulic composition (C4).
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (C4). The results are shown in Table 4.

  As shown in Table 4, compared to Comparative Example 4 in which only the polycarboxylic acid copolymer (2) was used as an additive for a pozzolanic substance-containing hydraulic composition (C4), a polycarboxylic acid copolymer ( In Examples 20 and 21, in which polyacrylic acid (salt) or polyphosphoric acid (salt) was added as a strength improver to 2), the long-term curability improvement effect of the hydraulic composition containing hydraulic cement and pozzolanic substance It can be seen that can be expressed sufficiently.

[Example 22]
As shown in Table 5, the polycarboxylic acid copolymer (3) obtained in Production Example 3 and the polyacrylic acid (4) obtained in Example 4 were blended to form a pozzolanic substance-containing hydraulic composition. A product additive (16) was obtained.
Various evaluations were performed using an additive (16) for a pozzolanic substance-containing hydraulic composition. The results are shown in Table 5.

Example 23
As shown in Table 5, the polycarboxylic acid copolymer (3) obtained in Production Example 3 and sodium tripolyphosphate (manufactured by Taihei Chemical Sangyo Co., Ltd.) are blended to add a pozzolanic substance-containing hydraulic composition. (17) was obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (17). The results are shown in Table 5.

[Comparative Example 5]
As shown in Table 5, only the polycarboxylic acid copolymer (3) obtained in Production Example 3 was used as a pozzolanic substance-containing hydraulic composition additive (C5) without using a strength improver.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (C5). The results are shown in Table 5.

  As shown in Table 5, as compared with Comparative Example 5 in which only the polycarboxylic acid copolymer (3) was used as an additive for a pozzolanic substance-containing hydraulic composition (C5), a polycarboxylic acid-based polymer was used as a strength improver. In Examples 23 and 23 in which polyacrylic acid (salt) or polyphosphoric acid (salt) was added to the copolymer (3), the long-term curability improving effect of the hydraulic composition containing hydraulic cement and pozzolanic substance It can be seen that can be expressed sufficiently.

Example 24
As shown in Table 6, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (4) obtained in Example 4 were blended to form a pozzolanic substance-containing hydraulic composition. A product additive (18) was obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (18). The results are shown in Table 6.

Example 25
As shown in Table 6, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and sodium tripolyphosphate (manufactured by Taihei Chemical Sangyo) are blended, and an additive for a pozzolanic substance-containing hydraulic composition. (19) was obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (19). The results are shown in Table 6.

[Comparative Example 6]
As shown in Table 6, without using a strength improver, only the polycarboxylic acid copolymer (1) obtained in Production Example 1 was used as an additive for a pozzolanic substance-containing hydraulic composition (C6).
Various evaluation was performed using the pozzolanic substance-containing hydraulic composition additive (C6). The results are shown in Table 6.

  As shown in Table 6, only the polycarboxylic acid copolymer (1) is used for a hydraulic composition containing a pozzolanic substance, even for a hydraulic composition with increased pozzolanic substances as in mortar formulation 2. Examples 24 and 25 in which polyacrylic acid (salt) or polyphosphoric acid (salt) was added as a strength improver to the polycarboxylic acid copolymer (1) as compared with Comparative Example 6 in which the strength improver (C6) was used. It can be seen that the effect of improving the long-term curability of a hydraulic composition containing a hydraulic cement and a pozzolanic substance can be sufficiently exhibited.

Example 26
As shown in Table 7, as a sulfonic acid-based dispersant, a naphthalene sulfonic acid formaldehyde condensate, Mighty 150 (manufactured by Kao), and polyacrylic acid (4) obtained in Example 4 are blended to form a pozzolanic substance. The additive (20) for containing hydraulic compositions was obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (20). The results are shown in Table 7.

Example 27
As shown in Table 7, Mighty 150 (manufactured by Kao) and sodium tripolyphosphate (manufactured by Taihei Chemical Sangyo) are blended as a sulfonic acid dispersant, and an additive for pozzolanic substance-containing hydraulic composition (21) Obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (21). The results are shown in Table 7.

[Comparative Example 7]
As shown in Table 7, the strength improver was not used, and only the sulfonic acid dispersant Mighty 150 (manufactured by Kao) was used as an additive for a pozzolanic substance-containing hydraulic composition (C7).
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (C7). The results are shown in Table 7.

  As shown in Table 7, compared with Comparative Example 7 in which only Mighty 150 was used as a sulfonic acid-based dispersant as an additive for pozzolanic substance-containing hydraulic composition (C7), Mighty 150 contained polyacrylic acid as a strength improver. In Examples 26 and 27 to which (salt) or polyphosphoric acid (salt) was added, it can be seen that the long-term curability improving effect of the hydraulic composition containing hydraulic cement and pozzolanic substance can be sufficiently exhibited. .

Example 28
As shown in Table 8, Master Pozzolith No. 1 which is lignin sulfonic acid as a sulfonic acid-based dispersant. 8 (manufactured by BASF Japan) and the polyacrylic acid (4) obtained in Example 4 were blended to obtain a pozzolanic substance-containing hydraulic composition additive (22).
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (22). The results are shown in Table 8.

Example 29
As shown in Table 8, as the sulfonic acid-based dispersant, Master Pozzolith No. 8 (manufactured by BASF Japan) and sodium tripolyphosphate (manufactured by Taihei Chemical Industry) were blended to obtain a pozzolanic substance-containing hydraulic composition additive (23).
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (23). The results are shown in Table 8.

[Comparative Example 8]
As shown in Table 8, without using a strength improver, Master Pozoris No. which is a sulfonic acid-based dispersant. Only 8 (manufactured by BASF Japan) was used as an additive for a pozzolanic substance-containing hydraulic composition (C8).
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (C8). The results are shown in Table 8.

  As shown in Table 8, as the sulfonic acid-based dispersant, Master Pozzolith No. Compared to Comparative Example 8 in which only the pozzolanic substance-containing hydraulic composition additive (C8) was used, the master pozzolith No. 8 was used. In Examples 28 and 29 in which polyacrylic acid (salt) or polyphosphoric acid (salt) was added as a strength improver to No. 8, the long-term curability improvement effect of the hydraulic composition containing hydraulic cement and pozzolanic substance was obtained. It turns out that it can fully express.

[Reference Example 1]
As shown in Table 9, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and the polyacrylic acid (4) obtained in Example 4 were blended to form a pozzolanic substance-containing hydraulic composition. A product additive (R1) was obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (R1). The results are shown in Table 9.

[Reference Example 2]
As shown in Table 9, the polycarboxylic acid copolymer (1) obtained in Production Example 1 and sodium tripolyphosphate (manufactured by Taihei Chemical Sangyo) are blended, and an additive for a pozzolanic substance-containing hydraulic composition (R2) was obtained.
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (R2). The results are shown in Table 9.

[Reference Example 3]
As shown in Table 9, the polycarboxylic acid copolymer (1) obtained in Production Example 1 was used as a pozzolanic substance-containing hydraulic composition additive (R3).
Various evaluations were performed using the pozzolanic substance-containing hydraulic composition additive (R3). The results are shown in Table 9.

  As shown in Table 9, for the hydraulic composition containing no pozzolanic substance as in mortar formulation 3, only the polycarboxylic acid copolymer (1) is used for the pozzolanic substance-containing hydraulic composition. In Reference Examples 2 and 3 in which polyacrylic acid (salt) or polyphosphoric acid (salt) was added as a strength improver to the polycarboxylic acid copolymer (1) as well as Reference Example 3 as an additive (R3) However, the long-term curability improvement effect is not found.

The strength improver for pozzolanic substance-containing hydraulic compositions and the additive for pozzolanic substance-containing hydraulic compositions of the present invention can be suitably used as materials for concrete compositions such as cement paste, mortar, and concrete.

Claims (15)

A strength improving agent for a hydraulic composition containing a hydraulic cement and a pozzolanic substance,
Including at least one selected from polyacrylic acid (salt), polyphosphoric acid (salt), and phosphoric acid group-containing copolymer (salt),
Strength improving agent for hydraulic compositions containing pozzolanic substances.   The pozzolanic substance-containing hydraulic composition according to claim 1, 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. Strength improver.   The strength improver for a pozzolanic substance-containing hydraulic composition according to claim 1 or 2, wherein the pozzolanic substance includes fly ash. An additive for a hydraulic composition containing a hydraulic cement and a pozzolanic substance,
A hydraulic material dispersant containing at least one selected from a sulfonic acid-based dispersant and a polycarboxylic acid-based copolymer;
A strength improving agent for a pozzolanic substance-containing hydraulic composition containing at least one selected from polyacrylic acid (salt), polyphosphoric acid (salt), and a phosphoric acid group-containing copolymer (salt);
including,
Additive for hydraulic composition containing pozzolanic substance. The hydraulic material dispersant is 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). The additive for a pozzolanic substance-containing hydraulic composition according to claim 4, which is a polycarboxylic acid copolymer containing a structural unit (II) derived from a monomer based on monomer (b).

(In General Formula (1), R ¹ and R ² are the same or different and each represents a hydrogen atom or a methyl group; R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms; Represents an oxyalkylene group having 2 to 18 carbon atoms, n represents the average number of added moles of the oxyalkylene group represented by AO, n is a number from 1 to 500, and x is an integer from 0 to 2 And y is 0 or 1.)

(In general formula (2), R ^{4 to} R ⁶ 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.) The unsaturated polyalkylene glycol monomer (a) represented by the general formula (1) is an unsaturated polyalkylene glycol monomer (c) represented by the general formula (3). 5. The additive for a pozzolanic substance-containing hydraulic composition according to 5.
YO— (R ⁷ O) _n —R ⁸ (3)
(In General Formula (3), Y represents an alkenyl group having 2 to 8 carbon atoms, R ⁷ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms, and n represents R ⁷ O. The average addition mole number of the oxyalkylene group represented by the formula (1), n is 1 to 500, and R ⁸ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.)   Y in the general formula (3) 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 a pozzolanic substance-containing hydraulic composition according to claim 6, which is any one of -3-butenyl groups.   The pozzolanic property according to any one of claims 4 to 7, 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. Additive for substance-containing hydraulic composition.   The additive for a pozzolanic substance-containing hydraulic composition according to any one of claims 4 to 8, wherein the pozzolanic substance contains fly ash.   A concrete composition comprising a hydraulic composition containing a hydraulic cement and a pozzolanic substance, and the strength improver for a pozzolanic substance-containing hydraulic composition according to any one of claims 1 to 3.   The concrete composition according to claim 10, wherein a content ratio of the pozzolanic substance is larger than 30% by mass with respect to a total amount of the hydraulic cement and the pozzolanic substance in the hydraulic composition.   The concrete composition according to claim 10 or 11, wherein the pozzolanic substance includes fly ash.   A concrete composition comprising a hydraulic composition containing a hydraulic cement and a pozzolanic substance, and the additive for a pozzolanic substance-containing hydraulic composition according to any one of claims 4 to 9.   The concrete composition according to claim 13, 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. 15. A concrete composition according to claim 13 or 14, wherein the pozzolanic material comprises fly ash.