JP2017057135A - Dispersant for hydraulic composition and hydraulic composition comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a dispersant for a hydraulic composition which has high dispersibility even in a wide concrete blending range from ordinary-strength concrete to ultrahigh-strength concrete, has no ceiling of dispersibility, can reduce concrete viscosity and shorten setting time and can be used for a wide area of concrete from ultrahigh-strength concrete to ordinary-strength concrete; and a hydraulic composition comprising the same.SOLUTION: THere is provided a dispersant for a hydraulic composition which comprises: a structural unit derived from a specific unsaturated monocarboxylic acid ester-based monomer and an unsaturated monocarboxylic acid-based monomer; and a polycarboxylic acid-based copolymer having a specific molecular weight distribution shape or a salt (A) thereof.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a dispersant for a hydraulic composition and a hydraulic composition containing the dispersant.

  In order to improve the workability and durability of concrete, it is effective to reduce the amount of unit water in the concrete. However, it is known that when the unit water amount is reduced, the fluidity of concrete is lowered and the workability is impaired. Therefore, in order to ensure efficient workability of the concrete even when the unit water amount is reduced, various dispersants for hydraulic compositions having a function of dispersing cement particles are used.

  In recent years, ultra-high-strength concrete with a significantly reduced water binder ratio has been put into practical use. Ultra-high strength concrete has demands such as high dispersibility at a low water binder ratio, reduction of concrete viscosity, and quick setting time. In the ultra-high strength region, there is a problem that the dispersibility reaches a peak even when the amount of the dispersant added is increased, and it is necessary to increase a limit value that can exhibit the dispersibility.

  On the other hand, not only ultra-high-strength concrete with a significantly reduced water binder ratio, but also a wide range of concrete that exhibits dispersibility and can reduce concrete viscosity when producing concrete in areas where the water binder ratio is high There is a need for a dispersant that can be used in the compounding range.

  Various polycarboxylic acid-based dispersants have been reported so far as dispersants for hydraulic compositions (for example, Patent Documents 1 to 7). Patent Document 8 discloses a cement dispersant mainly composed of a water-soluble polymer, which is obtained by subtracting an area ratio of a predetermined low molecular weight side portion from an area ratio of a predetermined high molecular weight side portion of a gel permeation chromatography chart. It is described that the obtained cement dispersant having an area ratio of 13 to 60% is excellent in initial dispersibility or fluidity retention. In Patent Document 9, cement admixtures containing specific copolymers (A) and (B), respectively, differ in the content of predetermined constituent parts of each copolymer, and the weight of each copolymer. It is described that the difference in average molecular weight or peak top molecular weight has a predetermined relationship, thereby improving the water-reducing and fluidity, slump retention performance, and workability of the cement composition. In Patent Document 10, in a molecular weight distribution curve by gel permeation chromatography, a ratio of a peak area in the vicinity of a predetermined elution end time to a sum of the peak area and the peak area from the elution start time to the peak top is predetermined. It is described that a cement composition excellent in fluidity and holding performance can be obtained by being within the range.

JP 09-86990 A JP 09-286645 A JP 2005-281022 A JP 2008-127221 A JP 2009-001683 A JP 2009-242197 A International Publication No. 2011-125869 JP 2003-206169 A International Publication No. 2005/066095 JP 2006-282864 A

  However, the dispersant for hydraulic composition described in Patent Documents 1 to 7 has a problem in use for ultra-high strength concrete, and there is room for improvement in terms of use in a wide range of concrete blending. . In Patent Documents 8 to 10, although detailed studies have been made regarding molecular weight and molecular weight distribution, there is room for further study.

  In the present invention, in order to solve the above-mentioned problems, an object of the present invention is to provide a dispersant for a hydraulic composition that can be applied to a wide range of concrete blending from general strength concrete to ultrahigh strength concrete, and used for ultrahigh strength concrete. In some cases, a hydraulic composition that can exhibit high dispersibility even at a low water binder ratio, has no peak of dispersibility due to the water binder ratio or amount added, can reduce concrete viscosity, and can shorten the setting time. It is an object to provide a dispersing agent.

  As a result of intensive studies to achieve the above object, the present inventors have found that the structural unit derived from each of the specific unsaturated monocarboxylic acid ester monomer and the unsaturated monocarboxylic acid monomer. A dispersant for a hydraulic composition containing a polycarboxylic acid copolymer having a specific molecular weight in a predetermined range and satisfying a specific condition in a gel permeation chromatogram or a salt thereof (A) It was found that the problem can be solved, and the present invention has been achieved.

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に、水素原子または炭素原子数１〜３のアルキル基を表す。ｍは、０〜２の数を表す。Ａ¹Ｏ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、１〜２００の数を表す。Ｘは、水素原子または炭素原子数１〜３０の炭化水素基を表す。）で表される単量体（Ｉ）に由来する構成単位と、
不飽和モノカルボン酸系単量体（ＩＩ）に由来する構成単位と、
単量体（Ｉ）〜（ＩＩ）と共重合可能なその他の単量体（ＩＩＩ）に由来する構成単位とを含み、
各単量体の共重合時の重量比率が５０≦（Ｉ）≦９７、１≦（ＩＩ）≦５０、０≦（ＩＩＩ）≦５０であるポリカルボン酸系共重合体またはその塩（Ａ）を含有し、
ポリカルボン酸系共重合体またはその塩（Ａ）は、
ゲルパーミエーションクロマトグラフィーにより測定される重量平均分子量が７,０００〜１５,０００であり、
ゲルパーミエーションクロマトグラム上のポリマーピークの重量平均分子量Ｍｗ_(AH)およびＭｗ_(AL)の差が、８，０００〜１２，０００（ただし、Ｍｗ_(AH)＞Ｍｗ_(AL)である）であり、
ゲルパーミエーションクロマトグラム上の高分子量側のピーク面積をＡＨ、低分子量側のピーク面積をＡＬとしたときに、ＡＨ／（ＡＨ＋ＡＬ）×１００が７０％〜８０％である、
水硬性組成物用分散剤。
〔２〕ｎ₁が１０以上１００未満の数である〔１〕に記載の水硬性組成物用分散剤。
〔３〕共重合可能なその他の単量体（ＩＩＩ）がポリエチレングリコールジメタクリレートである〔１〕または〔２〕に記載の水硬性組成物用分散剤。
〔４〕超高強度コンクリート用のセメント分散剤である〔１〕〜〔３〕のいずれかに記載の水硬性組成物用分散剤。
〔５〕〔１〕〜〔４〕のいずれかに記載の水硬性組成物用分散剤を含む水硬性組成物。 That is, the present invention includes the following [1] to [5].
[1] The following general formula (1),

(In the formula, R ¹ , R ² and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. M represents a number of 0 to 2. A ¹ O is the same. Or, differently, it represents an oxyalkylene group having 2 to 18 carbon atoms, n ₁ is an average addition mole number of the oxyalkylene group, and represents a number of 1 to 200. X is a hydrogen atom or 1 carbon atom. A structural unit derived from the monomer (I) represented by -30 hydrocarbon groups),
A structural unit derived from an unsaturated monocarboxylic acid monomer (II);
A structural unit derived from another monomer (III) copolymerizable with the monomers (I) to (II),
Polycarboxylic acid copolymer or salt thereof (A) wherein the weight ratio of each monomer during copolymerization is 50 ≦ (I) ≦ 97, 1 ≦ (II) ≦ 50, 0 ≦ (III) ≦ 50 Containing
The polycarboxylic acid copolymer or salt (A) is
The weight average molecular weight measured by gel permeation chromatography is 7,000 to 15,000;
The difference between the weight average molecular weights Mw _(AH) and Mw _(AL) of the polymer peak on the gel permeation chromatogram is 8,000 to 12,000 (provided that Mw _(AH) > Mw _(AL) ). ,
When the peak area on the high molecular weight side on the gel permeation chromatogram is AH and the peak area on the low molecular weight side is AL, AH / (AH + AL) × 100 is 70% to 80%.
Dispersant for hydraulic composition.
[2] The dispersant for hydraulic composition according to [1], wherein n ₁ is a number of 10 or more and less than 100.
[3] The dispersant for hydraulic composition according to [1] or [2], wherein the other copolymerizable monomer (III) is polyethylene glycol dimethacrylate.
[4] The dispersant for hydraulic composition according to any one of [1] to [3], which is a cement dispersant for ultra high strength concrete.
[5] A hydraulic composition containing the dispersant for hydraulic composition according to any one of [1] to [4].

  According to the present invention, it is a dispersant for a hydraulic composition that can be applied to a wide range of concrete blending from general strength concrete to ultra-high strength concrete, and can exhibit high dispersibility regardless of the water binder ratio, and the concrete viscosity is Dispersants for hydraulic compositions that can be reduced, set time can be shortened, and limit dispersibility can be increased, and hydraulic compositions containing the same are provided.

FIG. 1 is an example of a chromatogram of a polycarboxylic acid copolymer or a salt thereof (A), and is a diagram for explaining a weight average molecular weight and an area ratio of a polymer peak.

  The dispersant for hydraulic composition of the present invention contains a polycarboxylic acid copolymer or a salt (A) thereof.

  The polycarboxylic acid copolymer or salt (A) satisfies the following conditions (i) to (iii).

<Condition (i)>
The condition (i) is that the weight average molecular weight Mw _{(A) of the} polycarboxylic acid copolymer or its salt _(A) is 7,000 to 15,000.

The weight average molecular weight is measured by gel permeation chromatography (GPC). The measurement of GPC may be performed under the following conditions by a known method in terms of polyethylene glycol.
Measuring apparatus; Tosoh product column; Shodex Column OH-pak SB-806HQ, SB-804HQ, SB-802.5HQ
Eluent: 0.05M sodium nitrate / acetonitrile 8/2 (v / v)
Eluent flow rate: 1.00 ml / min
Column temperature: 50 ° C
Measurement sample concentration: 0.5% by weight
Standard material: Polyethylene glycol (Tosoh, GL Science)
Detector: differential refractometer (manufactured by Tosoh)
Calibration curve; polyethylene glycol standard

  The weight average molecular weight of the polycarboxylic acid copolymer or salt (A) thereof is preferably 7,000 or more, and more preferably 8,000 or more. The upper limit of the weight average molecular weight is preferably 15,000 or less. The weight average molecular weight is preferably 7,000 to 15,000, and more preferably 8,000 to 15,000. By making the weight average molecular weight within this range, it can be applied to a wide range of concrete blending from general strength concrete to ultra high strength concrete, high dispersibility in the ultra high strength region can be obtained, and there is no peak in dispersibility, The limit addition rate can be reduced.

  The molecular weight distribution (Mw / Mn) of the polycarboxylic acid copolymer or its salt (A) is preferably 1.2 or more, and more preferably 1.25 or more. The upper limit is preferably 2.0 or less, and more preferably 1.70 or less. The molecular weight distribution is preferably in the range of 1.25 to 1.70.

<Condition (ii)>
Condition (ii) is that the difference between the weight average molecular weights Mw _(AH) and Mw _(AL) of the polymer peak on the gel permeation chromatogram of the polycarboxylic acid copolymer or salt (A) is 8,000-12. , 000.

  The two polymer peaks may be confirmed by preparing a baseline by obtaining a GPC chromatogram of the polycarboxylic acid copolymer or its salt (A) after the GPC measurement. The GPC chromatogram may be obtained by taking the peak intensity (mV) on the vertical axis and the elution time (Retention Time) on the horizontal axis. The baseline is usually from the elution start time to the elution end time of the polymer peak. If the elution end time is not clearly recognized, a baseline is created and then divided at a midpoint between the peak and the valley of the peak, and that point may be used as the elution end time of the polymer peak.

As illustrated in FIG. 1, two polymer peaks are usually confirmed. When three or more polymer peaks are present in the polycarboxylic acid copolymer or its salt (A), the peak predicted to be derived from the polycarboxylic acid copolymer or its salt (A) (usually the larger one) From two polymer peaks). In the example of FIG. 1, two polymer peaks are adjacent to each other, but when three or more polymer peaks are present, the two selected peaks may not necessarily be adjacent to each other. The weight average molecular weight on the high molecular weight side in terms of polyethylene glycol is Mw _(AH) , and the weight average molecular weight on the low molecular weight side is Mw _(AL) . That is, there is a relationship of Mw _(AH) > Mw _(AL) .

When the difference between Mw _(AH) and Mw _(AL) is in the range of 8,000 to 12,000, the dispersibility can be maintained well and the concrete viscosity can be kept low.

Mw _(AH) is usually 11,000 to 16,000, more preferably 12,000 to 16,000 or 11,000 to 15,000, and 12,000 to 14,000. Is more preferable. Mw _(AL) is usually 3,000 to 6,000, preferably 3,500 to 5,000.

<Condition (iii)>
Condition (iii) is that when the high molecular weight side peak area on the gel permeation chromatogram of the polycarboxylic acid copolymer or salt (A) is AH and the low molecular weight side peak area is AL, AH / (AH + AL) × 100 (area ratio of AH) is 70% to 80%.

  The peak area on the high molecular weight side refers to the ridgeline of the polymer peak on the high molecular weight side described in (ii), the line vertically drawn from the lowest intensity point (so-called valley) on both sides to the baseline, and the baseline It is the area of the part surrounded by. The peak area on the low molecular weight side is the ridge line of the polymer peak on the low molecular weight side described in (ii), the line drawn vertically from the lowest intensity point (so-called valley) on both sides to the baseline, and the baseline It is the area of the part surrounded by. If the area ratio of AH is 70% to 80%, the influence on the dispersibility can be suppressed, the dispersibility can be improved, and the concrete viscosity can be kept low.

<Polycarboxylic acid copolymer (A)>
The polycarboxylic acid copolymer (A) is composed of a structural unit derived from the monomer (I) represented by the general formula (1) (hereinafter sometimes referred to as the monomer (I)) and unsaturated. And a structural unit derived from a monocarboxylic acid monomer (II) (hereinafter sometimes referred to as monomer (II)). If necessary, a structural unit derived from another monomer (III) copolymerizable with the monomers (I) to (II) (hereinafter sometimes referred to as monomer (III)). May be included.

  The polymerization ratio at the time of copolymerization of each monomer is as follows. In the case of copolymerization, since a part of the monomer usually remains in the reaction system without copolymerization, it is difficult to specify the proportion of each structural unit in the polycarboxylic acid copolymer (A). .

  The weight ratio of the monomer (I) is 50 ≦ (I) ≦ 97, preferably 60 ≦ (I) ≦ 97, and more preferably 65 ≦ (I) ≦ 97.

  The weight ratio of the monomer (II) is 1 ≦ (II) ≦ 50, preferably 5 ≦ (II) ≦ 50, more preferably 5 ≦ (II) ≦ 40.

  The weight ratio of the monomer (III) is 0 ≦ (III) ≦ 50, preferably 0 ≦ (III) ≦ 40, more preferably 0 ≦ (III) ≦ 30, and 0 ≦ (III) ≦ 10. More preferably, 0 ≦ (III) ≦ 1 is even more preferable, and 0 ≦ (III) ≦ 0.5 is particularly preferable.

  The weight ratio is a weight ratio when the weight ratio of monomer (I) + the weight ratio of monomer (II) + the weight ratio of monomer (III) = 100% by weight.

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に、水素原子または炭素原子数１〜３のアルキル基を表す。ｍは、０〜２の数を表す。Ａ^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、１〜２００の数を表す。Ｘは、水素原子または炭素原子数１〜３０の炭化水素基を表す。） Hereinafter, first, the monomer (I) will be described.

(In the formula, R ¹ , R ² and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. M represents a number of 0 to 2. A ¹ O is the same. Or, differently, it represents an oxyalkylene group having 2 to 18 carbon atoms, n ₁ is an average addition mole number of the oxyalkylene group, and represents a number of 1 to 200. X is a hydrogen atom or 1 carbon atom. Represents a hydrocarbon group of ˜30.)

R ¹ , R ² and R ³ in the general formula (1) each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

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 plurality of A ¹ O are contained in the general formula (1) (when n ₁ is 2 or more), each A ¹ O may be the same oxyalkylene group. It may be different (two or more) oxyalkylene groups. 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.

N ₁ in the general formula (1) is the average number of moles of the oxyalkylene group. The lower limit is 1 or more, preferably 5 or more, and more preferably 10 or more. The upper limit is 200 or less, for example, 100 or less, less than 100, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less. Accordingly, n ₁ represents a number of 1 to 200, preferably 5 to 200, more preferably 5 to 100, still more preferably 10 or more and less than 100, and 10 or more and 50 or less. Even more preferred.

The monomer (I) may be a monomer represented by the general formula (1) alone or a combination of two or more. Two or more combinations are the two monomers (Ia) and (Ib) having different average addition moles of oxyalkylene groups (provided that the average addition moles of oxyalkylene groups are n _1a and n _1b , respectively) n _1a <n _1b .) is preferable, and such a combination is more preferable. Monomer (Ia) and monomer (Ib) differ from each other only in the average addition mole number n _{1 of the} oxyalkylene group, and R ₁ , R ₂ , R ₃ , m and X are the same monomers In addition to n ₁ , at least one of R ₁ , R ₂ , R ₃ , m, and X may be a different monomer. n _1a is, for example, 15 or less, 14 or less, or 13 or less. n _1a is preferably 1 to 15, more preferably 1 to 14, further preferably 1 to 13, and still more preferably 1 to 9. n _1b may be any number larger than n _1a and is, for example, 14 or more, 15 or more, 16 or more, 17 or more, or 18 or more. Preferably it is 10-200, 14-200, 15-200, 16-200, 17-200, or 18-200, and 10 or more, less than 100, 14 or more, less than 100, 15 or more, less than 100, 16 or more, 100 Less than, 17 or more, less than 100, or 18 or more and less than 100, more preferably 10 or more and 50 or less, 14 or more and 50 or less, 15 or more and 50 or less, 16 or more and 50 or less, 17 or more and 50 or less, or 18 or more and 50 or less. Even more preferably.

  When the monomer (I) is a combination of the monomers (Ia) and (Ib), the respective weight ratios (total is 100% by weight) are such that (Ia) / (Ib) is (0.1 To 99.9) / (99.9 to 0.1), more preferably (1 to 99) / (99 to 1), and (10 to 90) / (90 to 10). Is more preferable, and (25 to 75) / (75 to 25) is particularly preferable.

  X in the general formula (1) represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. X can be a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms because the cement dispersibility of the dispersant for a hydraulic composition can be further exerted by the group having a relatively small number of carbon atoms. It is preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group.

  Examples of the monomer (I) 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. Also, for example, (poly) ethylene glycol (meth) acrylate, (poly) ethylene (poly) propylene glycol (meth) acrylate, (poly) ethylene (poly) butylene glycol (meth) acrylate, methoxy (poly) ethylene glycol (meth) Examples include (poly) alkylene glycol (meth) acrylates such as acrylate, methoxy (poly) ethylene (poly) propylene glycol (meth) acrylate, and methoxy (poly) ethylene (poly) butylene glycol (meth) acrylate. The monomer (I) can be used alone or in combination of two or more thereof, but (poly) alkylene glycol (meth) acrylate is preferably used, and (poly) ethylene glycol (meth) acrylate ( For example, it is more preferable to use at least one of hydroxyethyl acrylate), (poly) propylene glycol (meth) acrylate (eg, hydroxypropyl acrylate) and methoxy (poly) ethylene glycol (meth) acrylate. The average number of added moles of (poly) alkylene glycol is preferably 1-50. When the monomer (Ia) is (poly) alkylene glycol, the number of added moles of (poly) alkylene glycol as the monomer (Ia) is preferably 1 to 9. When the monomer (Ib) is (poly) alkylene glycol, the number of added moles of (poly) alkylene glycol as the monomer (Ib) is preferably 10 to 200, and preferably 10 to 100. Is more preferable. When the monomer (Ia) is a methoxy (poly) alkylene glycol (meth) acrylate, the added mole number of the methoxy (poly) alkylene glycol (meth) acrylate as the monomer (Ia) is 1-13, It is preferable that it is 14, 1-15, 1-16, or 1-17. When the monomer (Ib) is a methoxy (poly) alkylene glycol (meth) acrylate, the added mole number of the methoxy (poly) alkylene glycol (meth) acrylate as the monomer (Ib) is 14 to 200, 15 to 15, It is preferably 200, 16 to 200, 17 to 200, or 18 to 200, more preferably 14 to 100, 15 to 100, 16 to 100, 17 to 100, or 18 to 100.

Next, the monomer (II) will be described. The monomer (II) is an unsaturated monocarboxylic acid-based monomer, and examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and salts thereof (for example, monovalent metal salts, divalent salts) Metal salts, ammonium salts, organic amine salts). The unsaturated carboxylic acid monomer (II) may be one or more of these. When using 2 or more, it is preferable to contain 1 or 2 or more selected from the group which consists of acrylic acid, methacrylic acid, and any one of these salts, and it is preferable that it is 1 or 2 or more selected from such a group.
When acrylic acid and methacrylic acid are used in combination, the acrylic acid / methacrylic acid is usually (0.1% to 99.9%) / (99.9% to 100% by weight). 0.1%), preferably (1% to 99%) / (99% to 1%).

  The monocarboxylic acid is preferably a mixture containing a monomer and a dimer. In the case of acrylic acid, a mixture of acrylic acid monomer and dimer is preferable. The ratio of the two (the total is 100% by weight) is preferably acrylic acid monomer / acrylic acid dimer = (90.0% by weight to 100% by weight) / (0% by weight to 10% by weight).

  Subsequently, the monomer (III) will be described. The monomer (III) is not particularly limited as long as it is a monomer copolymerizable with one or more monomers selected from the group consisting of monomers (I) and (II). Monomer (III) does not include monomer (I) and monomer (II).

  As the monomer (III), the following can be exemplified, and one or more of these can be used;

で示されるジアリルビスフェノール類、例えば４，４’−ジヒドロキシジフェニルプロパン、４，４’−ジヒドロキシジフェニルメタン、４，４’−ジヒドロキシジフェニルスルホンの３および３’位アリル置換物； General formula (III-1):

Diallyl bisphenols, such as 4,4′-dihydroxydiphenylpropane, 4,4′-dihydroxydiphenylmethane, and 3 and 3 ′ allyl substitutes of 4,4′-dihydroxydiphenylsulfone;

で示されるモノアリルビスフェノール類、例えば４，４’−ジヒドロキシジフェニルプロパン、４，４’−ジヒドロキシジフェニルメタン、４，４’−ジヒドロキシジフェニルスルホンの３位アリル置換物； General formula (III-2):

Monoallyl bisphenols represented by the formula: for example, 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, 3-position allyl substitute of 4,4'-dihydroxydiphenylsulfone;

で示されるアリルフェノール； General formula (III-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;

(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;
Unsaturation such as aminoethyl (meth) acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, vinylpyridine, etc. Amines;
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).

  Monomer (III) may be individual and may be a combination of two or more.

  Monomer (III) preferably comprises 3 and 3 'allylic substitutions of 4,4'-dihydroxydiphenylsulfone and / or (poly) alkylene glycol di (meth) acrylate. The (poly) alkylene glycol di (meth) acrylate is preferably (poly) ethylene glycol di (meth) acrylate. The addition mole number of the oxyalkylene group in the (poly) alkylene glycol di (meth) acrylate is, for example, 1 to 200, 5 to 200, 5 to 100, preferably 10 or more and less than 100, and more preferably 10 or more and 50 or less. .

  If necessary, the polycarboxylic acid copolymer (A) is a structural unit derived from a monomer other than the monomer (I), the monomer (II), and the monomer (III) (for example, described later). Monomer (IV) or the like.

<Polycarboxylic acid salt (A)>
The dispersant for hydraulic composition of the present invention may contain the salt (A) of the polycarboxylic acid copolymer described above. Examples of the salt include monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts.

  The dispersant for a hydraulic composition of the present invention may contain a polycarboxylic acid copolymer or a salt thereof (A) alone, or a different polycarboxylic acid copolymer or a salt thereof (A). A combination of two or more of these may be used.

<Manufacturing method>
In the present invention, the polycarboxylic acid copolymer or its salt (A) is produced by copolymerizing the monomer (I), the monomer (II) and the monomer (III) used as necessary. can do. Although the method of copolymerization is not limited, For example, polymerization methods, such as superposition | polymerization in a solvent and block polymerization, are mentioned.

  Examples of the solvent used in the copolymerization in the solvent include water; lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; aromatic hydrocarbons such as benzene, toluene, and xylene; cyclohexane, n-hexane, and the like. Aliphatic hydrocarbons; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone. From the viewpoint of 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 dropped continuously into each reaction vessel. Also good. Alternatively, a solvent may be charged into the reaction vessel, and a mixture of the monomer and the solvent and a polymerization initiator solution may be continuously dropped into the reaction vessel, or a part or all of the monomer may be charged into the reaction vessel and polymerized. The initiator may be continuously dropped.

  When carrying out copolymerization in a solvent, it is preferable to mix each monomer in a container different from the reaction container previously set in the container in which the reaction is carried out and then continuously drop it into the reaction container.

  After completion of the copolymerization reaction, the polycarboxylic acid copolymer or its salt (A) may be contained in the hydraulic composition as it is containing the reaction solvent or the like, and further subjected to some treatment. It may be contained in a state. Examples of the treatment include removal of the reaction solvent, concentration adjustment by concentration or dilution, purification, and pH adjustment. After the completion of the reaction, it is preferable to adjust the concentration and / or adjust the pH in a container installed after the reaction container. The method for adjusting the concentration is not particularly limited, but may be performed by, for example, concentration or dilution by hydration. The pH adjustment will be described later.

  The polymerization initiator that can be used for copolymerization is, for example, persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; and water-soluble such as t-butyl hydroperoxide. An organic peroxide is mentioned. In this case, an accelerator such as sodium hydrogen sulfite and a mol salt can be used in combination. When copolymerization is performed in a solvent such as a lower alcohol, aromatic hydrocarbon, aliphatic hydrocarbon, ester or ketone, for example, peroxides such as benzoyl peroxide and lauryl peroxide; cumene peroxide Hydroperoxides such as azo compounds such as azobisisobutyronitrile can be used as the polymerization initiator. In this case, an accelerator such as an amine compound can be used in combination. Furthermore, when copolymerization is carried out in a water-lower alcohol mixed solvent, it can be used by appropriately selecting from the aforementioned polymerization initiator or a combination of a polymerization initiator and an accelerator. 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.

  In the copolymerization, the molecular weight may be adjusted using a chain transfer agent as necessary. Examples of the chain transfer agent used include mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid (β-mercaptopropionic acid), thiomalic acid, octyl thioglycolate, and Known thiol compounds such as 2-mercaptoethanesulfonic acid: phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogensulfite, dithionite , Metabisulfite, and salts thereof (sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.) And salts thereof; Moreover, you may use polymerization inhibitors, such as 4-methoxyphenol and a phenothiazine. Each of the chain transfer agent and the polymerization inhibitor may be used alone or in combination of two or more.

  In addition to the monomers (I) and (II) and (III) used as necessary, a monomer (IV) having a higher chain transfer property may be used. Thereby, the molecular weight of a polycarboxylic acid-type copolymer or its salt (A) can be adjusted. Examples of the monomer (IV) include (meth) allylsulfonic acid (salt) monomers. The weight ratio at the time of copolymerization of the monomer (IV) is usually 20% by weight or less, and preferably 10% by weight or less. The weight ratio is a weight ratio when the weight ratio of monomer (I) + the weight ratio of monomer (II) + the weight ratio of monomer (III) = 100% by weight.

In the case of copolymerization in an aqueous solvent, the pH at the time of 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 the monomer before polymerization or may be performed on the copolymer solution after polymerization. In addition, these may be subjected to polymerization by adding a part of an alkaline substance before polymerization, and then the pH of the copolymer may be further adjusted.

  The dispersant for hydraulic composition of the present invention can be used in the form of an aqueous solution or in the form of powder after drying. In addition, the time which adds a dispersing agent to a hydraulic composition is not specifically limited. For example, the hydraulic composition may be used. In addition, a component for a hydraulic composition of the present invention in a powdered form is mixed in advance with a component other than water (for example, cement powder, dry mortar) constituting the hydraulic composition, It can also be used as a premix product to which water is added for floor finishing, grout and the like.

  The dispersant for hydraulic composition of the present invention can be added to a hydraulic material such as cement and used as a hydraulic composition for cement paste, mortar, concrete, plaster and the like.

  The hydraulic composition of this invention should just contain the dispersing agent for hydraulic compositions, and the hydraulic material to combine is not specifically 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, but, for example, Portland cement (ordinary, early strength, ultra-early strength, moderate heat, sulfate-resistant and each low alkali type), 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 heat cement (low heat blast furnace cement, fly ash mixing) Low exothermic blast furnace cement, cement with high belite content), ultra-high strength cement, cement-based solidified material, eco-cement (cement manufactured using at least one of municipal waste incineration ash and sewage sludge incineration ash) It is done. Of these, ultra high strength cement is preferred. Blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, limestone powder and other fine powders, gypsum, and the like may be added to the cement.

  Moreover, the hydraulic 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

  There is no particular limitation on the blending ratio of the dispersant for hydraulic composition in the hydraulic composition. For example, when the hydraulic composition is mortar or concrete, the addition amount (blending amount) of the polycarboxylic acid copolymer or salt (A) contained in the dispersant for hydraulic composition is cement. Is usually 0.01 to 5.0% by weight, preferably 0.02 to 2.0% by weight, and more preferably 0.05 to 1.0% by weight. By setting this addition amount, the obtained hydraulic composition has various preferable effects such as reduction in unit water amount, increase in strength, and improvement in durability. If the blending ratio is less than 0.01% by weight, the resulting hydraulic composition may not be sufficient in terms of performance. Conversely, even if a large amount exceeding 5.0% by weight is used, the effect is substantially There is a risk that it will hit the peak and be disadvantageous in terms of economy.

  The above hydraulic composition includes, for example, ultra-high-strength concrete, ready-mixed concrete, concrete for secondary concrete products (precast concrete), concrete for centrifugal molding, concrete for vibration compaction, steam-cured concrete, shotcrete, etc. It is effective as concrete. 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 such as.

  When the dispersant for hydraulic composition of the present invention is used in an ultrahigh strength region, the hydraulic composition preferably has a low water binder (material) ratio (W / B). Thereby, the characteristics of the present invention such as high dispersibility at a low water binder ratio, reduction of concrete viscosity, and quick setting time can be exhibited. The water binder ratio is preferably 30% or less, and more preferably 20% or less. The lower limit of the water binder ratio is usually 10% or more.

  The dispersant for hydraulic composition of the present invention can be used in a wide range of concrete blending from general strength concrete to ultra high strength concrete. Normally used concrete water binder (material) ratio (W / B) is in the range of 60 to 10%. Generally, when the water binder (material) ratio (W / B) increases, the strength decreases, and when it decreases, the strength increases.

  The hydraulic composition of the present invention includes other dispersants for cement hydraulic compositions, water-soluble polymers, polymer emulsions, air entrainers, cement wetting agents, swelling agents, waterproofing agents, retarders, thickeners, One or more selected from known additives for concrete such as a flocculant, a drying shrinkage reducing agent, a strength enhancer, a curing accelerator, an antifoaming agent, an AE agent and other surfactants may be contained.

  Other dispersants for cement hydraulic compositions include, for example, polycarboxylic acid-based dispersants other than the dispersant for hydraulic compositions described in the present invention (for example, production described in JP-A-2014-105140) Example 1 and polycarboxylic acid copolymer of Production Example 5), naphthalene sulfonic acid formaldehyde condensate, melamine sulfonic acid formaldehyde condensate, dispersant for sulfonic acid hydraulic composition such as lignin sulfonate (S) Can be mentioned. The content of the sulfonic acid-based hydraulic composition dispersant (S) in the hydraulic composition is 0.01% by weight to 50% with respect to the content of the polycarboxylic acid-based copolymer or a salt thereof (A). It is preferable that it is weight%.

  Examples of the water-soluble polymer (P) include polyalkylene glycol, specifically, polyethylene glycol, polypropylene glycol, polyethylene polypropylene glycol, polyethylene polybutylene glycol, and the like. The content of the water-soluble polymer (P) in the hydraulic composition is 0.01% by weight to 50% by weight with respect to the content of the polycarboxylic acid copolymer or the salt (A) thereof. preferable.

  Examples of the retarder include oxycarboxylic acids such as gluconic acid (salt) and citric acid (salt), sugars such as glucose, and sugar alcohols (G) such as sorbitol. The content of the sugar alcohols (G) in the hydraulic composition is preferably 0.01% by weight to 50% by weight with respect to the content of the polycarboxylic acid copolymer or the salt (A) thereof. .

  Examples of the hardening accelerator include soluble calcium salts such as calcium chloride, calcium nitrite and calcium nitrate, chlorides such as iron chloride and magnesium chloride, and formate salts (K) such as thiosulfate, formic acid and calcium formate. Can be mentioned. The content of the curing accelerator (K) in the hydraulic composition is preferably 0.01% by weight to 50% by weight with respect to the content of the polycarboxylic acid copolymer or its salt (A). .

  Examples of the thickener include hydroxypropylmethylcellulose, carboxymethylcellulose, known cellulose nanofibers, and known cellulose nanocrystals (Z). The content of the thickener (Z) in the hydraulic composition is 0.01% by weight to 50% by weight with respect to the content of the polycarboxylic acid copolymer of the present invention or the salt (A) thereof. It is preferable.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. In the examples, unless otherwise indicated, “%” means “% by weight” and “parts” means “parts by weight”.

<Production Example 1>
Into a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dropping device, 3930 parts of water was charged, the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 100 ° C. in a nitrogen atmosphere. Thereafter, an aqueous monomer solution obtained by mixing 605 parts of methoxypolyethylene glycol methacrylate (average number of moles of added ethylene oxide 13), 155 parts of methacrylic acid, 9 parts of β-mercaptopropionic acid and 300 parts of water, 9 parts of sodium persulfate and water 191 parts of the mixed solution was continuously dropped into a reaction vessel maintained at 100 ° C. for 2 hours each. Furthermore, after making it react for 1 hour in the state hold | maintained at 100 degreeC, the aqueous solution of copolymer (A-1) was obtained by making aqueous solution pH 6 using 48 weight% NaOH.

<Production Example 2>
Into a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dropping device, 3930 parts of water was charged, the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 100 ° C. in a nitrogen atmosphere. Thereafter, an aqueous monomer solution in which 672 parts of methoxypolyethylene glycol methacrylate (average added mole number of ethylene oxide 18), 190 parts of methacrylic acid, 9 parts of β-mercaptopropionic acid and 300 parts of water were mixed, 9 parts of sodium persulfate and water 191 parts of the mixed solution was continuously dropped into a reaction vessel maintained at 100 ° C. for 2 hours each. Furthermore, after making it react for 1 hour in the state hold | maintained at 100 degreeC, the aqueous solution of copolymer (A-2) was obtained by making aqueous solution pH 6 using 48 weight% NaOH.

<Production Example 3>
Into a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dropping device, 3930 parts of water was charged, the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 100 ° C. in a nitrogen atmosphere. Thereafter, 333 parts of methoxypolyethylene glycol methacrylate (average number of added moles of ethylene oxide 50), 105 parts of methacrylic acid, 16 parts of acrylic acid (monomer / dimer = 99% by weight / 1% by weight), 7 parts of β-mercaptopropionic acid And a monomer aqueous solution in which 500 parts of water were mixed, and a mixed liquid of 10 parts of sodium persulfate and 190 parts of water were continuously dropped into a reaction vessel maintained at 100 ° C. for 2 hours. Furthermore, after making it react for 1 hour in the state hold | maintained at 100 degreeC, the aqueous solution of copolymer (A-3) was obtained by making aqueous solution pH 6 using 48 weight% NaOH.

<Production Example 4>
Into a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dropping device, 3930 parts of water was charged, the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 100 ° C. in a nitrogen atmosphere. Then, 605 parts of methoxypolyethylene glycol methacrylate (average added mole number of ethylene oxide 13), 2 parts of polyethylene glycol dimethacrylate (average added mole number of ethylene oxide 13), 1.5 parts of 4-methoxyphenol, 155 methacrylic acid 1 part of the mixture, 9 parts of β-mercaptopropionic acid and 300 parts of water and an initiator mixed solution of 9 parts of sodium persulfate and 191 parts of water were started to be dropped at the same time. The liquid was continuously added dropwise to the reaction vessel maintained at 100 ° C. in 2 hours and 30 minutes. Furthermore, after making it react for 1 hour in the state hold | maintained at 100 degreeC, it moved to another reaction container, and the aqueous solution of a copolymer (A-4) was made by making aqueous solution pH 7 using 48 weight% NaOH. Got.

<Production Example 5>
Into a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dropping device, 3930 parts of water was charged, the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 100 ° C. in a nitrogen atmosphere. Thereafter, 672 parts of methoxypolyethylene glycol methacrylate (average added mole number of ethylene oxide 18), 2 parts of polyethylene glycol dimethacrylate (average added mole number of ethylene oxide 18), 2 parts of 4-methoxyphenol, 190 parts of methacrylic acid, A monomer aqueous solution in which 12 parts of β-mercaptopropionic acid and 300 parts of water were mixed, and an initiator mixed solution of 9 parts of sodium persulfate and 191 parts of water were started to be dropped at the same time. In 2 hours and 30 minutes, it was continuously added dropwise to a reaction vessel maintained at 100 ° C. Furthermore, after making it react for 1 hour in the state hold | maintained at 100 degreeC, it moved to another reaction container, and the aqueous solution of a copolymer (A-5) was made by making aqueous solution pH 6 using 48 weight% NaOH. Got.

<Production Example 6>
Into a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dropping device, 3930 parts of water was charged, the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 100 ° C. in a nitrogen atmosphere. Thereafter, 333 parts of methoxypolyethylene glycol methacrylate (average added mole number of ethylene oxide 50), 0.1 part of polyethylene glycol dimethacrylate (average added mole number of ethylene oxide 50), 1 part of 4-methoxyphenol, 105 of methacrylic acid Part, acrylic acid (monomer / dimer = 99% by weight / 1% by weight) 16 parts, β-mercaptopropionic acid 7 parts and water 500 parts mixed monomer aqueous solution, sodium persulfate 10 parts and water 190 parts initiator The mixed solution was simultaneously added dropwise, and the monomer aqueous solution was continuously added dropwise to the reaction vessel maintained at 100 ° C. in 2 hours and the initiator mixed solution in 2 hours and 30 minutes. Furthermore, after making it react for 1 hour in the state hold | maintained at 100 degreeC, it moved to another reaction container, and the aqueous solution of a copolymer (A-6) was made by making aqueous solution pH 6 using 48 weight% NaOH. Got.

<Production Example 7>
1540 parts of water was charged in a glass reaction vessel equipped with a thermometer, a stirring device, a reflux device, and a dropping device, and the temperature of the reaction vessel was raised to 100 ° C. with stirring. Thereafter, 694 parts of methoxypolyethylene glycol methacrylate (average added mole number of ethylene oxide 13), 892 parts of methoxypolyethylene glycol methacrylate (average added mole number of ethylene oxide 18), polyethylene glycol dimethacrylate (average added mole of ethylene oxide) Formula 13) 2 parts, 2 parts of polyethylene glycol dimethacrylate (average number of added moles of ethylene oxide 18), 1 part of 4-methoxyphenol, 240 parts of methacrylic acid, 24 parts of β-mercaptopropionic acid and 560 parts of water were mixed. A monomer aqueous solution and an initiator mixture solution of 23 parts of sodium persulfate and 480 parts of water were started to be dropped at the same time, and the monomer aqueous solution was added in 2 hours and the initiator mixture solution was kept at 100 ° C. in 2 hours and 30 minutes. Continuous Beat was. Furthermore, after making it react for 1 hour in the state hold | maintained at 100 degreeC, it moved to another reaction container, and the aqueous solution of a copolymer (A-7) was made by making 48 aqueous solution pH into 7 using 48 weight% NaOH. Got.

<Production Comparative Example 1>
Into a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dropping device, 3500 parts of water was charged, and the temperature of the reaction vessel was raised to 100 ° C. with stirring. Thereafter, 140 parts of methacrylic acid, 333 parts of methoxypolyethylene glycol methacrylate (average number of added moles of ethylene oxide 23), a monomer aqueous solution mixed with 600 parts of water, and a mixed solution of 12 parts of ammonium persulfate and 288 parts of water, In 2 hours, it was continuously dropped into a reaction vessel maintained at 100 ° C. Furthermore, after making it react for 1 hour in the state hold | maintained at 100 degreeC, the aqueous solution of copolymer (A-8) was obtained by making aqueous solution pH 6 using 48 weight% NaOH.

<Production Comparative Example 2>
3000 parts of water was charged in a glass reaction vessel equipped with a thermometer, a stirring device, a reflux device, a nitrogen introducing tube and a dropping device, and the reaction vessel was heated to 100 ° C. with stirring. Thereafter, 160 parts of methacrylic acid, 400 parts of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added 22), 2 parts of compound in which 3 and 3 'positions of 4,4'-dihydroxydiphenylsulfone are allyl substituted, 450 parts of water A monomer aqueous solution mixed with 13 parts of ammonium persulfate and 287 parts of water was continuously added dropwise to a reaction vessel maintained at 100 ° C. for 2 hours. Furthermore, after making it react for 1 hour in the state hold | maintained at 100 degreeC, the aqueous solution of copolymer (A-9) was obtained by making aqueous solution pH 6 using 48 weight% NaOH.

<Production Comparative Example 3>
3000 parts of water was charged in a glass reaction vessel equipped with a thermometer, a stirring device, a reflux device, a nitrogen introducing tube and a dropping device, and the reaction vessel was heated to 100 ° C. with stirring. Then, 90 parts of methacrylic acid, 308 parts of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added 8), 3 parts of β-mercaptopropionic acid, 87 parts of water, 8 parts of ammonium persulfate and 92 parts of water Part of the mixed solution was continuously dropped into a reaction vessel maintained at 100 ° C. for 2 hours each. Furthermore, after making it react for 1 hour in the state hold | maintained at 100 degreeC, the aqueous solution of copolymer (A-10) was obtained by making aqueous solution pH 6 using 48 weight% NaOH.

<Examples 1-7 and Comparative Examples 1-3>
Weight average molecular weight, molecular weight distribution of aqueous solutions of copolymers obtained in Production Examples 1 to 7 and Production Comparative Examples 1 to 3, Mw _(AH) , Mw _(AL) , Mw _(AH) -Mw _(AL) , The area ratio of AH was measured according to the conditions described in the previous stage. Table 1 shows the measurement results. In addition, at the ambient temperature (20 ° C.), fine aggregates, cement, water blended as shown in Table 2 and the dispersants for the hydraulic compositions of the examples and comparative examples were added and mechanically kneaded with a mortar mixer. The mixture was kneaded at a low speed for 300 seconds, allowed to stand for 300 seconds, and then kneaded at a low speed for 30 seconds (the dispersing agent for hydraulic composition was mixed with water and added). The mortar flow of each mortar, the mortar viscosity evaluation, and the maximum temperature arrival time in the simple adiabatic temperature change test were evaluated.

[Measurement of mortar flow value]
The above-mentioned mortar is packed in a hollow cylindrical mini slump cone with a bottom diameter of 20 cm, a top diameter of 10 cm, and a height of 30 cm, and the average value of the two directions of the mortar spread on the table when the mini slump cone is lifted vertically. Was the mortar flow value. When the addition amount of the admixture was changed and the mortar flow value did not increase even when the addition amount increased, it was evaluated that the peak of dispersibility was observed.

[Viscosity / State Evaluation Criteria]
The mortar after scouring is evaluated by sensory evaluation when mixed 20 times with a spatula. ○: Less resistance, mortar glossy △: Resistance is slightly higher, mortar glossiness is slightly inferior ×: Resistance Is difficult to knead and the mortar is not glossy

[Evaluation criteria for condensation rate: Simple adiabatic temperature measurement]
The mortar after kneading is put into a plastic cup having a diameter of 6.5 cm and a height of 6.5 cm, and placed in a heat insulating container of 20 cm × 20 cm × 20 cm. A thermocouple was inserted into the mortar in the heat insulating container, and the temperature was continuously measured with an external recording device. The time to reach the maximum temperature was read from the temperature history with the start of mortar kneading as 0 minutes, and the time was reached. The shorter the maximum temperature arrival time, the faster the setting time.

  The results are shown in Tables 1-3.

B, W, and S in Table 2 mean the following.
B: Silica fume cement (Mitsubishi Materials Corporation, specific gravity 3.08)
W: Tap water S: Land sand from Kakegawa, Shizuoka Prefecture (fine aggregate, specific gravity 2.57)

  In Table 3, the addition amount indicates the solid content addition rate of each copolymer with respect to the silica fume cement. Moreover, SLF shows mortar flow, respectively.

<Examples 8 to 14 and Comparative Examples 4 to 6>
Examples 1-7 and Comparative Example 1 except that the composition of fine aggregate, cement and water to be blended in the dispersants for hydraulic compositions of Production Examples 1 to 7 and Production Comparative Examples 1 to 3 were as shown in Table 4. In the same manner as in Examples 1 to 3, mortar flow measurement of each mortar, mortar viscosity evaluation, and maximum temperature arrival time evaluation in a simple adiabatic temperature change test were performed. The results are shown in Table 5.

B, W, and S in Table 4 mean the following.
B: Ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd., specific gravity 3.16)
W: Tap water S: Land sand from Kakegawa, Shizuoka Prefecture (fine aggregate, specific gravity 2.57)

  In Table 5, the addition amount indicates the solid content addition rate of each copolymer with respect to ordinary Portland cement. Moreover, SLF shows mortar flow, respectively.

  From Table 3, when the mortar of each example and the mortar of each comparative example were compared, the following could be confirmed. Compared with the comparative example, the mortar flow was better in the examples and increased according to the amount added. The viscosity and state of the mortars of the examples were better than those of the comparative examples, the resistance was low, and the mortar was glossy. From Table 5, when the mortar of each Example was compared with the mortar of each Comparative Example, the viscosity and state of the mortar were good in the Examples. Combining the results in Table 3 and Table 5, it can be seen that a wide range of water binder ratios from low water binder ratios to high water binder ratios can also be used. In Table 3, the maximum temperature arrival time of Examples 1 to 7 was shorter than that of Comparative Examples 1 to 3, that is, the setting time was faster. In general, it is known that when the addition amount of the dispersant is increased, the maximum temperature arrival time is delayed. However, in Examples 1 to 7, the delay in the maximum temperature arrival time was suppressed even when the addition amount was increased. . In Table 5, the maximum temperature arrival times of Examples 8 to 14 were the same or shorter than those of Comparative Examples 4 to 6, and the setting time was faster. These results show that the dispersant for hydraulic compositions of the present invention exhibits excellent dispersibility, can reduce the viscosity when made into a hydraulic composition, and also has a setting time even when the amount of dispersant added increases. This indicates that the present invention can be applied to ultra high strength concrete having a low water binder ratio to general strength concrete having a high water binder ratio.

Claims (5)

The following general formula (1),

(In the formula, R ¹ , R ² and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. M represents a number of 0 to 2. A ¹ O is the same. Or, differently, it represents an oxyalkylene group having 2 to 18 carbon atoms, n ₁ is an average addition mole number of the oxyalkylene group, and represents a number of 1 to 200. X is a hydrogen atom or 1 carbon atom. A structural unit derived from the monomer (I) represented by -30 hydrocarbon groups),
A structural unit derived from an unsaturated monocarboxylic acid monomer (II);
A structural unit derived from another monomer (III) copolymerizable with the monomers (I) to (II),
Polycarboxylic acid copolymer or salt thereof (A) wherein the weight ratio of each monomer during copolymerization is 50 ≦ (I) ≦ 97, 1 ≦ (II) ≦ 50, 0 ≦ (III) ≦ 50 Containing
The polycarboxylic acid copolymer or salt (A) is
The weight average molecular weight measured by gel permeation chromatography is 7,000 to 15,000,
The difference between the weight average molecular weights Mw _(AH) and Mw _(AL) of the polymer peak on the gel permeation chromatogram is 8,000 to 12,000 (provided that Mw _(AH) > Mw _(AL) ). ,
When the peak area on the high molecular weight side on the gel permeation chromatogram is AH and the peak area on the low molecular weight side is AL, AH / (AH + AL) × 100 is 70% to 80%.
Dispersant for hydraulic composition. The dispersant for hydraulic composition according to claim 1, wherein n ₁ is a number of 10 or more and less than 100.   The dispersant for a hydraulic composition according to claim 1 or 2, wherein the other copolymerizable monomer (III) is polyethylene glycol dimethacrylate.   The dispersant for hydraulic composition according to any one of claims 1 to 3, which is a cement dispersant for ultra-high strength concrete.   The hydraulic composition containing the dispersing agent for hydraulic compositions of any one of Claims 1-4.

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