JP2017088469A - Viscosity-reducing agent for pozzolanic substance-containing hydraulic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a viscosity-reducing agent for a pozzolanic substance-containing hydraulic composition that can sufficiently reduce a viscosity of a hydraulic composition containing hydraulic cement and a pozzolanic substance and to provide a concrete composition including the viscosity-reducing agent for a pozzolanic substance-containing hydraulic composition.SOLUTION: The viscosity-reducing agent for a pozzolanic substance-containing hydraulic composition is a viscosity-reducing agent for reducing a viscosity of a hydraulic composition containing hydraulic cement and a pozzolanic substance, and includes (A) a polycarboxylic acid copolymer including (I) a structural unit derived from (a) a specific unsaturated polyalkylene glycol monomer and (II) a structural unit derived from (b) a specific unsaturated carboxylic acid monomer, in which an average addition mole number n of oxyalkylene groups in the specific unsaturated polyalkylene glycol monomer (a) is 1-40, and a mass average molecular weight of the polycarboxylic acid copolymer (A) is 20,000 or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a viscosity reducing agent for a pozzolanic substance-containing hydraulic composition. The present invention also relates to 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. An alternative substituted pozzolanic substance-containing hydraulic composition has attracted attention (for example, Patent Document 1).

  One advantage of using a pozzolanic substance as a partial substitute for hydraulic cement is that the viscosity of the concrete composition is reduced. This is because if the viscosity of the concrete composition is reduced, the workability when placing the concrete composition is improved.

  However, at present, the effect of reducing the viscosity of a concrete composition by using a pozzolanic substance as a partial substitute for hydraulic cement is still insufficient, and there is a strong demand for expression of a higher viscosity reducing effect.

JP 2004-10387 A

  The subject of this invention is providing the viscosity reducing agent for pozzolanic substance containing hydraulic compositions which can fully reduce the viscosity of the hydraulic composition containing a hydraulic cement and a pozzolanic substance. Moreover, it is providing the concrete composition containing the viscosity reducing agent for such a pozzolanic substance containing hydraulic composition.

（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、同一または異なって、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、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。） The viscosity reducing agent for a pozzolanic substance-containing hydraulic composition of the present invention,
A viscosity reducing agent for reducing the viscosity of a hydraulic composition containing a hydraulic cement and a pozzolanic substance,
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 polycarboxylic acid copolymer (A) containing the structural unit (II):
N in the general formula (1) is 1 to 40,
The mass average molecular weight of the polycarboxylic acid copolymer (A) is 20000 or less.

(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; Are the same or different and represent an oxyalkylene group having 2 to 18 carbon atoms, n represents the average number of moles added of the oxyalkylene group represented by AO, x is an integer of 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.)

  As 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 substance includes fly ash.

As one embodiment, the unsaturated polyalkylene glycol monomer (a) represented by the general formula (1) is converted into 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 number of added moles of the oxyalkylene group represented by the formula (1), n is 1 to 40, 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 a butenyl group and a 2-methyl-3-butenyl group.

The concrete composition of the present invention comprises:
The hydraulic composition containing a hydraulic cement and a pozzolanic substance, and the viscosity reducing agent for a pozzolanic substance-containing hydraulic composition of the present invention are included.

  As 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 substance includes fly ash.

  ADVANTAGE OF THE INVENTION According to this invention, the viscosity reducing agent for pozzolanic substance containing hydraulic compositions which can fully reduce the viscosity of the hydraulic composition containing a hydraulic cement and a pozzolanic substance can be provided. Moreover, the concrete composition containing the viscosity reducing agent for such a pozzolanic substance containing hydraulic composition can be provided.

It is a schematic sectional drawing of J14 funnel according to Japan Society of Civil Engineers standard JSCE-F541 for measuring funnel flow time.

  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 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 the like. 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.

≪Viscosity reducing agent for pozzolanic substance-containing hydraulic composition≫
The viscosity reducing agent for a pozzolanic substance-containing hydraulic composition of the present invention contains a specific polycarboxylic acid copolymer (A). The viscosity reducing agent for a pozzolanic substance-containing hydraulic composition according to the present invention contains a specific polycarboxylic acid copolymer (A), so that the viscosity of the hydraulic composition containing the hydraulic cement and the pozzolanic substance is increased. Can be sufficiently reduced.

  The polycarboxylic acid copolymer (A) in the viscosity reducing agent for a pozzolanic substance-containing hydraulic composition of the present invention may be only one type or two or more types.

  In the viscosity reducing agent for a pozzolanic substance-containing hydraulic composition of the present invention, the content ratio of the polycarboxylic acid copolymer (A) 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%. If the content ratio of the polycarboxylic acid copolymer (A) in the viscosity reducing agent for a pozzolanic substance-containing hydraulic composition of the present invention is within the above range, the hydraulic contains a hydraulic cement and a pozzolanic substance. The viscosity of the composition can be reduced more sufficiently.

<Polycarboxylic acid copolymer (A)>
The polycarboxylic acid copolymer (A) 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). 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, is 1 to 40, preferably 2 to 35, and more preferably 3 It is -30, More preferably, it is 4-25. If n is in the above range, the viscosity of the hydraulic composition containing the hydraulic cement and the pozzolanic substance can be more sufficiently reduced.

  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 40 mol of alkylene oxide to any one of 2-methyl-3-buten-1-ol; more preferably, alkylene oxide is added to 3-methyl-3-buten-1-ol. It is a compound with 1 mol to 40 mol added.

  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 the general formula (3), n represents an average addition mol number of the oxyalkylene group represented by ^{R 7} O, 1 to 40, preferably 2 to 35, more preferably 3 to 30 More preferably, it is 4-25. If n is in the above range, the viscosity of the hydraulic composition containing the hydraulic cement and the pozzolanic substance can be more sufficiently reduced.

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 unsaturated carboxylic acid monomer (b) represented by the general formula (2) is a structural unit (II) derived from the unsaturated carboxylic acid monomer (b) represented by the general formula (2). 1 type may be sufficient and 2 or more types may be sufficient.

  The total content of the structural unit (I) and the structural unit (II) in the polycarboxylic acid copolymer (A) is preferably 50% by mass to 100% by mass, and more preferably 70% by mass. It is -100 mass%, More preferably, it is 80 mass%-100 mass%, Most preferably, it is 90 mass%-100 mass%, Most preferably, it is 95 mass%-100 mass%. If the total content of the structural unit (I) and the structural unit (II) in the polycarboxylic acid copolymer (A) is within the above range, a hydraulic composition containing a hydraulic cement and a pozzolanic substance. The viscosity of an object can be reduced more sufficiently.

  In the polycarboxylic acid copolymer (A), 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. Moreover, it is derived from the various monomers calculated based on the amount of the various monomers used when producing the polycarboxylic acid copolymer (A) without performing the various structural analyzes as described above. In the polycarboxylic acid copolymer (A), the proportion of the structural unit (I), the proportion of the structural unit (II), the structural unit (I) and the structural unit (II) It is good also as a total content rate. That is, the content ratio of unsaturated polyalkylene glycol monomer (a) in all monomer components used when producing polycarboxylic acid copolymer (A), unsaturated carboxylic acid monomer The content ratio of (b), the content ratio of the total mass of the unsaturated polyalkylene glycol monomer (a) and the unsaturated carboxylic acid monomer (b), and the polycarboxylic acid copolymer (A ), 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), and the like.

  The polycarboxylic acid copolymer (A) 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 an alkyl (poly) alkylene glycol obtained by adding 1 to 500 mol (preferably 1 to 40 mol) of an alkylene oxide having 2 to 18 carbon atoms to an amine; and the above-mentioned unsaturated dicarboxylic acids; Diesters of alkyl (poly) alkylene glycols obtained by adding 1 to 500 mol (preferably 1 to 40 mol) of an alkylene oxide having 2 to 18 carbon atoms to an amine and the above unsaturated dicarboxylic acids; Addition of acids and glycols having 2 to 18 carbon atoms or these glycols Half esters with polyalkylene glycols having a mole number of 2 to 500 (preferably 2 to 40); the unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or addition moles of these glycols of 2 to 500 (preferably 2-40) diesters with polyalkylene glycols; half amides of maleamic acid and glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 addition moles (preferably 2 to 40) of these glycols (Poly) ethylene glycol di (meth) acrylate, (poly) alkylene glycol di (meth) acrylates such as (poly) propylene glycol di (meth) acrylate; hexanediol di (meth) acrylate, trimethylolpropane tri ( Multifunctional such as (meth) acrylate (Meth) acrylates; (poly) alkylene glycol dimaleates such as polyethylene glycol dimaleate; unsaturated sulfonic acids such as vinyl sulfonate, (meth) allyl sulfonate, 2-methylpropane sulfonic acid (meth) acrylamide, styrene sulfonic acid (Salts); Amides of unsaturated monocarboxylic acids such as methyl (meth) acrylamide and amines having 1 to 30 carbon atoms; Vinyl aromatics such as styrene, α-methylstyrene and vinyltoluene; 1,4 Alkanediol mono (meth) acrylates such as butanediol mono (meth) acrylate; dienes such as butadiene and isoprene; (meth) acrylic (alkyl) amide, N-methylol (meth) acrylamide, N, N-dimethyl ( Unsaturated amino such as (meth) acrylamide Unsaturated cyanides such as (meth) acrylonitrile; Unsaturated esters such as vinyl acetate; Unsaturated amines such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, vinylpyridine; and divinylbenzene Divinyl aromatics such as (meth) allyl alcohol, allyls such as glycidyl (meth) allyl ether; vinyl ethers such as (methoxy) polyethylene glycol monovinyl ether; (methoxy) polyethylene glycol mono (meth) allyl ether ( (Meth) allyl ethers; and the like.

  The content ratio of the structural unit (III) in the polycarboxylic acid copolymer (A) can be known, for example, by various structural analyzes (for example, NMR) of the polycarboxylic acid copolymer (A). . Moreover, it is derived from the various monomers calculated based on the amount of the various monomers used when producing the polycarboxylic acid copolymer (A) without performing the various structural analyzes as described above. It is good also as content rate of structural unit (III) in a polycarboxylic acid type copolymer (A) with the content rate of these structural units. That is, the content ratio of the mass of the other monomer (c) in the total monomer component used when the polycarboxylic acid copolymer (A) is produced is changed to the polycarboxylic acid copolymer (A). It may be handled as the content ratio of the structural unit (III) in it.

  The content ratio of the structural unit (I), the structural unit (II), and the structural unit (III) in the polycarboxylic acid copolymer (A) is a mass ratio (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 More preferably (I) / (II) / (III) = 55 to 98/2 to 45/0 to 40, and particularly preferably (I) / (II) / (III) = 60 to 97/3 to 40/0 to 30.

  The mass average molecular weight (Mw) of the polycarboxylic acid copolymer (A) is 20000 or less, preferably 1000 to 20000 as a mass average molecular weight (Mw) in terms of polyethylene glycol by gel permeation chromatography (GPC). More preferably, it is 2000-18000, More preferably, it is 3000-16000, Most preferably, it is 4000-15000. When the mass average molecular weight (Mw) of the polycarboxylic acid copolymer (A) is within the above range, it is possible to achieve greater cost reduction and more sufficient environmental load reduction of the hydraulic cement.

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

  An unsaturated polyalkylene glycol monomer (a), an unsaturated carboxylic acid monomer (b) that can be used for the production of the polycarboxylic acid copolymer (A), and other monomers as required. The amount of the monomer (c) used is appropriately adjusted so that the proportion of the structural unit derived from each monomer in all the structural units constituting the polycarboxylic acid copolymer (A) is as described above. That's fine. Preferably, assuming that the polymerization reaction proceeds quantitatively, each unit has the same proportion as the proportion of structural units derived from each monomer in all the structural units constituting the polycarboxylic acid copolymer (A) described above. A mer may be used.

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

  The produced viscosity reducing agent 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, and a viscosity reducing agent for the pozzolanic substance-containing hydraulic composition of the present 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 cement dispersant composition of the present invention. Can be mentioned.

  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 order to make the effect of the viscosity reducing agent for a pozzolanic substance-containing hydraulic composition of the present invention more effective, 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 concretely, this invention is not limited to these Examples at all. Unless otherwise specified, parts and% in the examples are based on 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 ± 10 mm.

<Rotation time>
The obtained mortar was poured into a J14 funnel as shown in FIG. 1, and the flow-down time was measured in accordance with the Japan Society of Civil Engineers standard JSCE-F541. A shorter flow time means a lower viscosity.

[Example 1]
A glass reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and 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 58 ° C. under a nitrogen atmosphere. Warm up. Next, an aqueous monomer solution of 3-methyl-3-buten-1-ol in 23 mol of ethylene oxide adduct: 208.1 g and acrylic acid: 31.9 g dissolved in water: 300.0 g was added dropwise over 5 hours. . At the same time as the dropping of the monomer aqueous solution, an aqueous solution in which 2.5 g of ammonium persulfate was dissolved in 50.0 g of water and L-ascorbic acid: 0.5 g, 2-mercaptopropionic acid: 1.6 g of water: An aqueous solution dissolved in 50.0 g was added dropwise over 5 hours. Thereafter, the temperature was continuously maintained at 58 ° C. for 1 hour to complete the polymerization reaction. After cooling, the solution was neutralized with a 30% NaOH aqueous solution until the pH reached 6.
When the GPC measurement of the obtained polycarboxylic acid-type copolymer (1) was performed, the mass mean molecular weight was 14000. The results are shown in Table 2.
Using the obtained polycarboxylic acid copolymer (1) as a viscosity reducing agent (1) for a hydraulic composition containing a pozzolanic substance, a mortar was prepared according to the composition 1 in Table 1, and the flow value and funnel flow time were measured. did. The results are shown in Table 3.

[Example 2]
Except having changed the usage-amount of 2-mercaptopropionic acid into 2.3 g, it carried out similarly to Example 1 and obtained the polycarboxylic acid type copolymer (2).
When the GPC measurement of the obtained polycarboxylic acid type copolymer (2) was performed, the mass mean molecular weight was 10900. The results are shown in Table 2.
Using the obtained polycarboxylic acid copolymer (2) as a viscosity reducing agent (2) for a hydraulic composition containing a pozzolanic substance, a mortar was prepared according to Formulation 1 in Table 1, and the flow value and funnel flow time were measured. did. The results are shown in Table 3.

Example 3
A polycarboxylic acid copolymer (3) was obtained in the same manner as in Example 1 except that the amount of 2-mercaptopropionic acid used was changed to 4.1 g.
When the GPC measurement of the obtained polycarboxylic acid-type copolymer (3) was performed, the mass mean molecular weight was 6900. The results are shown in Table 2.
Using the resulting polycarboxylic acid copolymer (3) as a pozzolanic substance-containing hydraulic composition viscosity reducing agent (3), a mortar was prepared according to Formulation 1 in Table 1, and the flow value and funnel flow time were measured. did. The results are shown in Table 3.

Example 4
The monomer aqueous solution was changed to an aqueous monomer solution in which 15 mol of 3-methyl-3-buten-1-ol adduct of ethylene oxide: 195.8 g and acrylic acid: 44.2 g were dissolved in water: 300.0 g; A polycarboxylic acid copolymer (4) was obtained in the same manner as in Example 1 except that the amount of mercaptopropionic acid used was changed to 1.7 g.
When the GPC measurement of the obtained polycarboxylic acid type copolymer (4) was performed, the mass mean molecular weight was 13800. The results are shown in Table 2.
Using the obtained polycarboxylic acid copolymer (4) as a pozzolanic substance-containing hydraulic composition viscosity reducing agent (4), a mortar was prepared according to Formulation 1 in Table 1, and the flow value and funnel flow time were measured. did. The results are shown in Table 3.

Example 5
A polycarboxylic acid copolymer (5) was obtained in the same manner as in Example 4 except that the amount of 2-mercaptopropionic acid used was changed to 2.4 g.
When the GPC measurement of the obtained polycarboxylic acid type copolymer (5) was performed, the mass mean molecular weight was 10500. The results are shown in Table 2.
Using the obtained polycarboxylic acid copolymer (5) as a viscosity reducing agent (5) for a hydraulic composition containing a pozzolanic substance, a mortar was prepared according to Formulation 1 in Table 1, and the flow value and funnel flow time were measured. did. The results are shown in Table 3.

Example 6
The monomer aqueous solution was changed to a monomer aqueous solution prepared by dissolving 178.1 g of 3-methyl-3-buten-1-ol in an ethylene oxide 9 mol adduct: 178.1 g and acrylic acid: 61.9 g in water: 300.0 g. A polycarboxylic acid copolymer (6) was obtained in the same manner as in Example 1 except that the amount of mercaptopropionic acid used was changed to 1.1 g.
When the GPC measurement of the obtained polycarboxylic acid type copolymer (6) was performed, the mass mean molecular weight was 19,200. The results are shown in Table 2.
Using the resulting polycarboxylic acid copolymer (6) as a viscosity reducing agent (6) for a pozzolanic substance-containing hydraulic composition, a mortar was prepared according to Formulation 1 in Table 1, and the flow value and funnel flow time were measured. did. The results are shown in Table 3.

Example 7
A polycarboxylic acid copolymer (7) was obtained in the same manner as in Example 6 except that the amount of 2-mercaptopropionic acid used was changed to 2.3 g.
When the GPC measurement of the obtained polycarboxylic acid type copolymer (7) was performed, the mass mean molecular weight was 10700. The results are shown in Table 2.
Using the obtained polycarboxylic acid copolymer (7) as a viscosity reducing agent (7) for a pozzolanic substance-containing hydraulic composition, a mortar was prepared according to Formulation 1 in Table 1, and the flow value and funnel flow time were measured. did. The results are shown in Table 3.

Example 8
Except having changed the usage-amount of 2-mercaptopropionic acid into 6.9g, it carried out similarly to Example 6 and obtained the polycarboxylic acid type copolymer (8).
When the GPC measurement of the obtained polycarboxylic acid-type copolymer (8) was performed, the mass mean molecular weight was 4600. The results are shown in Table 2.
Using the resulting polycarboxylic acid copolymer (8) as a viscosity reducing agent (8) for a hydraulic composition containing a pozzolanic substance, a mortar was prepared according to Formulation 1 in Table 1, and the flow value and funnel flow time were measured. did. The results are shown in Table 3.

Example 9
The aqueous monomer solution was changed to an aqueous monomer solution in which 146.2 g of 3-methyl-3-buten-1-ol adduct of ethylene oxide and 143.8 g of acrylic acid: 93.8 g were dissolved in 300.0 g of water. A polycarboxylic acid copolymer (9) was obtained in the same manner as in Example 1 except that the amount of mercaptopropionic acid used was changed to 2.3 g.
When the GPC measurement of the obtained polycarboxylic acid-type copolymer (9) was performed, the mass mean molecular weight was 10600. The results are shown in Table 2.
Using the obtained polycarboxylic acid copolymer (9) as a viscosity reducing agent (9) for a pozzolanic substance-containing hydraulic composition, a mortar was prepared according to the composition 1 in Table 1, and the flow value and funnel flow time were measured. did. The results are shown in Table 3.

Example 10
A polycarboxylic acid copolymer (10) was obtained in the same manner as in Example 9 except that the amount of 2-mercaptopropionic acid used was changed to 3.1 g.
When the GPC measurement of the obtained polycarboxylic acid type copolymer (10) was performed, the mass mean molecular weight was 8600. The results are shown in Table 2.
Using the obtained polycarboxylic acid copolymer (10) as a viscosity reducing agent (10) for a hydraulic composition containing a pozzolanic substance, a mortar was prepared according to Formulation 1 in Table 1, and the flow value and funnel flow time were measured. did. The results are shown in Table 3.

Example 11
The monomer aqueous solution was changed to a monomer aqueous solution in which 20 mol of 2-methyl-2-propen-1-ol ethylene oxide adduct: 204.0 g and acrylic acid: 36.0 g were dissolved in water: 300.0 g, A polycarboxylic acid copolymer (11) was obtained in the same manner as in Example 1 except that the amount of mercaptopropionic acid used was changed to 1.6 g.
When the GPC measurement of the obtained polycarboxylic acid type copolymer (11) was performed, the mass mean molecular weight was 14500. The results are shown in Table 2.
Using the resulting polycarboxylic acid copolymer (11) as a viscosity reducing agent (11) for a pozzolanic substance-containing hydraulic composition, a mortar was prepared according to Formulation 1 in Table 1, and the flow value and funnel flow time were measured. did. The results are shown in Table 3.

Example 12
The monomer aqueous solution was changed to a monomer aqueous solution in which 204.5 g of methoxypolyethylene glycol (average number of added moles = 23) methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 35.5 g of methacrylic acid were dissolved in 300.0 g of water, Except having changed the usage-amount of 2-mercaptopropionic acid into 1.6 g, it carried out similarly to Example 1 and obtained the polycarboxylic acid type copolymer (12).
When the GPC measurement of the obtained polycarboxylic acid-type copolymer (12) was performed, the mass mean molecular weight was 14000. The results are shown in Table 2.
Using the obtained polycarboxylic acid copolymer (12) as a viscosity reducing agent (12) for a pozzolanic substance-containing hydraulic composition, a mortar was prepared according to the formulation 1 in Table 1, and the flow value and funnel flow time were measured. did. The results are shown in Table 3.

Example 13
The monomer aqueous solution was changed to a monomer aqueous solution in which 35 moles of 3-methyl-3-buten-1-ol ethylene oxide adduct: 217.4 g and acrylic acid: 22.6 g were dissolved in water: 300.0 g. Except having changed the usage-amount of mercaptopropionic acid into 2.2 g, it carried out similarly to Example 1 and obtained the polycarboxylic acid type copolymer (13).
When the GPC measurement of the obtained polycarboxylic acid type copolymer (13) was performed, the mass mean molecular weight was 11000. The results are shown in Table 2.
Using the resulting polycarboxylic acid copolymer (13) as a viscosity reducing agent (13) for a pozzolanic substance-containing hydraulic composition, a mortar was prepared according to Formulation 1 in Table 1, and the flow value and funnel flow time were measured. did. The results are shown in Table 3.

[Comparative Example 1]
The monomer aqueous solution was changed to a monomer aqueous solution in which 20 mol of 3-methyl-3-buten-1-ol ethylene oxide adduct: 204.0 g and acrylic acid: 36.0 g were dissolved in 300.0 g of water, and 2- A polycarboxylic acid copolymer (C1) was obtained in the same manner as in Example 1 except that the amount of mercaptopropionic acid used was changed to 0.5 g.
When the GPC measurement of the obtained polycarboxylic acid-type copolymer (C1) was performed, the mass mean molecular weight was 35000. The results are shown in Table 2.
Using the obtained polycarboxylic acid copolymer (C1) as a pozzolanic substance-containing hydraulic composition viscosity reducing agent (C1), a mortar was prepared according to Formulation 1 in Table 1, and the flow value and funnel flow time were measured. did. The results are shown in Table 3.

[Comparative Example 2]
The monomer aqueous solution was changed to a monomer aqueous solution in which 23 mol of 3-methyl-3-buten-1-ol ethylene oxide adduct: 175.4 g and acrylic acid: 64.6 g were dissolved in water: 300.0 g; A polycarboxylic acid copolymer (C2) was obtained in the same manner as in Example 1 except that the amount of mercaptopropionic acid used was changed to 0.5 g.
When the GPC measurement of the obtained polycarboxylic acid-type copolymer (C2) was performed, the mass mean molecular weight was 33000. The results are shown in Table 2.
Using the obtained polycarboxylic acid copolymer (C2) as a pozzolanic substance-containing hydraulic composition viscosity reducing agent (C2), a mortar was prepared according to Formulation 1 in Table 1, and the flow value and funnel flow time were measured. did. The results are shown in Table 3.

[Comparative Example 3]
The monomer aqueous solution was changed to a monomer aqueous solution in which 20 mol of 3-methyl-3-buten-1-ol ethylene oxide adduct: 204.0 g and acrylic acid: 36.0 g were dissolved in 300.0 g of water, and 2- A polycarboxylic acid copolymer (C3) was obtained in the same manner as in Example 1 except that the amount of mercaptopropionic acid used was changed to 1.8 g.
When the GPC measurement of the obtained polycarboxylic acid-type copolymer (C3) was performed, the mass mean molecular weight was 13000. The results are shown in Table 2.
Using the obtained polycarboxylic acid copolymer (C3) as a pozzolanic substance-containing hydraulic composition viscosity reducing agent (C3), a mortar was prepared according to Formulation 1 in Table 1, and the flow value and funnel flow time were measured. did. The results are shown in Table 3.

  As can be seen from Table 3, the funnel flow-down time in Comparative Example 1 (the average addition mole number of the oxyalkylene group exceeds 40 and the mass average molecular weight of the polycarboxylic acid copolymer exceeds 20000) In Example 1 to Example 13 (average added mole number of oxyalkylene group is 40 or less and the mass average molecular weight of the polycarboxylic acid copolymer is 20000 or less), The ratio of the funnel flow time is 0.61 to 0.88, and the viscosity of the hydraulic composition containing the hydraulic cement and the pozzolanic substance can be sufficiently reduced. On the other hand, in Comparative Example 2 (the average addition mole number of the oxyalkylene group is 40 or less, but the mass average molecular weight of the polycarboxylic acid copolymer exceeds 20000), the funnel flow time ratio is 0. In Comparative Example 3 (the weight average molecular weight of the polycarboxylic acid copolymer is 20000 or less, but the average number of added moles of the oxyalkylene group is more than 40), The ratio is 0.97, and the viscosity of the hydraulic composition containing the hydraulic cement and the pozzolanic substance cannot be sufficiently reduced.

Example 14
The procedure was the same as Example 3 except that the mortar formulation was changed to the formulation 2 in Table 1. The results are shown in Table 4.

Example 15
The same procedure as in Example 5 was performed except that the mortar formulation was changed to the formulation 2 in Table 1. The results are shown in Table 4.

Example 16
The same operation as in Example 7 was performed except that the mortar composition was changed to the composition 2 in Table 1. The results are shown in Table 4.

[Comparative Example 4]
The same procedure as in Comparative Example 1 was performed except that the mortar formulation was changed to the formulation 2 in Table 1. The results are shown in Table 4.

  As can be seen from Table 4, in Examples 14 to 16 (average added mole number of oxyalkylene group is 40 or less and the mass average molecular weight of the polycarboxylic acid copolymer is 20000 or less), water Contains hydraulic cement and pozzolanic substance even if the substitution rate of pozzolanic substance in hydraulic composition containing hard cement and pozzolanic substance is increased from 40% (formulation 1) to 50% (formulation 2) The viscosity of the hydraulic composition is sufficiently reduced.

  The viscosity reducing agent for a pozzolanic substance-containing hydraulic composition of the present invention can be suitably used as a material for a concrete composition such as cement paste, mortar or concrete.

Claims (8)

A viscosity reducing agent for reducing the viscosity of a hydraulic composition containing a hydraulic cement and a pozzolanic substance,
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 polycarboxylic acid copolymer (A) containing the structural unit (II):
N in the general formula (1) is 1 to 40,
The weight average molecular weight of the polycarboxylic acid copolymer (A) is 20000 or less.
A viscosity reducing agent for a hydraulic composition containing a pozzolanic substance.

(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; Are the same or different and represent an oxyalkylene group having 2 to 18 carbon atoms, n represents the average number of moles added of the oxyalkylene group represented by AO, x is an integer of 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 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. Viscosity reducing agent.   The viscosity reducing agent for a pozzolanic substance-containing hydraulic composition according to claim 1 or 2, wherein the pozzolanic substance contains fly ash. 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). The viscosity reducing agent for pozzolanic substance-containing hydraulic compositions according to any one of 1 to 3.
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 number of added moles of the oxyalkylene group represented by the formula (1), n is 1 to 40, 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 viscosity reducing agent for pozzolanic substance-containing hydraulic compositions according to claim 4, which is a -3-butenyl group.   A concrete composition comprising a hydraulic composition containing a hydraulic cement and a pozzolanic substance, and the viscosity reducing agent for a pozzolanic substance-containing hydraulic composition according to any one of claims 1 to 5.   The concrete composition according to claim 6, 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 6 or 7, wherein the pozzolanic substance includes fly ash.

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