JP2014214070A - Hydraulic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydraulic composition which can reduce viscosity without decreasing underwater inseparability and is suitable as underwater inseparable concrete and the like.SOLUTION: The hydraulic composition comprises, under a specific condition: a combination of a cationic surfactant (A1) and an anionic surfactant (A2), or a quaternary cationic compound containing a quaternary cationic group (a1) having 10 or more but 26 or less carbon atoms and an aromatic anionic group (a2); a specific nonionic surfactant having HLB of 5 or more but 16 or less; hydraulic powder; and water.

Description

  The present invention relates to a hydraulic composition and a method for producing the hydraulic composition.

  Due to the recent increase in safety awareness, there is an increasing demand for concrete work even in places with water, such as seismic protection work for revetments in civil engineering-related work, and the demand for underwater non-separable concrete is also increasing.

  Underwater non-separable concrete contains various thickeners so that cement components are not dispersed and dissolved in water. The inseparability of concrete in water can be improved with an increase in the amount of thickener added, but on the other hand, it increases the viscosity of the concrete and may adversely affect handling properties. For example, there are cases where the fluidity of concrete decreases and causes poor filling, and when pumping, a load exceeding the pumping capacity is applied to the pump, causing poor pumping. In addition, in order to prevent poor pumping, it is necessary to install a pump with high pumping capability in advance, leading to an increase in cost.

  In order to prevent these problems, there is a demand for underwater inseparable concrete capable of reducing concrete viscosity without reducing underwater inseparability.

  Patent Document 1 discloses that a specific slurry rheology modifier containing two kinds of water-soluble low molecular weight compounds can impart rheological properties such as material separation resistance. Patent Document 2 discloses a one-component rheology modifier containing a specific quaternary salt type cationic compound. Patent Document 3 discloses that high pumpability can be obtained by specifying the composition of the polymer cement mortar.

JP 2003-313536 A JP 2004-124007 A JP 2006-44949 A

  The present invention provides a hydraulic composition suitable for underwater inseparable concrete and the like that can reduce viscosity without lowering underwater inseparability.

The present invention is a hydraulic composition containing the following component (A), the following component (B), a hydraulic powder, and water,
(A) Content of a component is 0.75 mass part or more and 5.0 mass parts or less with respect to 100 mass parts of water phases of a hydraulic composition,
(B) Content of a component is 0.010 mass part or more and 1.5 mass parts or less with respect to 100 mass parts of water phases of a hydraulic composition,
The mass ratio of the content of the component (A) and the content of the component (B) is [content of the component (B) / content of the component (A)] and is 0.0080 or more and 0.32 or less. ,
When the content of the component (A) is 2.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the aqueous phase of the hydraulic composition, the content of the component (A) and (B) The mass ratio of the component content is [(B) component content / (A) component content], which is 0.032 or more and 0.32 or less.
It relates to a hydraulic composition.
Component (A): a combination of a cationic surfactant (A1) and an anionic aromatic compound (A2), or a quaternary cationic group (a1) having at least one hydrocarbon group having 10 to 26 carbon atoms Quaternary salt type cationic compound (A3) containing aromatic anionic group (a2)
Component (B): Nonionic surfactant having an HLB of 5 or more and 16 or less (however, those having a monoester structure of sorbitan and a fatty acid, when the number of carbon atoms of the fatty acid-derived moiety of the ester is 18, The fatty acid-derived group of the ester has one unsaturated bond, and the average added mole number of ethylene oxide is 6 or less)

Further, the present invention is a method for producing a slurry-type hydraulic composition, comprising a step of mixing the following component (A), the following component (B), a hydraulic powder, and water,
(A) A component is 0.75 mass part or more and 5.0 mass parts or less with respect to 100 mass parts of water phases of a hydraulic composition, (B) A component is 100 mass parts of water phases of a hydraulic composition. Is mixed at a ratio of 0.010 parts by mass or more and 1.5 parts by mass or less,
The mass ratio of the amount of component (A) and the amount of component (B) is 0.0080 or more and 0.32 or less in [amount of component (B) / amount of component (A)],
When the component (A) is mixed at a ratio of 2.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the aqueous phase of the hydraulic composition, the amount of the component (A) and (B) The mass ratio of the component amounts is 0.032 or more and 0.32 or less in [(B) component amount / (A) component amount].
The present invention relates to a method for producing a hydraulic composition.
Component (A): a combination of a cationic surfactant (A1) and an anionic aromatic compound (A2), or a quaternary cationic group (a1) having at least one hydrocarbon group having 10 to 26 carbon atoms Quaternary salt type cationic compound (A3) containing aromatic anionic group (a2)
Component (B): Nonionic surfactant having an HLB of 5 or more and 16 or less (however, those having a monoester structure of sorbitan and a fatty acid, when the number of carbon atoms of the fatty acid-derived moiety of the ester is 18, The fatty acid-derived group of the ester has one unsaturated bond, and the average added mole number of ethylene oxide is 6 or less)

  Moreover, this invention relates to the pumping method of the hydraulic composition which pumps the hydraulic composition of the said invention.

  Moreover, this invention is a casting method of the hydraulic composition which has the process of pumping the hydraulic composition of the said invention with the pump, and the process of casting the hydraulic composition pumped with the pump.

The present invention also relates to a viscosity reducing agent for a hydraulic composition comprising the following component (B), wherein the hydraulic composition contains the following component (A).
Component (B): Nonionic surfactant having an HLB of 5 or more and 16 or less (however, those having a monoester structure of sorbitan and a fatty acid, when the number of carbon atoms of the fatty acid-derived moiety of the ester is 18, The fatty acid-derived group of the ester has one unsaturated bond, and the average added mole number of ethylene oxide is 6 or less)
Component (A): a combination of a cationic surfactant (A1) and an anionic aromatic compound (A2), or a quaternary cationic group (a1) having at least one hydrocarbon group having 10 to 26 carbon atoms Quaternary salt type cationic compound (A3) containing aromatic anionic group (a2)

  ADVANTAGE OF THE INVENTION According to this invention, the hydraulic composition suitable as underwater inseparable concrete etc. which can reduce a viscosity, without reducing inseparability in water is provided.

  The present inventors have found that the viscosity of concrete can be reduced without reducing the inseparability in water by adding the component (B) in the hydraulic composition using the component (A). The component (B) having a predetermined HLB selected in the present invention sufficiently penetrates into the string-like micelle formed by the component (A), and as a result, reduces the viscosity of the hydraulic composition. Inferred. In addition, in the present invention, by setting the mass ratio of the component (A) to the component (B) as a predetermined condition, the amount of penetration of the component (B) into the string micelle becomes appropriate, and the string micelle is appropriately subdivided. It is considered that the viscosity is reduced by changing to a rod-like or spherical micelle.

[Hydraulic composition]
<(A) component>
One of the components (A) is a combination of a cationic surfactant (A1) and an anionic aromatic compound (A2). Another component (A) is a quaternary salt containing a quaternary cation group (a1) having at least one hydrocarbon group having 10 to 26 carbon atoms and an aromatic anion group (a2). Type cationic compound (A3). Note that the quaternary salt type cationic compound having an aromatic anion group (a2) is excluded from the cationic surfactant (A1).

  From the viewpoint of forming string micelles, the component (A) includes a quaternary cation group (a1) having at least one hydrocarbon group having 10 to 26 carbon atoms and an aromatic anion group (a2). A salt-type cationic compound (A3) is preferred.

  The cationic surfactant (A1) is preferably a quaternary salt type cationic surfactant, and the quaternary salt type cationic surfactant has 10 to 26 carbon atoms in the structure. Those having at least one saturated or unsaturated linear or branched alkyl group containing are preferable. For example, alkyl (10 to 26 carbon atoms) trimethylammonium salt, alkyl (10 to 26 carbon atoms) pyridinium salt, alkyl (10 to 26 carbon atoms) imidazolinium salt, alkyl (10 to 10 carbon atoms) 26 or less) dimethylbenzylammonium salt, and the like. Specifically, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, tallow trimethylammonium chloride, tallow trimethylammonium bromide, Hydrogenated tallow trimethylammonium chloride, hydrogenated tallow trimethylammonium bromide, hexadecylethyldimethylammonium chloride Ride, octadecylethyldimethylammonium chloride, hexadecylpropyldimethylammonium chloride, hexadecylpyridinium chloride, 1,1-dimethyl-2-hexadecylimidazolinium chloride, hexadecyldimethylbenzylammonium chloride, and the like. You may use together. Specifically, from the viewpoint of water solubility and thickening effect, hexadecyltrimethylammonium chloride (for example, Cotamin 60W manufactured by Kao Corporation), octadecyltrimethylammonium chloride, hexadecylpyridinium chloride, and the like are preferable. In addition, two or more kinds of cationic surfactants having different carbon numbers in the above alkyl group can be used in combination.

  In addition, when the slurry rheology modifier of the present invention is applied to concrete or the like, a quaternary ammonium salt that does not contain halogen such as chlorine can be used from the viewpoint of preventing corrosion of the reinforcing steel and salt deterioration due to salt damage.

  Examples of quaternary salts containing no halogen such as chlorine include ammonium salts and imidazolinium salts. Specifically, hexadecyltrimethylammonium methosulfate, hexadecyldimethylethylammonium etosulphate, octadecyltrimethylammonium methosulfate, octadecyl. Dimethylethylammonium ethosulphate, tallow trimethylammonium methosulphate, tallow dimethylethylammonium ethosulphate, 1,1-dimethyl-2-hexadecylimidazolinium methosulphate, hexadecyldimethylhydroxyethylammonium acetate, octadecyldimethylhydroxyethylammonium acetate, Hexadecyldimethylhydroxyethylammonium propionate, oct Decyl dimethyl hydroxyethyl ammonium propionate, tallow dimethyl hydroxyethyl ammonium acetate, tallow dimethyl hydroxyethyl ammonium propionate, and the like. A quaternary ammonium salt containing no halogen such as chlorine can be obtained, for example, by quaternizing a tertiary amine with dimethyl sulfate or diethyl sulfate.

  Preferable cationic surfactant (A1) includes a cationic surfactant represented by the following general formula (A1-1).

[Wherein R ¹ is an alkyl group or alkenyl group having 10 to 26 carbon atoms, preferably an alkyl group, R ² is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms. , R ³ and R ⁴ are each an alkyl group having 1 to 3 carbon atoms. X ⁻ represents an anionic group (excluding an anionic group derived from an anionic aromatic compound). ]

In General Formula (A1-1), R ¹ is preferably 12 or more carbon atoms, more preferably 14 or more carbon atoms. Preferably it is 22 or less carbon atoms, More preferably, it is 20 or less. R ² , R ³ and R ⁴ are each preferably a methyl group. X ⁻ is preferably an anionic group selected from chloride ion, sulfate ion, methyl sulfate ion and ethyl sulfate ion.

  Examples of the anionic aromatic compound (A2) include carboxylic acids having an aromatic ring and salts thereof, phosphonic acids and salts thereof, sulfonic acids and salts thereof, specifically, salicylic acid, p-toluenesulfonic acid, Sulfosalicylic acid, benzoic acid, m-sulfobenzoic acid, p-sulfobenzoic acid, 4-sulfophthalic acid, 5-sulfoisophthalic acid, p-phenolsulfonic acid, m-xylene-4-sulfonic acid, cumenesulfonic acid, methylsalicylic acid Styrene sulfonic acid, chlorobenzoic acid and the like, and these may form a salt, and two or more of these may be used in combination. However, in the case of a polymer, the weight average molecular weight (for example, gel permeation chromatography method / polyethylene oxide conversion) is preferably less than 500.

  The molar ratio of the cationic surfactant (A1) to the anionic aromatic compound (A2) is cationic surfactant (A1) / anionic aromatic compound (A2), preferably 0.15 or more, more preferably Is 0.40 or more, more preferably 0.80 or more, and preferably 1.5 or less, more preferably 1.2 or less, and still more preferably 1.0 or less.

  The quaternary salt type cationic compound (A3) has at least one quaternary cationic group (a1) having at least one hydrocarbon group having 10 to 26 carbon atoms. In the quaternary cation group (a1), the hydrocarbon group preferably has 12 or more, more preferably 14 or more, and preferably 22 or less, and more preferably 18 or less.

  Examples of the quaternary cationic group include a long-chain alkyl (C10 or more and 26 or less) hydroxyethyldimethylammonium group and a mono long-chain alkyl (C10 or more and 26 or less) trimethylammonium group. The quaternary cationic group (a1) can be derived from a quaternary salt type cationic compound. Specific examples of the compound include tetradecylhydroxyethyldimethylammonium, hexadecylhydroxyethyldimethylammonium, and octadecylhydroxyethyl. Dimethyl ammonium, oleyl hydroxyethyl dimethyl ammonium, tallow hydroxy ethyl dimethyl ammonium, hydrogenated tallow hydroxy ethyl dimethyl ammonium, tetradecyl trimethyl ammonium, hexadecyl trimethyl ammonium, octadecyl trimethyl ammonium, oleyl trimethyl ammonium, tallow trimethyl ammonium, hydrogenated tallow trimethyl ammonium , Hexadecyl dihydroxyethyl methyl ammonium, octadecyl dihydride Ciethylmethylammonium, oleyldihydroxyethylmethylammonium, tarodihydroxyethylmethylammonium, hydrogenated tarodihydroxyethylmethylammonium, hexadecylpyridinium, 1,1-dimethyl-2-hexadecylimidazolinium, etc. Can be mentioned. Of these, hexadecyltrimethylammonium, octadecyltrimethylammonium, tallowtrimethylammonium, and hydrogenated tallowtrimethylammonium are more preferable.

  The quaternary salt type cationic compound (A3) contains one or more aromatic anionic groups (a2). Examples of the anionic group include a sulfone group and a carboxyl group, and examples of the aromatic group include a benzene ring. The aromatic anionic group (a2) can be derived from an anionic aromatic compound, and specific examples of the compound include paratoluenesulfonate, salicylate, metaxylenesulfonate, cumenesulfonate, styrenesulfonate, benzenesulfonate, Examples include benzoate. Of these, p-toluenesulfonate is preferred.

  In the quaternary salt type cationic compound (A3), the length of the hydrocarbon group is different as the quaternary cation group (a1) of the quaternary salt type cationic compound (A3) in that the temperature range for thickening can be widened. It is preferable that two or more quaternary cation groups are present. For this purpose, two or more quaternary salt type cationic compounds (A) having different quaternary cation group hydrocarbon groups may be used, Even if the quaternary salt type cationic compound (A) having a quaternary cation group in which two or more hydrocarbon groups having different lengths are bonded to one cation group, the quaternary having different hydrocarbon group lengths is used. Either a quaternary salt type cationic compound (A) having two or more cationic groups may be used, or a combination thereof may be used. Of these, two or more quaternary salt type cationic compounds (A) having different quaternary cationic hydrocarbon groups are used in combination with water solubility and rheology modification effect. Is preferred.

  Examples of the quaternary salt type cationic compound (A3) include compounds represented by the following general formula (A3-1) [hereinafter referred to as cationic compound (A3-1)].

Wherein, R ^ll is 10 or more carbon atoms, 26 an alkyl group, R ^l2 is 1 or more carbon atoms, 22 an alkyl group or the number 2 or 3 hydroxy alkyl group having a carbon, R ^l3 and R ^l4 are each , An alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 2 or 3 carbon atoms, at least one of which is a hydroxyalkyl group having 2 or 3 carbon atoms. X ¹⁻ represents an anionic group derived from an anionic aromatic compound, preferably p-toluenesulfonic acid. ]

In general formula (A3-1), ^Rll is preferably an alkyl group having 12 or more carbon atoms, more preferably 14 or more, and preferably 22 or less, more preferably 20 or less. Further, it is preferable that at least one of R ^l2, R ^l3 and R ^l4 is a hydroxyalkyl group having 2 or 3 carbon atoms. If R ¹² is not a hydroxyalkyl group having 2 or 3 carbon atoms, R ^l2 is a methyl group is preferable.

  The cationic compound (A3-1) is a compound obtained by using an amine and an anionic aromatic compound as raw materials in a molar ratio of anionic aromatic compound / amine = 0.93 or more and 1.02 or less. . The reaction between the amine and the anionic aromatic compound can be carried out batchwise or continuously, and in any case, the molar ratio is the same as that used to produce the cationic compound (A3-1). It is calculated based on the number of moles of the amine and the anionic aromatic compound. In addition, the cationic compound (A3-1) is preferably a compound obtained by reacting an amine and an anionic aromatic compound in the molar ratio at an amine reaction rate of 99 to 100%. Here, the reaction rate of amine means a quaternization rate.

  In the method for producing the cationic compound (A3-1), the cationic compound (A3-1) is a compound obtained by using an epoxy compound as a raw material, that is, an amine and an anionic aromatic as a raw material. A compound obtained by using a compound and an epoxy compound, preferably a compound having an anionic aromatic compound / amine molar ratio of 0.93 or more and 1.02 or less. Also in this case, the reaction rate of the amine is preferably 99 or more and 100% or less. Therefore, the cationic compound (A3-1) is a step in which an epoxy compound is added to an amine in the presence of an anionic aromatic compound having a molar ratio of 0.93 to 1.02 with respect to the amine ( Compounds obtained by the production process having I) are preferred.

  In the present invention, including the case where an epoxy compound is added, the molar ratio of the anionic aromatic compound to the raw material amine is preferably an anionic aromatic compound / raw material amine, preferably 0.93 or more, more preferably 0.94 or more. Further, it is preferably 0.95 or more, more preferably 0.98 or more, and preferably 1.02 or less, more preferably 1.01 or less, and further preferably 1.00 or less. If this molar ratio is 0.93 or more, a cord-like micelle component is likely to be generated, so an appropriate slurry viscosity is obtained, and if it is 1.02 or less, there are not too many anionic aromatic compounds. A moderate slurry viscosity can be obtained without shortening the relaxation time.

  The amine is a compound derived from the quaternary cation group in the general formula (A3-1), specifically, dodecyldimethylamine, tetradecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, behenyldimethylamine. , Hexadecanoic acid amidopropyldimethylamine, octadecanoic acid amidopropyldimethylamine, hexadecanoic acid amidoethyl dimethylamine, and the like, preferably an amine selected from hexadecyldimethylamine, octadecyldimethylamine, and behenyldimethylamine, more preferably Is hexadecyldimethylamine and / or octadecyldimethylamine.

The cationic compound (A3-1) includes a compound (A-C ₁₆ ) in which R ¹¹ in the general formula (A3-1) is an alkyl group having 16 carbon atoms and a compound (A-) that is an alkyl group having 18 carbon atoms. C ₁₈ ) are preferably contained, and these ratios are (A−C ₁₆ ) / (A−C ₁₈ ) = 20/80 or more in terms of molar ratio from the viewpoint of product stability and temperature dependency of performance. 40/60 or more is more preferable, 45/55 or more is more preferable, 80/20 or less is preferable, 60/40 or less is more preferable, 55/45 or less is further preferable, and still more preferably 50 / 50. Further, the cationic compound (A3-1) is a ratio of the compound in which R ¹¹ in the general formula (A3-1) is an alkyl group having a carbon number other than an alkyl group having 16 carbon atoms and an alkyl group having 18 carbon atoms. However, from the viewpoint of the effect of imparting viscosity to the slurry, the total amount of the cationic compound (A3-1) is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 1 mol% or less. It is preferable to select the type and composition of the amine so as to satisfy the molar ratio and the ratio.

Examples of the aromatic anionic compound include compounds having X ⁻ in the general formula (A3-1) and having an anionic group such as a sulfonic acid group and a carboxyl group and an aromatic group such as a benzene ring. Specific examples include p-toluenesulfonic acid, salicylic acid, benzoic acid, metaxylenesulfonic acid, cumenesulfonic acid, styrenesulfonic acid, and benzenesulfonic acid. Of these, p-toluenesulfonic acid is preferred. These compounds may be used in the form of salts such as sodium paratoluenesulfonate.

In the cationic compound (A3-1), the hydroxyalkyl groups of R ¹³ and R ⁴⁴ in the general formula (A3-1) can be generated by adding an epoxy compound to an amine. After addition of one molecule of the epoxy compound, addition is continuously performed, and a compound having a chain such as diethylene glycol and polyethylene glycol may be included.

  Examples of the epoxy compound include those having 2 or 3 carbon atoms, and specific examples include ethylene oxide, propylene oxide, and epichlorohydrin from the viewpoint of reactivity.

  The molar ratio of the epoxy compound to the amine used as a raw material can be determined from the viewpoint of the production efficiency and production cost of the cationic compound (A3-1), and is preferably an epoxy compound / amine, preferably 1.0 or more. More preferably, it is 1.1 or more, More preferably, it is 1.2 or more, Preferably it is 3.0 or less, More preferably, it is 2.0 or less, More preferably, it is 1.5 or less. If the molar ratio is 1.0 or more, string-like micelles are sufficiently formed and the effect of imparting viscosity to the slurry is good. If the molar ratio is 3.0 or less, the relaxation time of the string-like micelles is appropriate. The effect is good.

When the cationic compound (A3-1) is a compound obtained by further using an epoxy compound as a raw material, the cationic compound (A3-1) is a production method having the following steps (I) and (II): The total amount of anionic aromatic compounds used in step (I) and step (II) is 0.93 or more and 1.02 in terms of molar ratio to the amine used in step (I). The following is preferable.
Step (I): Adding an epoxy compound to an amine in the presence of an anionic aromatic compound Step (II): Further adding an anionic aromatic compound to the reaction product obtained in Step (I) Process

  Step (I) is a step of adding an epoxy compound to a raw material amine in the presence of a predetermined amount of an anionic aromatic compound. The addition reaction of an epoxy compound can be performed according to a known method. For example, the reaction temperature is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, and preferably 150 ° C. or lower, more preferably 120 ° C. The reaction time is preferably 0.05 hours or longer, more preferably 0.1 hours or longer, and preferably 20 hours or shorter, more preferably 10 hours or shorter. The completion of the addition reaction of the epoxy compound can be confirmed by quantifying the residual amount of amine used as a raw material. The residual amount of raw material amine can be determined by back titration using potentiometric titration.

  In the present invention, addition of an anionic aromatic compound to the reaction product obtained in step (I) can further enhance the addition reaction of the epoxy compound, that is, the quaternization reaction is performed. Since it progresses, it is preferable from the rheology modifier excellent in viscoelasticity expression being obtained. However, when the step (II) is performed, the total of the anionic aromatic compounds used in the step (I) and the step (II) is 0. 0 by mole with respect to the amine used as the raw material used in the step (I). 93 or more and 1.02 or less. That is, based on the amine charged in step (I), the total molar ratio of the anionic aromatic compound used in step (I) and the anionic aromatic compound further added in step (II) is 0.93. As described above, an anionic aromatic compound is further added to the reaction product obtained in the step (I) so as to be 1.02 or less.

  The molar ratio of the anionic aromatic compound to the amine in step (I) is preferably 0.90 or more, more preferably 0.92 or more, and preferably 0.98 or less, more preferably 0.96 or less. The molar ratio of the anionic aromatic compound to the amine used in step (I) in step (II) is preferably 0.01 or more, more preferably 0.03 or more, and preferably 0.12 or less. Preferably it is 0.06 or less.

  Further, the ratio (M1) of the molar ratio of the anionic aromatic compound to the amine in the step (I) and the molar ratio (M2) of the anionic aromatic compound to the amine used in the step (I) in the step (II) ( M2) / (M1) is preferably 0.01 or more, more preferably 0.03 or more, and preferably 0.13 or less, more preferably 0.07 or less.

  Since the cationic compound (A3-1) is a quaternary salt type compound having both a quaternary cation group and an aromatic anion group having a function of forming an aggregate and increasing the viscosity in an aqueous solution or slurry, 4 There is no need to separately meter and add two kinds of chemicals, a secondary cationic compound and an aromatic anionic compound, and the same thickened state can be obtained by metering and adding one kind of chemicals, resulting in excellent workability.

  Since the cationic compound (A3-1) does not contain a halogen element due to its production method, there is no risk of accelerating its corrosion even when a metal is present at the place of use.

The cationic compound (A3-1) preferably has two or more quaternary cationic groups having different carbon numbers of R ^{11 in} the general formula (A3-1) from the viewpoint of widening the temperature range in which the viscosity is increased. Further, from the viewpoint of enhancing the solubility of the rheology modifier in water and the effect of the rheology modification, two types of cationic compounds (A3-1) having different alkyl group (R ¹¹ ) lengths of the quaternary cationic groups are used. It is preferable to use the above.

<(B) component>
The component (B) is a nonionic surfactant having an HLB of 5 or more and 16 or less (however, those having a monoester structure of sorbitan and a fatty acid, when the number of carbons in the fatty acid-derived moiety of the ester is 18) The fatty acid-derived group of the ester has one unsaturated bond, and the average added mole number of ethylene oxide is 6 or less.

  The HLB of the component (B) is 5 or more, preferably 6 or more, more preferably 7 or more, still more preferably 9 or more, 16 or less, preferably 15 or less, more preferably 14 or less, from the viewpoint of viscosity reduction. More preferably, it is 12 or less. Here, the HLB of the component (B) is defined by the HLB of Griffin.

  As the component (B), glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene alkyl ether, polyoxy One or more types of nonionic surfactants selected from the group consisting of ethylene alkylamines can be mentioned.

  As the component (B), from the viewpoint of viscosity reduction, polyoxyethylene hydrogenated castor oil, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene alkyl ether and One or more nonionic surfactants selected from the group consisting of polyoxyethylene alkylamines are preferred.

  As polyoxyethylene hydrogenated castor oil, from the viewpoint of viscosity reduction, the average added mole number of ethylene oxide is preferably 10 or more, more preferably 20 or more, and preferably 60 or less, more preferably 40 or less. . Castor oil is a non-drying oil taken from the seeds of castor (castor bean), and is mainly composed of glycerin ester of ricinoleic acid, which is reacted with hydrogen to convert unsaturated bonds to saturated bonds. Further, hydrogenated castor oil is obtained, and polyoxyethylene hydrogenated castor oil is obtained by further reacting with ethylene oxide.

  Moreover, as polyoxyethylene fatty acid ester, from the viewpoint of viscosity reduction, ethylene oxide average added mole number is preferably 5 or more, more preferably 10 or more, and preferably 40 or less, more preferably 30 or less. It is done. Examples of the fatty acid include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid and stearic acid.

  The polyoxyethylene sorbitan fatty acid ester includes those having an average added mole number of ethylene oxide of more than 0, preferably 2 or more, and preferably 20 or less, more preferably 10 or less from the viewpoint of viscosity reduction. Examples of fatty acids of sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters include fatty acids having 8 to 20 carbon atoms, and fatty acids selected from lauric acid and oleic acid. The sorbitan fatty acid ester and the polyoxyethylene sorbitan fatty acid ester may each be a monoester, a diester, a triester, or a tetraester, or a mixture thereof. However, for those having a monoester structure of sorbitan and a fatty acid, that is, sorbitan monofatty acid ester and polyoxyethylene sorbitan monofatty acid ester, when the number of carbons in the fatty acid-derived portion of the ester is 18, the fatty acid of the ester The group of the origin part has one unsaturated bond, and the average added mole number of ethylene oxide is 6 or less. Therefore, in the case of sorbitan monofatty acid ester, when the number of carbons in the fatty acid-derived portion of the ester is 18, the group of the fatty acid-derived portion of the ester has one unsaturated bond. For polyoxyethylene sorbitan mono-fatty acid ester, when the number of carbons in the fatty acid-derived portion of the ester is 18, the group of the fatty acid-derived portion of the ester has one unsaturated bond, and the average addition of ethylene oxide The number of moles is 6 or less and more than 0.

  The polyoxyethylene sorbite fatty acid ester has an ethylene oxide average addition mole number of preferably 5 or more, more preferably 10 or more, and preferably 60 or less, more preferably 40 or less, from the viewpoint of viscosity reduction. Can be mentioned. Examples of the fatty acid of the polyoxyethylene sorbit fatty acid ester include fatty acids having 8 to 20 carbon atoms, and fatty acids selected from lauric acid and oleic acid.

  The polyoxyethylene alkyl ether has an ethylene oxide average addition mole number of preferably 2 or more, more preferably 5 or more, and preferably 60 or less, more preferably 40 or less from the viewpoint of viscosity reduction. It is done. In addition, from the same viewpoint, the alkyl group preferably has 8 or more carbon atoms, more preferably 10 or more carbon atoms, and preferably 22 or less, more preferably 20 or less.

  In addition, the polyoxyethylene alkylamine has an ethylene oxide average addition mole number of preferably 2 or more, more preferably 4 or more, and preferably 40 or less, more preferably 20 or less from the viewpoint of viscosity reduction. It is done. In addition, from the same viewpoint, the alkyl group preferably has 8 or more carbon atoms, more preferably 10 or more carbon atoms, and preferably 22 or less, more preferably 20 or less.

<Hydraulic powder>
The hydraulic powder is a powder that hardens when mixed with water. Eco-cement (for example, JIS R5214 etc.) is mentioned. Among these, from the viewpoint of shortening the time required to reach the required strength of the hydraulic composition, a cement selected from early strong Portland cement, ordinary Portland cement, sulfate-resistant Portland cement, and white Portland cement is preferable. Portland cement and ordinary Portland cement are more preferable.

  The hydraulic powder may include blast furnace slag, fly ash, silica fume and the like, and may include non-hydraulic fine limestone powder and the like. As the hydraulic powder, silica fume cement or blast furnace cement in which cement and blast furnace slag, fly ash, silica fume and the like are mixed may be used.

<Aggregate>
The hydraulic composition of the present invention preferably contains an aggregate. Examples of the aggregate include fine aggregate and coarse aggregate. The fine aggregate is preferably mountain sand, land sand, river sand and crushed sand, and the coarse aggregate is preferably mountain gravel, land gravel, river gravel and crushed stone. Depending on the application, lightweight aggregates may be used. The term “aggregate” is based on “Concrete Overview” (published on June 10, 1998, published by Technical Shoin).

<Dispersant>
The hydraulic composition of the present invention preferably contains a dispersant. The dispersant is a dispersant for hydraulic powder, and from the viewpoint of shortening the time required to reach the required strength of the hydraulic composition, the dispersant is selected from naphthalene polymers and polycarboxylic acid copolymers. Is preferred.

  As the naphthalene polymer, naphthalene sulfonate formaldehyde condensate (for example, Mighty 150 manufactured by Kao Corporation), and as the melamine polymer, melamine sulfonate formaldehyde condensate (for example, Mighty 150-V2 manufactured by Kao Corporation), phenol Phenol sulfonic acid formaldehyde condensates (compounds described in JP-A-49-104919) and the like as lignin polymers, and lignin sulfonate (Ultragin NA from Borregard, Nippon Paper Chemical Co., Ltd.) Company-extracted sun extract, vanillex, pearl rex, etc.) can be used.

  As the polycarboxylic acid-based copolymer, a copolymer of a monoester of polyalkylene glycol and (meth) acrylic acid and a carboxylic acid such as (meth) acrylic acid (for example, described in JP-A-8-12397) Compounds), copolymers of unsaturated alcohols having polyalkylene glycol and carboxylic acids such as (meth) acrylic acid, copolymers of unsaturated alcohols having polyalkylene glycol and dicarboxylic acids such as maleic acid, etc. Can be used. Here, (meth) acrylic acid means a carboxylic acid selected from acrylic acid and methacrylic acid.

  As a polycarboxylic acid copolymer, a monomer (1) represented by the following general formula (1) and a monomer (2) represented by the following general formula (2) are polymerized. The resulting copolymer [hereinafter referred to as polycarboxylic acid copolymer (I)] can be used.

[Where,
R ¹ , R ² : hydrogen atom or methyl group 1: number of 0 or more and 2 or less m: number of 0 or 1 AO: alkyleneoxy group of 2 or more and 4 or less carbon atoms n: average number of added moles of AO, A number between 5 and 150,
R ^{3 represents a} hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[Where,
R ⁴ , R ⁵ , R ⁶ : hydrogen atom, methyl group, or (CH ₂ ) _m1 COOM ²
M ¹ and M ² : each represents a number of hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium, alkylammonium, or substituted alkylammonium m1: 0 to 2; Note that (CH ₂ ) _m1 COOM ² may form an anhydride with COOM ¹ . ]

  In general formula (1), AO is preferably an alkyleneoxy group (ethyleneoxy group) having 2 or 3 carbon atoms, more preferably 2 carbon atoms, from the viewpoint of fluidity of the hydraulic composition.

  From the viewpoint of improving the strength of the hydraulic composition after 24 hours, n is preferably a number of 9 or more, more preferably 20 or more, still more preferably 50 or more, and still more preferably 70 or more. From the viewpoint of initial fluidity of the hydraulic composition, n is preferably a number of 150 or less, more preferably 130 or less.

When m is 0, l is preferably 1 or 2. When m is 1, l is preferably 0. From the viewpoint of polymerizability at the time of polymerization of the copolymer, m is preferably 1. When m is 0, R ³ is preferably a hydrogen atom from the viewpoint of ease of production of the monomer. When m is 1, R ³ is preferably an alkyl group having 1 to 4 carbon atoms from the viewpoint of ease of production of the monomer, and more preferably a methyl group from the viewpoint of water solubility.

  As the monomer (1), for example, an ester of a polyalkylene glycol and (meth) acrylic acid, an ether obtained by adding an alkylene oxide to an alkenyl alcohol, or the like can be used. Monomer (1) is preferably an ester of polyalkylene glycol and (meth) acrylic acid from the viewpoint of polymerizability during polymerization of the copolymer.

  As an ester of polyalkylene glycol and (meth) acrylic acid, an ester of alkylene glycol and (meth) acrylic acid blocked at one end can be used. Specifically, one or more kinds such as methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methacrylate, ethoxypolyethylene glycol acrylate, and ethoxypolyethylene glycol methacrylate can be used.

  Further, as an ether in which an alkylene oxide is added to an alkenyl alcohol, an allyl alcohol ethylene oxide adduct or the like can be used. Specifically, an ethylene oxide adduct of methallyl alcohol, an ethylene oxide adduct of 3-methyl-3-buten-1-ol, and the like can be used.

  As a monomer (2), 1 or more types chosen from acrylic acid or its salt, methacrylic acid or its salt, maleic acid or its salt, maleic anhydride, etc. can be used. The monomer (2) is preferably methacrylic acid or a salt thereof from the viewpoint of polymerizability at the time of polymerization of the copolymer when m of the monomer (1) is 1. When m is 0, maleic acid or a salt thereof and maleic anhydride are preferred from the viewpoint of polymerizability at the time of polymerization of the copolymer.

<Other ingredients>
The hydraulic composition may further contain other components as long as the effects of the present invention are not affected. For example, AE agent, retarder, foaming agent, thickener, foaming agent, waterproofing agent, fluidizing agent, antifoaming agent and the like can be mentioned.

<Composition of hydraulic composition>
In the hydraulic composition of the present invention, the content of the component (A) is 0.75 parts by mass or more with respect to 100 parts by mass of the aqueous phase of the hydraulic composition from the viewpoint of ensuring inseparability in water and reducing the viscosity. 5.0 parts by mass or less. From the viewpoint of securing inseparability in water, the content of component (A) is 0.75 parts by mass or more, preferably 0.85 parts by mass or more, more preferably 100 parts by mass of the aqueous phase of the hydraulic composition. Is 1.0 part by mass or more, and from the viewpoint of viscosity reduction, 5.0 parts by mass or less, preferably 4.0 parts by mass or less, more preferably 2.5 parts by mass or less, and still more preferably 1.5 parts by mass. Less than parts by weight. When the component (A) is a combination of the cationic surfactant (A1) and the anionic aromatic compound (A2), this content is the total content thereof. In addition, unless otherwise indicated, content of (A) component is content of effective component conversion, and mass ratio is also based on content of effective component conversion.

  Here, the aqueous phase of the hydraulic composition is a liquid phase containing water obtained by removing a solid phase insoluble in water such as hydraulic powder from the hydraulic composition. As the water of the hydraulic composition according to the present invention, those usually used in the art for the preparation of concrete can be used, and examples thereof include tap water. The aqueous phase can be based on that formed at the temperature in use. Usually, a liquid phase formed at a temperature within this range can be used as a water phase based on a dissolved state at 5 ° C. or more and 35 ° C.

  In the hydraulic composition of the present invention, the content of the component (B) is 0.010 parts by mass or more with respect to 100 parts by mass of the aqueous phase of the hydraulic composition, from the viewpoint of reducing viscosity and securing inseparability in water. 1.5 parts by mass or less. From the viewpoint of reducing the viscosity, the content of the component (B) is 0.010 parts by mass or more, preferably 0.015 parts by mass or more, more preferably 0.005 parts by mass with respect to 100 parts by mass of the aqueous phase of the hydraulic composition. It is 020 parts by mass or more, and from the viewpoint of ensuring inseparability in water, it is 1.5 parts by mass or less, preferably 1.0 part by mass or less, more preferably 0.50 part by mass or less. In addition, unless otherwise indicated, content of (B) component is content of effective component conversion, and mass ratio is also based on content of effective component conversion.

  In the hydraulic composition of the present invention, the mass ratio of the content of the component (A) and the content of the component (B) is [[content of component (B) / (A) Content of component] is 0.0080 or more and 0.32 or less. From the viewpoint of ensuring inseparability in water and reducing the viscosity, the mass ratio of the content of the component (B) / the content of the component (A) is 0.0080 or more, preferably 0.0090 or more, from the viewpoint of viscosity reduction. More preferably, it is 0.010 or more, more preferably 0.020 or more, and from the viewpoint of ensuring inseparability in water, it is 0.32 or less, preferably 0.30 or less, more preferably 0.10 or less. . In addition, when content of (A) component is 2.5 mass parts or more and 5.0 mass parts or less with respect to 100 mass parts of water phases of a hydraulic composition, content / (B) component / The mass ratio of the content of component (A) is 0.032 or more, preferably 0.036 or more, more preferably 0.040 or more, and 0.32 or less, preferably 0.30 or less, more preferably Is 0.10 or less. Moreover, when content of (A) component is 0.75 mass part or more and less than 2.5 mass parts with respect to 100 mass parts of water phases of a hydraulic composition, content of (B) component The mass ratio of the content of the / (A) component is 0.0080 or more, preferably 0.0090 or more, more preferably 0.010 or more, and 0.32 or less, preferably 0.30 or less, more preferably 0.10 or less.

  In the hydraulic composition of the present invention, the hydraulic powder content is preferably 30 parts by mass or more, more preferably 40 parts by mass with respect to 100 parts by mass of the aqueous phase of the hydraulic composition from the viewpoint of strength development. Part or more, more preferably 50 parts by weight or more, and from the viewpoint of viscosity reduction, it is preferably 700 parts by weight or less, more preferably 600 parts by weight or less, still more preferably 500 parts by weight or less.

  In the hydraulic composition of the present invention, the content of the dispersant is preferably 0.02 parts by mass or more, more preferably 0.06, with respect to 100 parts by mass of the aqueous phase, from the viewpoint of expressing the fluidity of fresh concrete. From the viewpoint of ensuring retainability, it is preferably 2 parts by mass or less, more preferably 1.4 parts by mass or less, and still more preferably 1 part by mass or less. is there.

<Method for producing hydraulic composition, pumping method, viscosity reducing agent>
According to the present invention, there is provided a method for producing a hydraulic composition comprising a step of mixing the component (A), the component (B), a hydraulic powder, and water,
(A) A component is 0.75 mass part or more with respect to 100 mass parts of water phases of a hydraulic composition, Preferably it is 0.85 mass part or more, More preferably, it is 1.0 mass part or more. 0 parts by mass or less, preferably 4.0 parts by mass or less, more preferably 2.5 parts by mass or less, still more preferably 1.5 parts by mass or less, and (B) component, 100 parts by mass of the aqueous phase of the hydraulic composition To 0.010 parts by mass or more, preferably 0.015 parts by mass or more, more preferably 0.020 parts by mass or more, and 1.5 parts by mass or less, preferably 1.0 parts by mass or less. Is mixed at a ratio of 0.50 parts by mass or less,
The mass ratio of the amount of the component (A) to the amount of the component (B) is 0.0080 or more, preferably 0.0090 or more, more preferably [(B) component amount / (A) component amount]. 0.010 or more and 0.32 or less, preferably 0.30 or less, more preferably 0.10 or less,
When the component (A) is mixed at a ratio of 2.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the aqueous phase of the hydraulic composition, the amount of the component (A) and (B) The mass ratio of the component amounts is 0.032 or more, preferably 0.036 or more, more preferably 0.040 or more, and 0.32 in [(B) component amount / (A) component amount]. Or less, preferably 0.30 or less, more preferably 0.10 or less,
A method for producing a hydraulic composition is provided. In this method for producing a hydraulic composition, the component (A) and the component (B) are mixed so as to have the predetermined ratio with respect to 100 parts by mass of the aqueous phase of the hydraulic composition. As the preferred embodiment of the component A), the component (B), the hydraulic powder, and the preferred embodiment of the other components, those described in the hydraulic composition can be applied. Moreover, the amount of the component (A) and the amount of the component (B) are the content in terms of the effective component, respectively, and the mass ratio is also based on the content in terms of the effective component.

As a method for producing the hydraulic composition of the present invention,
(A) component is a combination of a cationic surfactant (A1) and an anionic aromatic compound (A2),
A step (1) of obtaining a mixture (1) by mixing an anionic aromatic compound (A2), a component (B), a hydraulic powder and water;
A step (2) of mixing the cationic surfactant (A1) and water to obtain a mixture (2), and a step (3) of mixing the mixture (1) and the mixture (2);
The manufacturing method of the hydraulic composition which has this is mentioned.

  In the method for producing a hydraulic composition of the present invention, it is preferable to mix aggregate in any of the production steps of the hydraulic composition. Moreover, in the manufacturing method of the hydraulic composition of this invention, it is preferable to mix a dispersing agent in either of the manufacturing process of a hydraulic composition. The dispersant is preferably 0.02 parts by mass or more, more preferably 0.06 parts by mass or more, still more preferably 0.1 parts by mass or more, and preferably 100 parts by mass of the aqueous phase of the hydraulic composition. Is 2 parts by mass or less, more preferably 1.4 parts by mass or less, and still more preferably 1 part by mass or less.

  In the method for producing the hydraulic composition of the present invention, all the existing devices can be used for mixing each component. For example, a tilting barrel mixer, a pan-type mixer, a biaxial forced mixer, an omni mixer, a Henschel mixer, V Examples thereof include a mold mixer and a nauter mixer.

  Examples of the method for placing the hydraulic composition according to the present invention include a method having a step of pumping the hydraulic composition with a pump and a step of placing the hydraulic composition pumped with the pump.

  According to the present invention, the hydraulic composition of the present invention is transported to a casting place and then poured into a mold to perform casting. Although the method of conveyance is mentioned generally and the method of conveyance is not specifically limited, The method of pumping with a pump, the method of conveying with a mixer car, the method of pouring and moving to a hopper from a mixer, etc. are mentioned. From the viewpoint of reducing the viscosity, when placing in a place where it cannot be transported by a mixer-car or a hopper, there is an advantage that it can be pumped even by a low-capacity pump.

  In the case of pumping the hydraulic composition of the present invention, the hydraulic composition adjusted to the desired physical properties and kneaded can be carried out by pumping to a suitably arranged pipe. A hydraulic composition can also be pumped using pumps, such as a pump car, after conveyance with a mixer truck.

  The type of pump includes a squeeze type and a piston type that are generally used, and is not particularly limited.

  According to the present invention, there is provided a viscosity reducing agent for a hydraulic composition comprising the component (B), wherein the hydraulic composition contains the component (A).

Embodiments of the present invention are shown below.
<1> A hydraulic composition containing the following component (A), the following component (B), a hydraulic powder, and water,
(A) Content of a component is 0.75 mass part or more and 5.0 mass parts or less with respect to 100 mass parts of water phases of a hydraulic composition,
(B) Content of a component is 0.01 mass part or more and 1.5 mass parts or less with respect to 100 mass parts of water phases of a hydraulic composition,
The mass ratio of the content of the component (A) and the content of the component (B) is [content of the component (B) / content of the component (A)] and is 0.0080 or more and 0.32 or less. ,
When the content of the component (A) is 2.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the aqueous phase of the hydraulic composition, the content of the component (A) and (B) The mass ratio of the component content is [(B) component content / (A) component content], which is 0.032 or more and 0.32 or less.
Hydraulic composition.
Component (A): a combination of a cationic surfactant (A1) and an anionic aromatic compound (A2), or a quaternary cationic group (a1) having at least one hydrocarbon group having 10 to 26 carbon atoms Quaternary salt type cationic compound (A3) containing aromatic anionic group (a2)
Component (B): Nonionic surfactant having an HLB of 5 or more and 16 or less (however, those having a monoester structure of sorbitan and a fatty acid, when the number of carbon atoms of the fatty acid-derived moiety of the ester is 18, The fatty acid-derived group of the ester has one unsaturated bond, and the average added mole number of ethylene oxide is 6 or less)

<2> The hydraulic composition according to <1>, wherein the cationic surfactant (A1) is a quaternary salt type cationic surfactant.

<3> The hydraulic composition according to <1> or <2>, wherein the cationic surfactant (A1) is a cationic surfactant represented by the following general formula (A1-1).

[Wherein R ¹ is an alkyl group or alkenyl group having 10 to 26 carbon atoms, preferably an alkyl group, R ² is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms. , R ³ and R ⁴ are each an alkyl group having 1 to 3 carbon atoms. X ⁻ represents an anionic group (excluding an anionic group derived from an anionic aromatic compound). ]

<4> The anionic aromatic compound (A2) is one or more anionic aromatic compounds selected from carboxylic acids having an aromatic ring and salts thereof, phosphonic acids and salts thereof, and sulfonic acids and salts thereof. The hydraulic composition according to any one of <1> to <3>.

<5> The component (A) is a combination of a cationic surfactant (A1) and an anionic aromatic compound (A2), and the moles of the cationic surfactant (A1) and the anionic aromatic compound (A2) The ratio of cationic surfactant (A1) / anionic aromatic compound (A2) is preferably 0.15 or more, more preferably 0.40 or more, still more preferably 0.80 or more, and preferably The hydraulic composition according to any one of <1> to <4>, wherein is 1.5 or less, more preferably 1.2 or less, and still more preferably 1.0 or less.

<6> A quaternary salt type cationic compound in which the component (A) includes a quaternary cation group (a1) having at least one hydrocarbon group having 10 to 26 carbon atoms and an aromatic anion group (a2). The hydraulic composition according to any one of <1> to <5>, which is (A3).

<7> The quaternary salt type cationic compound (A3) is a compound represented by the following general formula (A3-1) [hereinafter referred to as a cationic compound (A3-1)]. The hydraulic composition according to any one of 6>.

Wherein, R ^ll is 10 or more carbon atoms, 26 an alkyl group, R ^l2 is 1 or more carbon atoms, 22 an alkyl group or the number 2 or 3 hydroxy alkyl group having a carbon, R ^l3 and R ^l4 are each , An alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 2 or 3 carbon atoms, at least one of which is a hydroxyalkyl group having 2 or 3 carbon atoms. X ¹⁻ represents an anionic aromatic compound residue. ]

<8> The water according to any one of <1> to <7>, wherein the cationic compound (A3-1) contains two or more compounds having different carbon numbers of R ^{11 in} the general formula (A3-1). Hard composition.

<9> cationic compound (A3-1) is the general formula (A3-1) compound R ¹¹ is an alkyl group of the compound (A-C ₁₆₎ and 18 carbon atoms is an alkyl group of 16 carbon atoms in the (A-C ₁₈ ), and the molar ratio of the compound (A-C ₁₆ ) to the compound (A-C ₁₈ ) is (A-C ₁₆ ) / (A-C ₁₈ ), preferably 20/80 Or more, more preferably 40/60 or more, still more preferably 45/55 or more, and 80/20 or less, preferably 60/40 or less, more preferably 55/45 or less, and still more preferably 50 / The hydraulic composition according to any one of <1> to <8>, which is 50.

<10> In the total amount of the cationic compound (A3-1), a compound in which R ¹¹ in the general formula (A3-1) is an alkyl group having a carbon number other than an alkyl group having 16 carbon atoms and an alkyl group having 18 carbon atoms. The hydraulic composition according to any one of <1> to <9>, wherein the ratio is preferably 10 mol% or less, more preferably 5 mol% or less, and still more preferably 1 mol% or less.

<11> (B) component is polyoxyethylene hydrogenated castor oil, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene alkyl ether and polyoxyethylene alkyl The hydraulic composition according to any one of <1> to <10>, wherein the hydraulic composition is at least one nonionic surfactant selected from the group consisting of amines.

<12> The component (B) is selected from polyoxyethylene hydrogenated castor oil having an ethylene oxide average added mole number of preferably 10 or more, more preferably 20 or more, and preferably 60 or less, more preferably 40 or less. The hydraulic composition according to any one of <1> to <10>, wherein the hydraulic composition is at least one nonionic surfactant.

<13> The hydraulic composition according to any one of <1> to <12>, further containing a dispersant.

<14> The hydraulic composition according to <13>, wherein the dispersant is a dispersant selected from naphthalene-based polymers and polycarboxylic acid-based copolymers.

<15> A copolymer obtained by polymerizing a monomer (1) represented by the following general formula (1) and a monomer (2) represented by the following general formula (2). The hydraulic composition according to <13> or <14>, which is a polymer [hereinafter referred to as polycarboxylic acid copolymer (I)].

[Where,
R ¹ , R ² : hydrogen atom or methyl group 1: number of 0 or more and 2 or less m: number of 0 or 1 AO: alkyleneoxy group of 2 or more and 4 or less carbon atoms n: average number of added moles of AO 5 or more, preferably 9 or more, more preferably 20 or more, still more preferably 50 or more, still more preferably 70 or more, and 150 or less, preferably 130 or less,
R ^{3 represents a} hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[Where,
R ⁴ , R ⁵ , R ⁶ : hydrogen atom, methyl group, or (CH ₂ ) _m1 COOM ²
M ¹ and M ² : each represents a number of hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium, alkylammonium, or substituted alkylammonium m1: 0 to 2; Note that (CH ₂ ) _m1 COOM ² may form an anhydride with COOM ¹ . ]

<16> The content of the component (A) is 0.75 parts by mass or more, preferably 0.85 parts by mass or more, more preferably 1.0 parts by mass with respect to 100 parts by mass of the aqueous phase of the hydraulic composition. The above <1> to << 5.0 parts by mass, preferably 5.0 parts by mass or less, preferably 4.0 parts by mass or less, more preferably 2.5 parts by mass or less, and still more preferably 1.5 parts by mass or less. The hydraulic composition according to any one of 15>.

<17> The content of the component (B) is 0.010 parts by mass or more, preferably 0.015 parts by mass or more, more preferably 0.020 parts by mass with respect to 100 parts by mass of the aqueous phase of the hydraulic composition. The hydraulic composition according to any one of <1> to <16>, which is at least 1.5 parts by mass, preferably 1.0 parts by mass or less, more preferably 0.50 parts by mass or less. object.

<18> The mass ratio of the content of the component (A) and the content of the component (B) is [content of the component (B) / content of the component (A)] of 0.0080 or more, preferably 0. .0090 or more, more preferably 0.010 or more, further preferably 0.020 or more, and 0.32 or less, preferably 0.30 or less, more preferably 0.10 or less,
When the content of the component (A) is 2.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the aqueous phase of the hydraulic composition, the content of the component (B) / (A The mass ratio of the component content is 0.032 or more, preferably 0.036 or more, more preferably 0.040 or more, and 0.32 or less, preferably 0.30 or less, more preferably 0. .10 or less,
The hydraulic composition according to any one of <1> to <17>.

<19> The content of the hydraulic powder is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and still more preferably 50 parts by mass or more with respect to 100 parts by mass of the aqueous phase of the hydraulic composition. And the hydraulic composition in any one of said <1>-<18> which is 700 mass parts or less preferably, More preferably, it is 600 mass parts or less, More preferably, it is 500 mass parts or less.

<20> The content of the dispersant is preferably 0.02 parts by mass or more, more preferably 0.06 parts by mass or more, still more preferably 0.1 parts by mass or more, with respect to 100 parts by mass of the aqueous phase. And the hydraulic composition in any one of said <13>-<19>, Preferably it is 2 mass parts or less, More preferably, it is 1.4 mass parts or less, More preferably, it is 1 mass part or less.

<21> A method for producing a hydraulic composition, comprising a step of mixing the following component (A), the following component (B), a hydraulic powder, and water,
(A) A component is 0.75 mass part or more with respect to 100 mass parts of water phases of a hydraulic composition, Preferably it is 0.85 mass part or more, More preferably, it is 1.0 mass part or more. 0 parts by mass or less, preferably 4.0 parts by mass or less, more preferably 2.5 parts by mass or less, still more preferably 1.5 parts by mass or less, and (B) component, 100 parts by mass of the aqueous phase of the hydraulic composition To 0.010 parts by mass or more, preferably 0.015 parts by mass or more, more preferably 0.020 parts by mass or more, and 1.5 parts by mass or less, preferably 1.0 parts by mass or less. Is mixed at a ratio of 0.50 parts by mass or less,
The mass ratio of the amount of the component (A) to the amount of the component (B) is 0.0080 or more, preferably 0.0090 or more, more preferably [(B) component amount / (A) component amount]. 0.010 or more and 0.32 or less, preferably 0.30 or less, more preferably 0.10 or less,
When the component (A) is mixed at a ratio of 2.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the aqueous phase of the hydraulic composition, the amount of the component (A) and (B) The mass ratio of the component amounts is 0.032 or more, preferably 0.036 or more, more preferably 0.040 or more, and 0.32 in [(B) component amount / (A) component amount]. Or less, preferably 0.30 or less, more preferably 0.10 or less,
A method for producing a hydraulic composition.
Component (A): a combination of a cationic surfactant (A1) and an anionic aromatic compound (A2), or a quaternary cationic group (a1) having at least one hydrocarbon group having 10 to 26 carbon atoms Quaternary salt type cationic compound (A3) containing aromatic anionic group (a2)
Component (B): Nonionic surfactant having an HLB of 5 or more and 16 or less (however, those having a monoester structure of sorbitan and a fatty acid, when the number of carbon atoms of the fatty acid-derived moiety of the ester is 18, The fatty acid-derived group of the ester has one unsaturated bond, and the average added mole number of ethylene oxide is 6 or less)

<22> The component (A) is a combination of a cationic surfactant (A1) and an anionic aromatic compound (A2),
A step (1) of obtaining the mixture (1) by mixing the anionic aromatic compound (A2), the component (B) and the hydraulic powder;
A step (2) of mixing the cationic surfactant (A1) and water to obtain a mixture (2), and a step (3) of mixing the mixture (1) and the mixture (2);
The manufacturing method of the hydraulic composition as described in said <21> which has.

<23>
The method for producing a hydraulic composition according to <21> or <22>, wherein the dispersant is mixed in any of the steps for producing the hydraulic composition.

<24>
The method for producing a hydraulic composition according to any one of <21> to <23>, wherein the aggregate is mixed in any of the production steps of the hydraulic composition.

<25> A hydraulic composition pumping method, wherein the hydraulic composition according to any one of <1> to <20> is pumped.

<26> Placing the hydraulic composition having a step of pumping the hydraulic composition according to the above <1> to <20> with a pump and a step of placing the hydraulic composition pumped with the pump Method.

<27> A viscosity reducing agent for a hydraulic composition comprising the following component (B), wherein the hydraulic composition contains the following component (A).
Component (B): Nonionic surfactant having an HLB of 5 or more and 16 or less (however, those having a monoester structure of sorbitan and a fatty acid, when the number of carbon atoms of the fatty acid-derived moiety of the ester is 18, The fatty acid-derived group of the ester has one unsaturated bond, and the average added mole number of ethylene oxide is 6 or less)
Component (A): a combination of a cationic surfactant (A1) and an anionic aromatic compound (A2), or a quaternary cationic group (a1) having at least one hydrocarbon group having 10 to 26 carbon atoms Quaternary salt type cationic compound (A3) containing aromatic anionic group (a2)

<Preparation of mortar>
(1-1) Materials Used / Cement (C): Ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd./Sumitomo Osaka Cement Co., Ltd. = 1/1, mass ratio), density 3.16 g / cm ³
-Fine aggregate (S): produced in Jyoyo, mountain sand, FM = 2.67, density 2.56 g / cm ³
-Water phase (W): Tap water, cement dispersant (AD), mixed system of components (A), (B)-Cement dispersant (AD): High-performance water reducing agent Mighty 3000H (effective) manufactured by Kao Corporation (20% by weight aqueous solution)
A1-1: 29% by mass aqueous solution of a mixture of hexadecyltrimethylammonium chloride / octadecyltrimethylammonium chloride in a 50/50 (mass ratio) A2-1: 20% by mass aqueous solution of sodium paratoluenesulfonate A3- 1: An aqueous solution produced in Synthesis Example 1 below and having a dimethylhydroxyethylalkylammonium paratoluenesulfonate (component (A)) concentration of 25% by mass

<Synthesis Example 1>
The flask was charged with 404 g (1.48 mol) of hexadecyldimethylamine and 444 g (1.48 mol) of octadecyldimethylamine, and the temperature was raised to 65 ° C. In the amine mixture, the compound having an alkyl group having 18 carbon atoms was 50 mol%. Further, 893 g of 1,2-propylene glycol, 1871 g of ion-exchanged water, 760 g of a 63.2% by mass aqueous solution of p-toluenesulfonic acid [2.81 mol as p-toluenesulfonic acid, all the above amines (hereinafter also simply referred to as amines) The molar ratio was 0.95] and stirred for 1 hour to make it uniform. The entire amount of the obtained mixed aqueous solution was charged into an autoclave, heated to 85 ° C., stirred, and the system was purged with nitrogen. 157 g (3.56 mol) of ethylene oxide was charged and reacted at 80 to 90 ° C. for 3 hours. Then, it cooled to 65 degreeC, the residual pressure in a reactor was blown out of the system, and 400 torr (53.3 kPa) and deaeration for 15 minutes were performed at 65 degreeC. Furthermore, 40 g of a 63.2% by weight aqueous solution of p-toluenesulfonic acid (0.15 mol as p-toluenesulfonic acid, a molar ratio of 0.05 with respect to the total amine) and a silicone antifoaming agent (manufactured by Toray Dow Corning Co., Ltd.) , 0.12 g of self-emulsifying compound DK Q1-1183) was charged. Further, 476.4 g of itaconic acid, 59.6 g of decanoic acid, and 850.8 g of a 35 mass% aqueous solution of poly (methacryloyloxyethyldimethylethylammonium ethyl sulfate) (weight average molecular weight 120,000) were stirred and homogenized for 0.5 hour. To produce a mixed aqueous solution A3-1. The composition of the mixed aqueous solution A3-1 was as follows: dimethylhydroxyethylalkylammonium paratoluenesulfonate [(A) component] 25.0 mass%, 1,2-propylene glycol 15.0 mass%, itaconic acid 8.0 mass%, decane The acid content was 1.0% by mass, and poly (methacryloyloxyethyldimethylethylammonium ethyl sulfate) was 5.0% by mass.

-Component (B): Nonionic surfactants shown in Table 3 were used. For the preparation of the mortar, a nonionic surfactant was used diluted 10 times (mass ratio) with ion-exchanged water. In Tables 1 and 2, for the sake of convenience, nonionic surfactants not corresponding to the component (B) are also listed in the column of the component (B).

(1-2) Preparation of mortar Kneading of the mortar was performed at a room temperature of 20 ° C. using a mortar mixer (Universal Kneader and Stirrer Model: 5DM-03-V). Cement (C) and fine aggregate (S) are added and kneaded for 10 seconds. Water (W), cement dispersant (AD), and nonionic surfactant [component (B)] are added and stirred for 1 minute. did. In addition, the addition amount of a cement dispersing agent (AD) employ | adopted the quantity from which mortar flow will be set to target 24 +/- 1cm. In any mortar formulation, since the dispersant became 1.0 parts by mass with respect to 100 parts by mass of the mortar aqueous phase, the mortar flow was performed in each of the examples and comparative examples. . In this mortar flow, the mortar that does not use the component (A) and the component (B) is immediately packed in two layers in the flow cone according to JIS R 5201, and the flow cone is correctly removed upward, and the cone is removed. It was measured after 5 minutes. When A3-1 was used, A3-1 was then added, and the mixture was further stirred for 1 minute to obtain a mortar for use. Moreover, when using A1-1 and A2-1, it is the same method as the above except that only A2-1 is added at the time of addition of the dispersing agent (AD), stirred for 1 minute, and then A1-1 is added. A mortar was obtained. Tables 1 and 2 show the specific amounts of each component. In the table, the mass of water (W) was expressed as the mass including A1-1, A2-1, A3-1, and cement dispersant (AD).

<Evaluation>
(2-1) Evaluation of underwater inseparability Underwater inseparability refers to the method for testing the degree of underwater inseparability of underwater inseparable concrete under the specifications for underwater inseparable admixture quality standards for concrete (JSCE-D 104-2007). The suspension was evaluated by measuring the turbidity of the suspension by the following method.
200 ml of ion-exchanged water was weighed into a 300 ml beaker, and 80 g of mortar after kneading was weighed into another 300 ml beaker. 80 g of mortar was poured into 200 ml of ion-exchanged water in 10 minutes, about 8 g at a time. After leaving it to stand for 3 minutes, 100 ml of the supernatant was collected, and the turbidity was measured using a lacom tester turbidimeter TN-100 manufactured by ASONE Co., Ltd. The results are shown in Tables 1 and 2.
The smaller the turbidity, the better the inseparability in water, and it is determined as follows, and a, b, and c are acceptable levels.
a: Turbidity is 100 or less b: Turbidity is more than 100, 150 or less c: Turbidity is more than 150, 200 or less d: Turbidity is more than 200, 333 or less e: Turbidity is more than 333

(2-2) Pump pumpability Pump pumpability is affected by the viscosity of the mortar. In this example, the pumpability was evaluated by the mortar flow time.
The kneaded mortar is immediately packed in two layers in a flow cone based on JIS R 5201, the flow cone is removed correctly upward, and the time for the average flow length to reach 20 cm (hereinafter referred to as mortar flow time) It was measured and used as an index of pumpability. The results are shown in Tables 1 and 2.
The smaller the mortar flow time, the better the pumpability, and it is determined as follows, and a and b are acceptable levels.
a: Mortar flow time is 30 seconds or less b: Mortar flow time is more than 30 seconds, 45 seconds or less c: Mortar flow time is more than 45 seconds

  In Tables 1 and 2, the dispersant in the mortar blending, the blending amount (g) of the component (A) indicates the blending amount (g) as an aqueous solution. In Tables 1 and 2, the mass ratio of (B) / (A) in the mortar blending indicates a mass ratio based on the blended amount in terms of the effective component. Moreover, the mass part with respect to 100 mass parts of water phase of a dispersing agent, (A) component, and (B) component in Tables 1 and 2 is a mass part of effective part conversion, respectively.

Claims (11)

A hydraulic composition containing the following component (A), the following component (B), a hydraulic powder, and water,
(A) Content of a component is 0.75 mass part or more and 5.0 mass parts or less with respect to 100 mass parts of water phases of a hydraulic composition,
(B) Content of a component is 0.010 mass part or more and 1.5 mass parts or less with respect to 100 mass parts of water phases of a hydraulic composition,
The mass ratio of the content of the component (A) and the content of the component (B) is [content of the component (B) / content of the component (A)] and is 0.0080 or more and 0.32 or less. ,
When the content of the component (A) is 2.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the aqueous phase of the hydraulic composition, the content of the component (A) and (B) The mass ratio of the component content is [(B) component content / (A) component content], which is 0.032 or more and 0.32 or less.
Hydraulic composition.
Component (A): a combination of a cationic surfactant (A1) and an anionic aromatic compound (A2), or a quaternary cationic group (a1) having at least one hydrocarbon group having 10 to 26 carbon atoms Quaternary salt type cationic compound (A3) containing aromatic anionic group (a2)
Component (B): Nonionic surfactant having an HLB of 5 or more and 16 or less (however, those having a monoester structure of sorbitan and a fatty acid, when the number of carbon atoms of the fatty acid-derived moiety of the ester is 18, The fatty acid-derived group of the ester has one unsaturated bond, and the average added mole number of ethylene oxide is 6 or less)   The component (B) comprises polyoxyethylene hydrogenated castor oil, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene alkyl ether and polyoxyethylene alkylamine. The hydraulic composition according to claim 1, wherein the hydraulic composition is at least one nonionic surfactant selected from the group.   The hydraulic composition according to claim 1 or 2, wherein the cationic surfactant (A1) is a quaternary salt type cationic surfactant.   The hydraulic composition according to any one of claims 1 to 3, wherein a content of the hydraulic powder is 30 parts by mass or more and 700 parts by mass or less with respect to 100 parts by mass of the aqueous phase of the hydraulic composition. object.   Furthermore, the hydraulic composition of any one of Claims 1-4 containing a dispersing agent. A method for producing a hydraulic composition, comprising a step of mixing the following component (A), the following component (B), a hydraulic powder, and water,
(A) A component is 0.75 mass part or more and 5.0 mass parts or less with respect to 100 mass parts of water phases of a hydraulic composition, (B) A component is 100 mass parts of water phases of a hydraulic composition. Is mixed at a ratio of 0.010 parts by mass or more and 1.5 parts by mass or less,
The mass ratio of the amount of component (A) and the amount of component (B) is 0.0080 or more and 0.32 or less in [amount of component (B) / amount of component (A)],
When the component (A) is mixed at a ratio of 2.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the aqueous phase of the hydraulic composition, the amount of the component (A) and (B) The mass ratio of the component amounts is 0.032 or more and 0.32 or less in [(B) component amount / (A) component amount].
A method for producing a hydraulic composition.
Component (A): a combination of a cationic surfactant (A1) and an anionic aromatic compound (A2), or a quaternary cationic group (a1) having at least one hydrocarbon group having 10 to 26 carbon atoms Quaternary salt type cationic compound (A3) containing aromatic anionic group (a2)
Component (B): Nonionic surfactant having an HLB of 5 or more and 16 or less (however, those having a monoester structure of sorbitan and a fatty acid, when the number of carbon atoms of the fatty acid-derived moiety of the ester is 18, The fatty acid-derived group of the ester has one unsaturated bond, and the average added mole number of ethylene oxide is 6 or less) (A) component is a combination of a cationic surfactant (A1) and an anionic aromatic compound (A2),
A step (1) of obtaining a mixture (1) by mixing an anionic aromatic compound (A2), a component (B), a hydraulic powder and water;
A step (2) of mixing the cationic surfactant (A1) and water to obtain a mixture (2), and a step (3) of mixing the mixture (1) and the mixture (2);
The manufacturing method of the hydraulic composition of Claim 6 which has these.   The manufacturing method of the hydraulic composition of Claim 6 or 7 which mixes a dispersing agent in either of the manufacturing process of a hydraulic composition.   The hydraulic composition pumping method of pumping the hydraulic composition according to any one of claims 1 to 5.   A method for placing a hydraulic composition, comprising: a step of pumping the hydraulic composition according to any one of claims 1 to 5 by a pump; and a step of placing the hydraulic composition pumped by the pump. A viscosity reducing agent for a hydraulic composition comprising the following component (B), wherein the hydraulic composition contains the following component (A).
Component (B): Nonionic surfactant having an HLB of 5 or more and 16 or less (however, those having a monoester structure of sorbitan and a fatty acid, when the number of carbon atoms of the fatty acid-derived moiety of the ester is 18, The fatty acid-derived group of the ester has one unsaturated bond, and the average added mole number of ethylene oxide is 6 or less)
Component (A): a combination of a cationic surfactant (A1) and an anionic aromatic compound (A2), or a quaternary cationic group (a1) having at least one hydrocarbon group having 10 to 26 carbon atoms Quaternary salt type cationic compound (A3) containing aromatic anionic group (a2)