Method for producing powdery thickener composition

Abstract

To provide a method for producing a powdery thickener composition having excellent moisture resistance.SOLUTION: A method for producing a powdery thickener composition includes mixing (A) two or more compounds represented by the formula (1), (B) aromatic sulfonic acid or a salt thereof, (C) a water-soluble polymer compound, and (D) inorganic powder. The (A) two or more compounds have different X's in the formula (1). In at least one of the two or more compounds, R1a or R1b of X in the formula (1) is a compound of alkenyl group. A liquid component containing the components (A) and (B) is mixed with a powdery component containing the (D) component. The formula (1) is: N-X(R2)(R3) →O [where X is a group represented by R1a or R1b-[CONH-CH2CH2CH2]n-. R1a and R1b each represent an alkyl group or alkenyl group having a predetermined number of carbon atoms. n is an integer of 1-3. R2 and R3 each represent a C1-4 alkyl group or -(C2H4O)pH. p is a total of R2 and R3 to represent 0-5].SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a powdered thickener composition. [Background technology]

[0002] Thickeners are widely used in foods, cosmetics, and other industrial products, and increase the viscosity of the system by retaining and binding solvents, dispersants, and dispersoids, thereby achieving the appropriate texture required for each application and improving the stability of the system.

[0003] Based on the idea that thickeners hold and restrain solvents, dispersion media, and dispersoids, their molecular design is considered to have structural units that exhibit an interactive force with solvents, dispersion media, and dispersoids. Typical thickeners include cellulose ether-based thickeners, acrylic-based thickeners, polyvinyl alcohol-based thickeners, polyoxyethylene-based thickeners, clay-based thickeners, and surfactant-based thickeners.

[0004] Furthermore, because thickeners exhibit their thickening properties by dissolving or dispersing in a solvent or dispersant, most of them are distributed in powder form, with the solvent or dispersant removed as much as possible, from the standpoint of handling and transportation.

[0005] In hydraulic slurries containing hydraulic powder such as cement, thickeners (rheology modifiers) are sometimes used to improve physical properties such as viscosity and resistance to material separation. Patent Document 1 discloses a rheology modifier characterized by the combined use of two different types of amine oxide surfactants. Patent Document 2 discloses a method of spray-drying an amine oxide together with a carrier salt. Patent Document 3 discloses a method of powdering an aqueous solution or an alcoholic aqueous solution of an amine oxide by supporting it on zeolite. Patent Document 4 discloses a method for producing solid granules having improved storage stability and attrition resistance by adding a hygroscopic polyol. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2020-76022 [Patent Document 2] Special Publication No. 49-1443 [Patent Document 3] Japanese Patent Application Publication No. 57-54159 [Patent Document 4] Special Publication No. 2007-535597 Summary of the Invention [Problem to be solved by the invention]

[0007] Since surfactant thickeners form higher-order structures to modify the rheology of aqueous solutions or slurries, anionic aromatic compounds may be added to adjust the interaction between the surfactants to improve or optimize their functionality.

[0008] However, many anionic aromatic compounds are hygroscopic or deliquescent, and when used in powder form, there is a risk that their storage stability may be impaired due to moisture absorption.

[0009] The present invention provides a method for producing a powdery thickener composition that has excellent moisture resistance. [Means for solving the problem]

[0010] The present invention provides a method for producing a powdery thickener composition, which comprises mixing (A) two or more compounds represented by the following general formula (1) [hereinafter referred to as component (A)], (B) an aromatic sulfonic acid or a salt thereof [hereinafter referred to as component (B)], (C) a water-soluble polymer compound [hereinafter referred to as component (C)], and (D) an inorganic powder [hereinafter referred to as component (D)], The two or more compounds of (A) have different X's in the general formula (1), and at least one of the two or more compounds has R of X's in the general formula (1). 1a or R1b is a compound having an alkenyl group, The present invention relates to a method for producing a powdery thickener composition, which comprises mixing a liquid component containing components (A) and (B) with a powdery component containing at least component (D). [ka] [Wherein X is R 1a or R 1b -[CONH-CH2CH2CH2] n R is a group represented by the formula 1a R is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 14 to 22 carbon atoms. 1b is an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. n is an integer of 1 to 3. 2 and R 3 are each independently an alkyl group having 1 to 4 carbon atoms or -(C2H4O) p H. p is the average number of moles added, and R 2 and R 3 The sum of these is a number between 0 and 5. [Effects of the Invention]

[0011] According to the present invention, a method for producing a powdery thickener composition having excellent moisture resistance can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0012] In recent years, the Sustainable Development Goals (SDGs) have been proposed to realize a sustainable society. By providing a powdery thickener composition with excellent moisture resistance, the present invention is considered to be a technology that can contribute to achieving SDGs Nos. 6, 7, 8, 9, 11, 12, 13, and 14, for example.

[0013] The inventors have found that if a mixture of (A) two or more compounds represented by the above general formula (1) and (B) an aromatic sulfonic acid or a salt thereof is mixed, and the mixture is supported on (D) an inorganic powder and powdered, the moisture resistance of the resulting powdery thickener composition is improved.

[0014] The mechanism by which the moisture resistance of the powdery thickener composition obtained by the present invention is improved is not entirely clear, but is presumed to be as follows. The hygroscopicity of the (B) aromatic sulfonic acid compound is presumed to be due to functional groups and their salts that have a high affinity for water molecules, and moisture absorption can be considered to be based on the penetration of water vapor into the medium at a microscopic level. On the other hand, the surfactant of component (A) is known to take various forms depending on its concentration in the composition, forming surfactant complexes such as micelles and lamellae at high concentrations, and high-concentration surfactant complexes are known to suppress the dissipation (transfer) of moisture. The (C) water-soluble polymer compound can strongly interact with water to reduce the amount of free water in a surfactant solution, and therefore is thought to locally form high-concentration surfactant complexes, reducing the permeability of water vapor and thereby reducing the moisture absorption of the powdery thickener composition. However, the present invention is not limited to this mechanism of action.

[0015] First, the components used in the method for producing the powdery thickener composition of the present invention will be described. In the present invention, a powdery thickener composition (hereinafter referred to as the powdery thickener composition of the present invention) is produced by mixing multiple components including (A) two or more compounds represented by the above general formula (1) [hereinafter referred to as component (A)], (B) an aromatic sulfonic acid or a salt thereof [hereinafter referred to as component (B)], (C) a water-soluble polymer compound [hereinafter referred to as component (C)], and (D) an inorganic powder [hereinafter referred to as component (D)].

[0016] The component (A) is two or more compounds selected from the compounds represented by the general formula (1) (hereinafter also referred to as compound (1)). The two or more compounds of the component (A) have different X's in the general formula (1), and at least one of the two or more compounds has a different R of X's in the general formula (1). 1a or R 1b is a compound having an alkenyl group.

[0017] Regarding the compound (1), when X in the general formula (1) is different, for example, when there are two kinds of compound (1), the following embodiments can be mentioned. In the following embodiments, R of at least one of the two kinds of compound (1) is different. 1a or R 1b is an alkenyl group. (i) One R 1a or R 1b is an alkyl group, and the other R 1a or R 1b is an alkenyl group. (ii) One R 1a or R 1b The number of carbon atoms in the other R 1a or R 1b The carbon numbers are different. (iii) One of the Xs is R 1a and the other X is R 1b -[CONH-CH2CH2CH2] n -It is. (iv) Both X and R 1b -[CONH-CH2CH2CH2] n - and one n is different from the other n. (v) A combination of (i) to (iv) above.

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

[0019] The powdery thickener composition of the present invention contains two or more, preferably five or less, more preferably two, compounds (1) having different X's in general formula (1). At least one of the two or more compounds (1) contained in the powdery thickener composition has a different R of X's in general formula (1). 1a or R 1b is an alkenyl group having 14 to 22 carbon atoms, that is, R in X in general formula (1) 1a an alkenyl group having 14 to 22 carbon atoms as R 1b It is a compound containing an alkenyl group having 13 to 21 carbon atoms as the alkyl group.

[0020] In the present invention, there are two types of compound (1), and one of the two types of compound (1), including the above (i) to (v), is a compound in which X in the general formula (1) is R 1a and a compound having an alkenyl group with a carbon number of 14 to 22. That is, the component (A) is two compounds selected from the compounds represented by the general formula (1), and the two compounds of the component (A) have different X in the general formula (1), and one of the two compounds has X in the general formula (1) that is R 1a and R 1a is an alkenyl group.

[0021] The component (A) is a compound in which X in the general formula (1) is R 1a or R 1b -[CONH-CH2CH2CH2]n - (wherein R 1a is an alkenyl group having 14 to 22 carbon atoms, and R 1b is an alkenyl group having from 13 to 21 carbon atoms), and compound (1b) in which X in general formula (1) is different from compound (1a). Specifically, the component (A) may include a compound (1a) represented by the following general formula (1a) and a compound (1b) represented by the following general formula (1b).

[0022] [ka]

[0023] [During the ceremony, n1 and n2 each independently represent an integer of 0 or more and 3 or less. R 11a When n1 is 0, it is an alkenyl group having 14 to 22 carbon atoms, and when n1 is 1 to 3, it is an alkenyl group having 13 to 21 carbon atoms. R 11b When n2 is 0, it is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 14 to 22 carbon atoms, and when n2 is 1 to 3, it is an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. However, if n1 and n2 are the same number, R 11b The alkenyl group in R 11a is an alkenyl group different from R 2 and R 3 are each independently an alkyl group having 1 to 4 carbon atoms or -(C2H4O) p H. p is the average number of moles added, and R 2 and R 3 The sum of these is a number between 0 and 5.

[0024] In general formula (1a), R 11a The number of carbon atoms is preferably 17 or more and preferably 22 or less. In the general formula (1a), n1 is preferably 0 or 1, and more preferably 0.

[0025] In the general formula (1b), n2 is 0 and R 11b When is an alkyl group, R 11b The number of carbon atoms is preferably 16 or more and preferably 22 or less. In the general formula (1b), n2 is 0 and R 11b When is an alkenyl group, R 11b The number of carbon atoms is preferably 18 or more and preferably 22 or less. In the general formula (1b), n2 is 1 to 3 and R 11b When is an alkyl group, R 11b The number of carbon atoms is preferably 15 or more and preferably 21 or less. In the general formula (1b), n2 is 1 to 3 and R 11b When is an alkenyl group, R 11b The number of carbon atoms is preferably 17 or more and preferably 21 or less. In general formula (1b), R 11b is preferably an alkyl group. In the general formula (1b), n2 is preferably 0 or 1.

[0026] In general formula (1a) or (1b), R 2 and R 3 are each independently preferably an alkyl group having 1 or 2 carbon atoms or -(C2H4O) p It is a group represented by H, and more preferably an alkyl group having 1 or 2 carbon atoms. In the general formula (1a) or (1b), p is preferably a number of 0 or more and 3 or less. If n1 and n2 are the same number, R 11b The alkenyl group in R 11a is an alkenyl group different from

[0027] A preferred embodiment of the component (A) of the present invention includes a compound (11a) represented by the following general formula (11a) and a compound (1b) represented by the following general formula (1b).

[0028] [ka]

[0029] [During the ceremony, n2 is an integer between 0 and 3 inclusive. R 11a is an alkenyl group having 14 to 22 carbon atoms. R 11b When n2 is 0, it is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 14 to 22 carbon atoms, and when n2 is 1 to 3, it is an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. However, if n2 is 0, R 11b The alkenyl group in R 11a is an alkenyl group different from R 2 and R 3 are each independently an alkyl group having 1 to 4 carbon atoms or -(C2H4O) p H. p is the average number of moles added, and R 2 and R 3 The sum of these is a number between 0 and 5.

[0030] The compound (11a) represented by the general formula (11a) corresponds to the compound in which n1 is 0 in the general formula (1a). 11a , R 2 and R 3 The preferred embodiments of the compound (1b) are the same as those of the general formula (1a). In this combination, the preferred embodiments of the compound (1b) are the same as those of the general formula (1a).

[0031] In component (A), the mass ratio of compound (1b) / compound (1a) is preferably 5 / 95 or more, more preferably 25 / 75 or more, even more preferably 40 / 60 or more, and is preferably 95 / 5 or less, more preferably 75 / 25 or less, even more preferably 60 / 40 or less, from the viewpoint of obtaining a rheology-modifying effect, for example, high viscoelasticity, over a wider temperature range.

[0032] In component (A), the mass ratio of compound (1b) / compound (11a) is preferably 5 / 95 or more, more preferably 25 / 75 or more, even more preferably 40 / 60 or more, and is preferably 95 / 5 or less, more preferably 75 / 25 or less, even more preferably 60 / 40 or less, from the viewpoint of obtaining a rheology-modifying effect, for example, high viscoelasticity, over a wider temperature range.

[0033] The powdery thickener composition of the present invention preferably contains a small amount of compounds having a structure similar to that of compound (1) and having an alkyl group or alkenyl group with a small number of carbon atoms. Specifically, it is preferable that the content of amine oxides having an alkyl group with less than 14 carbon atoms, an alkenyl group with less than 14 carbon atoms, or an acyl group with less than 14 carbon atoms (hereinafter also referred to as short-chain amine oxides) is small. The powdery thickener composition of the present invention preferably has a mass ratio of the total content of short-chain amine oxides to the total content of compound (1) of 50 / 50 or less, more preferably 25 / 75 or less, even more preferably 10 / 90 or less, and even more preferably 0 / 100, i.e., does not contain any short-chain amine oxides. For convenience, when considered in terms of general formula (1), a short-chain amine oxide is a compound represented by the formula: 1a is an alkyl group having less than 14 carbon atoms or an alkenyl group having less than 14 carbon atoms, and 1b is an alkyl group having less than 13 carbon atoms or an alkenyl group having less than 13 carbon atoms.

[0034] Component (B) is an aromatic sulfonic acid or a salt thereof. Examples of component (B) include one or more compounds selected from sulfonic acids having an aromatic ring or salts thereof. Component (B) is preferably an acid-type compound having a total carbon number of 6 to 12. Specific examples of component (B) include salicylic acid, p-toluenesulfonic acid, sulfosalicylic acid, m-sulfobenzoic acid, p-sulfobenzoic acid, 4-sulfophthalic acid, 5-sulfoisophthalic acid, p-phenolsulfonic acid, m-xylene-4-sulfonic acid, cumenesulfonic acid, and styrenesulfonic acid. These may form salts. Two or more types of component (B) may be used. Examples of salts include sodium salts, potassium salts, and calcium salts, with sodium salts and calcium salts being preferred.

[0035] Component (C) is a water-soluble polymer compound. Examples of component (C) include (C1) nonionic polymer compounds such as polyalkylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, and alcohol alkoxylate, and (C2) cationic polymer compounds such as polyamidepolyamine / epichlorohydrin condensates, dimethylamine / ammonia / epichlorohydrin condensates, dimethylamine / trimethylamine / epichlorohydrin condensates, vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymers, quaternized polyethyleneimines to which a polyoxyalkylene group may be added, and vinylpyrrolidone / alkylaminoacrylate copolymers. The polyvinyl alcohol may be a fully saponified polyvinyl alcohol or a partially unsaponified polyvinyl alcohol, for example, an intermediately saponified polyvinyl alcohol or a partially saponified polyvinyl alcohol, with a partially saponified polyvinyl alcohol being preferred. The alcohol alkoxylate may be an ether compound having a hydrocarbon group, preferably a hydrocarbon group having from 10 to 22 carbon atoms, and a polyoxyalkylene group having an average addition molar number of from 9 to 5,000. From the viewpoint of versatility, component (C) is preferably one or more polymeric compounds selected from polyalkylene glycol, polyvinyl alcohol, and polyvinylpyrrolidone, more preferably polyalkylene glycol and polyvinyl alcohol, and even more preferably polyethylene glycol, polypropylene glycol, a copolymer of ethylene oxide and propylene oxide, and polyvinyl alcohol. In the component (C), the water-soluble polymer compound may be a polymer compound that dissolves 1 g or more in 100 g of water at 20°C.

[0036] From the viewpoint of versatility, the weight-average molecular weight of component (C) is preferably 500 or more, more preferably 1,000 or more, and even more preferably 2,000 or more, and from the viewpoint of rheology-modifying effect, it is preferably 200,000 or less, more preferably 150,000 or less, even more preferably 100,000 or less, still more preferably 30,000 or less, and even more preferably 5,000 or less. The weight-average molecular weight of component (C) was measured by gel permeation chromatography (GPC) under the following conditions. *GPC conditions Apparatus: 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: 0.2 mg / mL Standard substance: Polyethylene glycol equivalent (monodisperse polyethylene glycol: molecular weight 250,000, 145,000, 87,500, 46,000, 24,000)

[0037] Component (D) is an inorganic powder, such as powders of inorganic salts such as calcium carbonate and calcium silicate, powders of clay minerals such as kaolinite and bentonite, fine powders of blast furnace slag and fly ash, sodium sulfate, aluminum sulfate, zeolite, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica powder (including fine silica powder and fine porous silica powder), or any combination thereof. Component (D) is preferably an inorganic powder having liquid-carrying ability, and from the viewpoint of anti-caking properties, silica powder (including fine silica powder and porous silica powder), powders of inorganic salts such as calcium carbonate and calcium silicate are preferred, and silica powder (including fine silica powder and porous silica powder) is more preferred.

[0038] In the present invention, the term "having a liquid-holding capacity" of component (D) means that the oil absorption capacity according to the method described in JIS K6220(-1995) is 100 ml / 100 g or more. The oil absorption capacity of component (D) is preferably 200 ml / 100 g or more, and preferably 450 ml / 100 g or less, more preferably 350 ml / 100 g or less.

[0039] The average particle size of component (D) is preferably 5 μm or more, more preferably 10 μm or more, and preferably 200 μm or less, more preferably 100 μm or less. This average particle size is calculated on a volume basis and is a value measured using a laser diffraction flow distribution analyzer: LA-920 (manufactured by Horiba, Ltd.).

[0040] From the viewpoint of miscibility, the specific surface area of ​​component (D) is preferably 50 m 2 / g or more, more preferably 100m 2 / g or more, and from the viewpoint of oil absorption capacity, preferably 300m 2 / g or less, more preferably 200m 2 / g or less. This specific surface area was measured using a fully automatic specific surface area measuring device, Macsorb HM-model 1201 (manufactured by Mountec Co., Ltd.).

[0041] The amorphous silica of component (D) can be, for example, synthetic amorphous silica commercially available as Nipsil NS-K (manufactured by Tosoh Silica Corporation). Here, amorphous silica refers to silica that has a network structure of Si-O and does not have a fixed crystalline structure.

[0042] <Composition and other components of the powdery thickener composition of the present invention> The powdery thickener composition of the present invention may contain component (A) in an amount of preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more from the viewpoint of thickening properties, and preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 15% by mass or less, and even more preferably 10% by mass or less from the viewpoint of the flowability of the powdery thickener composition.

[0043] The powdery thickener composition of the present invention may contain component (B) in an amount of preferably 1.0% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2.0% by mass or more from the viewpoint of thickening ability, and preferably 50.0% by mass or less, more preferably 30.0% by mass or less, even more preferably 15.0% by mass or less, and even more preferably 10.0% by mass or less from the viewpoint of storage stability.

[0044] In the powdery thickener composition of the present invention, the mass ratio (B) / (A) of the contents of the (A) component and the (B) component is preferably 0.01 or more, more preferably 0.25 or more, and even more preferably 0.50 or more from the viewpoint of thickening property, and is preferably 5.00 or less, more preferably 2.50 or less, even more preferably 1.50 or less, and even more preferably 1.00 or less from the viewpoint of storage stability.

[0045] The powdery thickener composition of the present invention may contain component (C) in an amount of preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more from the viewpoint of versatility, and preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less from the viewpoint of thickening properties.

[0046] In the powdery thickener composition of the present invention, the mass ratio (C) / (A) of the content of component (A) to the content of component (C) is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more from the viewpoint of versatility, and is preferably 20.0 or less, more preferably 10.0 or less, and even more preferably 5.0 or less from the viewpoint of thickening properties.

[0047] The powdery thickener composition of the present invention may contain component (D) in an amount of preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more from the viewpoint of the flowability of the powdery thickener composition, and in an amount of preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less from the viewpoint of thickening properties.

[0048] In the powdery thickener composition of the present invention, the mass ratio of the total content of the (A) component and the (B) component to the content of the (D) component, [(A) + (B)] / (D), is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.3 or more, from the viewpoint of thickening properties, and is preferably 2.0 or less, more preferably 1.5 or less, and even more preferably 1.0 or less, from the viewpoint of the flowability of the powdery thickener composition.

[0049] In the method for producing the powdery thickener composition of the present invention, an alcoholic solvent (E) (hereinafter referred to as component (E)) can be optionally used. Component (E) may be a compound having a molecular weight of less than 500, preferably less than 300, and having at least one hydroxyl group.

[0050] Examples of component (E) include alcohols such as methanol, ethanol, 1-propanol, benzyl alcohol, 2-phenoxyethanol, and diethylene glycol monobutyl ether, and glycol solvents such as propylene glycol, ethylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol, and 1,3-butanediol. These compounds may be used in combination as component (E). From the viewpoint of the thickening properties of the powdery thickener composition, component (E) is preferably a glycol-based solvent such as propylene glycol, ethylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol, or 1,3-butanediol, more preferably propylene glycol, ethylene glycol, or dipropylene glycol, and more preferably propylene glycol or ethylene glycol.

[0051] When the powdery thickener composition of the present invention contains component (E), the composition may contain component (E) in an amount of preferably 1% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more from the viewpoint of powdering efficiency, and preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less from the viewpoint of thickening properties.

[0052] The powdery thickener composition of the present invention may optionally contain a cement wetting agent, an expanding agent, a waterproofing agent, a retarder, a quick-setting agent, a foaming agent, a foaming agent, a waterproofing agent, a superplasticizer, a thickener other than the powdery thickener composition of the present invention, a flocculating agent, a drying shrinkage-reducing agent, a strength-enhancing agent, a hardening accelerator, a preservative, an antifoaming agent, a dispersant, water, and a solvent other than component (E). The water may be water mixed in during the production of component (A).

[0053] <Method of producing the powdery thickener composition of the present invention> The method for producing a powdery thickener composition of the present invention is a method for producing a powdery thickener composition by mixing (A) two or more compounds represented by the above general formula (1), (B) an aromatic sulfonic acid or a salt thereof, (C) a water-soluble polymer compound, and (D) an inorganic powder, The two or more compounds of (A) have different X's in the general formula (1), and at least one of the two or more compounds has R of X's in the general formula (1). 1a or R 1b is a compound having an alkenyl group, A liquid component containing the components (A) and (B) is mixed with a powder component containing at least the component (D).

[0054] In the method for producing the powdery thickener composition of the present invention, component (A) and component (B) are mixed to obtain a liquid component containing component (A) and component (B). The liquid component may contain water, or may contain water mixed in during the synthesis of component (A). When preparing the liquid component, water or component (E) may be mixed into the liquid component.

[0055] The amount of component (A) mixed relative to the total amount of mixed components used in the production of the powdered thickener composition is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of thickening properties, and is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 15% by mass or less, and even more preferably 10% by mass or less, from the viewpoint of the flowability of the powdered thickener composition.

[0056] The amount of component (B) mixed, relative to the total amount of mixed components used in the production of the powdery thickener composition, is preferably 1.0 mass% or more, more preferably 1.5 mass% or more, and even more preferably 2.0 mass% or more, from the viewpoint of thickening properties, and is preferably 50.0 mass% or less, more preferably 30.0 mass% or less, even more preferably 15.0 mass% or less, and even more preferably 10.0 mass% or less, from the viewpoint of storage stability.

[0057] The mass ratio (B) / (A) of the amount of component (A) mixed to the amount of component (B) mixed is preferably 0.01 or more, more preferably 0.25 or more, and even more preferably 0.50 or more, from the viewpoint of thickening properties, and is preferably 5.00 or less, more preferably 2.50 or less, even more preferably 1.50 or less, and even more preferably 1.00 or less, from the viewpoint of storage stability.

[0058] In the method for producing the powdery thickener composition of the present invention, a liquid component containing the components (A) and (B) is mixed with a powdery component containing at least the component (D). In the present invention, a powdery thickener composition having excellent moisture resistance can be produced by mixing a liquid component containing components (A) and (B) with component (D). Component (C) can be mixed with the liquid component containing components (A) and (B), with component (D) before it is mixed with the liquid component, or with component (D) after it has been mixed with the liquid component, and it is preferable to mix component (C) with component (D) before it is mixed with the liquid component. When component (E) is used, it is preferable to mix a liquid component containing component (E) with a powder component containing at least component (D).

[0059] The amount of component (C) mixed relative to the total amount of mixed components used in the production of the powdery thickener composition is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, from the viewpoint of versatility, and is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of thickening properties.

[0060] The mass ratio (C) / (A) of the amount of component (C) mixed to the amount of component (A) mixed is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more from the viewpoint of versatility, and is preferably 20.0 or less, more preferably 10.0 or less, and even more preferably 5.0 or less from the viewpoint of thickening properties.

[0061] The amount of component (D) mixed relative to the total amount of mixed components used in producing the powdered thickener composition is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of the fluidity of the powdered thickener composition, and is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less, from the viewpoint of thickening properties.

[0062] The mass ratio of the total amount of the (A) component and the (B) component to the amount of the (D) component, [(A) + (B)] / (D), is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.3 or more, from the viewpoint of thickening properties, and is preferably 2.0 or less, more preferably 1.5 or less, and even more preferably 1.0 or less, from the viewpoint of the flowability of the powdery thickener composition.

[0063] When component (E) is used in the method for producing the powdered thickener composition of the present invention, the amount of component (E) mixed relative to the total amount of mixed components used in producing the powdered thickener composition is preferably 1 mass% or more, more preferably 10 mass% or more, and even more preferably 20 mass% or more, from the viewpoint of powdering efficiency, and is preferably 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less, from the viewpoint of thickening properties.

[0064] In the method for producing the powdery thickener composition of the present invention, a liquid component containing components (A) and (B) and a powdery component containing at least component (D) are prepared, and the liquid component and powdery component are mixed to produce the powdery thickener composition. The liquid component may optionally contain component (E), and the powder component may contain component (C).

[0065] When a powdery thickener composition is produced by mixing a liquid component containing components (A) and (B) with a powdery component containing components (C) and (D), the mass ratio of the mixed amounts of the liquid component to the powdery component, (liquid component) / (powdered component), is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more, from the viewpoint of thickening property, and is preferably 5.0 or less, more preferably 3.0 or less, and even more preferably 1.0 or less, from the viewpoint of flowability of the powdery thickener composition. The mass of the liquid component may be the sum of the mixed amounts of components (A), (B), (E), and water mixed in during the production of component (A), and the mass of the powdery component may be the sum of the mixed amounts of components (C) and (D).

[0066] The content of component (D) in the powdered component is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, from the viewpoint of the flowability of the powdered thickener composition, and is preferably 100% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less, from the viewpoint of versatility.

[0067] In the method for producing the powdery thickener composition of the present invention, optionally, cement wetting agents, expanding agents, waterproofing agents, retarders, quick-setting agents, foaming agents, foaming agents, waterproofing agents, fluidizing agents, thickeners other than the powdery thickener composition of the present invention, flocculants, drying shrinkage reducing agents, strength enhancers, hardening accelerators, preservatives, antifoaming agents, and dispersants may be mixed.

[0068] The powdery thickener composition obtained by the method for producing a powdery thickener composition of the present invention has improved moisture resistance, and is useful as a thickener for, for example, hydraulic slurry compositions, coating compositions, electronic material compositions, polishing compositions, ejection compositions, pharmaceutical compositions, and sanitary compositions. [Example]

[0069] <Example 1 and Comparative Example 1> In Example 1 and Comparative Example 1, the following (A) amphoteric surfactant, (B) aromatic sulfonic acid or a salt thereof, (C) water-soluble polymer compound, (D) inorganic powder, and (E) alcoholic solvent were used.

[0070] (1) Components used in the preparation of the powdered thickener composition <Liquid ingredients> (A) Amphoteric surfactant (a-1): oleyldimethylamine oxide (in general formula (1a), R 11a : Alkenyl group with 18 carbon atoms (oleyl group), n1: 0, R 2 : Methyl group, R 3 : methyl group) (a-2): Oleic acid amide propyl dimethylamine oxide (in general formula (1a), R 11a : Alkenyl group having 17 carbon atoms, n1:1, R 2 : Methyl group, R 3 : methyl group) The component (A) used was a composition containing 30% by mass of effective solids and water. (B) Aromatic sulfonic acid (salt) (b-1): Sodium meta-xylene sulfonate monohydrate crystals, SXS-Y (manufactured by Itochu Chemical Frontier Corporation) (E) Alcoholic solvent (e-1): Propylene glycol (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0071] <Powdered ingredients> (C) Water-soluble polymer compound (c-1): Polyethylene glycol 4,000 (Fujifilm Wako Pure Chemical Industries, Ltd.) ·(c-2):Poly(ethylene oxide) average MV 200,000,powder(Merck KGaA) (D) Inorganic powder (d-1): Silica powder, Nipsil NS-K (manufactured by Tosoh Silica Corporation) (d-2): Ground blast furnace slag, Esment 4000 (manufactured by Nippon Steel Blast Furnace Cement Co., Ltd.)

[0072] (2) Method for producing powdery thickener composition First, a liquid component containing components (A), (B), and (E) was prepared in the proportions shown in Table 1. Specifically, components (A) and (B) were placed in a glass flask and vigorously stirred for 10 minutes using a magnetic stirrer to prepare a liquid component containing components (A) and (B). Next, a powdered component containing components (C) and (D) in the proportions shown in Table 1 was stirred for 10 seconds using a coffee mill GCM-56 (Device Style Holdings) to prepare a powdered component containing components (C) and (D). The liquid component containing components (A) and (B) was added to the obtained powder component and mixed for another minute until the powder became homogeneous, thereby producing a powdery thickener composition of the example. The powdery thickener composition of the example was passed through a sieve with 600 μm openings. On the other hand, a powdery thickener composition of the comparative example was produced by the following method. First, a powdery component containing components (B), (C), and (D) in the proportions shown in Table 1 was stirred for 10 seconds using a coffee mill GCM-56 (Device Style Holdings) to prepare a powdery component. Then, a liquid component containing component (A) was added to the obtained powdery component, and the mixture was mixed for another minute until the powder became homogeneous, thereby producing a powdery thickener composition of the comparative example. The powdery thickener composition used in the comparative example was one that had been passed through a sieve with an opening of 600 μm.

[0073] (3) Moisture resistance test, simple visual evaluation (appearance) The powdered thickener composition prepared by the method described in (2) was spread on an aluminum plate, and the mass (g) of the sample used in the moisture resistance test was recorded. The sample was then placed in a thermo-hygrostat PR-3J (manufactured by ESPEC EUROPE GmbH) under open conditions at a temperature of 30°C and a humidity of 90% RH for 12 hours. The sample was then removed, the aluminum plate was tilted 45 degrees vertically, and the powdered thickener composition was observed with the naked eye. The moisture resistance of the powdered thickener composition was evaluated based on the following criteria. The results are shown in Table 1. ○: No caking is observed and the product slides down evenly. ×: Some of the product has absorbed moisture and caking occurs, resulting in lumps that fall off.

[0074] (4) Evaluation of moisture resistance based on mass change of powdered thickener composition The mass (g) of the powdery thickener composition that had undergone the moisture resistance test according to the method described in (3) was measured, and the mass increment (%) of the powdery thickener composition was calculated based on the following formula. The results are shown in Table 1. It can be said that the smaller the mass increment of the powdery thickener composition, the more excellent its moisture resistance. Mass increment (%) = [[mass (g) of powdered thickener composition after moisture resistance test - mass (g) of powdered thickener composition subjected to moisture resistance test] × 100] / mass (g) of powdered thickener composition subjected to moisture resistance test

[0075] [Table 1]

[0076] *1: In the table, the amount of component (A) mixed is the amount of a composition containing 30 mass % of component (A) and water.

[0077] In Table 1, Examples 1-1 to 1-7 showed smaller mass increments (%) than Comparative Examples 1-1 to 1-5. This is thought to be because the formed surfactant complex inhibited the penetration of water vapor.

Claims

1. A method for producing a powdery thickener composition comprising mixing (A) two or more compounds represented by the following general formula (1) [hereinafter referred to as component (A)], (B) an aromatic sulfonic acid or a salt thereof [hereinafter referred to as component (B)], (C) a water-soluble polymer compound [hereinafter referred to as component (C)], and (D) an inorganic powder [hereinafter referred to as component (D)], The component (A) includes a compound (11a) represented by the following general formula (11a) and a compound (1b) represented by the following general formula (1b): A liquid component containing the (A) component and the (B) component is mixed with a powder component containing at least the (D) component; Method for producing a powdered thickener composition. 【Chemistry 1】 [Wherein X is R １ａ or R １ｂ -[CONH-CH ２ CH ２ CH ２ ] ｎ - is a group represented by R １ａ is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 14 to 22 carbon atoms. １ｂ is an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. n is an integer of 1 to 3. ２ and R ３ are each independently an alkyl group having 1 to 4 carbon atoms or -(C ２ H ４ O) ｐ H. p is the average number of moles added, and R ２ and R ３ The sum of these is a number between 0 and 5. 【Chemistry 2】 [During the ceremony, n2 is an integer of 1 or more and 3 or less. R 11a is an alkenyl group having 14 to 22 carbon atoms. R 11b is an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. R 2 and R 3 are each independently an alkyl group having 1 to 4 carbon atoms or a group represented by —(C 2 H 4 O) pH. p is the average number of moles added, and the total of R 2 and R 3 is a number of 0 to 5.

2. 2. The method for producing a powdery thickener composition according to claim 1, wherein the mass ratio (C) / (A) of the amount of component (C) mixed to the amount of component (A) mixed is 0.1 or more and 20.0 or less.

3. The method for producing a powdery thickener composition according to claim 1 or 2, wherein the liquid component further comprises (E) an alcoholic solvent.

4. The powder component includes component (C), 4. The method for producing the powdery thickener composition according to claim 1, wherein a liquid component containing the components (A) and (B) is prepared, and then the liquid component is mixed with the powdery component.

5. 5. The method for producing a powdery thickener composition according to claim 1, wherein the mass ratio of the total amount of the components (A) and (B) mixed to the amount of the component (D), [(A) + (B)] / (D), is 0.1 or more and 2.0 or less.

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