JP2007076969A - Admixture composition for hydraulic material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an admixture composition for a hydraulic material, wherein effective reduction of dry shrinkage is attained, and excellent fluidity/dispersibility is given to the hydraulic material such as concrete member. <P>SOLUTION: The admixture composition for the hydraulic material contains at least one kind of a structural unit (1) expressed by formula (1) (wherein R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>each independently represents a hydrogen atom, methyl group or -(CH<SB>2</SB>)<SB>p</SB>COOX group, wherein X represents a hydrogen atom, a univalent metal, a divalent metal, an ammonium group, an organic amine group or a hydrocarbon group and (p) is an integer of 0-2, and R<SP>4</SP>presents a 4-30C hydrocarbon group) as an essential component, and further contains: a dry shrinkage reducing agent containing a polymer having 25-50 mN/m surface tension in a solution in which the polymer is contained by 0.2 mass% in a supernatant solution of cement; and a high performance AE water reducing agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an admixture composition for hydraulic materials. In particular, the present invention relates to an admixture composition for a hydraulic material that imparts sufficient drying shrinkage reduction and fluidity / dispersibility to a hydraulic material, particularly a concrete member.

  Hydraulic materials are widely used in cement compositions such as cement paste, mortar, and concrete because they give cured products with excellent strength and durability, and are indispensable for building civil engineering and building structures. It is impossible. In such a hydraulic material, after curing, unreacted water evaporates from the surface of the structure due to the outside air temperature, humidity conditions, etc., but drying shrinkage considered to be caused by this proceeds, Cracks are often a problem. This cracking not only detracts from the aesthetics of the structure, but in the long term, deterioration factors such as air (especially carbon dioxide) and rainwater (especially acid and chloride ions) infiltrate through the cracked part in the concrete. It has been pointed out that it causes many complex deteriorations, such as promoting the corrosion of steel and the corrosion of reinforcing bars. In recent years, early deterioration of these concrete structures has become a social problem, and the demand for structures with excellent durability that suppress cracking has increased. Recognizing the importance of suppressing the progress of technology, technological innovation is actively being carried out.

Against this background, many research reports on shrinkage have been made, and methods for reducing shrinkage (and thus suppressing cracking) include the use of an expanding material and the unit water content of a concrete composition using a water reducing agent. And a method using a drying shrinkage reducing agent. Of these, the method of reducing the unit water amount using a water reducing agent is widely used as the simplest method. As such a water reducing agent, naphthalene type, amino sulfonic acid type and polycarboxylic acid type are currently on the market, and in the polycarboxylic acid type high performance AE water reducing agent having the most excellent characteristics, various water-soluble vinyls are used. Copolymers have been proposed (see, for example, Patent Documents 1 to 5). However, in these water reducing agents, the drying shrinkage reducing property is not sufficient, and a method in which an expansion material or a drying shrinkage reducing agent is used in combination as required is employed. Under the present circumstances, various compounds are used as a drying shrinkage reducing agent used together (for example, refer patent documents 6-9). Among the above publications, Patent Document 6 discloses a drying shrinkage preventing agent for cement containing an addition polymer of propylene oxide and ethylene oxide. Patent Document 7 discloses a drying shrinkage reducing agent containing an alkylene oxide adduct of a diphenylmethane derivative.
JP-A-8-53522 JP-A-8-290948 JP-A-8-290955 Japanese Patent Laid-Open No. 9-2855 JP-A-10-81549 JP 59-21557 A JP 62-61450 A JP 59-3430 A Japanese Patent No. 2825855

  However, both the expansion agent and the drying shrinkage reducing agent need to be added to the concrete composition, and the dry shrinkage reducing agent has a high product price. Admixing of lead to a marked increase in unit price per unit volume of concrete. Such a problem contributes to the fact that the drying shrinkage reducing agent does not spread in the market.

  As a measure for solving these problems, for example, Patent Document 8 discloses a polymer obtained by graft polymerization of an ethylenically unsaturated carboxylic acid to an alkoxy polyalkylene glycol. However, the polymer disclosed in Patent Document 8 cannot satisfy dispersibility and drying shrinkage reduction at the same time, and cannot sufficiently solve the above problem.

  Thus, although there is a strong demand for an additive that can effectively reduce drying shrinkage and impart sufficient fluidity / dispersibility to a concrete member or the like, such an additive has not been obtained.

  Accordingly, the present invention has been made in view of the above circumstances, and is an admixture for hydraulic materials that can effectively reduce drying shrinkage and can impart sufficient fluidity / dispersibility to hydraulic materials such as concrete members. An object is to provide a composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have included and identified a structural unit having a hydrophobic group as an essential component, particularly while paying attention to the surface tension against water. Drying shrinkage reducing agents that exhibit the surface tension of the resin, especially drying shrinkage reducing agents containing a polymer having a specific structure have excellent drying shrinkage reducing properties and do not exhibit dispersibility even when the amount used is increased. The present inventors have found that the dispersibility and the drying shrinkage reduction property can be easily adjusted according to the purpose by using the dispersant together. As a result of intensive investigations to further improve the balance between drying shrinkage reduction and fluidity (dispersibility), the drying shrinkage reducing agent can be used as an appropriate high-performance AE water reducing agent, particularly polycarboxylic acid. It has been found that an admixture composition for hydraulic materials that simultaneously satisfies the desired dispersibility and high drying shrinkage reduction properties can be obtained by combining with a high performance AE water reducing agent. Based on these findings, the present inventors have completed the present invention.

  That is, the above object is achieved by the following formula (1):

In the ^formula, R 1, ^{R 2} and ^{R 3} are each independently a hydrogen atom, a methyl group or _- represents _(CH 2) p COOX group, this time, X is a hydrogen atom, a monovalent metal, Represents a divalent metal, an ammonium group, an organic amine group or a hydrocarbon group, p is an integer of 0 to 2; and R ⁴ represents a hydrocarbon group of 4 to 30 carbon atoms,
Dry shrinkage reduction comprising a polymer having a surface tension of 25 to 50 mN / m in a solution containing at least one structural unit (I) represented by formula (I) as an essential component and containing 0.2% by mass of the polymer in the cement supernatant. And an admixture composition for hydraulic materials, characterized by comprising an agent and a high performance AE water reducing agent.

  According to the present invention, desired dispersibility and high dry shrinkage can be obtained by combining a predetermined dry shrinkage reducing agent exhibiting excellent dry shrinkage reducing properties with an appropriate AE water reducing agent (particularly a high performance AE water reducing agent). It becomes possible to provide an admixture composition for hydraulic materials that simultaneously satisfies the reduction property.

  Therefore, the admixture composition for hydraulic materials of the present invention is applied to hydraulic materials such as cement paste, mortar, concrete, etc., and exhibits an excellent crack prevention effect, thereby improving the strength and durability of the cured product. It can be improved, and it is highly versatile, which can improve the safety of civil engineering / building structures and the like, and can suppress repair costs.

  Hereinafter, embodiments of the present invention will be described in detail.

  The first of the present invention is the following formula (1):

In the ^formula, R 1, ^{R 2} and ^{R 3} are each independently a hydrogen atom, a methyl group or _- represents _(CH 2) p COOX group, this time, X is a hydrogen atom, a monovalent metal, Represents a divalent metal, an ammonium group, an organic amine group or a hydrocarbon group, p is an integer of 0 to 2; and R ⁴ represents a hydrocarbon group of 4 to 30 carbon atoms,
At least one structural unit (I) represented by the formula (in the present specification, simply referred to as “structural unit (II-a)”) as an essential component, and 0.2% by mass of the polymer in the cement supernatant. A drying shrinkage reducing agent including a polymer having a surface tension (also referred to simply as “surface tension” in the present specification) of 25 to 50 mN / m, and a high-performance AE water reducing agent. The present invention provides an admixture composition for hydraulic materials.

1. Drying shrinkage reducing agent The admixture composition for hydraulic materials of the present invention has the following formula (1) as a first component:

In the ^formula, R 1, ^{R 2} and ^{R 3} are each independently a hydrogen atom, a methyl group or _- represents _(CH 2) p COOX group, this time, X is a hydrogen atom, a monovalent metal, Represents a divalent metal, an ammonium group, an organic amine group or a hydrocarbon group, p is an integer of 0 to 2; and R ⁴ represents a hydrocarbon group of 4 to 30 carbon atoms,
And a dry shrinkage reducing agent containing a polymer having a surface tension of 25 to 50 mN / m.

The dry shrinkage reducing agent is excellent in dry shrinkage reducing performance, but its clear mechanism is unknown. However, the following mechanism has been estimated. That is, drying shrinkage is caused by the tensile stress of water acting on the interface between the water in the capillary and the hardened body when water moves in the capillary in the hardened cement body by drying. When the hydrophobic group of R ⁴ derived from the structural unit (I) is introduced, the interfacial tension between the cured body and water is lowered, the tensile stress of water causing drying shrinkage is reduced, and as a result, drying shrinkage can be suppressed. Conceivable. In addition to the structural unit (I), the polymer has the following formula (2):

A structural unit (II-a) (also referred to simply as “structural unit (II-a)” in the present specification) and the following formula (3):

Containing at least one structural unit (II) selected from the structural unit (II-b) represented by the formula (herein also simply referred to as “structural unit (II-b)”) as an essential component; Following formula (4):

It is preferable that 0 to 30% by mass of the whole polymer is contained in at least one structural unit (III) represented by the formula (hereinafter, also simply referred to as “structural unit (III)”). The clear mechanism by which the polymer can suppress drying shrinkage is also unclear, but it is considered that the polymer according to the present invention suppresses drying shrinkage as follows. That is, in addition to the action of the structural unit (I) in the polymer according to the present invention, the structural unit (III) that particularly acts to exert dispersibility is 0 to 30% by mass of the whole polymer in the polymer. By making it exist in a low ratio, water-solubility can be exhibited without exhibiting dispersibility. Moreover, the dispersibility according to a use and the objective and high dry shrinkage reduction property can be exhibited by combined use with the high performance AE water reducing agent mentioned later. If the structural unit (III) is present in a large amount exceeding 30% by mass in the polymer, the acid is excessively incorporated in the polymer, and the resulting polymer is adsorbed on the cement and becomes dispersible. This will cause problems such as causing delay in curing. Of the above structural units, the structural unit (II) has the effect of imparting water solubility to the polymer. Therefore, the drying shrinkage reducing agent of the present invention is usually used in various portland cements such as early strength, moderate heat, low heat, and sulfate-resistant salts, high belite containing cement, alumina cement, blast furnace cement, fly ash cement, various mixed cements, etc. It is suitably used for the purpose of effectively reducing drying shrinkage to other hydraulic cements or hydraulic materials other than cement such as gypsum.

  The polymer according to the present invention must contain a polymer having a surface tension of 25 to 50 mN / m in a solution containing the structural unit (I) as an essential component and 0.2% by mass of the polymer in the cement supernatant. It is. At this time, if the surface tension is within the above range, the feasibility at the industrial level can be sufficiently satisfied, and the shrinkage of the cement after hardening can be effectively suppressed. Even if it is used for a structure that does not have any distortion, it does not cause distortion with the hardened cement body, so that problems such as cracks do not occur. On the other hand, when the surface tension of the polymer exceeds 50 mN / m, a sufficient shrinkage suppressing effect cannot be obtained. For example, when used in a reinforcing bar, the cured cement body contracts, and the reinforcing bar and the cement are hardened. Distortion occurs between the body and causes phenomena such as cracks. In the present invention, the lower the surface tension, the better. However, considering the feasibility at the industrial level, the lower limit of the surface tension is set to 25 mN / m. In the present invention, the surface tension of the polymer solution containing 0.2% by mass of the polymer in the cement supernatant is preferably 25 to 46 mN / m, more preferably 25 to 42 mN / m, particularly preferably 25 to 25 mN / m. 38 mN / m.

  In the present specification, “surface tension in a solution containing 0.2% by mass of a polymer in a cement supernatant” means a value measured according to the following conditions and procedures.

<Measurement conditions>
Measuring instrument: BYK-Chemie, Dynameter (trade name)
Ring: Platinum φ19.5mm
Standard solution: pure water 72.8 mN / m (20 ° C.)
Table speed: 1.5 mm / min Measurement temperature: 20 ° C.
<Measurement procedure>
Taiheiyo Cement was prepared by placing 200 parts by mass of ion-exchanged water at 25 ° C. into a 300 ml glass beaker containing a 39 mm-long stirrer chip and stirring the mixture with a magnetic stirrer in an atmosphere at 25 ° C. 100 parts by mass of ordinary Portland cement made is charged. After the addition, the rotation speed is set to 700 rpm, and the mixture is stirred for 30 minutes so that the water-soluble components in the cement particles are sufficiently eluted in water, and then allowed to stand for 10 minutes. The supernatant was filtered with suction using filter paper (Advantech Toyo Co., Ltd., quantitative filter paper 5C), and the filtrate was further filtered with an aqueous filter (Chromatodisc 25A, Kurabo Industries, GL Sciences sales) with a pore size of 0.45 μm. Thus, a cement supernatant aqueous solution is obtained. Place the adjusted cement supernatant in a container, seal with nitrogen, seal tightly and store.

  On the other hand, 25 ° C. ion exchange water is added to the drying shrinkage reducing agent or comparative copolymer of the present invention to prepare an aqueous solution having a solid content concentration of 5 mass%. 5 parts by mass of the aqueous solution containing the drying shrinkage reducing agent or comparative copolymer of the present invention is added to 120 parts by mass of the cement supernatant and mixed well to prepare a 0.2% by mass aqueous sample solution. The sample aqueous solution is put in a container, sealed with nitrogen, sealed, and adjusted to 20 ° C.

  Next, a sufficiently washed platinum ring is attached to a dynometer, submerged in a standard solution (pure water) adjusted to 20 ° C. for 3 mm, and the table on which this standard solution is placed is at a speed of 1.5 mm / min. To descend. At this time, the point at which the value indicated by the dynamometer is maximized is calibrated as the surface tension of water. Next, a platinum ring that has been sufficiently washed in a sample solution adjusted to 20 ° C. is submerged 3 mm, and the table on which the aqueous solution is placed is lowered at a rate of 1.5 mm / min, and the value indicated by the dynamometer becomes the largest. The point is defined as the surface tension of the drying shrinkage reducing agent (component of the present invention).

In the above formula (1), R ¹ , R ² and R ³ represent a hydrogen atom, a methyl group or a — (CH ₂ ) _p COOX group, preferably a hydrogen atom or a methyl group. At this time, R ¹ , R ² and R ³ may be the same or different. In the formula: (CH ₂ ) _p COOX, X represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group (—NH ₂ ), an organic amine group, or a hydrocarbon group. In this case, examples of the monovalent metal include lithium, sodium, and potassium. Examples of the divalent metal include magnesium, calcium, strontium, barium and the like. In addition, when X is a divalent metal, it takes the form of an anhydride with two -COO-. Examples of the organic amine group include groups derived from primary amines such as methylamine, ethylamine, propylamine, n-butylamine, sec-butylamine, tert-butylamine, cyclohexylamine, benzylamine and phenylamine; dimethylamine, diethylamine, diamine Groups derived from secondary amines such as propylamine, dibutylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, dicyclohexylamine, dibenzylamine and diphenylamine; trimethylamine, triethylamine, tripropylamine, tributylamine, Groups derived from tertiary amines such as tricyclohexylamine, tribenzylamine and triphenylamine; and ethanolamine, diethanolamine, triethanolamine It includes groups derived from alkanolamines are. Among these, alkanolamine groups such as ethanolamine group, diethanolamine group and triethanolamine group, and triethylamine group are preferable. The hydrocarbon group is, for example, preferably a hydrocarbon group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms. Examples of the hydrocarbon group having 1 to 30 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl Linear or branched alkyl groups such as, undecyl, dodecyl, isooctyl, 2,3,5-trimethylhexyl, 4-ethyl-5-methyloctyl and 2-ethylhexyl, tetradecyl, octadecyl, icosyl; cyclopropyl, cyclobutyl, Cyclic alkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; phenyl, benzyl, phenethyl, o-, m- or p-tolyl, 2,3- or 2,4-xylyl, mesityl, naphthyl, anthryl, phenane Lil, biphenylyl, benzhydryl, and the like aryl groups such as trityl, and pyrenyl. Among these, X is preferably a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group or an organic amine group, and particularly preferably a hydrogen atom, sodium or calcium. Moreover, in the said Formula (1), p is an integer of 0-2, Preferably it is 0 or 1, Especially 0. R ⁴ represents a hydrocarbon group having 4 to 30 carbon atoms. At this time, if the number of carbon atoms of R ⁴ is 3 or less, the desired drying shrinkage reduction property cannot be obtained, and if it is 31 or more, it becomes difficult to balance the hydrophilicity and hydrophobicity of the polymer. 4 to 30 is preferred. The number of carbon atoms of R ⁴ is preferably 4 to 30, more preferably 4 to 18, still more preferably 4 to 12, and most preferably 5 to 12. Examples of such hydrocarbon groups include butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isooctyl, 2, 3, 5 Linear and branched alkyl groups such as trimethylhexyl, 4-ethyl-5-methyloctyl and 2-ethylhexyl, tetradecyl, octadecyl and icosyl; cyclic alkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; phenyl Aryl groups such as benzyl, phenethyl, o-, m- or p-tolyl, 2,3- or 2,4-xylyl, mesityl, naphthyl, anthryl, phenanthryl, biphenylyl, benzhydryl, trityl and pyrenyl. It is. Among these, in consideration of dispersibility of the hardened cement and reduction of drying shrinkage, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, Alkyl groups having 4 to 12 carbon atoms such as dodecyl, isooctyl, 2,3,5-trimethylhexyl, 4-ethyl-5-methyloctyl and 2-ethylhexyl are preferred.

Monomers (hereinafter also simply referred to as “monomer (a)”) that give the structural unit (I) used in the present invention include monools having 4 to 30 carbon atoms, that is, butanol, isobutanol. , Sec-butanol, tert-butanol, 1-pentanol, 1-hexanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, etc., saturated fat having 4 to 30 carbon atoms Unsaturated alcohols having 4 to 30 carbon atoms such as aliphatic alcohols, oleyl alcohol, alicyclic alcohols having 4 to 30 carbon atoms such as cyclohexanol, phenol, phenylmethanol (benzyl alcohol), methylphenol (Cresol), p-ethylphenol, dimethylphenol Xylenol), pt-butylphenol, nonylphenol, dodecylphenol, phenylphenol, naphthol and other aromatic alcohols having 6 to 30 carbon atoms, and unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid, or And ester compounds with unsaturated dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid and fumaric acid. In addition, when R ¹ , R ² and R ³ are each independently a hydrogen atom or a methyl group, a copolymerizable surface with a monomer that gives the structural unit (II) described in detail below. Therefore, it is preferable to use, as the monomer (a), an ester compound of an alcohol having 4 to 30 carbon atoms and an unsaturated monocarboxylic acid such as (meth) acrylic acid or crotonic acid. Further, the formula (1) wherein at least one of R ¹ , R ² or R ³ represents a — (CH ₂ ) _p COOX group, and X represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group or an organic amine group. The monomer (a) having the structural unit (I) is an unsaturated monocarboxylic acid monomer such as acrylic acid, methacrylic acid, crotonic acid and their metal salts, ammonium salts, amine salts, etc. Can be mentioned. Further, as the unsaturated dicarboxylic acid-based monomer, maleic acid, itaconic acid, citraconic acid, fumaric acid, or metal salts thereof, ammonium salts, amine salts, etc., and further as anhydrides thereof, maleic anhydride, Examples thereof include itaconic anhydride and citraconic anhydride. Of these, unsaturated monocarboxylic acid monomers are preferable, and (meth) acrylic acid and salts thereof are particularly preferable. In addition, the said monomer (a) may be used independently or may be used with the form of a 2 or more types of mixture.

  Specific examples of such a monomer (a) include butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 1-pentyl (meth) acrylate. 1-hexyl (meth) acrylate, 1-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl Various alkyl (meth) acrylates such as (meth) acrylate; various alkyl malates such as (di) propyl malate, (di) butyl malate, (di) 2-ethylhexyl malate; (di) propyl fumarate , (Di) Butyl fumaray , (Di) of 2-ethylhexyl fumarate, etc., various alkyl fumarates, and the like can be mentioned. In this case, these monomers (a) or structural units (I) may be used alone or in combination of two or more.

In the above formula (2), R ⁵ , R ⁶ and R ⁷ represent a hydrogen atom or a methyl group, and preferably at least one of R ⁵ and R ⁶ represents a hydrogen atom. At this time, R ⁵ , R ⁶ and R ⁷ may be the same or different. s is an integer of 0 to 2, preferably 0 or 1, and more preferably 0. R ⁸ O represents an oxyalkylene group having 2 to 18 carbon atoms, preferably an oxyalkylene group having 2 to 8 carbon atoms, more preferably an oxyalkylene group having 2 to 4 carbon atoms. Preferred examples of such oxyalkylene group include oxyethylene group, oxypropylene group, oxybutylene group, oxyisobutylene group, oxy1-butene group, oxy2-butene group, and oxystyrene group, but more preferably An oxyethylene group, an oxypropylene group, and an oxybutylene group, still more preferably an oxyethylene group and an oxypropylene group. When a plurality of these oxyalkylene groups are present in one structural unit (that is, in formula (2), n is 2 or more), even if one kind is present in one structural unit. Alternatively, it may exist in the form of a mixture of two or more. When two or more oxyalkylene groups are present, any addition form such as random addition, block addition, and alternate addition may be used. When only one type of structural unit is used as the structural unit (II-a), it is preferable to include an oxyethylene group as an essential component in the oxyalkylene group in order to ensure a balance between hydrophilicity and hydrophobicity. The mol% or more is preferably an oxyethylene group.

In the above formula (2), u represents an average addition mole number of the oxyalkylene group ^(R 8 O), the number of 1 to 300. When u exceeds 300, the resulting polymer exhibits dispersibility, which makes it impossible to add any amount, making it difficult to obtain the desired drying shrinkage reduction property. Furthermore, if u exceeds 300, air entrainment becomes high, and it becomes difficult to adjust the air amount, which causes a decrease in strength and a decrease in freeze-thaw resistance. Under the present circumstances, u is preferable in the order of 1-150, 1-100, 1-80, 1-50, 1-30. R ⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or 1 to 18 carbon atoms. And particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. Specific examples of such hydrocarbon groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, Neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isooctyl, 2,3,5-trimethylhexyl, 4-ethyl-5-methyloctyl and 2-ethylhexyl Group, tetradecyl group, octadecyl group, icosyl group or the like linear or branched alkyl group; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or the like cyclic alkyl group; phenyl group, benzyl group, phenethyl group O, m- or p-tolyl group, 2,3-young 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, a biphenylyl group, a benzhydryl group, and aryl groups such as trityl group and pyrenyl group.

As a monomer (hereinafter, also simply referred to as “monomer (b)”) that provides the structural unit (II-a) used in the present invention, dehydrogenation (oxidation) of (meth) acrylic acid, crotonic acid, or fatty acid. ) Addition of alkylene oxide having 2 to 18 carbon atoms to the reaction product, or methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, octanol, 2-ethyl-1-hexanol C 3-30 saturated aliphatic alcohols such as nonyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, etc., allyl alcohol, methallyl alcohol, crotyl alcohol, oleyl alcohol, etc. C3-C30 alicyclic alcohols such as saturated aliphatic alcohols and cyclohexanol Carbon atoms such as phenols, phenol, phenylmethanol (benzyl alcohol), methylphenol (cresol), p-ethylphenol, dimethylphenol (xylenol), pt-butylphenol, nonylphenol, dodecylphenol, phenylphenol, naphthol Examples include ester compounds of alkoxypolyalkylene glycols obtained by adding alkylene oxides having 2 to 18 carbon atoms to any of 6 to 30 aromatic alcohols and (meth) acrylic acid or crotonic acid. However, in the formula (2), an ester compound of an alkoxypolyalkylene glycol and (meth) acrylic acid or crotonic acid corresponding to the case where R ⁹ is a hydrocarbon group is preferable. The monomer (b) may be used alone or in the form of a mixture of two or more.

  Specific examples of the monomer (b) include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate, and ethoxy polyethylene glycol mono (meth) acrylate. 1-propoxy polyethylene glycol mono (meth) acrylate, 2-propoxy polyethylene glycol mono (meth) acrylate, 1-butoxy polyethylene glycol mono (meth) acrylate, 2-butoxy polyethylene glycol mono (meth) acrylate, 2-methyl-1 -Propoxypolyethylene glycol mono (meth) acrylate, 2-methyl-2-propoxypolyethylene glycol mono (meth) acrylate, 1-pentyloxy Polyethylene glycol mono (meth) acrylate, 1-hexyloxypolyethylene glycol mono (meth) acrylate, cyclohexyloxypolyethylene glycol mono (meth) acrylate, 1-octyloxypolyethylene glycol mono (meth) acrylate, 2-ethyl-1-hexyloxy Polyethylene glycol mono (meth) acrylate, nonylalkoxypolyethyleneglycol mono (meth) acrylate, laurylalkoxypolyethyleneglycolmono (meth) acrylate, cetylalkoxypolyethyleneglycolmono (meth) acrylate, stearylalkoxypolyethyleneglycolmono (meth) acrylate, phenoxypolyethylene Glycol mono (meth) acrylate, phenylmethoxypo Ethylene glycol mono (meth) acrylate, methylphenoxypolyethylene glycol mono (meth) acrylate, p-ethylphenoxypolyethylene glycol mono (meth) acrylate, dimethylphenoxypolyethyleneglycol mono (meth) acrylate, pt-butylphenoxypolyethyleneglycol mono ( (Meth) acrylate, nonylphenoxypolyethylene glycol mono (meth) acrylate, dodecylphenoxypolyethylene glycol mono (meth) acrylate, phenylphenoxypolyethyleneglycol mono (meth) acrylate, naphthoxypolyethyleneglycol mono (meth) acrylate, ethylene oxide ( Esterified product of (meth) allyl alcohol and (meth) acrylic acid, ethylene Various alkoxy polyethylene glycol mono (meth) acrylates such as esterified products of crotyl alcohol to which oxide is added and (meth) acrylic acid; methoxypolypropylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, 1 -Propoxy polypropylene glycol mono (meth) acrylate, 2-propoxy polypropylene glycol mono (meth) acrylate, 1-butoxy polypropylene glycol mono (meth) acrylate, propylene oxide added (meth) allyl alcohol and (meth) acrylic acid Alkoxy polypropylene glycols such as esterified products of crotyl alcohol with propylene oxide and (meth) acrylic acid (Meth) acrylates; methoxypolyethylenepolypropyleneglycol mono (meth) acrylate, methoxypolyethylenepolybutyleneglycolmono (meth) acrylate, ethoxypolyethylenepolypropyleneglycolmono (meth) acrylate, ethoxypolyethylenepolybutyleneglycolmono (meth) acrylate, 1 -Propoxypolyethylenepolypropylene glycol mono (meth) acrylate, 1-propoxypolyethylenepolybutyleneglycol mono (meth) acrylate, 2-propoxypolyethylenepolypropyleneglycol mono (meth) acrylate, 2-propoxypolyethylenepolybutyleneglycolmono (meth) acrylate, 1 -Butoxypolyethylene polypropylene glycol mono (meth) a Lilate, 1-butoxypolyethylene polybutylene glycol mono (meth) acrylate, esterified product of (meth) allyl alcohol and (meth) acrylic acid to which ethylene oxide and propylene oxide or ethylene oxide and butylene oxide are added, ethylene oxide and propylene oxide or ethylene oxide Alkoxypolyalkylene glycols such as esterified products of alcohol and (meth) acrylic acid added with two or more types of alkylene oxides such as esterified products of crotyl alcohol and (meth) acrylic acid added with styrene and butylene oxide And mono (meth) acrylates. In this case, these monomers (b) or structural units (II-a) may be used alone or in combination of two or more.

In the above formula (3), R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, and preferably at least one of R ¹⁰ and R ¹¹ represents a hydrogen atom. At this time, R ¹⁰ , R ¹¹ and R ¹² may be the same or different. x is an integer of 0 to 2, preferably 0 or 1, and more preferably 0. R ¹³ O represents an oxyalkylene group having 2 to 18 carbon atoms, preferably an oxyalkylene group having 2 to 8 carbon atoms, more preferably an oxyalkylene group having 2 to 4 carbon atoms. Such an oxyalkylene group is the same as R ⁸ O in the above formula (2). In the case where a plurality of these oxyalkylene groups are present in one structural unit (that is, in the formula (3), n is 2 or more), even if one kind is present in one structural unit. Alternatively, it may exist in the form of a mixture of two or more. When two or more kinds of oxyalkylene groups are present, the addition form may be any of random addition, block addition, alternating addition, and the like. When only one type of structural unit is used as the structural unit (II-b), it is preferable to include an oxyethylene group as an essential component in the oxyalkylene group in order to ensure a balance between hydrophilicity and hydrophobicity. The mol% or more is preferably an oxyethylene group. Moreover, y represents the average addition mole number of an oxyalkylene group (R < ¹³ > O), and is a number of 1-300. If y exceeds 300, the resulting polymer exhibits dispersibility, which makes it impossible to add any amount, making it difficult to obtain the desired drying shrinkage reduction property. Furthermore, if y exceeds 300, air entrainment becomes high, adjustment of the amount of air becomes difficult, and this causes a decrease in strength and freeze-thaw resistance. y is preferably in the order of 1 to 150, 1 to 100, 1 to 80, 1 to 50, and 1 to 30. R ¹⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or 1 to 18 carbon atoms. And particularly preferably a hydrocarbon group having 1 to 12 carbon atoms. In addition, since the definition of the substituent “R ¹⁴ ” in the formula (3) is the same as the definition of the substituent “R ⁹ ” in the formula (2), description thereof is omitted here.

  As the monomer (hereinafter, also simply referred to as “monomer (c)”) that provides the structural unit (II-b) used in the present invention, the number of carbon atoms in alcohols such as vinyl alcohol or isoprene alcohol is 2 -18 alkylene oxide adducts and the like. In addition, the said monomer (c) may be used independently or may be used with the form of a 2 or more types of mixture.

  Specific examples of the monomer (c) include (poly) ethylene glycol-3-methyl-3-butenyl ether, (poly) propylene glycol-3-methyl-3-butenyl ether, poly) butylene glycol-3. -Methyl-3-butenyl ether, (poly) ethylene glycol (poly) propylene glycol-3-methyl-3-butenyl ether, (poly) ethylene glycol (poly) butylene glycol-3-methyl-3-butenyl ether Etc. In this case, these monomers (c) or structural units (II-b) may be used alone or in combination of two or more.

In the above formula (4), R ¹⁵ , R ¹⁶ and R ¹⁷ represent a hydrogen atom, a methyl group or a — (CH ₂ ) _q COOZ ′ group. At this time, R ¹⁵ , R ¹⁶ and R ¹⁷ may be the same or different. In this case, Z ′ represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group or an organic amine group. Q is an integer of 0 to 2, preferably 0 or 1, particularly 0. Z represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group or an organic amine group. In this case, the definitions of the substituents “Z” and “Z ′” are the same as the definition of the substituent “X” in the formula (1) except that they do not represent a hydrocarbon group. When two or three COOZ ′ are present, these COOZ ′ may be the same or different. Further, when two or more COOZ and COOZ ′ are present, two of these may form an anhydride.

Specific examples of the monomer (hereinafter, also simply referred to as “monomer (d)”) that provides the structural unit (III) used in the present invention include acrylic acid, Examples include methacrylic acid, crotonic acid, and metal salts, ammonium salts, and amine salts thereof. Further, as the unsaturated dicarboxylic acid-based monomer, maleic acid, itaconic acid, citraconic acid, fumaric acid, or metal salts thereof, ammonium salts, amine salts and the like, and as anhydrides thereof, maleic anhydride, Examples thereof include itaconic anhydride and citraconic anhydride. Among these, unsaturated monocarboxylic acid monomers corresponding to the case where R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom or a methyl group are preferable, and (meth) acrylic acid and salts thereof are particularly preferable. . In this case, these monomers (d) or structural units (III) may be used alone or in combination of two or more.

  The polymer contained in the drying shrinkage reducing agent which is a constituent component of the present invention contains the constituent unit (I) and the constituent unit (II-a) and / or the constituent unit (II-b) as essential constituent units. The structural unit (III) is contained at a ratio of 0 to 30% by mass of the whole polymer. At this time, each of the structural units (I), (II-a) and (II-b), and the structural unit (III) may be a single structural unit or two or more structural units. The structural unit (I), the structural unit (II-a), the structural unit (II-b), and the structural unit (III) may be in a block form or in a random form, respectively. It may be. Further, the polymer according to the present invention may further have at least one other different structural unit (hereinafter, also simply referred to as “structural unit (IV)”) in addition to the above structural unit. In any case, these structural units may be block-shaped or random.

  Examples of the monomer that gives such other structural unit (IV) (hereinafter, also simply referred to as “monomer (e)”) include monomers that are copolymerizable with other monomer components, Specific examples of such a monomer include half esters and diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and the like, and alcohols having 1 to 4 carbon atoms; An alkyl (poly) alkylene glycol obtained by adding 1 to 500 moles of an alkylene oxide having 2 to 18 carbon atoms to the alcohol or amine, and the unsaturated dicarboxylic acids. Half-esters, diesters; and unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or addition moles of these glycols of 2 to 50 Half-esters and diesters of polyalkylene glycols with maleic acid and glycols having 2 to 18 carbon atoms or polyalkylene glycols having an addition mole number of these glycols of 2 to 500; triethylene glycol di (meth) acrylate , (Poly) alkylene glycol di (meth) acrylates such as (poly) ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) propylene glycol di (meth) acrylate; hexane Difunctional (meth) acrylates such as diol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate; triethylene glycol dimer And (poly) alkylene glycol dimaleates such as polyethylene glycol dimaleate; vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate, 3- ( (Meth) acryloxy-2-hydroxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropyl sulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxybutyl sulfonate, Unsaturated sulfonic acids such as (meth) acrylamidomethylsulfonic acid, (meth) acrylamidoethylsulfonic acid, 2-methylpropanesulfonic acid (meth) acrylamide, styrenesulfonic acid, and monovalents thereof Metal salts, divalent metal salts, ammonium salts and organic amine salts; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, glycidyl (meth) acrylate, methyl crotonate, ethyl crotonate, propyl crotonate An ester of an unsaturated monocarboxylic acid such as, and an alcohol having 1 to 4 carbon atoms; an amide of an unsaturated monocarboxylic acid and an amine having 1 to 30 carbon atoms such as methyl (meth) acrylamide; styrene, Vinyl aromatics such as α-methylstyrene, vinyltoluene, p-methylstyrene; 1,4-butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono Alkanediol mono (meth) a such as (meth) acrylate Relates; dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene; (meth) acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide Unsaturated amides such as N, N-dimethyl (meth) acrylamide; Unsaturated cyans such as (meth) acrylonitrile and α-chloroacrylonitrile; Unsaturated esters such as vinyl acetate and vinyl propionate; (meth) acrylic Unsaturated amines such as aminoethyl acid, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, vinylpyridine; Divinyl aromatics such as benzene; triallylsia Cyanurates such as acrylate; allyls such as (meth) allyl alcohol and glycidyl (meth) allyl ether; unsaturated amino compounds such as dimethylaminoethyl (meth) acrylate; methoxy polyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxy Vinyl ethers or allyl ethers such as polyethylene glycol mono (meth) allyl ether and polyethylene glycol mono (meth) allyl ether; polydimethylsiloxanepropylaminomaleamic acid, polydimethylsiloxaneaminopropylaminoaminomaleamic acid, polydimethylsiloxane-bis -(Propylaminomaleamic acid), polydimethylsiloxane-bis- (dipropylaminomaleamic acid), polydi Tylsiloxane- (1-propyl-3-acrylate), polydimethylsiloxane- (1-propyl-3-methacrylate), polydimethylsiloxane-bis- (1-propyl-3-acrylate), polydimethylsiloxane-bis- ( Siloxane derivatives such as 1-propyl-3-methacrylate); unsaturated phosphate esters such as 2-acryloyloxyethyl phosphate and 2-methacryloyloxyethyl phosphate. In this case, these monomer (e) or the structural unit (IV) derived from the monomer (e) may be used alone or in combination of two or more.

  The method for producing the polymer contained in the drying shrinkage reducing agent which is a constituent component of the present invention is not particularly limited, and a known polymerization method can be used. What is necessary is just to polymerize a body component. The polymerization method of the monomer component is not particularly limited, and a known polymerization method can be used similarly or modified, but the polymerization can be performed by a method such as polymerization in a solvent or bulk polymerization, for example. . Polymerization in a solvent can be carried out either batchwise or continuously. The solvent used here is water; lower alcohols such as methyl alcohol, ethyl alcohol, 2-propanol; benzene, toluene, xylene, cyclohexane, Examples include aromatic or aliphatic hydrocarbons such as n-hexane; ester compounds such as ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone. Considering the solubility of the raw material monomer and the resulting polymer and the convenience of using this polymer, use at least one selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms. Are preferred, and lower alcohols having 1 to 4 carbon atoms are more preferred, and methyl alcohol, ethyl alcohol, 2-propanol and the like are particularly effective.

  The polymerization initiator used when the polymerization is carried out in an aqueous medium is not particularly limited, and a known polymerization initiator can be used. For example, water-soluble such as ammonium or alkali metal persulfate or hydrogen peroxide. A polymerization initiator is used. In this case, an accelerator such as sodium bisulfite, Mole salt, ascorbic acid (salt), Rongalite and the like can be used in combination. In addition, the polymerization initiator used when performing polymerization using a lower alcohol, aromatic hydrocarbon, aliphatic hydrocarbon, ester compound or ketone compound as a solvent is not particularly limited, and a known polymerization initiator is used. Specifically, peroxides such as benzoyl peroxide and lauroyl peroxide; hydroperoxides such as cumene hydroperoxide; azo compounds such as azobisisobutyronitrile are used as the polymerization initiator. In this case, 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 addition amount of the polymerization initiator is not particularly limited, and the same amount as that used in a known polymerization method can be used. Also, the polymerization conditions are not particularly limited, and the same conditions as known polymerization conditions can be used. For example, the polymerization temperature is appropriately determined depending on the solvent and polymerization initiator used, but is usually in the range of 0 to 120 ° C. Is done within.

  Also in the case of bulk polymerization, the method, the type and amount of the polymerization initiator used, the polymerization conditions, etc. are not particularly limited, and known methods can be used. For example, as the polymerization initiator, peroxides such as benzoyl peroxide and lauroyl peroxide; hydroperoxides such as cumene hydroperoxide; azo compounds such as azobisisobutyronitrile can be used. Moreover, block polymerization is performed within the temperature range of 50-200 degreeC, for example.

Moreover, hypophosphorous acid (salt) and a thiol chain transfer agent can be used in combination for the purpose of adjusting the molecular weight of the resulting polymer. The thiol chain transfer agent used at this time is represented by the formula: HS-R ¹⁸ -E _g (wherein R ¹⁸ represents an alkyl group having 1 to 2 carbon atoms, and E represents —OH, — COOM, —COOR ¹⁹ or SO ₃ M group, wherein M represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group or an organic amine group, and R ¹⁹ has 1 to 10 carbon atoms. For example, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, thioglycol. Examples include octyl acid, octyl 3-mercaptopropionate, and the like. These chain transfer agents may be used alone or in the form of a mixture of two or more. Furthermore, in order to adjust the molecular weight of the polymer, it is also effective to use a monomer having a high chain transfer property such as (meth) allylsulfonic acid (salt) as the monomer (e).

  The polymer thus obtained may be used as it is as a drying shrinkage reducing agent, but may be handled in the form of an aqueous solution not containing an organic solvent. Inorganic substances such as monovalent and divalent metal hydroxides, chlorides and carbon salts; ammonia; organic amines (preferably monovalent metal hydroxides such as sodium hydroxide and potassium hydroxide) It may be neutralized and used as a drying shrinkage reducing agent in the form of a polymer salt.

The polymer contained in the drying shrinkage reducing agent which is a constituent component of the present invention contains the constituent unit (I) as an essential constituent unit. At this time, the ratio of the structural unit (I) is, as described above, due to the introduction of the hydrophobic group of R ⁴ derived from the structural unit (I) to lower the interfacial tension between the cured product and water and cause drying shrinkage. Since it has the effect | action which lowers the tensile stress of a certain water, it is especially important at the point of the suppression effect of drying shrinkage. Considering such action, the proportion of the structural unit (I) is 7 to 99% by mass, 7 to 70% by mass, 10 to 60% by mass, 15 to 60% by mass, 15 to 50% by mass of the whole polymer. % In order. At this time, if the proportion of the structural unit (I) is less than the above lower limit, a sufficient amount of hydrophobic groups are not introduced into the polymer, so that the effect of reducing the tensile stress of water cannot be sufficiently exerted, and the polymer shrinks by drying. It may be inferior to the suppression effect. On the contrary, when the proportion of the structural unit (I) exceeds the above upper limit, the hydrophobic group is excessively introduced into the polymer, becomes insoluble in water, does not become an aqueous solution form, The interfacial tension cannot be lowered, and there is a possibility that a sufficient drying shrinkage suppressing effect cannot be obtained.

  In addition to the structural unit (I), the polymer contained in the drying shrinkage reducing agent that is a structural component of the present invention must include the structural unit (II-a) and / or the structural unit (II-b). It is preferable to include the structural unit as a structural unit, include the structural unit (III) in a proportion of 0 to 30% by mass of the whole polymer, and further include the structural unit (IV) if necessary. In such a case, the ratio of the structural unit (I) in the polymer is the same as the above ratio, and other structural units (II-a), (II-b), (III) and (IV) The ratio of is not particularly limited as long as it does not exhibit dispersibility and can exhibit an excellent effect of reducing and suppressing drying shrinkage of a cement cured body. However, in view of these effects, the structural unit (II-a) Is 1 to 90% by mass of the whole polymer, more preferably 5 to 80% by mass, and the proportion of the structural unit (II-b) is preferably 1 to 90% by mass of the whole polymer. The proportion of the structural unit (III) is 0-30 mass% of the whole polymer; and the proportion of the structural unit (IV) is 0-30 of the whole polymer. It is preferable that it is 0 mass%, More preferably, it is 0-20 mass%. Among the above ratios, it is essential that the structural unit (III) is present in the polymer in a proportion of 0 to 30% by mass of the whole polymer. At this time, if the proportion of the structural unit (III) exceeds 30% by mass, the acid is excessively incorporated into the polymer, and the resulting polymer is adsorbed on the cement and exhibits dispersibility. Furthermore, since the curing time is extended in proportion to the amount of the structural unit (III) added, the structural unit (III) is preferably present in a small amount as much as possible in the polymer. ) Is preferably 0-20% by weight, more preferably 0-15% by weight, even more preferably 0-10% by weight, and most preferably 0-5% by weight of the total polymer. Under the present circumstances, the sum total of the ratio of structural unit (I), (II-a), (II-b), (III) and (IV) is 100 mass%. In addition, the polymer according to the present invention includes an unsaturated monocarboxylic acid monomer such as acrylic acid, methacrylic acid, and crotonic acid, and a monomer (for example, monomer (a)) that provides the structural unit (I). It may be produced by directly esterifying an alkoxypolyalkylene glycol with respect to at least one part of the carboxyl group of a copolymer obtained by copolymerizing a monomer component containing as an essential component.

  The weight average molecular weight of the polymer according to the present invention is suitably in the range of 500 to 500,000 in terms of polystyrene by gel permeation chromatography (hereinafter referred to as “GPC”), but in the range of 500 to 300,000. Is preferable, the range of 500 to 200,000 is more preferable, the range of 500 to 100,000 is more preferable, and the range of 500 to 80,000 is particularly preferable. In the present specification, the weight average molecular weight of the polymer as the drying shrinkage reducing agent is a value measured under the following GPC measurement conditions unless otherwise specified.

<GPC molecular weight measurement conditions>
Column used: Tosoh Corporation, TSK-GEL SUPER HM-H + TSK-GEL SUPER HM-H + TSK-GEL SUPER H2000
Eluent: Tetrahydrofuran (THF)
Driving amount: 20 μL
Sample concentration: 0.2% by weight
Eluent flow rate: 0.6 mL / sec
Column temperature: 40 ° C
Standard substance: polystyrene, weight average molecular weight (Mw) 587000, 354000, 189000, 98900, 37200, 17100, 9830, 5870, 2500
Detector: manufactured by Tosoh Corporation, differential refraction detector Analysis software: manufactured by Tosoh Corporation, GPC8020 model II Data collection Version 4.20.

  The drying shrinkage reducing agent described above may be composed of only one kind of polymer as described above, or may be composed of two or more kinds of polymers as described above.

2. High performance AE water reducing agent The admixture composition for hydraulic materials of the present invention contains a high performance AE water reducing agent as a second component in addition to the above-described drying shrinkage reducing agent. Such a high-performance AE water reducing agent is not particularly limited as long as it can assist the dispersibility / fluidity of the admixture composition for hydraulic materials of the present invention to a desired level. AE water reducing agent can be used. Specifically, an alkenyl ether monomer obtained by adding ethylene oxide or the like to a specific unsaturated alcohol such as 3-methyl-3-buten-1-ol as disclosed in JP-A-62-68806. , Unsaturated carboxylic acid monomers, copolymers comprising monomers copolymerizable with these monomers, or salts thereof, various sulfonic acid-based high-performance AE water-reducing products having sulfonic acid groups in the molecule Known high performance AE water reducing agents such as various polycarboxylic acid type high performance AE water reducing agents having a polyoxyalkylene chain and a carboxyl group in the molecule can be used. Examples of the sulfonic acid-based high-performance AE water reducing agent include, for example, naphthalenesulfonic acid formalin condensate; melamine sulfonic acid formalin condensate; polystyrene sulfonate; aminoaryl sulfonic acid-phenol-formaldehyde condensate, etc. (See Kaihei 1-113419). Among these, considering the ease of control of dispersibility / fluidity when combined with the above-described first shrinkage drying shrinkage reducing agent, high shrinkage reduction performance, etc., the polycarboxylic acid-based high performance AE A water reducing agent is preferred.

  The polycarboxylic acid-based high-performance AE water reducing agent is not particularly limited, and a known polycarboxylic acid-based high-performance AE water reducing agent can be used, but the following formula (2):

And a structural unit (II-a) represented by the following formula (4):

A polycarboxylic acid-based high-performance AE water reducing agent (A) containing the structural unit (III) represented by formula (3) as an essential structural unit:

A polycarboxylic acid-based high-performance AE water reducing agent (B) containing the structural unit (II-b) represented by formula (4) and the structural unit (III) represented by the above formula (4) as essential structural units; JP-A-7-53645 A hydrophilic graft polymer obtained by graft polymerization of an unsaturated carboxylic acid monomer to a polyether compound as described in JP-A-8-208769 and JP-A-8-208770 is preferred. Among these, it is particularly preferable to use the polycarboxylic acid-based high-performance AE water reducing agent (A) and the polycarboxylic acid-based high-performance AE water reducing agent (B).

  Hereinafter, the polycarboxylic acid-based high-performance AE water reducing agent (A) and the polycarboxylic acid-based high-performance AE water-reducing agent (B), which are preferred forms of the polycarboxylic acid-based high-performance AE water reducing agent, will be described. The polycarboxylic acid-based high-performance AE water reducing agent (A) and the polycarboxylic acid-based high-performance AE water reducing agent (B) may be used alone or in the form of a mixture of two or more types. You may use together 1 type, or 2 or more types of a carboxylic acid type high performance AE water reducing agent (A) and a polycarboxylic acid type high performance AE water reducing agent (B).

In the above formula (2), R ⁵ , R ⁶ and R ⁷ represent a hydrogen atom or a methyl group, and preferably at least one of R ⁵ and R ⁶ represents a hydrogen atom. At this time, R ⁵ , R ⁶ and R ⁷ may be the same or different. s is an integer of 0 to 2, preferably 0 or 1, and more preferably 0. R ⁸ O represents an oxyalkylene group having 2 to 18 carbon atoms, preferably an oxyalkylene group having 2 to 8 carbon atoms, more preferably an oxyalkylene group having 2 to 4 carbon atoms. Preferred examples of such oxyalkylene group include oxyethylene group, oxypropylene group, oxybutylene group, oxyisobutylene group, oxy1-butene group, oxy2-butene group, and oxystyrene group, but more preferably An oxyethylene group, an oxypropylene group, and an oxybutylene group, still more preferably an oxyethylene group and an oxypropylene group. In the case where a plurality of these oxyalkylene groups are present in one structural unit (that is, in the formula (1), u is 2 or more), even if one kind is present in one structural unit. Alternatively, it may exist in the form of a mixture of two or more. When two or more oxyalkylene groups are present, any addition form such as random addition, block addition, and alternate addition may be used. When only one type of structural unit is used as the structural unit (II-a), it is preferable to include an oxyethylene group as an essential component in the oxyalkylene group in order to ensure a balance between hydrophilicity and hydrophobicity. The mol% or more is preferably an oxyethylene group.

In the above formula (2), u represents an average addition mole number of the oxyalkylene group ^(R 7 O), the number of 1 to 300. When u exceeds 300, the resulting polymer exhibits dispersibility, which makes it impossible to add any amount, making it difficult to obtain the desired drying shrinkage reduction property. Furthermore, if u exceeds 300, air entrainment becomes high, and it becomes difficult to adjust the air amount, which causes a decrease in strength and a decrease in freeze-thaw resistance. Under the present circumstances, u is preferable in the order of 1-150, 1-100, 1-80, 1-50, 1-30. R ⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or 1 to 18 carbon atoms. And particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. Specific examples of such hydrocarbon groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, Neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isooctyl, 2,3,5-trimethylhexyl, 4-ethyl-5-methyloctyl and 2-ethylhexyl Group, tetradecyl group, octadecyl group, icosyl group or the like linear or branched alkyl group; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or the like cyclic alkyl group; phenyl group, benzyl group, phenethyl group O, m- or p-tolyl group, 2,3-young 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, a biphenylyl group, a benzhydryl group, and aryl groups such as trityl group and pyrenyl group.

  In the polycarboxylic acid-based high-performance AE water reducing agent that is a constituent of the present invention, a monomer that gives the structural unit (II-a) (hereinafter also simply referred to as “monomer (a)”) has the following formula ( 5):

However, in the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , s and u are the same as defined in the above formula (2).
It is an oxyalkylene group containing monomer (a) shown by these. As such a monomer (a), an adduct of an alkylene oxide having 2 to 18 carbon atoms to a dehydrogenation (oxidation) reaction product of (meth) acrylic acid, crotonic acid or fatty acid, or methanol, ethanol Saturated alcohols having 1 to 30 carbon atoms such as 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol Unsaturated alcohols having 3 to 30 carbon atoms such as aromatic alcohols, allyl alcohol, methallyl alcohol, crotyl alcohol and oleyl alcohol, alicyclic alcohols having 3 to 30 carbon atoms such as cyclohexanol, Phenol, phenylmethanol (benzyl alcohol), methyl Carbon atoms in any of aromatic alcohols having 6 to 30 carbon atoms such as enol (cresol), p-ethylphenol, dimethylphenol (xylenol), pt-butylphenol, nonylphenol, dodecylphenol, phenylphenol, naphthol Examples include an ester compound of an alkoxypolyalkylene glycol obtained by adding an alkylene oxide of 2 to 18 and (meth) acrylic acid or crotonic acid. In the formula (2), R ⁹ is a hydrocarbon. An ester compound of an alkoxypolyalkylene glycol and (meth) acrylic acid or crotonic acid corresponding to the group is preferred. In addition, the said monomer (a) may be used independently or may be used with the form of a 2 or more types of mixture.

  Specific examples of the monomer (a) include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate, and ethoxy polyethylene glycol mono (meth) acrylate. 1-propoxy polyethylene glycol mono (meth) acrylate, 2-propoxy polyethylene glycol mono (meth) acrylate, 1-butoxy polyethylene glycol mono (meth) acrylate, 2-butoxy polyethylene glycol mono (meth) acrylate, 2-methyl-1 -Propoxypolyethylene glycol mono (meth) acrylate, 2-methyl-2-propoxypolyethylene glycol mono (meth) acrylate, 1-pentyloxy Polyethylene glycol mono (meth) acrylate, 1-hexyloxypolyethylene glycol mono (meth) acrylate, cyclohexyloxypolyethylene glycol mono (meth) acrylate, 1-octyloxypolyethylene glycol mono (meth) acrylate, 2-ethyl-1-hexyloxy Polyethylene glycol mono (meth) acrylate, nonylalkoxypolyethyleneglycol mono (meth) acrylate, laurylalkoxypolyethyleneglycolmono (meth) acrylate, cetylalkoxypolyethyleneglycolmono (meth) acrylate, stearylalkoxypolyethyleneglycolmono (meth) acrylate, phenoxypolyethylene Glycol mono (meth) acrylate, phenylmethoxypo Ethylene glycol mono (meth) acrylate, methylphenoxypolyethylene glycol mono (meth) acrylate, p-ethylphenoxypolyethylene glycol mono (meth) acrylate, dimethylphenoxypolyethyleneglycol mono (meth) acrylate, pt-butylphenoxypolyethyleneglycol mono ( (Meth) acrylate, nonylphenoxypolyethylene glycol mono (meth) acrylate, dodecylphenoxypolyethylene glycol mono (meth) acrylate, phenylphenoxypolyethyleneglycol mono (meth) acrylate, naphthoxypolyethyleneglycol mono (meth) acrylate, ethylene oxide ( Esterified product of (meth) allyl alcohol and (meth) acrylic acid, ethylene Various alkoxy polyethylene glycol mono (meth) acrylates such as esterified products of crotyl alcohol to which oxide is added and (meth) acrylic acid; methoxypolypropylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, 1 -Propoxy polypropylene glycol mono (meth) acrylate, 2-propoxy polypropylene glycol mono (meth) acrylate, 1-butoxy polypropylene glycol mono (meth) acrylate, propylene oxide added (meth) allyl alcohol and (meth) acrylic acid Alkoxy polypropylene glycols such as esterified products of crotyl alcohol with propylene oxide and (meth) acrylic acid (Meth) acrylates; methoxypolyethylenepolypropyleneglycol mono (meth) acrylate, methoxypolyethylenepolybutyleneglycolmono (meth) acrylate, ethoxypolyethylenepolypropyleneglycolmono (meth) acrylate, ethoxypolyethylenepolybutyleneglycolmono (meth) acrylate, 1 -Propoxypolyethylenepolypropylene glycol mono (meth) acrylate, 1-propoxypolyethylenepolybutyleneglycol mono (meth) acrylate, 2-propoxypolyethylenepolypropyleneglycol mono (meth) acrylate, 2-propoxypolyethylenepolybutyleneglycolmono (meth) acrylate, 1 -Butoxypolyethylene polypropylene glycol mono (meth) a Lilate, 1-butoxypolyethylene polybutylene glycol mono (meth) acrylate, esterified product of (meth) allyl alcohol and (meth) acrylic acid to which ethylene oxide and propylene oxide or ethylene oxide and butylene oxide are added, ethylene oxide and propylene oxide or ethylene oxide Alkoxypolyalkylene glycols such as esterified products of alcohol and (meth) acrylic acid added with two or more types of alkylene oxides such as esterified products of crotyl alcohol and (meth) acrylic acid added with styrene and butylene oxide And mono (meth) acrylates. In this case, these monomers (a) or structural units (II-a) may be used alone or in combination of two or more.

In the above formula (3), R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, and preferably at least one of R ¹⁰ and R ¹¹ represents a hydrogen atom. At this time, R ¹⁰ , R ¹¹ and R ¹² may be the same or different. x is an integer of 0 to 2, preferably 0 or 1, and more preferably 0. R ¹³ O represents an oxyalkylene group having 2 to 18 carbon atoms, preferably an oxyalkylene group having 2 to 8 carbon atoms, more preferably an oxyalkylene group having 2 to 4 carbon atoms. Such an oxyalkylene group is the same as R ⁸ O in the above formula (2). When a plurality of these oxyalkylene groups are present in one structural unit (that is, in formula (3), y is 2 or more), even if one kind is present in one structural unit. Alternatively, it may exist in the form of a mixture of two or more. When two or more kinds of oxyalkylene groups are present, the addition form may be any of random addition, block addition, alternating addition, and the like. When only one type of structural unit is used as the structural unit (II), it is preferable to include an oxyethylene group as an essential component in the oxyalkylene group in order to ensure a balance between hydrophilicity and hydrophobicity, and further 50 mol%. The above is preferably an oxyethylene group. Moreover, y represents the average addition mole number of an oxyalkylene group (R < ¹³ > O), and is a number of 1-300. If y exceeds 300, the resulting polymer exhibits dispersibility, which makes it impossible to add any amount, making it difficult to obtain the desired drying shrinkage reduction property. Furthermore, if y exceeds 300, air entrainment becomes high, adjustment of the amount of air becomes difficult, and this causes a decrease in strength and freeze-thaw resistance. y is preferably in the order of 1 to 150, 1 to 100, 1 to 80, 1 to 50, and 1 to 30. R ¹⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or 1 to 18 carbon atoms. And particularly preferably a hydrocarbon group having 1 to 12 carbon atoms. In addition, since the definition of the substituent “R ¹⁴ ” in the formula (3) is the same as the definition of the substituent “R ⁹ ” in the formula (2), description thereof is omitted here.

  In the polycarboxylic acid-based high-performance AE water reducing agent that is a constituent of the present invention, a monomer that gives the structural unit (III-b) (hereinafter, also simply referred to as “monomer (b)”) has the following formula ( 6):

However, in formula, R < ¹⁰ >, R < ¹¹ >, R < ¹² >, R <^13> , R <^14> , x, and y are the same as the definition in said Formula (3),
It is an oxyalkylene group containing monomer (b) shown by these. Examples of such a monomer (b) include adducts of alkylene oxides having 2 to 18 carbon atoms to alcohols such as vinyl alcohol or isoprene alcohol. The monomer (b) may be used alone or in the form of a mixture of two or more.

  Specific examples of the monomer (b) include (poly) ethylene glycol-3-methyl-3-butenyl ether, (poly) propylene glycol-3-methyl-3-butenyl ether, poly) butylene glycol-3. -Methyl-3-butenyl ether, (poly) ethylene glycol (poly) propylene glycol-3-methyl-3-butenyl ether, (poly) ethylene glycol (poly) butylene glycol-3-methyl-3-butenyl ether Etc. In this case, these monomers (b) or structural units (II-b) may be used alone or in combination of two or more.

In the above formula (4), R ¹⁵ , R ¹⁶ and R ¹⁷ represent a hydrogen atom, a methyl group or a — (CH ₂ ) _q COOM ′ group. At this time, R ¹⁵ , R ¹⁶ and R ¹⁷ may be the same or different. In this case, M ′ represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group (—NH ₂ ) or an organic amine group. Q is an integer of 0 to 2, preferably 0 or 1, particularly 0. M represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group (—NH ₂ ) or an organic amine group. In this case, examples of the monovalent metal include lithium, sodium, and potassium. Examples of the divalent metal include magnesium, calcium, strontium, barium and the like. In addition, when M is a divalent metal, it takes the form of an anhydride with two -COO-. Examples of the organic amine group include groups derived from primary amines such as methylamine, ethylamine, propylamine, n-butylamine, sec-butylamine, tert-butylamine, cyclohexylamine, benzylamine and phenylamine; dimethylamine, diethylamine, diamine Groups derived from secondary amines such as propylamine, dibutylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, dicyclohexylamine, dibenzylamine and diphenylamine; trimethylamine, triethylamine, tripropylamine, tributylamine, Groups derived from tertiary amines such as tricyclohexylamine, tribenzylamine and triphenylamine; and ethanolamine, diethanolamine, triethanolamine It includes groups derived from alkanolamines are. Among these, alkanolamine groups such as ethanolamine group, diethanolamine group and triethanolamine group, and triethylamine group are preferable. Among these, M is preferably a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group or an organic amine group, and particularly preferably a hydrogen atom, sodium or calcium. In addition, since the definition of the substituent “M ′” in the formula (4) is the same as the definition of the substituent “M” in the formula, description thereof is omitted here. In addition, when two or three COOM ′ are present, these COOM ′ may be the same or different. Moreover, when two or more of COOM and COOM ′ are present in total, two of these may form an anhydride.

  In the polycarboxylic acid-based high-performance AE water reducing agent that is a constituent of the present invention, a monomer that gives the structural unit (III) (hereinafter also simply referred to as “monomer (c)”) is represented by the following formula (7): :

However, in the formula, R ¹⁵ , R ¹⁶ , R ¹⁷ , and M are the same as defined in the above formula (4).
It is an unsaturated carboxylic acid-type monomer (c) shown by these. Examples of such a monomer (c) include acrylic acid, methacrylic acid, crotonic acid, and unsaturated monocarboxylic acid monomers such as metal salts, ammonium salts, and amine salts thereof; maleic acid, itaconic acid, Citraconic acid, fumaric acid, and unsaturated dicarboxylic acid monomers such as metal salts, ammonium salts, and amine salts thereof; and anhydrides such as maleic anhydride, itaconic anhydride, and citraconic anhydride. Among these, unsaturated monocarboxylic acid monomers corresponding to the case where R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom or a methyl group are preferable, and (meth) acrylic acid and salts thereof are particularly preferable. . In this case, these monomers (c) or structural units (III) may be used alone or in combination of two or more.

  The polycarboxylic acid-based high-performance AE water reducing agent (A) is a polymer containing the structural unit (II-a) of the above formula (2) and the structural unit (III) of the above formula (4) as essential structural units. However, it may further contain a structural unit (IV) derived from another copolymerizable monomer (e) described in detail below. Each of these structural units in the polycarboxylic acid-based high-performance AE water reducing agent (A) may be one kind or two or more kinds.

  In the polycarboxylic acid-based high-performance AE water reducing agent (A), the ratio of the structural unit (II-a) to the structural unit (III) and, if necessary, the structural unit (IV) (structural unit (II-a) / structure Unit (III) / constituent unit (IV)) (mass ratio) is 99 to 1/1 to 99/0 to 50, more preferably 99 to 30/1 to 70/0 to 40, and particularly preferably 99 to 50. / 1 to 50/0 to 30 is preferable. Under the present circumstances, the sum total of the ratio of structural unit (II-a), (III) and (IV) is 100 mass%. Moreover, as a total ratio (mass%) of the structural unit (II-a) and the structural unit (III) in the polycarboxylic acid-based high-performance AE water reducing agent (A), the polycarboxylic acid-based high-performance AE water reducing agent ( A) 50-100 mass% of the whole is preferable, and 70-100 mass% is more preferable.

  The polycarboxylic acid-based high performance AE water reducing agent (B) is a polymer containing the structural unit (II-b) of the above formula (3) and the structural unit (III) of the above formula (4) as essential structural units. However, it may further contain a structural unit (IV) derived from another copolymerizable monomer (e) described in detail below. Each of these structural units in the polycarboxylic acid-based high-performance AE water reducing agent (B) may be one kind or two or more kinds.

  In the polycarboxylic acid-based high-performance AE water reducing agent (B), the structural unit (II-b) and the structural unit (III) each occupy 1% by mass or more of the total structural units, and the structural unit (II-b) It is preferable that the ratio which occupies is 50 mol% or less in all the structural units. When the proportion of the structural unit (II-b) is less than 1% by mass, the content of the oxyalkylene group derived from the (poly) alkylene glycol ether monomer contained in the polycarboxylic acid-based high performance AE water reducing agent (B) is On the other hand, when the proportion of the structural unit (III) is less than 1% by mass, the content of the carboxyl group derived from the unsaturated monocarboxylic acid monomer contained in the polycarboxylic acid-based high performance AE water reducing agent (B) Is too small, dispersibility tends to decrease. Further, since the unsaturated (poly) alkylene glycol ether monomer has low polymerizability, in order to obtain a highly dispersible polycarboxylic acid-based high performance AE water reducing agent (B) in a high yield, the structural unit ( The proportion of II-b) is preferably 50 mol% or less in all the structural units. Therefore, the ratio of the structural unit (II-b) to the structural unit (III) in the polycarboxylic acid-based high-performance AE water reducing agent (B) and the structural unit (IV) if necessary (the structural unit (II-b ) / Constituent unit (III) / constituent unit (IV)) (mass ratio) is 99 to 1/1 to 99/0 to 50, more preferably 99 to 30/1 to 70/0 to 40, particularly preferably. It is preferable that it is 99-50 / 1-50 / 0-30. Under the present circumstances, the sum total of the ratio of structural unit (II-b), (III) and (IV) is 100 mass%. Moreover, as a total ratio (mass%) of the structural unit (II-b) and the structural unit (III) in the polycarboxylic acid-based high-performance AE water reducing agent (B), the polycarboxylic acid-based high-performance AE water reducing agent ( B) 50-100 mass% of the whole is preferable, and 70-100 mass% is more preferable.

  The other copolymerizable monomer (e) that can be used in the polycarboxylic acid-based high-performance AE water reducing agent (A) and / or (B) is a monomer that can be copolymerized with other monomer components. Specific examples of such monomers include half esters and diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and alcohols having 1 to 4 carbon atoms; Half amides and diamides of unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms; alkyl (poly) alkylene glycols obtained by adding 1 to 500 moles of alkylene oxides having 2 to 18 carbon atoms to the alcohols and amines; Half-esters and diesters with unsaturated dicarboxylic acids; the unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or their glycols Half-esters and diesters of polyalkylene glycols having an addition mole number of 2 to 500; half-amides of maleamic acid and glycols having 2 to 18 carbon atoms or polyalkylene glycols having an addition mole number of 2 to 500 of these glycols; (Poly) alkylene glycol di (meth) acrylate such as ethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) propylene glycol di (meth) acrylate (Meth) acrylates; bifunctional (meth) acrylates such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate; (Poly) alkylene glycol dimaleates such as tylene glycol dimaleate and polyethylene glycol dimaleate; vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate, 3 -(Meth) acryloxy-2-hydroxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropylsulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxybutyl Unsaturated sulfonic acids such as sulfonate, (meth) acrylamide methyl sulfonic acid, (meth) acrylamide ethyl sulfonic acid, 2-methylpropane sulfonic acid (meth) acrylamide, styrene sulfonic acid And monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts thereof; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, glycidyl (meth) acrylate, methyl crotonate, Esters of unsaturated monocarboxylic acids such as ethyl crotonate and propyl crotonate and alcohols having 1 to 4 carbon atoms; unsaturated monocarboxylic acids such as methyl (meth) acrylamide and amines having 1 to 30 carbon atoms Amides thereof; vinyl aromatics such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene; 1,4-butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, Alkanes such as 1,6-hexanediol mono (meth) acrylate All mono (meth) acrylates; dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene; (meth) acrylamide, (meth) acrylalkylamide, N- Unsaturated amides such as methylol (meth) acrylamide and N, N-dimethyl (meth) acrylamide; Unsaturated cyans such as (meth) acrylonitrile and α-chloroacrylonitrile; Unsaturated esters such as vinyl acetate and vinyl propionate ; Such as aminoethyl (meth) acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, vinylpyridine, etc. Saturated amines; divinyl benzene such as divinylbenzene Cyanurates such as triallyl cyanurate; Allyls such as (meth) allyl alcohol and glycidyl (meth) allyl ether; Unsaturated amino compounds such as dimethylaminoethyl (meth) acrylate; Methoxypolyethylene glycol monovinyl ether; Vinyl ethers or allyl ethers such as polyethylene glycol monovinyl ether, methoxy polyethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) allyl ether; polydimethylsiloxanepropylaminomaleamic acid, polydimethylsiloxaneaminopropyleneaminomaleamic acid Polydimethylsiloxane-bis- (propylaminomaleamic acid), polydimethylsiloxane-bis- (dipropyleneaminomaleic acid) Amide acid), polydimethylsiloxane- (1-propyl-3-acrylate), polydimethylsiloxane- (1-propyl-3-methacrylate), polydimethylsiloxane-bis- (1-propyl-3-acrylate), polydimethyl Examples thereof include siloxane derivatives such as siloxane-bis- (1-propyl-3-methacrylate); unsaturated phosphate esters such as 2-acryloyloxyethyl phosphate and 2-methacryloyloxyethyl phosphate. In this case, these monomer (e) or the structural unit (IV) derived from the monomer (e) may be used alone or in combination of two or more.

  A method for producing a polymer as a polycarboxylic acid-based high-performance AE water reducing agent, which is a preferred constituent of the present invention, is not particularly limited, and a known polymerization method can be used, but in general, a polymerization initiator is used. And the monomer component may be polymerized. The polymerization method of the monomer component is not particularly limited, and a known polymerization method can be used similarly or modified, but the polymerization can be performed by a method such as polymerization in a solvent or bulk polymerization, for example. . Polymerization in a solvent can be carried out either batchwise or continuously. The solvent used here is water; lower alcohols such as methyl alcohol, ethyl alcohol, 2-propanol; benzene, toluene, xylene, cyclohexane, Examples include aromatic or aliphatic hydrocarbons such as n-hexane; ester compounds such as ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone. Considering the solubility of the raw material monomer and the resulting polymer and the convenience of using this polymer, use at least one selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms. Are preferred, and lower alcohols having 1 to 4 carbon atoms are more preferred, and methyl alcohol, ethyl alcohol, 2-propanol and the like are particularly effective.

  The polymerization initiator used when the polymerization is carried out in an aqueous medium is not particularly limited, and a known polymerization initiator can be used. For example, water-soluble such as ammonium or alkali metal persulfate or hydrogen peroxide. A polymerization initiator is used. In this case, an accelerator such as sodium bisulfite, Mole salt, ascorbic acid (salt), Rongalite and the like can be used in combination. In addition, the polymerization initiator used when performing polymerization using a lower alcohol, aromatic hydrocarbon, aliphatic hydrocarbon, ester compound or ketone compound as a solvent is not particularly limited, and a known polymerization initiator is used. Specifically, persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; hydrogen peroxide; peroxides such as benzoyl peroxide and lauroyl peroxide; hydroperoxides such as cumene hydroperoxide; azobis Azo compounds such as -2-methylpropionamidine hydrochloride and azobisisobutyronitrile are used as the polymerization initiator. In this case, a reducing agent such as sodium hydrogen sulfite, sodium sulfite, molle salt, sodium pyrobisulfite, formaldehyde sodium sulfoxylate, ascorbic acid, or the like; an accelerator such as an amine compound such as ethylenediamine, sodium ethylenediaminetetraacetate, or glycine is used in combination. You can also These polymerization initiators and accelerators may be used alone or in combination of two or more. 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 addition amount of the polymerization initiator is not particularly limited, and the same amount as that used in a known polymerization method can be used. Also, the polymerization conditions are not particularly limited, and the same conditions as known polymerization conditions can be used. For example, the polymerization temperature is appropriately determined depending on the solvent and polymerization initiator used, but is usually in the range of 0 to 120 ° C. Is done within.

  Also in the case of bulk polymerization, the method, the type and amount of the polymerization initiator used, the polymerization conditions, etc. are not particularly limited, and known methods can be used. For example, as the polymerization initiator, peroxides such as benzoyl peroxide and lauroyl peroxide; hydroperoxides such as cumene hydroperoxide; azo compounds such as azobisisobutyronitrile can be used. Moreover, block polymerization is performed within the temperature range of 50-200 degreeC, for example.

  Moreover, a chain transfer agent can be used for the purpose of adjusting the molecular weight of the obtained polymer (polycarboxylic acid-based high-performance AE water reducing agent). Such a chain transfer agent is not particularly limited, and both hydrophilic and hydrophobic chain transfer agents can be used.

  Here, as the hydrophilic chain transfer agent, known ones can be used, for example, thioglycerol, thioglycolic acid, mercaptopropionic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, 2 -Thiol chain transfer agents such as mercaptoethanesulfonic acid; primary alcohols such as 2-aminopropan-1-ol; secondary alcohols such as isopropanol; phosphorous acid, hypophosphorous acid and salts thereof (hypophosphorous acid) Sodium, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite and its salts (sodium sulfite, sodium bisulfite, sodium dithionite, sodium metabisulfite, potassium sulfite, hydrogen sulfite) Potassium, potassium dithionite, potassium metabisulfite, etc.) Beauty salts thereof are preferable. In this case, the hydrophilic chain transfer agent may be used alone or in the form of a mixture of two or more.

  In addition, examples of the hydrophobic chain transfer agent include alkyl mercaptan chain transfer agents, and alkyl mercaptan chain transfer agents having a hydrocarbon group having 3 or more carbon atoms can be preferably used. This is because when an alkyl mercaptan-based chain transfer agent is used, an alkyl mercaptan group is introduced at the end of the copolymer, thereby improving the drying shrinkage reduction property. The alkyl mercaptan-based hydrophobic chain transfer agent having a hydrocarbon group having 3 or more carbon atoms is not particularly limited, but butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexyl mercaptan. , Thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate, 2-mercaptoethyl ester octanoate, 1,8-dimercapto-3,6-di Examples include oxaoctane, decane trithiol, dodecyl mercaptan and the like. In this case, the hydrophilic chain transfer agent and the hydrophobic chain transfer agent may be used alone or in combination of two or more.

  The chain transfer agent may be added to the reaction vessel either continuously or stepwise, but it is preferable to apply a continuous charging method such as dropping or split charging. Further, the chain transfer agent may be introduced alone into the reaction vessel, and the monomers (a) and (c) described above and, if necessary, the monomer (e) or the monomer (b), (c ) And if necessary, it may be mixed in advance with the monomer component of monomer (e), a solvent and the like.

  The polymer thus obtained may be used as it is or as a polycarboxylic acid-based high performance AE water reducing agent, but may be handled in the form of an aqueous solution containing no organic solvent. In addition, the polymer is further converted into monovalent and divalent metal hydroxides, inorganic substances such as chlorides and carbon salts; ammonia; organic amines and the like (preferably monohydric metal hydroxides such as sodium hydroxide and potassium hydroxide) ), And may be used as a polymer salt in a polycarboxylic acid-based high-performance AE water reducing agent.

  In addition, the weight average molecular weight of the polymer as the polycarboxylic acid-based high performance AE water reducing agent (A) according to the present invention is not particularly limited as long as the obtained polymer can exhibit sufficient dispersibility / fluidity. The range of 5000 to 1000000 is appropriate in terms of polyethylene glycol by GPC. The range of 5,000 to 500,000 is more preferable, and the range of 5,000 to 200,000 is particularly preferable. Further, the weight average molecular weight of the polymer as the polycarboxylic acid-based high performance AE water reducing agent (B) according to the present invention is not particularly limited as long as the obtained polymer can exhibit sufficient dispersibility / fluidity. However, the range of 5000 to 1000000 is suitable in terms of polyethylene glycol by GPC. The range of 5,000 to 500,000 is more preferable, and the range of 5,000 to 200,000 is particularly preferable. In the above range, when the weight average molecular weight exceeds the upper limit, the water reducing performance and slump loss preventing ability of the polycarboxylic acid-based high performance AE water reducing agent may be reduced. There exists a possibility that the water reduction performance of an acid type high performance AE water reducing agent may fall.

  In the present specification, the weight average molecular weight of the polycarboxylic acid-based high-performance AE water reducing agent is a value measured under the following GPC measurement conditions unless otherwise specified.

<GPC molecular weight measurement conditions>
Column used: Tosoh Corporation, TSK guard column SWXL + TSK ge1 G4000SWXL + G3000SWXL + G2000SWXL
Eluent: Dissolve 115.6 g of sodium acetate trihydrate in a mixed solvent of 10999 g of water and 6001 g of acetonitrile, and use an eluent adjusted to pH 6.0 with 30% aqueous sodium hydroxide solution.
Sample concentration: 0.5% by weight
Eluent flow rate: 0.8mL / sec
Column temperature: 35 ° C
Reference material: polyethylene glycol, weight average molecular weight (Mw) 272500, 219300, 85000, 46000, 24000, 12600, 4250, 7100, 1470
Detector: manufactured by Japan Waters, differential refraction detector Analysis software: manufactured by Japan Waters, MILLENNIUM Ver. 2.18.

  The polycarboxylic acid-based high-performance AE water reducing agent of the present invention may be composed of only one kind of polymer as described above or may be composed of two or more kinds of polymers as described above.

  The above-described drying shrinkage reducing agent and the above-described high-performance AE water reducing agent (preferably, a polycarboxylic acid-based high-performance AE water reducing agent) are essential components of the admixture composition for hydraulic materials of the present invention. By using in combination, it is possible to achieve dispersibility / fluidity and high drying shrinkage reduction according to the purpose.

3. As described above, the admixture composition for hydraulic materials of the present invention comprises (a) a predetermined drying shrinkage reducing agent, and (a) a high-performance AE water reducing agent (preferably polycarboxylic acid). Acid-based high-performance AE water reducing agent) as an essential component. The above (a) exhibits high drying shrinkage reduction properties, but may be inferior in dispersibility / fluidity. Therefore, an admixture composition for a hydraulic material that exhibits high dry shrinkage reduction and dispersibility / fluidity can be obtained by combining (a) with (b) a high-performance AE water reducing agent. In addition to the above-mentioned advantages, by appropriately combining (a) and (b) as described above, it is possible to exhibit high drying shrinkage reduction and dispersibility / fluidity compared to conventional ones, such as cement. The amount of the composition added to the hydraulic material can be significantly reduced as compared with the conventional case.

  The composition of (a) and (b) is not particularly limited as long as the desired drying shrinkage reduction property and dispersibility / fluidity can be achieved, and is appropriately selected in consideration of these desired performances. . The mass ratio (A: I) of (A) to (A) in the composition of the present invention is preferably 99.5: 0.5 to 0.5: 99.5, more preferably 99 to 1: 1. 99, most preferably 98-2: 2-98.

  The admixture composition for hydraulic material of the present invention may be used in the form of an aqueous solution, or after neutralizing with a hydroxide of a divalent metal such as calcium or magnesium to obtain a polyvalent metal salt. You may use it by making it dry or carrying | supporting to inorganic powders, such as a silica type fine powder, and making it dry.

  The admixture composition for hydraulic materials of the present invention can be used for various hydraulic materials, that is, hydraulic materials other than cement such as cement and gypsum. And the hydraulic composition which contains a hydraulic material, water, and the admixture composition for hydraulic materials of this invention, and further contains fine aggregate (sand etc.) and coarse aggregate (crushed stone etc.) as needed. For example, cement paste, mortar, concrete and plaster are suitable.

  Among the hydraulic compositions, a cement composition using cement as a hydraulic material is the most common, and such a cement composition is an admixture composition for hydraulic materials according to the present invention, cement and water. As an essential component. Such a cement composition is also one aspect of the present invention.

  Examples of the cement used in the cement composition of the present invention include Portland cement (ordinary, early strength, ultra-early strength, moderate heat, sulfate-resistant and their respective low alkali types), various mixed cements (blast furnace cement, silica cement, Fly ash cement), white Portland cement, alumina cement, super fast cement (1 clinker fast cement, 2 clinker fast cement, magnesium phosphate cement), grout cement, oil well cement, low exothermic cement (low exothermic blast furnace cement) , Fly ash mixed low heat generation type blast furnace cement, belite high content cement), ultra high strength cement, cement-based solidified material, eco-cement (cement manufactured from one or more of municipal waste incineration ash and sewage sludge incineration ash) In addition, blast furnace slag, fly Mesh, cinder ash, clinker ash, husk ash, silica fume, silica powder, a fine powder and gypsum limestone powder may be added. In addition to gravel, crushed stone, granulated slag, recycled aggregate, etc., the aggregates are siliceous, clay, zircon, high alumina, silicon carbide, graphite, chrome, chromic, magnesia. Refractory aggregate such as can be used.

In the admixture composition for hydraulic material of the present invention, the unit water amount per 1 m ³ , the amount of cement used, and the water / cement ratio are 100 to 185 kg / m ³ , and the amount of cement used is 250 to 800 kg / m ^3. The water / cement ratio (mass ratio) is preferably 0.1 to 0.7, more preferably the unit water amount 120 to 175 kg / m ³ , the amount of cement used 270 to 800 kg / m ³ , and the water / cement ratio. (Mass ratio) = 0.2 to 0.65 is recommended, and can be used widely from poor blending to rich blending, high-strength concrete with a large amount of unit cement, poor blended concrete with a unit cement amount of 300 kg / m ³ or less It is effective for any of these.

  The blending ratio of the admixture composition for hydraulic material of the present invention is not particularly limited as long as it can achieve the desired drying shrinkage reduction and dispersibility / fluidity. For example, when added to a hydraulic material such as mortar or concrete using hydraulic cement, the amount of the admixture composition for a hard material of the present invention is preferably 10 parts by mass with respect to 100 parts by mass of the hydraulic material. Hereinafter, more preferably 0.01 to 5 parts by mass, and still more preferably 0.05 to 3 parts by mass. Thus, sufficient shrinkage reduction performance and dispersibility / fluidity can be ensured with a smaller amount than in the past.

  The admixture composition for hydraulic materials of the present invention is also effective for ready-mixed concrete, concrete for concrete secondary products (precast concrete), centrifugal molded concrete, vibration compacted concrete, steam-cured concrete, shotcrete, etc. In addition, medium-fluidity concrete (concrete with a slump value of 22 to 25 cm), high fluidity concrete (concrete with a slump value of 25 cm or more and a slump flow value of 50 to 70 cm), self-filling concrete, self-leveling material, etc. It is also effective for mortar and concrete that require high fluidity.

  Furthermore, the admixture composition for hydraulic materials of the present invention can contain other known cement additives (materials) as exemplified in the following (1) to (21).

  (1) Shrinkage reducing agent: Shrinkage reducing agent represented by the following formula (8):

In the above formula (8), R ¹⁸ and R ²⁰ represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. At this time, R ¹⁸ and R ²⁰ may be the same or different. Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ¹⁸ and R ²⁰ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and isopentyl. , Neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isooctyl, 2,3,5-trimethylhexyl, 4-ethyl-5-methyloctyl and 2-ethylhexyl, tetradecyl, octadecyl, icosyl, etc. 4-30 linear and branched alkyl groups; cyclic alkyl groups such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; phenyl, benzyl, phenethyl, o-, m- or p-tolyl, 2, 3 -Or 2,4-xylyl, Aryl groups such as til, naphthyl, anthryl, phenanthryl, biphenylyl, benzhydryl, trityl and pyrenyl and these aryl groups having an alkyl group ((alkyl) aryl groups); hydrogenation in which at least a part of the aryl group is hydrogenated These hydrogenated aryl groups having an aryl group and an alkyl group ((alkyl) hydrogenated aryl group); and (alkyl) aralkyl groups such as benzyl, methylbenzyl, phenethyl, naphthylmethyl, naphthylethyl, and the like. Among these, R ¹⁸ and R ²⁰ are preferably hydrogen or a hydrocarbon group having 1 to 15 carbon atoms, hydrogen, methyl, ethyl, n-propyl, i-propyl, t-butyl, i-octyl, 2-ethylhexyl. More preferred is dodecyl. R ¹⁹ O represents an oxyalkylene group having 2 to 18 carbon atoms, preferably an oxyalkylene group having 2 to 8 carbon atoms, more preferably an oxyalkylene group having 2 to 4 carbon atoms. Preferred examples of such oxyalkylene group include oxyethylene group, oxypropylene group, oxybutylene group, oxyisobutylene group, oxy1-butene group, oxy2-butene group, and oxystyrene group, but more preferably An oxyethylene group, an oxypropylene group, and an oxybutylene group, still more preferably an oxyethylene group and an oxypropylene group. One kind of these oxyalkylene groups may be present in one compound of the formula (8), or a mixture of two or more kinds may be present. When two or more kinds of oxyalkylene groups are present, the addition form may be any of random addition, block addition, alternating addition, and the like. Further, m represents an average addition mol number of the oxyalkylene group ^{(R 19} O), the number of 2 or more, preferably 2 to 30, more preferably 2 to 20.

  (2) Water-soluble polymer material: polyacrylic acid (sodium), polymethacrylic acid (sodium), polymaleic acid (sodium), unsaturated carboxylic acid polymer such as sodium salt of acrylic acid / maleic acid copolymer; methylcellulose , Nonionic cellulose ethers such as ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxypropyl cellulose; alkylation of polysaccharides such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose; Hydrophobic substituents in which part or all of the hydroxyl groups of the hydroxyalkylated derivative have a hydrocarbon chain having 8 to 40 carbon atoms as a partial structure, a sulfonic acid group or Polysaccharide derivatives substituted with an ionic hydrophilic substituent containing such a salt as a partial structure; yeast glucan, xanthan gum, β-1.3 glucans (both linear and branched) For example, polysaccharides produced by microbial fermentation such as curdlan, paramylon, pachyman, scleroglucan, laminaran, etc.); polyacrylamide; polyvinyl alcohol; starch; starch phosphate ester; sodium alginate; gelatin; Copolymers of acrylic acid having groups and quaternary compounds thereof.

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

  (4) retarder: oxycarboxylic such as gluconic acid, glucoheptonic acid, alabonic acid, malic acid or citric acid, and inorganic salts or organic salts thereof such as sodium, potassium, calcium, magnesium, ammonium, triethanolamine, etc. Acid; monosaccharides such as glucose, fructose, galactose, saccharose, xylose, apiose, ribose, isomerized sugar, oligosaccharides such as disaccharide and trisaccharide, oligosaccharides such as dextrin, polysaccharides such as dextran, etc. Sugars such as molasses; sugar alcohols such as sorbitol; magnesium silicofluoride; phosphoric acid and its salts or borate esters; aminocarboxylic acids and salts thereof; alkali-soluble proteins; humic acid; tannic acid; Polyhydric alcohols such as glycerin; aminotri (methylenephos Acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and their alkali metal salts, alkaline earth metal salts and other phosphonic acids and their derivatives etc.

  (5) Early strengthening agent / accelerator: 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.

  (6) Mineral oil-based antifoaming agent: cocoon oil, liquid paraffin, etc.

  (7) Fat and oil-based antifoaming agents: animal and vegetable oils, sesame oil, castor oil, and alkylene oxide adducts thereof.

  (8) Fatty acid-based antifoaming agent: oleic acid, stearic acid, and these alkylene oxide adducts.

  (9) Fatty acid ester antifoaming agent: glycerin monoricinoleate, alkenyl succinic acid derivative, sorbitol monolaurate, sorbitol trioleate, natural wax and the like.

  (10) Oxyalkylene antifoaming agents: polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene (Poly) oxyalkyl ethers such as 2-ethylhexyl ether and oxyethyleneoxypropylene adducts to higher alcohols having 12 to 14 carbon atoms; (poly) oxy such as polyoxypropylene phenyl ether and polyoxyethylene nonylphenyl ether Alkylene (alkyl) aryl ethers; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3-methyl-1 Acetylene ethers obtained by addition polymerization of alkylene oxide to acetylene alcohol such as butyn-3-ol; (poly) oxyalkylene fatty acid esters such as diethylene glycol oleate, diethylene glycol laurate, ethylene glycol distearate; polyoxyethylene (Poly) oxyalkylene sorbitan fatty acid esters such as sorbitan monolaurate and polyoxyethylene sorbitan trioleate; (poly) oxyalkylene alkyl such as sodium polyoxypropylene methyl ether sulfate and sodium polyoxyethylene dodecylphenol ether sulfate ( Aryl) ether sulfate salts; (Poly) oxypolyethylene stearyl phosphate, etc. (poly) Xylene polyoxyalkylene alkyl phosphoric acid esters; polyoxyethylene such as polyoxyethylene lauryl amine (poly) oxyalkylene alkyl amines; polyoxyalkylene amide.

  (11) Alcohol-based antifoaming agent: octyl alcohol, hexadecyl alcohol, 2-ethylhexyl alcohol, acetylene alcohol, glycols and the like.

  (12) Amide antifoaming agent: acrylate polyamine and the like.

  (13) Phosphate ester antifoaming agent: tributyl phosphate, sodium octyl phosphate, etc.

  (14) Metal soap type antifoaming agent: aluminum stearate, calcium oleate, etc.

  (15) Silicone antifoaming agent: dimethyl silicone oil, silicone paste, silicone emulsion, organically modified polysiloxane (polyorganosiloxane such as dimethylpolysiloxane), fluorosilicone oil and the like.

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

  (17) Other surfactants: aliphatic monohydric alcohol having 6 to 30 carbon atoms in the molecule such as octadecyl alcohol and stearyl alcohol, and 6 to 30 carbon atoms in the molecule such as abiethyl alcohol Intramolecular such as alicyclic monohydric alcohol, dodecyl mercaptan, etc. Intramolecular such as monovalent mercaptan having 6-30 carbon atoms in the molecule, such as nonylphenol, alkylphenol having 6-30 carbon atoms in the molecule, dodecylamine, etc. 10 mol or more of an alkylene oxide such as ethylene oxide or propylene oxide was added to a carboxylic acid having 6 to 30 carbon atoms in the molecule such as an amine having 6 to 30 carbon atoms, lauric acid or stearic acid. Polyalkylene oxide derivatives having an alkyl or alkoxy group as a substituent Alkyl diphenyl ether sulfonates in which two phenyl groups having a sulfone group are ether-bonded; various anionic surfactants; various cationic surfactants such as alkylamine acetate and alkyltrimethylammonium chloride; various nonionics Surfactant; various amphoteric surfactants.

  (18) Waterproofing agent: fatty acid (salt), fatty acid ester, oil and fat, silicon, paraffin, asphalt, wax and the like.

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

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

  Other known cement additives (materials) include cement wetting agents, thickeners, separation reducing agents, flocculants, strength enhancers, self-leveling agents, colorants, fungicides and the like. The above-mentioned known cement additives (materials) can be used in combination.

  Hereinafter, the present invention will be described more specifically with reference to examples. In the present specification, unless otherwise specified, “%” represents “mass%” and “part” represents “part by mass”. Further, the technical scope of the present invention is not limited only to the following examples.

Production Example 1: Production of SRA-1 In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, 198.91 parts of 2-propanol, 47.30 parts of 2-ethylhexyl methacrylate, Methoxypolyethylene glycol monomethacrylate (average number of added moles of ethylene oxide: 9; that is, in the above formula (2), R ⁵ = H, R ⁶ = H, R ⁷ = CH ₃ , R ⁸ = C ₂ H ₄ , R ⁹ = CH ₃ , s = 0, u = 9) 71.09 parts, 4.11 parts of methacrylic acid, and 0.91 part of 3-mercaptopropionic acid as a chain transfer agent, and the inside of the reaction vessel was purged with nitrogen under stirring And heated to 65 ° C. under a nitrogen atmosphere. Next, an initiator solution consisting of 1.41 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 28.6 parts of 2-propanol was added dropwise over 5 hours. Thereafter, the temperature was maintained at 65 ° C. for 1 hour to complete the polymerization reaction, and after 2-propanol was distilled off, water was added so that the copolymer concentration was 25% by mass, and 30% hydroxylation was performed. The polymer (SRA-1) as a drying shrinkage reducing agent comprising a copolymer aqueous solution having a weight average molecular weight of 13,000 was obtained by neutralization with an aqueous sodium solution. The weight average molecular weight is a value measured under the GPC conditions (conditions using THF as an eluent).

Production Example 2: Production of SRA-2 In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, 198.91 parts of 2-propanol, 46.92 parts of 2-ethylhexyl methacrylate, Methoxypolyethylene glycol monomethacrylate (average number of added moles of ethylene oxide: 9; that is, in the above formula (2), R ⁵ = H, R ⁶ = H, R ⁷ = CH ₃ , R ⁸ = C ₂ H ₄ , R ⁹ = CH ₃ , s = 0, u = 9) 75.58 parts, and 0.62 part of 3-mercaptopropionic acid as a chain transfer agent were charged, the inside of the reaction vessel was purged with nitrogen under stirring, and 65 under a nitrogen atmosphere. Heated to ° C. Next, an initiator solution consisting of 1.41 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 28.6 parts of 2-propanol was added dropwise over 5 hours. Thereafter, the temperature was maintained at 65 ° C. for 1 hour to complete the polymerization reaction, and after 2-propanol was distilled off, water was added so that the copolymer concentration was 25% by mass. A polymer (SRA-2) as a drying shrinkage reducing agent comprising a copolymer aqueous solution was obtained. The weight average molecular weight is a value measured under the same conditions as in Production Example 1.

Production Example 3: Production of SRA-3 In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, 199.34 parts of 2-propanol, 46.92 parts of 2-ethylhexyl acrylate, IPN10 (in formula (3), R ¹⁰ = H, R ¹¹ = H, R ¹² = CH ₃ , R ¹³ = C ₂ H ₄ , R ¹⁴ = H, x = 2, y = 10) 75.58 parts As a chain transfer agent, 0.63 part of 3-mercaptopropionic acid was charged, and the reaction vessel was purged with nitrogen under stirring, and heated to 65 ° C. in a nitrogen atmosphere. Next, an initiator solution consisting of 1.84 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 28.2 parts of 2-propanol was added dropwise over 5 hours. Thereafter, the temperature was maintained at 65 ° C. for 1 hour to complete the polymerization reaction, and 2-propanol was distilled off, and then water was added so that the copolymer concentration was 25% by mass. A polymer (SRA-3) as a drying shrinkage reducing agent comprising an aqueous copolymer solution was obtained. The weight average molecular weight is a value measured under the same conditions as in Production Example 1.

Production Example 4: Production of SRA-4 In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, 198.91 parts of 2-propanol, 47.30 parts of lauryl methacrylate, methoxypolyethylene Glycol monomethacrylate (average number of added moles of ethylene oxide: 9; that is, in the above formula (2), R ⁵ = H, R ⁶ = H, R ⁷ = CH ₃ , R ⁸ = C ₂ H ₄ , R ⁹ = CH ₃ , s = 0, u = 9) 71.09 parts, 4.11 parts of methacrylic acid, and 1.12 parts of 3-mercaptopropionic acid as a chain transfer agent, the inside of the reaction vessel was purged with nitrogen under stirring, Heat to 65 ° C. under nitrogen atmosphere. Next, an initiator solution consisting of 1.41 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 28.6 parts of 2-propanol was added dropwise over 5 hours. Thereafter, the temperature was maintained at 65 ° C. for 1 hour to complete the polymerization reaction, and after 2-propanol was distilled off, water was added so that the copolymer concentration was 25% by mass, and 30% hydroxylation was performed. Neutralization with an aqueous sodium solution yielded a polymer (SRA-4) as a drying shrinkage reducing agent comprising a copolymer aqueous solution having a weight average molecular weight of 12600. The weight average molecular weight is a value measured under the same conditions as in Production Example 1.

Production Example 5: Production of SRA-5 In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, 198.91 parts of 2-propanol, 30.89 parts of 2-ethylhexyl methacrylate, Methoxypolyethylene glycol monomethacrylate (average number of added moles of ethylene oxide: 9; that is, in the above formula (2), R ⁵ = H, R ⁶ = H, R ⁷ = CH ₃ , R ⁸ = C ₂ H ₄ , R ⁹ = CH ₃ , s = 0, u = 9) 87.50 parts, 4.11 parts of methacrylic acid, and 0.81 part of 3-mercaptopropionic acid as a chain transfer agent were added, and the inside of the reaction vessel was purged with nitrogen under stirring. And heated to 65 ° C. under a nitrogen atmosphere. Next, an initiator solution consisting of 1.41 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 28.6 parts of 2-propanol was added dropwise over 5 hours. Thereafter, the temperature was maintained at 65 ° C. for 1 hour to complete the polymerization reaction, and after 2-propanol was distilled off, water was added so that the copolymer concentration was 25% by mass, and 30% hydroxylation was performed. Neutralization with an aqueous sodium solution gave a polymer (SRA-5) as a drying shrinkage reducing agent comprising a copolymer aqueous solution having a weight average molecular weight of 13400. The weight average molecular weight is a value measured under the same conditions as in Production Example 1.

Production Example 6: Production of SRA-6 In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, 198.91 parts of 2-propanol, 12.36 parts of 2-ethylhexyl methacrylate, Methoxypolyethylene glycol monomethacrylate (average number of added moles of ethylene oxide: 9; that is, in the above formula (2), R ⁵ = H, R ⁶ = H, R ⁷ = CH ₃ , R ⁸ = C ₂ H ₄ , R ⁹ = CH ₃ , s = 0, u = 9) 106.03 parts, 4.11 parts of methacrylic acid, and 0.86 part of 3-mercaptopropionic acid as a chain transfer agent were charged, and the inside of the reaction vessel was purged with nitrogen under stirring. And heated to 65 ° C. under a nitrogen atmosphere. Next, an initiator solution consisting of 1.41 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 28.6 parts of 2-propanol was added dropwise over 5 hours. Thereafter, the temperature was maintained at 65 ° C. for 1 hour to complete the polymerization reaction, and after 2-propanol was distilled off, water was added so that the copolymer concentration was 25% by mass, and 30% hydroxylation was performed. Neutralization with an aqueous solution of sodium gave a polymer (SRA-6) as a drying shrinkage reducing agent comprising a copolymer aqueous solution having a weight average molecular weight of 12,000. The weight average molecular weight is a value measured under the same conditions as in Production Example 1.

  About the polymer (SRA-1 to SRA-6) obtained in Production Examples 1 to 6, the surface tension in a solution containing 0.2% by mass of the polymer in the cement supernatant was measured by the above-described method. The measurement results are shown in Table 1 below together with the composition of the polymer.

Production Example 7: Production of PC-1 Into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, 1698 parts of ion-exchanged water was charged, and the inside of the reaction vessel was purged with nitrogen under stirring. And heated to 80 ° C. under a nitrogen atmosphere. Next, 1668 parts of methoxypolyethylene glycol monomethacrylate (average number of added moles of ethylene oxide of 25), 332 parts of methacrylic acid and 500 parts of ion-exchanged water are mixed, and 16.7 parts of 3-mercaptopropionic acid is further added as a chain transfer agent. A monomer mixture aqueous solution was prepared by mixing uniformly. The monomer mixture aqueous solution and 184 parts of a 10% ammonium persulfate aqueous solution were added dropwise over 4 hours, and after completion of the addition, 46 parts of a 10% ammonium persulfate aqueous solution was added dropwise over 1 hour. Thereafter, the temperature was continuously maintained at 80 ° C. for 1 hour to complete the polymerization reaction. Thereafter, the solution is neutralized with an aqueous sodium hydroxide solution at a temperature not higher than the polymerization reaction temperature, diluted with water so that the concentration of the polymerization component is 25% by mass, and the polycarboxylic acid-based high-performance AE water reducing agent (A). An aqueous solution of a copolymer (PC-1) (weight average molecular weight 24,000; pH 7.0) corresponding to the above was obtained. The weight average molecular weight of the copolymer (PC-1) is a value measured under the above GPC conditions (conditions using water / acetonitrile as an eluent).

Production Example 8: Production of PC-2 In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, 76.91 parts of ion-exchanged water and 3-methyl-3-butene- 149.28 parts of an unsaturated polyalkylene glycol ether in which 50 mol of ethylene oxide was added to 1-ol on average was charged, and the reaction vessel was purged with nitrogen under stirring, and heated to 60 ° C. in a nitrogen atmosphere. When the internal temperature was stabilized at 60 ° C., an aqueous hydrogen peroxide solution containing 0.23 parts of hydrogen peroxide and 11.71 parts of water was added. Next, 20.17 parts of acrylic acid was added dropwise over 3 hours, and at the same time, an aqueous solution in which 0.3 part of L-ascorbic acid and 0.79 part of 3-mercaptopropionic acid were dissolved in 40.74 parts of water was added 3.5. It was added dropwise over time. Thereafter, the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction. Thereafter, the solution is neutralized with an aqueous sodium hydroxide solution at a temperature not higher than the polymerization reaction temperature, diluted with water so that the concentration of the polymerization component becomes 40% by mass, and the polycarboxylic acid-based high-performance AE water reducing agent (B). An aqueous solution of a copolymer (PC-2) (weight average molecular weight: 37,000; pH 6.5) corresponding to The weight average molecular weight of the copolymer (PC-2) is a value measured under the same conditions as in Production Example 7.

Production Example 9: Production of PC-3 In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tank and a reflux condenser, 3.1 parts of ion-exchanged water, 3-methyl-3-butene-1 -66.9 parts of 80% aqueous solution of polyalkylene glycol monoalkenyl ether monomer (hereinafter referred to as IPN-50) obtained by adding 50 moles of ethylene oxide to ol, and 2.8 parts of 30% aqueous solution of hydrogen peroxide. Charged and heated to 58 ° C. under nitrogen atmosphere. Next, a mixed solution of 267.6 parts of an 80% solution of IPN-50, 34.7 parts of deionized water and 2.5 parts of lauryl mercaptan, 36.2 parts of acrylic acid and 9.0 parts of ion-exchanged water was added. The mixture was added dropwise over 3 hours, and at the same time, a mixture of 1.1 parts of L-ascorbic acid and 19.9 parts of ion-exchanged water was added dropwise over 3.5 hours. After the dropwise addition, the mixture was subsequently aged at 58 ° C. for 1 hour, cooled to room temperature, neutralized with an aqueous sodium hydroxide solution, diluted with water so that the concentration of the polymerization component was 25% by mass, An aqueous solution of copolymer (PC-3) (weight average molecular weight 21,900; pH 6.7) corresponding to the high performance AE water reducing agent (B) was obtained. The weight average molecular weight of the copolymer (PC-3) is a value measured under the same conditions as in Production Example 7.

<Performance evaluation>
Any one of the polymers (SRA-1 to SRA-6) (addition amount: 1.5 wt% / C) obtained in Production Examples 1 to 6 as a drying shrinkage reducing agent, and a polycarboxylic acid-based high-performance AE water-reducing agent Using any of the polymers (PC-1 to PC-3) obtained in Production Examples 7 to 9 as an agent, the drying shrinkage reduction rate of the mortar was measured. Moreover, as a comparative sample, either SRA-1 to SRA-6 (addition amount: 1.5 wt% / C) and Pozzolith No. The drying shrinkage reduction rate of mortar combined with 70 (lignin sulfonic acid compound polyol composite system dispersant, manufactured by Pozzolith) was measured. High performance AE water reducing agents (PC-1 to PC-3) and Pozzolith No. The amount of 70 added was determined by the following method. Note that “wt% / C” indicates the percentage by mass of the agent added to the cement mass.

<High performance AE water reducing agents (PC-1 to PC-3) and Pozzolith No. Determination of 70 addition amount>
The addition amount of SRA-1 to SRA-6, which is a drying shrinkage reducing agent, is 1.5 wt% / C. The addition amount of 70 (comparative sample) was determined by the following method.

  Any of SRA-1 to SRA-6 (addition amount: 1.5 wt% / C), any of PC-1 to PC-3, which is a high-performance AE water reducing agent, or Pozzolith No. 70, and 213.7 g of an air conditioning agent weighed and diluted with water if necessary, 485.8 g of ordinary Portland cement manufactured by Taiheiyo Cement, and standard sand for cement strength test (JIS R 5201-1997 attachment) The mortar was kneaded in accordance with JIS R 5201-1997 using 1350 g of Hobart type mortar mixer: Model No. N-50 (trade name, manufactured by Hobart). Specifically, 213.7 g of diluted water was charged into a kneading bowl, and 485.8 g of cement was added thereto, and immediately started at a low speed (spinning speed: 140 ± 5 rpm, revolution speed: 62 ± 10 rpm). 30 seconds after starting, 1350 g of sand was put in over 30 seconds. This mixture was kneaded for 30 seconds at a high speed (spinning speed: 285 ± 10 rpm, revolution speed: 125 ± 10 rpm), and the kneading was stopped for 90 seconds. At this time, scraping was performed during the first 15 seconds of the rest. After the suspension, the mixture was kneaded again at a high speed for 60 seconds to complete the kneading.

  After the kneading, the mortar was taken out from the smelting pot, and the air amount and the mortar flow value were measured. Under the present circumstances, the kind and addition amount of the air amount adjusting agent were adjusted so that the air amount might be 5.0-10.0 vol%. For a mortar with controlled air amount, the mortar flow value is measured according to the method described in JIS R 5201-1997, and the high-performance AE water reducing agent and pozzolith so that the mortar flow value becomes 180 ± 10 mm / 15 strokes. No. The amount of 70 added was determined. The determined addition amount and the mortar flow value at that time are shown in Table 2 below.

<Measurement of drying shrinkage reduction rate>
Subsequently, about the mortar obtained above, the drying shrinkage reduction rate was measured by the following method.

  Preparation of a mortar specimen (40 × 40 × 160 cm) for evaluating drying shrinkage reduction was performed according to JIS R 5201.

  In addition, silicone grease was applied to the mold in advance to stop the water, and the mold could be easily removed. Gauge plugs for measuring changes in length were attached to both ends of the specimen. After the mortar obtained by kneading was poured into a mold, it was placed in a sealed container and subjected to initial curing at 20 ± 2 ° C. for 48 hours. The mold was removed after the initial curing, and the silicon grease adhering to the surface of the specimen was washed with water using a scourer, and then cured in still water at 20 ° C. for 5 days (water curing).

  The length change was measured using a dial gauge (manufactured by West Japan Testing Machine Co., Ltd.) according to the method described in JIS A 1129-3. Wipe the surface water of the specimens cured for 5 days in still water with a paper towel, store it in a constant temperature and humidity room set at 20 ± 1 ° C and humidity 60 ± 5%, and then measure the length. Based on the length. Thereafter, the sample was stored in a constant temperature and humidity chamber set at a temperature of 20 ± 1 ° C. and a humidity of 60 ± 5% for 180 days, and timely measured. At this time, as shown by the following formula, the drying shrinkage reduction rate is a value that can reduce the shrinkage when the composition of the present invention is added to the shrinkage amount of the reference mortar, and the larger the value, the more the shrinkage can be reduced. Indicates. In addition, as a reference mortar at the time of measuring the drying shrinkage reduction rate, in the above-described blended mortar composition for evaluation, in place of the composition of the present invention, POZOLIS No. A specimen prepared by adding 70 to 0.25 wt% / C was used.

  From Table 2 above, Pozoris No. Even if the predetermined drying shrinkage reducing agent of the present invention (SRA series) is used in combination with 70, the shrinkage reduction rate is as low as 20% or less, and the effect of suppressing cracking cannot be sufficiently obtained. In contrast, when the polycarboxylic acid-based high-performance AE water reducing agent (PC series) and the predetermined drying shrinkage reducing agent (SRA series) of the present invention are used in combination, a high shrinkage reduction rate of 20% or more can be achieved. Further, when the polycarboxylic acid-based high-performance AE water reducing agent (PC series) is polymerized using an alkyl mercaptan having 3 or more carbon atoms as a chain transfer agent (PC-3), the shrinkage reduction rate is further increased. It can be shown that it can be improved.

  The drying shrinkage reducing agent of the present invention has the above-described configuration, and is applied to hydraulic materials such as cement paste, mortar, concrete, etc., and exerts an excellent crack prevention effect, thereby improving the strength and durability of the cured product. It is a highly versatile material that can improve the safety, improve the safety of civil engineering / building structures, etc., and suppress the repair cost.

Claims (7)

Following formula (1):

In the ^formula, R 1, ^{R 2} and ^{R 3} are each independently a hydrogen atom, a methyl group or _- represents _(CH 2) p COOX group, this time, X is a hydrogen atom, a monovalent metal, Represents a divalent metal, an ammonium group, an organic amine group or a hydrocarbon group, p is an integer of 0 to 2; and R ⁴ represents a hydrocarbon group of 4 to 30 carbon atoms,
Dry shrinkage reduction comprising a polymer having a surface tension of 25 to 50 mN / m in a solution containing at least one structural unit (I) represented by formula (I) as an essential component and containing 0.2% by mass of the polymer in the cement supernatant. Agent,
A high-performance AE water reducing agent, and an admixture composition for hydraulic materials. The polymer includes at least one structural unit (I) represented by the formula (1); and the following formula (2):

In the ^formula, R 5, ^{R 6} and ^{R 7} each independently represent a hydrogen atom or a methyl group; s is an integer from 0 to 2; ^{R 8} O is 2 to 18 carbon atoms Represents one or a mixture of two or more oxyalkylene groups; u represents the average number of moles added of the oxyalkylene group (R ⁸ O), is a number from 1 to 300; and R ⁹ is a hydrogen atom Or a hydrocarbon group having 1 to 30 carbon atoms,
And a structural unit (II-a) represented by the following formula (3):

In the ^formula, R ^{10, R 11} and ^{R 12} each independently represent a hydrogen atom or a methyl group; x is an integer from 0 to ^{2; R 13} O is 2 to 18 carbon atoms Represents one or a mixture of two or more oxyalkylene groups; y represents the average number of moles added of the oxyalkylene group (R ¹³ O), is a number from 1 to 300; and R ¹⁴ is a hydrogen atom Or a hydrocarbon group having 1 to 30 carbon atoms,
And at least one structural unit (II) selected from structural units (II-b) represented by formula (4):

In the formula, R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, a methyl group or a — (CH ₂ ) _q COOZ ′ group, where Z ′ represents a hydrogen atom, a monovalent Represents a metal, a divalent metal, an ammonium group or an organic amine group, and q is an integer of 0 to 2; and Z represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group or an organic amine group. , COOZ ′ and COOZ are present when two or more thereof, two of these may form an anhydride,
The admixture composition for hydraulic materials according to claim 1, comprising 0 to 30% by mass of at least one structural unit (III) represented by   The admixture composition for hydraulic materials according to claim 1 or 2, wherein the structural unit (I) of the polymer is present in a proportion of 7 to 99% by mass of the whole polymer.   The admixture composition for hydraulic materials according to any one of claims 1 to 3, wherein the high-performance AE water reducing agent is a polycarboxylic acid-based high-performance AE water reducing agent.   The polycarboxylic acid-based high-performance AE water reducing agent comprises the structural unit (II-a) and the structural unit (III) as essential structural units, and a polycarboxylic acid-based high-performance AE water reducing agent (A), and It is at least 1 sort (s) chosen from the polycarboxylic acid type | system | group high performance AE water reducing agent (B) which contains this structural unit (II-b) and this structural unit (III) as an essential structural unit. Admixture composition for hydraulic materials.   The admixture composition for hydraulic materials according to claim 4 or 5, wherein the polycarboxylic acid-based high-performance AE water reducing agent is polymerized using an alkyl mercaptan having 3 or more carbon atoms as a chain transfer agent.   The blending mass ratio of the drying shrinkage reducing agent and the polycarboxylic acid-based high-performance AE water reducing agent is 99.5: 0.5 to 0.5: 99.5, according to any one of claims 4 to 6. The admixture composition for hydraulic materials described.