Thickener composition

Abstract

To provide a thickener composition with superior thickening performance.SOLUTION: A thickener composition contains (A) hydroxypropyl cellulose and (B) aromatic sulfonic acid formaldehyde condensate or salts thereof.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Thickeners are widely used in foods, cosmetics and other industrial products to increase the viscosity of the system by retaining and binding solvents, dispersion media and 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 particular, for industrial product applications such as those in the civil engineering and construction fields, cellulose ether thickeners, which are ether-modified cellulose obtained from natural raw materials such as pulp and cotton, are mainly used from the standpoint of safety, as well as their thickening properties. Representative cellulose ether thickeners include hydroxypropyl methylcellulose, carboxymethylcellulose, methylcellulose, hydroxyethyl methylcellulose, and hydroxyethyl cellulose.

[0005] In addition, since such thickeners exhibit their thickening properties by dispersing or dissolving in a solvent or dispersing medium, many of them are often distributed as powdered products from the standpoint of handling and transportation, with as little solvent or dispersing medium removed as possible.

[0006] On the other hand, surfactants are amphiphilic molecules that have, within the same molecule, a hydrophilic group that has a high affinity for water and a hydrophobic group that has a high affinity for oil. They control emulsification, dispersion, foaming, wetting, etc., and are indispensable agents for industrial products. They are often used in combination with the above-mentioned cellulose ether thickeners.

[0007] Patent Document 1 discloses an agricultural chemical composition containing an agricultural chemical active ingredient, an ionic surfactant, a water-soluble polymer having an IOB value of 3.5 or less, and water.

[0008] Patent Document 2 discloses a method for improving soft soil in which, when a screw conveyor is used to transport excavated soil at the front of a shield machine to remove the soil, if the soil is soft and prone to flow, an improvement agent mainly composed of water-soluble polysaccharides or modified polysaccharides is added to the screw conveyor, and the soil and improvement agent are mixed inside the screw conveyor to improve the fluidity of the soft soil.

[0009] Patent Document 3 discloses a stable hydrocolloid composition in which hydrocolloids consisting of welan gum, methyl cellulose, hydroxypropyl methyl cellulose (HPMC), hydroxyethyl cellulose (HEC), polyvinyl alcohol (PVA), starch, etc. are uniformly dispersed in a superplasticizer such as sulfonated naphthalene, sulfonated melamine, modified lignosulfate, derivatives thereof, and mixtures thereof. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] JP 2018-197209 A [Patent Document 2] Japanese Patent Application Publication No. 1-207384 [Patent Document 3] Special Publication No. 2001-517251 Summary of the Invention [Problem to be solved by the invention]

[0011] However, although hydroxypropyl cellulose, which is a type of cellulose ether thickener, is less likely to form lumps and has excellent uniform dispersibility in water, there is a problem in that the viscosity of an aqueous dispersion or solution of hydroxypropyl cellulose is lower than that of other cellulose ether thickeners, particularly hydroxypropyl methylcellulose. The present invention provides a thickener composition having excellent thickening properties, an additive for the thickener composition, a powder mixture, and a hydraulic composition. [Means for solving the problem]

[0012] The present invention relates to a thickener composition comprising (A) hydroxypropyl cellulose (hereinafter referred to as component (A)) and (B) an aromatic sulfonic acid-formaldehyde condensate or a salt thereof (hereinafter referred to as component (B)).

[0013] The present invention also relates to a thickener composition additive for use in a thickener composition containing component (A), the thickener composition additive including component (B).

[0014] The present invention also relates to a powder mixture comprising a hydraulic powder, component (A), and component (B).

[0015] The present invention also relates to a hydraulic composition comprising a hydraulic powder, water, component (A), and component (B). Effect of the Invention

[0016] According to the present invention, there are provided a thickener composition having excellent thickening properties, an additive for the thickener composition, a powder mixture, and a hydraulic composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] In recent years, the SDGs have been proposed to realize a sustainable society. The present invention is believed to be a technology that can contribute to the achievement of SDGs Nos. 9, 11, 12, 13, and 15 by reducing the amount of hydroxypropyl cellulose required to thicken a system through the improvement of the thickening properties of hydroxypropyl cellulose.

[0018] The present inventors have found that when an aqueous dispersion or solution of the thickener composition of the present invention containing components (A) and (B) is prepared, the viscosity of the dispersion or solution increases significantly. Although the reason why such an effect is exhibited is not entirely clear, it is presumed to be as follows. It is believed that cellulose ether thickeners form a network structure between cellulose ether polymer chains starting from the hydrophobic part in an aqueous solution by alkylating or alkoxylating cellulose, thereby unraveling the hydrophobic crystal structure of cellulose and hydrophilizing it, and that thickening properties are exhibited by partially hydrophobizing cellulose. Hydroxypropyl cellulose is hydrophilized by hydroxypropylation and has excellent water dispersibility, but it is presumed that it is inferior in terms of thickening properties to hydroxypropyl methylcellulose hydrophobically modified by alkylation because of its low entanglement density due to its hydrophobic structure. On the other hand, naphthalene sulfonate formalin condensate is a surfactant, and therefore has hydrophilic and hydrophobic parts, and by interacting with hydroxypropyl cellulose non-covalently, it forms a network structure in which hydroxypropyl cellulose polymer chains are bridged, increasing the entanglement density, and exhibiting remarkable thickening properties. The thickener composition, the additive for the thickener composition, the powder mixture, and the hydraulic composition of the present invention are not limited to the above-mentioned mechanism of action.

[0019] <Thickener composition> The thickener composition of the present invention contains (A) hydroxypropyl cellulose (hereinafter referred to as component (A)) and (B) a naphthalenesulfonic acid-formaldehyde condensate or a salt thereof (hereinafter referred to as component (B)).

[0020] <Component (A)> Component (A) is hydroxypropyl cellulose. From the viewpoint of the viscosity of the aqueous dispersion or solution of component (A), the viscosity of a 2% by mass aqueous solution of component (A) at 20°C, as measured with a B-type viscometer, is preferably 10 mPa s or more and 10,000 mPa s or less. The viscosity of a 2 mass% aqueous solution of component (A) at 20°C, from the viewpoint of the viscosity of the aqueous dispersion or solution, is preferably 10 mPa·s or more, more preferably 25 mPa·s or more, even more preferably 50 mPa·s or more, still more preferably 75 mPa·s or more, still more preferably 100 mPa·s or more, and is preferably 10,000 mPa·s or less, more preferably 5,000 mPa·s or less, still more preferably 3,000 mPa·s or less, and still more preferably 1,000 mPa·s or less.

[0021] <Method of measuring viscosity> The viscosity of a 2% by mass aqueous solution of component (A) at 20°C is measured using a B-type viscometer (Tokyo Keiki Co., Ltd.) at 20°C, with No. 2 rotor, at 60 rpm, and after 10 seconds. However, if the viscosity exceeds 500 mPa·s when measured with the No. 2 rotor under these conditions (hereinafter referred to as the No. 2 measurement), then it is measured at 20°C, with No. 2 rotor, at 6 rpm, and after 10 seconds; if the viscosity exceeds 5,000 mPa·s when measured with the No. 2 rotor, then it is measured at 20°C, with No. 4 rotor, at 60 rpm, and after 10 seconds; if the viscosity exceeds 10,000 mPa·s when measured with the No. 4 rotor, then it is measured at 20°C, with No. 4 rotor, at 6 rpm, and after 10 seconds.

[0022] From the viewpoint of the viscosity of the aqueous dispersion or solution, the hydroxypropyl cellulose of component (A) preferably has a hydroxypropoxy group substitution molar number of 2.5 or more, more preferably 3.0 or more, and preferably 4.0 or less, more preferably 3.6 or less. Here, the "molar number of hydroxypropoxy group substitutions" refers to the average number of moles of hydroxypropoxy groups introduced per mole of glucose unit (having three hydroxyl groups) of cellulose.

[0023] The weight average molecular weight of component (A) is, from the viewpoint of the viscosity of the aqueous dispersion or solution, preferably 10,000 or more, more preferably 50,000 or more, even more preferably 100,000 or more, and still more preferably 200,000 or more, and from the viewpoint of water dispersibility or water solubility, preferably 2,500,000 or less, more preferably 2,000,000 or less, even more preferably 1,500,000 or less, and still more preferably 1,000,000 or less. The weight average molecular weight of component (A) is a value measured by gel permeation chromatography under the following measurement conditions, using polyethylene glycol of known molecular weight as a standard sample. <Method for measuring weight average molecular weight of component (A)> Column: α-M + α-M (cation) Eluent: 50 mmоl / L LiCl, ethanol / water = 3:7 mass% mixture Flow rate: 0.6mL / min Column temperature: 40℃ Detector: RI

[0024] Hydroxypropyl cellulose may be produced by a known method, for example, as described in JP-A-9-202801, or a commercially available product may be used. Commercially available products include, for example, the HPC series manufactured by Nippon Soda Co., Ltd. and the KLUCEL series manufactured by Sansho Co., Ltd. Among these commercially available products, those having a 2 mass % viscosity of 10 mPa·s or more and 10,000 mPa·s or less include NISSO HPC L (6.0-10.0), NISSO HPC M (150-400), NISSO HPC H (1,000-4,000), and NISSO HPC VH (4,001-6,000) manufactured by Nippon Soda Co., Ltd., and KLUCEL manufactured by Hercules Incorporated (now Ashland Inc.). TM G(300), KLUCEL TM M(5,000), KLUCEL TM H(30,000) and the like. The numbers in parentheses for the commercially available products above indicate the 2 mass % viscosity (mPa s).

[0025] <(B) component> The component (B) is an aromatic sulfonic acid formalin condensate or a salt thereof. The component (B) may be one or a combination of two or more selected from aromatic sulfonic acid formalin condensates and their salts. The component (B) is a condensate of an aromatic sulfonic acid and formaldehyde or a salt thereof. Examples of the aromatic sulfonic acid of the component (B) include monocyclic aromatic sulfonic acids such as cresol sulfonic acid and phenol sulfonic acid; and alkylnaphthalenesulfonic acids such as α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, α-naphtholsulfonic acid, β-naphtholsulfonic acid, methylnaphthalenesulfonic acid, and butylnaphthalenesulfonic acid. Among these, α-naphthalenesulfonic acid and β-naphthalenesulfonic acid are preferred.

[0026] Examples of aromatic sulfonic acid formalin condensates or salts thereof include α- or β-naphthalenesulfonic acid formalin condensates (hereinafter, α-naphthalenesulfonic acid formalin condensates or β-naphthalenesulfonic acid formalin condensates are collectively referred to simply as “naphthalenesulfonic acid formalin condensates”) or salts thereof. The component (B) is preferably a naphthalenesulfonic acid formalin condensate or a salt thereof. The naphthalenesulfonic acid-formaldehyde condensate of component (B) may contain other structural units within the range that does not impair the effects of the present invention. Examples of the other structural units include structural units derived from copolymerizable compounds such as alkylnaphthalenesulfonic acids.

[0027] Examples of the salt of component (B) include sodium salts, potassium salts, ammonium salts, etc. Among these, one or more selected from sodium salts and ammonium salts are preferred.

[0028] The weight average molecular weight of component (B) is, from the viewpoint of the viscosity of the aqueous dispersion or solution, 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, and from the viewpoint of water dispersibility or water solubility, preferably 200,000 or less, more preferably 100,000 or less, even more preferably 80,000 or less, and even more preferably 50,000 or less.

[0029] <Method for measuring weight average molecular weight of component (B)> The weight average molecular weight of the component (B) is measured by gel permeation chromatography (GPC) under the following conditions. [GPC conditions] Equipment: Tosoh Corporation HLC-8320GPC Column: Tosoh Corporation G4000SWXL+G2000SWXL Eluent: 30mMCH3COONa / CH3CN=6 / 4 Flow rate: 0.7mL / min Detector: UV 280nm Sample size: 3.33mg / mL Standard material: Sodium polystyrene sulfonate (SCIENTIFIC POLYMER PRODUCTS, INC.) SODIUM POLYSTYRENE SULFONATE - narrow distribution -: MW = 1,690, 7,540, 16,000, 68,300, 126,700, 587,600

[0030] The aromatic sulfonic acid-formaldehyde (formalin) condensate can be produced, for example, by a method in which an aromatic sulfonic acid and formaldehyde are subjected to a condensation reaction to obtain a condensate, and the condensate is neutralized with a basic substance. After the neutralization, water-insoluble matters present in the system may be removed. Commercially available salts of aromatic sulfonic acid-formalin condensates include 150, HS, 150R, 150RX, 150V, 150HB-2, and 100 from the "Mitei" series manufactured by Kao Corporation, and AS, MS, N, NL, RN, RN-L, SC-30, SC-B, SN-B, SS-L, T, and T-45 from the "Demol" series, etc.

[0031] <Composition of thickener composition and other components> The thickener composition of the present invention contains component (A) in an amount of preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more from the viewpoint of the viscosity of the aqueous dispersion or solution, and in an amount of preferably 99% by mass or less, more preferably 75% by mass or less, and even more preferably 50% by mass or less from the viewpoint of the handleability of the aqueous dispersion or solution.

[0032] From the viewpoint of the viscosity of the aqueous dispersion or solution, the thickener composition of the present invention is used so that, when used, the amount of component (A) per 100 parts by mass of water blended into the aqueous dispersion or solution containing the thickener composition 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 8 parts by mass or less, more preferably 4 parts by mass or less, even more preferably 2 parts by mass or less, still more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less.

[0033] The thickener composition of the present invention contains, from the viewpoint of the viscosity of the aqueous dispersion or solution, preferably 0.001% by mass or more of component (B), more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, and from the viewpoint of the viscosity of the aqueous dispersion or solution, preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less.

[0034] From the viewpoint of the viscosity of the aqueous dispersion or solution, the thickener composition of the present invention is used so that, when used, the amount of component (B) per 100 parts by mass of water blended into the aqueous dispersion or solution containing the thickener composition of the present invention is preferably 0.01 part by mass or more, more preferably 0.02 parts by mass or more, even more preferably 0.04 parts by mass or more, and preferably 4 parts by mass or less, more preferably 2 parts by mass or less, even more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less.

[0035] In the thickener composition of the present invention, the mass ratio (B) / (A) of the content of the (B) component to the content of the (A) component is preferably 0.02 or more, more preferably 0.05 or more, and even more preferably 0.1 or more, from the viewpoint of the viscosity of the aqueous dispersion or aqueous solution, and is preferably 2.5 or less, more preferably 2 or less, and even more preferably 1.5 or less, from the viewpoint of the viscosity of the aqueous dispersion or aqueous solution.

[0036] <(C) component> The thickener composition of the present invention can contain (C) water (hereinafter referred to as component (C)). The water may be tap water, purified water, groundwater, or industrial water. Component (C) is used as the balance excluding components (A), (B), and the optional components described below. From the viewpoint of the handleability of the thickener composition, the thickener composition of the present invention contains component (C) in an amount of preferably 1 mass % or more, more preferably 5 mass % or more, and even more preferably 10 mass % or more, and from the viewpoint of the viscosity of the aqueous dispersion or solution, it contains preferably 99.9 mass % or less, more preferably 75 mass % or less, and even more preferably 50 mass % or less.

[0037] The thickener compositions of the present invention may optionally contain preservatives, antifoaming agents, and stabilizers.

[0038] The thickener composition of the present invention may also contain an inorganic powder. The inorganic powder may be used for a water dispersion (slurry) of a hydraulic powder, for example, hydraulic powder such as cement or gypsum, powder having pozzolanic action and / or latent hydraulic property such as blast furnace slag, ash, amorphous silica, or kaolin, stone powder (calcium carbonate powder), etc. A preferred embodiment of the hydraulic powder will be described in detail in the hydraulic composition of the present invention. Examples of inorganic powders include inorganic powders for producing ceramics, such as alumina, zirconia, barium titanate, hydroxyapatite, silicon carbide, silicon nitride, fluorite, boron nitride, ferrite, lead zirconate titanate, steatite, and zinc oxide. Examples of inorganic powders include inorganic powders that are coloring materials (pigments), such as iron oxide, carbon black, chromium oxide, titanium oxide, zinc oxide, talc, kaolin, mica, and sericite; inorganic powders for granulated materials such as cat litter, such as bentonite and zeolite; and inorganic powders that are conductive materials, such as silver and its alloys, copper and its alloys, gold and its alloys, aluminum and its alloys, magnesium and its alloys, tungsten and its alloys, molybdenum and its alloys, zinc and its alloys, nickel and its alloys, iron and its alloys, platinum and its alloys, tin and its alloys, steel and its alloys, lead and its alloys, and mercury and its alloys.

[0039] The thickener composition of the present invention may contain a monomer, such as a copolymerizable monomer having a vinyl group or an aryl group, for example, (meth)acrylic acid and its derivatives, ethylene and its derivatives, styrene and its derivatives, propylene and its derivatives, alkylene glycol and its derivatives, dicarboxylic acid and its derivatives, benzene and its derivatives, and naphthalene and its derivatives. The thickener composition of the present invention may also contain pulp, pulp sludge, sawdust, used tea leaves, and the like as powders for granulated materials such as cat litter, and carbon and its alloys, and the like as conductive powders.

[0040] The thickener composition of the present invention may be one or more types of thickener compositions selected from those for aqueous dispersions (slurries) of hydraulic powders, those for dispersions of inorganic powders for ceramic production, those for emulsified dispersions of monomers and the like, those for dispersions of coloring materials and the like, those for granulated materials such as cat litter, and those for dispersions of conductive materials and the like, and is suitable as a thickener composition for aqueous dispersions of hydraulic powders. As an example of the water dispersion of hydraulic powder containing the thickener composition of the present invention, the following hydraulic composition of the present invention can be mentioned.

[0041] The thickener composition of the present invention contains an inorganic powder in an amount of preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, from the viewpoint of the viscosity of the aqueous dispersion or solution, and preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, from the viewpoint of the viscosity of the aqueous dispersion or solution.

[0042] From the viewpoint of the viscosity of the aqueous dispersion or solution, the thickener composition of the present invention is used so that, when used, the amount of inorganic powder blended per 100 parts by mass of water blended into the aqueous dispersion or solution containing the thickener composition of the present invention is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, and preferably 200 parts by mass or less, more preferably 100 parts by mass or less, even more preferably 50 parts by mass or less.

[0043] <Hydraulic composition> The present invention provides a hydraulic composition comprising a hydraulic powder, water, a component (A), and a component (B). The hydraulic composition of the present invention may be a hydraulic composition containing a hydraulic composition, water, and the thickener composition of the present invention. In the hydraulic composition of the present invention, preferred embodiments of the components (A) and (B) and optional components are the same as those described in the thickener composition of the present invention. In the hydraulic composition of the present invention, the water is tap water, lake water, river water, groundwater, or the like.

[0044] The hydraulic powder 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, moderate-heat Portland cement, white Portland cement, and ecocement (e.g., JIS R5214, etc.). Among these, from the viewpoints of procurement and handling, cement selected from early-early-strength Portland cement, ordinary Portland cement, sulfate-resistant Portland cement, and white Portland cement is preferred, and early-early-strength Portland cement and ordinary Portland cement are more preferred.

[0045] The hydraulic powder may include blast furnace slag, fly ash, silica fume, anhydrous gypsum, etc., and may also include non-hydraulic limestone fine powder, etc. As the hydraulic powder, blast furnace cement, fly ash cement, or silica fume cement, which is a mixture of cement with blast furnace slag, fly ash, silica fume, etc., may also be used.

[0046] The hydraulic composition of the present invention may contain an aggregate. The aggregate may be selected from fine aggregate and coarse aggregate. Examples of fine aggregates include those specified by number 2311 in JIS A0203-2014. Examples of fine aggregates include river sand, land sand, mountain sand, sea sand, lime sand, silica sand and crushed sands thereof, blast furnace slag fine aggregate, ferro-nickel slag fine aggregate, lightweight fine aggregate (artificial and natural), and recycled fine aggregate. Furthermore, examples of the coarse aggregate include those specified by number 2312 in JIS A0203-2014. For example, examples of the coarse aggregate include river gravel, land gravel, mountain gravel, sea gravel, limestone gravel, crushed stones thereof, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural), and recycled coarse aggregate. Different types of fine aggregate and coarse aggregate may be mixed and used, or a single type may be used.

[0047] The hydraulic composition of the present invention has a water / hydraulic powder ratio (W / C) of preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more from the viewpoint of homogeneity of the hydraulic composition, and preferably 300% by mass or less, more preferably 150% by mass or less, and even more preferably 75% by mass or less from the viewpoint of strength of the set body of the hydraulic composition. The water / hydraulic powder ratio (W / C) is the ratio of water to hydraulic powder in the hydraulic composition of the present invention expressed as a mass percentage (mass%) and is calculated as (water / hydraulic powder) x 100. In addition, when the hydraulic powder includes powders selected from powders having pozzolanic action, powders having latent hydraulic properties, and stone powder (calcium carbonate powder) in addition to powders having properties that harden through hydration reactions such as cement, the amounts of these powders are also included in the amount of hydraulic powder in the present 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.

[0048] The hydraulic composition of the present invention contains, from the viewpoint of viscosity development of the hydraulic composition slurry, preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and even more preferably 0.1 part by mass or more of component (A) relative to 100 parts by mass of water contained in the hydraulic composition, and from the viewpoint of homogeneity of the hydraulic composition, preferably 8 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 2 parts by mass or less.

[0049] The hydraulic composition of the present invention contains, from the viewpoint of viscosity development of the hydraulic composition slurry, preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and even more preferably 0.1 part by mass or more of the (B) component relative to 100 parts by mass of water contained in the hydraulic composition, and from the viewpoint of the strength of the set body of the hydraulic composition, preferably 4 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1 part by mass or less.

[0050] In the hydraulic composition of the present invention, the mass ratio (B) / (A) of the content of the component (B) to the content of the component (A) is preferably 0.02 or more, more preferably 0.08 or more, even more preferably 0.32 or more, from the viewpoint of the hydraulic composition slurry viscosity, and is preferably 2.5 or less, more preferably 2 or less, even more preferably 1.5 or less, from the viewpoint of the hydraulic composition slurry viscosity.

[0051] <Powder mixture> The thickener composition of the present invention may be in the form of a powder mixture (dry mix) in which it is premixed with a hydraulic powder. That is, the present invention provides a powder mixture containing the hydraulic powder, component (A), and component (B). Preferred embodiments of the component (A), the component (B) and any optional components in the powder mixture of the present invention are the same as those described in the thickener composition of the present invention. In addition, the preferred embodiments of the hydraulic powder and aggregate in the powder mixture of the present invention are the same as those described in the hydraulic composition of the present invention. In addition, in the powder mixture of the present invention, the preferred contents of the (A) component, the (B) component, and the (C) component relative to the hydraulic powder contained in the powder mixture, and the mass ratios of the contents, (B) / (A) and (C) / (B), are the same as those described in the hydraulic composition of the present invention.

[0052] The powder mixture of the present invention contains, from the viewpoint of viscosity expression of the hydraulic composition slurry, preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and even more preferably 0.1 mass % or more of component (A) relative to the hydraulic powder contained in the powder mixture, and from the viewpoint of homogeneity of the hydraulic composition, preferably 8 mass % or less, more preferably 4 mass % or less, and even more preferably 2 mass % or less.

[0053] The powder mixture of the present invention contains, from the viewpoint of viscosity expression of the hydraulic composition slurry, preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and even more preferably 0.1 mass % or more of the (B) component relative to the hydraulic powder contained in the powder mixture, and from the viewpoint of the strength of the hardened body of the hydraulic composition, preferably 4 mass % or less, more preferably 2 mass % or less, and even more preferably 1 mass % or less.

[0054] <Additives for thickener compositions> The present invention provides a thickener composition additive for use in a thickener composition containing (A) hydroxypropyl cellulose (component (A)), the thickener composition additive comprising (B) an aromatic sulfonic acid-formaldehyde condensate or a salt thereof (component (B)). Specific examples and preferred examples of the (A) component, the (B) component and optional components in the thickener composition additive of the present invention are the same as those described in the thickener composition of the present invention. Also, in the thickener composition additive of the present invention, the preferred content of the (A) component in the thickener composition is the same as those described in the thickener composition of the present invention.

[0055] The thickener composition additive of the present invention contains the (B) component in an amount of preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 1.5% by mass or more from the viewpoint of the viscosity of the aqueous dispersion, aqueous solution, or hydraulic composition slurry, and for example, 100% by mass or less, further 75% by mass or less, and further 50% by mass or less from the viewpoint of the viscosity of the aqueous dispersion, aqueous solution, or hydraulic composition slurry. The thickener composition additive of the present invention may contain the (B) component in an amount of 100% by mass.

[0056] The thickener composition additive of the present invention is used so that the mass ratio (B) / (A) of the content of the (B) component to the content of the (A) component contained in the thickener composition is preferably 0.02 or more, more preferably 0.05 or more, and even more preferably 0.1 or more, from the viewpoint of the viscosity of the aqueous dispersion, aqueous solution, or hydraulic composition slurry, and is preferably 2.5 or less, more preferably 2 or less, and even more preferably 1.5 or less, from the viewpoint of the viscosity of the aqueous dispersion, aqueous solution, or hydraulic composition slurry. That is, the thickener composition additive of the present invention may be an additive for a thickener composition in which the component (B) is used relative to the component (A) in the above-mentioned mass ratio (B) / (A).

[0057] <Kit for producing thickener composition> The present invention provides a kit for producing a thickener composition comprising multiple agents including components selected from the following component (A) and component (B), wherein component (A) and component (B) are contained in separate agents: (A) Component: Hydroxypropyl cellulose Component (B): Aromatic sulfonic acid-formaldehyde condensate or its salt

[0058] An example of the kit of the present invention is a kit composed of an agent containing component (A) but not component (B), and an agent containing component (B) but not component (A).

[0059] Specific examples and preferred examples of the component (A), the component (B) and the optional components in the kit of the present invention are the same as those described in the thickener composition of the present invention. The matters described in the thickener composition of the present invention can be applied to the kit of the present invention.

[0060] In each of the agents constituting the kit of the present invention, the contents of the (A) component and the (B) component may be, for example, amounts such that a thickener composition of the present invention containing these components in the contents or mass ratios within the above-mentioned ranges can be produced.

[0061] A plurality of ingredients including a component selected from component (A) and component (B) are mixed and further diluted with water to prepare a desired thickener composition. The kit for producing the thickener composition of the present invention is suitably used for preparing the thickener composition of the present invention.

[0062] The agent containing the component (A) preferably contains the component (A) in an amount of 1 mass% or more, further 5 mass% or more, further 25 mass% or more, and 100 mass% or less, further 90 mass% or less, and may contain 100 mass% of the component (A). Furthermore, the agent containing the (B) component preferably contains 1 mass % or more, further 5 mass % or more, further 25 mass % or more, and 100 mass % or less, further 90 mass % or less of the (B) component, and may contain 100 mass %. The agent containing component (A) and / or the agent containing component (B) may contain an optional component such as component (C) mentioned in the thickener composition of the present invention.

[0063] <Method of producing thickener composition> The present invention provides a method for producing a thickener composition, which comprises mixing (A) hydroxypropyl cellulose (component (A)) with an aqueous solution obtained by mixing (B) an aromatic sulfonic acid-formalin condensate or a salt thereof (component (B)) and (C) water (component (C)). Specific examples and preferred examples of optional components such as components (A), (B) and (C) in the method for producing the thickener composition of the present invention are the same as those described in the thickener composition of the present invention. The preferred contents and mass ratios of components (A), (B), (C) and optional components in the thickener composition of the present invention can be read as the preferred mixing amounts and mixing ratios of components (A), (B), (C) and optional components in the method for producing the thickener composition of the present invention. EXAMPLES

[0064] <Example 1 and Comparative Example 1> Using an agent containing component (A) and an agent containing component (B), aqueous dispersions of the thickener composition shown in Tables 1 and 2 were prepared and evaluated as follows. The aqueous dispersions of the thickener composition contain, as active ingredients of the thickener composition, the components (A) and (B) in the parts by mass shown in Tables 1 and 2 per 100 parts by mass of water blended in the aqueous dispersion.

[0065] <Components of aqueous dispersion of thickener composition> The blended components used in Example 1 and Comparative Example 2 are shown below. The blended components used in Example 2 and Comparative Example 2, which will be described in detail later, are also shown here. <Component (A)> *The viscosity of a 2% by weight aqueous solution of each component at 20°C (catalog value) is shown in parentheses for each component. A-1: Hydroxypropyl cellulose (1,000-4,000 mPa·s), manufactured by Tokyo Chemical Industry Co., Ltd. A-2: Hydroxypropyl cellulose (150-400 mPa·s), manufactured by Tokyo Chemical Industry Co., Ltd. <Component (A')> A'-1: Methylcellulose (3,500-5,600 mPa·s), manufactured by Tokyo Chemical Industry Co., Ltd. A'-2: Hydroxyethyl cellulose (4,500-6,500 mPa·s), manufactured by Tokyo Chemical Industry Co., Ltd. A'-3: Sodium carboxymethylcellulose, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. A'-4: Hydroxypropyl methylcellulose (100,000 mPa·s), Metolose 90SH-100000, manufactured by Shin-Etsu Chemical Co., Ltd. A'-5: Hydroxypropyl methylcellulose (4,000 mPa·s), Metolose 60SH-4000, manufactured by Shin-Etsu Chemical Co., Ltd. <(B) component> (B) Component: sodium salt of naphthalenesulfonic acid formalin condensate (weight average molecular weight: 13,000), manufactured by Kao Corporation <(C) component> Water: Tap water (Wakayama City tap water, specific gravity 1.00) <Hydraulic powder> Plaster: Sakura brand A-grade calcined gypsum, manufactured by Yoshino Gypsum Co., Ltd.

[0066] (1) Preparation of aqueous dispersion of thickener composition Water and component (B) were placed in a 100 mL disposable cup and stirred for 10 seconds with a stirrer (Pencil Mixer DX, AS ONE Corporation, stirring rod type 3, rotation speed 7,000 rpm) to prepare an aqueous solution containing component (B). Water was added so that the total mass of the water placed in the disposable cup and the water in which component (B) was dissolved was 100 g. In addition, component (B) was added to the disposable cup so that the solid mass (g) per 100 g of water was the mass parts shown in Tables 1 and 2. Next, to this aqueous solution was added component (A) or component (A') in an amount of parts by mass (g) of solid content per 100 g of water as shown in Table 1 or 2, and the mixture was stirred for 2 minutes with a stirrer (Pencil Mixer DX, AS ONE Corporation, Stirring Rod Type 3, rotation speed 7,000 rpm) to prepare an aqueous dispersion of the thickener composition.

[0067] (2) Evaluation of the degree of dispersion of lumps in an aqueous dispersion of a thickener composition The aqueous dispersion of the thickener composition prepared by the method described in (1) was visually observed, and the degree of dispersion of the lumps in the aqueous dispersion of the thickener composition was evaluated based on the following index. The results are shown in Tables 1 and 2. [Indicator of the degree of dispersion of powder] ○: No splices were found, or splices less than 2 mm in diameter were found. ×: Spikes with a diameter of 2 mm or more were observed.

[0068] (3) Measurement of Viscosity of Water Dispersion of Thickener Composition The viscosity of the aqueous dispersion of the thickener composition prepared by the method described in (1) was measured using a B-type viscometer (Tokyo Keiki Co., Ltd.) at 20°C, No. 2 rotor, and 60 rpm, and the viscosity was recorded 10 seconds after the start of the measurement. If the viscosity exceeded 500 mPa·s when measured with the No. 2 rotor under these conditions (hereinafter referred to as the No. 2 measurement), the viscosity was measured at 20°C, No. 2 rotor, and 6 rpm, and the viscosity was recorded 10 seconds after the start of the measurement. If the viscosity exceeded 5,000 mPa·s when measured with the No. 2 rotor, the viscosity was measured at 20°C, No. 4 rotor, and 60 rpm, and the viscosity was recorded 10 seconds after the start of the measurement. If the viscosity exceeded 10,000 mPa·s when measured with the No. 4 rotor, the viscosity was measured at 20°C, No. 4 rotor, and 6 rpm, and the viscosity was recorded 10 seconds after the start of the measurement. The results are shown in Tables 1 and 2.

[0069] (4) Evaluation of the effect of component (B) on improving aqueous dispersions of cellulose ether-based thickeners Based on the viscosity of the aqueous dispersion of the thickener composition measured and recorded by the method described in (3) (hereinafter referred to as viscosity A) and the viscosity of an aqueous dispersion of a comparative thickener composition containing the same component (A) or (A') as the thickener composition but not containing the component (B) (hereinafter referred to as viscosity B), the degree of thickening improvement (times) was calculated according to the following formula (1). The results are shown in Tables 1 and 2. In Table 1, the viscosity of the dispersion of the thickener composition of Comparative Example 1-1 or Comparative Example 1-2 was used as viscosity B, and in Table 2, the viscosity of the dispersion of the thickener composition of Comparative Example 1-8 etc. was used as viscosity B. Viscosity improvement rate (times) = (viscosity A) / (viscosity B) (1)

[0070] [Table 1]

[0071] [Table 2]

[0072] *1: In Tables 1 and 2, the parts by mass of component (A) or component (B) are the parts by mass of component (A) or component (B) per 100 parts by mass of water. *2: In Table 2, the column for component (A) also shows component (A'), which is a comparative component to component (A), for ease of explanation.

[0073] In Table 1, Examples 1-1 to 1-6 showed superior thickening properties compared to Comparative Examples 1-1 to 1-4, and Examples 1-7 and 1-8 showed superior thickening properties compared to Comparative Examples 1-7 to 1-9. This is believed to be because hydroxypropyl cellulose, represented by components A-1 and A-2, was efficiently dispersed while the formation of a network structure and thickening were promoted by the addition of naphthalenesulfonic acid-formaldehyde condensate.

[0074] <Example 2 and Comparative Example 2> (1) Preparation of gypsum paste Water and component (B) were added to a 100 mL disposable cup, and the mixture was stirred for 10 seconds with a stirrer (Pencil Mixer DX, AS ONE Corporation, stirrer type 3, rotation speed 7,000 rpm) to prepare an aqueous solution. Water was added so that the total mass of the water added to the disposable cup and the water in which component (B) was dissolved was 50 g. Component (B) was added to the disposable cup so that the solid mass (g) per 100 g of the total mass of water added to the disposable cup was the mass part shown in Table 3. Next, 50 g of gypsum and half the mass of component (A) listed in Table 3 were mixed by inversion in a polyethylene bag for 10 seconds, and the mixed powder was then poured into a 100 mL disposable cup containing water and component (B) and stirred for 2 minutes with a mixer (Pencil Mixer DX, AS ONE Corporation, Stirring Rod Type 3, rotation speed 7,000 rpm) to prepare a gypsum paste.

[0075] (2) Measurement of viscosity of gypsum paste The viscosity of the gypsum paste prepared by the method described in (1) was measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 20 ° C., No. 2 rotor, 60 rpm, and the viscosity was recorded 10 seconds after the start of the measurement. If the viscosity exceeded 500 mPa·s in the measurement with the No. 2 rotor under these conditions (hereinafter referred to as the measurement with No. 2), the viscosity was measured at 20 ° C., No. 2 rotor, 6 rpm, and the viscosity was recorded 10 seconds after the start of the measurement. If the viscosity exceeded 5,000 mPa·s in the measurement with the No. 2 rotor, the viscosity was measured at 20 ° C., No. 4 rotor, 60 rpm, and the viscosity was recorded 10 seconds after the start of the measurement. If the viscosity exceeded 10,000 mPa·s in the measurement with the No. 4 rotor, the viscosity was measured at 20 ° C., No. 4 rotor, 6 rpm, and the viscosity was recorded 10 seconds after the start of the measurement. The results are shown in Table 3.

[0076] [Table 3]

[0077] In Table 3, Example 2-1 showed excellent viscosity development in the early stage of kneading the gypsum paste compared to Comparative Example 2-1. This is considered to be because hydroxypropyl cellulose represented by Components A-1 and A-2 was efficiently dispersed in the gypsum paste while the formation of a network structure and thickening were promoted by the addition of naphthalenesulfonic acid-formaldehyde condensate.

Claims

1. A thickener composition comprising (A) hydroxypropyl cellulose (hereinafter referred to as component (A)) and (B) an aromatic sulfonic acid-formalin condensate or a salt thereof (hereinafter referred to as component (B)).

2. 2. The thickener composition according to claim 1, wherein the mass ratio (B) / (A) of the content of the component (B) to the content of the component (A) is 0.02 or more and 2.5 or less.

3. 3. The thickener composition according to claim 1, wherein a 2% by mass aqueous solution of the component (A) has a viscosity at 20°C of 10 mPa·s or more and 10,000 mPa·s or less.

4. 3. The thickener composition according to claim 1, wherein the weight average molecular weight of component (B) is 1,000 or more and 200,000 or less.

5. The thickener composition according to claim 1 or 2, further comprising (C) water.

6. The thickener composition according to claim 1 or 2, which is for use in an aqueous dispersion of an inorganic powder.

7. The thickener composition according to claim 6 , wherein the inorganic powder is a hydraulic powder.

8. 1. A thickener composition additive for use in a thickener composition containing (A) hydroxypropyl cellulose, the thickener composition additive comprising (B) an aromatic sulfonic acid-formalin condensate or a salt thereof.

9. A powder mixture comprising a hydraulic powder, (A) hydroxypropyl cellulose, and (B) an aromatic sulfonic acid-formalin condensate or a salt thereof.

10. A hydraulic composition comprising a hydraulic powder, water, (A) hydroxypropyl cellulose, and (B) an aromatic sulfonic acid-formalin condensate or a salt thereof.