Rheology modifier

Abstract

To provide: a rheology modifier that can increase viscosity when contained in a hydraulic slurry composition; and a hydraulic slurry composition whose viscosity has been increased.SOLUTION: A rheology modifier comprises a compound represented by the general formula (1) in the figure, and an anionic surfactant having an aliphatic hydrocarbon group. [In the formula, X represents a group represented by R1a or R2a-[CONH-CH2CH2CH2]n-; R1a is a C14-22 alkyl group or a C14-22 alkenyl group; R2a is a C13-21 alkyl group or a C13-21 alkenyl group; n is an integer from 1 to 3; R2 and R3 each independently represent a C1-4 alkyl group or a group represented by -(C2H4O)pH; and p is the average number of added moles, and the sum of the p values in R2 and R3 is a number from 0 to 5.]SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a rheology modifier. [Background technology]

[0002] Many industrial products used in the form of an aqueous solution or slurry contain various kinds of additives to improve their physical properties. For example, in order to modify the rheology of an aqueous solution or slurry, it may be desirable to adjust the viscosity appropriately according to the purpose or use. Conventionally, measures such as the addition of a thickener or a viscosity reducer, heating or cooling operations, and adjustment of electrolyte concentration have been adopted to adjust the viscosity of an aqueous solution or slurry. It is also known that surfactants affect the viscosity, elasticity, thickening, etc. of an aqueous solution or slurry. In hydraulic slurries containing hydraulic powders such as cement, rheology modifiers are sometimes used to improve physical properties such as viscosity and resistance to material separation.

[0003] Patent Document 1 describes a rheology modifier containing two or more compounds represented by general formula (1), in which X in the general formula (1) is different for the two or more compounds, and at least one of the two or more compounds is R of X in the general formula (1). 1a or R 1b A rheology modifier which exhibits a rheology modifying effect over a wide temperature range and which is a compound having an alkenyl group is disclosed. Patent Document 2 discloses an admixture for concrete that improves the aesthetic appearance of the surface of concrete products, comprising an anionic surfactant having a surface tension of 40 dyne / cm or less in a 1% aqueous solution, dextrin, and an alkylamine oxide. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2020-76022 A [Patent Document 2] Japanese Patent Application Publication No. 4-170346 Summary of the Invention [Problem to be solved by the invention]

[0005] As described in Patent Document 1, a specific amine oxide surfactant can increase the viscosity when contained in a hydraulic slurry composition, but further improvements are required. The present invention provides a rheology modifier capable of increasing the viscosity when contained in a hydraulic slurry composition, and a hydraulic slurry composition having increased viscosity. [Means for solving the problem]

[0006] The present invention relates to a rheology modifier comprising a compound represented by the following general formula (1) [hereinafter referred to as compound (A)] and an anionic surfactant having an aliphatic hydrocarbon group [hereinafter referred to as compound (B)].

[0007] [ka]

[0008] [Wherein, X is R 1a or R 2a -[CONH-CH2CH2CH2] n R is a group represented by the formula: 1a R is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 14 to 22 carbon atoms. 2a is 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.

[0009] The present invention also relates to a hydraulic slurry composition containing the rheology modifier of the present invention, a hydraulic powder, and water.

[0010] The present invention also relates to a method for increasing the viscosity of a hydraulic slurry composition and increasing the bleeding rate by mixing the rheology modifier of the present invention with a hydraulic slurry composition containing a hydraulic powder and water. Effect of the Invention

[0011] According to the present invention, there are provided a rheology modifier capable of increasing the viscosity when contained in a hydraulic slurry composition, and a hydraulic slurry composition having increased viscosity.

[0012] Furthermore, the rheology modifier of the present invention can increase the viscosity when contained in a hydraulic slurry composition, and further can increase the bleeding rate under specific blending conditions, and is suitable for applications in which it is desired to increase the viscosity of hydraulic slurry compositions such as root hardening liquids and pile circumference fixing liquids used when driving concrete piles, thereby imparting anti-separation properties underwater, but bleeding must not be suppressed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The reason why the rheology modifier of the present invention can increase the viscosity when it is contained in a hydraulic slurry composition and the viscosity of the hydraulic slurry composition of the present invention is increased is not necessarily clear, but is presumed to be as follows. The specific amine oxide, which is the compound (A) of the present invention, can thicken the hydraulic slurry composition by forming worm-like micelles in water. In addition, the anionic surfactant having an aliphatic hydrocarbon group, which is the compound (B) of the present invention, is incorporated into the worm-like micelles of the compound (A) when it is contained in water with the compound (A) due to the hydrophobic interaction of the aliphatic hydrocarbon group. As a result, it is considered that the packing state has changed to the optimum state for thickening. On the other hand, for example, when the compound (A) is used in combination with an aromatic anionic surfactant, the CH-π interaction between the aromatic ring and the alkyl group of the compound (A) also works in addition to the hydrophobic interaction of the alkyl group, and the strong interaction causes a different behavior such as penetrating deeper into the micelle, and it is considered that the packing state is different from that of the compound (B), so that the compound (B) is considered to be optimal. Furthermore, when compound (A) and compound (B) are added to a hydraulic slurry composition, the anionic groups of compound (B) can be easily adsorbed because the surface charge of the hydraulic powder is positive, and it is believed that the viscosity of the system can be further significantly improved by not only the entanglement of the string-like micelles but also the action of cross-linking the hydraulic powder. When compound (A) and compound (B) are added to a hydraulic slurry composition, the crosslinking points can be adjusted by the ratio of compound (B) to compound (A). As the number of crosslinking points increases, the action of agglomerating the hydraulic powder becomes stronger, and the increase in particle size promotes the settling of the hydraulic powder, which is thought to cause bleeding of the hydraulic slurry composition.

[0014] [Rheology modifier] The rheology modifier of the present invention contains a compound represented by the above general formula (1) [hereinafter referred to as compound (A)].

[0015] In the compound (A), preferred embodiments are as follows. In the general formula (1), X is R 1a or R2a -[CONH-CH2CH2CH2] n -, preferably R 2a -[CONH-CH2CH2CH2] n It is a group represented by the following formula: R 1a represents an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 14 to 22 carbon atoms, preferably an alkenyl group having 14 to 22 carbon atoms, and more preferably an alkenyl group having 18 carbon atoms. R 1a When is an alkenyl group, the number of carbon atoms is preferably 14 or more, more preferably 16 or more, and preferably 22 or less, more preferably 20 or less, and even more preferably 18, from the viewpoints of temperature versatility and availability. R 1a When the alkyl group is an alkyl group, the number of carbon atoms is preferably 14 or more, more preferably 16 or more, and is preferably 20 or less, more preferably 18 or less, from the viewpoints of temperature versatility and availability. R 1b represents an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms, preferably an alkenyl group having 13 to 21 carbon atoms, and more preferably an alkenyl group having 17 carbon atoms. R 1b When is an alkenyl group, the number of carbon atoms is preferably 13 or more, more preferably 15 or more, and preferably 21 or less, more preferably 19 or less, and even more preferably 17, from the viewpoints of temperature versatility and availability. R 1b When the alkyl group is an alkyl group, the number of carbon atoms is preferably 13 or more, more preferably 15 or more, and is preferably 19 or less, more preferably 17 or less, from the viewpoints of temperature versatility and availability. n is preferably 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.

[0016] From the viewpoint of temperature versatility and viscosity increasing property of the hydraulic slurry composition, the compound (A) is 1a is an alkenyl group having 18 carbon atoms, and R 1b is an alkenyl group having 17 carbon atoms.

[0017] The rheology modifier of the present invention contains an anionic surfactant having an aliphatic hydrocarbon group (hereinafter referred to as compound (B)).

[0018] The number of carbon atoms in the aliphatic hydrocarbon group of the compound (B) is preferably 8 or more, more preferably 9 or more, even more preferably 10 or more, and is preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, from the viewpoint of thickening property of the hydraulic slurry composition. From the viewpoint of the bleeding property of the hydraulic slurry composition, the number of carbon atoms in the aliphatic hydrocarbon group of the compound (B) is preferably 10 or more, more preferably 11 or more, even more preferably 12 or more, and is preferably 18 or less, more preferably 16 or less, even more preferably 14 or less.

[0019] The anionic group contained in the compound (B) is preferably one or more selected from a sulfate group, a phosphate group, and a carboxylate group, more preferably one or more selected from a sulfate group and a phosphate group, and further preferably a sulfate group, from the viewpoint of thickening property and bleeding property of the hydraulic slurry composition.

[0020] From the viewpoint of thickening property and bleeding property of the hydraulic slurry composition, the compound (B) is preferably a compound having no oxyalkylene group or having an average added mole number of oxyalkylene groups of 4.0 or less, preferably 3.5 or less, and more preferably 3.0 or less.

[0021] Examples of the compound (B) include sulfonic acid compounds, ether sulfate compounds, carboxylic acid compounds, phosphonic acid compounds, and phosphate compounds having an aliphatic hydrocarbon group. More specifically, compound (B) can be one or more selected from alkyl or alkenyl sulfate esters having an alkyl group or an alkenyl group, alkyl or alkenyl sulfonic acids having an alkyl group or an alkenyl group, polyoxyalkylene alkyl or alkenyl ether sulfate esters having an alkyl group or an alkenyl group, monocarboxylic acids having an alkyl group or an alkenyl group, dicarboxylic acids having an alkyl group or an alkenyl group, alkyl or alkenyl phosphate esters having an alkyl group or an alkenyl group, polyoxyalkylene alkyl or alkenyl ether phosphate esters having an alkyl group or an alkenyl group, di- or mono-alkyl or alkenyl sulfosuccinic acids having an alkyl group or an alkenyl group, and salts thereof. From the viewpoints of availability, thickening property and bleeding property of the hydraulic slurry composition, the compound (B) is preferably one or more selected from alkyl or alkenyl sulfate esters having an alkyl group or an alkenyl group, polyoxyalkylene alkyl or alkenyl ether sulfate esters having an alkyl group or an alkenyl group, polyoxyalkylene alkyl or alkenyl ether phosphate esters having an alkyl group or an alkenyl group, and salts thereof, and more preferably one or more selected from alkyl or alkenyl sulfate esters having an alkyl group or an alkenyl group, polyoxyalkylene alkyl or alkenyl ether sulfate esters having an alkyl group or an alkenyl group, and salts thereof. Examples of the salts of these compounds (B) include at least one selected from alkali metal salts such as sodium salts and potassium salts, ammonium salts, and amine salts such as triethanolamine, diethanolamine, and methyldiethanolamine. The number of carbon atoms in the alkyl or alkenyl group in these compounds (B) is preferably 8 or more, more preferably 9 or more, even more preferably 10 or more, and preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, from the viewpoint of thickening property of the hydraulic slurry composition. The number of carbon atoms in the alkyl or alkenyl group in these compounds (B) is preferably 10 or more, more preferably 11 or more, even more preferably 12 or more, and is preferably 18 or less, more preferably 16 or less, even more preferably 14 or less, from the viewpoint of the bleeding property of the hydraulic slurry composition. The average number of moles of oxyalkylene groups added in these compounds (B) is 4.0 or less, preferably 3.5 or less, and more preferably 3.0 or less, from the viewpoints of thickening property and bleeding property of the hydraulic slurry composition.

[0022] From the viewpoint of thickening property of the hydraulic slurry composition, the alkyl or alkenyl sulfate ester having an alkyl or alkenyl group preferably has an alkyl or alkenyl group having 8 or more carbon atoms, more preferably 9 or more, even more preferably 10 or more, and preferably 20 or less, more preferably 16 or less, even more preferably 14 or less, and preferably an alkyl group. From the viewpoint of the bleeding property of the hydraulic slurry composition, the alkyl or alkenyl sulfate ester having an alkyl or alkenyl group preferably has an alkyl or alkenyl group having 10 or more carbon atoms, more preferably 11 or more, even more preferably 12 or more, and preferably 18 or less, more preferably 16 or less, even more preferably 14 or less, and preferably an alkyl group.

[0023] The polyoxyalkylene alkyl or alkenyl ether sulfate having an alkyl or alkenyl group has an alkyl or alkenyl group, preferably an alkyl group, having a carbon number of preferably 8 or more, more preferably 9 or more, even more preferably 10 or more, and preferably 20 or less, more preferably 14 or less, even more preferably 12 or less, from the viewpoint of the thickening property and bleeding property of the hydraulic slurry composition, the oxyalkylene group is an oxyethylene group or an oxypropylene group, preferably an oxyethylene group, and the average number of moles added of the oxyalkylene group is 4.0 or less, preferably 3.5 or less, more preferably 3.0 or less, from the viewpoint of the thickening property and bleeding property of the hydraulic slurry composition.

[0024] From the viewpoint of thickening property and bleeding property of the hydraulic slurry composition, the monocarboxylic acid having an alkyl group or an alkenyl group has an alkyl group or an alkenyl group, preferably having 8 or more carbon atoms, more preferably 10 or more, even more preferably 12 or more, and preferably 20 or less, more preferably 16 or less, even more preferably 14 or less, and preferably an alkyl group. The dicarboxylic acid having an alkyl or alkenyl group has an alkyl or alkenyl group, preferably having 8 or more carbon atoms, more preferably 12 or more, even more preferably 14 or more, and preferably 20 or less, more preferably 19 or less, even more preferably 18 or less, and preferably an alkyl group, from the viewpoints of thickening property and bleeding property of the hydraulic slurry composition, product stability, and availability.

[0025] From the viewpoint of thickening property of the hydraulic slurry composition, the alkyl or alkenyl phosphate ester having an alkyl or alkenyl group preferably has an alkyl or alkenyl group having 8 or more carbon atoms, more preferably 9 or more, even more preferably 10 or more, and preferably 20 or less, more preferably 16 or less, even more preferably 12 or less, and preferably an alkyl group. From the viewpoint of the bleeding property of the hydraulic slurry composition, the alkyl or alkenyl phosphate ester having an alkyl or alkenyl group preferably has an alkyl or alkenyl group having 10 or more carbon atoms, more preferably 11 or more, even more preferably 12 or more, and preferably 18 or less, more preferably 16 or less, even more preferably 14 or less, and preferably an alkyl group.

[0026] The polyoxyalkylene alkyl or alkenyl ether phosphate ester having an alkyl or alkenyl group has an alkyl or alkenyl group, preferably an alkyl group, having a carbon number of preferably 8 or more, more preferably 9 or more, even more preferably 10 or more, and preferably 20 or less, more preferably 16 or less, even more preferably 12 or less, from the viewpoint of thickening properties and bleeding properties of a hydraulic slurry composition; the oxyalkylene group is an oxyethylene group or oxypropylene group, preferably an oxyethylene group; and the average number of moles of the oxyalkylene group added is 4.0 or less, preferably 3.5 or less, more preferably 3.0 or less, from the viewpoint of thickening properties and bleeding properties of a hydraulic slurry composition.

[0027] From the viewpoint of thickening property of the hydraulic slurry composition, the di- or mono-alkyl or alkenyl sulfosuccinic acid having an alkyl or alkenyl group preferably has an alkyl or alkenyl group having 8 or more carbon atoms, more preferably 10 or more, even more preferably 12 or more, and preferably 20 or less, more preferably 18 or less, even more preferably 14 or less, and preferably an alkyl group. The di- or mono-alkyl or alkenyl sulfosuccinic acid having an alkyl or alkenyl group preferably has an alkyl or alkenyl group having 10 or more carbon atoms, more preferably 11 or more, even more preferably 12 or more carbon atoms, and preferably 18 or less, more preferably 16 or less, even more preferably 14 or less, and preferably an alkyl group, from the viewpoint of the bleeding property of the hydraulic slurry composition.

[0028] In the rheology modifier of the present invention, from the viewpoints of ease of handling and compactness, the content of compound (A) is preferably 1 mass % or more, more preferably 10 mass % or more, even more preferably 15 mass % or more, and preferably 99.9 mass % or less, more preferably 80 mass % or less, even more preferably 50 mass % or less.

[0029] In the rheology modifier of the present invention, from the viewpoints of ease of handling and compactness, the content of compound (B) is preferably 0.1 mass % or more, more preferably 10 mass % or more, even more preferably 20 mass % or more, and preferably 60 mass % or less, more preferably 50 mass % or less, even more preferably 40 mass % or less. In the present invention, the mass of compound (B) is expressed as a value converted into a sodium salt.

[0030] In the rheology modifier of the present invention, the mass ratio (B) / (A) of the content of the compound (A) to the content of the compound (B) is, from the viewpoints of thickening property and economic efficiency of the hydraulic slurry composition, preferably 0.001 or more, more preferably 0.01 or more, even more preferably 0.1 or more, and preferably 1.5 or less, more preferably 1.2 or less, even more preferably 1.0 or less. In the rheology modifier of the present invention, the mass ratio (B) / (A) of the content of the compound (A) to the content of the compound (B) is preferably 0.1 or more, more preferably 0.13 or more, even more preferably 0.15 or more, and is preferably 1 or less, more preferably 0.9 or less, even more preferably 0.7 or less, from the viewpoints of thickening property, bleeding property and economical efficiency of the hydraulic slurry composition.

[0031] The rheology modifier of the present invention may contain water, i.e., the rheology modifier of the present invention may be a liquid rheology modifier. When the rheology modifier of the present invention contains water, the content of water in the rheology modifier of the present invention is preferably 1 mass % or more, more preferably 10 mass % or more, even more preferably 30 mass % or more, and preferably 99 mass % or less, more preferably 90 mass % or less, even more preferably 70 mass % or less.

[0032] The rheology modifier of the present invention may contain a dispersant. When the subject to which the rheology modifier of the present invention is applied is a hydraulic slurry composition, the dispersant is a preferred component from the viewpoint of exhibiting a good rheology modifying effect and fluidity.

[0033] The dispersant is not particularly limited, but examples thereof include naphthalene-based polymers, polycarboxylic acid-based polymers, melamine-based polymers, phenol-based polymers, and lignin-based polymers.

[0034] More specifically, the dispersant may be one or more dispersants selected from (C1) naphthalene-based dispersants, (C2) polycarboxylic acid-based dispersants, (C3) dispersants made of the polycondensation products described below (hereinafter also referred to as PAE-based dispersants), (C4) lignin-based dispersants, and (C5) melamine-based dispersants. <Polycondensation products> A polycondensation product consisting of the following components C31, C33, and optionally C32: [Component C31] Aromatic or heteroaromatic compounds having from 5 to 10 carbon or heteroatoms and containing, on average, from 1 to 300 oxyethylene and / or oxypropylene groups per molecule, attached to said aromatic or heteroaromatic compounds via O or N atoms. [Component C32] (C32-1) phenol, (C32-2) phenol ether, (C32-3) naphthol, (C32-4) naphthol ether, (C32-5) aniline, (C32-6) furfuryl alcohol, and (C32-7) an aminoplast former selected from the group consisting of melamine or a derivative thereof, urea or a derivative thereof, and a carboxamide, hydroxybenzoic acid, benzoic acid, isophthalic acid, and oxynaphthoic acid, as an optional component, at least one aromatic compound selected from the group consisting of hydroxybenzoic acid, benzoic acid, isophthalic acid, and oxynaphthoic acid. [Component C33] an aldehyde selected from the group consisting of formaldehyde, glyoxylic acid, and benzaldehyde, or a mixture thereof, wherein the benzaldehyde is further a , SO3M a , and PO3M a (wherein M is H, an alkali metal or alkaline earth metal, ammonium, or an organic amine group, and a can be 1 / 2, 1, or 2).

[0035] From the viewpoint of fluidity of the hydraulic slurry composition, the dispersant is preferably at least one selected from (C1) a naphthalene-based dispersant, (C2) a polycarboxylic acid-based dispersant, and (C4) a lignin-based dispersant, more preferably at least one selected from (C4) a lignin-based dispersant, and (C2) a polycarboxylic acid-based dispersant, and further preferably (C2) a polycarboxylic acid-based dispersant. The dispersant will be described below.

[0036] (C1) Naphthalene-based dispersant As the naphthalene-based dispersant, preferably, naphthalene sulfonic acid formaldehyde condensate or its salt can be mentioned. Naphthalene sulfonic acid formaldehyde condensate or its salt is a condensate of naphthalene sulfonic acid and formaldehyde or its salt. Naphthalene sulfonic acid formaldehyde condensate may be co-condensed with aromatic compounds that can be co-condensed with naphthalene sulfonic acid as a monomer, such as, for example, methylnaphthalene, ethylnaphthalene, butylnaphthalene, hydroxynaphthalene, naphthalene carboxylic acid, anthracene, phenol, cresol, creosote oil, tar, melamine, urea, sulfanilic acid and / or their derivatives, as long as the performance is not impaired.

[0037] The naphthalenesulfonic acid formaldehyde condensate or its salt may be, for example, a commercially available product such as Mighty 150, DEMOL N, DEMOL RN, DEMOL MS, DEMOL SN-B, DEMOL SS-L (all manufactured by Kao Corporation), Celluflow 120, Labelin FD-40, Labelin FM-45 (all manufactured by Daiichi Kogyo Co., Ltd.), etc.

[0038] From the viewpoint of improving the fluidity of the hydraulic slurry composition, the naphthalenesulfonic acid formaldehyde condensate or its salt has a weight average molecular weight of preferably 200,000 or less, more preferably 100,000 or less, even more preferably 80,000 or less, even more preferably 50,000 or less, and even more preferably 30,000 or less. From the viewpoint of improving the fluidity of the hydraulic slurry composition, the naphthalenesulfonic acid formaldehyde condensate or its salt has a weight average molecular weight of preferably 1,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, and even more preferably 5,000 or more. The naphthalenesulfonic acid formaldehyde condensate may be in an acid state or a neutralized product.

[0039] The molecular weight of the naphthalenesulfonic acid-formaldehyde condensate or its salt can be measured by gel permeation chromatography under the following conditions. [GPC conditions] Column: G4000SWXL+G2000SWXL (Tosoh) Eluent: 30mM CH3COONa / CH3CN=6 / 4 Flow rate: 0.7ml / min Detection: UV280nm Sample size: 0.2mg / ml Standard material: Nishio Kogyo Co., Ltd., polystyrene sulfonate sodium conversion (monodisperse polystyrene sulfonate sodium: molecular weight, 206, 1,800, 4,000, 8,000, 18,000, 35,000, 88,000, 780,000) Detector: Tosoh Corporation UV-8020

[0040] (C2) Polycarboxylic acid dispersant Examples of polycarboxylic acid dispersants that can be used include copolymers of monoesters of polyalkylene glycol and (meth)acrylic acid and carboxylic acids such as (meth)acrylic acid (e.g., compounds described in JP-A-8-12397), copolymers of unsaturated alcohols having polyalkylene glycol and carboxylic acids such as (meth)acrylic acid, and copolymers of unsaturated alcohols having polyalkylene glycol and dicarboxylic acids such as maleic acid. Here, (meth)acrylic acid means a carboxylic acid selected from acrylic acid and methacrylic acid.

[0041] As the polycarboxylic acid-based dispersant, a copolymer containing a monomer (c21) represented by the following general formula (c21) as a constituent monomer is preferred from the viewpoint of initial fluidity. The polycarboxylic acid-based dispersant is more preferably a copolymer containing, as constituent monomers, a monomer (c21) represented by the following general formula (c21) and a monomer (c22) represented by the following general formula (c22).

[0042] [ka]

[0043] [During the ceremony, R 1c , R 2c may be the same or different, and may be a hydrogen atom or a methyl group. R 3c : Hydrogen atom or -COO(AO) n1 X 1c X 1c : Hydrogen atom or an alkyl group having 1 to 4 carbon atoms AO: a group selected from an ethyleneoxy group and a propyleneoxy group n1: the average number of moles of AO added, a number between 1 and 300 q: a number between 0 and 2 p: number of 0 or 1 Indicates the following.

[0044] [ka]

[0045] [During the ceremony, R 4c , R 5c , R 6c may be the same or different, and may be a hydrogen atom, a methyl group or (CH2) r COOM 2c and (CH2) r COOM 2c COOM 1c or other (CH2) r COOM 2c and an anhydride may be formed, in which case, M 1c , M 2c does not exist. M 1c , M 2c : may be the same or different, and are a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. r: A number between 0 and 2.

[0046] As the polycarboxylic acid-based dispersant, two or more dispersants differing in the average number of moles of AO added or the ratio of the monomer (c21) to the monomer (c22) may be used.

[0047] A preferred PAE-based dispersant is a dispersant consisting of a polycondensation product of the following components C31, C32, and C33, in which the molar ratio of component C33:(component C31+component C32) is 1:0.01 to 1:10, and the molar ratio of component C31:component C32 is 10:1 to 1:10. [Component C31] A compound in which an average of 1 to 300 oxyethylene groups and / or oxypropylene groups are bonded per molecule via O atoms or N atoms to an aromatic compound selected from the group consisting of phenol, cresol, resorcinol, nonylphenol, methoxyphenol, naphthol, methylnaphthol, butylnaphthol, and bisphenol A. [Component C32] At least one aromatic compound selected from the group consisting of phenoxyacetic acid, phenoxyethanol, phenoxyethanol phosphate, phenoxydiglycol, and phenoxy(poly)ethylene glycol phosphate, hydroxybenzoic acid, benzoic acid, isophthalic acid, and oxynaphthoic acid. [Component C33] an aldehyde selected from the group consisting of formaldehyde, glyoxylic acid, and benzaldehyde, or mixtures thereof, where the benzaldehyde may further have an acidic group represented by the formula COOMa, SO3Ma, or PO3Ma, where M is H, an alkali metal or alkaline earth metal, ammonium, or an organic amine group, and a may be 1 / 2, 1, or 2;

[0048] When the rheology modifier of the present invention contains a dispersant, the content of the dispersant in the rheology modifier of the present invention is, from the viewpoints of fluidity and thickening property of the hydraulic slurry composition, preferably 1 mass % or more, more preferably 5 mass % or more, even more preferably 10 mass % or more, and preferably 99 mass % or less, more preferably 90 mass % or less, even more preferably 80 mass % or less.

[0049] The rheology modifier of the present invention may contain other components, such as air-enhancing agents, retarders, early-strength agents, accelerators, foaming agents, foaming agents, defoamers, rust inhibitors, colorants, antifungal agents, crack-reducing agents, expansion agents, dyes, pigments, and the like (excluding the above-mentioned compound (A), solvent (B), and dispersants), so long as the performance of the modifier is not adversely affected.

[0050] From the viewpoint of ease of handling, the viscosity of the rheology modifier of the present invention at 20°C is preferably 1 mPa·s or more, more preferably 10 mPa·s or more, even more preferably 100 mPa·s or more, and preferably 2000 mPa·s or less, more preferably 1500 mPa·s or less, even more preferably 1000 mPa·s or less. Here, the viscosity of the rheology modifier is measured using a TVB-10 (B-type viscometer) manufactured by Toki Sangyo Co., Ltd., with an M1 rotor at 12 rpm.

[0051] The rheology modifier of the present invention is suitable for use in hydraulic slurry compositions. In particular, the rheology modifier of the present invention can be suitably used in grouting materials used in ground improvement methods, columnar continuous walls, injection methods, and the like, cement milk for drilling, self-leveling materials, lightweight embankments, crack repair materials, lightweight mortars, high-fluidity concrete, fiber-reinforced concrete, pile circumference fixing liquid, underwater embankments, void filling materials, porous concrete, air grout materials, concrete for ECL, PC grout, concrete fluidizers, rebound reducing agents, thickeners for extrusion molding, high-fluidity concrete, underwater non-segregating concrete, concrete for shield construction, concrete for SENS construction, and the like.

[0052] [Hydraulic Slurry Composition] The present invention provides a hydraulic slurry composition containing the rheology modifier of the present invention, water, and a hydraulic powder. That is, the hydraulic slurry composition of the present invention contains compound (A), compound (B), water, and hydraulic powder. The matters described in relation to the rheology modifier of the present invention can be appropriately applied to the hydraulic slurry composition of the present invention.

[0053] The hydraulic powder used in the hydraulic slurry 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 slurry 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.

[0054] The hydraulic powder may contain blast furnace slag, fly ash, silica fume, anhydrous gypsum, etc., or may contain 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 be used. Also, clay such as bentonite may be contained.

[0055] The hydraulic slurry composition of the present invention may contain aggregate. Examples of aggregate include fine aggregate and coarse aggregate, and 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 aggregate may be used. The term aggregate is based on "Concrete Overview" (published by Gijutsu Shoin on June 10, 1998).

[0056] The hydraulic slurry composition of the present invention may contain other components other than the compound (A) and the compound (B) within the range that does not affect the effects of the present invention. For example, the above-mentioned dispersants, AE agents, retarders, foaming agents, thickeners, foaming agents, waterproofing agents, fluidizing agents, antifoaming agents, etc. may be mentioned.

[0057] In the hydraulic slurry composition of the present invention, the content of the rheology modifier of the present invention is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, even more preferably 0.1 part by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, based on 100 parts by mass of water, from the viewpoints of thickening property, anti-bleeding property, and economical efficiency.

[0058] In the hydraulic slurry composition of the present invention, the content of the compound (A) is, from the viewpoints of thickening property, bleeding property and economical efficiency, preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, even more preferably 0.1 part by mass or more, and preferably 4 parts by mass or less, more preferably 1.2 parts by mass or less, even more preferably 0.3 parts by mass or less, relative to 100 parts by mass of water.

[0059] In the hydraulic slurry composition of the present invention, the content of the compound (B) is, from the viewpoints of thickening property, bleeding property and economical efficiency, preferably 0.0001 part by mass or more, more preferably 0.0005 part by mass or more, even more preferably 0.001 part by mass or more, still more preferably 0.005 part by mass or more, still more preferably 0.01 part by mass or more, and preferably 6 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 1.8 parts by mass or less, still more preferably 0.9 parts by mass or less, and still more preferably 0.2 parts by mass or less, relative to 100 parts by mass of water.

[0060] In the hydraulic slurry composition of the present invention, the mass ratio (B) / (A) of the content of the compound (A) to the content of the compound (B) is, from the viewpoints of thickening property and economic efficiency, preferably 0.001 or more, more preferably 0.01 or more, even more preferably 0.1 or more, and preferably 1.5 or less, more preferably 1.2 or less, even more preferably 1.0 or less. In the hydraulic slurry composition of the present invention, the mass ratio (B) / (A) of the content of the compound (A) to the content of the compound (B) is preferably 0.1 or more, more preferably 0.13 or more, even more preferably 0.15 or more, and is preferably 1 or less, more preferably 0.9 or less, even more preferably 0.7 or less, from the viewpoints of thickening property, bleeding property and economical efficiency.

[0061] In the hydraulic slurry composition of the present invention, the mass percentage of the water content and the hydraulic powder content (water / hydraulic powder ratio (W / P)) is, from the viewpoints of fluidity and economy, preferably 30 mass% or more, more preferably 40 mass% or more, even more preferably 50 mass% or more, and preferably 150 mass% or less, more preferably 100 mass% or less, even more preferably 80 mass% or less. Here, the water / hydraulic powder ratio (W / P) is the mass percentage (mass%) of water and hydraulic powder in the hydraulic slurry composition, and is calculated by water / hydraulic powder x 100. The water / hydraulic powder ratio is calculated based on the amount of powder that has the physical property of hardening by hydration reaction. When the hydraulic powder is cement, W / P may be expressed as W / C. 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.

[0062] When the hydraulic slurry composition of the present invention contains the above-mentioned dispersant, the content of the dispersant in the hydraulic slurry composition of the present invention is, from the viewpoints of fluidity and economy, preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, even more preferably 0.05 part by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less, relative to 100 parts by mass of water.

[0063] The hydraulic slurry composition of the present invention can be suitably used for grout materials used in grouting for ground improvement methods, columnar continuous walls, injection methods, etc., cement milk for drilling, self-leveling materials, lightweight embankments, crack repair materials, lightweight mortar, high-fluidity concrete, fiber-reinforced concrete, pile circumference fixing liquid, underwater embankments, void filling materials, porous concrete, air grout materials, concrete for ECL, PC grout, concrete fluidizers, rebound reducing agents, thickeners for extrusion molding, high-fluidity concrete, underwater non-segregating concrete, concrete for shield construction, concrete for SENS construction, etc.

[0064] <Method for producing hydraulic slurry composition> The present invention provides a method for producing a hydraulic slurry composition, which comprises mixing the rheology modifier of the present invention, a hydraulic powder, and water. In the method for producing a hydraulic slurry composition of the present invention, the above-mentioned dispersant can be further mixed. To the method for producing the hydraulic slurry composition of the present invention, the matters described in relation to the rheology modifier of the present invention and the hydraulic slurry composition of the present invention can be appropriately applied. In the method for producing the hydraulic slurry composition of the present invention, the mixed amount of the rheology modifier of the present invention, the mixed amount of the compound (A), the mixed amount of the compound (B), the mixed amount of the dispersant, the mass ratio (B) / (A) of the mixed amount of the compound (A) to the mixed amount of the compound (B), and the mass percentage of the mixed amount of the water to the mixed amount of the hydraulic powder (water / hydraulic powder ratio (W / P)) relative to 100 parts by mass of water can be appropriately applied by replacing the content of the rheology modifier of the present invention, the content of each component, and their mass ratios described in the hydraulic slurry composition of the present invention with the mixed amount of the rheology modifier of the present invention and the content of each component with the mixed amount.

[0065] In the method for producing the hydraulic slurry composition of the present invention, it is preferable to prepare a hydraulic slurry containing water and hydraulic powder in advance, add the rheology modifier of the present invention to the hydraulic slurry, and mix to produce the hydraulic slurry composition.

[0066] <Method for increasing viscosity and bleeding rate of hydraulic slurry composition> The rheology modifier of the present invention is a combination of compound (A) and compound (B), in which compound (B) is incorporated into the worm-like micelles formed by compound (A) in the hydraulic slurry composition, strengthening the worm-like micelles and improving the viscosity. In addition, although the detailed reason is not clear, at a specific mass ratio of compound (A) and compound (B), the anionic group of compound (B) is adsorbed to the cement, which allows the cement to aggregate, and the bleeding rate can be increased while increasing the viscosity. Therefore, the rheology modifier of the present invention is suitable for a method of mixing the rheology modifier of the present invention into a hydraulic slurry composition to increase the viscosity of the hydraulic slurry composition and increase the bleeding rate. That is, the present invention provides a method for increasing the viscosity of a hydraulic slurry composition and increasing the bleeding rate by mixing the rheology modifier of the present invention with a hydraulic slurry composition containing a hydraulic powder and water (hereinafter referred to as the method for increasing the bleeding rate of the present invention). The hydraulic slurry composition of the present invention is a composition containing a hydraulic powder and water and further containing the rheology modifier of the present invention. In the method of the present invention for increasing the bleeding rate, the above-mentioned dispersant can be further mixed. To the method for increasing the bleeding rate of the present invention, the matters described in relation to the rheology modifier of the present invention, the hydraulic slurry composition of the present invention and the production method thereof can be appropriately applied. In the method for increasing the bleeding rate of the present invention, the mixed amount of the rheology modifier of the present invention, the mixed amount of the compound (A), the mixed amount of the compound (B), the mixed amount of the dispersant, the mass ratio (B) / (A) of the mixed amount of the compound (A) to the mixed amount of the compound (B), and the mass percentage of the mixed amount of the water to the mixed amount of the hydraulic powder (water / hydraulic powder ratio (W / P)) can be appropriately applied by replacing the mixed amount of the rheology modifier of the present invention and the content of each component and their mass ratios described in the hydraulic slurry composition of the present invention with the mixed amount of the rheology modifier of the present invention and the content of each component. The hydraulic slurry composition produced by the method for increasing the bleeding rate of the present invention has an increased viscosity and a high bleeding rate, and is therefore suitable for applications in which it is desired to increase the viscosity of the hydraulic slurry composition to impart non-separation properties underwater, such as a root hardening liquid or a pile circumference fixing liquid used when driving a concrete pile, but bleeding must not be suppressed. EXAMPLES

[0067] The components used in the examples and comparative examples are shown below. <Compound (A)> Oleyl amide propyl dimethylamine oxide: In the general formula (1), X is R 2a -[CONH-CH2CH2CH2] n -, R 2a is an alkenyl group having 17 carbon atoms, n is 1, and R 2 is a methyl group, R 3 is a methyl group, compound (a1) Oleyldimethylamine oxide: In the general formula (1), X is R 1a -, R 1a is an alkenyl group having 18 carbon atoms, R 2 is a methyl group, R 3is a methyl group, compound (a2)

[0068] <Compound (B)> · Polyoxyethylene (2.9) dodecyl ether sulfate sodium: Sodium salt of polyoxyethylene dodecyl ether sulfate with an average number of oxyethylene groups added of 2.9. Sodium dodecyl sulfate Oleic acid · Sodium polyoxyethylene (3.2) alkyl ether phosphate: Sodium salt of polyoxyethylene alkyl ether phosphate with an average added mole number of oxyethylene groups of 3.2 and an alkyl group carbon number of 12 to 13 (mass ratio of carbon number 12 / 13=1 / 1). Potassium alkyldicarboxylate: Potassium salt of alkyldicarboxylate with alkyl group having 16-18 carbon atoms Sodium ditridecyl sulfosuccinate Lauric acid Sodium decyl sulfate Sodium tetradecyl sulfate Sodium octyl sulfate

[0069] <Compound (B') (Comparative component of compound (B))> Polyoxyethylene (2.9) dodecyl ether: Polyoxyethylene dodecyl ether with an average added mole number of oxyethylene groups of 2.9.

[0070] <Preparation of hydraulic slurry composition> Water (Wakayama City tap water) and cement (ordinary Portland cement, manufactured by Taiheiyo Cement Co., Ltd.) adjusted to a predetermined temperature in each formulation shown in Table 1 were mixed and stirred for 30 seconds using a commercially available hand mixer, and then compound (A) shown in Table 2 and compound (B) or compound (B') shown in Tables 3 and 5 were added as rheology modifiers in the amounts and mass ratios shown in Tables 3 and 5, and stirring was continued for 3 minutes after the addition of the rheology modifier to prepare a hydraulic slurry composition. When foaming was intense, 20 mass% of a silicone-based defoamer, Asahi Silicone AF-146 (manufactured by Asahi Chemical Industry Co., Ltd.), was added to compound (A). The total amount of water added to the cement initially and the amount of water in each composition was adjusted to the amount of water shown in each formulation in Table 1. The amount of compound (A) per 100 parts by mass of water in each hydraulic slurry composition and the mass ratio (B) / (A) of the amount of compound (A) to the amount of compound (B) were as shown in Tables 3 and 5. In addition, the mass percentage (water / hydraulic powder ratio (W / C)) (mass%) of the amount of water and the amount of hydraulic powder in each hydraulic slurry composition was as shown in each formulation in Table 1. In addition, for Table 3, the tests were conducted by adjusting the temperature of each hydraulic slurry to 20°C ± 2, and for Table 5, the tests were conducted by adjusting the temperature of each hydraulic slurry to 10°C ± 2.

[0071] [Table 1]

[0072] [Table 2]

[0073] [Evaluation of hydraulic slurry composition] Evaluation of J14 funnel / P funnel flow time For each hydraulic slurry composition immediately after preparation, the hydraulic slurry composition in Table 3 was tested for J14 funnel flow time according to "JSCE-F 541-1999 Test method for fluidity of filling mortar" described in the Standard Specifications for Concrete (Standards Edition) issued by the Japan Society of Civil Engineers, and the hydraulic slurry composition in Table 5 was tested for P funnel flow time according to "Test method for fluidity of injection mortar for prepacked concrete (Method using P funnel) (JSCB-F 521-1999)" described in the same. The results are shown in Tables 3 and 5. The inner diameter of the outlet of the J14 funnel is 14 mm, and the inner diameter of the outlet of the P funnel is 13 mm. It is judged that the longer the flow time, the higher the viscosity.

[0074] (2) Measurement of rotational viscosity The viscosity of each hydraulic slurry composition immediately after preparation was measured using a B-type viscometer (RION Corporation, VISCOTESTER VT-04E, rotor No. 1, rotation speed: 62.5 rpm). In this evaluation, it is preferable that the viscosity is higher than that of compound (A) alone. That is, in Table 3, the viscosity is preferably 2200 mPa s or more, and in Table 5, the viscosity is preferably 950 mPa s or more. The results are shown in Tables 3 and 5.

[0075] Breeding Evaluation For some of the hydraulic slurry compositions in Table 3 and some of the hydraulic slurry compositions in Table 5, the bleeding rate 1 hour and / or 24 hours after preparation was calculated in accordance with 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 4 and 6.

[0076] 28-day strength rating For some of the hydraulic slurry compositions in Table 3, the strength 28 days after preparation (28-day strength) was measured according to the strength measurement method for foot consolidation fluid described in "Compressive strength test method for foot consolidation fluid and pile circumference fixing fluid used in embedding method" published by the Concrete Pile Construction Technology Association. The results are shown in Table 4.

[0077] [Table 3]

[0078] [Table 4]

[0079] [Table 5]

[0080] [Table 6]

[0081] In Tables 3 to 6, "amount of compound (A) (parts by mass)" indicates the amount of compound (A) (parts by mass) per 100 parts by mass of water in the hydraulic slurry composition. Moreover, "(B) / (A) (mass ratio)" indicates the mass ratio (B) / (A) of the amount of compound (A) to the amount of compound (B) in the hydraulic slurry composition. In Table 5, in Example 2-8, the viscosity of the hydraulic slurry composition was high in the evaluation of the P funnel flow time, and the P funnel was clogged, so the flow time could not be measured. In addition, in Examples 2-3 and 2-8, the viscosity of the hydraulic slurry composition was high, and the viscosity measuring tool slipped, so the rotational viscosity could not be measured.

Claims

1. A rheology modifier comprising a compound represented by the following general formula (1) [hereinafter referred to as compound (A)] and an anionic surfactant having an aliphatic hydrocarbon group [hereinafter referred to as compound (B)]: 【Chemistry 1】 [Wherein, X is R １ａ Or R ２ａ -[CONH-CH ２ CH ２ CH ２ ] ｎ R is a group represented by -. １ａ R is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 14 to 22 carbon atoms. ２ａ is 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 each independently represents an alkyl group having 1 to 4 carbon atoms or -(C ２ H ４ O) 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.

2. 2. The rheology modifier according to claim 1, wherein the aliphatic hydrocarbon group of compound (B) has 8 or more and 20 or less carbon atoms.

3. 3. The rheology modifier according to claim 1 or 2, wherein the anionic group contained in the compound (B) is at least one type selected from the group consisting of a sulfate group, a phosphate group and a carboxylate group.

4. The rheology modifier according to any one of claims 1 to 3, wherein compound (B) is a compound which has no oxyalkylene groups or has an average added mole number of oxyalkylene groups of 4.0 or less.

5. The compound (A) is R １ａ is an alkenyl group having 18 carbon atoms, and １ｂ The rheology modifier according to any one of claims 1 to 4, wherein the compound is at least one selected from the group consisting of compounds in which

6. The rheology modifier according to any one of claims 1 to 5, wherein a mass ratio (B) / (A) of the content of the compound (A) to the content of the compound (B) is 0.001 or more and 1.50 or less.

7. The rheology modifier according to any one of claims 1 to 6, which is for use in a hydraulic slurry composition.

8. A hydraulic slurry composition comprising the rheology modifier according to any one of claims 1 to 6, a hydraulic powder, and water.

9. The hydraulic slurry composition according to claim 8, wherein the content of the compound (A) is 0.01 parts by mass or more and 4 parts by mass or less based on 100 parts by mass of water.

10. A method for increasing the viscosity of a hydraulic slurry composition and increasing the bleeding rate thereof, comprising mixing the rheology modifier according to any one of claims 1 to 6 with a hydraulic slurry composition containing a hydraulic powder and water.

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