JP2000290056A - Hydraulic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a hydraulic composition having good resistance to the separation of materials and superior flow properties without taking a lot of trouble. SOLUTION: The hydraulic composition contains a (meth)acrylic acid-base material separation suppressor, a high performance water-reducing agent, a hydraulic material and water as essential components. The material separation suppressor has a >=4C hydrocarbon group and a (poly)oxyalkylene group in each constituent unit of a polymer and has <=100 mm mortar flow value and >=1 wt.% solubility in a supernatant aqueous solution of cement.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a hydraulic composition. More specifically, cement paste, mortar,
The present invention relates to a hydraulic composition having good material separation resistance and excellent fluidity in a so-called cement compound such as concrete.

[0002]

2. Description of the Related Art Since the early deterioration of concrete structures became a social problem in 1981, it has been necessary to reduce the amount of water in hydraulic compositions represented by concrete, mortar, etc., and to improve their workability and durability. However, in recent years, the development of a so-called high fluidity hydraulic composition that further enhances the fluidity of the hydraulic composition before curing has been actively pursued. A typical example is high fluidity concrete. This high-fluidity concrete has higher fluidity than conventional concrete, and has excellent self-filling properties.Even when filling into a tightly arranged formwork, compaction by vibration of a vibrator or the like is possible. A hydraulic composition that is unnecessary and can improve workability. Although this high-fluidity concrete does not yet have an established definition, the concrete has a slump flow value of 50 cm or more, preferably 50 to 50 cm, according to the JIS A-1101 method.
It is about 70 cm. Therefore, so-called high-performance water reducing agents, which are required for such high-fluidity concrete and can obtain excellent fluidity, have been vigorously developed by admixture manufacturers, and currently, naphthalene-based,
Aminosulfonic acid-based and polycarboxylic acid-based products are commercially available, and polycarboxylic acid-based high-performance water-reducing agents having the excellent feature that the highest water reduction rate can be obtained include various water-soluble vinyl copolymers. Has been proposed.

[0003] However, these known high-performance water reducing agents have problems in strength. That is, when the addition amount is increased to increase the fluidity of the hydraulic composition,
A large amount of floating water after construction of concrete (breathing)
And the material separation between the binder and the aggregate in the hydraulic composition becomes remarkable, and the aggregates are entangled with each other, resulting in poor filling properties. This breathing is a kind of separation phenomenon caused by the difference in specific gravity between the moisture in the concrete and the binder or aggregate. The homogeneity and denseness of the concrete structure are impaired by the path, and the strength is reduced after hardening. As a method of suppressing this breathing, generally, the viscosity is increased by adding a fine powder or a thickener,
Although a method of increasing material separation resistance has been adopted, there are problems in handling and economics at the time of compounding, it can not be said to be a drastic measure, and it can be satisfied in both performance and handling,
At present, a hydraulic composition having high fluidity and material separation resistance has not been obtained.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a hydraulic composition having good resistance to material separation and excellent fluidity, which can be prepared without any trouble.

[0005]

A water-soluble vinyl copolymer which can be used as a high-performance water reducing agent is disclosed in Japanese Unexamined Patent Publication No.
-144906, JP-A-8-53522, JP-A-9-2
41056, JP-A-9-241057, JP-A-10-8
No. 1549 discloses polyalkylene glycol (meth) acrylate copolymers having various hydrophobic groups, but the cement admixtures disclosed in these publications have excellent fluidity. Is a cement dispersant used for the purpose of imparting to a hydraulic composition such as concrete, which has a high cement dispersibility, and imparts material separation resistance to the hydraulic composition. It is not a material separation reducing agent used for the purpose.

The present inventor has conducted intensive studies in order to solve the above problems. And a water-soluble vinyl copolymer having an oxyalkylene group or a polyoxyalkylene group, and having a hydrophobic hydrocarbon group having a specific carbon number in its molecular structure, a high-performance water reducing agent, a hydraulic substance, and water It has been found that a hydraulic composition containing as an essential component has excellent resistance to material separation, good fluidity, and easy preparation, and has completed the present invention.

That is, the present invention is a hydraulic composition shown in the following (1) to (3). (1) having a hydrocarbon group having 4 or more carbon atoms and an oxyalkylene group or a polyoxyalkylene group in a constituent unit of the polymer, and having a mortar flow value of 100 mm or less, and in a cement supernatant aqueous solution. (Meth) acrylic acid-based material separation reducing agent (a), high-performance water reducing agent (a), hydraulic substance (c) and water (d), which have two characteristics that the dissolution rate of the compound is 1% by weight or more. Hydraulic composition containing as a. (2) (Meth) acrylic acid-based material separation reducing agent (A)
Is a polymer (A) containing a structural unit (I) represented by the following general formula (1) as an essential structural unit.

General formula (1)

[0009]

Embedded image

(Wherein, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, m represents a number of 0 to 2, and R ³ O represents an oxyalkylene group having 2 to 18 carbon atoms.) Represents one or a mixture of two or more kinds, and in the case of two or more kinds, they may be added in a block form or in a random form, and n is the average number of moles of the oxyalkylene group added, and The above positive numbers are represented, and R ⁴ is a hydrocarbon group having 4 or more carbon atoms.) (3) (Meth) acrylic acid-based material separation reducing agent (A)
Is a polymer (B) containing a structural unit (II) represented by the following general formula (2) and a structural unit (III) represented by the following general formula (3) as essential structural units. The hydraulic composition according to the above (1).

General formula (2)

[0012]

Embedded image

(Wherein, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, m represents a number of 0 to 2, and R ⁷ O represents an oxyalkylene group having 2 to 18 carbon atoms.) Represents one or a mixture of two or more kinds, and in the case of two or more kinds, it may be added in a block form or in a random form, and p is the average number of moles of the oxyalkylene group added, and R ⁸ represents a hydrogen atom or a hydrocarbon group having 1 or more carbon atoms.) General formula (3)

[0014]

Embedded image

(Wherein R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a methyl group or (CH ₂ ) qCOOX)
R ¹² represents a hydrocarbon group having 4 or more carbon atoms, X represents hydrogen, a monovalent metal, a divalent metal, an ammonium group, an organic amine group or a hydrocarbon group, and q represents 0 to 2
Represents an integer. )

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the hydraulic composition according to the present invention will be described in detail. First, the hydraulic composition of the present invention,
(Meth) acrylic acid-based material separation reducing agent (a)
It contains a high-performance water reducing agent (a), a hydraulic substance (c) and water (d) as essential components.

The (meth) acrylic acid-based material separation reducing agent (A) has a hydrocarbon group having 4 or more carbon atoms and an oxyalkylene group or a polyoxyalkylene group in a structural unit of the polymer (meth). ) An acrylic acid polymer having the following properties (1) and (2).

Characteristics (1) Mortar flow value is 100 mm
It is as follows.

Property (2) The dissolution rate in an aqueous cement supernatant solution is 1% by weight or more.

The mortar flow value of the above-mentioned property (1) is an index of a performance capable of imparting fluidity to a hydraulic composition such as mortar, concrete, etc., that is, an index of a dispersion performance for a hydraulic substance. Is measured by the evaluation method (1).

Evaluation method (1) Ordinary Portland cement 4 temperature-controlled at 25 ° C.
00 parts by weight and 800 parts by weight of Toyoura standard sand are mixed with a Hobart mortar mixer (model number N-50, manufactured by Hobart Co.).
After kneading at a low speed for 0 second, 240 parts by weight of 25 ° C. ion-exchanged water containing 2.0 parts by weight (based on cement: 0.5% by weight) of a measurement sample ((meth) acrylic acid-based polymer) in terms of solid content. And kneading at medium speed for 3 minutes to obtain a mortar.

The obtained mortar is filled into a hollow cylinder placed on a horizontal table and having both an inner diameter and a height of 55 mm until fraying. This cylinder is gently lifted vertically, and then the mortar spread on the table and the major axis and the short axis of the mortar spread. The diameter is measured, and the average value is defined as a mortar flow value. The measurement of the mortar flow value is performed 5 minutes, 30 minutes, and 60 minutes after the start of kneading, and the larger value is defined as the maximum mortar flow value.

The evaluation method (1) has a correlation with a general slump value measuring method according to JIS A-1101 as a method for evaluating the fluidity of concrete, which is a typical hydraulic composition, and JIS A-1101. Is high, that is, when the dispersibility of the cement dispersant used is high, the mortar flow value in the evaluation method (1) shows a high value. For example, concrete prepared using a certain cement dispersant is JIS A-11.
In the case where the slump value according to No. 01 shows a high fluidity of about 18 to 20 cm, the mortar prepared by using the cement dispersant according to the evaluation method (1) is 100%.
The mortar flow value was higher than 1 mm, indicating that this cement dispersant had high dispersibility.

A (meth) acrylic acid polymer having a maximum mortar flow value of 100 mm or less, preferably 90 mm or less, more preferably 80 mm or less in the evaluation method (1) is effective as a material separation reducing agent. When the mortar flow value is more than 100 mm, the dispersing performance of the hydraulic material is too high, and it has dispersibility that can be used alone as a cement dispersant. In addition, the required material separation resistance cannot be obtained.

The dissolution rate of the above-mentioned property (2) in an aqueous solution of cement supernatant is an index of the solubility of the polymer in a hydraulic composition such as mortar, concrete, and the like. ).

Evaluation method (2) Ordinary Portland cement 1 temperature-controlled in an atmosphere of 25 ° C.
200 parts by weight of ion exchange water at 25 ° C. were added to 00 parts by weight,
The mixture is stirred for 10 minutes using a magnetic stirrer so that the cement particles are sufficiently in contact with water, and then left to stand for 10 minutes. The supernatant is suction-filtered using a filter paper, and the filtrate is further filtered through an aqueous filter having a pore size of 0.45 μm to obtain a cement supernatant aqueous solution. On the other hand, ion exchange water at 25 ° C. is added to the measurement sample ((meth) acrylic acid-based polymer) to prepare an aqueous solution having a solid content concentration of 5% (% by weight). This measurement sample ((meth) acrylic acid polymer)
Is added to 4 parts by weight of the aqueous cement supernatant solution and mixed well to prepare a sample aqueous solution. This sample aqueous solution was filtered through an aqueous filter having a pore size of 0.45 μm to collect a filtrate, and the amount of organic carbon in the filtrate was measured by organic carbon analysis (TOC). Alternatively, the dissolution rate (% by weight) in the aqueous solution of the cement supernatant is calculated by comparing the result of the analysis of the amount of organic carbon in the solid content (TOC) of the comparative copolymer.

The dissolution rate in the cement supernatant aqueous solution is 1% by weight or more, preferably 2% by weight or more, more preferably 3% by weight or more, further preferably 4% by weight or more, and most preferably 5% by weight or more. When the (meth) acrylic acid-based polymer is effective as a material separation reducing agent, and the dissolution rate in the cement supernatant aqueous solution is less than 1% by weight, the dissolution in a hydraulic composition such as mortar, concrete, etc. The required material separation resistance cannot be obtained because the property is too low.

As described above, in the (meth) acrylic acid-based polymer having a hydrocarbon group having 4 or more carbon atoms and an oxyalkylene group or a polyoxyalkylene group in the constituent units of the polymer, the cement dispersant It is used as the (meth) acrylic acid-based material separation reducing agent (A) of the present invention only when it does not have a high dispersing performance and has a certain level of solubility in a hydraulic composition. It is possible.

The (meth) acrylic acid-based material separation-reducing agent (A) contains 4 or more (preferably 5 or more, more preferably 6 or more, more preferably 8 or more, particularly preferably 8 or more, carbon atoms in the structural unit of the polymer. (Preferably 12 or more) (meth) acrylic acid-based polymer having a hydrocarbon group and an oxyalkylene group or a polyoxyalkylene group. The polymer is a (meth) acrylic acid-based polymer having a hydrocarbon group having 4 or more carbon atoms and an oxyalkylene group or a polyoxyalkylene group in a side chain of the polymer. It is sufficient that the side chain part has a hydrocarbon group having 4 or more carbon atoms and further has an oxyalkylene group or a polyoxyalkylene group in a constituent unit of the polymer, and a hydrocarbon group, an oxyalkylene group or The mode of bonding with the polyoxyalkylene group is not particularly limited. That is, in the case where a hydrocarbon group having 4 or more carbon atoms and an oxyalkylene group or a polyoxyalkylene group are present in a specific type of structural unit of the polymer, or a specific type of the polymer. It may be any case where a hydrocarbon group having 4 or more carbon atoms is present in the structural unit, and an oxyalkylene group or a polyoxyalkylene group is present in another specific type of structural unit. For example, an alkoxy (poly) alkylene glycol in which a hydrocarbon group having 4 or more carbon atoms is introduced into the terminal of an oxyalkylene group or a polyoxyalkylene group by an ether bond is used as the (meth) acrylic acid-based unit constituting the main chain. Polymers introduced by an ester bond or an amide bond; (poly) alkylene glycols having a hydrogen atom at the terminal or alkoxy (poly) alkylene glycols having a hydrocarbon group having 1 or more carbon atoms introduced at the terminal thereof through an ether bond. Introduced into the (meth) acrylic acid-based unit constituting the chain by an ester bond or an amide bond, and
Polymers in which a hydrocarbon group having 4 or more carbon atoms is introduced into a (meth) acrylic acid-based unit constituting a main chain via an ester bond or an amide bond without passing through an oxyalkylene group or a polyoxyalkylene group; Can be
The number of carbon atoms of the hydrocarbon group having 4 or more carbon atoms in the structural unit of the polymer of the (meth) acrylic acid-based material separation reducing agent (i) is preferably in the range of 4 to 30, more preferably 5 to 30.
The range of 30 to 30 is more preferable, the range of 6 to 30 is further preferable, the range of 8 to 30 is particularly preferable, and the range of 12 to 30 is preferable.
A range of 30 is most preferred.

Preferred examples of the (meth) acrylic acid-based material separation-reducing agent (A) include a polymer containing the structural unit (I) represented by the general formula (1) as an essential structural unit. A), and preferably further includes a structural unit (IV) represented by the following general formula (4) as an essential structural unit, and further includes a structural unit (V) represented by the following general formula (5). Or a structural unit (VI) derived from the monomer (f) described below.

General formula (4)

[0032]

Embedded image

(Wherein, R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, a methyl group or (CH ₂ ) rCOO
Y represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group or an organic amine group (preferably a monovalent metal, an ammonium group or an organic amine group), and r represents an integer of 0 to 2. In the case where two COOY groups are present, an anhydride may be formed. ) General formula (5)

[0034]

Embedded image

(Wherein, R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a methyl group, m represents a number of 0 to 2, and R ¹⁸ O represents an oxyalkylene group having 2 to 18 carbon atoms.) Represents one or a mixture of two or more kinds, and in the case of two or more kinds, they may be added in block form or in random form, and s is an average number of moles of oxyalkylene group added, and The above positive numbers are represented, and R ¹⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.) The ratio of each structural unit constituting the polymer (A) is such that the polymer (A) has the above-mentioned characteristic. It is not particularly limited as long as it is within the range having (1) and the property (2), but the structural unit (I) is 1% by weight or more (preferably 5% by weight or more of the whole polymer (A),
More preferably 10% by weight or more, further preferably 20% by weight.
% By weight, particularly preferably 30% by weight or more, and most preferably 40% by weight or more). As the ratio of each structural unit, the structural unit (I) / the structural unit (I
V) / Structural unit (V) / Structural unit (VI) = 1 to 99 /
The range of 1 to 99/0 to 80/0 to 70 (% by weight) is appropriate, and the structural unit (I) / the structural unit (IV) / the structural unit (V) / the structural unit (VI) = 5 to 98 / 2-95 / 0
The range of 70/0 to 60 (% by weight) is preferable, and the structural unit (I) / the structural unit (IV) / the structural unit (V) / the structural unit (VI) = 10 to 97/3 to 90/0 to 60 / 0-50
(% By weight) is more preferable, and the structural unit (I) / the structural unit (IV) / the structural unit (V) / the structural unit (VI) =
20-96 / 4-80 / 0-50 / 0-40 (% by weight)
Is more preferable, and the structural unit (I) / the structural unit (IV) / the structural unit (V) / the structural unit (VI) = 30 to
The range of 96/4 to 70/0 to 50/0 to 40 (% by weight) is particularly preferable, and the structural unit (I) / the structural unit (I)
V) / Structural unit (V) / Structural unit (VI) = 40 to 96
The most preferred range is / 4 to 60/0 to 40/0 to 30 (% by weight).

The polymer (A) contains, for example, a monomer (for example, a monomer (a) to be described later) which gives a structural unit (I) as an essential component, and a monomer which gives a structural unit (IV). (For example, it can be produced by copolymerizing a monomer component which may further contain a monomer (d) described below). The monomer component may further include a monomer (for example, a monomer (e) described later) that provides the structural unit (V), and a monomer that provides the structural unit (VI) (for example,
It may further contain a monomer (f) described below.

The polymer (A) is obtained by copolymerizing a (meth) acrylic acid-based monomer, that is, a monomer component containing any one of acrylic acid, methacrylic acid and crotonic acid as an essential component. At least a part of the carboxyl groups of the obtained copolymer may be directly esterified with an alkoxy (poly) alkylene glycol having a hydrocarbon group having 4 or more carbon atoms at one end.

Another preferred example of the (meth) acrylic acid-based material separation reducing agent (A) is the above-mentioned general formula (2)
And a polymer (B) containing, as an essential structural unit, a structural unit (II) represented by the following general formula (3) and a structural unit (III) represented by the above general formula (3). It is preferable to further include a structural unit (IV) represented by the following as an essential structural unit, and may also include a structural unit (VII) derived from a monomer (g) described below.

The ratio of each structural unit constituting the polymer (B) is not particularly limited as long as the polymer (B) has the above-mentioned properties (1) and (2).
I) is 1% by weight or more (preferably 2%) of the entire polymer (B).
% By weight or more, more preferably 5% by weight or more, further preferably 10% by weight or more, particularly preferably 15% by weight.
Or more, most preferably 20% by weight or more) and the structural unit (I
II) is 1% by weight or more (preferably 2% by weight or more, more preferably 5% by weight or more, further preferably 10% by weight or more, particularly preferably 15% by weight or more, most preferably 20% by weight or more of the whole polymer (B). % By weight or more). As the ratio of each structural unit, the structural unit (II)
/ Structural unit (III) / structural unit (IV) / structural unit (VII) = 1 to 98/1 to 98/1 to 98/0 to 70
(% By weight), and the structural unit (II) / the structural unit (III) / the structural unit (IV) / the structural unit (VI
I) = 2 to 97/2 to 97/1 to 96/0 to 50 (% by weight) are preferable, and the structural unit (II) / the structural unit (III) / the structural unit (IV) / the structural unit (VII) =
The range of 5 to 94/5 to 94/1 to 90/0 to 40 (% by weight) is more preferable, and the structural unit (II) / the structural unit (I
II) / Structural unit (IV) / Structural unit (VII) = 10
-88/10 to 88/2 to 80/0 to 30 (% by weight) is more preferable, and the structural unit (II) / the structural unit (III) / the structural unit (IV) / the structural unit (VII) =
The range of 15 to 83/15 to 78/2 to 60/0 to 30 (% by weight) is particularly preferred, and the structural unit (II) / the structural unit (III) / the structural unit (IV) / the structural unit (VI)
I) = 20-78 / 20-68 / 2-2-60 / 0-30
(% By weight) is most preferable.

The polymer (B) includes, for example, a structural unit (I)
The monomer giving I) (for example, monomer (b) described below)
And a monomer (for example, a monomer (d) described below) containing a monomer (for example, a monomer (c) described below) as an essential component and providing a structural unit (IV). ) Can be produced by copolymerizing a monomer component which may further contain a). The monomer component has a structural unit (V
It may further contain a monomer that gives II) (for example, a monomer (g) described later).

The polymer (B) is obtained by copolymerizing a (meth) acrylic acid monomer, that is, a monomer component containing any one of acrylic acid, methacrylic acid and crotonic acid as an essential component. The number of carbon atoms is at least 4 (preferably 5 or more,
More preferably, it may be produced by directly esterifying an alcohol having 6 or more, more preferably 8 or more, particularly preferably 12 or more) hydrocarbon group and alkoxy (poly) alkylene glycol.

In the general formulas (1), (2) and (5)
And R¹, R^Two, R^Five, R⁶, R¹⁶And R ¹⁷Is a hydrogen atom or
Represents a methyl group, and m represents a number of 0 to 2 (preferably 0)
And R^ThreeO, R⁷O and R¹⁸O is a carbon atom having 2 to 18 carbon atoms.
Represents one or a mixture of two or more xyalkylene groups;
However, when two or more types are added,
It may be added in a dam shape. n, p and s are oxya
The average number of moles of addition of the alkylene group, wherein one or more positive numbers are
Express. R^FourIs an alkyl group having 4 or more carbon atoms,
A phenyl group having 6 or more atoms, an alkylphenyl group,
Substituted with a nylalkyl group or an (alkyl) phenyl group
Aromatic having benzene ring such as phenyl group and naphthyl group
Group or a carbon source such as an alkenyl group having 4 or more carbon atoms
4 or more (preferably 5 or more, more preferably 6 or more
Above, more preferably 8 or more, particularly preferably 12 or more
Above), but within the range of carbon atoms
Is preferably in the range of 4 to 30, more preferably 5 to 30.
The range of 6 to 30 is more preferable, and the range of 8 to 30 is more preferable.
Is particularly preferable, and the range of 12 to 30 is most preferable.
Good. R⁸Is a hydrogen atom or a group having 1 or more carbon atoms
Alkyl group, phenyl group having 6 or more carbon atoms, alkyl
Phenyl group, phenylalkyl group, (alkyl) phenyl
Benzene such as phenyl and naphthyl substituted with
Ring-containing aromatic groups or alkenes having 2 or more carbon atoms
A hydrocarbon group having 1 or more carbon atoms such as a nyl group (preferably
A hydrocarbon group having 1 to 30 carbon atoms, more preferably carbon
A hydrocarbon group having 1 to 22 atoms, more preferably a carbon atom
A hydrocarbon group having 1 to 12 carbon atoms, particularly preferably a carbon atom
A hydrocarbon group having 1 to 6 carbon atoms, most preferably 1 carbon atom
To 3 hydrocarbon groups). R¹⁹Is a hydrogen atom, or
Is an alkyl group having 1 to 3 carbon atoms, or a carbon atom
A hydrocarbon group having 1 to 3 carbon atoms such as an alkenyl group having 3
(Preferably a hydrocarbon group having 1 to 3 carbon atoms, more preferably
Or a hydrocarbon group having 1 to 2 carbon atoms, most preferably
Methyl group).

In the general formula (3), R ⁹ , R ¹⁰ and R ^9
11 is each independently a hydrogen atom, a methyl group or (CH ₂ )
q represents a COOX group (preferably a hydrogen atom or a methyl group), and X represents hydrogen, a monovalent metal, a divalent metal, an ammonium group, an organic amine group or a hydrocarbon group (preferably a monovalent metal, ammonium group or an organic amine group). ), And q represents a number from 0 to 2 (preferably 0). R ¹² has a benzene ring such as an alkyl group having 4 or more carbon atoms, a phenyl group having 6 or more carbon atoms, an alkylphenyl group, a phenylalkyl group, a phenyl group substituted with an (alkyl) phenyl group, and a naphthyl group. Aromatic group or 4 carbon atoms
It represents a hydrocarbon group having 4 or more carbon atoms (preferably 5 or more, more preferably 6 or more, still more preferably 8 or more, particularly preferably 12 or more) such as the above alkenyl group. The range of 4 to 30 is preferable, the range of 5 to 30 is more preferable, the range of 6 to 30 is more preferable, the range of 8 to 30 is particularly preferable, and the range of 12 to 30 is most preferable.

The monomer (a) which provides the structural unit (I) used in the present invention includes 1-butanol, 1-pentanol, 1-hexanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, C4 to C30 saturated aliphatic alcohols such as lauryl alcohol, cetyl alcohol and stearyl alcohol; C4 to C30 unsaturated aliphatic alcohols such as oleyl alcohol; C4 to C4 such as cyclohexanol 3
0 alicyclic alcohols, phenol, phenylmethanol (benzyl alcohol), methylphenol (cresol), p-ethylphenol, dimethylphenol (xylenol), pt-butylphenol, nonylphenol, dodecylphenol, phenylphenol, naphthol, etc. Alkoxy (poly) obtained by adding an alkylene oxide having 2 to 18 carbon atoms to any of aromatic alcohols having 6 to 30 carbon atoms
An ester compound of an alkylene glycol and (meth) acrylic acid or crotonic acid may, for example, be mentioned.

Specific examples of the monomer (a) include 1-butoxy (poly) ethylene glycol mono (meth) acrylate, 2-butoxy (poly) ethylene glycol mono (meth) acrylate, and 2-methyl-1-propoxy. (Poly) ethylene glycol mono (meth) acrylate, 2-methyl-2-propoxy (poly) ethylene glycol mono (meth) acrylate, 1-pentyloxy (poly) ethylene glycol mono (meth) acrylate, 1-hexyloxy (poly ) Ethylene glycol mono (meth) acrylate, cyclohexyloxy (poly) ethylene glycol mono (meth) acrylate,
-Octyloxy (poly) ethylene glycol mono (meth) acrylate, 2-ethyl-1-hexyloxy (poly) ethylene glycol mono (meth) acrylate, nonylalkoxy (poly) ethylene glycol mono (meth) acrylate, lauryl alkoxy (poly) ) Ethylene glycol mono (meth) acrylate, cetyl alkoxy (poly) ethylene glycol mono (meth) acrylate, stearyl alkoxy (poly) ethylene glycol mono (meth) acrylate, phenoxy (poly)
Ethylene glycol mono (meth) acrylate, phenylmethoxy (poly) ethylene glycol mono (meth) acrylate, methylphenoxy (poly) ethylene glycol mono (meth) acrylate, p-ethylphenoxy (poly) ethylene glycol mono (meth) acrylate, dimethyl Phenoxy (poly) ethylene glycol mono (meth) acrylate, pt-butylphenoxy (poly) ethylene glycol mono (meth) acrylate, nonylphenoxy (poly) ethylene glycol mono (meth) acrylate, dodecylphenoxy (poly) ethylene glycol mono (Meth) acrylate, phenylphenoxy (poly) ethylene glycol mono (meth) acrylate, naphthoxy (poly) ethylene glycol mono (meth) acrylate Various alkoxy (poly) ethylene glycol monoacrylates; 1-butoxy (poly) propylene glycol mono (meth) acrylate, 2-butoxy (poly) propylene glycol mono (meth) acrylate, 2-methyl-1-propoxy (poly) Propylene glycol mono (meth) acrylate, 2-methyl-2-propoxy (poly) propylene glycol mono (meth) acrylate, 1-pentyloxy (poly) propylene glycol mono (meth) acrylate, 1-hexyloxy (poly) propylene glycol Mono (meth) acrylate, cyclohexyloxy (poly) propylene glycol mono (meth) acrylate, 1-octyloxy (poly) propylene glycol mono (meth) acrylate, 2-ethyl-1-hexyl Luoxy (poly) propylene glycol mono (meth) acrylate, nonylalkoxy (poly) propylene glycol mono (meth) acrylate, laurylalkoxy (poly) propylene glycol mono (meth) acrylate, cetyl alkoxy (poly) propylene glycol mono (meth) acrylate , Stearylalkoxy (poly) propylene glycol mono (meth) acrylate,
Phenoxy (poly) propylene glycol mono (meth)
Acrylate, phenylmethoxy (poly) propylene glycol mono (meth) acrylate, methylphenoxy (poly) propylene glycol mono (meth) acrylate, p-ethylphenoxy (poly) propylene glycol mono (meth) acrylate, dimethylphenoxy (poly) propylene glycol Mono (meth) acrylate,
pt-butylphenoxy (poly) propylene glycol mono (meth) acrylate, nonylphenoxy (poly) propylene glycol mono (meth) acrylate,
Various alkoxy (poly) propylene glycol mono (meth) such as dodecylphenoxy (poly) propylene glycol mono (meth) acrylate, phenylphenoxy (poly) propylene glycol mono (meth) acrylate, naphthoxy (poly) propylene glycol mono (meth) acrylate Acrylates; 1-butoxy (poly)
Ethylene (poly) propylene glycol mono (meth) acrylate, 1-butoxy (poly) ethylene (poly) butylene glycol mono (meth) acrylate, 1-pentyloxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate, 1 -Pentyloxy (poly) ethylene (poly) butylene glycol mono (meth) acrylate, 1-hexyloxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate, 1-hexyloxy (poly) ethylene (poly) butylene glycol Mono (meth) acrylate, cyclohexyloxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate, cyclohexyloxy (poly) ethylene (poly) butylene glycol mono (meth) acrylate 2-ethyl-1-hexyloxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate, 2-ethyl-1-hexyloxy (poly) ethylene (poly) butylene glycol mono (meth) acrylate, nonylalkoxy (poly) ) Ethylene (poly) propylene glycol mono (meth) acrylate, nonylalkoxy (poly) ethylene (poly) butylene glycol mono (meth) acrylate, lauryl alkoxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate, lauryl alkoxy ( Poly) ethylene (poly) butylene glycol mono (meth) acrylate, cetylalkoxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate, cetylalkoxy (poly) ethylene (poly ) Butylene glycol mono (meth) acrylate, stearylalkoxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate, stearylalkoxy (poly) ethylene (poly) butylene glycol mono (meth) acrylate, phenoxy (poly) ethylene (poly) ) Propylene glycol mono (meth) acrylate
Phenoxy (poly) ethylene (poly) butylene glycol mono (meth) acrylate, phenylmethoxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate, phenylmethoxy (poly) ethylene (poly) butylene glycol mono (meth) acrylate, Nonylphenoxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate, nonylphenoxy (poly) ethylene (poly) butylene glycol mono (meth) acrylate, naphthoxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate, Esterified product of (meth) acrylic acid and alcohol to which two or more kinds of alkylene oxides such as naphthoxy (poly) ethylene (poly) butylene glycol mono (meth) acrylate are added Various alkoxy polyalkylene glycol mono (meth) acrylate; and the like.

The average addition mole number n of the oxyalkylene group of the monomer (a) and the structural unit (I) is a positive number of 1 or more. On the other hand, since the reactivity decreases as the average number of moles increases, a positive number of 1 to 500 is preferable,
Is more preferable, a positive number of 2 to 300 is further preferable, and a positive number of 10 to 300 is particularly preferable.
A positive number of 300 is most preferred.

The carbon number of the oxyalkylene group R ³ O of the monomer (a) and the structural unit (I) is suitably in the range of 2 to 18, preferably 2 to 8, and more preferably 2 to 8. The range of 4 is more preferable. As for any two or more kinds of alkylene oxide adducts selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc., any of random addition, block addition, alternate addition and the like can be used.

As the monomer (a) or the structural unit (I), 1
When only the types are used, it is preferable to include an oxyethylene group as an essential component in the oxyalkylene group in order to secure a balance between hydrophilicity and hydrophobicity.
The above is preferably an oxyethylene group.

Further, two or more kinds of these monomers (a) or structural units (I) may be used. Or 1
It is preferable that an oxyethylene group is contained as an essential component in the oxyalkylene group of the monomer (a) or the structural unit (I).

In the general formula (1), by using two or more kinds of monomers (a) or structural units (I) having different carbon atoms of R ⁴ , high material separation resistance and high fluidity are obtained. And a material separation reducing agent which provides a hydraulic composition having an excellent self-filling property. In this case, the difference in the number of carbon atoms of each R ⁴ is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. Further, one or more types of the monomer (a) or the structural unit (I) in which the number of carbon atoms of R ⁴ is in the range of 4 to 11, and the number of carbon atoms of R ⁴ is 12 or more (preferably 12 to 30) Use of at least one of the monomer (a) or the structural unit (I) and one or more of the monomers (a) or the structural units (I) having different carbon atoms of R ^4. Is particularly preferred.

The monomer (b) that provides the structural unit (II) used in the present invention includes a (meth) acrylic acid, crotonic acid or fatty acid having 2 carbon atoms to be dehydrogenated (oxidized).
To 18 alkylene oxides, or methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, lauryl alcohol, cetyl alcohol And saturated aliphatic alcohols having 1 to 30 carbon atoms such as stearyl alcohol; unsaturated aliphatic alcohols having 3 to 30 carbon atoms such as allyl alcohol, methallyl alcohol, crotyl alcohol and oleyl alcohol; cyclohexanol and the like Alicyclic alcohols having 3 to 30 carbon atoms, phenol, phenylmethanol (benzyl alcohol), methylphenol (cresol), p-ethylphenol, dimethylphenol (xylenol), p-
alkoxy (poly) alkylene obtained by adding an alkylene oxide having 2 to 18 carbon atoms to any of aromatic alcohols having 6 to 30 carbon atoms such as t-butylphenol, nonylphenol, dodecylphenol, phenylphenol, and naphthol Examples include ester compounds of glycols and (meth) acrylic acid or crotonic acid. In general formula (2), alkoxy (poly), which corresponds to the case where R ⁸ is a hydrocarbon group,
An ester compound of an alkylene glycol and (meth) acrylic acid or crotonic acid is preferred.

Specific examples of the monomer (b) include methoxy (poly) ethylene glycol mono (meth) acrylate, ethoxy (poly) ethylene glycol mono (meth)
Acrylate, 1-propoxy (poly) ethylene glycol mono (meth) acrylate, 2-propoxy (poly) ethylene glycol mono (meth) acrylate, esterified product of acrylic acid with allyl alcohol to which ethylene oxide has been added, ethylene oxide has been added Various alkoxy (poly) ethylene glycol mono (meth) acrylates such as esterified products of methallyl alcohol and acrylic acid, and esterified products of crotyl alcohol and acrylic acid added with ethylene oxide; methoxy (poly) propylene glycol mono ( Meth) acrylate, ethoxy (poly) propylene glycol mono (meth) acrylate, 1-propoxy (poly) propylene glycol mono (meth) acrylate, 2-propoxy (poly) propylene Recohol mono (meth) acrylate, esterified product of allylic alcohol with propylene oxide and acrylic acid, esterified product of methallyl alcohol with propylene oxide added with acrylic acid, crotyl alcohol with propylene oxide added Various alkoxy (poly) propylene glycol mono (meth) acrylates such as esterified products with acrylic acid; methoxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate, methoxy (poly) ethylene (poly) butylene glycol mono ( Meta)
Acrylate, ethoxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate, ethoxy (poly) ethylene (poly) butylene glycol mono (meth) acrylate, 1-propoxy (poly) ethylene (poly) propylene glycol mono (meth) Acrylate, 1-propoxy (poly) ethylene (poly) butylene glycol mono (meth) acrylate, 2-propoxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate, 2-propoxy (poly) ethylene (poly) butylene glycol Mono (meth) acrylate, esterified product of (meth) acrylic acid with allyl alcohol to which ethylene oxide and propylene oxide or ethylene oxide and butylene oxide are added, ethylene oxide and propylene Oxide or ethylene oxide and a methallyl alcohol obtained by adding butylene oxide (meth) ester of acrylic acid, crotyl alcohol obtained by adding ethylene oxide and propylene oxide or ethylene oxide and butylene oxide (meth)
Various alkoxypolyalkylene glycol mono (meth) acrylates such as an esterified product of (meth) acrylic acid and an alcohol to which two or more kinds of alkylene oxides such as an esterified product of acrylic acid are added; The above-mentioned various alkoxy (poly) alkylene glycol mono (meth) acrylates; (poly) ethylene glycol mono (meth) acrylate, (poly) propylene glycol mono (meth) acrylate, (poly) ethylene (poly) ) Various (poly) alkylene glycol mono (meth) acrylates, such as butylene glycol mono (meth) acrylate;

Oxygen of monomer (b) and structural unit (II)
The average number of added moles p of the silalkylene group is a positive number of 1 or more.
However, the hydrophilicity decreases as the average number of moles decreases.
On the other hand, the reactivity decreases as the average number of moles increases.
For lowering, a positive number of 1 to 500 is preferable, and
Is more preferable, and a positive number of 2 to 300 is more preferable.
And a positive number of 10 to 300 is particularly preferable.
A positive number of 300 is most preferred. The monomer (b) and the structure
Hydrocarbon group R of unit (II)⁸The carbon number of
Therefore, the hydrophobicity increases, so the balance between hydrophilicity and hydrophobicity
For the purpose of securing, the average addition mole number p of this oxyalkylene group
Must be increased, and the hydrocarbon group R ⁸Has 4 carbon atoms
In the above cases, p is preferably a positive number of 10 or more.
And a hydrocarbon group R⁸When p has 2 or more carbon atoms, p is 2
It is preferably a positive number of 0 or more, and the hydrocarbon group R⁸of
When the number of carbon atoms is 10 or more, p is a positive number of 30 or more
Is preferred.

The carbon number of the oxyalkylene group R ⁷ O in the monomer (b) and the structural unit (II) is suitably in the range of 2 to 18, preferably 2 to 8, and more preferably 2 to 8. 4
Is more preferable. As for any two or more kinds of alkylene oxide adducts selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc., any of random addition, block addition, alternate addition and the like can be used.

When only one type is used as the monomer (b) or the structural unit (II), the oxyalkylene group must contain an oxyethylene group as an essential component in order to secure a balance between hydrophilicity and hydrophobicity. It is preferable that 50 mol% or more is an oxyethylene group.

The monomer (b) or the structural unit (I)
Two or more types of I) may be used, and when two or more types of the monomer (b) or the structural unit (II) are used, any one of them may be used.
It is preferable that the oxyalkylene group of the monomer (b) or the structural unit (II) contains an oxyethylene group as an essential component.

The monomer (c) which provides the structural unit (III) used in the present invention includes 1-butanol, 1-pentanol, 1-hexanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, C4 to C30 saturated aliphatic alcohols such as lauryl alcohol, cetyl alcohol and stearyl alcohol; C4 to C30 unsaturated aliphatic alcohols such as oleyl alcohol; C4 such as cyclohexanol
To 30 alicyclic alcohols, phenol, phenylmethanol (benzyl alcohol), methylphenol (cresol), p-ethylphenol, dimethylphenol (xylenol), pt-butylphenol,
C6-C30 aromatic alcohols such as nonylphenol, dodecylphenol, phenylphenol and naphthol, and unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid, or maleic acid, itaconic acid and citraconic acid And ester compounds with unsaturated dicarboxylic acids such as fumaric acid.

From the viewpoint of copolymerizability with the monomer (b),
As the monomer (c), it is preferable to use an ester compound of the above alcohol having 4 to 30 carbon atoms and an unsaturated monocarboxylic acid such as (meth) acrylic acid and crotonic acid.

Specific examples of the monomer (c) include butyl (meth) acrylate, 1-pentyl (meth) acrylate, 1-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate. , Various alkyl (meth) acrylates, such as cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth) acrylate;
Various alkyl fumarates such as (di) 2-ethylhexyl fumarate; various alkyl fumarates such as (di) butyl fumarate and (di) 2-ethylhexyl fumarate;

R of monomer (c) and structural unit (III)
^{As for 12} , when the number of carbon atoms is 3 or less, a hydrocarbon group having 4 or more carbon atoms is appropriate because a hydrophobicity is insufficient and a separation reducing effect cannot be obtained, and a hydrocarbon group having 5 or more carbon atoms is preferable. More preferred, on the other hand, as the number of carbon atoms increases, the hydrophobicity increases, and it becomes difficult to balance the hydrophilicity and the hydrophobicity of the copolymer. Therefore, the number of carbon atoms is preferably 5 to 30, More preferably 5 to 22, further preferably 6 to 18, particularly preferably 6 to 12.
Range. Incidentally, two or more of these monomers (c) or structural units (III) may be used.

Specific examples of the monomer (d) that provides the structural unit (IV) used in the present invention include acrylic acid, methacrylic acid, crotonic acid and their unsaturated monocarboxylic acid monomers. Salts, ammonium salts, amine salts and the like. Further, as unsaturated dicarboxylic acid monomers, maleic acid, itaconic acid, citraconic acid, fumaric acid, or metal salts thereof, ammonium salts, amine salts, and the like, and further, as anhydrides thereof, maleic anhydride,
Examples include itaconic anhydride and citraconic anhydride. Among them, unsaturated monocarboxylic acid monomers are preferable, and (meth) acrylic acid and salts thereof are particularly preferable. still,
Two or more of these monomers (d) may be used in combination.

The monomer (e) that gives the structural unit (V) used in the present invention includes a compound having 2 to 2 carbon atoms to dehydrogenate (oxidize) a (meth) acrylic acid, crotonic acid or fatty acid.
An alkylene oxide adduct of 18 or a saturated aliphatic alcohol having 1 to 3 carbon atoms such as methanol, ethanol, 1-propanol and 2-propanol, and an unsaturated aliphatic alcohol having 3 carbon atoms such as allyl alcohol (Poly) obtained by adding an alkylene oxide having 2 to 18 carbon atoms to any of the groups
An ester compound of an alkylene glycol and a (meth) acrylic acid or crotonic acid may be mentioned. In the general formula (5), an alkoxy (poly) alkylene glycol corresponding to the case where R ¹⁹ is a hydrocarbon group is used. When,
An ester compound with (meth) acrylic acid or crotonic acid is preferred.

Specific examples of the monomer (e) include methoxy (poly) ethylene glycol mono (meth) acrylate, ethoxy (poly) ethylene glycol mono (meth)
Acrylate, 1-propoxy (poly) ethylene glycol mono (meth) acrylate, 2-propoxy (poly) ethylene glycol mono (meth) acrylate, and various alkoxy (poly) such as esterified products of acrylic acid with allyl alcohol to which ethylene oxide is added. ) Ethylene glycol mono (meth) acrylates; methoxy (poly) propylene glycol mono (meth) acrylate, ethoxy (poly) propylene glycol mono (meth) acrylate, 1-propoxy (poly) propylene glycol mono (meth) acrylate, 2- Various alkoxy (poly) propylene glycos such as propoxy (poly) propylene glycol mono (meth) acrylate and esterified product of acrylic acid and allyl alcohol with propylene oxide added Rumono (meth) acrylates; methoxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate, methoxy (poly) ethylene (poly) butylene glycol mono (meth) acrylate, ethoxy (poly) ethylene (poly) propylene glycol mono (Meth) acrylate, ethoxy (poly) ethylene (poly) butylene glycol mono (meth)
Acrylate, 1-propoxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate,
1-propoxy (poly) ethylene (poly) butylene glycol mono (meth) acrylate, 2-propoxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate, 2-propoxy (poly) ethylene (poly) butylene glycol mono ( (Meth) acrylate, an alcohol having two or more alkylene oxides added thereto, such as an esterified product of (meth) acrylic acid and allyl alcohol having ethylene oxide and propylene oxide or ethylene oxide and butylene oxide, and (meth) acrylic acid. Various alkoxypolyalkylene glycol mono (meth) acrylates such as esterified products; (poly) ethylene glycol mono (meth) acrylate, (poly) propylene glycol mono (meth) acrylate, (poly) ethyl Down (poly) such as butylene glycol mono (meth) acrylate, various types of (poly) alkylene glycol mono (meth) acrylate; and the like.

The average addition mole number p of the oxyalkylene group of the monomer (e) and the structural unit (V) is a positive number of 1 or more. On the other hand, since the reactivity decreases as the average number of moles increases, a positive number of 1 to 500 is preferable,
Is more preferable, a positive number of 2 to 300 is further preferable, and a positive number of 10 to 300 is particularly preferable.
A positive number of 300 is most preferred.

The carbon number of the oxyalkylene group R ¹⁹ O in the monomer (e) and the structural unit (V) is suitably in the range of 2 to 18, preferably 2 to 8, and more preferably 2 to 8. A range of 4 is more preferred. As for any two or more kinds of alkylene oxide adducts selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like, any of random addition, block addition, alternate addition and the like can be used. In order to ensure the balance between the properties and the hydrophobicity, it is preferable that the oxyalkylene group contains an oxyethylene group as an essential component, and it is more preferable that 50 mol% or more is an oxyethylene group. Further, two or more of these monomers (e) or structural units (V) may be used.

The monomer (g) which gives the structural unit (VII) in the polymer (B) of the present invention is a monomer copolymerizable with other monomer components, Specific examples of the half-esters and diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid and alcohols having 1 to 3 carbon atoms; the unsaturated dicarboxylic acids and 1 to 30 carbon atoms Half amide with amine,
Diamide; a half ester or diester 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 a diester of the unsaturated dicarboxylic acid; Half-esters and diesters of 2 to 18 glycols or polyalkylene glycols having 2 to 500 moles of these glycols added; maleamic acid and glycols having 2 to 18 carbon atoms or poly (2 to 500 moles of these glycols added) Half amide with alkylene glycol; triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) propylene (Poly) alkylene glycol di (meth) acrylates such as recall di (meth) acrylate; bifunctional (meth) acrylates such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane di (meth) acrylate A) acrylates; (poly) alkylene glycol dimaleates such as triethylene glycol dimaleate and polyethylene glycol dimaleate; vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acrylic Roxypropyl 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 And unsaturated sulfonic acids such as 2-methylpropanesulfonic acid (meth) acrylamide and styrenesulfonic acid, and their monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts; methyl (meth) acrylate, ethyl ( Esters of unsaturated monocarboxylic acids such as meth) acrylate, propyl (meth) acrylate, glycidyl (meth) acrylate, methyl crotonate, ethyl crotonate, propyl crotonate and alcohols having 1 to 3 carbon atoms Amides of unsaturated monocarboxylic acids and amines having 1 to 30 carbon atoms such as methyl (meth) acrylamide; vinyl aromatics such as styrene, α-methylstyrene, vinyltoluene and p-methylstyrene; Alkanediol mono (meth) acrylates such as butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, and 1,6-hexanediol mono (meth) acrylate;
Dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;
(Meth) acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide, N, N
Unsaturated amides such as dimethyl (meth) acrylamide; unsaturated cyanates such as (meth) acrylonitrile and α-chloroacrylonitrile; unsaturated esters such as vinyl acetate and vinyl propionate; aminoethyl (meth) acrylate; Methylaminoethyl (meth) acrylate,
Unsaturated amines such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dibutylaminoethyl (meth) acrylate and vinylpyridine; divinyl aromatics such as divinylbenzene; triallyl cyanurate and the like Allyls such as (meth) allyl alcohol and glycidyl (meth) allyl ether; unsaturated amino compounds such as dimethylaminoethyl (meth) acrylate; methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether and methoxypolyethylene glycol Vinyl ethers or allyl ethers such as mono (meth) allyl ether and polyethylene glycol mono (meth) allyl ether; polydimethylsiloxane propylaminomaleamide Polydimethylsiloxane aminopropyleneaminomaleamic acid, polydimethylsiloxane-bis- (propylaminomaleamic acid), polydimethylsiloxane-bis- (dipropyleneaminomaleamic acid), polydimethylsiloxane- (1-propyl-3) -Acrylate), polydimethylsiloxane- (1-propyl-3-methacrylate), polydimethylsiloxane-bis- (1-propyl-3-acrylate), polydimethylsiloxane-bis- (1-propyl-3-methacrylate), etc. Siloxane derivatives; unsaturated phosphoric acid esters such as 2-acryloyloxyethyl phosphate and 2-methacryloyloxyethyl phosphate; and the like, and one or more of these can be used.

The monomer (f) which gives the structural unit (VI) in the polymer (A) of the present invention is a monomer copolymerizable with other monomer components, and Specific examples of the above include, in addition to the various monomers mentioned as specific examples of the monomer (g), the various monomers mentioned as specific examples of the monomer (c). One or more of these can be used.

To obtain the polymer (A) or the polymer (B),
What is necessary is just to polymerize the said monomer component using a polymerization initiator. The polymerization can be performed by a method such as polymerization in a solvent or bulk polymerization. The polymerization in the solvent can be carried out batchwise or continuously, and the solvent used in this case is water; lower alcohols such as methyl alcohol, ethyl alcohol and 2-propanol; benzene, toluene,
Aromatic or aliphatic hydrocarbons such as xylene, cyclohexane and n-hexane; ester compounds such as ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone;
And the like. Raw material monomer and obtained polymer (A)
From the solubility of the polymer and the polymer (B) and the convenience at the time of using the polymer (A) and the polymer (B), water and the number of carbon atoms are 1 to 4
At least one selected from the group consisting of lower alcohols
Preferably, a seed is used. In that case, the number of carbon atoms is 1
Among the lower alcohols of 4, methyl alcohol, ethyl alcohol, 2-propanol and the like are particularly effective.

When the polymerization is carried out in an aqueous medium, a water-soluble polymerization initiator such as ammonium or alkali metal persulfate or hydrogen peroxide is used as the polymerization initiator. At this time, an accelerator such as sodium bisulfite, Mohr's salt, ascorbic acid (salt), or Rongalit can be used in combination. For polymerization using lower alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, ester compounds or ketone compounds as solvents, peroxides such as benzoyl peroxide and lauroyl peroxide; hydroperoxides such as cumene hydroperoxide; An azo compound such as bisisobutyronitrile is used as a polymerization initiator. In this case, an accelerator such as an amine compound can be used in combination. Further, when a water-lower alcohol mixed solvent is used, it can be appropriately selected from the above-mentioned various polymerization initiators or a combination of the polymerization initiator and the accelerator. The polymerization temperature is appropriately determined depending on the solvent and the polymerization initiator used, but is usually in the range of 0 to 120 ° C.

The bulk polymerization is carried out using a polymerization initiator such as a peroxide such as benzoyl peroxide or lauroyl peroxide; a hydroperoxide such as cumene hydroperoxide; an azo compound such as azobisisobutyronitrile at 50 to 200 ° C. Within the temperature range of

For controlling the molecular weight of the resulting polymer (A) or polymer (B), hypophosphorous acid (salt) or a thiol-based chain transfer agent can be used in combination. Thiol chain transfer agents used in this case, the general formula HS-R ²⁰ -
Eg (wherein, R ²⁰ represents an alkyl group having 1 to 2 carbon atoms, E represents an —OH, —COOM, —COOR ²¹ or SO ₃ M group, M represents a hydrogen atom, a monovalent metal, It represents a valence metal, an ammonium group or an organic amine group, R ²¹
Represents an alkyl group having 1 to 10 carbon atoms, and g represents 1 to
Represents an integer of 2. ), For example, mercaptoethanol, thioglycerol, thioglycolic acid, 2
-Mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, and the like, and one or more of these can be used.

The polymer (A) or polymer (B) thus obtained can be used as it is as a material separation reducing agent (A), but when the solubility in water is insufficient, In order to improve solubility in water and handle in the form of an aqueous solution containing no organic solvent, inorganic substances such as hydroxides, chlorides and carbon salts of monovalent and divalent metals; ammonia; organic amines (preferably Is a material separation reducing agent (a) which is obtained by neutralizing a polymer salt obtained by neutralization with an alkaline substance such as sodium hydroxide, potassium hydroxide or other monovalent metal hydroxide.
It is preferred to use

The weight average molecular weight of the polymer (A) and the polymer (B) used as the material separation reducing agent (A) of the present invention is suitably in the range of 500 to 500,000. It is preferably in the range of 3,000 to 300,000. In particular, when the weight average molecular weight is less than 500,
It is not preferable because the material separation reducing performance of the material separation reducing agent (A) is reduced.

High performance water reducing agent (A) used in the present invention
Is not particularly limited, a carboxylic acid-based or sulfonic acid-based high-performance water reducing agent can be used, and a polycarboxylic acid-based high-performance water reducing agent, which is a compound having a carboxylic acid group, a sulfonic acid group. A known high-performance water reducing agent such as a formaldehyde cocondensate-based or aromatic sulfonic acid-based high-performance water reducing agent, which is a compound having the following, can be used, and a plurality of these known high-performance water reducing agents can be used in combination.

The polycarboxylic acid-based high-performance water reducing agent is obtained by polymerizing one or more monomers selected from the group consisting of unsaturated monocarboxylic acids and derivatives thereof, unsaturated dicarboxylic acids and derivatives thereof. The resulting polymer or copolymer can be used. For example, as disclosed in JP-A-7-267705, a copolymer of a polyalkylene glycol mono (meth) acrylate compound and a (meth) acrylic compound is used as the component (a). As a component (b), a copolymer of a polyalkylene glycol mono (meth) allyl ether-based compound and maleic anhydride and / or a hydrolyzate thereof and / or a salt thereof, as a component (c) Copolymer of polyalkylene glycol mono (meth) allyl ether compound and maleic acid ester of polyalkylene glycol compound and / Or cement dispersing agent consisting of a salt thereof, a copolymer of the component A as Patent Publication No. 2508113 (meth) polyalkylene glycol esters of acrylic acid and (meth) acrylic acid (salt),
A concrete admixture comprising a specific polyethylene glycol polypropylene glycol compound as the B component and a specific surfactant as the C component, JP-A-62-2169.
50 (poly) glycol (meth) acrylic acid polyethylene (propylene) glycol ester or polyethylene (propylene) glycol mono (meth) allyl ether, (meth) allyl sulfonic acid (salt), (meth) acrylic acid (salt) As described in JP-A-1-226557, polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) allylsulfonic acid (salt),
Copolymer of (meth) acrylic acid (salt), Tokuho 5
From polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) allylsulfonic acid (salt) or p- (meth) allyloxybenzenesulfonic acid (salt) or (meth) acrylic acid (salt) as in 36376 A copolymer of polyethylene glycol mono (meth) allyl ether and maleic acid (salt) as disclosed in JP-A-4-149056, a polyethylene glycol ester of (meth) acrylic acid as disclosed in JP-A-5-170501, (Meth) allylsulfonic acid (salt), (meth) acrylic acid (salt), alkanediol mono (meth) acrylate, polyalkylene glycol mono (meth) acrylate, α, β-unsaturated monomer having an amide group in the molecule Copolymer consisting of a polymer, polyethylene glycol mono (JP-A-6-191918) (Meth) allyl ether, polyethylene glycol mono (meth) acrylate, (meth)
Alkyl acrylate, (meth) acrylic acid (salt), (meth) allyl sulfonic acid (salt) or p-
A copolymer comprising (meth) allyloxybenzenesulfonic acid (salt), a copolymer of alkoxypolyalkylene glycol monoallyl ether and maleic anhydride as described in JP-A-5-43288, or a hydrolyzate or a salt thereof; Copolymers of polyethylene glycol monoallyl ether, maleic acid, and monomers copolymerizable with these monomers, or salts or esters thereof, as in JP-B-58-38380, as in JP-B-59-18338. Polyalkylene glycol mono (meth) acrylate monomers, (meth) acrylate monomers, and copolymers composed of monomers copolymerizable with these monomers, (Meth) acrylic acid ester having a sulfonic acid group and a monomer copolymerizable therewith if necessary. A copolymer or a salt thereof, an esterification reaction product of a copolymer of alkoxypolyalkylene glycol monoallyl ether with maleic anhydride and a polyoxyalkylene derivative having an alkenyl group at a terminal, as described in JP-A-6-271347, Kaihei 6-29855
5, esterification product of a copolymer of an alkoxypolyalkylene glycol monoallyl ether and maleic anhydride and a polyoxyalkylene derivative having a hydroxyl group at a terminal, and 3-methyl-3 as disclosed in JP-A-62-68806.
Alkenyl ether-based monomers obtained by adding ethylene oxide or the like to a specific unsaturated alcohol such as -buten-1-ol, unsaturated carboxylic acid-based monomers, and monomers copolymerizable with these monomers. Or a known high-performance water reducing agent such as a copolymer thereof or a salt thereof.

The formaldehyde co-condensate-based or aromatic sulfonic acid-based high-performance water reducing agent is selected from naphthalene, melamine, phenol, urea and aniline selected from the group consisting of methylol compounds and sulfonates.
A formaldehyde condensate of a compound of at least one kind can be used. For example, a naphthalene sulfonate formaldehyde condensate (for example, Mighty 150: manufactured by Kao Corporation), a melamine sulfonate formaldehyde condensate (for example,
Mighty 150-V2: manufactured by Kao Corporation), JP-A 1-1
Known high-performance water reducing agents such as 13419, such as aminoarylsulfonic acid-phenol-formaldehyde cocondensate, phenolsulfonate formaldehyde condensate, and polystyrenesulfonate.

The hydraulic substance (C) used in the present invention is:
It is a substance that has the property of hardening by hydration reaction.Specifically, ordinary, early-strength, and various types of Portland cement, such as ultra-high-strength, blast furnace slag,
Fly ash, Cinder ash, Clinker ash, Husk ash, or various mixed cements mixed with silica, white cement, ultra-rapid hardening cement, and hydraulic cement such as alumina cement, and hydraulic materials such as gypsum can be used. .

The hydraulic composition of the present invention comprises the above (meth) acrylic acid-based material separation reducing agent (A), a high-performance water reducing agent (A), a hydraulic substance (C) and water (D) as essential components. Includes, for example, cement paste, mixed with aggregates such as sand and gravel and used as mortar, concrete, self-leveling material, plaster, etc., and high fluidity such as high fluidity concrete, self-compacting concrete, etc. It is also effective for mortar and concrete that require properties. Furthermore, there is no drawback that the viscosity becomes extremely high unlike the concrete to which a thickener such as cellulose has been added, which has been conventionally used to increase the resistance to material separation. It is also effective for wet-sprayed fresh concrete and high-strength wet-sprayed ready-mixed concrete used in the spraying concrete method.

The mixing ratio of the (meth) acrylic acid-based material separation reducing agent (a) and the high-performance water reducing agent (a) in the hydraulic composition of the present invention is not particularly limited. The compounding weight ratio of the material separation reducing agent (A) to the high-performance water reducing agent (A) can be used in the range of 1:99 to 99: 1, but is preferably in the range of 5:95 to 95: 5. ,
The range of 5:95 to 90:10 is more preferable, and 10: 9.
The range of 0 to 80:20 is more preferable. When used for mortar or concrete using hydraulic cement as the hydraulic substance (c), the (meth) acrylic acid-based material separation reducing agent (a) is 0% based on the weight of the hydraulic substance (c). 0.001 to 5%, preferably 0.01 to 3%, more preferably 0.02 to 2%, and the high-performance water reducing agent (a) is added to the hydraulic fluid (c) in an amount of 0.1 to 5%. 01-1
0%, preferably 0.02-6%, more preferably 0.1%.
The range is from 0.5 to 3%. If the amount of the (meth) acrylic acid-based material separation reducing agent (a) is too small, or if the amount of the high-performance water reducing agent (a) is too large, the fluidity becomes too high, causing material separation. Not preferred. On the other hand, if the blending amount of the (meth) acrylic acid-based material separation reducing agent (a) is too large, or the blending amount of the high-performance water reducing agent (a) is too small, the fluidity becomes too low and the filling becomes poor. Is not preferred.

In the hydraulic composition of the present invention, 1 m
There is no limitation on the amount of hydraulic substance (c) used per ³ or the amount of water (d) used (unit water amount), but a unit water amount of 100
185 kg / m ³ , amount of hydraulic material used 250-800
kg / m ³ , water / hydraulic weight ratio = 0.10-0.
7, preferably a unit water volume of 120 to 175 kg / m ³ , an amount of hydraulic material to be used of 270 to 800 kg / m ³ , and a water / hydraulic material weight ratio of 0.2 to 0.65 are recommended. High-strength concrete that can be used widely and has a large unit cement amount, unit cement amount is 300 kg / m
It is effective for any poorly mixed concrete of ³ or less.

The hydraulic composition of the present invention may contain a known cement water reducing agent having a low water reducing performance which is not classified as a high-performance water reducing agent. Examples thereof include salts, oxycarboxylates, and polyol derivatives, and a plurality of these known cement dispersants can be used in combination.

Further, the hydraulic composition of the present invention may contain other known cement additives (materials) as exemplified in the following (1) to (20). (1) Water-soluble polymer: unsaturated carboxylic acid polymer such as polyacrylic acid (sodium), polymethacrylic acid (sodium), polymaleic acid (sodium), sodium salt of acrylic acid / maleic acid copolymer; polyethylene Polyoxyethylene or polyoxypropylene polymers such as glycol and polypropylene glycol or copolymers thereof; nonionics such as methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxyethylcellulose, and hydroxypropylcellulose Cellulose ethers; methyl cellulose, ethyl cellulose, hydroxyethyl cellulose,
Hydroxy atoms of some or all of the hydroxyl groups of alkylated or hydroxyalkylated derivatives of polysaccharides such as hydroxypropylcellulose have a hydrophobic substituent having a hydrocarbon chain having 8 to 40 carbon atoms as a partial structure, and a sulfonic acid group. Or a polysaccharide derivative substituted with an ionic hydrophilic substituent containing a salt thereof as a partial structure; nonionic cellulose ethers; yeast glucan, xanthan gum, β-1.
Polysaccharides produced by microbial fermentation such as tri-glucans (either linear or branched, for example, curdlan, baramiron, bakiman, scleroglucan, laminaran, etc.); polyacrylamide; polyvinyl Alcohol; starch; starch phosphate; sodium alginate; gelatin; copolymers of acrylic acid having an amino group in the molecule and quaternary compounds thereof. (2) Polymer emulsion: a copolymer of various vinyl monomers such as alkyl (meth) acrylate. (3) retarders: gluconic acid, glucoheptonic acid, arabonic acid, malic acid or citric acid, and oxycarboxylic acids such as inorganic salts or organic salts such as sodium, potassium, calcium, magnesium, ammonium and triethanolamine; Acids; monosaccharides such as glucose, fructose, galactose, saccharose, xylose, apiose, ribose, isomerized sugars, oligosaccharides such as disaccharides and trisaccharides, oligosaccharides such as dextrin, and polysaccharides such as dextran; Saccharides such as molasses; sugar alcohols such as sorbitol; magnesium silicofluoride; phosphoric acid and salts or borates thereof; aminocarboxylic acids and salts thereof; alkali-soluble proteins; humic acid; tannic acid; Polyhydric alcohols such as glycerin;
Aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta
(Methylene phosphonic acid) and phosphonic acids such as alkali metal salts and alkaline earth metal salts thereof and derivatives thereof. (4) Fasteners / promoters: Soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide, calcium iodide; chlorides such as iron chloride and magnesium chloride; sulfates; potassium hydroxide; Sodium hydroxide; carbonate; thiosulfate; formate such as formic acid and calcium formate; alkanolamine; alumina cement; calcium aluminate silicate; (5) Mineral oil-based antifoaming agents: kerosene, liquid paraffin and the like. (6) Oil-based antifoaming agents: animal and vegetable oils, sesame oil, castor oil, alkylene oxide adducts thereof and the like. (7) Fatty acid antifoaming agents: oleic acid, stearic acid, alkylene oxide adducts thereof and the like. (8) Fatty acid ester antifoaming agents: glycerin monoricinoleate, alkenyl succinic acid derivatives, sorbitol monolaurate, sorbitol trioleate, natural wax and the like. (9) oxyalkylene antifoaming agents: polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adduct; diethylene glycol heptyl ether;
Polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene 2-ethylhexyl ether, having 12 to 12 carbon atoms
(Poly) oxyalkyl ethers such as oxyethyleneoxypropylene adducts to higher alcohols of No. 14; (poly) oxyalkylene (alkyl) aryl ethers such as polyoxypropylene phenyl ether and polyoxyethylene nonylphenyl ether; 4,7,9
-Tetramethyl-5-decyne-4,7-diol, 2,
5-dimethyl-3-hexyne-2,5-diol, 3-
Acetylene ethers obtained by addition-polymerizing an alkylene oxide to an acetylene alcohol such as methyl-1-butyn-3-ol; (poly) oxyalkylene fatty acid esters such as diethylene glycol oleate, diethylene glycol laurate, and ethylene glycol distearate (Poly) oxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan trioleate; (poly) such as sodium polyoxypropylene methyl ether sulfate and sodium polyoxyethylene dodecyl phenol ether sulfate Oxyalkylene alkyl (aryl) ether sulfates; (poly) oxyethylene stearyl phosphate, etc. (Poly) oxyalkylene alkyl phosphoric acid esters; polyoxyethylene such as polyoxyethylene lauryl amine (poly) oxyalkylene alkyl amines; polyoxyalkylene amide. (10) Alcohol antifoaming agents: octyl alcohol, hexadecyl alcohol, acetylene alcohol, glycols and the like. (11) Amide-based antifoaming agent: acrylate polyamine and the like. (12) Phosphate ester antifoam: tributyl phosphate,
Sodium octyl phosphate and the like. (13) Metal soap-based antifoaming agents: aluminum stearate, calcium oleate and the like. (14) silicone antifoaming agent: dimethyl silicone oil,
Silicone paste, silicone emulsion, organically modified polysiloxane (polyorganosiloxane such as dimethylpolysiloxane), fluorosilicone oil and the like. (15) AE agent: resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, ABS (alkylbenzene sulfonic acid), L
AS (linear alkylbenzene sulfonic acid), alkane sulfonate, polyoxyethylene alkyl (phenyl)
Ether, polyoxyethylene alkyl (phenyl) ether sulfate or salt thereof, polyoxyethylene alkyl (phenyl) ether phosphate or salt thereof, protein material, alkenyl sulfosuccinic acid, α-olefin sulfonate and the like. (16) Other surfactants: aliphatic monohydric alcohols having 6 to 30 carbon atoms in a molecule such as octadecyl alcohol and stearyl alcohol, and 6 to 30 carbon atoms in a molecule such as abiethyl alcohol Alicyclic 1
6 to 6 in the molecule of polyhydric alcohol, dodecyl mercaptan, etc.
Monovalent mercaptans having 30 carbon atoms, nonylphenols and the like, and alkylphenols having 6 to 30 carbon atoms, dodecylamine and the like in the molecule have 6 to 3 carbon atoms.
Polyalkylene oxide obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to a carboxylic acid having 6 to 30 carbon atoms in a molecule such as an amine having 0 carbon atoms or lauric acid or stearic acid in an amount of 10 mol or more. Derivatives; alkyl diphenyl ether sulfonates, which may have an alkyl group or an alkoxy group as a substituent, and two phenyl groups having a sulfone group are ether-bonded; various anionic surfactants; alkyl amine acetate, alkyl Various cationic surfactants such as trimethylammonium chloride; various nonionic surfactants; various amphoteric surfactants and the like. (17) Waterproofing agents: fatty acids (salts), fatty acid esters, oils and fats, silicon, paraffin, asphalt, wax and the like. (18) Rust inhibitors: nitrites, phosphates, zinc oxide and the like. (19) Crack reducing agent: polyoxyalkyl ether and the like. (20) Expansive materials: ettringite, lime, etc.

Other known cement additives (materials) include cement wetting agents, thickening agents, coagulants, drying shrinkage reducing agents, strength enhancers, self-leveling agents, rust inhibitors, coloring agents, and fungicides. , Pozzolans, zeolites and the like, and the hydraulic composition may contain a plurality of these known cement additives (materials).

Particularly preferred embodiments include the following 1) to
4).

1) A combination comprising two components of the hydraulic composition of the present invention and an oxyalkylene-based antifoaming agent.
The weight ratio of the oxyalkylene-based antifoaming agent is 0.01 to 10% by weight based on the total amount of the (meth) acrylic acid-based material separation reducing agent (A) and the high-performance water reducing agent (A). % Is preferred.

2) A combination comprising two components of the hydraulic composition of the present invention and lignin sulfonate as essential components. still,
The weight ratio of the ligninsulfonate is preferably in the range of 1 to 90% by weight based on the total amount of the (meth) acrylic acid-based material separation reducing agent (A) and the high-performance water reducing agent (A). The range of 5 to 80% by weight is more preferable.

3) A combination comprising two components of the hydraulic composition of the present invention and a retarder. In addition, as a retarder,
Oxycarboxylic acids such as gluconic acid (salt) and citric acid (salt), sugars such as glucose, sugar alcohols such as sorbitol, phosphonic acids such as aminotri (methylenephosphonic acid) and the like can be used. Incidentally, the compounding weight ratio of the retarder is (meth) acrylic acid-based material separation reducing agent (A)
0.1 to 50 with respect to the total amount of
% By weight, more preferably from 1 to 30% by weight.

4) A combination comprising two components of the hydraulic composition of the present invention and an accelerator. In addition, as an accelerator,
Soluble calcium salts such as calcium chloride, calcium nitrite, and calcium nitrate, chlorides such as iron chloride and magnesium chloride, thiosulfates, and formate salts such as formic acid and calcium formate can be used. The mixing weight ratio of the accelerator was 0.1 to the total amount of the (meth) acrylic acid-based material separation reducing agent (A) and the high-performance water reducing agent (A).
The range is preferably from 90 to 90% by weight, more preferably from 1 to 80% by weight.

[0089]

The present invention will be described more specifically with reference to the following examples. In the examples, unless otherwise specified,% means% by weight,
In addition, parts are parts by weight, and the weight average molecular weight is
It represents the weight average molecular weight in terms of polyethylene glycol by gel permeation chromatography (GPC). Production Example 1 Production of Material Separation Reducing Agent (1) 89.6 parts of methanol was charged into a glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, and the inside of the reactor was stirred. It replaced with nitrogen and heated to 65 degreeC under nitrogen atmosphere. Next, 75 parts of lauryl alkoxy polyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 45), methacrylic acid 1
4.9 parts, ion-exchanged water 81.7 parts, methanol 8.2
Part and a monomer solution obtained by mixing 0.11 part of 3-mercaptopropionic acid as a chain transfer agent was dropped in 4 hours,
An initiator solution consisting of 1.0 part of ammonium persulfate, 14.5 parts of ion-exchanged water and 14.5 parts of methanol was dropped in 5 hours from the start of dropping the monomer solution. Thereafter, the temperature was maintained at 65 ° C. for 1 hour to complete the polymerization reaction, neutralized with a 30% aqueous sodium hydroxide solution, and then methanol was distilled off to obtain a copolymer aqueous solution having a weight average molecular weight of 36,100. A material separation reducing agent (1) corresponding to the polymer (A) of the present invention was obtained. Production Example 2 Production of Material Separation Reducing Agent (2) 390 parts of ion-exchanged water was charged into a glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, and the inside of the reactor was stirred. The atmosphere was replaced with nitrogen and heated to 80 ° C. in a nitrogen atmosphere. Next, 50 parts of lauryl alkoxy polyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 75), methacrylic acid 1
0 parts, 90 parts of ion-exchanged water, and 3- as a chain transfer agent
A monomer aqueous solution obtained by mixing 0.14 parts of mercaptopropionic acid was dropped in 4 hours, and an initiator aqueous solution composed of 0.7 parts of ammonium persulfate and 59.3 parts of ion-exchanged water was dropped in 5 hours from the start of dropping the monomer aqueous solution. . afterwards,
Subsequently, the temperature was maintained at 80 ° C. for 1 hour to complete the polymerization reaction, and the mixture was neutralized with a 30% aqueous sodium hydroxide solution to give a polymer (A) of the present invention comprising a copolymer aqueous solution having a weight average molecular weight of 34,500. The corresponding material separation reducing agent (2) was obtained. Production Example 3 Production of Material Separation Reducing Agent (3) 119.5 parts of ion-exchanged water was charged into a glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, and the reactor was stirred. The inside was replaced with nitrogen and heated to 80 ° C. in a nitrogen atmosphere. Next, 55.1 parts of phenoxy polyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 6) and methacrylic acid 4.
9 parts, 90 parts of ion-exchanged water, and 3- as a chain transfer agent
A monomer aqueous solution obtained by mixing 0.45 parts of mercaptopropionic acid was dropped in 4 hours, and an initiator aqueous solution comprising 0.7 parts of ammonium persulfate and 29.3 parts of ion-exchanged water was dropped in 5 hours from the start of dropping the monomer aqueous solution. . afterwards,
Subsequently, the temperature was maintained at 80 ° C. for 1 hour to complete the polymerization reaction, and the mixture was neutralized with a 30% aqueous sodium hydroxide solution to give a polymer (A) of the present invention comprising a copolymer aqueous solution having a weight average molecular weight of 40,500. The corresponding material separation reducing agent (3) was obtained. Production Example 4 Production of Material Separation Reducing Agent (4) 89.5 parts of methanol was charged into a glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, and the inside of the reactor was stirred. It replaced with nitrogen and heated to 65 degreeC under nitrogen atmosphere. Next, 46.9 parts of laurylalkoxy polyethylene glycol monomethacrylate (average number of moles of ethylene oxide 25), 28.2 parts of methoxy polyethylene glycol monomethacrylate (average number of moles of ethylene oxide 23), 14.9 parts of methacrylic acid Then, a monomer solution obtained by mixing 51.1 parts of ion-exchanged water, 38.8 parts of methanol and 0.50 part of 3-mercaptopropionic acid as a chain transfer agent was added dropwise over 4 hours, and 1.0 part of ammonium persulfate and 1.0 parts of ion-exchanged water were added. 1
An initiator solution consisting of 4.5 parts and 14.5 parts of methanol was dropped in 5 hours from the start of dropping the monomer solution. Thereafter, the temperature was maintained at 65 ° C. for 1 hour to complete the polymerization reaction. After neutralization with a 30% aqueous sodium hydroxide solution, methanol was distilled off, and the weight average molecular weight was 36,800.
A material separation reducing agent (4) corresponding to the polymer (A) of the present invention comprising an aqueous copolymer solution of the above was obtained. Production Example 5 Production of Material Separation Reducing Agent (5) A glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser was charged with 210.0 parts of methanol and 164.4 parts of ion-exchanged water. Then, the inside of the reaction vessel was replaced with nitrogen under stirring, and heated to 65 ° C. in a nitrogen atmosphere. Next, 150.0 parts of laurylalkoxy polyethylene glycol monomethacrylate (average number of moles of ethylene oxide 25), 60.0 parts of methoxy polyethylene glycol monomethacrylate (average number of moles of ethylene oxide 23), 71.7 parts of methacrylic acid ,
A monomer solution obtained by mixing 60.4 parts of ion-exchanged water and 0.74 parts of 3-mercaptopropionic acid as a chain transfer agent was added dropwise over 4 hours, and 6.9 parts of sodium persulfate and 93.1 parts of ion-exchanged water were added. Was dropped in 5 hours from the start of the dropping of the monomer solution. Thereafter, the temperature was maintained at 65 ° C. for 1 hour, and the polymerization reaction was completed.
After neutralization with a 0% aqueous sodium hydroxide solution, methanol was distilled off to obtain a material separation reducing agent (5) corresponding to the polymer (A) of the present invention comprising a copolymer aqueous solution having a weight average molecular weight of 53,600. Was. Production Example 6 Production of material separation reducing agent (6) 6-propanol 63.0 was placed in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser.
And 99.4 parts of ion-exchanged water were charged, the inside of the reaction vessel was replaced with nitrogen under stirring, and heated to 65 ° C. under a nitrogen atmosphere. Next, 29.3 parts of stearylalkoxy polyethylene glycol monomethacrylate (average number of moles of ethylene oxide 25), 29.3 parts of 1-pentyloxy polyethylene glycol monomethacrylate (average number of moles of ethylene oxide 25), methoxy polyethylene glycol A monomer solution obtained by mixing 13.5 parts of monomethacrylate (average number of added moles of ethylene oxide: 23), 14.3 parts of methacrylic acid, 20.9 parts of ion-exchanged water, and 0.12 part of 3-mercaptopropionic acid as a chain transfer agent. Was added dropwise over 4 hours, and sodium persulfate was added.
An initiator solution composed of 1 part and 27.9 parts of ion-exchanged water was dropped in 5 hours from the start of dropping the monomer solution. Thereafter, the temperature was maintained at 65 ° C. for 1 hour, and the polymerization reaction was completed. After that, 2-propanol was distilled off, and the polymer (A) of the present invention comprising an aqueous solution of a copolymer having a weight average molecular weight of 60,600 was obtained. (6) was obtained. Production Example 7 Production of Material Separation Reducing Agent (7) 2-Propanol 181. was placed in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser.
3 parts, ion-exchanged water 6.1 parts, methoxy polyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 23) 22.7 parts, lauryl methacrylate 22.7 parts, methacrylic acid 36.2 parts, and as a chain transfer agent 0.28 parts of 3-mercaptopropionic acid was charged, the inside of the reaction vessel was replaced with nitrogen under stirring, and heated to 65 ° C under a nitrogen atmosphere. Next, an initiator solution composed of 2.1 parts of sodium persulfate and 27.9 parts of ion-exchanged water was added dropwise over 5 hours. Thereafter, the temperature was maintained at 65 ° C. continuously for 1 hour to complete the polymerization reaction, and after distilling off 2-propanol, the mixture was neutralized with a 30% aqueous sodium hydroxide solution.
A material separation reducing agent (7) corresponding to the polymer (B) of the present invention, comprising a copolymer aqueous solution having a weight average molecular weight of 32,000, was obtained. Production Example 8 Production of Comparative Copolymer (1) 74.9 parts of methanol was charged into a glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, and the inside of the reactor was stirred. It replaced with nitrogen and heated to 65 degreeC under nitrogen atmosphere. Next, 58.8 parts of lauryl alkoxy polyethylene glycol monomethacrylate (average number of moles of added ethylene oxide: 25), 31.2 parts of methacrylic acid, 64 parts of ion-exchanged water, 26 parts of methanol, and 3-mercaptopropionic acid as a chain transfer agent 0.
The mixture was added dropwise over 4 hours, and an initiator solution comprising 1.0 part of ammonium persulfate, 22 parts of ion-exchanged water and 22 parts of methanol was added dropwise over 5 hours from the start of the addition of the monomer solution. Thereafter, the temperature was maintained at 65 ° C. for 1 hour to complete the polymerization reaction. After neutralization with a 30% aqueous sodium hydroxide solution, methanol was distilled off, and the aqueous solution was composed of a copolymer aqueous solution having a weight average molecular weight of 42,300. A comparative copolymer (1) was obtained. Production Example 9 Production of Comparative Copolymer (2) 2-propanol 179. was placed in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube, and a reflux condenser.
7 parts, ion-exchanged water 14.8 parts, methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 23) 58.5 parts, lauryl methacrylate 6.8 parts, methacrylic acid 19.7 parts, and as a chain transfer agent 0.33 parts of 3-mercaptopropionic acid was charged, the inside of the reaction vessel was replaced with nitrogen under stirring, and heated to 65 ° C under a nitrogen atmosphere. Next, an initiator solution composed of 2.1 parts of sodium persulfate and 27.9 parts of ion-exchanged water was added dropwise over 5 hours. Thereafter, the temperature was maintained at 65 ° C. continuously for 1 hour to complete the polymerization reaction, neutralized with a 30% aqueous sodium hydroxide solution, and then 2-propanol was distilled off.
A comparative copolymer (2) consisting of an aqueous solution of a copolymer having a weight average molecular weight of 36,400 was obtained. Production Example 10 Production of high-performance water reducing agent (1) 848.3 parts of ion-exchanged water was charged into a glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, and the reactor was stirred. The inside was replaced with nitrogen and heated to 80 ° C. in a nitrogen atmosphere. Next, 275.6 parts of methoxypolyethylene glycol monomethacrylate (average number of moles of added ethylene oxide: 75), methacrylic acid 2
A monomer aqueous solution obtained by mixing 4.4 parts, 200 parts of ion-exchanged water, and 1.7 parts of 3-mercaptopropionic acid as a chain transfer agent was dropped into the reaction vessel over 4 hours, and 3.4 parts of ammonium persulfate and ion were added. An aqueous initiator solution consisting of 146.6 parts of exchanged water was dropped into the reaction vessel over 5 hours from the start of dropping the aqueous monomer solution. Thereafter, the temperature was maintained at 80 ° C. for 1 hour to complete the polymerization reaction, thereby obtaining a high-performance water reducing agent (1) comprising a copolymer aqueous solution having a weight average molecular weight of 56,000. Production Example 11 Production of high-performance water reducing agent (2) 746.6 parts of ion-exchanged water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, and the reaction vessel was stirred. The inside was replaced with nitrogen and heated to 80 ° C. in a nitrogen atmosphere. Next, 275.6 parts of methoxypolyethylene glycol monomethacrylate (average number of added moles of ethylene oxide: 150), 24.4 parts of methacrylic acid, 300 parts of ion-exchanged water, and 3.4 parts of 3-mercaptopropionic acid as a chain transfer agent. Was dropped into the reaction vessel over 4 hours, and an initiator aqueous solution consisting of 3.4 parts of ammonium persulfate and 146.6 parts of ion-exchanged water was added for 5 hours from the start of dropping of the monomer aqueous solution.
It was dropped into the reaction vessel over time. Thereafter, the temperature was maintained at 80 ° C. for 1 hour to complete the polymerization reaction, thereby obtaining a high-performance water reducing agent (2) comprising a copolymer aqueous solution having a weight average molecular weight of 45,500. Production Example 12 Production of high-performance water reducing agent (3) 847.7 parts of ion-exchanged water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, and the reaction vessel was stirred. The inside was replaced with nitrogen and heated to 80 ° C. in a nitrogen atmosphere. Next, 275.6 parts of 1-butoxypolyethylene glycol monomethacrylate (average number of moles of added ethylene oxide: 75), 24.4 parts of methacrylic acid, 200 parts of ion-exchanged water, and 3-mercaptopropionic acid as a chain transfer agent. The monomer aqueous solution obtained by mixing 3 parts was dropped into the reaction vessel over 4 hours, and an initiator aqueous solution consisting of 3.4 parts of ammonium persulfate and 146.6 parts of ion-exchanged water was reacted for 5 hours from the start of dropping the monomer aqueous solution. It was dropped into the container. Thereafter, the temperature was maintained at 80 ° C. continuously for 1 hour to complete the polymerization reaction,
Consisting of an aqueous solution of a copolymer having a weight average molecular weight of 37,300,
A high performance water reducing agent (3) was obtained. Production Example 13 Production of high-performance water reducing agent (6) 1698 parts of water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube, and a reflux condenser.
The atmosphere in the reaction vessel was replaced with nitrogen under stirring, and 80
Heated to ° C. Next, a monomer aqueous solution obtained by mixing 1668 parts of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide of 25), 332 parts of methacrylic acid, 500 parts of ion-exchanged water and 16.7 parts of 3-mercaptopropionic acid as a chain transfer agent. Is dropped into the reaction vessel over 4 hours, and ammonium persulfate 2 is added.
An aqueous initiator solution consisting of 3 parts and 207 parts of water was dropped into the reaction vessel over 5 hours from the start of dropping the aqueous monomer solution.
Thereafter, the temperature was maintained at 80 ° C. for 1 hour to complete the polymerization reaction, and then neutralized with a 30% aqueous solution of sodium hydroxide to obtain a high-performance water reducing agent comprising a copolymer aqueous solution having a weight average molecular weight of 24,000 ( 6) was obtained. (High-performance water reducing agent used other than the above) High-performance water reducing agent (4) According to Example 1 of JP-A-H10-236858, 3
-Unsaturated alcohol / maleic acid obtained by adding 48 mol of ethylene oxide to methyl-3-buten-1-ol =
A copolymer having a weight average molecular weight of 25,300, produced using 87.5 / 12.5 (weight ratio). High performance water reducing agent (5) Naphthalene sulfonate formaldehyde condensate (trade name: Mighty 150, manufactured by Kao Corporation).

Evaluation Test of Material Separation-Reducing Agent Using the material separation-reducing agent of the present invention obtained in the above Production Examples or the comparative copolymer, evaluation tests of the properties (1) and (2) were carried out by the following methods. went.

Evaluation test of property (1) [Evaluation method (1)] 400 parts by weight of ordinary Portland cement manufactured by Chichibu Onoda Cement (Taiheiyo Cement) and 800 parts by weight of standard sand from Toyoura were heated at 25 ° C. After kneading at a low speed for 30 seconds with a Hobart mortar mixer (model number N-50, manufactured by Hobart) at 25 ° C. in an atmosphere, the material separation-reducing agent of the present invention or the comparative copolymer is 2.0 wt. Mortar was obtained by adding 240 parts by weight of ion-exchanged water at 25 ° C. containing 0.5 parts by weight (based on cement: 0.5% by weight) and kneading at medium speed for 3 minutes.

The obtained mortar was filled into a hollow cylinder placed on a horizontal table and having both an inner diameter and a height of 55 mm until it was worn out. This cylinder was gently lifted vertically, and then the mortar spread on the table and the longer and shorter mortar. The diameter was measured, and the average value was taken as the mortar flow value. This mortar flow value was measured 5 minutes, 30 minutes, and 60 minutes after the start of kneading, and the larger value was taken as the maximum mortar flow value. Table 1 shows the results.

Evaluation test of characteristic (2) [Evaluation method (2)] 200 parts of 25 ° C. ion-exchanged water was added to 100 parts by weight of ordinary Portland cement manufactured by Chichibu Onoda Cement (Taiheiyo Cement), which was temperature-controlled in a 25 ° C. atmosphere. Then, the mixture is stirred for 10 minutes using a magnetic stirrer so that the water-soluble component in the cement particles is sufficiently eluted in water, and then left to stand for 10 minutes. The supernatant is filtered through a filter paper (Advantech Toyosha,
After suction filtration using a quantitative filter paper 5C), the filtrate was further filtered through a 0.45 μm pore size aqueous filter (Chromatodisk 25A, manufactured by Kurabo Industries, sold by GL Sciences) to obtain an aqueous cement supernatant solution. Separately, ion-exchanged water at 25 ° C. was added to the material separation reducing agent or the comparative copolymer of the present invention to prepare an aqueous solution having a solid content of 5% (% by weight). One part by weight of the aqueous solution containing the material separation reducing agent or the comparative copolymer of the present invention was added to 4 parts by weight of the above cement supernatant aqueous solution, and mixed well to prepare a sample aqueous solution. The aqueous sample solution was filtered through a 0.45 μm pore size aqueous filter (Chromatodisk 25A, manufactured by Kurabo Co., Ltd., sold by GL Sciences) to collect a filtrate. The amount of organic carbon in the filtrate was analyzed by organic carbon analysis (TO
C) The dissolution rate (wt%) in the cement supernatant aqueous solution measured by C) and compared with the organic carbon content analysis (TOC) result in the solid content of the material separation reducing agent or the comparative copolymer not subjected to the above treatment Was calculated. Table 1 shows the results.

[0094]

[Table 1]

From Table 1, it can be seen that the material separation reducing agent (1) of the present invention was used.
(7) or the maximum mortar flow value of the mortar containing the comparative copolymer (1) was less than 80 mm. Therefore, these polymers have almost no dispersibility in cement and can be used alone. It can be seen that high fluidity cannot be obtained. On the other hand, in the case of the high-performance water reducing agent (3), the structural unit contains the structural unit (I) essential for the polymer (A), and the maximum mortar flow value of the mortar containing the structural unit exceeds 100 mm. As a result, the dispersibility in cement was high, and it was found that the above property (1) was not satisfied. Similarly, the comparative copolymer (2) structurally contains the structural units (II) and (III) essential to the polymer (B), but the maximum mortar flow of the mortar containing the structural units. It can be seen that the value exceeds 100 mm, the dispersibility in cement is high, and the above property (1) is not satisfied. On the other hand, regarding the dissolution rate in the cement supernatant aqueous solution, the material separation reducing agents (1) to (7), the high-performance water reducing agent (3), and the comparative copolymer (2) of the present invention are all 5% by weight or more. It can be seen that the comparative copolymer (1) was hardly dissolved at less than 1% by weight, whereas

Mortar Test A mortar using the above-mentioned material separation reducing agent or comparative copolymer of the present invention in combination with the above-mentioned high-performance water reducing agent and a mortar containing the above-mentioned high-performance water reducing agent alone were prepared. And the amount of separated water were measured.

The mortar test was performed in a 25 ° C. atmosphere using a material adjusted to 25 ° C.
400 parts by weight of ordinary Portland cement made by Chichibu Onoda Cement (Taiheiyo Cement), 800 parts by weight of Toyoura standard sand,
It is 250 parts by weight of ion-exchanged water containing the material separation reducing agent or the comparative copolymer of the present invention and the above-mentioned high-performance water reducing agent or ion-exchanged water containing only the above-mentioned high-performance water reducing agent.
Table 2 shows the amounts of the respective material separation reducing agents, comparative copolymers and high-performance water reducing agents added (% by weight of solids based on cement).

The mortar was prepared by kneading only cement and sand at a low speed for 30 seconds with a Hobart type mortar mixer (model N-50, manufactured by Hobart), then adding the above ion-exchanged water and kneading at a medium speed for 3 minutes. Prepared. The obtained mortar is filled into a hollow cylinder placed on a horizontal table and having a 55 mm inner diameter and a height of 55 mm.
After a minute, the cylinder was gently lifted vertically and the major axis and minor axis of the mortar spread on the table were measured, and the average value was taken as the mortar flow value. On the other hand, 500 ml of the prepared mortar was filled into a 500 ml glass measuring cylinder and allowed to stand, and the amount of water separated on the upper part of the mortar after 15 minutes, 30 minutes, 45 minutes and 60 minutes was measured and defined as the amount of separated water. Table 2 shows the results.

[0099]

[Table 2]

Table 2 shows that the comparative copolymer and the high-performance water reducing agent
Alternatively, the mortar to which only the high-performance water reducing agent is added can obtain high fluidity but has a large amount of separated water, whereas the mortar to which the material separation reducing agent and the high-performance water reducing agent of the present invention are added has excellent fluidity. It shows that the material has good resistance to material separation because it has water resistance and the amount of separated water is small. In particular, in Example 10 in which the material separation reducing agent (6) and the high-performance water reducing agent (6) were combined, the amount of separated water was 0 despite the high mortar flow value.
It can be seen that excellent material separation resistance was obtained while maintaining high fluidity.

The material separation reducing agent of the present invention is neutralized with an aqueous sodium hydroxide solution after completion of the polymerization reaction.
Since all of them could be obtained as aqueous solutions after the alcohol was distilled off, measurement and blending of mortar were easy.

[0102]

As described above, the hydraulic composition according to the present invention exhibits high material separation resistance and excellent fluidity,
Because it is easy to prepare, it can be used for self-compacting high-fluidity concrete, and the method of using a hydraulic composition such as mortar and concrete and the method of construction are greatly improved.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hirokatsu Kawakami 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (72) Mari Masanaga Inventor 5-8 Nishi-Maburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd.

Claims (3)

[Claims] 1. A polymer having a hydrocarbon group having 4 or more carbon atoms, an oxyalkylene group or a polyoxyalkylene group in a constituent unit thereof, and having a mortar flow value of 100.
(meth) acrylic acid-based material separation-reducing agent (a), high-performance water-reducing agent (a), and hydraulic substance ( A hydraulic composition containing (c) and water (d) as essential components. 2. A polymer (A) comprising a (meth) acrylic acid-based material separation-reducing agent (A) containing a structural unit (I) represented by the following general formula (1) as an essential structural unit. The hydraulic composition according to claim 1. General formula (1) (Wherein, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, m represents a number of 0 to 2, and R ³ O
Represents one or a mixture of two or more oxyalkylene groups having 2 to 18 carbon atoms, and in the case of two or more, they may be added in block form or in random form, and n is oxyalkylene The average number of moles of the group, which represents a positive number of 1 or more, and R ⁴ represents a hydrocarbon group having 4 or more carbon atoms. ) 3. The (meth) acrylic acid-based material separation-reducing agent (A) comprises a structural unit (I) represented by the following general formula (2):
I) and the structural unit (II) represented by the following general formula (3)
The hydraulic composition according to claim 1, which is a polymer (B) containing I) as an essential constituent unit. General formula (2) (Wherein, in the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, m represents a number of 0 to 2, and R ⁷ O
Represents one or a mixture of two or more oxyalkylene groups having 2 to 18 carbon atoms. In the case of two or more, they may be added in blocks or in random, and p is oxyalkylene. It is an average number of moles of the group, and represents one or more positive numbers, and R ⁸ represents a hydrogen atom or a hydrocarbon group having one or more carbon atoms. ) General formula (3) (Wherein, R ⁹ , R ¹⁰ , and R ¹¹ each independently represent a hydrogen atom, a methyl group, or a (CH ₂ ) qCOOX group;
R ¹² represents a hydrocarbon group having 4 or more carbon atoms, X represents hydrogen, a monovalent metal, a divalent metal, an ammonium group, an organic amine group or a hydrocarbon group, and q represents an integer of 0 to 2. )