Modifier for powder thickeners

Abstract

To provide a modifier for powder thickener which, when a powder thickener is made into a slurry, makes fluidity of the slurry lowered and, when obtaining a prescribed product using the slurry, makes the original thickening effect exhibited.SOLUTION: A modifier for powder thickener comprises (A) a compound which contains carbon atom, hydrogen atom, and hetero atom other than carbon atom and hydrogen atom, does not have a ring structure comprising carbon atom and hydrogen atom, and has an HLB value according to the Davis method of 8 or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a modifier for powder thickeners. [Background technology]

[0002] Thickeners are chemical compounds widely used in food, cosmetics and other industrial products. They increase the viscosity of a system by retaining or binding solvents, dispersion media or dispersoids, thereby contributing to achieving the appropriate texture required for each application and improving the stability of the system.

[0003] Based on the idea of ​​the thickener retaining and binding the solvent, dispersion medium, and dispersoid, the molecular design is considered to have a structural unit that exhibits an interactive force with the solvent, dispersion medium, and dispersoid. Representative thickeners include cellulose ether thickeners, acrylic thickeners, polyvinyl alcohol thickeners, polyoxyethylene thickeners, clay thickeners, etc.

[0004] In addition, since such thickeners exhibit their thickening properties by dissolving or dispersing in a solvent or dispersant, many of them are often distributed as powdered products from the standpoint of handling and transportation, with as little solvent or dispersant as possible removed.

[0005] Patent Document 1 discloses a jelly containing 10 to 70% by weight of a metal ion jelly of pectin or alginic acid. Patent Document 2 discloses a carboxymethylcellulose slurry containing carboxymethylcellulose, polyethylene glycol having an average molecular weight of less than about 1000 g / l, and an inactive powder or dispersion liquid in a predetermined ratio. Patent Document 3 discloses nonionic cellulose ethers that are substituted with nonionic substituents selected from the group consisting of methyl, hydroxyethyl, and hydroxypropyl to an extent sufficient to render the nonionic cellulose ether water soluble, and that are further substituted with long chain alkyl groups having 10 to 24 carbon atoms in an amount between about 0.2% by weight and an amount that renders the cellulose ether less than 1% by weight water soluble. Patent Document 4 discloses a composition that contains a specific adhesive composition and a specific non-fibrous compound, and that can be mixed with water to produce a sagging-resistant adhesive composition. Patent Document 5 describes a particle size of about 0.01 to 1000 μ and a particle size of about 10,000 to 2×10 6 A slurry composition is disclosed that comprises a particulate water-soluble cellulose ether having a molecular weight of 100 g / gram molecule, an oxygenated organic carrier that is at least substantially a non-solvent for the polymer, and a particulate thickener, each in predetermined proportions, and is substantially salt-free, substantially water-free, and stable for at least one week. Patent Document 6 discloses a viscous detergent composition containing an anionic surfactant, a nonionic cellulose derivative, and ethanol and / or a polyhydric alcohol having an IOB value (inorganic value / organic value) of 3.4 or less, each in a specified ratio. Patent Document 7 discloses an ophthalmic composition for contact lenses, which contains a polymer compound and amino acids. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 61-52252 [Patent Document 2] Special Publication No. 7-505426 [Patent Document 3] Japanese Patent Application Publication No. 55-110103 [Patent Document 4] Japanese Patent Application Laid-Open No. 53-104641 [Patent Document 5] Special Publication No. 2001-503101 [Patent Document 6] Special publication 2014 / 129257 publication [Patent Document 7] JP 2001-187733 A Summary of the Invention [Problem to be solved by the invention]

[0007] When used, powder thickeners are dissolved or dispersed in a solvent or dispersion medium. In this case, there is a problem that the powder thickener forms flocks or swells and thickens rapidly, impairing the fluidity of the powder thickener slurry. In addition, in a mixture prepared from a powder thickener slurry with poor fluidity, it is difficult to obtain a homogeneous mixture due to poor mixing and dispersion, or it often takes a long time to prepare. In order to improve the fluidity of the powder thickener slurry, it is possible to increase the amount of the solvent or dispersion medium, but this results in a dilute slurry with a small proportion of the active ingredient, and the thickening effect is significantly reduced. In order to maintain the thickening effect, it is necessary to increase the amount of the dilute slurry used, which is not preferable in practical use from the viewpoint of workability, etc. In particular, when preparing a slurry containing water with a powder thickener that thickens water, the fluidity of the slurry is significantly impaired, making it difficult to provide a product with a high concentration of the powder thickener.

[0008] The present invention provides a modifier for powder thickeners, which improves the fluidity of a slurry of a powder thickener when the powder thickener is made into a slurry, and at the same time, quickly exerts the original thickening effect when the slurry is used to obtain a specified product. [Means for solving the problem]

[0009] The present invention relates to a modifier for powder thickeners, which contains (A) a compound (hereinafter referred to as component (A)) which contains carbon atoms, hydrogen atoms, and heteroatoms other than carbon and hydrogen atoms, has no ring structure consisting of carbon atoms and hydrogen atoms, and has an HLB value of 8 or more as measured by the Davis method.

[0010] The present invention also relates to a thickener composition containing the powder thickener modifier of the present invention, a powder thickener, and water.

[0011] The present invention also relates to a method for producing a thickener composition, which comprises mixing component (A), a powdery thickener, and water.

[0012] The present invention also relates to a method for producing a hydraulic composition, which comprises mixing the thickener composition of the present invention, a hydraulic powder, and water.

[0013] The present invention also relates to a method for producing a hardened body, which comprises producing a hydraulic composition by the above-mentioned production method of the present invention, filling the hydraulic composition into a form and hardening it.

[0014] The present invention also relates to a thickening method, which comprises preparing a thickening composition from a powder thickener, water, and component (A), and adding the thickening composition to an object containing water in an amount greater than the amount of water in the thickening composition, thereby thickening the object. Effect of the Invention

[0015] According to the present invention, there is provided a modifier for powder thickeners, which improves the fluidity of a slurry of a powder thickener when the powder thickener is made into a slurry, and at the same time, when the slurry is used to obtain a predetermined product, the original thickening effect is quickly exerted. By using the modifier for powder thickeners of the present invention, it is possible to prepare a thickener slurry that has excellent fluidity, contains a high concentration of powder thickener, and quickly exerts a thickening effect. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The inventors have discovered that by blending a compound having a heteroatom covalently bonded to two or more acyclic hydrocarbons in the same molecule and having an HLB value of 8 or more as calculated by the Davis method with a slurry containing a general powder thickener and water, the formation of stepchildren (flocs) and rapid swelling and thickening are suppressed, resulting in a powder thickener slurry with excellent fluidity, and that this powder thickener slurry quickly exhibits an excellent thickening effect when used on the target object. The reason why such an effect is manifested is not necessarily clear, but is presumed to be as follows. In order to efficiently thicken a system, most aqueous thickeners are composed of a hydrophilic unit that interacts with water molecules and a hydrophobic unit that interacts with the thickener (molecule) itself or with dispersoids. The compound of the present invention has a heteroatom having a lone pair of electrons that can form a chelate structure, a flexible structure, and appropriate hydrophilicity and hydrophobicity (hydrophilic-hydrophobic balance; HLB), and therefore forms a complex with the hydrophilic unit of the aqueous thickener through hydrogen bond-like interaction force, thereby mitigating the interaction with water molecules, and thus it is believed that the formation of flocs, rapid swelling, and thickening are suppressed. In addition, the mechanism by which the powder thickener slurry having excellent fluidity prepared from the compound of the present invention can rapidly exhibit thickening properties in practical systems such as in water or in a hydraulic composition slurry is not entirely clear, but is presumed to be as follows. When this compound, which has formed a complex with the hydrophilic units of an aqueous thickener through hydrogen bonding-type interaction, is added to an aqueous system as a powder thickener slurry, the ratio of the compound to water molecules decreases significantly, and the interaction between the hydrophilic units of the aqueous thickener and the compound becomes relatively weak due to diffusion, so that the powder thickener that was modified by the compound once again begins to interact strongly with water molecules, allowing it to quickly exert its thickening effect in the system.

[0017] In recent years, the SDGs have been proposed to realize a sustainable society. This invention can reduce the labor required for the mixing process of powder thickeners and improve the self-filling properties of the slurry, thereby saving labor. It is believed that this technology can contribute to SDGs No. 8, 9, 13, and 15, for example.

[0018] [Modifier for powder thickeners] The modifier for powder thickeners of the present invention contains component (A). Component (A) may contain one or more types. Examples of the heteroatom of the component (A) include an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom, etc. The component (A) is preferably a compound containing an atom selected from an oxygen atom, a nitrogen atom, and a phosphorus atom as a heteroatom.

[0019] The component (A) includes a compound selected from an alcohol, an ether, an organic acid, and an amine. Examples of component (A) include compounds selected from polyhydric alcohols having only hydroxyl groups as functional groups, polyhydric alcohol ethers, polycarboxylic acids having only carboxy groups as functional groups and salts thereof, hydroxycarboxylic acids and salts thereof, aminocarboxylic acids and salts thereof, aminophosphonic acids and salts thereof, aminophosphoric acids and salts thereof, alkanolamines and salts thereof, polyamines and salts thereof, polyimines, and polymeric carboxylic acids and salts thereof. Examples of component (A) include compounds selected from polyhydric alcohols having only hydroxyl groups as functional groups, polyvalent carboxylic acids and their salts having only carboxy groups as functional groups, hydroxycarboxylic acids and their salts, aminocarboxylic acids and their salts, alkanolamines and their salts, polyamines and their salts, and polymeric carboxylic acids and their salts.

[0020] When component (A) is an acidic compound, examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, etc. Examples of the alkali metal salts include sodium salts and potassium salts. When the component (A) is a basic compound, the salt may be an organic acid salt or an inorganic acid salt. The organic acid may or may not fall under the category of the component (A). In the present invention, a compound (salt, ester, ether, etc.) consisting of multiple compounds belonging to component (A), such as a salt of citric acid and an alkanolamine, is treated as one component (A) if the HLB of the entire compound is 8 or higher.

[0021] Examples of polyhydric alcohols having only hydroxyl groups as functional groups include glycol and its derivatives, vinyl alcohol and its derivatives, and sugar alcohols and their derivatives, such as glycerin, erythritol, mannitol, sorbitol, and xylitol.

[0022] Examples of polyhydric alcohol ethers include glycol ethers, glyceryl ethers, vinyl alcohol ethers, sugar alcohol ethers, and glycidyl ethers.

[0023] Examples of polyvalent carboxylic acids and salts thereof having only carboxy groups as functional groups include succinic acid and salts thereof, fumaric acid and salts thereof, maleic acid and salts thereof, and adipic acid and salts thereof.

[0024] Examples of hydroxycarboxylic acids and their salts include glycolic acid and its salts, glyceric acid and its salts, lactic acid and its salts, gluconic acid and its salts, tartaric acid and its salts, malic acid and its salts, ascorbic acid and its salts, and citric acid and its salts.

[0025] Examples of aminocarboxylic acids and salts thereof include amino acids and salts thereof, such as α-amino acids and salts thereof, β-amino acids and salts thereof, γ-amino acids and salts thereof, 6-aminohexanoic acid and salts thereof, peptides and salts thereof, and the like. A preferred embodiment of the present invention is a powder thickener modifier containing, as component (A), one or more compounds selected from aminocarboxylic acids and their salts, and one or more compounds selected from amino acids and their salts. The amino acids may have a molecular weight of 75 or more, preferably 85 or more, and 100,000 or less, preferably 1,000 or less.

[0026] The mechanism by which a powder thickener modifier containing one or more compounds selected from aminocarboxylic acids and their salts, and one or more compounds selected from amino acids and their salts, is a preferred embodiment of the present invention is not entirely clear, but it is thought that this is because the modifier is an amphoteric molecule having functional groups in the same molecule that become anionic and cationic upon ionization, and therefore can form hydrogen bonds efficiently regardless of the environment in the vicinity of the powder thickener.

[0027] The aminophosphonic acids and salts thereof include aminoalkylphosphonic acids and salts thereof.

[0028] Examples of aminophosphoric acids and their salts include O-phosphorylalkanolamines and their salts.

[0029] Examples of alkanolamines and their salts include methanolamine and its salts, ethanolamine and its salts, propanolamine and its salts, diethanolamine and its salts, triethanolamine and its salts, N-methylethanolamine and its salts, N,N-dimethyl-2-aminoethanol and its salts, etc. The alkanolamines preferably have only hydroxyl groups or only hydroxyl groups and amino groups as functional groups.

[0030] Examples of polyamines and salts thereof include linear or branched polyethyleneimine polymers or copolymers and salts thereof, alkylamine-epichlorohydrin copolymers and salts thereof, allylamine polymers or copolymers and salts thereof, diallylamine polymers or copolymers and salts thereof, alkylallylamine polymers or copolymers and salts thereof, alkyldiallylamine polymers or copolymers and salts thereof, allylamine amide sulfate polymers or copolymers and salts thereof, diallylamine amide sulfate polymers or copolymers and salts thereof, alkyldiallylamine amide sulfate polymers or copolymers and salts thereof, diallyldialkylammonium chloride polymers or copolymers, and diallyldialkylammonium ethylsulfate polymers or copolymers.

[0031] The weight average molecular weight of the polyamine and its salt is 100 or more, preferably 500 or more, more preferably 1,000 or more, from the viewpoint of dispersibility of the powder thickener particles, and is 100,000 or less, preferably 50,000 or less, more preferably 10,000 or less, from the viewpoint of slurry viscosity. This weight average molecular weight is measured by gel permeation chromatography (GPC) under the following conditions. *GPC conditions Column: α-M (Tosoh) 2 columns connected Eluent: 0.15 mol / L sodium sulfate, 1% acetic acid aqueous solution Flow rate: 1.0mL / min Temperature: 40℃ Detector: RI Molecular weight standard: Pullulan

[0032] The polyimine to be used can be selected from those available to those skilled in the art and has an HLB value of 8 or more.

[0033] Examples of polymeric carboxylic acids and salts thereof include (1) polyacrylic acid and salts thereof, (2) polymethacrylic acid and salts thereof, (3) acrylic acid-maleic anhydride copolymers and salts thereof, (4) copolymers of a monomer selected from acrylic acid, methacrylic acid, and maleic anhydride with a monomer having a structure in which ethylene oxide is added to a compound selected from acrylic acid, methacrylic acid, and maleic acid, and salts thereof, and (5) copolymers of a monomer selected from acrylic acid, methacrylic acid, and maleic anhydride with a monomer having a structure in which ethylene oxide is added to a compound selected from vinyl alcohol, allyl alcohol, methallyl alcohol, and isoprenyl alcohol, and salts thereof.

[0034] The weight average molecular weight of the polymeric carboxylic acid and its salt is preferably 1,000 or more, more preferably 3,000 or more, even more preferably 5,000 or more, and even more preferably 10,000 or more from the viewpoint of dispersibility of the powder thickener particles, and is preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 50,000 or less from the viewpoint of the slurry viscosity. This weight average molecular weight is measured by gel permeation chromatography (GPC) under the following conditions. *GPC conditions Equipment: GPC (HLC-8320GPC) manufactured by Tosoh Corporation Column: G4000PWXL+G2500PWXL (Tosoh Corporation) Eluent: 0.2M phosphate buffer / CH3CN=9 / 1 Flow rate: 1.0mL / min Column temperature: 40℃ Detection: RI Sample size: 0.2mg / mL Standard substance: Polyethylene glycol equivalent (monodisperse polyethylene glycol: molecular weight 24,000, 46,000, 87,500, 145,000, 250,000)

[0035] From the viewpoint of affinity with the dispersion medium, component (A) has an HLB value of at least 8 as determined by the Davis method. The HLB value of component (A) is at least 8, preferably at least 9, more preferably at least 10, and from the viewpoint of slurry viscosity, it is preferably at most 3,000, more preferably at most 1,500, and even more preferably at most 500. Hereinafter, when referring to the HLB value, it means the HLB value as determined by the Davis method, unless otherwise specified.

[0036] When component (A) is a polyhydric alcohol having only hydroxyl groups as functional groups, the HLB is 8 or more, preferably 9 or more, more preferably 10 or more, and preferably 1,000 or less, more preferably 500 or less, and even more preferably 100 or less.

[0037] When component (A) is a polyhydric alcohol ether, the HLB is preferably 8 or more, preferably 9 or more, more preferably 10 or more, and preferably 1,000 or less, more preferably 500 or less, and even more preferably 100 or less.

[0038] When component (A) is a polyvalent carboxylic acid or a salt thereof having only carboxy groups as functional groups, the HLB is 8 or more, preferably 9 or more, more preferably 10 or more, and preferably 100 or less, more preferably 75 or less, and even more preferably 50 or less.

[0039] When component (A) is a hydroxycarboxylic acid or a salt thereof, the HLB is 8 or more, preferably 9 or more, more preferably 10 or more, and preferably 100 or less, more preferably 70 or less, and even more preferably 40 or less.

[0040] When component (A) is an aminocarboxylic acid or a salt thereof, the HLB is 8 or more, preferably 9 or more, more preferably 10 or more, and preferably 1000 or less, more preferably 500 or less, and even more preferably 50 or less.

[0041] When component (A) is an aminophosphonic acid or a salt thereof, the HLB is 8 or more, preferably 16 or more, more preferably 24 or more, and preferably 100 or less, more preferably 80 or less, and even more preferably 60 or less.

[0042] When component (A) is an amino phosphoric acid or a salt thereof, the HLB is 8 or more, preferably 12 or more, more preferably 16 or more, and preferably 100 or less, more preferably 80 or less, and even more preferably 40 or less.

[0043] When component (A) is an alkanolamine or a salt thereof, the HLB is 8 or more, preferably 9.5 or more, more preferably 9 or more, and preferably 60 or less, more preferably 40 or less, and even more preferably 20 or less.

[0044] When component (A) is a polyamine or a salt thereof, the HLB is preferably 10 or more, more preferably 50 or more, even more preferably 100 or more, and preferably 3,000 or less, more preferably 2,000 or less, even more preferably 1,000 or less.

[0045] When component (A) is a polymeric carboxylic acid or a salt thereof, the HLB is preferably 10 or more, more preferably 50 or more, even more preferably 100 or more, and preferably 3,000 or less, more preferably 2,000 or less, even more preferably 1,000 or less.

[0046] The modifier for powder thickeners of the present invention contains component (A) in an amount of preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, and preferably 90% by mass or less, more preferably 60% by mass or less, even more preferably 30% by mass or less. The modifier for powder thickeners of the present invention may consist of component (A).

[0047] The powder thickener modifier of the present invention can be used for various powder thickeners. For example, the powder thickener may be selected from a cellulose-based polymer compound and an ether-based polymer compound.

[0048] Examples of the cellulose-based polymer compound include hydrophobically modified cellulose, in particular alkyl- or hydroxyalkyl-modified cellulose, such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, and hydroxypropyl methyl cellulose.

[0049] Examples of the ether-based polymer compound include polymers or copolymers of alkylene glycols, such as ethylene glycol. When the compound is an ethylene glycol polymer, from the viewpoint of hydrophilicity / hydrophobicity, the weight average molecular weight is preferably 100,000 or more and 10,000,000 or less.

[0050] Other powder thickeners include clay minerals such as bentonite and montmorillonite that have been hydrophobically modified with a hydrophobically modified cellulosic polymer compound.

[0051] [Thickener composition] The thickener composition of the present invention contains the powder thickener modifier of the present invention, a powder thickener, and water. The thickener composition of the present invention may be a thickener composition containing component (A), a powder thickener, and water. The thickener composition of the present invention can be appropriately applied to the matters described in the modifier for powder thickeners of the present invention. Specific examples and preferred embodiments of the component (A) and the powder thickener are also the same as those of the modifier for powder thickeners of the present invention. The thickener composition of the present invention may be a slurry, in which at least a portion of the powdered thickener is dispersed in a solid state.

[0052] From the viewpoints of workability and viscosity in a use system, the thickener composition of the present invention has a viscosity at 20° C. of preferably 15 mPa·s or more, more preferably 50 mPa·s or more, even more preferably 100 mPa·s or more, and preferably 1,000 mPa·s or less, more preferably 750 mPa·s or less, even more preferably 500 mPa·s or less. This viscosity is measured with a rheometer Physica MCR301 manufactured by Anton Paar using a plate jig with a diameter of 25 mm, with a gap of 1 mm, a rotation speed of 600 rpm, and at 20° C.

[0053] The powdered thickener of the present invention is preferably a thickener that thickens water, and more preferably a thickener that thickens alkaline water. The powder thickener of the present invention has a viscosity of 100 mPa·s or more, further 500 mPa·s or more, further 1,000 mPa·s or more, and 100,000 mPa·s or less, further 75,000 mPa·s or less, and further 50,000 mPa·s or less, measured at 20° C. in an aqueous solution of 2% by mass and pH 12. This viscosity is measured in the same manner as the viscosity of the thickener composition described above, for an aqueous solution in which the powder thickener is dissolved at a concentration of 2% by mass in water adjusted to pH 12 with a 1 mol / L aqueous sodium hydroxide solution (FUJIFILM Wako Pure Chemical Corporation).

[0054] From the viewpoints of workability and viscosity in the application system, the thickener composition of the present invention contains a powder thickener in an amount of, for example, 0.1% by mass or more, further 1% by mass or more, further 5% by mass or more, and 50% by mass or less, further 35% by mass or less, and further 20% by mass or less.

[0055] From the viewpoints of slurry fluidity and workability, the thickener composition of the present invention has a mass ratio of component (A) / powder thickener of preferably 0.001 or more, more preferably 0.01 or more, even more preferably 0.1 or more, and preferably 20 or less, more preferably 10 or less, even more preferably 5 or less.

[0056] The thickener composition of the present invention contains water. Water is the remainder of the composition and is used in an amount that makes the composition of the thickener composition 100% by mass. The thickener composition of the present invention contains water, for example, 5% by mass or more, further 30% by mass or more, further 60% by mass or more, and 99% by mass or less, further 95% by mass or less, further 90% by mass or less.

[0057] The thickener composition of the present invention may contain optional components within the range that does not impair the effects of the present invention. Examples of optional components include cement dispersants, water-soluble polymer compounds, air entraining agents, cement wetting agents, expansive agents, waterproofing agents, retarders, quick-setting agents, foaming agents, foaming agents, waterproofing agents, fluidizing agents, liquid thickeners, flocculants, drying shrinkage reducing agents, strength enhancers, hardening accelerators, preservatives, defoamers, and rust inhibitors.

[0058] The thickener composition of the present invention can be used to thicken various objects. For example, the thickener composition of the present invention can be used in hydraulic compositions, water purification compositions, coating compositions, electronic material compositions, polishing compositions, ejection compositions, food compositions, beverage compositions, feed compositions, pharmaceutical compositions, and sanitary compositions.

[0059] The thickener composition of the present invention is a thickener composition containing component (A), a powder thickener, and water, The viscosity of the powdered thickener, measured in an aqueous solution of 2% by mass and pH 12 at 20°C, is 100 mPa s or more. The viscosity measured at 20°C is 15 mPa·s or more and 1,000 mPa·s or less. A thickener composition is included. Further, the thickener composition of the present invention is a thickener composition containing the component (A), a powder thickener, and water, Contains 5% by mass or more and 50% by mass or less of a powder thickener, The viscosity of the powdered thickener, measured in an aqueous solution of 2% by mass and pH 12 at 20°C, is 100 mPa s or more. The viscosity measured at 20°C is 15 mPa·s or more and 1,000 mPa·s or less. A thickener composition is included.

[0060] [Method of manufacturing thickener composition] The method for producing the thickener composition of the present invention is a method for producing a thickener composition by mixing component (A), a powdery thickener, and water. The method for producing the thickener composition of the present invention can be appropriately applied to the matters described in the description of the powder thickener modifier and the thickener composition of the present invention. Specific examples and preferred embodiments of the component (A) and the powder thickener are also the same as those of the powder thickener modifier of the present invention.

[0061] In the method for producing the thickener composition of the present invention, the modifier for powder thickeners of the present invention, a powder thickener, and water can be mixed together.

[0062] In the manufacturing method of the thickener composition of the present invention, from the viewpoint of uniformity of the slurry, the powder thickener can be mixed in a ratio of, for example, 0.1 mass% or more, further 1 mass% or more, further 5 mass% or more, and 50 mass% or less, further 35 mass% or less, and further 20 mass% or less of the total amount of the components to be mixed.

[0063] In the method for producing the thickener composition of the present invention, from the viewpoint of the fluidity and uniformity of the slurry, the (A) component and the powdered thickener are mixed so that the mass ratio of the (A) component / powdered thickener is, for example, 0.001 or more, further 0.01 or more, further 0.1 or more, and 20 or less, further 10 or less, further 5 or less.

[0064] The order in which component (A), the powdered thickener, and the water are mixed does not matter, but it is preferable to first mix component (A) and the powdered thickener, and then add water and further mix.

[0065] [Method of manufacturing hydraulic composition] The method for producing a hydraulic composition of the present invention comprises mixing the thickener composition of the present invention, a hydraulic powder, and water. The items described in the powder thickener modifier, thickener composition, and method for producing a thickener composition of the present invention can be appropriately applied to the method for producing the hydraulic composition of the present invention. Specific examples and preferred embodiments of the component (A) and the powder thickener are also the same as those of the powder thickener modifier of the present invention.

[0066] The hydraulic powder is a powder that hardens when mixed with water, and examples thereof include cement. Examples of cement include normal 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 high-early-strength Portland cement, normal Portland cement, sulfate-resistant Portland cement, and white Portland cement is preferred, and a cement selected from high-early-strength Portland cement and normal Portland cement is more preferred.

[0067] The hydraulic powder may contain blast furnace slag, fly ash, clinker ash, bottom ash, super ash, silica fume, anhydrous gypsum, etc., and may also 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 and blast furnace slag, fly ash, clinker ash, bottom ash, super ash, silica fume, etc., may also be used. In addition, clay such as bentonite may also be contained.

[0068] In the method for producing a hydraulic composition of the present invention, water and hydraulic powder are mixed so that the water / hydraulic powder ratio is preferably 20% by mass or more, more preferably 25% by mass or more, and preferably 200% by mass or less, more preferably 50% by mass or less. Here, the water / hydraulic powder ratio (W / P) is the mass percentage (mass%) of water and hydraulic powder, and is calculated by water / hydraulic powder x 100. The water / hydraulic powder ratio is calculated based on the amount of powder having a physical property that hardens by hydration reaction. When the hydraulic powder is cement, W / P may be written as W / C. In addition to powder having a physical property that hardens by hydration reaction such as cement, when the hydraulic powder includes powder selected from powder having pozzolanic action, powder having latent hydraulicity, and stone powder (calcium carbonate powder), in the present invention, the amount of these powders is also included in the amount of hydraulic powder. In addition, when the powder having the physical property of hardening by hydration reaction 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 mass % etc. that are related to the mass of the hydraulic powder.

[0069] In the method for producing a hydraulic composition of the present invention, from the viewpoint of uniformity of the hydraulic composition, the thickener composition and water are mixed so that the mass ratio of the thickener composition / water is preferably 0.01 or more, more preferably 0.1 or more, even more preferably 1 or more, and preferably 20 or less, more preferably 15 or less, even more preferably 10 or less.

[0070] In the method for producing a hydraulic composition of the present invention, from the viewpoint of uniformity of the hydraulic composition, the thickener composition and water are mixed so that the mass ratio of component (A) / water in the thickener composition is preferably 0.0001 or more, more preferably 0.001 or more, even more preferably 0.01 or more, and preferably 9 or less, more preferably 6 or less, even more preferably 3 or less.

[0071] In the method for producing a hydraulic composition of the present invention, optional components can be mixed within a range that does not impair the effects of the present invention. Examples of optional components include cement dispersants, water-soluble polymer compounds, air entraining agents, cement wetting agents, expansive agents, waterproofing agents, retarders, quick-setting agents, foaming agents, foaming agents, waterproofing agents, fluidizing agents, liquid thickeners, flocculants, drying shrinkage reducing agents, strength enhancers, hardening accelerators, preservatives, defoamers, and rust inhibitors.

[0072] In the method for producing the hydraulic composition of the present invention, the thickener composition of the present invention, the hydraulic powder, and water can be mixed in any order, but it is preferable to premix the (A) component and the powdery thickener, add water and further mix the mixture, and then add it to the hydraulic powder, or to premix the (A) component, the powdery thickener, and the hydraulic powder, add water and further mix the mixture.

[0073] Examples of the hydraulic composition include mortar and concrete. The hydraulic composition is useful in any field, such as box culvert (wall), bridge substructure, tunnel lining, marine structure, PC structure, ground improvement, UHPC, self-leveling material, grout, and cold weather use.

[0074] [Method of manufacturing the hardened body] The method for producing a hardened body of the present invention comprises producing a hydraulic composition by the production method of the present invention, filling the hydraulic composition into a form and hardening it. The method for producing the hardened body of the present invention can be appropriately applied to the matters described in the modifier for powder thickener, the thickener composition, the method for producing the thickener composition, and the method for producing the hydraulic composition of the present invention. Specific examples and preferred aspects of the component (A) and the powder thickener are also the same as those of the modifier for powder thickener of the present invention.

[0075] In the present invention, the hydraulic composition produced by the production method of the present invention is filled into a form in an uncured state, and cured as necessary to harden. Examples of the form include a form for a structure, a form for a concrete product, and the like. Examples of a method for filling the form include a method of directly pouring from a mixer, a method of pumping the hydraulic composition into the form, and the like. When filling the form and after filling, vibration may be added from the viewpoint of improving the filling property. In addition, in the case of a self-leveling material application, the hydraulic composition prepared by adding water in a pail can or the like can be directly spread on the floor, and in this case, a dragonfly or the like may be used from the viewpoint of improving the filling property. In addition, in the case of a grout material application, the hydraulic composition prepared by any of the above methods can be directly filled into the target location.

[0076] In the method for producing a hardened body of the present invention, additional energy such as steam heating may be added during curing of the hydraulic composition to promote curing. In the present invention, the curing temperature of the hydraulic composition filled in the formwork is preferably 0° C. or higher, more preferably 5° C. or higher, and preferably less than 50° C., more preferably 40° C. or lower, and even more preferably 30° C. or lower. Curing can be performed in air at room temperature.

[0077] Even when heat curing with steam or the like is performed, the heat curing time is preferably short from the viewpoint of reducing energy. The heat curing time may be 0 hours. In other words, heat curing does not have to be performed.

[0078] The hardened hydraulic composition is removed from the form to obtain a hardened product of the hydraulic composition. The hardened product obtained can be used for the applications described above for the hydraulic composition.

[0079] In the present invention, the time from contacting the hydraulic powder with water in the preparation of the hydraulic composition to demolding can be, for example, from 4 hours to 14 days from the viewpoint of obtaining the strength required for demolding and improving the production cycle.

[0080] The hardened product may be a building material, for example, an exterior wall material, a floor material, etc. One example of the present invention is a method for producing an exterior wall material or a floor material, in which the thickener composition of the present invention, a hydraulic powder, and water are mixed to produce a hydraulic composition, and the hydraulic composition is filled into a formwork and compression molded.

[0081] [Thickening method] The present invention has discovered that component (A) is involved in behavior such as the fluidity of a slurry when a powder thickener is used as a slurry and the thickening effect on an object. That is, the present invention provides a thickening method in which a thickener composition is prepared from a powder thickener, water, and component (A), and the thickener composition is added to an object containing water in an amount greater than the amount of water in the thickener composition to thicken the object. The thickening method of the present invention can be appropriately applied to the matters described in the modifier for powder thickener, the thickener composition, the method for producing the thickener composition, the method for producing the hydraulic composition, and the method for producing the hardened body of the present invention. Specific examples and preferred aspects of the (A) component and the powder thickener are also the same as those of the modifier for powder thickener of the present invention.

[0082] In the thickening method of the present invention, the powder thickener is used in an amount of, for example, 0.1% by mass or more, further 1% by mass or more, further 5% by mass or more, and 50% by mass or less, further 35% by mass or less, and further 20% by mass or less, of the total amount of components used to prepare the thickener composition.

[0083] In the thickening method of the present invention, the (A) component and the powdered thickener are used in such a manner that the mass ratio of the (A) component / powdered thickener is preferably 0.001 or more, more preferably 0.01 or more, even more preferably 0.1 or more, and is preferably 20 or less, more preferably 10 or less, even more preferably 5 or less.

[0084] In the thickening method of the present invention, the thickener composition is added so that the mass ratio to water in the target object, thickener composition / water, is preferably 0.01 or more, more preferably 0.1 or more, even more preferably 1 or more, and preferably 20 or less, more preferably 15 or less, even more preferably 10 or less.

[0085] In the thickening method of the present invention, the thickener composition is added so that the mass ratio of the (A) component in the thickener composition to the water in the target object, that is, component (A) / water in the thickener composition, is preferably 0.0001 or more, more preferably 0.001 or more, even more preferably 0.01 or more, and preferably 9 or less, more preferably 6 or less, even more preferably 3 or less.

[0086] The target of the thickening method of the present invention is various compositions containing water, such as hydraulic compositions, water purification compositions, coating compositions, electronic material compositions, polishing compositions, ejection compositions, food compositions, beverage compositions, feed compositions, pharmaceutical compositions, and sanitary compositions. EXAMPLES

[0087] <Ingredients used> The components used in the examples and comparative examples are shown below. [Component (A)] (A-1) Polyethylene glycol, molecular weight 200, HLB value: 11.2 (NOF Corporation) (A-2) Polyoxyethylene monomethyl ether, molecular weight 400, HLB value: 10.1 (manufactured by NOF Corporation) (A-3) Polyoxyethylene (10) monomethyl ether HLB value: 10.8 (manufactured by Kao Corporation, the number in parentheses is the average number of moles of ethylene oxide added (same below)) (A-4) Methoxypolyoxyethylene (10) methacrylate HLB value: 12.2 (Kao Corporation) (A-5) Polyoxyethylene (20) monomethyl ether HLB value: 15.0 (Kao Corporation) (A-6) Polyoxyethylene dimethyl ether, molecular weight 400, HLB value: 8.7 (manufactured by NOF Corporation) (A-7) Polyglycerin #310 HLB value: 23.2 (manufactured by Sakamoto Pharmaceutical Co., Ltd.) (A-8) Polyglycerin #750 HLB value: 40.9 (manufactured by Sakamoto Pharmaceutical Co., Ltd.) (A-9) Lactic acid HLB value: 10.5 (Corbion PURAC) (A-10) Sodium lactate solution (approximately 50%) HLB value: 27.2 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A-11) Sodium glycolate HLB value: 27.5 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A-12) DL-Glyceric acid (20% aqueous solution, approx. 2 mol / L) HLB value: 12.0 (Tokyo Chemical Industry Co., Ltd.) (A-13) 50% gluconic acid solution HLB value: 16.2 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A-14) Sodium gluconate HLB value: 33.2 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A-15) (+)-Sodium tartrate dihydrate HLB value: 48.1 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A-16) L(-)-Sodium Malate HLB value: 46.2 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A-17) L(+)-Sodium ascorbate HLB value: 14.6 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A-18) 2-Ethylhexyl glyceryl ether HLB value: 8.3 (Kao Corporation) (A-19) Polyoxyethylene glyceryl ether, molecular weight 200, HLB value: 12.0 (NOF Corporation) (A-20) 2-Aminoethanol HLB value: 8.0 (Tokyo Chemical Industry Co., Ltd.) (A-21) N-Methyldiethanolamine HLB value: 8.4 (Tokyo Chemical Industry Co., Ltd.) (A-22) Triethanolamine HLB value: 9.9 (Tokyo Chemical Industry Co., Ltd.) (A-23) Polyethyleneimine (average molecular weight approx. 600) HLB value: 127.8 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A-24) Polyethyleneimine, branched, MW 10,000, 99% HLB value: 2018.1 (FUJIFILM Wako Pure Chemical Industries, Ltd.) (A-25) DT-EH HLB value: 453.3 or more (polyalkylene polyamine-epichlorohydrin condensate, Mw: 5,000 or more, manufactured by Yokkaichi Chemical Co., Ltd.) (A-26) Disodium malonate HLB value: 44.7 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A-27) Disodium succinate HLB value: 44.3 (FUJIFILM Wako Pure Chemical Industries, Ltd.) (A-28) Trisodium citrate HLB value: 64.8 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A-29) Sodium adipate HLB value: 43.3 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., added as sodium salt to increase water solubility) (A-30) Polyacrylic acid sodium salt HLB value: 1266.6 (Kao Corporation, weight average molecular weight 5,000) (A-31) Methacrylic acid / methoxypolyethylene (25) glycol methacrylate = 75 / 25 mol% copolymer sodium salt HLB value: 2826.9 (manufactured by Kao Corporation, weight average molecular weight 50,000) (A-32) Glycine HLB value: 8.6 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A-33) Sodium L-glutamate HLB value: 26.8 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A-34) Collagen peptide, average molecular weight 3000, HLB value: 111.2, enzymatic hydrolysis product (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A-35) Nitrilotris(methylenephosphonic acid) (approximately 50% aqueous solution, approximately 2.2 mol / L) HLB value: 54.9 (manufactured by Tokyo Chemical Industry Co., Ltd.) (A-36) O-phosphorylethanolamine HLB value: 30.1 (Tokyo Chemical Industry Co., Ltd.) (A-37) L(-)-Proline HLB value: 16.6 (FUJIFILM Wako Pure Chemical Industries, Ltd.) (A-38) β-alanine HLB value: 17.6 (Tokyo Chemical Industry Co., Ltd.) (A-39) 6-Aminohexanoic acid HLB value: 16.1 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A-40) Glycylglycine HLB value: 20.0 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A-41) Sarcosine HLB value: 17.6 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0088] <(A') component: Comparative component> (A'-1) Polyoxyethylene (2) lauryl ether HLB value: 3.9 (Kao Corporation) (A'-2) Polyoxyethylene (30) sorbitol tetraoleate HLB value: -3.1 (Kao Corporation) (A'-3) Polyoxyethylene (6) sorbitan monooleate HLB value: 8.7 (Kao Corporation) (A'-4) Alkyl (carbon number 9-11) polyglucoside HLB value: 11.5 (Kao Corporation) (A'-5) Sucrose HLB value: 17.8 (manufactured by Ensuiko Sugar Refining Co., Ltd.) (A'-6) D-(-)-Fructose HLB value: 15.0 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A'-7) D-(+)-Mannose HLB value: 15.0 (Tokyo Chemical Industry Co., Ltd.) (A'-8) D-(+)-glucose HLB value: 15.0 (Tokyo Chemical Industry Co., Ltd.) (A'-9) D-(+)-Glucuronolactone HLB value: 14.2 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A'-10) Dextrin hydrate HLB value: 14.4 or more (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A'-11) Starch hydrolyzed, derived from potatoes, HLB value: 14.4 or higher (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A'-12) N-Butyldiethanolamine HLB value: 7.0 (Tokyo Chemical Industry Co., Ltd.) (A'-13) N,N-Diethylethanolamine HLB value: 6.1 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A'-14) Sodium salicylate HLB value: 25.2 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A'-15) 3,4-Dihydroxybenzoic acid HLB value: 10.1 (Tokyo Chemical Industry Co., Ltd., added as sodium salt to increase water solubility) (A'-16) Gallic acid monohydrate HLB value: 12.0 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (A'-17) Methyl gallate HLB value: 11.8 (Tokyo Chemical Industry Co., Ltd.) (A'-18) 1% by mass sodium hydroxide aqueous solution (prepared by diluting 48% by mass sodium hydroxide aqueous solution manufactured by Kanto Chemical Co., Ltd. with tap water) (A'-19) 1% by mass hydrochloric acid (prepared by diluting 10% by mass hydrochloric acid manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. with tap water)

[0089] <Component (B): Powdered thickener> (B-1) Asuka Clean D (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 3,811 mPa s) (B-2) Methylcellulose (Tokyo Chemical Industry Co., Ltd., viscosity: 408 mPa s) (B-3) Metrose SM-4000 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 586 mPa s) (B-4) Metrose 60SH-4000 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 350 mPa s) (B-5) Metrose 90SH-4000 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 926 mPa s) (B-6) Metrose 90SH-30000 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 993 mPa s) (B-7) Metrose hi90SH-4000 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 1,840 mPa s) (B-8) Metrose hi90SH-30000 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 3,514 mPa s) (B-9) HEC AW-15F (Sumitomo Seika Chemicals Co., Ltd., viscosity: 1,676 mPa s) (B-10) Hydroxyethyl cellulose (200-300 mPa·s, manufactured by Tokyo Chemical Industry Co., Ltd., viscosity: 218 mPa·s) (B-11) Hydroxyethyl cellulose (800-1500 mPa·s, manufactured by Tokyo Chemical Industry Co., Ltd., viscosity: 811 mPa·s) (B-12) Hydroxypropyl cellulose (1000-4000 mPa·s, manufactured by Tokyo Chemical Industry Co., Ltd., viscosity: 1,878 mPa·s) (B-13) Polyethylene glycol with a molecular weight of 2,000,000 (manufactured by Fujifilm Wako Pure Chemical Corporation, viscosity: 2,844 mPa·s)

[0090] <Solvent or dispersion medium> Water (tap water in Wakayama City)

[0091] <Method for calculating HLB value> The HLB values of the above components (A) and (A’) are the HLB values calculated by the Davis method based on the following calculation formula. HLB value = 7 + sum of the number of hydrophilic groups + sum of the number of lipophilic groups

[0092] <Example 1 and Comparative Example 1> (1) Method for preparing powder thickener slurry Weighed 1.5 g of various powder thickeners as the above component (B) into a 30 mL vial, added the above component (A) or (A’) in the addition amounts shown in Tables 1 to 5, and then added tap water in the addition amounts shown in Tables 1 to 5. After that, a powder thickener slurry was prepared by vigorously stirring with a magnetic stirrer. When the component (A) or (A’) was not added, a powder thickener slurry was prepared by adding only water. Note that the addition amounts in the table are apparent addition amounts.

[0093] (2) Evaluation of fluidity of powder thickener slurry The 30 mL vial containing the powder thickener slurry prepared by the method of (1) was allowed to stand at 20 °C for 1 hour, then tilted 90 degrees horizontally and inverted in 1 second, and the flow (deformation) of the powder thickener slurry was observed and evaluated. The evaluation was carried out based on visual observation with the naked eye. The evaluation criteria are as shown below. The results are shown in Tables 1 to 5. 〇… Flows (deforms) by its own weight by the above operation ×… Significantly thickened and no flow (deformation) occurs

[0094] (3) Viscosity measurement of powder thickener slurry The viscosity of the powder thickener slurry prepared by method (1) was measured using a rheometer Physica MCR301 manufactured by Anton Paar, using a plate jig with a diameter of 25 mm, a gap of 1 mm, a rotation speed of 600 rpm, and 20° C. The results are shown in Table 1.

[0095] [Table 1]

[0096] [Table 2]

[0097] [Table 3]

[0098] [Table 4]

[0099] [Table 5]

[0100] In Tables 1 to 5, Examples 1-1 to 1-102 showed superior powder thickener slurry fluidity compared to Comparative Examples 1-1 to 1-22. This is believed to be because the powder thickener surface was modified by the powder thickener modifier of the present invention, and the interaction with water molecules was alleviated, thereby suppressing the formation of flocks and rapid swelling and thickening.

[0101] <Example 2 and Comparative Example 2> (1) Preparation method of aqueous mixture for evaluation The powder thickener slurries prepared in Example 1 and Comparative Example 1 were added to a 100 mL disposable cup, and water (tap water) was added thereto in the amounts shown in Table 6. Then, the mixture was vigorously stirred with a magnetic stirrer to prepare an aqueous mixture for evaluation.

[0102] (2) Viscosity measurement method for aqueous mixtures for evaluation The viscosity of the aqueous mixture for evaluation prepared by method (1) was measured at 20°C using a Brookfield viscometer (jig #3). Measurements were taken immediately after the addition of tap water in (1), and 30, 60, 120, 180, 240, 300, and 15 minutes after the start of stirring. The viscosity of the aqueous mixture for evaluation at each time point after the start of stirring was measured and recorded to provide an index of thickening. The results are shown in Table 6.

[0103] [Table 6]

[0104] <Example 3 and Comparative Example 3> (1) Preparation method of cement bleeding water A 20-liter steel container was filled with 5 kg of ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd., 5 kg of ordinary Portland cement manufactured by Taiheiyo Cement Co., Ltd., 10 kg of tap water, and mixed for 2 minutes with a handy mixer to prepare a cement paste. The cement paste was then left to stand in the steel container for 24 hours, and the supernatant liquid was collected and used as the cement bleeding water.

[0105] (2) Preparation method of aqueous mixture for evaluation An aqueous mixture for evaluation was prepared in the same manner as in Example 2 and Comparative Example 2, except that the cement-bleeding water of (1) was used instead of water (tap water).

[0106] (3) Viscosity measurement method for aqueous mixtures for evaluation The viscosity of the aqueous mixture for evaluation prepared by method (2) was measured in the same manner as in Example 2 and Comparative Example 2. The results are shown in Table 7.

[0107] [Table 7]

[0108] In Tables 6 and 7, Examples 2-1 to 2-15 and 3-1 to 3-15 showed excellent thickening behavior and high thickening effect at a short time after the start of stirring compared to Comparative Examples 2-1 to 2-2 and 3-1 to 3-2. This is believed to be because the powder thickener surface was modified by the powder thickener modifier of the present invention, and the interaction with water molecules was alleviated, suppressing the formation of flocks and rapid swelling and thickening, and water molecules effectively penetrated the thickener (molecules), and the thickening effect was restored by the diffusion of the modifier, resulting in more effective interaction of the thickener with water molecules.

[0109] <Example 4 and Comparative Example 4> (1) Method for preparing mixing water An aqueous mixture for evaluation was prepared in the same manner as in Example 2 and Comparative Example 2, except that a 300 mL disposable cup was used instead of a 100 mL disposable cup. This aqueous mixture for evaluation was used as mixing water for preparing cement paste.

[0110] (2) Preparation of cement paste In a 300mL disposable cup, 100g of ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd. and 100g of ordinary Portland cement manufactured by Pacific Cement Co., Ltd. were placed, and the mixing water (1) was added thereto. Then, the mixture was stirred with a hand mixer at 620 rpm for 30 seconds to prepare a cement paste. Comparative Example 4-3 was carried out as a comparison for the method of adding the powder thickener, and 100g of ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd. and 100g of ordinary Portland cement manufactured by Pacific Cement Co., Ltd. were placed in a 300mL disposable cup, and the (B) component was added in the amount shown in Table 8, and then the mixture was dry mixed by stirring with a hand mixer at 620 rpm for 10 seconds, and tap water was further added in the amount shown in Table 8, and the mixture was stirred with a hand mixer at 620 rpm for 30 seconds to prepare a cement paste.

[0111] (3) Method for measuring viscosity of cement paste The viscosity of the cement paste prepared by method (2) was measured at 20°C using a B-type viscometer (jig #4) at a rotation speed of 30 rpm. The measurements were performed immediately after the preparation of the cement paste in (2) (30 seconds after the start of mixing), 60 seconds, 120 seconds, 180 seconds, 240 seconds, and 300 seconds later, and the viscosity of the cement paste at each elapsed time from the start of mixing was measured and recorded to be used as an index of thickening. The results are shown in Table 8.

[0112] [Table 8]

[0113] In Table 8, Examples 4-1 to 4-13 showed excellent thickening behavior and high thickening effect at a short time after the start of stirring compared to Comparative Examples 4-1 to 4-6. This is considered to be because the powder thickener surface was modified by the powder thickener modifier of the present invention, and the interaction with water molecules was alleviated, suppressing the formation of flocks and rapid swelling and thickening, and water molecules effectively penetrated the thickener (molecules), and the thickening effect was restored by the diffusion of the modifier, resulting in more effective interaction of the thickener with water molecules and hydraulic composition particles.

Claims

1. (A) A modifier for a powder thickener, comprising a compound (hereinafter referred to as component (A)) that contains carbon atoms, hydrogen atoms, and heteroatoms other than carbon atoms and hydrogen atoms, has no ring structure, and has an HLB value of 8 or more as measured by the Davis method, the component (A) is a compound selected from a polyhydric alcohol having only hydroxyl groups as functional groups, a polyvalent carboxylic acid having only carboxy groups as functional groups and a salt thereof, an aminocarboxylic acid and a salt thereof, an aminophosphonic acid and a salt thereof, an aminophosphoric acid and a salt thereof, a polyamine and a salt thereof, and a polyimine; Used as a powder thickener for hydraulic compositions. Modifier for powder thickeners.

2. 2. The powder thickener modifier according to claim 1, wherein the component (A) is a compound selected from the group consisting of polyhydric alcohols having only hydroxyl groups as functional groups, polyvalent carboxylic acids and their salts having only carboxy groups as functional groups, aminocarboxylic acids and their salts, and polyamines and their salts.

3. 3. The modifier for powder thickeners according to claim 1 or 2, wherein component (A) is a compound selected from aminocarboxylic acids and salts thereof.

4. The modifier for powder thickeners according to any one of claims 1 to 3, wherein the component (A) is a compound selected from the group consisting of amino acids and salts thereof.

5. The modifier for powder thickeners according to any one of claims 1 to 4, wherein the HLB of component (A) is 8 or more and 3,000 or less.

6. The powder thickener according to any one of claims 1 to 5, which is a powder thickener selected from the group consisting of cellulose-based polymer compounds and polymer compounds having an ether bond in the main skeleton. Modifier for.

7. A thickener composition for hydraulic compositions, comprising the powder thickener modifier according to any one of claims 1 to 6, a powder thickener for hydraulic compositions, and water, The form is a slurry, and at least a portion of the powdered thickener is dispersed in a solid state. A thickener composition for a hydraulic composition.

8. The thickener composition for hydraulic compositions according to claim 7, having a viscosity at 20°C of 15 mPa·s or more and 1,000 mPa·s or less.

9. The thickener composition for hydraulic compositions according to claim 7 or 8, comprising 0.1% by mass or more and 50% by mass or less of a powder thickener.

10. The thickener composition for hydraulic compositions according to any one of claims 7 to 9, wherein a mass ratio of the (A) component to the powder thickener is 0.001 or more and 20 or less.

11. A method for producing a thickener composition for hydraulic compositions, comprising mixing (A) a compound (hereinafter referred to as component (A)) containing carbon atoms, hydrogen atoms, and heteroatoms other than carbon atoms and hydrogen atoms, having no ring structure, and having an HLB value of 8 or more as determined by the Davis method, a powdery thickener for hydraulic compositions, and water, The component (A) is a compound selected from a polyhydric alcohol having only a hydroxyl group as a functional group, a polyvalent carboxylic acid having only a carboxy group as a functional group and a salt thereof, an aminocarboxylic acid and a salt thereof, an aminophosphonic acid and a salt thereof, an aminophosphoric acid and a salt thereof, a polyamine and a salt thereof, and a polyimine. A method for producing a thickener composition for a hydraulic composition.

12. A method for producing the thickener composition for hydraulic compositions according to claim 11, comprising mixing the modifier for powder thickeners according to any one of claims 1 to 6, a powder thickener for hydraulic compositions, and water.

13. The method for producing a thickener composition for hydraulic compositions according to claim 11 or 12, wherein the powder thickener for hydraulic compositions is mixed in an amount of 0.1 mass % or more and 50 mass % or less based on the total amount of the components to be mixed.

14. The method for producing the thickener composition for hydraulic compositions according to any one of claims 11 to 13, wherein the component (A) and the powder thickener for hydraulic compositions are mixed so that the mass ratio of the component (A) / the powder thickener for hydraulic compositions is 0.001 or more and 20 or less.

15. A method for producing a hydraulic composition, comprising mixing the thickener composition for hydraulic compositions according to any one of claims 7 to 10, hydraulic powder, and water.

16. The method for producing a hydraulic composition according to claim 15, wherein the thickener composition for hydraulic compositions and water are mixed so that a mass ratio of the thickener composition for hydraulic compositions / water is 0.01 or more and 10 or less.

17. The method for producing a hydraulic composition according to claim 15 or 16, wherein the thickener composition for hydraulic compositions and water are mixed so that the mass ratio of the component (A) / water in the thickener composition for hydraulic compositions is 0.001 or more and 0.2 or less.

18. Water and hydraulic powder are mixed together so that the water / hydraulic powder ratio is 20% by mass or more and 100% by mass or less. The method for producing the hydraulic composition according to any one of claims 15 to 17, comprising mixing the above components as follows:

19. A method for producing a hardened body, comprising producing a hydraulic composition by the method according to any one of claims 15 to 18, filling the hydraulic composition into a form and hardening it.

20. A method for thickening a hydraulic composition, comprising the steps of: preparing a thickener composition for a hydraulic composition from a powdery thickener for a hydraulic composition, water, and a compound (A) which contains carbon atoms, hydrogen atoms, and heteroatoms other than carbon atoms and hydrogen atoms, has no ring structure, and has an HLB value of 8 or more as determined by the Davis method [hereinafter referred to as component (A)]; and adding the thickener composition for a hydraulic composition to a hydraulic composition containing water in an amount greater than the amount of water in the thickener composition for a hydraulic composition to thicken the hydraulic composition, The component (A) is a compound selected from a polyhydric alcohol having only a hydroxyl group as a functional group, a polyvalent carboxylic acid having only a carboxy group as a functional group and a salt thereof, an aminocarboxylic acid and a salt thereof, an aminophosphonic acid and a salt thereof, an aminophosphoric acid and a salt thereof, a polyamine and a salt thereof, and a polyimine. A method for thickening a hydraulic composition.

21. The method for thickening a hydraulic composition according to claim 20, wherein the powdery thickener for hydraulic compositions is used in an amount of 0.1 mass % to 50 mass % of the total amount of components used to prepare the thickener composition for hydraulic compositions.

22. The method for thickening a hydraulic composition according to claim 20 or 21, wherein the component (A) and the powdery thickener for hydraulic compositions are used in a mass ratio of the component (A) / powdery thickener for hydraulic compositions of 0.001 or more and 20 or less.

23. The method for thickening a hydraulic composition according to any one of claims 20 to 22, wherein the thickener composition for hydraulic compositions is added so that the mass ratio of the thickener composition for hydraulic compositions to water in the hydraulic composition, i.e., the thickener composition for hydraulic compositions / water, is 0.01 or more and 10 or less.

24. The method for thickening a hydraulic composition according to any one of claims 20 to 23, wherein the thickener composition for hydraulic compositions is added so that the mass ratio of the (A) component in the thickener composition for hydraulic compositions to the water in the hydraulic composition, that is, the (A) component / water in the thickener composition for hydraulic compositions, is 0.001 or more and 0.2 or less.

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