Thickener composition for hydraulic composition

Abstract

To provide a thickener composition for a hydraulic composition which increases viscosity of a hydraulic composition slurry after preparation and increases a breathing rate, and a hydraulic composition which has a high viscosity of a slurry after preparation and a high breathing rate.SOLUTION: A thickener composition for a hydraulic composition comprises: (a) an alkylnaphthalene sulfonic acid having two or more carbons in an alkyl group, or a salt thereof; and (b) one or more selected from an amphoteric surfactant and a cationic surfactant.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a thickener composition for a hydraulic composition, and a hydraulic composition. [Background technology]

[0002] In a hydraulic composition slurry containing a hydraulic powder such as cement, a thickener may be added to the hydraulic composition slurry in order to improve physical properties such as viscosity and material separation resistance after the slurry preparation.

[0003] For example, Patent Document 1 discloses a rheology modifier that contains two or more specific amine oxide compounds as a rheology modifier that exhibits a rheology modifying effect over a wide temperature range. Patent Document 2 discloses an additive for hydraulic compositions that can impart excellent fluidity and separation resistance to a hydraulic composition without retarding setting or inhibiting the effects of a high-performance water reducing agent, and that is also excellent in strength, particularly in initial strength development. The additive contains a first water-soluble low-molecular-weight compound (hereinafter referred to as compound (A)) and a second water-soluble low-molecular-weight compound (hereinafter referred to as compound (B)) different from compound (A), and the combination of compounds (A) and (B) is selected from the group consisting of (1) a combination of a compound selected from amphoteric surfactants and a compound selected from anionic surfactants, (2) a combination of a compound selected from cationic surfactants and a compound selected from anionic aromatic compounds, and (3) a combination of a compound selected from cationic surfactants and a compound selected from brominated compounds. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2020-76022 A [Patent Document 2] JP 2003-238222 A Summary of the Invention [Problem to be solved by the invention]

[0005] On the other hand, if the hydraulic composition causes bleeding to a certain extent before hardening, the strength of the hardened product of the hydraulic composition tends to be improved. The techniques of Patent Documents 1 and 2 can suppress material separation by thickening the hydraulic composition slurry before hardening, but it is difficult to intentionally cause bleeding in order to improve the strength of the slurry after hardening. Even if a thickener such as a cellulose-based thickener used in hydraulic compositions is used, it is difficult to simultaneously increase the viscosity of the hydraulic composition slurry and cause bleeding.

[0006] The present invention provides a thickener composition for a hydraulic composition, which increases the viscosity and bleeding rate of a hydraulic composition slurry after preparation, and a hydraulic composition, the viscosity of which is high and the bleeding rate of which is high after preparation. [Means for solving the problem]

[0007] The present invention relates to a thickener composition for hydraulic compositions, which contains (a) an alkylnaphthalenesulfonic acid having an alkyl group with two or more carbon atoms, or a salt thereof (hereinafter referred to as component (a)), and (b) one or more surfactants selected from an amphoteric surfactant and a cationic surfactant (hereinafter referred to as component (b)).

[0008] The present invention also relates to a hydraulic composition comprising component (a), component (b), hydraulic powder, and water. Effect of the Invention

[0009] According to the present invention, there are provided a thickener composition for hydraulic compositions which increases the viscosity and bleeding rate of a hydraulic composition slurry after preparation, and a hydraulic composition which has a high viscosity and a high bleeding rate of a prepared slurry.

[0010] The hydraulic composition obtained according to the present invention has excellent resistance to material separation due to the increased viscosity of the prepared hydraulic composition slurry, and has excellent strength after hardening due to the increased bleeding rate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present inventors have found that when a hydraulic composition is added with a thickener composition for hydraulic compositions, which contains components (a) and (b), the viscosity of the hydraulic composition slurry after preparation can be increased and the bleeding rate can be increased. The reason why such effects are exhibited is not necessarily clear, but is presumed to be as follows. An anionic surfactant having an aromatic ring has a large π-conjugated system in the aromatic ring portion, and therefore, when it coexists with the component (b) of the present invention, it is likely to cause a cation-π interaction with the cationic group or amphoteric group in the component (b). Therefore, when both of them coexist, it is believed that the anionic surfactant having an aromatic ring exists in the vicinity of the cationic functional group or amphoteric functional group in the component (b) and forms an association. Therefore, it is believed that the association between the component (b) and the anionic surfactant having an aromatic ring cancels out the charge repulsion between the hydrophilic groups by their mutual charges, and the packing parameter approaches 1 / 2, forming a worm-like micelle or a rod-like micelle. However, when the aromatic ring is a naphthalene ring, it is believed that the steric repulsion is large and the curvature is unlikely to change even if the charge repulsion is canceled out. The component (a) of the present invention has a naphthalene ring but also has an alkyl chain at the same time, so that it can enter the hydrophobic group side of the component (b) due to its high hydrophobic interaction, and does not inhibit the curvature change of the association. Furthermore, naphthalene rings also show cation-π interactions with inorganic ions such as aluminum ions and calcium ions. The infinitely long pseudo-polymer structure, like a worm-like micelle, has an adsorption group such as naphthalene rings, and therefore acts like a flocculant. Although highly viscous, when left to stand the cement flocculates and is separated from the water, which is thought to cause bleeding.

[0012] [Thickener composition for hydraulic composition] <Component (a)> The thickener composition for hydraulic compositions of the present invention contains, as component (a), an alkylnaphthalenesulfonic acid having an alkyl group with 2 or more carbon atoms, or a salt thereof. From the viewpoint of the balance between hydrophobic interaction and water solubility, the number of carbon atoms in the alkyl group in the alkylnaphthalenesulfonic acid of component (a) is 2 or more, preferably 3 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 4. Furthermore, the position of the alkyl group in the naphthalene ring may be any position. From the viewpoint of packing properties, the number of alkyl group substituents in the alkylnaphthalenesulfonic acid of component (a) is preferably 1 or more and preferably 3 or less, more preferably 2 or less, and even more preferably 1. Furthermore, when the number of alkyl group substituents is 2 or more, it is sufficient that at least one of the alkyl groups has 2 or more carbon atoms. From the viewpoint of interaction with component (b), the number of sulfo group substituents in the alkylnaphthalenesulfonic acid of component (a) is preferably 1 or more and preferably 3 or less, more preferably 2 or less, and even more preferably 1. In addition, with regard to the position of the sulfo group in the naphthalene ring, it is preferable that at least one sulfo group is at position 1. Examples of the salt of alkylnaphthalenesulfonic acid of the component (a) include one or more salts selected from alkali metal salts such as sodium salts and potassium salts, and ammonium salts.

[0013] Specific examples of the compound of component (a) include one or more selected from butylnaphthalenesulfonic acid, ethylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, hexylnaphthalenesulfonic acid, octylnaphthalenesulfonic acid, decylnaphthalenesulfonic acid, and salts thereof. From the viewpoint of the balance between hydrophobic interaction and water solubility, preferred is one or more selected from butylnaphthalenesulfonic acid, ethylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, and salts thereof, more preferred is one or more selected from butylnaphthalenesulfonic acid, ethylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, and salts thereof, and even more preferred is butylnaphthalenesulfonic acid or a salt thereof.

[0014] <(b) Component> The thickener composition for hydraulic compositions of the present invention contains, as component (b), one or more selected from (b1) amphoteric surfactants (hereinafter referred to as component (b1)) and (b2) cationic surfactants (hereinafter referred to as component (b2)). The component (b) is preferably one or more selected from amphoteric surfactants having a nitrogen atom and cationic surfactants having a nitrogen atom.

[0015] The amphoteric surfactant of the component (b1) is preferably an amine oxide surfactant, and more preferably a compound represented by the following general formula (b1).

[0016] [ka]

[0017] [Wherein, X is R 11b or R 12b -[CONH-CH2CH2CH2] n R is a group represented by the formula: 11b R is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 14 to 22 carbon atoms. 12bis an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. n is an integer of 1 to 3. 2 and R 3 are each independently an alkyl group having 1 to 4 carbon atoms or -(C2H4O) p H. p is the average number of moles added, and R 2 and R 3 The sum of these is a number between 0 and 5.

[0018] In the general formula (b1), X is R 11b or R 12b -[CONH-CH2CH2CH2] n - is a group represented by the formula: R 11b is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 14 to 22 carbon atoms. R 11b When is an alkenyl group, it preferably has 18 or more carbon atoms and preferably has 22 or less carbon atoms. R 11b When is an alkyl group, it preferably has 16 or more carbon atoms and preferably has 22 or less carbon atoms. R 12b is an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. R 12b When is an alkenyl group, it preferably has 17 or more carbon atoms and preferably has 21 or less carbon atoms. R 12b When it is an alkyl group, it preferably has 15 or more carbon atoms and preferably has 21 or less carbon atoms. n is preferably 0 or 1. R 2 and R 3 are each independently preferably an alkyl group having 1 to 2 carbon atoms or -(C2H4O) p It is a group represented by H. p is preferably a number between 0 and 3.

[0019] Specific examples of the compound of component (b1) include one or more selected from oleyl dimethylamine oxide, oleic acid amidopropyl dimethylamine oxide, stearyl dimethylamine oxide, and palmityl dimethylamine oxide.

[0020] The cationic surfactant of component (b2) is preferably a quaternary ammonium surfactant, and more preferably at least one selected from the group consisting of compounds represented by the following general formula (b21) and compounds represented by the following general formula (b22).

[0021] [ka]

[0022] [In the formula, R 21b is an aliphatic hydrocarbon group having 8 to 22 carbon atoms, R 22b is a group selected from an aliphatic hydrocarbon group having 8 to 22 carbon atoms, an alkyl group having 1 to 3 carbon atoms, and a hydroxyalkyl group having 1 to 3 carbon atoms; R 23b and R 24b are each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms; X - is an anion.

[0023] [ka]

[0024] [In the formula, R 25b is an aliphatic hydrocarbon group having 8 to 22 carbon atoms, R 26b and R 27b are each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms; X - is an anion.

[0025] In general formula (b21), R 21bFrom the viewpoint of the balance between water solubility and high hydrophobicity that easily interacts with component (a), the number of carbon atoms in R is 8 or more, preferably 10 or more, more preferably 14 or more, and even more preferably 16 or more, and is 22 or less, preferably 20 or less, and more preferably 18 or less. 21b is preferably an alkyl group or an alkenyl group, and is preferably an alkyl group. In general formula (b21), R 22b is a group selected from an aliphatic hydrocarbon group having 8 to 22 carbon atoms, an alkyl group having 1 to 3 carbon atoms, and a hydroxyalkyl group having 1 to 3 carbon atoms. R 22b is an aliphatic hydrocarbon group having 8 to 22 carbon atoms, R 22b is 8 or more, preferably 10 or more, more preferably 14 or more, even more preferably 16 or more, and 22 or less, preferably 20 or less, more preferably 18 or less, and is an alkyl group or an alkenyl group, preferably an alkyl group. R 22b is preferably an alkyl group having 1 to 3 carbon atoms.

[0026] In general formula (b21), R 23b and R 24b are each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms. 23b and R 24b are preferably each independently selected from alkyl groups having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of the hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

[0027] In general formula (b21), X - is an anion. Examples of an anion include halogen ions such as chloride ion, bromide ion, and iodide ion. Examples of an anion include alkyl sulfate ions having 1 to 3 carbon atoms such as methyl sulfate ion, ethyl sulfate ion, and propyl sulfate ion.

[0028] Preferred examples of the compound of general formula (b21) include one or more selected from N-alkyl-N,N,N-trimethylammonium salts in which the alkyl group has 8 or more and 22 or less carbon atoms, N,N-dialkyl-N,N-dimethyl-ammonium salts in which the alkyl group has 8 or more and 22 or less carbon atoms, N,N-dialkyl-N-ethyl-N-methylammonium salts in which the alkyl group has 8 or more and 22 or less carbon atoms, and N-alkyl-N,N-dimethyl-N-ethylammonium salts in which the alkyl group has 8 or more and 22 or less carbon atoms. Specific examples of the compound of component (b21) include one or more selected from lauryltrimethylammonium salt, myristyltrimethylammonium salt, palmityltrimethylammonium salt, and stearyltrimethylammonium salt.

[0029] In general formula (b22), R 25b R is an aliphatic hydrocarbon group having 8 to 22 carbon atoms. 25b From the viewpoint of the balance between water solubility and high hydrophobicity that easily interacts with component (a), the number of carbon atoms in R is 8 or more, preferably 12 or more, more preferably 14 or more, and even more preferably 16 or more, and is 22 or less, preferably 20 or less, and more preferably 18 or less. 25b is preferably an alkyl group or an alkenyl group, and is preferably an alkyl group.

[0030] In general formula (b22), R 26b and R 27b are each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms. 26b and R 27b are preferably each independently selected from alkyl groups having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of the hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

[0031] In general formula (b22), X - is an anion. Examples of an anion include halogen ions such as chloride ion, bromide ion, and iodide ion. Examples of an anion include alkyl sulfate ions having 1 to 3 carbon atoms such as methyl sulfate ion, ethyl sulfate ion, and propyl sulfate ion.

[0032] Specific examples of the compound of general formula (b22) include N-octyl-N,N-dimethyl-N-benzyl ammonium salt, N-decyl-N,N-dimethyl-N-benzyl ammonium salt, N-dodecyl-N,N-dimethyl-N-benzyl ammonium salt, N-tridecyl-N,N-dimethyl-N-benzyl ammonium salt, N-tetradecyl-N,N-dimethyl-N-benzyl ammonium salt, N-pentadecyl-N,N-dimethyl-N-benzyl ammonium salt, N-hexadecyl-N,N-dimethyl-N-benzyl ammonium salt, N-dodecyl-N,N-diethyl-N-benzyl ammonium salt, N-tridecyl-N,N-diethyl ... and N-hexadecyl-N,N-diethyl-N-benzyl ammonium salt, N-tetradecyl-N,N-diethyl-N-benzyl ammonium salt, N-pentadecyl-N,N-diethyl-N-benzyl ammonium salt, N-hexadecyl-N,N-diethyl-N-benzyl ammonium salt, N-dodecyl-N-methyl-N-ethyl-N-benzyl ammonium salt, N-tridecyl-N-methyl-N-ethyl-N-benzyl ammonium salt, N-tetradecyl-N-methyl-N-ethyl-N-benzyl ammonium salt, N-pentadecyl-N-methyl-N-ethyl-N-benzyl ammonium salt, and N-hexadecyl-N-methyl-N-ethyl-N-benzyl ammonium salt.

[0033] <Composition, etc.> The thickener composition for hydraulic compositions of the present invention is preferably in the form of an aqueous solution from the viewpoint of handleability. In the case of an aqueous solution, the thickener composition contains, from the viewpoints of economy and ease of handleability, preferably 0.15% by mass or more of component (a), more preferably 1% by mass or more, even more preferably 3% by mass or more, and preferably 66% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less of component (a). In the present invention, the mass of component (a) is defined as the value of component (a) converted into a sodium salt.

[0034] The thickener composition for hydraulic compositions of the present invention is preferably in the form of an aqueous solution from the viewpoint of handleability. In the case of an aqueous solution, the thickener composition contains the component (b) in an amount of preferably 0.4% by mass or more, more preferably 1% by mass or more, even more preferably 8% by mass or more, and preferably 87% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, from the viewpoints of economy and ease of handling. In the present invention, when component (b2) is contained as component (b), the mass of component (b2) is the value calculated as the chlorine salt of component (b2).

[0035] In the thickener composition for hydraulic compositions of the present invention, the mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) is, from the viewpoint of adjusting the packing parameters that maintain the micelle shape in a string or rod shape and thereby increasing the bleeding rate and thickening property, preferably 0.15 or more, more preferably 0.2 or more, even more preferably 0.3 or more, and preferably 2 or less, more preferably 1.5 or less, even more preferably 1 or less, still more preferably 0.8 or less, and even more preferably 0.6 or less.

[0036] The thickener composition for hydraulic compositions of the present invention may contain an antifoaming agent as component (c) from the viewpoint of suppressing a decrease in strength due to a reduction in coarse bubbles. The defoaming agent is preferably one or more selected from silicone defoaming agents, fatty acid ester defoaming agents, ether defoaming agents, and aliphatic amine defoaming agents, and more preferably silicone defoaming agents.The silicone defoaming agent is more preferably dimethylpolysiloxane, the fatty acid ester defoaming agent is more preferably polyalkylene glycol fatty acid ester, the ether defoaming agent is more preferably polyalkylene glycol alkyl ether, and the aliphatic amine defoaming agent is more preferably alkyldimethylamine or its salt.

[0037] When the thickener composition for hydraulic compositions of the present invention contains the component (c), the mass ratio (c) / [(a)+(b)] of the content of the component (c) to the total content of the components (a) and (b) in the composition is, from the viewpoints of defoaming property, economic efficiency, and not inhibiting performance, preferably 0.00001 or more, more preferably 0.00005 or more, even more preferably 0.0001 or more, and preferably 0.1 or less, more preferably 0.05 or less, even more preferably 0.02 or less.

[0038] From the viewpoint of temperature versatility, the thickener composition for hydraulic compositions of the present invention may contain an anionic surfactant having a benzene ring as component (d). However, component (d) excludes those corresponding to component (a). Specific examples of component (d) include paratoluenesulfonic acid, salicylic acid, benzoic acid, metaxylenesulfonic acid, cumenesulfonic acid, styrenesulfonic acid, and benzenesulfonic acid. These components may be in the form of a salt. Examples of the salt include alkali metal salts such as sodium salts and potassium salts, and alkaline earth metal salts, and alkali metal salts are preferred. Component (d) is preferably one or more compounds selected from paratoluenesulfonic acid, metaxylenesulfonic acid, salicylic acid, and salts thereof, and more preferably metaxylenesulfonic acid or a salt thereof.

[0039] When the thickener composition for hydraulic composition of the present invention contains the component (d), the mass ratio (d) / (b) of the content of the component (d) to the content of the component (b) in the composition is, from the viewpoint of thickening property of the hydraulic composition, preferably 0.01 or more, more preferably 0.02 or more, even more preferably 0.05 or more, still more preferably 0.08 or more, still more preferably 0.1 or more, and preferably 2 or less, more preferably 1 or less, even more preferably 0.8 or less, still more preferably 0.6 or less, still more preferably 0.4 or less, and still more preferably 0.2 or less.

[0040] The thickener composition for hydraulic compositions of the present invention may contain optional components within the range that does not impair the effects of the present invention. The optional components may include dispersants, AE agents, fluidizing agents, retarders, early strength agents, setting accelerators, hardening accelerators, foaming agents, thickeners, waterproofing agents, shrinkage reducing agents, expansion agents, water-soluble polymers, etc. (excluding those corresponding to components (a), (b), (c), and (d)).

[0041] The thickener composition for hydraulic compositions of the present invention may contain water. That is, the thickener composition for hydraulic compositions of the present invention may be in the form of a liquid containing water, preferably an aqueous solution, from the viewpoint of improving the handling properties. When the thickener composition for hydraulic compositions of the present invention contains water, the thickener composition contains water in an amount of preferably 0.1 mass % or more, more preferably 0.5 mass % or more, even more preferably 1 mass % or more, and preferably 99.99 mass % or less, more preferably 99.9 mass % or less, even more preferably 99 mass % or less.

[0042] The thickener composition for hydraulic compositions of the present invention can be produced by mixing component (a), component (b), optionally component (c), optionally component (d), and optionally water. That is, the present invention provides a method for producing a thickener composition for hydraulic compositions, which comprises mixing component (a), component (b), and optionally component (c), optionally component (d), and optionally water. The thickener composition for hydraulic compositions of the present invention can be mixed with water to form an aqueous solution, from the viewpoint of improving the handling properties. The manufacturing method of the thickener composition for hydraulic compositions of the present invention can be appropriately applied to the matters described in the thickener composition for hydraulic compositions of the present invention. For example, specific examples and preferred aspects of each component are the same as those of the thickener composition for hydraulic compositions of the present invention. In addition, the content and mass ratio of each component in the thickener composition for hydraulic compositions of the present invention can be applied to the manufacturing method of the thickener composition for hydraulic compositions of the present invention by replacing the content of each component with the mixed amount.

[0043] The thickener composition for hydraulic compositions of the present invention is suitably used as a thickener for hydraulic compositions in applications requiring appropriate viscosity such as suppression of material separation, suppression of underwater separation, prevention of water leakage into the ground, etc. For example, it can be used for sprayed concrete, tunnel repair, application to non-horizontal walls, additives for well drilling, foot protection liquid, pile circumference fixing liquid, underwater non-separating concrete, prepacked concrete, plastic grout, etc.

[0044] [Hydraulic composition] The present invention provides a hydraulic composition comprising component (a), component (b), hydraulic powder, and water. The hydraulic composition of the present invention may further contain the above-mentioned component (c). The hydraulic composition of the present invention may further contain the above-mentioned component (d). The present invention also relates to a hydraulic composition containing the thickener composition for hydraulic compositions of the present invention, hydraulic powder, and water. The components (a), (b), (c) and (d) are the same as those described in the thickener composition for hydraulic compositions of the present invention. The hydraulic composition of the present invention can be appropriately applied with the embodiments described in the thickener composition for hydraulic composition of the present invention.

[0045] The hydraulic powder used in the hydraulic composition of the present invention is a powder that hardens when mixed with water, and examples thereof include ordinary Portland cement, high-early-strength Portland cement, ultra-high-early-strength Portland cement, sulfate-resistant Portland cement, low-heat Portland cement, white Portland cement, and ecocement (e.g., JIS R5214, etc.). Among these, from the viewpoint of shortening the time required for the hydraulic composition to reach a required strength, a cement selected from early-early-strength Portland cement, ordinary Portland cement, sulfate-resistant Portland cement, and white Portland cement is preferred, and a cement selected from early-early-strength Portland cement and ordinary Portland cement is more preferred.

[0046] The hydraulic powder may include blast furnace slag, fly ash, silica fume, anhydrous gypsum, etc., and may also include non-hydraulic limestone fine powder, etc. As the hydraulic powder, blast furnace cement, fly ash cement, or silica fume cement, which is a mixture of cement with blast furnace slag, fly ash, silica fume, etc., may also be used. The hydraulic powder may be cement or a mixed powder of cement and bentonite.

[0047] The hydraulic composition of the present invention contains, relative to 100 parts by mass of water, preferably 0.001 part by mass or more of component (a) from the viewpoint of thickening property, more preferably 0.01 part by mass or more, even more preferably 0.015 parts by mass or more, and still more preferably 0.02 parts by mass or more, and from the viewpoints of economy and the occurrence of bleeding, preferably 4 parts by mass or less, more preferably 2 parts by mass or less, even more preferably 1 part by mass or less, still more preferably 0.5 parts by mass or less, and still more preferably 0.1 part by mass or less.

[0048] The hydraulic composition of the present invention contains, relative to 100 parts by mass of water, preferably 0.01 part by mass or more of component (b) from the viewpoint of thickening property, more preferably 0.02 part by mass or more, even more preferably 0.05 part by mass or more, and from the viewpoints of economy and the occurrence of bleeding, preferably 1 part by mass or less, more preferably 0.8 part by mass or less, even more preferably 0.5 part by mass or less, still more preferably 0.3 part by mass or less, and even more preferably 0.2 part by mass or less.

[0049] In the hydraulic composition of the present invention, the mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) is, from the viewpoint of adjusting the packing parameter for maintaining the micelle shape in a string or rod shape and thereby increasing the bleeding rate and thickening property, preferably 0.15 or more, more preferably 0.2 or more, even more preferably 0.3 or more, and preferably 2 or less, more preferably 1.5 or less, even more preferably 1 or less, still more preferably 0.8 or less, and even more preferably 0.6 or less.

[0050] When the hydraulic composition of the present invention contains the component (c), the mass ratio (c) / [(a)+(b)] of the content of the component (c) to the total content of the components (a) and (b) in the hydraulic composition is, from the viewpoints of defoaming property, economic efficiency, and not impairing performance, preferably 0.00001 or more, more preferably 0.00005 or more, even more preferably 0.0001 or more, and preferably 0.1 or less, more preferably 0.05 or less, even more preferably 0.02 or less.

[0051] When the hydraulic composition of the present invention contains the component (d), the mass ratio (d) / (b) of the content of the component (d) to the content of the component (b) in the hydraulic composition is, from the viewpoint of thickening property, preferably 0.01 or more, more preferably 0.02 or more, even more preferably 0.05 or more, still more preferably 0.08 or more, still more preferably 0.1 or more, and preferably 2 or less, more preferably 1 or less, still more preferably 0.8 or less, still more preferably 0.6 or less, still more preferably 0.4 or less, and still more preferably 0.2 or less.

[0052] In the hydraulic composition of the present invention, the mass percentage of water and hydraulic powder in the hydraulic composition (water / hydraulic powder ratio (W / C)) is, from the viewpoints of economy and flowability, preferably 45 mass% or more, more preferably 50 mass% or more, even more preferably 60 mass% or more, and preferably 150 mass% or less, more preferably 120 mass% or less, even more preferably 100 mass% or less. Here, the water / hydraulic powder ratio (W / C) is the mass percentage (mass%) of water and hydraulic powder in the hydraulic composition, and is calculated as water / hydraulic powder×100. In addition, when the hydraulic powder includes powders selected from powders having pozzolanic action, powders having latent hydraulic properties, and stone powder (calcium carbonate powder) in addition to powders having properties that harden through hydration reactions such as cement, the amounts of these powders are also included in the amount of hydraulic powder in this invention. In addition, when the powder having properties that harden through hydration reactions contains a high-strength admixture, the amount of the high-strength admixture is also included in the amount of hydraulic powder. This also applies to other parts by mass that are related to the mass of the hydraulic powder.

[0053] The hydraulic composition of the present invention may contain aggregate. Examples of aggregates include aggregates selected from fine aggregates and coarse aggregates. Examples of fine aggregates include those specified by number 2311 in JISA0203-2014. Examples of fine aggregates include river sand, land sand, mountain sand, sea sand, lime sand, silica sand and crushed sands thereof, blast furnace slag fine aggregate, ferronickel slag fine aggregate, lightweight fine aggregate (artificial and natural), and recycled fine aggregate. Examples of coarse aggregates include those specified by number 2312 in JIS A 0203-2014. For example, examples of coarse aggregates include river gravel, land gravel, mountain gravel, sea gravel, lime gravel, crushed stones thereof, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural), and recycled coarse aggregate. Fine aggregates and coarse aggregates of different types may be mixed and used, or a single type may be used.

[0054] When the hydraulic composition is concrete, the amount of coarse aggregate used is preferably 50% or more, more preferably 55% or more, even more preferably 60% or more, in terms of the expression of strength of the hydraulic composition, reducing the amount of hydraulic powder such as cement used, and improving the filling property into a formwork, and is preferably 100% or less, more preferably 90% or less, even more preferably 80% or less in bulk volume, from the viewpoint of improving the filling property of the hydraulic composition and reducing the amount of hydraulic powder such as cement used. 3 It is the ratio of the volume of coarse aggregate (including voids) in the concrete. When the hydraulic composition is concrete, the amount of fine aggregate used is preferably 500 kg / m from the viewpoint of improving the filling property into a formwork or the like. 3 More preferably, 600 kg / m 3 More preferably, 700 kg / m 3 and preferably 1000 kg / m 3 Less than or equal to 900 kg / m 3 The following is the result. When the hydraulic composition is a mortar, the amount of fine aggregate used is preferably 800 kg / m 3 More preferably, 900kg / m 3 More preferably, 1000 kg / m 3 and preferably 2000 kg / m 3 Less than or equal to 1800 kg / m 3 More preferably, 1700 kg / m 3 The following is the result.

[0055] The hydraulic composition of the present invention is excellent in material separation resistance, underwater separation inhibition, and prevention of water leakage into the ground by increasing the viscosity of the prepared hydraulic composition slurry, and is excellent in strength after hardening by increasing the bleeding rate, so that it can be used, for example, for sprayed concrete, tunnel repair, application to non-horizontal walls, additives for well drilling, foot protection liquid, pile circumference fixing liquid, underwater non-separating concrete, prepacked concrete, plastic grout, etc.

[0056] The hydraulic composition of the present invention can be produced by mixing hydraulic powder, water, component (a), and component (b). That is, the present invention provides a method for producing a hydraulic composition by mixing hydraulic powder, water, component (a), and component (b). In the method for producing the hydraulic composition of the present invention, component (c) can be further mixed. In the method for producing the hydraulic composition of the present invention, component (d) can be further mixed. The hydraulic composition of the present invention may be produced by mixing the thickener composition for hydraulic compositions of the present invention, hydraulic powder, and water. The matters described in the thickener composition for hydraulic compositions and hydraulic compositions of the present invention can be appropriately applied to the manufacturing method of the hydraulic composition of the present invention. For example, specific examples and preferred aspects of each component are the same as those of the thickener composition for hydraulic compositions and hydraulic compositions of the present invention. In addition, the content and mass ratio of each component in the thickener composition for hydraulic compositions and hydraulic compositions of the present invention can be applied to the manufacturing method of the hydraulic composition of the present invention by replacing the content of each component with the mixed amount. EXAMPLES

[0057] The materials used in the Examples, Comparative Examples, and Reference Examples are shown below. <Component (a)> Sodium butylnaphthalene sulfonate: Sodium butylnaphthalene sulfonate, manufactured by Kao Corporation <Component (a') (comparison component for component (a))> Sodium naphthalenesulfonate: Sodium 1-naphthalenesulfonate, manufactured by Tokyo Chemical Industry Co., Ltd. Sodium aminonaphthalenesulfonate: Sodium 2-amino-1-naphthalenesulfonate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Dimethylaminonaphthalenesulfonic acid: 5-dimethylaminonaphthalene-1-sulfonic acid, manufactured by Tokyo Chemical Industry Co., Ltd. Naphthalenesulfonic acid formalin condensate: β-naphthalenesulfonic acid formalin condensate sodium salt, Demol NL, manufactured by Kao Corporation

[0058] <(b) Component> Oleyldimethylamine oxide: component (b1), in which X is R 11b and R 11b is an alkenyl group having 18 carbon atoms, R 2 and R 3 The compound in which is a methyl group was synthesized with reference to JP 2020-76022 A. Oleic acid amidopropyl dimethylamine oxide: component (b1), in the general formula (b1), X is R 12b -[CONH-CH2CH2CH2] n - and R 12b is an alkenyl group having 18 carbon atoms, n is 1, n2 is 1, R 2 and R 3 Compound (b12), in which is a methyl group, was synthesized with reference to JP 2020-76022 A. Alkyl (C16 / C18) trimethylammonium chloride: component (b2), in general formula (b21), R 21b is an alkyl group having 16 and 18 carbon atoms (C16 / C18 (mass ratio) = 6 / 4), R 22b , R 23b and R 24b is a methyl group, X - A compound in which the ion is chloride, manufactured by Kao Corporation

[0059] <(c) component> Asahi Silicone AF-146: Silicone defoamer, manufactured by Asahi Chemical Industry Co., Ltd. DK Q1-1183: Silicone defoamer, manufactured by Dow Chemical <(d) component> Sodium m-xylene sulfonate: Sodium m-xylene sulfonate, manufactured by Tokyo Chemical Industry Co., Ltd.

[0060] Cement: Ordinary Portland cement (a 50 / 50 mix of Pacific Cement and Sumitomo Osaka Cement, specific gravity 3.16) Water: Tap water (Wakayama City tap water, specific gravity 1.00)

[0061] [Examples and Comparative Examples] Preparation of hydraulic composition Water adjusted to a predetermined temperature shown in Tables 2 to 4, 50 parts by mass of which had been removed, was mixed with cement, and the mixture was stirred for 30 seconds using a commercially available hand mixer. Then, a thickener composition for hydraulic composition having a composition shown in Tables 2 to 4 was added, and stirring was continued for 1 minute after the addition of the thickener composition for hydraulic composition to prepare a slurry of the hydraulic composition. The thickener composition for hydraulic composition was prepared by mixing the (a) or (a') component, the (b), (c), and (d) components in the formulation shown in Table 1 in amounts corresponding to the contents of the hydraulic compositions in Tables 2 to 4, with 50 parts by mass of water removed from the water previously adjusted to a temperature, until the mixture was uniform. The total amount of water added to the cement initially and the amount of water in each composition was adjusted to be the amount of water shown in Tables 2-4. In addition, in each hydraulic composition, the water content (parts by mass), the cement (hydraulic powder) content (parts by mass), the mass percentage of water to hydraulic powder (water / hydraulic powder ratio (W / C)), the content (parts by mass) of component (a) relative to 100 parts by mass of water, the content (parts by mass) of component (b) relative to 100 parts by mass of water, the mass ratio (a) / (b) of the content of component (a) to the content of component (b), the mass ratio (c) / [(a)+(b)] of the content of component (c) to the total content of component (a) and component (b), and the mass ratio (d) / (b) of the content of component (b) to the content of component (d) were as shown in Tables 2 to 4, respectively. In addition, in Comparative Examples 1-15 to 1-17, sodium m-xylenesulfonate corresponds to component (d), but for convenience it is listed in the column for component (a').

[0062] [Table 1]

[0063] Breathing rate measurement For each prepared hydraulic composition, the bleeding rate was measured several hours after preparation as described in Tables 2 to 4 according to JSCE-F 522-2007 Test method for bleeding rate and expansion rate of injection mortar for prepacked concrete (polyethylene bag method). The results are shown in Tables 2 to 4. The higher the bleeding rate value, the better the strength of the hardened body of the hydraulic composition. A bleeding rate of 1% or more was judged as "good".

[0064] Measurement of viscosity (J14 funnel) According to the Japan Society of Civil Engineers standard "PC Grout Test Method (JCSE-F531)", about 630 ml of cement paste, which is each hydraulic composition immediately after preparation, was poured into a J14 funnel, and the flow time (sec.) from the J14 funnel was measured. The results are shown in Tables 2 to 4. In addition, for the flow time of each of the obtained Examples and Comparative Examples, the increase rate (%) of the flow time was calculated based on Comparative Example 1-1 for Examples 1-1 to 1-14 and Comparative Examples 1-1 to 1-21, based on Comparative Example 2-1 for Examples 2-1 to 2-2 and Comparative Examples 2-1 to 2-5, and based on Comparative Example 3-1 for Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-4, and is shown in the table. The higher the increase rate, the higher the viscosity of the hydraulic composition slurry and the better the material separation resistance. The evaluation was made as follows: an increase in flow time of 10% or more was rated as "good".

[0065] (4) Measurement of inseparability in water 800mL of water was measured into a 1000mL beaker, and about 500g of cement paste, which is each hydraulic composition immediately after preparation, was gently poured into the beaker over 10 to 15 seconds, and the mixture was left to stand for 3 minutes, after which 600mL of the supernatant was separated by decantation. The turbidity of the obtained supernatant was measured using a turbidity meter (TN-100 Turbidity Meter manufactured by AS ONE Co., Ltd.), and the pH was measured using a pH meter to determine the non-separability in water. The results are shown in Tables 3 and 4. The smaller the turbidity measurement value, the better the non-separability in water. In the table, the turbidity described as "above the upper limit of measurement" indicates that the turbidity exceeded the upper limit of measurement, 1000 or more. In addition, according to JSCE-104 "Quality Standard for Non-Separable Admixtures for Concrete in Water (Draft)", if the pH is less than 12, it can be determined that there is non-separability in water.

[0066] [Table 2]

[0067] [Table 3]

[0068] [Table 4]

[0069] [Reference example] As in the Examples and Comparative Examples, water adjusted to a prescribed temperature shown in Table 5 was mixed with cement and stirred for 30 seconds using a commercially available hand mixer. Thereafter, as shown in Table 5, component (b) and component (c) in the formulation shown in Table 1 were added as a thickener composition for hydraulic compositions. After the addition of the thickener composition for hydraulic compositions, stirring was continued for 1 minute to prepare a slurry of the hydraulic composition. The total amount of water added to the cement initially and the amount of water in each composition was adjusted to the amount shown in Table 5. In addition, in each hydraulic composition, the water content (parts by mass), the cement (hydraulic powder) content (parts by mass), the mass percentage of water to hydraulic powder (water / hydraulic powder ratio (W / C)), the content (parts by mass) of component (b) per 100 parts by mass of water, and the mass ratio (c) / (b) of the content of component (c) to the content of component (b) were each as shown in Table 5.

[0070] For each hydraulic composition prepared, the bleeding rate and viscosity (J14 funnel) were measured in the same manner as described above. The compressive strength of each hydraulic composition prepared after 28 days was measured by the following method. The specimens were prepared according to JSCE-F 506-2010 "Procedure for preparing cylindrical specimens for compressive strength tests of mortar or cement paste (draft)". The obtained specimens were cured in water at 20°C. The strength was measured according to JSCE-G 505-2010 "Procedure for testing compressive strength of mortar or cement paste using cylindrical specimens (draft)". The results are shown in Table 5.

[0071] [Table 5]

[0072] As shown in the results of Table 5, when component (b) is added as a thickener to the hydraulic composition, the viscosity of the hydraulic composition slurry can be increased, but the increase in viscosity leads to a decrease in the bleeding rate. When the bleeding rate decreases, the strength of the hydraulic composition hardened body decreases, as shown in the results of Table 5. In other words, the strength of the hydraulic composition hardened body can be increased by increasing the bleeding rate. On the other hand, in the examples of the present invention, by using components (a) and (b), the bleeding rate can be increased and the strength after hardening can be increased despite increasing the viscosity of the hydraulic composition slurry after preparation.

Claims

1. A thickener composition for a hydraulic composition, containing (a) an alkylnaphthalenesulfonic acid having an alkyl group with 2 or more carbon atoms, or a salt thereof (hereinafter referred to as component (a)), and one or more selected from an amphoteric surfactant and a cationic surfactant (hereinafter referred to as component (b)).

2. The thickener composition for a hydraulic composition according to Claim 1, wherein component (a) is butylnaphthalenesulfonic acid or a salt thereof.

3. The thickener composition for a hydraulic composition according to Claim 1 or 2, wherein the mass ratio (a) / (b) of the content of component (a) to the content of component (b) is 0.15 or more and 2 or less.

4. A hydraulic composition, containing (a) an alkylnaphthalenesulfonic acid having an alkyl group with 2 or more carbon atoms, or a salt thereof (hereinafter referred to as component (a)), one or more selected from an amphoteric surfactant and a cationic surfactant (hereinafter referred to as component (b)), hydraulic powder, and water.

5. The hydraulic composition according to Claim 4, wherein component (a) is butylnaphthalenesulfonic acid or a salt thereof.

6. The hydraulic composition according to Claim 4 or 5, wherein the mass ratio (a) / (b) of the content of component (a) to the content of component (b) is 0.15 or more and 2 or less.

7. The hydraulic composition according to Claim 4 or 5, wherein the content of component (b) is 0.01 part by mass or more and 1 part by mass or less with respect to 100 parts by mass of water.

8. The hydraulic composition according to Claim 4 or 5, wherein the mass percentage of water and hydraulic powder in the hydraulic composition (water / hydraulic powder ratio) is 50% by mass or more and 120% by mass or less.