JP2003226565A - Concrete composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a concrete composition in which air contents caused by the extension of kneading time are not increased on its production and entrained air contents can be stably retained, and from which a hardened material having excellent strength and durability can be formed. <P>SOLUTION: The concrete composition contains a polyoxyalkylene based compound, cement, water, a fine aggregate, and a coarse aggregate as essential components. In the polyoxyalkylene based compound, provided that the total additional molar number of oxyethylene groups in oxyalkylene groups is defined as u, and the total additional molar number of ≥3C oxyalkylene groups is defined as v, the relation of 0.15<u/(u+v)<0.9 is satisfied, and the polyoxyalkylene based compound has at least one aliphatic hydrocarbon group in which five or more carbon atoms are continuously bonded in the molecule. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a concrete composition. More specifically, the present invention relates to a concrete composition containing cement, water, fine aggregate and coarse aggregate as essential components and giving a cured product excellent in strength and durability.

[0002]

2. Description of the Related Art Concrete compositions include cement, water,
It is produced by mixing fine aggregate and coarse aggregate, and gives a cured product having excellent strength and durability as compared with paste and mortar among cement compositions, so that it can be used for building outer wall materials, building structures, etc. Widely used for various purposes. In such a concrete composition, the performance of the cured product will be improved by reducing the amount of unit water contained therein, but in the recent concrete industry, improvement of the strength and durability of concrete structures is strongly demanded. Therefore, reducing the amount of unit water is an important issue.

Admixtures for enhancing air entrainment and fluidity are usually added to such concrete compositions. The task of an admixture in a concrete composition is to achieve sufficient dispersibility even when the water content of the concrete composition is reduced, to ensure its fluidity and workability, and to improve durability and strength by reducing water and at the same time This is to obtain a good concrete composition while maintaining stable dispersibility. In recent years, the importance of such an admixture has been recognized, and technological innovation has been actively carried out.
Especially for polycarboxylic acid type dispersants, since they exhibit higher water reducing performance than conventional naphthalene type dispersants,
Many are being considered. When such a dispersant is used, the air entrainment becomes high and the bubble diameter becomes large. Therefore, it is carried out in combination with an AE agent in order to entrain fine fine bubbles and improve the freeze-thaw property. ing.

However, when a polycarboxylic acid type dispersant and an AE agent are used in combination, the amount of entrained air gradually increases as the concrete is continuously kneaded, which makes it difficult to obtain the desired concrete strength. Although it is possible to temporarily reduce the amount of entrained air by using a conventional defoaming agent, even in this case, the amount of entrained air increases as kneading continues. In addition, since it is difficult to add a defoaming agent immediately before placing concrete, considering the workability at the site, it is required to add the defoaming agent during concrete production. Particularly when the addition of the AE agent is indispensable as a measure against freezing and thawing, or when kneading is continued for a long time during transportation, the problem of increasing the amount of entrained air is serious.

By the way, it has been studied to use an alkylene oxide adduct of a specific compound in a concrete composition or the like. JP-A-60-27638 discloses that an amine compound is added with 20 to 300 moles of alkylene oxide, which necessarily contains ethylene oxide and propylene oxide, per one active hydrogen, and a molecular length of 6,000 to.
Regarding a cement dispersant containing 2,000,000 polyether polyol or polyether polyol derivative as an essential component, polyethyleneimine, ethylenediamine or diethylenetriamine, to which ethylene oxide and propylene oxide or, in addition thereto, styrene oxide are added is essential. A cement dispersant as a component is disclosed.

International Publication No. 17128 Pamphlet (2
000) relates to a mixture containing a liquefying agent of a polycarboxylic acid salt for an inorganic building material such as cement and a butoxylated polyalkylenepolyamine or a salt thereof used for deaeration. As the salt, a butylene oxide adduct of polyethyleneimine is disclosed.

Japanese Unexamined Patent Publication (Kokai) No. 63-11557 discloses an entrainment air for mixing a primary amine with an ethylene oxide derivative (I) and a water-soluble polycarboxylic acid polymer (II) in a specific weight ratio when mixing cement mortar or concrete. Regarding the method of adjusting the amount, ethylene oxide derivative (I) of primary amine
Discloses an ethylene oxide adduct of lauryl amine.

In JP-A-8-73250, 10 to 1000 mol of alkylene oxide is added to a monohydric alcohol having 6 to 30 carbon atoms in the molecule, a monohydric mercaptan, an alkylphenol, an amine or a carboxylic acid. A hydraulic composition containing a water-soluble polymer (a) composed of a polyalkylene oxide derivative, a high-performance water-reducing agent (b) and a hydraulic powder (c), wherein an ethylene oxide adduct of a mixture of stearyl alcohol and cetanol, nonylphenol Ethylene oxide and propylene oxide adduct, dodecyl mercaptan ethylene oxide adduct, palmityl alcohol ethylene oxide adduct, dodecylamine ethylene oxide adduct,
An ethylene oxide adduct of lauric acid and the like are disclosed.

However, in these techniques,
Stable keeping of the amount of entrained air in the concrete composition has not been sufficiently investigated, and therefore, in addition to exhibiting excellent performance in this respect, a concrete composition exhibiting excellent performance in strength and durability. There was room to devise the structure of the alkylene oxide adduct so that

[0010]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and it is possible to maintain a stable entrained air amount without an increase in the air amount associated with the extension of the kneading time during the production of a concrete composition. It is an object of the present invention to provide a concrete composition which can be formed and has excellent strength and durability.

[0011]

[Means for Solving the Problems] The inventors of the present invention have investigated an admixture which maintains a stable entrained air amount of a concrete composition, and a polyoxyalkylene compound represented by a specific general formula is a defoaming agent. It was noted that a concrete composition containing such a compound exhibits excellent strength and durability. In such a concrete composition, the ratio of the number of moles of addition of the oxyethylene group and the oxyalkylene group having 3 or more carbon atoms in the oxyalkylene group of the polyoxyalkylene compound is specified, and the polyoxyalkylene compound is a molecule. It was found that when at least one aliphatic hydrocarbon group in which five or more carbon atoms are continuously bonded is contained therein, the defoaming property is maintained. That is, conventionally, it has been considered that a defoaming agent in a concrete composition is preferably highly hydrophobic, but if the structure of the polyoxyalkylene compound is specified and the hydrophilicity of the oxyethylene group is increased, the AE agent It was found that the bubbles generated by the above can be effectively suppressed and the increase in the air amount due to the extension of the kneading time at the time of manufacturing the concrete composition can be suppressed, and the above problems can be solved satisfactorily. The polyoxyalkylene compounds include those having an alcohol residue or an amine residue, those having at least one nitrogen atom in the molecule, those having a molecular weight of 10,000 or less, and those having a carbon atom in the molecule. It has also been found that those having an aliphatic hydrocarbon group in which eight or more are continuously bonded are suitable, and the present invention has been achieved.

That is, the present invention is a concrete composition comprising a polyoxyalkylene compound, cement, water, fine aggregate and coarse aggregate as essential components, wherein the polyoxyalkylene compound has the following general formula (1) ); X-[(AO) n-R ¹ ] k (1) (In the formula, X represents a compound residue having active hydrogen.
¹ is the same or different and is a hydrogen atom, a hydrocarbon group,
^{-Y-NR 2 R 3, -COR} 4 or -CH ₂ CH ₂ NHCO
It represents a -R ^5. Y represents an alkylene group having 1 to 10 carbon atoms. R ² and R ³ are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. R ⁴ and R
⁵ represents a hydrocarbon group having 1 to 30 carbon atoms, or a group having at least one or more carboxyl groups or sulfonyl groups or salts thereof. AO is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. n
Are the same or different and represent the average number of moles of the added oxyalkylene group, and are 1 to 300. k is 1 to 30
It is 0. ), Where u is the total number of added oxyethylene groups in the oxyalkylene group and v is the total number of added oxyalkylene groups having 3 or more carbon atoms, 0.15 <u / (u + v) < The concrete composition satisfies the relationship of 0.9 and has at least one aliphatic hydrocarbon group in which 5 or more carbon atoms are continuously bonded in the molecule. The present invention is described in detail below.

First, the polyoxyalkylene compound in the concrete composition of the present invention will be described. The polyoxyalkylene compound in the present invention is represented by the above general formula (1), and one kind or two or more kinds can be used. In the general formula (1), X is
Represents a compound residue having active hydrogen. The compound residue having active hydrogen means a group having a structure obtained by removing active hydrogen from a compound having active hydrogen, but is not particularly limited to a group formed by a reaction with a compound having active hydrogen. Absent. In the polyoxyalkylene compound, the number of compound residues having active hydrogen may be one, or two or more. Examples of such groups include an alcohol residue having a structure in which active hydrogen is removed from an alcohol hydroxyl group, a carboxylic acid residue having a structure in which active hydrogen is removed from a carboxylic acid carboxyl group, and an amine amino group being active. An amine residue having a structure in which hydrogen is removed, an imine residue having a structure in which active hydrogen is removed from an imine group of imine, and a residue having a structure in which active hydrogen is removed from a thiol group of thiol are preferable. Among these, residues of alcohol and residues of amine and imine are preferable. The form of the compound residue having active hydrogen may be any of linear, branched, and three-dimensionally crosslinked structures. In a preferred form of the compound residue having the above active hydrogen, as the residue of the alcohol, a monohydric alcohol, trimethylolpropane,
A residue having a structure obtained by removing active hydrogen from a polyhydric alcohol such as pentaerythritol, polyglycerin or sorbitol is preferable, and as the amine residue, a structure obtained by removing active hydrogen from a monovalent amine or a polyvalent amine is used. The residue having is preferable, and as the imine residue, a residue having a structure in which active hydrogen is removed from diethyleneimine or polyethyleneimine is preferable.

In the above general formula (1), R ^{1 s} are the same or different and each represents a hydrogen atom, a hydrocarbon group or -Y-NR.
² R ^3, represents a -COR ⁴ or ^{_{-CH 2 CH 2 NHCO-R 5}} . As the hydrocarbon group, a linear or branched alkyl group having 1 to 30 carbon atoms; a phenyl group having 6 to 30 carbon atoms, an alkylphenyl group, a phenylalkyl group, a phenyl group substituted with an (alkyl) phenyl group, or a naphthyl group. An aromatic group having a benzene ring such as; an alkenyl group having 2 to 30 carbon atoms;
An alkynyl group having 2 to 30 carbon atoms is preferable. The carbon number of the hydrocarbon group is 1 or more, but 2 or more is preferable for the polyoxyalkylene compound to have high defoaming performance. More preferably, it is 5 or more. Also, 3
It is preferably 0 or less. More preferably, it is 22 or less,
More preferably, it is 18 or less. Further, among the hydrocarbon groups, straight chain, branched alkyl groups and alkenyl groups are particularly preferable.

The above Y represents an alkylene group having 1 to 10 carbon atoms, preferably 2 or more carbon atoms, and
It is preferably 8 or less. R ² and R ³ represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and an aliphatic hydrocarbon group having 5 or more carbon atoms bonded to X or AO in the general formula (1). When there is no, the number of carbon atoms of the hydrocarbon group in R ² and R ³ is preferably 5 or more. It is more preferably 8 or more, still more preferably 10 or more.
Moreover, 22 or less is preferable. On the contrary, when there is an aliphatic hydrocarbon group in which 5 or more carbon atoms are continuously bonded to X or AO, R ² and R ³ are preferably hydrogen atoms. R ⁴ and R ⁵ represent a hydrocarbon group having 1 to 30 carbon atoms, or a group having at least one or more carboxyl group or sulfonyl group or a salt thereof, and carbon in X or AO in the general formula (1). When there is no aliphatic hydrocarbon group in which 5 or more atoms are continuously bonded, a hydrocarbon group having 5 or more carbon atoms is preferable. On the contrary, when an aliphatic hydrocarbon group in which 5 or more carbon atoms are continuously bonded to X or AO is present, it is a group having at least one or more carboxyl group or sulfonyl group or a salt thereof. Preferably there is. Among the hydrocarbon groups, straight chain, branched alkyl groups and alkenyl groups are particularly preferable.

The above AO represents an oxyalkylene group having 2 to 18 carbon atoms, and the total added mole number of oxyethylene groups in the oxyalkylene group is u, and the total added mole number of oxyalkylene groups having 3 or more carbon atoms. Is defined as v, the relationship of 0.15 <u / (u + v) <0.9 is satisfied. When it is 0.9 or more, the hydrophilicity becomes too strong and the defoaming property becomes insufficient, and when it is 0.15 or less, the defoaming property cannot be maintained, and in any case, the cured product The strength will be reduced. The value of u / (u + v) is preferably more than 0.2. More preferably, it exceeds 0.35. Further, it is preferably less than 0.8. More preferably, it is less than 0.7. In the present invention, it does not mean that all the groups represented by each [(AO) n-R ¹ ] satisfy the above relationship, but all the groups represented by [(AO) n-R ¹ ] Where u is the total number of moles of oxyethylene groups added to the group and v is the total number of moles of oxyalkylene groups having 3 or more carbon atoms, the relationship of 0.15 <u / (u + v) <0.9 is obtained. Means to meet. Further, (u + v) is more preferably more than 5, and further preferably more than 10. Further, it is preferably less than 200, more preferably less than 150, further preferably less than 100, particularly preferably less than 80, most preferably less than 50. Note that (u + v)
Preferably satisfies the relationship of 1 <u + v <300.

In the above oxyalkylene group, the oxyalkylene group having 3 or more carbon atoms preferably has 8 or less carbon atoms. It is more preferably 6 or less, still more preferably 4 or less. The average added mole number n is 1 to 300, but is preferably 2 or more. It is more preferably 5 or more, still more preferably 10 or more. Further, it is preferably 200 or less. It is more preferably 100 or less, still more preferably 50 or less, and particularly preferably 40 or less. The average number of added moles means the average value of the number of moles of oxyalkylene groups added in 1 mole of the unit represented by [(AO) n-R ¹ ]. The addition form of the oxyalkylene group in which two or more kinds of alkylene oxides, that is, ethylene oxide and the alkylene oxide having 3 or more carbon atoms are added may be random addition, block addition, alternate addition, or the like. It may be. A preferred form is a block-shaped addition.

The above k is 1 to 300, but preferably 200 or less. More preferably, it is 100 or less. k
Is 2 or more, that is, X is-[(AO) n-R ¹ ].
When a plurality of groups represented by are bonded,-[(AO) n-R
^The groups represented by ¹ ] may be the same or different.

The polyoxyalkylene compound in the present invention has at least one aliphatic hydrocarbon group in which 5 or more carbon atoms are continuously bonded in the molecule. That is, in the general formula (1), at least one of the structures represented by R ¹ , X, R ¹ -AO and AO constituting the polyoxyalkylene compound has 5 carbon atoms.
It suffices that at least one aliphatic hydrocarbon group is continuously bonded. It is preferable to have an aliphatic hydrocarbon group in which 8 or more carbon atoms are continuously bonded in the molecule. In addition, as such an aliphatic hydrocarbon group, a group in which 10 or more carbon atoms are continuously bonded is more preferable. Moreover, 30 or less is preferable. More preferably,
22 or less.

In the present invention, the polyoxyalkylene compound preferably has at least one nitrogen atom in the molecule. Further, such a compound may be used after neutralizing the nitrogen atom with an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or an acidic substance such as acetic acid, propionic acid, (meth) acrylic acid. When such a polyoxyalkylene-based compound and a polycarboxylic acid-based polymer having a free carboxyl group described below are blended, the free carboxyl group of the polycarboxylic acid polymer is changed by the nitrogen atom in the polyoxyalkylene-based compound. The water solubility is improved because it is neutralized to form a salt, and the aqueous solution of the blend of the polyoxyalkylene compound and the polycarboxylic polymer can be stored while maintaining a uniform state without layer separation. it can.

The molecular weight of the polyoxyalkylene compound in the present invention is preferably 10,000 or less. More preferably, it is 5000 or less. Also, 10
It is preferably 0 or more. More preferably, 200
That is all.

As the polyoxyalkylene compound in the present invention, the following compounds are preferable. 1-3 carbons
Polyoxyalkylenes obtained by adding ethylene oxide and alkylene oxides having 3 to 18 carbon atoms to monohydric alcohols having 0 hydrocarbon group; polyoxyethylene polyoxyalkylenes having hydroxyl groups at both ends;
Polyoxyalkylenes obtained by adding ethylene oxide and an alkylene oxide having 3 to 18 carbon atoms to a polyhydric alcohol having 3 or more hydroxyl groups in the molecule; ethylene oxide and 3 carbon atoms in an alcohol having an acetylene group in the molecule Polyoxyalkylenes obtained by adding alkylene oxides of .about.18.

Examples of the monohydric alcohol having a hydrocarbon group having 1 to 30 carbon atoms include methanol, ethanol,
Propanol, isopropanol, butanol, pentanol, hexanol, octanol, lauryl alcohol, cetyl alcohol, stearyl alcohol, straight chain having 12 to 14 carbon atoms, straight chain such as branched alcohol, branched saturated alcohols; allyl alcohol, methallyl alcohol, 3-Methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-butene-
Unsaturated alcohols such as 2-ol and oleyl alcohol; aromatic alcohols such as phenol, nonylphenol and benzyl alcohol are preferable.

Examples of the polyoxyethylene polyoxyalkylenes having hydroxyl groups at both ends include AB type block types such as polyoxyethylene polyoxypropylene and polyoxyethylene polyoxybutylene; polyoxyethylene polyoxypropylene polyoxyethylene, ABA block types such as polyoxypropylene polyoxyethylene polyoxypropylene and polyoxyethylene polyoxybutylene polyoxyethylene are suitable.

As the polyhydric alcohol having three or more hydroxyl groups in the molecule, trimethylolpropane, pentaerythritol, polyglycerin and sorbitol are preferable.

Alcohols having an acetylene group in the molecule include 2,4,7,9-tetramethyl-5-
Decine-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3-methyl 1-butyne-3
-All is preferred.

Further, as the polyoxyalkylene compound in the present invention, the compounds described below are also suitable. Sodium polyoxyethylene polyoxypropylene methyl ether sulfate, polyoxyethylene polyoxypropylene dodecylphenol ether sodium sulfate, and other polyoxyalkylene alkyl (aryl) ether sulfate salts; polyoxyethylene polyoxypropylene stearyl phosphate, and other polyoxy esters Alkylene alkyl phosphates.

The following nitrogen-containing compounds are also suitable as the polyoxyalkylene compound in the present invention. (Di) methylamine, (di) ethylamine, (di)
Propylamine, (di) butylamine, (di) pentylamine, (di) hexylamine, (di) heptylamine, (di) octylamine, (di) nonylamine,
(Di) decaamine, (di) undecaamine, (di) dodecaamine, (di) tetradecaamine, (di) pentadecaamine, (di) hexadecaamine, (di) heptadecaamine, (di) octadecaamine, (Di) nonadecamine, (di) straight chain having 1 to 30 carbon atoms such as icosamine,
Primary amines having branched alkyl groups, secondary amines having the same kind of alkyl groups or different kinds of alkyl groups; primary amines derived from fatty acids obtained from coconut oil, primary amines derived from oleic acid, soybean oil Having a linear or branched alkyl group having 1 to 30 carbon atoms such as a primary amine derived from a fatty acid derived from, a primary amine derived from a fatty acid derived from beef tallow, a primary amine derived from a fatty acid derived from cured beef tallow, And primary amines in which different types of alkyl groups are mixed; secondary amine derived from fatty acid obtained from coconut oil, secondary amine derived from oleic acid, 2 derived from fatty acid obtained from soybean oil
Secondary amine derived from fatty acid obtained from beef tallow,
Secondary amines having a linear or branched alkyl group having 1 to 30 carbon atoms, such as secondary amine derived from fatty acid obtained from hardened beef tallow, and mixed with different types of alkyl groups; carbon number 6
To 30 phenyl group, alkylphenyl group, phenylalkyl group, phenyl group substituted with (alkyl) phenyl group, aromatic group having benzene ring such as naphthyl group, alkenyl group having 2 to 30 carbon atoms, and 2 carbon atoms Primary or secondary amines having ˜30 alkynyl groups; obtained by adding ethylene oxide and alkylene oxide having 3 to 18 carbon atoms to amines such as alkanolamines such as monoethanolamine, diethanolamine and triethanolamine Addendum.

As the polyoxyalkylene compound in the present invention, the following compounds containing two or more nitrogen atoms are also suitable. Ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine,
From polyalkylene polyamines such as dipropylene triamine and tetrapropylene pentamine and acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, stearic acid, oleic acid, fatty acids obtained from coconut oil, fatty acids obtained from soybean oil, and beef tallow. Ethylene oxide of amide amines obtained by dehydration condensation with fatty acids obtained, fatty acids such as fatty acids obtained from hardened beef tallow, and alkylene oxide adducts having 3 to 18 carbon atoms; ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, dipropylene. Triamine, polyalkylene polyamines such as tetrapropylene pentamine and acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, stearic acid, oleic acid, fatty acids obtained from coconut oil, fatty acids obtained from soybean oil, beef tallow Ethylene oxide and alkylene oxide adducts having 3 to 18 carbon atoms of imidazolines obtained by further dehydrating amidoamines obtained by dehydration condensation with fatty acids obtained by dehydration and fatty acids such as fatty acids obtained from hardened beef tallow; ethylenediamine, propylenediamine, Ethylene oxide and C 3-18 alkylene oxide adducts of polyalkylene polyamines such as diethylene triamine, triethylene tetramine, dipropylene triamine and tetrapropylene pentamine; C 1-30
Ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tetrapropylenepentamine, etc. modified with a hydrocarbon group of ethylene oxide and alkylene oxide adducts having 3 to 18 carbon atoms; Polyethyleneimine obtained by polymerizing alkyleneimine such as propyleneimine, ethylene oxide of polyalkyleneimine such as polypropyleneimine and adduct of alkylene oxide having 3 to 18 carbon atoms; modified with a hydrocarbon group having 1 to 30 carbon atoms Polyethyleneimines such as polyethyleneimine and polypropyleneimine obtained by polymerizing alkyleneimines such as ethyleneimine and propyleneimine, and ethylene oxide and C 3-18 amines. Alkylene oxide adducts; carbon atoms 1
Ethylene oxide and C3-18 alkylene oxide adducts of alkylaminopropylamines obtained by adding acrylonitrile to primary amines or secondary amines having a hydrocarbon group of -30 and then reducing them.

The compounds described below are also suitable as the nitrogen atom-containing polyoxyalkylene compound in the present invention. Monohydric alcohols having a hydrocarbon group of 1 to 30 carbon atoms, ethylene oxide and 3 to 1 carbon atoms
Amines having amino groups introduced into polyoxyalkylenes obtained by adding alkylene oxide of 8; amines having amino groups introduced into polyoxyethylene polyoxyalkylenes having hydroxyl groups at both ends; 3 in a molecule Amines in which amino groups are introduced into polyoxyalkylenes obtained by adding ethylene oxide and alkylene oxides having 3 to 18 carbon atoms to the above polyhydric alcohols having hydroxyl groups; ethylene oxide and alcohols having acetylene groups in the molecule Amines in which an amino group is introduced into polyoxyalkylenes obtained by adding an alkylene oxide having 3 to 18 carbon atoms. Although various methods can be considered for introducing the amino group, a method of converting the hydroxyl group itself into an amino group with various aminating reagents, and a method of adding an alkyleneimine such as ethyleneimine or propyleneimine to the hydroxyl group are preferable. is there.

Monohydric alcohols having a hydrocarbon group having 1 to 30 carbon atoms, polyoxyethylene polyoxyalkylenes having hydroxyl groups at both ends, polyhydric alcohols having three or more hydroxyl groups in the molecule, and intramolecular As the alcohol having an acetylene group, the same ones as described above are suitable.

In the above polyoxyalkylene compound, when no aliphatic hydrocarbon group in which 5 or more carbon atoms are continuously bonded is contained in the molecule,
An aliphatic hydrocarbon group can be appropriately introduced by partially adding an alkylene oxide having 5 or more carbon atoms or reacting with an alkyl halide having 5 or more carbon atoms during or after the synthesis. As a result, the polyoxyalkylene compound according to the present invention, that is, the compound having at least one aliphatic hydrocarbon group in which 5 or more carbon atoms are continuously bonded in the molecule is obtained.

Compounds obtained by further adding alkylene oxides such as ethylene oxide and alkyleneimines such as ethyleneimine to the terminal functional groups of the polyoxyalkylene compounds described above are also available. Can be used as the polyoxyalkylene compound in the present invention.

Further, the compound obtained by reacting the terminal functional group of the polyoxyalkylene compound described above with an acid anhydride such as acetic anhydride or butyric anhydride is also a polyoxyalkylene compound in the present invention. Can be used.

The following compounds are also suitable as the polyoxyalkylene compound in the present invention.
A compound in which the polyoxyalkylene compound described above and a compound having two or more carboxyl groups are ester-bonded leaving at least one carboxyl group; the polyoxyalkylene compound and the carboxyl group A compound having a sulfonyl group, which is ester-bonded leaving at least one sulfonyl group; the polyoxyalkylene compound and the compound having two or more carboxyl groups have at least one carboxyl group. A compound having an amide bond left behind; a compound in which the above polyoxyalkylene compound and a compound having a carboxyl group and a sulfonyl group are amide bonded leaving at least one sulfonyl group. In such a polyoxyalkylene compound, the remaining carboxyl group or sulfonyl group is sodium hydroxide, various metal salts such as calcium salt neutralized with a base such as calcium hydroxide, ammonium salt, amine Salt or the like may be used.

Examples of the compound having two or more carboxyl groups include unsaturated dicarboxylic acids such as maleic acid, fumaric acid, phthalic acid and itaconic acid, and metal salts thereof.
Ammonium salts, amine salts; Saturated dicarboxylic acids such as succinic acid, malonic acid, glutaric acid, adipic acid and their metal salts, ammonium salts, amine salts; unsaturated monocarboxylic acids such as acrylic acid oligomers, methacrylic acid oligomers and maleic acid oligomers Low molecular weight polymers of carboxylic acids or unsaturated dicarboxylic acids and their metal salts, ammonium salts, amine salts are preferred.

The polyoxyalkylene compound is obtained by reacting, for example, a polyoxyalkylene compound having a hydroxyl group at the terminal with an acid anhydride such as maleic anhydride or succinic anhydride in the absence of a solvent or in a suitable solvent. Can be obtained at At this time, it is preferable to use an appropriate base catalyst. In addition, it can also be obtained by esterification by dehydration reaction between a hydroxyl group-terminated polyoxyalkylene compound and a carboxylic acid, or by ester exchange reaction between a hydroxyl group-terminated polyoxyalkylene compound and an ester compound. .

In the present invention, among the polyoxyalkylene compounds represented by the general formula (1), when R ¹ is a hydrogen atom or when X has —OH or —NH ₂ ,
By performing esterification or amidation with an unsaturated carboxylic acid such as (meth) acrylic acid or maleic acid, an unsaturated monomer having a defoaming property can be synthesized. The unsaturated monomer having the defoaming property is used together with a monomer which gives a constitutional unit represented by the general formula (2), the general formula (3), the general formula (4) or the general formula (5) described later. The defoaming component can be incorporated into the polymer skeleton by polymerizing. Such a polymer is also one of the embodiments of the present invention.

Next, other essential components in the concrete composition of the present invention will be described. As the cement in the present invention, Portland cement (normal, early strength, ultra early strength, moderate heat, sulfate resistant and low alkali type of each), various mixed cement (blast furnace cement, silica cement, fly ash cement), white Portland sem Cement, alumina cement, super quick-setting cement (1 clinker quick-setting cement, 2 clinker quick-setting cement, magnesium phosphate cement), grout cement, oil well cement, low heat-generating cement (low heat-generating blast furnace cement, fly ash mixed low heat-generating type) Blast furnace cement, belite high content cement), ultra-high strength cement, cement-based solidifying material, eco-cement (cement manufactured from at least one of municipal waste incineration ash and sewage sludge incineration ash) are preferable, and further Blast furnace slag, fly ash, cinder ash Clinker ash, husk ash, silica fume, silica powder, a fine powder and gypsum limestone powder may be added. These may be used alone or in combination of two or more.

Sand is suitable as the fine aggregate in the present invention, and as coarse aggregate, in addition to gravel, crushed stone, granulated slag, recycled aggregate, etc., silica stone, clay, zircon, high alumina. It is possible to use refractory aggregates such as quality, silicon carbide, graphite, chrome, chromag, and magnesia. These may be used alone or in combination of two or more.

In the concrete composition of the present invention, the unit water amount per 1 m ³ , the amount of cement used, the amount of coarse aggregate and the water / cement ratio are 100 to 185 unit water amounts.
kg / m ³ , amount of cement used 250-800 kg / m ³ ,
The unit amount of coarse aggregate is preferably 500 to 1500 kg / m ³ , and the water / cement ratio (mass ratio) is preferably 0.1 to 0.7. The unit water amount is more preferably 120 kg / m ³ or more, and more preferably 175 kg / m ³ or less. The amount of cement used is more preferably 270 kg / m ³ or more,
Further, it is more preferably 800 kg / m ³ or less. The unit amount of coarse aggregate is more preferably 600 kg / m ³ or more, further preferably 800 kg / m ³ or more, and 1300
kg / m ³ or less is more preferable, and even more preferably 12
It is less than 00 kg / m ³ . Water / cement ratio (mass ratio)
Is more preferably 0.2 or more, and is more preferably 0.65 or less. INDUSTRIAL APPLICABILITY The concrete composition of the present invention can be widely used from poor mix to rich mix, and high strength concrete with a large amount of unit cement and a unit cement amount of 300 kg.
It is effective for any poorly mixed concrete of less than / m ³ .

The mixing ratio of the polyoxyalkylene compound in the concrete composition of the present invention is preferably 0.0001% by mass or more and 1.0% by mass or less based on the mass of cement. The above blending ratio is 0.
If it is less than 0001% by mass, the performance may be insufficient, and even if a large amount exceeding 1.0% by mass is used,
The effect is practically capped and there is a risk that it will be disadvantageous in terms of economy. More preferably 0.0005 mass%
It is above, and more preferably 0.001 mass% or above. Further, it is more preferably 0.5% by mass or less, further preferably 0.1% by mass or less, and an amount having such a ratio may be added. By this addition, various desirable effects such as reduction of unit water amount, increase of strength and improvement of durability will be brought about.

The concrete composition of the present invention also preferably contains a cement dispersant, which makes it possible to always obtain a concrete composition having a stable entrainment air amount during kneading of the concrete composition. Further, even when the concrete composition is allowed to stand still after kneading, a concrete composition having a stable entrainment air amount can always be obtained. Conventionally, what is mixed as a defoaming component in a cement dispersant has poor solubility in water, and there is a problem that the defoaming component is separated during storage when mixed with a cement dispersant liquid. Since the polyoxyalkylene compound in (3) is highly hydrophilic, it is relatively uniform in the cement dispersant liquid, and can be stably stored without separation. Thus, it is one of preferred embodiments of the present invention that the concrete composition contains the polyoxyalkylene compound and the cement dispersant as essential components.

As the above-mentioned cement dispersant, any one can be used as long as it can exhibit a water reducing property in a concrete composition, and one kind or two or more kinds can be used, but a polycarboxylic acid having a polyalkylene glycol in a side chain is used. Acid-based polymers are preferred. Such a polycarboxylic acid polymer can be an essential component of the cement dispersant, and is called a polycarboxylic acid cement dispersant or a water reducing agent. Such a cement dispersant may be composed only of the above polycarboxylic acid-based polymer or may contain other materials, but it is preferable that the polycarboxylic acid-based polymer is the main component.
The polycarboxylic acid-based polymer has the following general formula (2);

[0045]

[Chemical 1]

(In the formula, R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or a methyl group. R ⁹ O is
The same or different and represent an oxyalkylene group having 2 to 18 carbon atoms. a represents the average addition mole number of an oxyalkylene group, and is a number of 2 to 300. R ¹⁰ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ) A polyoxyalkylene ester-based structural unit (I) represented by the following general formula (3);

[0047]

[Chemical 2]

(In the formula, R ¹¹ , R ¹² and R ¹³ are the same or different and represent a hydrogen atom or a methyl group. M ¹ is
Represents a hydrogen atom, a monovalent metal, a divalent metal, ammonium or an organic amine. ) A carboxylic acid-based structural unit (I
The polycarboxylic acid polymer (A-1) having I) is preferable.

The above-mentioned polycarboxylic acid-based polymer has the following general formula (4);

[0050]

[Chemical 3]

(In the formula, R ¹⁴ , R ¹⁵ and R ¹⁶ are the same or different and each represents a hydrogen atom or a methyl group. R ¹⁷ is
It represents a hydrocarbon group having 1 to 5 carbon atoms. R ¹⁸ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. b represents the average number of moles of oxyalkylene groups added, and is a number of 2 to 300. R ¹⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ) A polyoxyalkylene ether type structural unit (III) represented by the following general formula (5);

[0052]

[Chemical 4]

(In the formula, R²⁰And R^{twenty one}Are the same or different
Becoming a hydrogen atom, a methyl group or -COOM³Represents
However, R²⁰And R^{twenty one}At the same time -COOM³Express
Yes. R^{twenty two}Is a hydrogen atom, a methyl group or -CH₂COOM^Four
Represents R^{twenty two}Is -CH₂COOM^FourWhen R²⁰And R
^{twenty one}Are the same or different and each represent a hydrogen atom or a methyl group.
Represent M ², M³And M^FourIs a hydrogen atom, monovalent metal, divalent
Represents a metal, ammonium or organic amine. )
Having a carboxylic acid-based structural unit (IV)
The acid polymer (A-2) is preferable. That is, the above
The dispersant is a polycarboxylic acid polymer (A-1) or
And / or containing the above polycarboxylic acid polymer (A-2)
It is preferable.

The above polycarboxylic acid polymers (A-1) and (A-2) are the above-mentioned essential constitutional units (repeating units).
And may further have a structural unit (V) derived from the below-mentioned monomer (e). Each of these structural units may be of one type or of two or more types.

The above polycarboxylic acid polymer (A-1)
Is an essential component of a monomer that gives the structural unit (I) (for example, the monomer (a) described later) and a monomer that gives the structural unit (II) (for example, the monomer (b) described later). Can be produced by copolymerization. Such a monomer component may be a monomer (eg, a monomer that provides the structural unit (V) (for example,
It may further contain the below-mentioned monomer (e). In addition,
When each constitutional unit is one kind, it is sufficient to use one kind of monomer which gives each constitutional unit, and when each constitutional unit is respectively two or more kinds, one kind of monomer which gives each constitutional unit is used. It is sufficient to use two or more of each.

The ratio of each structural unit constituting the polycarboxylic acid polymer (A-1) is a mass ratio of structural unit (I) / structural unit (II) / structural unit (V) = 1 to 1. 9
It is preferably 9/99 to 1/0 to 50. More preferably structural unit (I) / structural unit (II) / structural unit (V) = 50 to 99/50 to 1/0 to 49, and even more preferably structural unit (I) / structural unit (II) / structural unit. (V) = 60 to 95/40 to 5/0 to 30, most preferably structural unit (I) / structural unit (II) / structural unit (V) = 70 to 95/30 to 5/0 to 10. . However, the total of the structural unit (I), the structural unit (II) and the structural unit (V) is 100% by mass.

Further, the above polycarboxylic acid type polymer (A-
1) is an essential component containing an unsaturated monocarboxylic acid-based monomer such as acrylic acid, methacrylic acid, crotonic acid and the like and a monomer (for example, the monomer (b) described later) which provides the structural unit (II). The alkoxypolyalkylene glycol may be directly esterified to at least a part of the carboxyl group of the polymer obtained by copolymerizing the monomer component containing

In the general formula (2), the hydrocarbon group having 1 to 30 carbon atoms in R ¹⁰ has 1 to 1 carbon atoms.
An alkyl group having 30 carbon atoms, a phenyl group having 6 to 30 carbon atoms,
An aromatic group having a benzene ring such as an alkylphenyl group, a phenylalkyl group, a phenyl group substituted with an (alkyl) phenyl group, and a naphthyl group, and an alkenyl group having 2 to 30 carbon atoms are preferable. The average number of moles a of the oxyalkylene group added is 2 to 300 or less,
It is preferably 5 or more. It is more preferably 10 or more, still more preferably 15 or more, and most preferably 20 or more. Further, it is most preferably 200 or less. Further, the number of carbon atoms of R ¹⁰ is 1 or more, preferably 22 or less. It is more preferably 18 or less, still more preferably 12 or less, still more preferably 6 or less, particularly preferably 5 or less, and most preferably 3 or less.

The number of carbon atoms of the oxyalkylene group R ⁹ O in the above general formula (2) is suitably 2 to 18, but is preferably 8 or less. More preferably, it is 4 or less. In the case where there is only one type of structural unit (I), it is preferable to have an oxyethylene group as an essential component in the oxyalkylene group in order to secure the balance between hydrophilicity and hydrophobicity, and more preferably 50 mol% or more. Particularly preferably, 60 mol% or more is an oxyethylene group. On the other hand, when there are two or more types of structural units (I), it is preferable to essentially include an oxyethylene group in the oxyalkylene group of any one type of structural unit (I).

Monomer (a) giving the above structural unit (I)
As, the (meth) acrylic acid, crotonic acid or a dehydrogenation (oxidation) reaction product of a fatty acid, an addition product of an alkylene oxide having 2 to 18 carbon atoms, or methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, octanol, 2-ethyl-
1-hexanol, nonyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, and other saturated aliphatic alcohols having 1 to 30 carbon atoms, allyl alcohol, methallyl alcohol, crotyl alcohol,
Unsaturated aliphatic alcohols having 3 to 30 carbon atoms such as oleyl alcohol, alicyclic alcohols having 3 to 30 carbon atoms such as cyclohexanol, phenol, phenylmethanol (benzyl alcohol), methylphenol (cresol), p-ethylphenol, dimethylphenol (xylenol), pt-butylphenol,
Alkoxy polyalkylene glycols 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 nonylphenol, dodecylphenol, phenylphenol, and naphthol; An ester compound or the like with (meth) acrylic acid or crotonic acid is preferable, and in the general formula (2), alkoxy polyalkylene glycols corresponding to the case where R ¹⁰ is a hydrocarbon group,
Ester compounds with (meth) acrylic acid or crotonic acid are preferred.

The following are preferable as specific chemical names of the monomer (a). Methoxy polyethylene glycol mono (meth) acrylate, ethoxy polyethylene glycol mono (meth) acrylate, 1-propoxy polyethylene glycol mono (meth) acrylate, 2-propoxy polyethylene glycol mono (meth) acrylate, 1-butoxy polyethylene glycol mono (meth) acrylate , 2-butoxy polyethylene glycol mono (meth) acrylate, 2-methyl-
1-propoxy polyethylene glycol mono (meth) acrylate, 2-methyl-2-propoxy polyethylene glycol mono (meth) acrylate, 1-pentyloxy polyethylene glycol mono (meth) acrylate, 1-hexyloxy polyethylene glycol mono (meth) acrylate, Cyclohexyloxy polyethylene glycol mono (meth) acrylate, 1-octyloxy polyethylene glycol mono (meth) acrylate, 2-ethyl-1-hexyloxy polyethylene glycol mono (meth) acrylate, nonylalkoxy polyethylene glycol mono (meth) acrylate, lauryl alkoxy Polyethylene glycol mono (meta)
Acrylate, cetyl alkoxy polyethylene glycol mono (meth) acrylate, stearyl alkoxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol mono (meth) acrylate, phenylmethoxy polyethylene glycol mono (meth) acrylate, methylphenoxy polyethylene glycol mono (meth) acrylate , P-ethylphenoxy polyethylene glycol mono (meth) acrylate,
Dimethylphenoxy polyethylene glycol mono (meth) acrylate, pt-butylphenoxy polyethylene glycol mono (meth) acrylate, nonylphenoxy polyethylene glycol mono (meth) acrylate, dodecylphenoxy polyethylene glycol mono (meth) acrylate, phenylphenoxy polyethylene glycol mono ( (Meth) acrylate, naphthoxy polyethylene glycol mono (meth) acrylate, esterified product of (meth) allyl alcohol and (meth) acrylic acid to which ethylene oxide is added, crotyl alcohol and (meth) acrylic acid to which ethylene oxide is added Alkoxy polyethylene glycol mono (meth) acrylates such as esterified products of.

Methoxy polypropylene glycol mono (meth) acrylate, ethoxy polypropylene glycol mono (meth) acrylate, 1-propoxy polypropylene glycol mono (meth) acrylate, 2-propoxy polypropylene glycol mono (meth) acrylate, 1-butoxy polypropylene glycol mono ( Various alkoxy polypropylenes such as (meth) acrylates, esterified products of (meth) allyl alcohol to which propylene oxide is added and (meth) acrylic acid, and esterified products of crotyl alcohol to which propylene oxide is added and (meth) acrylic acid Glycol mono (meth) acrylates.

Methoxy polyethylene polypropylene glycol mono (meth) acrylate, methoxy polyethylene polybutylene glycol mono (meth) acrylate,
Ethoxy polyethylene polypropylene glycol mono (meth) acrylate, ethoxy polyethylene polybutylene glycol mono (meth) acrylate, 1-propoxy polyethylene polypropylene glycol mono (meth) acrylate, 1-propoxy polyethylene polybutylene glycol mono (meth) acrylate, 2-propoxy polyethylene Polypropylene glycol mono (meth) acrylate, 2-propoxy polyethylene polybutylene glycol mono (meth) acrylate, 1-butoxy polyethylene polypropylene glycol mono (meth) acrylate, 1-butoxy polyethylene polybutylene glycol mono (meth) acrylate, ethylene oxide and propylene oxide Or add ethylene oxide and butylene oxide Two or more kinds of alkylene such as esterified product of (meth) allyl alcohol and (meth) acrylic acid, esterified product of crotyl alcohol and (meth) acrylic acid to which ethylene oxide and propylene oxide or ethylene oxide and butylene oxide are added, and the like. Various alkoxypolyalkylene glycol mono (meth) acrylates such as esterified products of (meth) acrylic acid with alcohol to which oxide is added.

The structural unit represented by the above general formula (3) (I
As the monomer (b) which gives I), acrylic acid, methacrylic acid, crotonic acid and their metal salts, ammonium salts and amine salts are preferable. (Meth) acrylic acid and salts thereof are particularly preferable.

The above polycarboxylic acid polymer (A-2)
Is an essential component of a monomer that gives the structural unit (III) (for example, the monomer (c) described later) and a monomer that gives the structural unit (IV) (for example, the monomer (d) described later). Can be produced by copolymerization. Such a monomer component may further contain a monomer (for example, the monomer (e) described later) which gives the structural unit (V).

The ratio of each structural unit constituting the above polycarboxylic acid polymer (A-2) is a mass ratio, and the structural unit (I
II) / structural unit (IV) / structural unit (V) = 1 to 99
It is preferably / 99 to 1/0 to 50. More preferably structural unit (III) / structural unit (IV) / structural unit (V) = 50 to 99/50 to 1/0 to 49, and even more preferably structural unit (III) / structural unit (IV) / structural unit. (V) = 60 to 95/40 to 5/0 to 30, most preferably structural unit (III) / structural unit (IV) / structural unit (V) = 70 to 95/30 to 5/0 to 10. . However, the total of the structural unit (III), the structural unit (IV) and the structural unit (V) is 100% by mass.

Further, the above polycarboxylic acid type polymer (A-
2) is allyl alcohol, methallyl alcohol, 3-
A monomer that gives an unsaturated alcohol and a structural unit (IV) such as methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, and 2-methyl-3-buten-2-ol ( For example, an average of 2 to 300 mol of alkylene oxide is added to a polymer obtained by copolymerizing a monomer component containing the below-mentioned monomer (d)) as an essential component, or
It can also be obtained by a method of reacting an alkoxypolyalkylene glycol having an average added mole number of 2 to 300.

In the above general formula (4), the average number of moles of added oxyalkylene group, b, is from 2 to 300, but is preferably 5 or more. It is more preferably 10 or more, still more preferably 20 or more, and particularly preferably 25 or more. Further, 200 or less is particularly preferable. Further, the number of carbon atoms of R ¹⁹ is preferably 1 or more. Moreover, 22 or less is preferable. More preferably, 18
Or less, more preferably 12 or less, even more preferably 6 or less, particularly preferably 5 or less, and most preferably 3 or less. Further, the number of carbon atoms of R ¹⁷ is 1 to 5, but 4 or less is preferable. It is more preferably 3 or less, and particularly preferably-
_{CH 2 -, - (CH 2} ) 2 - or -C (CH _{3) 2} - is a structure.

The number of carbon atoms of the oxyalkylene group R ¹⁸ O in the above general formula (4) is 2 to 18, but preferably 8 or less. More preferably, it is 4 or less. Also,
When there is only one type of structural unit (III), it is preferable to essentially have an oxyethylene group in the oxyalkylene group in order to ensure the balance between hydrophilicity and hydrophobicity, more preferably 50 mol% or more, and particularly Preferably 6
It is that 0 mol% or more is an oxyethylene group.

The structural unit represented by the general formula (5) (I
Examples of the monomer (d) giving V) include acrylic acid, methacrylic acid, crotonic acid, and unsaturated monocarboxylic acid type monomers such as metal salts, ammonium salts, amine salts thereof; maleic acid, itaconic acid, Citraconic acid, fumaric acid, or unsaturated dicarboxylic acid-based monomers such as metal salts, ammonium salts, and amine salts thereof are preferable. Further, these anhydrides can also be used, and maleic anhydride, itaconic anhydride, and citraconic anhydride are preferable. Above all, R
It is preferable to use an unsaturated monocarboxylic acid type monomer corresponding to the case where ²⁰ , R ²¹ and R ²² are the same or different and are a hydrogen atom or a methyl group, and particularly (meth) acrylic acid, maleic acid, It is preferable to use maleic anhydride and salts thereof.

The monomer (e) which gives the structural unit (V) usable in the present invention may be any monomer which can be copolymerized with at least one of the other monomers. Is preferred. Half-esters and diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid with alcohols having 1 to 4 carbon atoms; Half of unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms Amide, diamide; 1 alkylene oxide having 2 to 18 carbon atoms is added to the above alcohol or amine.
˜500 moles of alkyl (poly) alkylene glycol and the above unsaturated dicarboxylic acids half ester, diester; the above unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms, or the addition mole numbers of these glycols 2 to 300 Half-esters and diesters with polyalkylene glycols.

Maleamic acid and glycol having 2 to 18 carbon atoms, or the number of added moles of these glycols is 2 to 300.
Half amide with polyalkylene glycol; triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) propylene glycol di (meth ) (Poly) alkylene glycol di (meth) acrylates such as acrylate; hexanediol di (meth)
Bifunctional (meth) acrylates such as acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane di (meth) acrylate; (poly) alkylene glycol dimaleates such as triethylene glycol dimaleate and polyethylene glycol dimaleate.

Vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate,
3- (meth) acryloxy-2-hydroxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropyl sulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxy Unsaturated sulfonic acids such as butyl sulfonate, (meth) acrylamidomethyl sulfonic acid, (meth) acrylamidoethyl sulfonic acid, 2-methylpropane sulfonic acid (meth) acrylamide, styrene sulfonic acid, and their monovalent metal salts, divalent Metal salts, ammonium salts and organic amine salts;
Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and their metal salts, ammonium salts, amine salts.

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, glycidyl (meth) acrylate, methyl crotonate,
Esters of unsaturated monocarboxylic acids such as ethyl crotonate and propyl crotonate with alcohols having 1 to 4 carbon atoms; unsaturated monocarboxylic acids such as methyl (meth) acrylamide and amines having 1 to 30 carbon atoms Amides; vinyl aromatics such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene; 1,4
-Butanediol mono (meth) acrylate, 1,5-
Pentanediol mono (meth) acrylate, 1,6-
Alkanediol mono (meth) acrylates such as hexanediol mono (meth) acrylate; butadiene,
Dienes such as 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; (meth)
Unsaturated cyanides such as acrylonitrile and α-chloroacrylonitrile.

Unsaturated esters such as vinyl acetate and vinyl propionate; aminoethyl (meth) acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate Unsaturated diamines such as dibutylaminoethyl (meth) acrylate and vinylpyridine; divinylaromatics such as divinylbenzene; cyanurates such as triallyl cyanurate; (meth) allyl alcohol, glycidyl (meth) allyl ether, etc. Allyls; unsaturated amino compounds such as dimethylaminoethyl (meth) acrylate; methoxy polyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether,
Vinyl ethers or allyl ethers such as methoxy polyethylene glycol mono (meth) allyl ether and polyethylene glycol mono (meth) allyl ether. Polydimethylsiloxane propylamino maleamic acid,
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) and other siloxane derivatives; 2-acryloyloxyethyl phosphate, 2-methacryloyloxyethyl phosphate and other unsaturated phosphorus Acid esters.

Polyethylenepolyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine and malonic acid, succinic acid, fumaric acid, maleic acid, azelaic acid. , Sebacic acid, or a dibasic acid such as an esterified product thereof with an alcohol having 1 to 20 carbon atoms, or a condensate of an ester of a dibasic acid and an alcohol having 1 to 20 carbon atoms, or (meth) acrylic acid or Polyamide polyamine obtained by condensing an esterified product of (meth) acrylic acid and an alcohol having 1 to 20 carbon atoms, an unsaturated epoxy compound such as glycidyl (meth) acrylate, and allyl glycidyl ether at a specific ratio with alkylene oxide. A specific amount added A compound; a compound obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to active hydrogen of polyalkyleneimine such as polyethyleneimine or polypropyleneimine, (meth) acrylic acid or (meth) acrylic acid, and an alcohol having 1 to 20 carbon atoms A cationic monomer having a nitrogen atom, such as an esterification product thereof or a condensation product with an unsaturated epoxidation product such as glycidyl (meth) acrylate and allyl glycidyl ether.

In order to obtain the polycarboxylic acid type polymers (A-1) and (A-2), the above-mentioned monomer components may be polymerized using a polymerization initiator. The polymerization can be carried out by a method such as polymerization in a solvent or bulk polymerization. Polymerization in a solvent can be carried out batchwise or continuously, and the solvent used in this case is water; a lower alcohol such as methyl alcohol, ethyl alcohol, 2-propanol; benzene, toluene, xylene, cyclohexane, One or more of aromatic or aliphatic hydrocarbons such as n-hexane; ester compounds such as ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone are preferable. Solubility of raw material monomer and polycarboxylic acid type polymer (A-1) or (A-2) obtained and polycarboxylic acid type polymer (A
For convenience of using -1) or (A-2), it is preferable to use at least one selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms. In that case,
Among the lower alcohols having 1 to 4 carbon atoms, methyl alcohol, ethyl alcohol, 2-propanol and the like are particularly effective.

When polymerization is carried out in an aqueous medium to obtain the polycarboxylic acid type polymers (A-1) and (A-2), ammonium or alkali metal persulfate or hydrogen peroxide is used as a polymerization initiator. It is preferable to use a water-soluble polymerization initiator such as At this time, an accelerator such as sodium bisulfite, Mohr's salt, ascorbic acid (salt), Rongalit or the like can be used in combination. Further, in the polymerization using a lower alcohol, an aromatic hydrocarbon, an aliphatic hydrocarbon, an ester compound or a ketone compound as a solvent, a peroxide such as benzoyl peroxide or lauroyl peroxide; a hydroperoxide such as cumene hydroperoxide; an azo It is preferable to use an azo compound such as bisisobutyronitrile as a polymerization initiator. At this time, an accelerator such as an amine compound may be used in combination. Further, when a water-lower alcohol mixed solvent is used, it can be appropriately selected and used from the above-mentioned various polymerization initiators or a combination of a polymerization initiator and an accelerator. The polymerization temperature is appropriately determined depending on the solvent and the polymerization initiator used,
It is usually 0 to 120 ° C., preferably 30 ° C. or higher. More preferably, it is 50 ° C. or higher. Further, it is preferably 100 ° C or lower. More preferably, it is 95 ° C. or lower.

When bulk polymerization is carried out, it is usual to use, as a polymerization initiator, a peroxide such as benzoyl peroxide or lauroyl peroxide; a hydroperoxide such as cumene hydroperoxide; an azo compound such as azobisisobutyronitrile. , 50-200 ° C.

Further obtained polycarboxylic acid type polymer (A
In order to control the molecular weight of -1) or (A-2), hypophosphorous acid (salt) or a thiol chain transfer agent can be used together. Thiol chain transfer agents used in this case, the general formula HS-R ³⁰ -Eg (wherein, R ³⁰ is -C 1-2
Represents an alkyl group. E is -OH, -COOM, -C
Represents an OOR ³¹ or SO ₃ M group. M represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group or an organic amine group. R ³¹ represents an alkyl group having 1 to 30 carbon atoms.
g represents an integer of 1 to 2. ), Mercaptoethanol, thioglycerol, thioglycolic acid, 2-
Mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate and octyl 3-mercaptopropionic acid are preferred. Further, a thiol compound having a hydrocarbon group having 3 or more carbon atoms and having no functional group such as a hydroxyl group or a carboxyl group may be used as a chain transfer agent. Butanethiol, octanethiol,
Decanethiol, dodecanethiol, hexadecanethiol, cyclohexylmercaptan, thiophenol and the like are suitable as such thiol compounds. Also,
Halides such as carbon tetrachloride, carbon tetrabromide, methylene chloride, bromoform and bromotrichloroethane; unsaturated hydrocarbon compounds such as α-methylstyrene dimer, α-terpinene, γ-terpinene and dipentene are used as chain transfer agents. May be. These 1 type (s) or 2 or more types can be used. In addition, a polycarboxylic acid-based polymer (A
In order to adjust the molecular weight of -1) or (A-2), it is effective to use a monomer having a high chain transfer property such as (meth) allylsulfonic acid (salt) as the monomer (e). is there.

The polycarboxylic acid type polymers (A-1) and (A-2) can be used as they are, but when the solubility in water is insufficient, the solubility in water is improved. In order to handle in the form of an aqueous medium liquid containing no organic solvent, inorganic substances such as hydroxides, chlorides and carbon salts of monovalent and divalent metals; ammonia; organic amines (preferably sodium hydroxide) , A hydroxide of a monovalent metal such as potassium hydroxide) is preferably used as a polymer salt obtained by neutralization with an alkaline substance.

The weight average molecular weight of the above polycarboxylic acid polymers (A-1) and (A-2) is 5,000 to 100 in terms of polyethylene glycol by gel permeation chromatography (hereinafter referred to as "GPC").
0000 is suitable, but 500000 or less is preferable. It is more preferably 10,000 or more. Further, it is more preferably 300,000 or less. If the weight average molecular weight is less than 5,000, the material separation reduction performance may be reduced, and if it exceeds 1,000,000, the dispersion performance may be reduced.

(Weight average molecular weight measurement conditions) Model: Waters LCM1 Detector: Waters 410 Differential refraction detector analysis software: Waters MILLENNIUM V
er. 2.18 Eluent: 115.6 g of sodium acetate trihydrate is dissolved in a mixed solution of 10999 g of water and 6001 g of acetonitrile, and the eluent is adjusted to pH 6.0 with a 30% aqueous sodium hydroxide solution. Eluent flow rate: 0.8 ml / min Column temperature: 35 ° C. Column: Tosoh TSKgel GuardColu
mnSWXL + G4000SWXL + G3000SWX
L + G2000SWXL Standard substance: polyethylene glycol, weight average molecular weight (Mw) 272500, 219300, 85000, 4
6000, 24000, 12600, 4250, 710
0, 1470

As the polycarboxylic acid type polymer, (A
In addition to -1) and (A-2), a polyoxyalkylene compound having a carboxyl group as a side chain can be used.
The polycarboxylic acid-based polymer can be obtained, for example, by graft-polymerizing an unsaturated carboxylic acid-based monomer with a polyoxyalkylene compound. Polyethylene glycol and polyoxyethylene polyoxypropylene are preferable as the polyoxyalkylene compound. As the unsaturated carboxylic acid-based monomer, acrylic acid, methacrylic acid, crotonic acid and unsaturated monocarboxylic acid-based monomers such as metal salts, ammonium salts and amine salts thereof; maleic acid, itaconic acid, Citraconic acid, fumaric acid, or
Unsaturated dicarboxylic acid type monomers such as these metal salts, ammonium salts and amine salts are preferable. Further, these anhydrides can also be used, and maleic anhydride, itaconic anhydride, and citraconic anhydride are preferable. Among them, (meth) acrylic acid, maleic acid, maleic anhydride and salts thereof are preferably used.

In addition to the above, the concrete composition of the present invention, in addition to the above-mentioned ones, can be added to the conventional cement dispersant, water-soluble polymer, air entraining agent, cement wetting agent, expanding agent, A waterproofing agent, a retarding agent, a quick-setting agent, a water-soluble polymer substance, a thickening agent, a coagulant, a drying shrinkage reducing agent, a strength enhancing agent, a curing accelerator and the like may be used in combination.

In the concrete composition of the present invention,
Alkyl ether type anionic surfactant type, modified rosin acid compound type anionic surfactant type, alkyl sulfonic acid compound type anionic surfactant type, high alkyl carboxylic acid salt type anionic surfactant type, modified alkyl carboxylic acid Various AE agents such as an acid compound-based anionic surfactant type, for example, Vinsol (trade name, manufactured by Yamasou Chemical Co., Ltd.) or Micro-Air (trade name, manufactured by Master Builders Co., Ltd.) may be used in combination, It does not reduce the effects of the present invention. Cement dispersants other than polycarboxylic acid type, shrinkage reducing agents, separation reducing agents, neutralizing agents, swelling agents, waterproofing agents, retarders, quick-setting agents, effect accelerators, water-soluble polymers, thickening agents Even if other concrete admixtures such as an agent, a coagulant, a cement wetting agent, and a rust preventive are used together, the effect is not reduced.

In the present invention, it is preferable to further contain an AE agent when high quality air is introduced into the concrete composition to improve freeze-thaw resistance. In this case, when using by extending the kneading time during the production of the concrete composition, that is, even when the kneading is continued for a long time during the transportation of the concrete composition, the entrained air amount is kept stable in the concrete composition, The cured product can have excellent freeze-thaw resistance, strength, and durability.

The cement composition of the present invention is produced by a method for producing a concrete composition including a step of mixing production raw materials containing polyoxyalkylene compounds, cement, water, fine aggregate and coarse aggregate as essential components. be able to. In this case, as long as it includes a step of mixing all the manufacturing raw materials constituting the concrete composition of the present invention,
The method of adding each production raw material and the order thereof are not particularly limited. The method for producing such a concrete composition,
This is one of the preferred embodiments of the present invention.

[0089]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, "%" means "mass%" unless otherwise specified.

Production Example 1 339.6 g of water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introducing tube and a reflux condenser.
The inside of the reaction vessel was replaced with nitrogen while stirring, and the reaction was performed in a nitrogen atmosphere at 80
Heated to degree. Next, methoxy polyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 25) 333.6 g, methacrylic acid 66.4 g,
Monomer aqueous medium liquid 503.5 in which 100 g of water and 3.5 g of 3-mercaptopropionic acid as a chain transfer agent are mixed
g for 4 hours and ammonium peroxodisulfate 4.
46 g of an aqueous solution in which 6 g was dissolved was added dropwise over 5 hours.
Then, the temperature was maintained at 80 ° C. for 1 hour to complete the polymerization reaction to obtain a copolymer (1) composed of a copolymer aqueous medium liquid having a weight average molecular weight of 23,800.

Table 1 shows the structures of the defoaming agents used in the following Examples and Comparative Examples. The basic structure is the addition of ethylene oxide and propylene oxide to an alcohol or amine. Here, ethylene oxide is described as EO and propylene oxide is described as PO. The number of moles of EO and PO is the average number of moles added. RaO has 12 carbon atoms
~ 14 secondary alcohol residues. RbN is a hardened tallow amine residue having 14 to 18 carbon atoms.

[0092]

[Table 1]

Examples 1 to 5 and Comparative Example 1 <Concrete Test> In the concrete test, Production Example 1 was used.
The aqueous solution of the copolymer (1) obtained in 1. was adjusted to pH 7 with an aqueous sodium hydroxide solution having a concentration of 30% and further diluted with ion-exchanged water to have a solid content concentration of 40%. Normal Portland cement (manufactured by Taiheiyo Cement Co., Ltd .: specific gravity 3.16) as cement, Oikawa water system land sand (specific gravity 2.62) as fine aggregate, Ome crushed stone (specific gravity 2.58) as coarse aggregate, and Yokosuka as water. Using city tap water, weigh each material with the following three types of compounding so that the kneading amount is 40 L, and use a tilting mixer (Koyo Machine Industry Co., Ltd .: KYC baby mixer) Kneading was performed. The rotation speed of the mixer was fixed at 20 rotations / minute.

<Formulation 1> Unit cement amount: 360.0 kg / m³ Unit water amount: 144.0 kg / m³ Unit fine aggregate amount: 767.1 kg / m³ Unit coarse aggregate amount: 1043.1 kg / m³ Water / cement ratio: 40% Fine aggregate rate: 42%

<Formulation 2> Unit cement amount: 360.0 kg / m³ Unit water amount: 144.0 kg / m³ Unit fine aggregate amount: 821.9 kg / m³ Unit coarse aggregate amount: 989.2 kg / m³ Water / cement ratio: 40% Fine aggregate rate: 45%

<Compound 3> Unit cement amount: 350.0 kg / m³ Unit water amount: 161.0 kg / m³ Unit fine aggregate amount: 877.1 kg / m³ Unit coarse aggregate amount: 899.0 kg / m³ Water / cement ratio: 46% Fine aggregate rate: 49%

<Kneading Method> (1) Only fine aggregate was put into a mixer, and after kneading for 30 seconds, rotation was stopped. (2) Cement was added and the mixture was further kneaded for 30 seconds. (3) The rotation was stopped, water containing a water reducing agent and an antifoaming agent (95% of the total predetermined amount of water) was added, and the mixture was further kneaded for 90 seconds. (4) The rotation was stopped again, the coarse aggregate was added, water (5% of the total predetermined amount of water) containing the AE agent was further added, and the mixture was kneaded for 150 seconds. (5) Part of the obtained concrete was taken out of the mixer, and the slump and the air amount were measured. The slump was measured in accordance with Japanese Industrial Standard JIS A 1101 and the amount of air was measured in accordance with Japanese Industrial Standard JIS A 1128. At this time, the slump value was S1 and the air amount was A1. (6) The concrete used for measuring the slump and the air amount was returned to the mixer and kneaded for 5 minutes, and then the slump and the air amount were measured again. At this point, the slump value was S2 and the air amount was A2. (7) The concrete used for the measurement again was returned and kneaded for 5 minutes. The slump and air content of the obtained concrete were measured. The slump value at this point is S3, and the air volume is A3
And The results are shown in Table 2.

[0098]

[Table 2]

Table 2 will be described. In the AE agent, Micro-Air (trade name) is an AE agent manufactured by Master Builders. The addition amount (mass% / C) is a mass ratio with respect to the cement solid content. The air content (%) is the volume% in the concrete composition.

<Compatibility test with admixture> A predetermined amount of antifoaming agents (3) and (4) were added to an aqueous solution of copolymer (1), the pH was adjusted with an aqueous sodium hydroxide solution, and the solid content was further adjusted. It was adjusted to 40% with ion-exchanged water. The appearance of the obtained aqueous solution was first observed at room temperature, and then left in a thermostatic chamber kept at 43 ° C., and the appearance was observed after 1 day and 6 months. In the case of the defoaming agent (2) and the comparative defoaming agent (1), the copolymer (1)
A predetermined amount of the above aqueous solution was added to the aqueous solution whose pH was adjusted to 7 with sodium hydroxide. Use ion-exchanged water to remove solids 4
After adjusting to 0%, the same operation as above was performed and the state of the aqueous solution was observed. The results are summarized in Table 3. (Appearance evaluation standard) ◎: Uniform and transparent △: White turbidity ×: Layer separation

[0101]

[Table 3]

Table 3 will be described below. In the structure of the defoaming agent, RaO is a secondary alcohol residue having 12 to 14 carbon atoms, and RbN is a hardened tallow amine residue having 14 to 18 carbon atoms (total amine value = 215.9). The solid content concentration (%) is mass% of solid content in the aqueous solution.

[0103]

EFFECTS OF THE INVENTION The concrete composition of the present invention has the above-mentioned constitution and does not increase the air amount due to the extension of the kneading time at the time of manufacturing the concrete composition, and can keep the entrained air amount stable, and It is possible to form a cured product having excellent durability.

Claims (5)

[Claims] 1. A concrete composition comprising a polyoxyalkylene compound, cement, water, fine aggregate and coarse aggregate as essential components, wherein the polyoxyalkylene compound has the following general formula (1); X - [(AO) ^{n-R 1]} k (1) (wherein, X represents a compound residue having active hydrogen .R
¹ is the same or different and is a hydrogen atom, a hydrocarbon group,
^{-Y-NR 2 R 3, -COR} 4 or -CH ₂ CH ₂ NHCO
It represents a -R ^5. Y represents an alkylene group having 1 to 10 carbon atoms. R ² and R ³ are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. R ⁴ and R
⁵ represents a hydrocarbon group having 1 to 30 carbon atoms, or a group having at least one or more carboxyl groups or sulfonyl groups or salts thereof. AO is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. n
Are the same or different and represent the average number of moles of the added oxyalkylene group, and are 1 to 300. k is 1 to 30
It is 0. ), The total number of moles of oxyethylene groups added to the oxyalkylene group is u, and the number of carbon atoms is 3
When the total number of added moles of the above oxyalkylene groups is v, the relationship of 0.15 <u / (u + v) <0.9 is satisfied, and five or more carbon atoms are continuously bonded in the molecule. A concrete composition having at least one aliphatic hydrocarbon group. 2. The concrete composition according to claim 1, wherein X in the general formula (1) is an alcohol residue or an amine residue. 3. The polyoxyalkylene compound is
The concrete composition according to claim 1 or 2, which has at least one nitrogen atom in the molecule. 4. The concrete composition according to claim 1, 2 or 3, wherein the polyoxyalkylene compound has a molecular weight of 10,000 or less. 5. The polyoxyalkylene compound is
The compound has an aliphatic hydrocarbon group in which eight or more carbon atoms are continuously bonded in the molecule,
The concrete composition according to 3 or 4.