JP2018030769A - Additive for hydraulic composition - Google Patents

Abstract

【選択図】なしThe present invention provides an additive for a hydraulic composition, which imparts moderate fluidity and material separation resistance to a hydraulic composition continuously and has good compatibility of the contained components.
SOLUTION: A water-soluble thickener (A),
A copolymer (B) containing a structural unit derived from the monomer (I) represented by the following general formula (1) and a structural unit derived from the monomer (II) represented by the following general formula (2) ) And
The weight ratio ((A) / (B)) of the water-soluble thickener (A) to the copolymer (B) is 0.0.
The additive for hydraulic compositions which is 1 / 99.99 to 25/75.
[Chemical 1]

[Selection figure] None

Description

  The present invention relates to an additive for hydraulic compositions.

  Along with environmental factors such as a reduction in the number of workers and an improvement in work efficiency during the construction of a hydraulic composition typified by a cement composition, an improvement in workability is required. In particular, a cement composition having high fluidity is required for an over-stressed reinforcing member for which it is difficult to use a vibration exciter or a synthetic structural member that is largely closed, and various additions to the cement composition are required. Agents have been developed.

  For example, Patent Document 1 describes an additive for a hydraulic composition containing an anionic aromatic compound, a cationic surfactant, and silica fume.

  Patent Document 2 describes that a high-flowing mortar composition capable of suppressing aggregate separation can be prepared by adding a water-soluble cellulose ether and a microbial fermentation polysaccharide.

  Patent Document 3 describes an additive for cement composition that can suppress bleeding, including a polycarboxylic acid copolymer, a water-soluble cellulose ether, and an antifoaming agent.

  Furthermore, Patent Document 4 describes a highly fluid concrete (cement composition) in which hydroxypropyl highly substituted hydroxypropylmethylcellulose is used as a thickener.

JP 2007-321064 A JP 2003-313069 A International Publication No. 2003/024884 JP 2014-101243 A

Under the circumstances as described above, there is a demand for development of a cement composition excellent in pumpability by having an appropriate material separation resistance and high fluidity. Addition for hydraulic composition that has both the properties of thickeners for imparting excellent material separation resistance and dispersants for hydraulic compositions such as high-performance AE water reducing agents for imparting long-term high fluidity An agent (rheology modifier) can be used.
However, when the technique of Patent Document 1 is used for a wide range of water-cement ratio, it is necessary to adjust the blending of additives and hydraulic composition. It involves complicated work. Moreover, although the technique of patent document 2 can maintain fluidity | liquidity for a long time by addition of microbial fermentation polysaccharide, setting time is significantly delayed and workability | operativity is deteriorated. In the technique of Patent Document 3, in a high temperature environment of about 40 ° C., the compatibility between the water-soluble cellulose ether and the polycarboxylic acid copolymer is poor, and the additive is separated into a solid and a liquid. It is difficult to use in high summer. On the other hand, there is a limit to increasing the thickener in order to impart high viscosity to the cement composition. Furthermore, the technique of Patent Document 4 has poor sustainability of cement fluidity, the fluidity drastically decreases with time after the admixture is added, and has a great influence on the pumpability when the cement composition is placed. obtain.
Therefore, the present invention aims to provide an additive for a hydraulic composition, which imparts moderate fluidity and material separation resistance to the hydraulic composition continuously and has good compatibility of the components contained therein. And

  As a result of intensive studies by the present inventors to solve the above problems, the additive for a hydraulic composition containing a water-soluble thickener and a specific copolymer at a specific weight ratio is used. We found that the problem could be solved.

（式中、Ｒ^１は、炭素原子数２〜５のアルケニル基を表す。Ａ^１Ｏは、同一若しくは異なって、炭素原子数２〜１８のオキシアルキレン基を表す。ｎ１は、オキシアルキレン基の平均付加モル数であり、１〜１００の数を表す。Ｒ^２は、水素原子又は炭素原子数１〜３０の炭化水素基を表す。）

（式中、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子又は炭素原子数１〜３のアルキル基を表す。ｍは、０〜２の数を表す。Ａ^２Ｏは、同一若しくは異なって、炭素原子数２〜１８のオキシアルキレン基を表す。ｎ２は、オキシアルキレン基の平均付加モル数であり、１〜１００の数を表す。Ｘは、水素原子又は炭素原子数１〜３０の炭化水素基を表す。）
［２］ 共重合体（Ｂ）が、更に下記一般式（３）で表される単量体（ＩＩＩ）に由来する構成単位を含む、［１］に記載の水硬性組成物用添加剤。

（式中、Ｒ^６、Ｒ^７、及びＲ^８は、それぞれ独立に、水素原子、−ＣＨ_３、又は−（ＣＨ_２）_ｒＣＯＯＭ^２を表し、−（ＣＨ２）_ｒＣＯＯＭ^２は、−ＣＯＯＭ^１又は他の−（ＣＨ_２）_ｒＣＯＯＭ^２と無水物を形成していてもよく、その場合、それらの基のＭ^１及びＭ^２は存在しない。Ｍ^１及びＭ^２は、同一若しくは異なって、水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、アルキルアンモニウム基、又は置換アルキルアンモニウム基を表す。ｒは０〜２の整数を示す。）
［３］ 共重合体（Ｂ）が、更に下記一般式（４）で表される単量体（ＩＶ）に由来する構成単位を含む、［１］又は［２］に記載の水硬性組成物用添加剤。

（式中、Ｒ^９、Ｒ^１０及びＲ^１１は、それぞれ独立に、水素原子又は炭素原子数１〜３のアルキル基を表す。Ｒ^１２は、炭素原子数１〜４のヘテロ原子を含んでよい炭化水素基を表す。ｓは、０〜２の整数を表す。ただし、一般式（４）で表される単量体（ＩＶ）には、一般式（１）〜（３）で表される単量体は含まれない。）
［４］ 共重合体（Ｂ）を２種以上含む、［１］〜［３］のいずれか１つに記載の水硬性組成物用添加剤。
［５］ 共重合体（Ｂ）が、単量体（ＩＩ）に由来する構成単位としてｎ２が１である単量体（ＩＩａ）に由来する構成単位及びｎ２が１より大きく１００以下である単量体（ＩＩｂ）に由来する構成単位を含み、単量体（ＩＩａ）に由来する構成単位の単量体（ＩＩｂ）に由来する構成単位に対する重量比率（（ＩＩａ）／（ＩＩｂ））が、１／９９〜９９／１である、［１］〜［４］のいずれか１つに記載の水硬性組成物用添加剤。
［６］ 共重合体（Ｂ）の重量平均分子量が、ポリエチレングリコール換算で５，０００〜６０，０００である、［１］〜［５］のいずれか１つに記載の水硬性組成物用添加剤。
［７］ 水溶性増粘剤（Ａ）を２種以上含む、［１］〜［６］のいずれか１つに記載の水硬性組成物用添加剤。
［８］ 水溶性増粘剤（Ａ）が、アルキルセルロース、ヒドロキシアルキルセルロース、及びヒドロキシアルキルアルキルセルロースから選ばれる少なくとも１種を含む、［１］〜［７］のいずれか１つに記載の水硬性組成物用添加剤。
［９］ 下記一般式（５）で表される単量体（Ｃ）を更に含む、［１］〜［８］のいずれか１つに記載の水硬性組成物用添加剤。

（式中、Ｒ^１ｃは、炭素原子数２〜５のアルケニル基を表す。Ａ^１ｃＯは、同一若しくは異なって、炭素原子数２〜１８のオキシアルキレン基を表す。ｎ１ｃは、オキシアルキレン基の平均付加モル数であり、１〜１００の数を表す。Ｒ^２ｃは、水素原子又は炭素原子数１〜３０の炭化水素基を表す。）
［１０］ 単量体（Ｃ）の共重合体（Ｂ）に対する含有割合が、０．１〜３０重量％である、［９］に記載の水硬性組成物用添加剤。
［１１］ 両末端基がヒドロキシ基である水溶性ポリアルキレングリコール（Ｄ）を、更に含む、［１］〜［１０］のいずれか１つに記載の水硬性組成物用添加剤。
［１２］ 両末端基がヒドロキシ基である水溶性ポリアルキレングリコール（Ｄ）の共重合体（Ｂ）に対する含有割合が、０．０１〜１０重量％である、［１１］に記載の水硬性組成物用添加剤。
［１３］ ［１］〜［１２］のいずれか１つに記載の水硬性組成物用添加剤を含む、水硬性組成物。 That is, the present invention provides the following.
[1] a water-soluble thickener (A);
A copolymer (B) containing a structural unit derived from the monomer (I) represented by the following general formula (1) and a structural unit derived from the monomer (II) represented by the following general formula (2) ) And
The weight ratio ((A) / (B)) of the water-soluble thickener (A) to the copolymer (B) is 0.0.
The additive for hydraulic compositions which is 1 / 99.99 to 25/75.

(In the formula, R ¹ represents an alkenyl group having 2 to 5 carbon atoms. A ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N1 represents an oxyalkylene group. (This is the average number of moles added and represents a number of 1 to 100. R ² represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.)

^(Wherein, R 3, ^{R 4} and ^{R 5} are each independently, .m represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, the .A ² O representing the number of 0 to 2, the same Or, differently, it represents an oxyalkylene group having 2 to 18 carbon atoms, n2 is an average added mole number of the oxyalkylene group, and represents a number of 1 to 100. X is a hydrogen atom or 1 to 1 carbon atoms. Represents 30 hydrocarbon groups.)
[2] The additive for a hydraulic composition according to [1], wherein the copolymer (B) further contains a structural unit derived from the monomer (III) represented by the following general formula (3).

^(Wherein, R 6, ^{R 7,} and ^{R 8} are each independently a hydrogen atom, -CH _3, or _- represents a ^{_{(CH 2) r COOM 2,}} - (CH2) r COOM 2 may -COOM ¹ Or other — (CH ₂ ) _r COOM ² and may form an anhydride, in which case M ¹ and M ² of those groups are absent, M ¹ and M ² may be the same or different, And represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, or a substituted alkylammonium group, and r represents an integer of 0 to 2.)
[3] The hydraulic composition according to [1] or [2], wherein the copolymer (B) further contains a structural unit derived from the monomer (IV) represented by the following general formula (4): Additives.

^(Wherein, R ^{9, R 10} and ^{R 11} are each independently, ^{.R 12} represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms may contain a hetero atom having 1 to 4 carbon atoms Represents a hydrocarbon group, and s represents an integer of 0 to 2. However, the monomer (IV) represented by the general formula (4) is represented by the general formulas (1) to (3). Monomers are not included.)
[4] The additive for a hydraulic composition according to any one of [1] to [3], comprising two or more types of copolymers (B).
[5] The copolymer (B) is a structural unit derived from the monomer (IIa) in which n2 is 1 as a structural unit derived from the monomer (II), and a single unit in which n2 is greater than 1 and 100 or less. The weight ratio ((IIa) / (IIb)) of the structural unit derived from the monomer (IIb) to the structural unit derived from the monomer (IIb) includes the structural unit derived from the monomer (IIb). The additive for hydraulic compositions according to any one of [1] to [4], which is 1/99 to 99/1.
[6] Addition for hydraulic composition according to any one of [1] to [5], wherein the copolymer (B) has a weight average molecular weight of 5,000 to 60,000 in terms of polyethylene glycol. Agent.
[7] The additive for a hydraulic composition according to any one of [1] to [6], including two or more water-soluble thickeners (A).
[8] The water according to any one of [1] to [7], wherein the water-soluble thickener (A) includes at least one selected from alkyl cellulose, hydroxyalkyl cellulose, and hydroxyalkylalkyl cellulose. Additive for hard composition.
[9] The additive for a hydraulic composition according to any one of [1] to [8], further including a monomer (C) represented by the following general formula (5).

(In the formula, R ^1c represents an alkenyl group having 2 to 5 carbon atoms. A ^1c O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N1c represents an oxyalkylene group. (This is the average number of moles added and represents a number of 1 to 100. R ^2c represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.)
[10] The additive for a hydraulic composition according to [9], wherein the content ratio of the monomer (C) to the copolymer (B) is 0.1 to 30% by weight.
[11] The additive for a hydraulic composition according to any one of [1] to [10], further including a water-soluble polyalkylene glycol (D) in which both terminal groups are hydroxy groups.
[12] The hydraulic composition according to [11], wherein the content ratio of the water-soluble polyalkylene glycol (D) having both hydroxyl groups as hydroxyl groups to the copolymer (B) is 0.01 to 10% by weight. Additives for products.
[13] A hydraulic composition comprising the additive for hydraulic composition according to any one of [1] to [12].

  According to the present invention, it is possible to provide an additive for a hydraulic composition that imparts moderate fluidity and material separation resistance to the hydraulic composition continuously and has good compatibility of the components contained therein. it can.

  The additive for hydraulic compositions of the present invention contains a water-soluble thickener (A) and a copolymer (B). Hereinafter, the water-soluble thickener (A) and the copolymer (B) will be described. In the present specification, the agent includes a composition.

1. Water-soluble thickener (A)
The water-soluble thickener (A) according to the present invention is not particularly limited as long as it exhibits water-solubility and can increase the viscosity of the aqueous solution after dissolution than before dissolution. For example, it contains a hydroxy group Polyethylene glycol thickeners, polyvinyl alcohol thickeners, polysaccharide derivative thickeners can be used, but water soluble thickeners (A ) Is preferably a polysaccharide derivative, more preferably a polysaccharide derivative in which a plurality of hydroxy groups of the polysaccharide are partially or entirely substituted with an alkyloxy group having 1 to 5 carbon atoms; A polysaccharide derivative in which a plurality of hydroxy groups possessed by a saccharide are partially or entirely substituted with an alkyloxy group having 1 to 5 carbon atoms having a hydroxy group; a plurality of hydroxy groups possessed by a polysaccharide; Partially or totally, a polysaccharide derivative substituted with an alkyloxy group having 1 to 5 carbon atoms having a hydroxy group and an alkyloxy group having 1 to 5 carbon atoms; or a plurality of polysaccharide derivatives Hydrophobic, wherein the hydrogen atom of a hydroxy group or an alkylated derivative of a polysaccharide or a plurality of hydroxy groups possessed by a hydroxyalkylated derivative partially or entirely has a hydrocarbon chain having 8 to 40 carbon atoms as a partial structure A polysaccharide derivative substituted with a substituent and an ionic hydrophilic substituent having, as a partial structure, one or more groups selected from the group consisting of a sulfo group and a sulfonate salt group. Examples of the polysaccharide derivative include alkyl cellulose, hydroxyalkyl cellulose, and hydroxyalkylalkyl cellulose.
The water-soluble thickener (A) according to the present invention is preferably at least one selected from alkyl cellulose, hydroxyalkyl cellulose, and hydroxyalkylalkyl cellulose, more preferably C _1-5 alkyl cellulose, hydroxy C. _1-5 alkylcellulose, and is a hydroxy C _1-5 alkyl C _1-5 one or more selected from alkyl celluloses, more preferably, at least one selected from hydroxypropylmethylcellulose and hydroxyethylcellulose.
Here, “C _1-5 alkyl” means an alkyl group having 1 to 5 carbon atoms.

In the present specification, the group of sulfonate _salts, ^-SO 3 - means a group represented by · ^{M +.} Here, M ⁺ represents a cation. Hereinafter, the hydrophobic substituent (P) is the hydrophobic substituent, the ionic hydrophilic substituent (Q) is the ionic hydrophilic substituent, and the polysaccharide derivative is preferable as the water-soluble thickener (A) of the present invention. , Referred to as polysaccharide derivative (A ′).

<Hydrophobic substituent>
The hydrophobic substituent (P) has 8 or more carbon atoms, preferably 12 or more, more preferably 16 or more, and from the viewpoint of obtaining good material separation resistance and rheology (appropriate fluidity) in poor blend concrete. An alkyl glyceryl ether group having a linear or branched alkyl group having 40 or less carbon atoms, preferably 36 or less, more preferably 24 or less;
Alkenyl glyceryl ether having a linear or branched alkenyl group having 8 or more carbon atoms, preferably 12 or more, more preferably 16 or more, and 40 or less, preferably 36 or less, more preferably 24 or less. A group; a hydroxy group may be substituted, and an oxycarbonyl group may be inserted; 8 or more carbon atoms, preferably 12 or more, more preferably 16 or more, and 40 or less carbon atoms, preferably A linear or branched alkyl group of 36 or less, more preferably 24 or less;
Hydroxyl group may be substituted and oxycarbonyl group may be inserted, having 8 or more carbon atoms, preferably 12 or more, more preferably 16 or more, and 40 or less carbon atoms, preferably 36 or less. More preferably 24 or less, a linear or branched alkenyl group; or a hydroxy group which may be substituted and an oxycarbonyl group may be inserted, having 8 or more carbon atoms, preferably 12 or more, More preferably, it is a linear or branched acyl group having 16 or more and 40 or less carbon atoms, preferably 36 or less, more preferably 24 or less. The hydrophobic substituent (P) is preferably selected from an alkyl glyceryl ether group, a long-chain alkyl group, and a 2-hydroxy long-chain alkyl group from the viewpoint of easy production and good pumpability in poor blended concrete. And more preferably an alkyl glyceryl ether group.
In this specification, the long chain means that the number of carbon atoms is 8 or more. The long chain usually has 40 or less carbon atoms.

In the present specification, the alkyl glyceryl ether group means a group having the structure of the remaining portion excluding one hydroxy group of a monoalkyl glyceryl ether, that is, a 2-hydroxy-3-alkoxypropyl group, 2- Alkoxy-1- (hydroxymethyl) ethyl group.
The alkenyl glyceryl ether group means a group having the structure of the remaining portion excluding one hydroxy group of monoalkenyl glyceryl ether, that is, a 2-hydroxy-3-alkenyloxypropyl group, 2-alkenyloxy group. A -1- (hydroxymethyl) ethyl group.
When these hydrophobic substituents (P) have a hydroxyalkyl group (eg, hydroxyethyl group, hydroxypropyl group) bonded to the polysaccharide molecule, the hydrophobic substituent (P) is bonded to the hydrogen atom of the hydroxy group of the bonded hydroxyalkyl group. May be substituted.

<Ionic hydrophilic substituent>
The ionic hydrophilic substituent (Q) is preferably a substituent having, as a partial structure, one or more groups selected from the group consisting of a sulfo group and a sulfonate salt group from the viewpoint of salt resistance in the hydraulic composition. It is. Specifically, from the viewpoint of salt resistance in the hydraulic composition, for example, a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted with a hydroxy group or a salt group thereof may be mentioned. More specifically, examples of the ionic hydrophilic substituent (Q) include 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfo-2-hydroxypropyl group, and 2-sulfo-1- (hydroxymethyl). ) An ethyl group and a group in which the sulfo group contained in these groups is a salt. The polysaccharide derivative (A ′) may have a plurality of ionic hydrophilic substituents (Q). When a plurality of ionic hydrophilic substituents (Q) have a plurality of sulfo groups, all of them may be in the form of a sulfonate salt group, or only some of them may be in the form of a sulfonate salt group. Good. Examples of the cation in the sulfonate salt group include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium and magnesium, organic cations such as amines, and ammonium ions.

<Degree of substitution>
The C1-C5 alkyloxy group or hydrophobic substituent (P) of the polysaccharide derivative (A ') and the C1-C5 alkyloxy group or ionic hydrophilic substituent having a hydroxyl group (Q The degree of substitution) is from the viewpoint of obtaining appropriate solubility and rheology (moderate fluidity) in kneaded water, and the degree of substitution by an alkyloxy group having 1 to 5 carbon atoms or a hydrophobic substituent (P) is 0.0001 or more per unit of constituent monosaccharide residue is preferable, 0.0005 or more is more preferable, 2 or less is preferable, and 1.5 or less is more preferable. The degree of substitution with an alkyloxy group having 1 to 5 carbon atoms or an ionic hydrophilic substituent (Q) having a hydroxyl group is preferably 0.001 or more, more preferably 0.01 or more per unit monosaccharide residue. Preferably, 3.0 or less is preferable, and 2.5 or less is more preferable.

<Polysaccharides>
Examples of the polysaccharide used as a raw material for the polysaccharide derivative (A ′) include cellulose; starch; rhizome polysaccharides such as konjac mannan and troolloi sticky material; sap polysaccharides such as gum arabic, gum tragacanth and karaya; And seed polysaccharides such as tamarind gum; seaweed polysaccharides such as agar, carrageenan and algin; animal polysaccharides such as chitin, chitosan, heparin and chondroitin sulfate; and microbial polysaccharides such as dextran and xanthan gum.
Examples of alkylated derivatives of polysaccharides include cellulose alkylated derivatives, and specific examples include methylcellulose and ethylcellulose. Examples of the hydroxyalkylated derivative of polysaccharide include a hydroxyalkylated derivative of cellulose. Specific examples include hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and the like.

As the polysaccharide as a raw material of the polysaccharide derivative (A ′), cellulose or a derivative thereof is preferable because it is particularly excellent in compatibility with the component B of the present invention described in detail later. In addition, in this specification, the water-soluble thickener (A) manufactured using cellulose or its derivative (s) as a raw material is called a cellulose thickener. Further, by introducing a substituent (eg, an alkyl group such as a methyl group and an ethyl group, a hydroxyalkyl group such as a hydroxyethyl group and a hydroxypropyl group, an alkyleneoxy group) into these polysaccharides, the polysaccharide derivative (A ′) and In this case, the plurality of substituents possessed by the polysaccharide derivative (A ′) may be a single kind of substituent or a plurality of kinds of substituents.
The degree of substitution per constituent monosaccharide residue by the substituent of the polysaccharide derivative (A ′) is preferably 0.1 or more, more preferably 0.5 or more, and preferably 5 or less. More preferably, it is 3 or less. When the substituent is a (poly) alkyleneoxy group, the degree of substitution, that is, the number of moles of (poly) alkyleneoxy group added per constituent monosaccharide residue is preferably 0.1 or more, more preferably Is 0.5 or more, and preferably 10 or less, more preferably 5 or less.

<Molecular weight of water-soluble thickener>
The weight average molecular weight of the water-soluble thickener (A) is preferably 100,000 or more from the viewpoint of obtaining good solubility in water and good pumpability in a hydraulic composition (eg, concrete), 200,000 or more is more preferable, 500,000 or more is more preferable, 5,000,000 or less is preferable, 2,000,000 or less is more preferable, and 1,000,000 or less is more preferable.

<Manufacture of polysaccharide derivatives>
<Introduction of substituents>
The polysaccharide derivative (A ′) can be produced by, for example, a known method using the above-mentioned polysaccharide as a raw material, and a commercially available product can be used as the polysaccharide derivative.
When the polysaccharide derivative (A ′) has a hydrophobic substituent (P) and an ionic hydrophilic substituent (Q), the hydrophobic substituent (P) and the ionic hydrophilic substitution on the polysaccharide derivative (A ′) The order of introduction of the group (Q) is not particularly limited, and the hydrophobic substituent (P) may be introduced first, and then the ionic hydrophilic substituent (Q) may be introduced, or the ionic hydrophilicity may be introduced. The substituent (Q) may be introduced first, and then the hydrophobic substituent (P) may be introduced, or the hydrophobic substituent (P) and the ionic hydrophilic substituent (Q) may be introduced simultaneously. You may go. For example, the polysaccharide derivative (A ′) is partially hydrophobized by introducing hydrogen atoms of a plurality of hydroxy groups of the polysaccharide or the alkylated derivative or hydroxyalkylated derivative of the polysaccharide (introduction of a hydrophobic substituent (P)). Alternatively, after hydrophilization (introduction of ionic hydrophilic substituent (Q)), it is obtained by hydrophilizing or hydrophobizing part or all of the remaining hydroxy groups, respectively, or hydrophobizing and hydrophilizing It is obtained by carrying out simultaneously.

<Introduction example of substituent>
Introduction of the hydrophobic substituent (P) and the ionic hydrophilic substituent (Q) can be performed, for example, as follows. That is, an alkyl glycidyl ether having a polysaccharide or an alkylated derivative or a hydroxyalkylated derivative of a polysaccharide and having an alkyl group having 8 to 40 carbon atoms in the presence of an alkali;
An alkenyl glycidyl ether having an alkenyl group having 8 to 40 carbon atoms;
Epoxides of straight or branched chain saturated hydrocarbons having 8 to 40 carbon atoms;
Epoxides of linear or branched unsaturated hydrocarbons having 8 to 40 carbon atoms;
A halide of a straight or branched chain saturated hydrocarbon having 8 to 40 carbon atoms;
A linear or branched unsaturated hydrocarbon halide having 8 to 40 carbon atoms;
A straight or branched chain saturated hydrocarbon halohydrin having 8 to 40 carbon atoms;
A straight or branched chain unsaturated hydrocarbon halohydrin having from 8 to 40 carbon atoms;
A linear or branched saturated hydrocarbon acyl halide having from 8 to 40 carbon atoms;
An acyl halide of a linear or branched unsaturated hydrocarbon having 8 to 40 carbon atoms;
Obtained by introducing a hydrophobic substituent (P) by reacting with an ester having an acyl group having 8 to 40 carbon atoms; or a carboxylic acid anhydride having an acyl group having 8 to 40 carbon atoms. The intermediate reaction product is further reacted with vinyl sulfonic acid; a haloalkane sulfonic acid having 1 to 5 carbon atoms optionally substituted with a hydroxyl group; or a salt thereof in the presence of an alkali to obtain ionic hydrophilicity. This can be done by introducing the substituent (Q).

<Content of water-soluble thickener (A)>
The content ratio of the water-soluble thickener (A) in the hydraulic composition additive of the present invention is not particularly limited, but the water-soluble thickener (A) is based on 100 parts by weight of the hydraulic composition additive. 0.1 parts by weight or more is preferred, 0.3 parts by weight or more is more preferred, 0.5 parts by weight or more is more preferred, 4.0 parts by weight or less is preferred, 3.0 parts by weight or less is more preferred, 2.0 parts by weight or less is more preferable. The blending ratio of the water-soluble thickener (A) to the hydraulic composition additive is not particularly limited, but is preferably 0.1 / 100 or more, more preferably 0.3 / weight by weight. It is 100 or more, More preferably, it is 0.5 / 100 or more, Preferably it is 4.0 / 100 or less, More preferably, it is 3.0 / 100 or less, More preferably, it is 2.0 / 100 or less is there. Usually, by blending in such a range, the above-mentioned preferable content ratio, more preferable content ratio, and further preferable content ratio can be realized.

  The additive for hydraulic composition of the present invention may contain only one type of water-soluble thickener (A) or two or more types.

2. Copolymer (B)
The copolymer (B) contained in the hydraulic composition additive of the present invention is a structural unit derived from the monomer (I) represented by the following general formula (1) and the following general formula (2). The structural unit derived from the monomer (II) represented is included. In addition, the ratio of each structural unit contained in a copolymer (B) corresponds with the preparation ratio of each structural unit normally.
The additive for hydraulic composition of the present invention may contain only one type of copolymer (B) or two or more types.

(Monomer (I) represented by general formula (1))
Hereinafter, first, the monomer (I) will be described.

  Monomer (I) is represented by the following general formula (1).

(In the formula, R ¹ represents an alkenyl group having 2 to 5 carbon atoms. A ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N1 represents an oxyalkylene group. (This is the average number of moles added and represents a number of 1 to 100. R ² represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.)

R ¹ in the general formula (1) represents an alkenyl group having 2 to 5 carbon atoms. The number of carbon atoms of the alkenyl group is preferably 3-5. Specific examples of R ¹ include, but are not limited to, an allyl group, a methallyl group, a residue of 3-methyl-3-buten-1-ol, and the like.

A ¹ O in the general formula (1) is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. Examples of the oxyalkylene group include oxyethylene group (ethylene glycol unit), oxypropylene group (propylene glycol unit), oxybutylene group (butylene glycol unit), oxyethylene group (ethylene glycol unit), oxypropylene Groups (propylene glycol units) are preferred.

The above “same or different” means that when A ¹ O is contained in the general formula (1) (when n1 is 2 or more), each A ¹ O may be the same oxyalkylene group. And different (two or more) oxyalkylene groups may be used. In the case where a plurality of A ¹ O are contained in the general formula (1), the oxyethylene group (ethylene glycol unit), the oxypropylene group (propylene glycol unit), and the oxybutylene group (butylene glycol unit) are used. An embodiment in which two or more selected oxyalkylene groups are mixed is exemplified, and an embodiment in which an oxyethylene group (ethylene glycol unit) and an oxypropylene group (propylene glycol unit) are mixed, or an oxyethylene group (ethylene glycol unit) and oxy A mode in which a butylene group (butylene glycol unit) is mixed is preferable, and a mode in which an oxyethylene group (ethylene glycol unit) and an oxypropylene group (propylene glycol unit) are mixed is more preferable. In an embodiment in which different oxyalkylene groups are mixed, the addition of two or more oxyalkylene groups may be a block addition or a random addition.

  N1 in General formula (1) is the average addition mole number of an oxyalkylene group, and represents the number of 1-100. n1 is preferably 1 to 50, more preferably 5 to 50, and still more preferably 8 to 50. The average number of moles added means the average number of moles of alkylene glycol units added to 1 mole of monomer.

R ² in the general formula (1) represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. When the number of carbon atoms increases, the cement dispersibility of the cement admixture may not be sufficiently exhibited. Therefore, R ² is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. A hydrocarbon group of 1 to 5 is more preferable, and a hydrogen atom or a methyl group is most preferable.

  As the monomer (I), for example, (poly) ethylene glycol allyl ether, (poly) ethylene glycol methallyl ether, (poly) ethylene glycol 3-methyl-3-butenyl ether, (poly) ethylene (poly) propylene Glycol allyl ether, (poly) ethylene (poly) propylene glycol methallyl ether, (poly) ethylene (poly) propylene glycol 3-methyl-3-butenyl ether, (poly) ethylene (poly) butylene glycol allyl ether, (poly) Ethylene (poly) butylene glycol methallyl ether, (poly) ethylene (poly) butylene glycol 3-methyl-3-butenyl ether, methoxy (poly) ethylene glycol allyl ether, methoxy (poly) ethylene glycol methallyl ether , Methoxy (poly) ethylene glycol 3-methyl-3-butenyl ether, methoxy (poly) ethylene (poly) propylene glycol allyl ether, methoxy (poly) ethylene (poly) propylene glycol methallyl ether, methoxy (poly) ethylene ( Poly) propylene glycol 3-methyl-3-butenyl ether, methoxy (poly) ethylene (poly) butylene glycol allyl ether, methoxy (poly) ethylene (poly) butylene glycol methallyl ether, methoxy (poly) ethylene (poly) butylene glycol 3-methyl-3-butenyl ether is mentioned. As the monomer (I), one or more of these may be used, but since the hydrophilicity and hydrophobicity of the copolymer (B) can be excellent, (poly) It is preferable to use one or more selected from ethylene glycol (meth) allyl ether, (poly) ethylene glycol 3-methyl-3-butenyl ether, and (poly) ethylene (poly) propylene glycol allyl ether. Also in the specific example of the monomer (I), the average added mole number of the oxyalkylene group (polyalkylene glycol unit) is preferably 1 to 50, more preferably 5 to 50, and 8 to 50. More preferably. In the present specification, “(poly)” means that one or two or more constituent elements or raw materials described immediately after that are bonded. In the present specification, “(meth) allyl” means “allyl or methallyl”.

The copolymer (B) may contain only one type of structural unit derived from the monomer (I), or may contain a combination of two or more types.
Monomer (I) is not particularly limited and can be produced by a known method. Examples of such a method include a method of adding 1 to 100 mol of alkylene oxide to an unsaturated alcohol such as allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol.

(Monomer (II) represented by general formula (2))
Monomer (II) is represented by the following general formula (2).

^(Wherein, R 3, ^{R 4} and ^{R 5,} .m representing each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, the .A ² O representing the number of 0 to 2, identical or Differently, it represents an oxyalkylene group having 2 to 18 carbon atoms, n2 is an average added mole number of the oxyalkylene group, and represents a number of 1 to 100. X is a hydrogen atom or 1 to 30 carbon atoms. Represents a hydrocarbon group of

R < ³ >, R < ⁴ > and R < ⁵ > in General formula (2) represent a hydrogen atom or a C1-C3 alkyl group each independently.

A ² O in the general formula (2) is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. Examples of the oxyalkylene group include oxyethylene group (ethylene glycol unit), oxypropylene group (propylene glycol unit), oxybutylene group (butylene glycol unit), oxyethylene group (ethylene glycol), oxypropylene group (Propylene glycol) is preferred.

The above “same or different” means that when A ² O is contained in the general formula (2) (when n2 is 2 or more), each A ² O may be the same oxyalkylene group. And different (two or more) oxyalkylene groups may be used. As a mode in case ^two or more A2O is contained in General formula (2), it is from the group which consists of an oxyethylene group (ethylene glycol unit), an oxypropylene group (propylene glycol unit), and an oxybutylene group (butylene glycol unit). An embodiment in which two or more selected oxyalkylene groups are mixed is exemplified, and an embodiment in which an oxyethylene group (ethylene glycol unit) and an oxypropylene group (propylene glycol unit) are mixed, or an oxyethylene group (ethylene glycol unit) and oxy A mode in which a butylene group (butylene glycol unit) is mixed is preferable, and a mode in which an oxyethylene group (ethylene glycol unit) and an oxypropylene group (propylene glycol unit) are mixed is more preferable. In an embodiment in which different oxyalkylene groups are mixed, the addition of two or more oxyalkylene groups may be a block addition or a random addition.

  N2 in General formula (2) is the average addition mole number of an oxyalkylene group, and represents the number of 1-100. n2 is preferably 1 to 50, more preferably 5 to 50, and still more preferably 8 to 50. The average number of moles added means the average number of moles of alkylene glycol units added to 1 mole of monomer.

  The copolymer (B) may contain only one type of structural unit derived from the monomer (II) represented by the general formula (2), or may contain a combination of two or more types. Good. In particular, it is preferable to include two types of monomers (II) having different average addition mole numbers of oxyalkylene groups. Monomer (IIa) and oxyalkylene having an average addition mole number n2 of oxyalkylene groups of 1 It is more preferable to include a combination of the monomer (IIb) in which the average added mole number n2 of the group is greater than 1 and 100 or less, and more preferably the combination. Thereby, even if the additive for hydraulic compositions of this invention is added to a hydraulic composition (for example, cement composition) and it passes for a long time, a hydraulic composition can have the fluidity | liquidity which was excellent.

  Examples of the monomer (IIa) include a compound represented by the formula (2) in which n2 is 1 and X is a hydrogen atom, such as 2-hydroxyethyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate is mentioned, The compound represented by Formula (2) whose n2 is 1 and X is a hydrogen atom is preferable, and 2-hydroxyethyl (meth) acrylate is preferable.

  When the structural unit derived from the monomer (II) includes a structural unit derived from the monomer (IIa) and a structural unit derived from the monomer (IIb), the structural unit derived from the monomer (IIa) Weight ratio of the structural unit derived from the monomer (IIb) ((IIa) / (IIb), provided that the structural unit derived from the monomer (IIa) and the structural unit derived from the monomer (IIb) The total is 100% by weight) is preferably 1/99 to 99/1, more preferably 3/97 to 50/50, and even more preferably 5/95 to 30/70. . The weight ratio of the structural unit derived from the monomer (IIa) to the structural unit derived from the monomer (IIb) is usually equal to the charged weight ratio of the monomer (IIa) to the monomer (IIb). To do.

  X in the general formula (2) represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. By not having too many carbon atoms, the dispersibility of the hydraulic composition additive (dispersant) hydraulic composition is sufficiently exhibited. Therefore, X is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and a hydrogen atom or a methyl group. Most preferred.

Examples of the monomer (II) include an unsaturated monocarboxylic acid such as (meth) acrylate (hereinafter, “(meth) acrylate” means “acrylate or methacrylate”), and (poly) ethylene glycol. , (Poly) ethylene (poly) propylene glycol, (poly) ethylene (poly) butylene glycol, methoxy (poly) ethylene glycol, methoxy (poly) ethylene (poly) propylene glycol, methoxy (poly) ethylene (poly) butylene glycol, etc. Of (poly) alkylene glycols.
Specifically, for example, (poly) ethylene glycol (meth) acrylate, (poly) ethylene (poly) propylene glycol (meth) acrylate, (poly) ethylene (poly) butylene glycol (meth) acrylate, methoxy (poly) ethylene (Poly) alkylene glycol (meth) acrylate, such as glycol (meth) acrylate, methoxy (poly) ethylene (poly) propylene glycol (meth) acrylate, methoxy (poly) ethylene (poly) butylene glycol (meth) acrylate, 4- Examples thereof include hydroxybutyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate. As the monomer (II), one or two or more of these may be used in combination, but (poly) alkylene glycol (meth) acrylate is preferably used, and (poly) ethylene glycol (meth) acrylate is preferred. More preferably, methoxy (poly) ethylene glycol (meth) acrylate is used. When monomer (II) is (poly) alkylene glycol (meth) acrylate, in monomer (II), the average number of added moles of (poly) alkylene glycol is preferably 1-50. When the monomer (IIa) is (poly) alkylene glycol (meth) acrylate, the average added mole number of (poly) alkylene glycol in the monomer (IIa) is 1, and the monomer (IIb) is ( In the case of poly) alkylene glycol (meth) acrylate, the average number of added moles of (poly) alkylene glycol in monomer (IIb) is preferably more than 1 and 100 or less, more preferably 5-50. Preferably, it is 8-50.

  Monomer (II) is not particularly limited and can be produced by a known method. Such methods include, for example, unsaturated monocarboxylic acids such as (meth) acrylic acid, (poly) ethylene glycol, (poly) ethylene (poly) propylene glycol, (poly) ethylene (poly) butylene glycol, methoxy Examples thereof include a method of esterifying with (poly) alkylene glycol such as (poly) ethylene glycol, methoxy (poly) ethylene (poly) propylene glycol, and methoxy (poly) ethylene (poly) butylene glycol.

(Monomer (III) represented by general formula (3))
The copolymer (B) may further contain a structural unit derived from the monomer (III) represented by the following general formula (3).

(In the formula, R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom, —CH ₃ , or — (CH ₂ ) _r COOM ² , and — (CH ₂ ) _r COOM ² represents —COOM. ¹ or other — (CH ₂ ) rCOOM ² may form an anhydride, in which case M ¹ and M ² of those groups are absent, M ¹ and M ² may be the same or different, And represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, or a substituted alkylammonium group, and r represents an integer of 0 to 2.)

Examples of the monomer (III) include unsaturated monocarboxylic acid monomers and unsaturated dicarboxylic acid monomers. Examples of the unsaturated monocarboxylic acid monomer include acrylic acid, methacrylic acid, and crotonic acid, and salts thereof (eg, salts with monovalent metal salts, ammonium salts, and organic amines). Examples of unsaturated dicarboxylic acid monomers include maleic acid, itaconic acid, citraconic acid, and fumaric acid, and salts thereof (eg, salts with monovalent metal salts, ammonium salts, and organic amines), and These anhydrides are mentioned.
In addition, the copolymer (B) may contain only 1 type of structural units derived from monomer (III), and may contain 2 or more types.

(Monomer (IV) represented by the general formula (4))
The copolymer (B) contained in the hydraulic composition additive of the present invention is further derived from a monomer represented by the following general formula (4) (hereinafter also referred to as monomer (IV)). The structural unit to be included may be included.

^(Wherein, R ^{9, R 10} and ^{R 11} are each independently, ^{.R 12} represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms may contain a hetero atom having 1 to 4 carbon atoms Represents a hydrocarbon group, and s represents an integer of 0 to 2. However, the monomer (IV) represented by the general formula (4) is represented by the general formulas (1) to (3). Monomers are not included.)

Preferably, R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a methyl group, more preferably R ⁹ , R ¹⁰ and R ¹¹ are a hydrogen atom, or R ¹⁰ is a methyl group And R ⁹ and R ¹¹ are hydrogen atoms.

Examples of the hydrocarbon group that may contain a hetero atom having 1 to 4 carbon atoms represented by R ¹² include an alkyl group having 1 to 4 carbon atoms and a monohydroxyalkyl group having 1 to 4 carbon atoms. More specifically, examples include a methyl group, an ethyl group, a propyl group, a butyl group, a glyceryl group, and a 2-hydroxypropyl group.
The hydrocarbon group that may contain a hetero atom having 1 to 4 carbon atoms represented by R ¹² is preferably a monohydroxyalkyl group having 1 to 4 carbon atoms, more preferably a hydroxypropyl group, More preferably, it is a 2-hydroxypropyl group.

As monomer (IV), the monoester of unsaturated monocarboxylic acid is mentioned, for example. Examples of monoesters of unsaturated monocarboxylic acids include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and glyceryl (meth) acrylate. Monomer (IV) is preferably a monohydroxyalkyl ester of 1 to 4 carbon atoms of (meth) acrylic acid, more preferably 2-hydroxypropyl (meth) acrylate.
In addition, the copolymer (B) may contain only 1 type of structural units derived from monomer (IV), and may contain 2 or more types.

(Other structural units)
The copolymer (B) may contain a structural unit derived from the monomer (V) other than the monomers (I) to (III) and the monomer (IV). The copolymer (B) may contain only 1 type as a structural unit derived from the monomer (V), and may contain 2 or more types. Examples of the monomer (V) include the following monomers. In addition, among the following illustrations, the monomers contained in the monomers (I) to (III) and the monomer (IV) are excluded from the monomer (V).
Formula (V-1):

Diallyl bisphenols such as 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, and 3,4'-allyldisubstituted sulfones of 4,4'-dihydroxydiphenylsulfone;

  General formula (V-2):

Monoallyl bisphenols, such as 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, and 3-allyl substituted 4,4'-dihydroxydiphenylsulfone;

  General formula (V-3):

An allylphenol;

Half esters and diesters of unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid and alcohols having 1 to 30 carbon atoms;
Half amides and diamides of the above unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms;
Half esters and diesters of 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 acid;
Half esters and diesters of the above unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 addition moles of these glycols;
Half amides of maleamic acid and glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 addition moles of these glycols;
Esters of an alkoxy (poly) alkylene glycol obtained by adding 1 to 500 moles of an alkylene oxide having 2 to 18 carbon atoms to an alcohol having 1 to 30 carbon atoms and an unsaturated monocarboxylic acid such as (meth) acrylic acid; Of alkylene oxides having 2 to 18 carbon atoms to unsaturated monocarboxylic acids such as (meth) acrylic acid, such as (poly) ethylene glycol monomethacrylate, (poly) propylene glycol monomethacrylate, (poly) butylene glycol monomethacrylate 1-500 mole adducts;

(Poly) alkylene glycols such as triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) propylene glycol di (meth) acrylate, etc. Di (meth) acrylates;
Polyfunctional (meth) acrylates such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate;
(Poly) alkylene glycol dimaleates such as triethylene 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) acryloxybutylsulfonate, (meth) acrylamidomethylsulfonic acid, (meth) acrylamidoethylsulfonic acid, 2- Unsaturated sulfonic acids such as methylpropanesulfonic acid (meth) acrylamide and styrenesulfonic acid, and monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts thereof;
Amides of unsaturated monocarboxylic acids such as methyl (meth) acrylamide and amines having 1 to 30 carbon atoms;
Vinyl aromatics such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene;
Alkanediol mono (meth) acrylates such as 1,4-butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate;
Dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;

Unsaturated amides such as (meth) acrylamide, (meth) acrylic alkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide;
Unsaturated cyanides such as (meth) acrylonitrile, α-chloroacrylonitrile;
Unsaturated esters such as vinyl acetate and vinyl propionate; aminoethyl (meth) acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, (meth ) Unsaturated amines such as dibutylaminoethyl acrylate and vinylpyridine;
Divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate;
Allyls such as (meth) allyl alcohol and glycidyl (meth) allyl ether;
Vinyl ethers or allyl ethers such as methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) allyl ether; and
Polydimethylsiloxanepropylaminomaleamic acid, polydimethylsiloxaneaminopropylaminomaleamic acid, polydimethylsiloxane-bis- (propylaminomaleamic acid), polydimethylsiloxane-bis- (dipropylaminomaleamic acid), polydimethyl Siloxane- (1-propyl-3-acrylate), polydimethylsiloxane- (1-propyl-3-methacrylate), polydimethylsiloxane-bis- (1-propyl-3-acrylate), polydimethylsiloxane-bis- (1 Siloxane derivatives such as -propyl-3-methacrylate).

  When obtaining a copolymer (B), you may use another monomer further as needed.

<Example of copolymer B>
Examples of the copolymer (B) include copolymers b-1 and b-2 shown below. The copolymer (B) is preferably a copolymer b-1 or a copolymer b-2 shown below. Copolymer (B) may contain only 1 type as a structural unit derived from the monomer represented by General formula (1)-(3), respectively, and may contain 2 or more types. .

(Copolymer b-1)
Copolymer b-1 is a structural unit derived from monomer (I) represented by general formula (1) and a structural unit derived from monomer (II) represented by general formula (2). And the monomer (III) represented by the general formula (3). Preferably, in copolymer b-1, by weight ratio, the structural unit derived from monomer (I) / the structural unit derived from monomer (II) / the structural unit derived from monomer (III) Is 1 to 98/1 to 98/1 to 50, preferably 5 to 90/5 to 90/1 to 50, more preferably 5 to 50/50 to 90/1 to 50, More preferably, it is 5-20 / 70-90 / 1-20. However, the sum of the weight ratio of the structural unit derived from the monomer (I), the weight ratio of the structural unit derived from the monomer (II), and the weight ratio of the structural unit derived from the monomer (III) is 100.

(Copolymer b-2)
Copolymer b-2 includes monomer (I) represented by general formula (1), monomer (II) represented by general formula (2), and monomer represented by general formula (3). The monomer (IV) represented by the monomer (III) and the general formula (4) is included. Preferably, in copolymer b-2, by weight ratio, the structural unit derived from monomer (I) / the structural unit derived from monomer (II) / (the structure derived from monomer (III) (Unit + structural unit derived from monomer (IV)) is 1 to 98/1 to 98/1 to 50, more preferably 5 to 90/5 to 90/1 to 50, and more preferably It is 5-50 / 50-90 / 1-50, More preferably, it is 5-20 / 70-90 / 1-20. However, the weight ratio of the structural unit derived from the monomer (I), the weight ratio of the structural unit derived from the monomer (II), the weight ratio of the structural unit derived from the monomer (III), and a single amount The total weight ratio of the structural units derived from the body (IV) is defined as 100.

  The copolymer b-1 and the copolymer b-2 can further contain a structural unit derived from the monomer (V), but are derived from the monomer (V) in the copolymer (B). It is preferable that the weight ratio of the structural unit to perform is 0-50. However, the weight ratio of the structural unit derived from the monomer (I), the weight ratio of the structural unit derived from the monomer (II), the weight ratio of the structural unit derived from the monomer (III), the monomer The total of the weight ratio of the structural unit derived from (IV) and the weight ratio of the structural unit derived from the monomer (V) is 100.

<Method for producing copolymer (B)>
The copolymer (B) in the present invention can be produced by copolymerizing each predetermined monomer by a known method. Examples of the method include polymerization methods such as polymerization in a solvent and bulk polymerization.

(Reaction solvent)
Examples of the solvent used in the polymerization in the solvent include water; lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; aromatic hydrocarbons such as benzene, toluene, and xylene; and fats such as cyclohexane and n-hexane. Examples thereof include cyclic or aliphatic hydrocarbons; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone. From the viewpoint of the solubility of the raw material monomer and the resulting copolymer, it is preferable to use one or more selected from the group consisting of water and lower alcohols, and it is more preferable to use water among them.
When copolymerization is performed in a solvent, each monomer and a polymerization initiator may be continuously dropped into each reaction vessel, or a mixture of each monomer and a polymerization initiator are continuously dropped into each reaction vessel. May be. Alternatively, the reaction vessel may be charged with a solvent, and the monomer and solvent mixture and the polymerization initiator solution may be continuously dropped into the reaction vessel, or part or all of the monomer may be charged into the reaction vessel, A polymerization initiator may be continuously dropped.

(Initiator)
The polymerization initiator that can be used for the copolymerization is not particularly limited. When copolymerization is performed in an aqueous solvent, for example, persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; t-butyl Water-soluble organic peroxides such as hydroperoxide are listed. At this time, an accelerator such as sodium hydrogen sulfite or a molle salt may be used in combination. When copolymerization is performed in a solvent such as a lower alcohol, aromatic hydrocarbon, alicyclic or aliphatic hydrocarbon, ester or ketone, for example, a peroxide such as benzoyl peroxide or lauryl peroxide. Hydroperoxides such as cumene peroxide; aromatic azo compounds such as azobisisobutyronitrile can be used as the polymerization initiator. At this time, an accelerator such as an amine compound may be used in combination. Furthermore, when copolymerization is carried out in a water-lower alcohol mixed solvent, for example, the polymerization initiator or a combination of a polymerization initiator and an accelerator can be appropriately selected and used. The polymerization temperature varies depending on the polymerization conditions such as the solvent used and the type of polymerization initiator, but is usually in the range of 50 to 120 ° C.

(Chain transfer agent)
Moreover, in copolymerization, you may adjust molecular weight using a chain transfer agent as needed. Examples of the chain transfer agent used include mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, and 2-mercaptoethanesulfonic acid. Known thiol compounds; phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite, and the like Lower oxides of salts (sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.) and salts thereof; It is done. These may be used alone or in combination of two or more. Furthermore, in order to adjust the molecular weight of the copolymer (B), as a monomer for obtaining the copolymer (B), in addition to the monomers (I) to (IV), a chain transfer property is further provided. High monomer (V) may be used. Examples of the monomer (V) having a high chain transfer property include (meth) allylsulfonic acid (salt) monomers. The blending ratio of the monomer (V) is usually 20% by weight or less and preferably 10% by weight or less in the copolymer (B). The blending ratio is as follows: monomer (I) blending ratio + monomer (II) blending ratio + monomer (III) blending ratio + monomer (IV) blending ratio = 100% by weight It is a blending rate when it is said.

(Neutralization)
When copolymerization is carried out in an aqueous solvent when obtaining a copolymer, the pH during polymerization usually becomes strongly acidic due to the influence of a monomer having an unsaturated bond, but this may be adjusted to an appropriate pH. . If it is necessary to adjust the pH during polymerization, adjust the pH using an acidic substance such as phosphoric acid, sulfuric acid, nitric acid, alkylphosphoric acid, alkylsulfuric acid, alkylsulfonic acid, or (alkyl) benzenesulfonic acid. Can do. Among these acidic substances, it is preferable to use phosphoric acid because it has a pH buffering action. However, in order to eliminate the instability of the ester bond of the ester monomer, it is preferable to perform the polymerization at pH 2-7. Moreover, although there is no limitation in particular in the alkaline substance which can be used for adjustment of pH, alkaline substances, such as NaOH and Ca (OH) _2, are common. The pH adjustment may be performed on a solution containing a monomer before polymerization or on a solution containing a copolymer after polymerization. Moreover, after adding some alkaline substances and superposing | polymerizing before superposition | polymerization, you may adjust pH further with respect to the solution containing a copolymer.

(Molecular weight)
The weight average molecular weight of the copolymer (B) is preferably 5,000 or more, more preferably 6,000 or more, and further preferably 6,500 or more. Thereby, the dispersibility of the hydraulic material of the additive for hydraulic composition is sufficiently exerted, and it is possible to obtain a water reduction rate exceeding the AE water reducing agent such as lignin sulfonic acid type or oxycarboxylic acid type. Or workability | operativity is improved and the target effect as a cement additive (cement dispersing agent) can fully be expressed. The upper limit of the weight average molecular weight is preferably 60,000 or less, more preferably 50,000 or less, and still more preferably 30,000 or less. Thereby, the aggregation effect | action of a cement particle is suppressed and workability | operativity can be made favorable. The weight average molecular weight is preferably 5,000 to 60,000.
The molecular weight distribution (Mw / Mn) of the copolymer (B) is preferably 1.0 or more, and more preferably 1.20 or more. The upper limit is preferably 3.0 or less, and more preferably 2.50 or less. The molecular weight distribution is preferably in the range of 1.0 to 3.0, more preferably in the range of 1.2 to 3.0.

In addition, the weight average molecular weight in this invention can be measured by the well-known method converted into polyethyleneglycol by gel permeation chromatography (GPC).
Although there is no limitation in particular as measurement conditions of GPC, the following conditions can be mentioned as an example. The weight average molecular weight in the latter examples is a value measured under these conditions.

Measuring device: manufactured by Tosoh Column: Shodex Column OH-pak SB-806HQ, SB-804HQ, SB-802.5HQ
Eluent: 0.05 mM sodium nitrate / acetonitrile 8/2 (v / v)
Reference material: Polyethylene glycol (Tosoh, GL Science)
Detector: differential refractometer (manufactured by Tosoh)
Calibration curve: Polyethylene glycol standard

<Contents of component A and component B>
Content of (A) component and (B) component in the additive for hydraulic compositions of this invention is not specifically limited. When the hydraulic composition additive is in the form of an aqueous solution to be described later, the content of the component (A) in the hydraulic composition additive is preferably relative to the hydraulic composition additive. 0.1% by weight to 1.5% by weight. The content of the component (B) in the hydraulic composition additive is preferably 4.5% by weight to 20% by weight with respect to the hydraulic composition additive.

<Weight ratio of component A to component B>
The weight ratio ((A) / (B)) of the water-soluble thickener (A) to the copolymer (B) in the hydraulic composition additive of the present invention is 0.01 / 99.99 to 25 / 75, preferably 0.02 / 99.98 or more, more preferably 1/99 or more, still more preferably 5/95 or more, and preferably 20/80 or less. The weight ratio ((A) / (B)) is preferably 0.01 / 99.99 to 20/80, more preferably 1/99 to 20/80.

<Contained form of component A and component B>
In the additive for hydraulic compositions of the present invention, there is no limitation on the form of the components (A) and (B), and the components (A) and (B) may be included as they are, or (A) and (B) B) Each component or both may be blended as a solution in which the component is dissolved in a solvent, a dispersed dispersion, or a suspended suspension.

  The additive for a hydraulic composition of the present invention can be in the form of an aqueous solution containing the components (A) and (B) in which the components (A) and (B) are dissolved in water.

<Other ingredients>
The additive for hydraulic composition of the present invention may further contain other components as necessary. Examples of other components include a monomer (C) represented by the following general formula (5), and a water-soluble polyalkylene glycol (D) in which both terminal groups are hydroxy groups.

(Monomer (C) Represented by General Formula (5))
The monomer (C) is represented by the following general formula (5).

(In the formula, R ^1c represents an alkenyl group having 2 to 5 carbon atoms. A ^1c O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N1c represents an oxyalkylene group. (This is the average number of moles added and represents a number of 1 to 100. R ^2c represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.)

Specific examples and preferred examples of R ^1c , A ^1c O, n1c and R ^2c are respectively R ¹ , A ¹ O and n1 described in the monomer (I) represented by the general formula (1). And the same as the specific examples and preferred examples of R ² .
The additive for a hydraulic composition of the present invention preferably contains a monomer (C). Thereby, the state of a hydraulic composition (for example, cement composition) can be improved, such as increasing moderate free water, and workability can be improved.

  The content ratio of the monomer (C) in the hydraulic composition additive of the present invention is preferably 30% by weight or less, more preferably 10% by weight or less, based on the copolymer (B). . When it is 30% by weight or less, a hydraulic material (eg, cement) can be sufficiently dispersed. Moreover, the minimum of the content rate of a monomer (C) is 0.1 weight% or more normally with respect to a copolymer (B). Thereby, sufficient workability improvement effect can be obtained.

  Specific examples and preferred examples of the monomer (C) are the same as the specific examples and preferred examples of the monomer (I) represented by the general formula (1). The monomer (C) may be the same as or different from the monomer (I). Further, the additive for hydraulic composition of the present invention may contain only one type of monomer (C), or may contain two or more types in combination.

  The monomer (C) may be blended separately from the copolymer (B). Or it may exist as a residue which was not copolymerized at the time of manufacture of copolymer (B) manufactured as follows, for example, without blending separately. When the copolymer (B) is produced, when the monomer (I) used as a raw material remains in the copolymer (B), the polymerization reaction is stopped, whereby the monomer ( A composition containing C) and the copolymer (B) can be obtained. The time point at which the polymerization reaction is stopped can be determined according to the blending ratio of the monomer (C) to the copolymer (B). That is, the polymerization reaction is stopped when the residual amount of the monomer (C) with respect to the copolymer (B) is preferably 30% by weight or less, more preferably 10% by weight or less. The polymerization reaction is stopped when the lower limit of the residual amount is usually 0.1% by weight or more, preferably 1% by weight or more.

(Water-soluble polyalkylene glycol (D))
As described above, the hydraulic composition additive of the present invention may further contain a water-soluble polyalkylene glycol (D) in which both terminal groups are hydroxy groups. That both terminal groups are hydroxy groups means that the terminal of the main chain is a hydroxy group, that is, the hydrogen atom of the hydroxy group at the terminal of the main chain is not substituted with another group. Water-soluble means that it is soluble in water at an arbitrary ratio. When the hydraulic composition additive of the present invention contains a water-soluble polyalkylene glycol (D), the content of the water-soluble polyalkylene glycol (D) is usually 0.01 with respect to the copolymer (B). -10% by weight. The water-soluble polyalkylene glycol (D) whose both terminal groups are hydroxy groups may be blended separately from the copolymer (B). Or, when producing monomer (I) as a raw material of copolymer (B), a water-soluble polyalkylene glycol in which both terminal groups are hydroxy groups may be generated as a by-product. May be. The weight average molecular weight of the water-soluble polyalkylene glycol (D) in which both terminal groups are hydroxy groups is preferably 300 to 5,000.

  Specific examples of the water-soluble polyalkylene glycol (D) in which both terminal groups are hydroxy groups include polyethylene glycol, polypropylene glycol, polyethylene polypropylene glycol, polyethylene polybutylene glycol, and the like. From polyethylene glycol and polyethylene polypropylene glycol One or more selected are preferable. The additive for hydraulic composition of the present invention may contain only one kind of water-soluble polyalkylene glycol (D) whose both terminal groups are hydroxy groups, or may contain two or more kinds in combination. .

  In the case where the additive for hydraulic composition of the present invention contains the component (C) and / or (D), there is no limitation on the content of the components (C) and (D), and (C) and (D) Ingredients may be included as they are, and each or both of the components (C) and (D) are blended as a solution in a solvent, a dispersed dispersion, and a suspended suspension. Also good.

<Usage form and usage of additive for hydraulic composition>
The additive for hydraulic composition of the present invention is usually preferably used in the form of an aqueous solution, but it can also be used in the form of dried powder. In addition, there is no limitation in particular at the time of containing the additive for hydraulic compositions in a hydraulic composition, For example, the time of use of a hydraulic composition may be sufficient. In addition, the additive for the hydraulic composition of the present invention in a powdered form is mixed in advance with components other than water constituting the cement composition, such as cement powder and dry mortar, and the plasterer, floor It can also be used as a premix product to which water is added during finishing, grouting and the like.

  The additive for hydraulic composition of the present invention can be added to a hydraulic material such as cement and used as a hydraulic composition (eg, cement composition) such as cement paste, mortar, concrete, plaster, and grout. it can. The additive for hydraulic compositions of the present invention can impart material separation resistance and appropriate fluidity to the hydraulic composition, and can adjust the initial fluidity of the hydraulic composition. Therefore, the hydraulic composition additive of the present invention can be suitably used particularly for medium-fluidity concrete, high-fluidity concrete, and underwater non-separable concrete, and also fills cavities, voids, and gaps. Therefore, it can be suitably used as an additive for a fluid liquid to be injected (grouting, pouring grout) or an additive for improving the condition of concrete in ordinary concrete.

<Hydraulic composition containing additive for hydraulic composition>
The hydraulic composition (eg, cement composition) of the present invention may contain an additive for hydraulic composition, and the hydraulic material to be combined is not particularly limited. Examples of the hydraulic material include cement, gypsum (semihydrate gypsum, dihydrate gypsum, etc.), and dolomite. The most common hydraulic material is cement.

  The cement is not particularly limited. For example, Portland cement (ordinary, early strength, very early strength, moderate heat, sulfate-resistant and low alkali type of each), 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 exothermic blast furnace cement, belite High-content cement), ultra-high-strength cement, cement-based solidified material, eco-cement (cement produced using at least one of municipal waste incineration ash and sewage sludge incineration ash). Blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, limestone powder and other fine powder, gypsum and the like may be added to the cement.

  Moreover, the cement composition may contain the aggregate. The aggregate may be either a fine aggregate or a coarse aggregate. Examples of aggregates include sand, gravel, crushed stone; granulated slag; recycled aggregate, etc .; siliceous, clay, zircon, high alumina, silicon carbide, graphite, chrome, chromic, magnesia Fireproof aggregates such as

  The blending ratio of the additive for hydraulic composition in the hydraulic composition (eg, cement composition) is not particularly limited. For example, the targeted hydraulic composition (eg, cement composition, concrete) An amount capable of realizing the rheology (fluidity) of may be blended. For example, when the hydraulic composition (cement composition) is mortar or concrete, the additive amount (blending amount) of the hydraulic composition additive of the present invention is preferably based on the total weight of the cement. Is 0.01 to 5.0% by weight, more preferably 0.02 to 2.0% by weight, still more preferably 0.05 to 1.0% by weight. By setting this addition amount, the obtained cement composition has various preferable properties such as material separation resistance, rheology, fluidity, reduction in unit water amount, increase in strength, and improvement in durability. The effect is fully brought. If the blending ratio is less than 0.01% by weight, the resulting cement composition may not be sufficient in terms of performance, and conversely, even if a large amount exceeding 5.0% by weight is used, the effect is substantially reduced. There is a risk that it will hit a peak and be disadvantageous in terms of economy.

  The cement composition is effective as, for example, ready mixed concrete, concrete for concrete secondary products (precast concrete), concrete for centrifugal molding, concrete for vibration compaction, steam-cured concrete, shotcrete, and the like. . Furthermore, 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 It is also effective as mortar or concrete that requires high fluidity.

  The additive for a hydraulic composition of the present invention can be used as a dispersant for a hydraulic material (eg, cement) or an AE water reducing agent as it is. In particular, since the additive for hydraulic composition of the present invention has less foaming, it is not necessary to use an antifoaming agent in combination. However, the hydraulic composition additive of the present invention may be used in combination with other optional components such as an antifoaming agent. For example, the additive for a hydraulic composition of the present invention further includes other dispersant for a hydraulic composition, water-soluble polymer, polymer emulsion, air entraining agent, cement wetting agent, swelling agent, waterproofing agent, retarder. , Thickeners, flocculants, drying shrinkage reducers, strength enhancers, effect accelerators, antifoaming agents, AE agents, and other surfactants for concrete may be used in combination. Other additives may be used alone or in combination of two or more. Examples of known additives for concrete include, but are not limited to, a carboxyl group and / or a salt-containing compound thereof (CA agent), a sulfonic acid group and / or a salt-containing compound thereof (SA agent).

  A carboxyl group and / or a salt-containing compound (CA agent) (eg, sodium polyacrylate, sodium gluconate). You may use 1 type, or 2 or more types among these compounds.

  A sulfonic acid group and / or a salt-containing compound (SA agent) (eg, sodium lignin sulfonate, naphthalene sulfonic acid). You may use 1 type, or 2 or more types among these compounds.

  When the additive for hydraulic composition of the present invention and the additive of the above (CA agent) and / or (SA agent) are used in combination, the ratio is not particularly limited. For example, when the two components are used in combination, the hydraulic composition additive of the present invention / ((CA agent) or (SA agent)) = 0.1 wt% / 99.9 wt% to 99.99 wt. 9% by weight / 0.1% by weight. When the three components are used in combination, the hydraulic composition additive of the present invention / ((CA agent) + (SA agent)) = 0.1 weight % / 99.9 wt% to 99.9 wt% / 0.1 wt%.

Examples Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, in the examples, parts are parts by weight, and% is% by weight.

<A component>
In Examples and Comparative Examples, as the component A, the following water-soluble thickeners (A-1) to (A-2)
)It was used.
(A-1) Hydroxypropylmethylcellulose (manufactured by Sankisha, NEOVISCO MC, molecular weight 750,000)
(A-2) Hydroxyethyl cellulose (Sanki Co., Ltd., SANHEC, molecular weight 600,000)

<B component>
In Examples and Comparative Examples, the following copolymers (B-1) to (B-5) were used as the B component.

<Production Example 1>
In a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dropping device, 157 parts of water and an ethylene oxide adduct of 3-methyl-3-buten-1-ol (polyethylene glycol 3-methyl -3-butenyl ether: average number of moles of ethylene oxide added 25) 111 parts were charged, the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 80 ° C. under a nitrogen atmosphere. Then, an aqueous monomer solution in which 8 parts of acrylic acid, 63 parts of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added 13), 30 parts of 2-hydroxyethyl acrylate, 5 parts of ascorbic acid and 165 parts of water were mixed, and ammonium persulfate A mixed solution of 3 parts and 47 parts of water was continuously dropped into a reaction vessel maintained at 80 ° C. for 2 hours each. Furthermore, the aqueous solution of the copolymer was obtained by making it react for 1 hour in the state hold | maintained at 80 degreeC. The weight ratio of each monomer was monomer I: II: III: IV: V = 52: 44: 4: 0: 0. The content of polyethylene glycol 3-methyl-3-butenyl ether in the copolymer was 25% by weight, and the content of water-soluble polyethylene glycol in which both terminal groups were hydroxy groups was 0.7% by weight. It was. This solution was adjusted to pH 7 with 30% NaOH aqueous solution. The copolymer in the liquid was the copolymer (B-1) (weight average molecular weight 28,000, Mw / Mn 1.9).

<Production Example 2>
129 parts of water and 52 parts of polyethylene glycol monoallyl ether (average added mole number of ethylene oxide 35) are charged into a glass reaction vessel equipped with a thermometer, a stirring device, a reflux device, a nitrogen introduction tube and a dropping device, and the reaction is carried out with stirring. The container was heated to 80 ° C. Then, 5 parts of methacrylic acid, 3 parts of acrylic acid, 155 parts of methoxypolyethylene glycol methacrylate (average added mole number of ethylene oxide 13), 21 parts of 2-hydroxyethyl acrylate, 8 parts of methyl methacrylate, 2-mercaptopropionic acid 2 And a monomer aqueous solution in which 24 parts of water were mixed and a mixed solution of 1 part of ammonium persulfate and 50 parts of water were continuously dropped into a reaction vessel maintained at 100 ° C. for 2 hours each. Furthermore, the aqueous solution of the copolymer was obtained by making it react for 1 hour in the state hold | maintained at 100 degreeC. The weight ratio of each monomer was monomer I: II: III: IV: V = 21: 72: 3.5: 3.5: 0. The content of polyethylene glycol monoallyl ether in the copolymer was 20% by weight, and the content of water-soluble polyethylene glycol in which both terminal groups were hydroxy groups was 0.5% by weight. This solution was adjusted to pH 4 with 31% NaOH aqueous solution. The copolymer in the liquid was a copolymer (B-2) (weight average molecular weight 15,000, Mw / Mn 1.8).

<Production Example 3>
In a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dropping device, 135 parts of water and polyethylene polypropylene glycol monoallyl ether (average added mole number of ethylene oxide 33, average added mole of propylene oxide) Formula 2, random addition of ethylene oxide and propylene oxide) 21 parts, 3 parts of 2-hydroxypropyl acrylate were charged, the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. Then, 11 parts of methacrylic acid, 1 part of acrylic acid, 73 parts of methoxypolyethylene glycol methacrylate (average added mole number of ethylene oxide 25), 89 parts of 2-hydroxypropyl acrylate, 4 parts of 3-mercaptopropionic acid, 36 parts of water The mixed monomer aqueous solution and a mixed solution of 3 parts of ammonium persulfate and 47 parts of water were continuously dropped into a reaction vessel maintained at 100 ° C. for 2 hours each. Furthermore, the aqueous solution of the copolymer was obtained by making it react for 1 hour in the state hold | maintained at 100 degreeC. The weight ratio of each monomer was monomer I: II: III: IV: V = 11: 36: 6: 47: 0. The content of polyethylene polypropylene glycol monoallyl ether in the copolymer was 15% by weight, and the content of water-soluble polyethylene glycol in which both terminal groups were hydroxy groups was 1.0% by weight. This solution was adjusted to pH 6 with 31% NaOH aqueous solution. The copolymer in the liquid was a copolymer (B-3) (weight average molecular weight 11,100, Mw / Mn1.5).

<Production Example 4>
A glass reaction vessel equipped with a thermometer, a stirring device, a reflux device, a nitrogen introducing tube and a dropping device was charged with 132 parts of water and 120 parts of polyethylene glycol monoallyl ether (an average added mole number of ethylene oxide of 52). The reaction vessel was purged with nitrogen below, and the temperature was raised to 100 ° C. in a nitrogen atmosphere. Thereafter, an aqueous monomer solution in which 27 parts of acrylic acid, 51 parts of methoxypolyethylene glycol methacrylate (average number of added moles of ethylene oxide of 25), 2 parts of 3-mercaptopropionic acid, and 103 parts of water were mixed, 2 parts of ammonium persulfate and water 48 parts of the mixed solution was continuously dropped into a reaction vessel maintained at 100 ° C. for 2 hours each. Furthermore, the aqueous solution of the copolymer was obtained by making it react for 1 hour in the state hold | maintained at 100 degreeC. The weight ratio of each monomer was monomer I: II: III: IV: V = 61: 25: 14: 0: 0. The content of polyethylene glycol monoallyl ether in the copolymer was 8% by weight, and the content of water-soluble polyethylene glycol in which both terminal groups were hydrogen atoms was 0.5% by weight. This solution was adjusted to pH 7 with 31% NaOH aqueous solution. The copolymer in the liquid was a copolymer (B-4) (weight average molecular weight 65,700, Mw / Mn 2.3).

In the comparative example, the following lignin sulfonic acid modified product (B-5) was used as the B component.
(B-5) Modified lignin sulfonic acid (manufactured by Nippon Paper Industries Co., Ltd., Sunflow RH)

<Examples 1-5 and Comparative Examples 1-3>
A component: A-1, A-2 and B component: B-1, B-2, B-3, B-4, and B-5 were blended in combinations shown in Table 1, and cement was added. An agent (additive for hydraulic composition) was prepared. The resulting cement additive was subjected to the following compatibility test, foaming evaluation, and viscosity measurement.

<Compatibility test>
The compatibility between the water-soluble thickener (component A) and the copolymer (component B) was tested according to the following procedure.
The cement additives of Examples 1 to 5 and Comparative Examples 1 to 3 were prepared (kneaded) and stored for 1 month at 20 ° C. and 40 ° C., and the degree of separation of the cement additives was evaluated. The evaluation criteria are as follows. The less turbidity, the less the separation and the better the compatibility between the components. The results of the compatibility test are shown in Table 3.
A: There is almost no turbidity.
○: Some turbidity is observed, but there is no problem in use.
Δ: Turbidity but no problem in use.
X: It is very muddy.

<Evaluation of foaming>
10 ml of the cement additives of Examples 1 to 5 and Comparative Examples 1 to 3 were added to a vial (with a volume of 50 ml) containing a stirrer bar and stirred for 1 minute at 300 rpm with a magnetic stirrer (Tokyo Science Instruments Co., Ltd.). The foaming on the liquid surface was visually evaluated. Table 2 shows the evaluation results of foaming.
A: Very little foaming.
○: Less foaming.
Δ: Foaming is observed, but there is no practical problem.
×: Many bubbles

<Viscosity measurement>
Viscosity measurements of the cement additives of Examples 1-5 and Comparative Examples 1-3 were also performed. The viscosity was measured at 20 ° C. and 60 rpm using a B-type viscometer. The results are shown in Table 3.

<Concrete test>
Concrete (cement composition, hydraulic composition) to which the cement additives of Examples 1 to 5 and Comparative Examples 1 to 3 were added was prepared according to the following procedure, and the obtained concrete was subjected to a slump test, air amount measurement, viscosity. Evaluation and bleeding evaluation were performed.

  At the ambient temperature (20 ° C.), the coarse aggregate, fine aggregate, cement, and water blended as shown in Table 4 and the cement additive shown in Table 1 were charged into the forced biaxial mixer, and the forced biaxial mixer was used. The mixture was kneaded for 90 seconds by mechanical kneading. The cement additive was mixed with water and charged into a forced biaxial mixer. Thereafter, immediately after the concrete was discharged from the forced biaxial mixer, a fresh concrete test (slump test JIS A1101 (measures the spread of fresh concrete as a flow value), air amount JIS A1128, concrete viscosity evaluation) was performed. The viscosity of concrete was evaluated by the following criteria by sensory evaluation by five evaluators. The test results are shown in Table 5.

<Viscosity evaluation criteria>
A: Handling is very good when the concrete is cut back with a scoop, and the separation of the concrete from the scoop is very good.
○: Good handling when the concrete is cut back with a scoop, and separation of the concrete from the scoop is good.
Δ: Slightly inferior when handling concrete with a scoop and inferior to the separation of the concrete from the scoop, but within the practical range.
X: Handling when the concrete is cut back with a scoop is poor, and the concrete is not separated from the scoop.

<Bleeding evaluation>
Evaluation was performed by the method defined in JIS A1123. The smaller the amount of bleeding,
It shows that concrete has material separation resistance. The results are shown in Table 5.

C: Equal weight mixture of the following three types of cement Normal Portland cement (manufactured by Ube Mitsubishi Cement Co., Ltd., specific gravity 3.16)
Ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd., specific gravity 3.16)
Normal Portland cement (Made by Tokuyama Co., Ltd., specific gravity 3.16)
W: Tap water S1: Kakegawa mountain sand (fine aggregate, specific gravity 2.57)
S2: Crushed sand from Iwase (fine aggregate, specific gravity 2.61)
G: Ome crushed stone (coarse aggregate, specific gravity 2.65)
Cement additive (solid content conversion) See Table 5

  In Table 5, “addition rate” of the cement additive indicates a solid addition rate of the additive to the cement. SLF indicates a slump flow.

  As is clear from the results shown in Tables 2 and 3, the cement additives of Examples 1 to 5 have such a degree that foaming is not problematic for practical use, and shows good compatibility. There was no problem. In particular, the cement additives of Examples 1 to 4 have less turbidity, good compatibility of the water-soluble thickener and the copolymer, and less foaming. Moreover, as is clear from the results shown in Table 5, the concrete using the cement additive of Examples 1 to 5 is good even if the addition rate of the cement additive is small compared to Comparative Examples 1 to 3. The amount of bleeding is shown. In particular, in the concrete using the cement additive of Examples 1 to 4, a predetermined fluidity can be continuously obtained, and the amount of bleeding is reduced compared to the concrete using the cement additive of Comparative Examples 1 to 3. We were able to. The above results show that the hydraulic composition additive of the present invention is excellent in compatibility of the contained components, and imparts rheological properties (appropriate fluidity) and material separation resistance to the hydraulic composition. Show you get.

Claims (13)

A water-soluble thickener (A),
A copolymer (B) containing a structural unit derived from the monomer (I) represented by the following general formula (1) and a structural unit derived from the monomer (II) represented by the following general formula (2) ) And
The weight ratio ((A) / (B)) of the water-soluble thickener (A) to the copolymer (B) is 0.0.
The additive for hydraulic compositions which is 1 / 99.99 to 25/75.

(In the formula, R ¹ represents an alkenyl group having 2 to 5 carbon atoms. A ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N1 represents an oxyalkylene group. (This is the average number of moles added and represents a number of 1 to 100. R ² represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.)

^(Wherein, R 3, ^{R 4} and ^{R 5} are each independently, .m represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, the .A ² O representing the number of 0 to 2, the same Or, differently, it represents an oxyalkylene group having 2 to 18 carbon atoms, n2 is an average added mole number of the oxyalkylene group, and represents a number of 1 to 100. X is a hydrogen atom or 1 to 1 carbon atoms. Represents 30 hydrocarbon groups.) The additive for hydraulic compositions according to claim 1, wherein the copolymer (B) further comprises a structural unit derived from the monomer (III) represented by the following general formula (3).

^(Wherein, R 6, ^{R 7,} and ^{R 8} are each independently a hydrogen atom, -CH _3, or _- represents a ^{_{(CH 2) r COOM 2,}} - (CH2) r COOM 2 may -COOM ¹ Or other — (CH ₂ ) _r COOM ² and may form an anhydride, in which case M ¹ and M ² of those groups are absent, M ¹ and M ² may be the same or different, And represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, or a substituted alkylammonium group, and r represents an integer of 0 to 2.) The additive for hydraulic compositions according to claim 1 or 2, wherein the copolymer (B) further comprises a structural unit derived from the monomer (IV) represented by the following general formula (4).

^(Wherein, R ^{9, R 10} and ^{R 11} are each independently, ^{.R 12} represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms may contain a hetero atom having 1 to 4 carbon atoms Represents a hydrocarbon group, and s represents an integer of 0 to 2. However, the monomer (IV) represented by the general formula (4) is represented by the general formulas (1) to (3). Monomers are not included.)   The additive for hydraulic compositions of any one of Claims 1-3 containing 2 or more types of copolymers (B).   The copolymer (B) is a structural unit derived from the monomer (IIa) in which n2 is 1 as a structural unit derived from the monomer (II), and a monomer (n2 is greater than 1 and 100 or less) The weight ratio of the structural unit derived from monomer (IIa) to the structural unit derived from monomer (IIb) ((IIa) / (IIb)) is 1/99. The additive for hydraulic compositions according to any one of claims 1 to 4, which is -99/1.   The additive for hydraulic compositions according to any one of claims 1 to 5, wherein the weight average molecular weight of the copolymer (B) is 5,000 to 60,000 in terms of polyethylene glycol.   The additive for hydraulic compositions according to any one of claims 1 to 6, comprising two or more water-soluble thickeners (A).   The addition for a hydraulic composition according to any one of claims 1 to 7, wherein the water-soluble thickener (A) comprises at least one selected from alkyl cellulose, hydroxyalkyl cellulose, and hydroxyalkylalkyl cellulose. Agent. The additive for hydraulic compositions according to any one of claims 1 to 8, further comprising a monomer (C) represented by the following general formula (5).

(In the formula, R ^1c represents an alkenyl group having 2 to 5 carbon atoms. A ^1c O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N1c represents an oxyalkylene group. (This is the average number of moles added and represents a number of 1 to 100. R ^2c represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.)   The additive for hydraulic compositions according to claim 9, wherein the content ratio of the monomer (C) to the copolymer (B) is 0.1 to 30% by weight.   The additive for hydraulic compositions according to any one of claims 1 to 10, further comprising a water-soluble polyalkylene glycol (D) whose both terminal groups are hydroxy groups.   The addition for a hydraulic composition according to claim 11, wherein the content ratio of the water-soluble polyalkylene glycol (D) in which both terminal groups are hydroxy groups to the copolymer (B) is 0.01 to 10% by weight. Agent.   The hydraulic composition containing the additive for hydraulic compositions of any one of Claims 1-12.