Gypsum slurry containing gas bubbles

Abstract

The present invention provides a bubble-containing gypsum slurry capable of increasing the bubble diameter in the gypsum slurry with a small amount of a foaming component in a bubble-containing gypsum slurry of the same specific gravity, and a method for producing the same. The bubble-containing gypsum slurry of the present invention contains a hydraulic powder including gypsum, water, the following (A1) component, an optional following (A2) component, and the following (B) component, and the mass ratio (B) / [(A1)+(A2)] of the content of the (B) component to the total content of the (A1) component and the (A2) component is 0.05 or more and 0.5 or less. The (A1) component is an alkyl or alkenyl sulfate or a salt thereof; the (A2) component is one or more selected from surfactants other than the (A1) component; and the (B) component is a nonionic compound having a LogP of 0 or more and 3.0 or less.

Description

Technical Field

[0001] This invention relates to gypsum slurry containing air bubbles and its manufacturing method. Background Technology

[0002] Lightweighting is achieved by introducing air bubbles into hydraulic compositions that use cement or gypsum as hardeners. Generally, lightweight hydraulic compositions containing air bubbles are manufactured by mixing foam obtained by foaming a liquid composition containing a foaming agent and water with a hydraulic composition, or fine aggregates, or various admixtures.

[0003] Japanese Patent Application Publication No. 7-291761 discloses a lightweight foaming agent for manufacturing gypsum board, comprising 100 parts of an anionic surfactant selected from the sulfates of ethylene oxide adducts of higher alcohols having carbon numbers of 8 and 10, and 5 to 100 parts of a 1 to 2 molar adduct of ethylene oxide from alcohols having carbon numbers of 1 to 4. According to the disclosure, this lightweight foaming agent for manufacturing gypsum board can achieve the desired volume with a small amount of usage, exhibits excellent adhesion between the base paper and the gypsum core even in the case of low-density gypsum board, and displays high core strength. Furthermore, in the examples, a foaming agent containing 35% by mass of alkyl ether sulfate and 17% by mass of ethylene glycol monobutyl ether is disclosed.

[0004] Japanese Patent Application Publication No. 2003-313060 discloses a hydraulic composition foaming agent containing an alkyl ether sulfate salt having a hydrocarbon group of 8 to 18 carbons and an alcohol having a carbon group of 8 to 18 carbons in a specific weight ratio. This hydraulic composition foaming agent can form stable foam when mixed with hydraulic substances and is suitable for manufacturing lightweight hydraulic compositions. Furthermore, in the examples, a foaming agent containing sodium lauryl ether sulfate and octanol in a mass ratio of 75 / 25 is disclosed.

[0005] Japanese Patent Application Publication No. 2018-535909 discloses a gypsum board comprising a hardened gypsum core disposed between two facing sheets. The hardened gypsum core comprises at least a gypsum crystal matrix formed from water, plaster, and a foaming agent. The foaming agent is formed from a foaming agent comprising at least one alkyl sulfate, at least one alkyl ether sulfate, or any combination thereof, and an aliphatic alcohol. Furthermore, the gypsum board of the disclosed embodiment contains 30% by weight of a surfactant and 1% by weight of an aliphatic alcohol, using an alkyl ether sulfate and alkyl sulfate in a 40:60 ratio, and 1% 1-octanol is used as the aliphatic alcohol. Summary of the Invention

[0006] Hydraulic compositions containing air bubbles, particularly gypsum slurries containing air bubbles, using cement or gypsum as hardeners, achieve weight reduction due to the lower specific gravity caused by the presence of air bubbles. However, this weight reduction also leads to a decrease in strength. As described in paragraph 0004 of Japanese Patent Application Publication No. 10-330174, increasing the diameter of air bubbles in the hydraulic compositions containing air bubbles can help suppress the decrease in strength; however, there is a limit to the increase in bubble diameter. Therefore, in hydraulic compositions containing air bubbles with the same specific gravity, there is a need to establish a technique that specifically increases the diameter of air bubbles in gypsum slurries containing air bubbles, balancing both weight reduction and strength. Furthermore, from the viewpoints of reducing reagent costs, minimizing environmental impact during transportation, and facilitating regeneration (reducing reagent residues in recycled gypsum), there is a need for a low addition amount of foaming agent compositions that serve as foaming raw materials in hydraulic compositions containing air bubbles, particularly in gypsum slurries containing air bubbles.

[0007] This invention provides a gypsum slurry containing air bubbles that can increase the diameter of air bubbles in a gypsum slurry of the same specific gravity with a smaller amount of foaming component, and a method for manufacturing the same gypsum slurry containing air bubbles.

[0008] The present invention relates to a gypsum slurry containing air bubbles, comprising a hydraulic powder containing gypsum, water, the following (A1) component, optionally the following (A2) component, and the following (B) component, wherein the mass ratio of the content of component (B) to the total content of components (A1) and (A2) is 0.05 or more and 0.5 or less.

[0009] (A1) Ingredients: Alkyl or alkenyl sulfates or their salts;

[0010] (A2) Component: One or more surfactants selected from those other than (A1) component;

[0011] (B) Components: Nonionic compounds with LogP values ​​of 0 or higher and 3.0 or lower.

[0012] In addition, the present invention relates to a method for manufacturing a gypsum slurry containing air bubbles, the method comprising the following steps 1 and 2.

[0013] <Process 1>

[0014] A process for obtaining foam by foaming a liquid composition containing a hydraulic composition, a foaming agent composition, and water, wherein the foaming agent composition contains the above-mentioned component (A1), optionally the above-mentioned component (A2), the above-mentioned component (B), and water, and the mass ratio of the content of component (B) to the total content of components (A1) and (A2) (B) / [(A1)+(A2)] is 0.05 or more and 0.5 or less.

[0015] <Process 2>

[0016] The process of mixing the foam obtained in step 1 with a gypsum slurry containing gypsum-containing hydraulic powder and water to obtain a gypsum slurry containing air bubbles.

[0017] In addition, the present invention relates to a hardened body of gypsum slurry containing air bubbles, which is formed by hardening the gypsum slurry containing air bubbles of the present invention, wherein the average bubble diameter is 200 μm or more and 800 μm or less.

[0018] In addition, the present invention relates to the use of a foaming agent composition for hydraulic compositions as a foaming agent for gypsum slurry, wherein the foaming agent composition for hydraulic compositions contains the above-mentioned (A1) component, optionally the above-mentioned (A2) component, the above-mentioned (B) component, and water, wherein the mass ratio of the content of (B) component to the total content of (A1) component and (A2) component (B) / [(A1)+(A2)] is 0.05 or more and 0.5 or less.

[0019] According to the present invention, a gypsum slurry containing air bubbles and a method thereof can be provided that can increase the diameter of air bubbles in the gypsum slurry with a smaller amount of foaming component in the gypsum slurry containing air bubbles of the same specific gravity.

[0020] Using this invention, the diameter of air bubbles in gypsum slurry of the same specific gravity containing air bubbles can be increased with a smaller amount of foaming component, thereby improving the strength of the hardened gypsum slurry. Detailed Implementation

[0021] The foaming agent composition for hydraulic compositions of the present invention can increase the bubble diameter in hydraulic compositions containing air bubbles, particularly gypsum slurries, with a smaller addition amount. Furthermore, the gypsum slurry containing air bubbles of the present invention can increase the bubble diameter in gypsum slurries containing air bubbles with a smaller amount of foaming component (i.e., the amount of foaming agent composition for hydraulic compositions added). While the reason for this is not necessarily certain, it can be inferred as follows.

[0022] In the past, for example, as disclosed in Japanese Patent Application Publication No. 2004-529050, the foaming properties in an aqueous system were adjusted by focusing on surfactants to control the size of bubbles in the hydraulic composition, especially in gypsum slurry, when a liquid composition containing a foaming agent composition and water is foamed.

[0023] However, in methods that focus solely on surfactants and control foaming properties in aqueous systems, achieving larger bubble diameters in hydraulic compositions, particularly gypsum slurries, requires promoting bubble coalescence. However, this leads to a decrease in foaming properties in the aqueous system, resulting in an increasing need for a foaming agent composition to introduce a certain amount of foam into the hydraulic composition, particularly gypsum slurry. Furthermore, if foaming properties are improved in the hydraulic composition, particularly gypsum slurry, without bubble breakage to reduce the necessary amount of foaming agent composition, the bubbles in the hydraulic composition, particularly gypsum slurry, become finer. In other words, the inventors have found that it is difficult to simultaneously reduce the amount of foaming agent composition added and achieve larger bubble diameters in the hydraulic composition, particularly gypsum slurry.

[0024] Therefore, the inventors have discovered that the aforementioned problems can be solved by controlling the critical micelle concentration of the foaming agent composition and the foaming rate in the hydraulic composition, especially in gypsum slurry.

[0025] More specifically, the aforementioned problem is solved by combining an alkyl or alkenyl sulfate or its salt as a foaming agent (A1) with a nonionic compound as a component (B) having a LogP of 0 or more and 3.0 or less.

[0026] It is known that specific anionic surfactants, which are components of the present invention (A1), have a higher critical micelle concentration than nonionic surfactants due to electrostatic repulsion between molecules. Furthermore, it is known that if a higher alcohol is used in conjunction with the anionic surfactant, the higher alcohol alleviates the electrostatic repulsion between anionic surfactant molecules during micelle formation, thereby lowering the critical micelle concentration.

[0027] That is, in the foaming agent composition for hydraulic compositions of the present invention, a (B) component, which is a nonionic compound with a LogP of 0 or more and 3.0 or less, is used in conjunction with a specific anionic surfactant as the (A1) component. This introduces the (B) component into the micelles formed by the (A1) component in water, thereby stabilizing the bubbles and lowering the critical micelle concentration. Therefore, it is possible to reduce the amount of foaming agent composition required for foaming. Here, an amount of (B) component within the range that can be introduced into the micelles containing the (A1) component of the surfactant is used. On the other hand, in hydraulic compositions, particularly in gypsum slurries, ions dissolved from the hydraulic powder cause the (A1) component to lose its surface activity, thereby transforming the hydrophobic (B) component into a bubble co-forming promoter, achieving larger bubble diameters in hydraulic compositions, particularly in gypsum slurries. It is presumed that these effects can achieve both a reduction in the amount of foaming agent composition for hydraulic compositions and larger bubble diameters in hydraulic compositions, particularly in gypsum slurries.

[0028] It should be noted that the present invention is not limited to the above-described performance mechanism.

[0029] [Fogging agent composition for hydraulic compositions]

[0030] <(A1) Ingredients>

[0031] The water-hardening composition of the present invention contains alkyl or alkenyl sulfates or their salts as (A1) components.

[0032] From the viewpoint of reducing the amount added to the hydraulic composition, the (A1) component preferably has an alkyl or alkenyl group with 8 or more carbon atoms, more preferably 10 or more, and more preferably 18 or less, more preferably 16 or less, further preferably 14 or less, and even more preferably 12 or less, and preferably has an alkyl group.

[0033] (A1) Salts can be selected from one or more of the following: sodium salts, potassium salts, alkali metal salts, ammonium salts, and organic ammonium salts.

[0034] Specifically, (A1) may include one or more selected from octyl sulfate, decyl sulfate, dodecyl sulfate, tetradecyl sulfate, hexadecyl sulfate, octadecyl sulfate, 2-ethylhexyl sulfate, 2-propylheptyl sulfate and their salts. From the viewpoint of reducing the amount added to the hydraulic composition, it is preferable to contain one or more compounds selected from decyl sulfate, dodecyl sulfate, tetradecyl sulfate and their salts, and more preferably to contain one or more compounds selected from decyl sulfate, dodecyl sulfate and their salts.

[0035] From the viewpoint of increasing the diameter of bubbles in the hydraulic composition, the (A1) component preferably contains alkyl or alkenyl sulfates or their salts having 10 carbon atoms.

[0036] (A1) Regarding the content of alkyl or alkenyl sulfates or their salts having 10 carbon atoms, from the viewpoint of increasing the diameter of bubbles in the hydraulic composition, it is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, and less than 100% by mass.

[0037] From the viewpoint of reducing the amount added to the hydraulic composition, the (A1) component preferably contains an alkyl or alkenyl sulfate or a salt thereof having an alkyl or alkenyl group having 6 or more but less than 10 carbon atoms (hereinafter referred to as the (A11) component) and an alkyl or alkenyl sulfate or a salt thereof having an alkyl or alkenyl group having 11 or more but less than 22 carbon atoms (hereinafter referred to as the (A12) component).

[0038] Regarding the mass ratio (A11) / (A12) of the content of component (A11) to the content of component (A12), from the viewpoint of increasing the diameter of bubbles in the hydraulic composition and reducing the amount added to the hydraulic composition, it is preferably 0.8 or more, more preferably 1.0 or more, even more preferably 1.3 or more, and preferably 200 or less, more preferably 50 or less, even more preferably 10 or less, and even more preferably 3.0 or less.

[0039] <(A2) Ingredients>

[0040] The foaming agent composition for hydraulic compositions of the present invention may contain one or more surfactants selected from components other than (A1) as optional components (A2).

[0041] As component (A2), one or more of anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants other than component (A1) can be included. From the viewpoint of reducing the amount added to the hydraulic composition, component (A2) preferably contains anionic surfactants other than component (A1).

[0042] As an anionic surfactant other than component (A1), examples include sulfonic acid compounds, ether sulfate compounds, carboxylic acid compounds, phosphonic acid compounds, phosphoric acid compounds, etc., which are selected from hydrocarbon groups having 8 or more carbon atoms and 18 or fewer carbon atoms. For example, examples include alkyl or alkenyl sulfonic acids having alkyl or alkenyl groups, olefin sulfonic acids, polyoxyalkylene alkyl or alkenyl ether sulfates having alkyl or alkenyl groups, polyoxyalkylene alkyl or alkenyl ether carboxylic acids having alkyl or alkenyl groups, and salts thereof.

[0043] Salts that can be used as these anionic surfactants can be selected from one or more alkali metal salts such as sodium and potassium salts, ammonium salts, and organic ammonium salts.

[0044] Examples of nonionic surfactants include epoxide alkane compounds and polyol compounds having a hydrocarbon group having 8 or more but less than 18 carbon atoms. Examples include one or more selected from alkyl monoglyceride, polyoxyalkylene monoalkyl or alkenyl ether, alkyl glucoside or alkyl polyglucoside (glucoside-type nonionic surfactant), sorbitol-based nonionic surfactant, aliphatic alkanolamide, fatty acid monoglyceride, and sucrose fatty acid ester.

[0045] Examples of cationic surfactants include ammonium compounds, imidazoline compounds, and pyridine compounds having a hydrocarbon group having 8 or more but less than 18 carbon atoms. Examples include one or more of alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylammonium salts, benzalkonium salts, benzylammonium salts, imidazoline salts, and pyridinium salts. Examples of salts include halide salts.

[0046] Examples of amphoteric surfactants include amine oxide compounds, carbonyl betaine compounds, amide betaine compounds, and imidazoline betaine, which have 8 or more but less than 18 carbon groups. For example, one or more of the following can be selected: alkyl dimethylamine oxide, alkyl dimethyl aminoacetic acid betaine, alkyl hydroxy sulfobetaine, alkyl amamidopropyl betaine, and alkyl carboxymethyl hydroxyethyl imidazoline betaine.

[0047] From the viewpoint of reducing the amount added to the hydraulic composition, the foaming agent composition for hydraulic compositions of the present invention may contain one or more polyoxyalkylene alkyl or alkenyl ether sulfates and their salts selected from alkyl or alkenyl groups having 8 or more carbon atoms and 16 or fewer carbon atoms (hereinafter referred to as (A21) component) as (A2) component. When (A21) component is contained as (A2) component, the content of (A21) component in (A2) component is preferably 80% by mass or more, more preferably 90% by mass or more, and preferably 100% by mass or less.

[0048] From the viewpoint of reducing the amount added to the hydraulic composition, the (A21) component preferably has an alkyl or alkenyl group with 8 or more carbon atoms, more preferably 10 or more, and more preferably 16 or less, more preferably 14 or less, and even more preferably 12 or less, and preferably has an alkyl group.

[0049] The oxoalkylene group of component (A21) is oxoethylene or oxopropylene, preferably oxoethylene. From the viewpoint of solubility in water, the average molar number of oxoalkylene addition is preferably 1 or more, more preferably 2 or more. Furthermore, from the viewpoint of reducing the amount added to the hydraulic composition, it is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less.

[0050] (A21) The salt of component (A21) can be selected from one or more alkali metal salts such as sodium salts and potassium salts, ammonium salts and organic ammonium salts.

[0051] Specifically, component (A21) can be selected from polyoxyethylene octyl ether sulfate, polyoxyethylene decyl ether sulfate, polyoxyethylene lauryl ether sulfate, polyoxyethylene tridecyl ether sulfate, polyoxyethylene myristyl ether sulfate, polyoxyethylene cetyl ether sulfate, polyoxyethylene stearyl ether sulfate, polyoxypropylene octyl ether sulfate, polyoxypropylene decyl ether sulfate, polyoxypropylene lauryl ether sulfate, polyoxypropylene tridecyl ether sulfate, polyoxypropylene myristyl ether sulfate, polyoxypropylene cetyl ether sulfate, polyoxypropylene stearyl ether sulfate, polyoxyethylene polyoxypropylene octyl ether sulfate, polyoxyethylene polyoxypropylene decyl ether sulfate, and polyoxyethylene polyoxypropylene lauryl ether. The sulfate ester, polyoxyethylene polyoxypropylene tridecyl ether sulfate, polyoxyethylene polyoxypropylene myristyl ether sulfate, polyoxyethylene polyoxypropylene cetyl ether sulfate, polyoxyethylene polyoxypropylene stearyl ether sulfate, and salts thereof, preferably selected from polyoxyethylene decyl ether sulfate, polyoxyethylene lauryl ether sulfate, polyoxyethylene myristyl ether sulfate, polyoxypropylene decyl ether sulfate, polyoxypropylene lauryl ether sulfate, polyoxyethylene myristyl ether sulfate, and salts thereof, from the viewpoint of foaming properties.

[0052] <(B) Component>

[0053] The water-hardening composition of the present invention contains a nonionic compound as component (B) having a LogP of 0 or more and 3.0 or less. When component (B) has a hydrocarbon group, it is preferable that it has 7 or fewer carbon atoms.

[0054] Regarding the LogP of component (B), from the viewpoint of increasing the average bubble diameter in the hydraulic composition and reducing the amount added to the hydraulic composition, it is 0 or more, preferably 0.4 or more, more preferably 0.8 or more, and even more preferably 1.0 or more. Moreover, from the viewpoint of the liquid phase stability of the foaming agent composition, it is 3.0 or less, preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.8 or less.

[0055] In this invention, the so-called logP value is a coefficient representing the affinity of an organic compound for water and 1-octanol. The 1-octanol / water partition coefficient P is the ratio of the equilibrium concentrations of the compound in each solvent in a partition equilibrium when a trace amount of the compound is dissolved as a solute in a two-liquid-phase solvent of 1-octanol and water, and is usually expressed as the logarithm of the compound relative to 10, logP. A large number of logP values ​​for compounds have been reported, and numerous values ​​are available in databases such as those of Daylight Chemical Information Systems, Inc. (Daylight CIS), which can be consulted. In the absence of measured logP values, calculations can be performed using programs such as "ClogP," which are available from Daylight CIS. When measured logP values ​​are available, the program can output the "calculated logP (ClogP)" value calculated using the fragment approach of Hansch and Leo, along with the measured value.

[0056] The fragmentation method considers the number of atoms and the type of chemical bonds based on the chemical structure of the compound (cf. A. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990). The ClogP value can be used instead of the measured logP value when selecting compounds. In this invention, if a measured logP value is available, it is used; otherwise, the ClogP value calculated using the CLOGP v4.01 program is used.

[0057] As a nonionic compound of component (B), one or more can be selected from alcohols, glycol ethers, and aldehydes. However, the logP of these nonionic compounds must satisfy the above-mentioned range.

[0058] As an alcohol, a monohydric alcohol is preferred, and examples include 1-propanol (logP: 0.25), 2-propanol (LogP: 0.05), 1-butanol (logP: 0.88), 2-butanol (LogP: 0.61), 2-methyl-1-propanol (LogP: 0.76), 2-methyl-2-propanol (LogP: 0.35), 1-pentanol (LogP: 1.51), 2-pentanol (LogP: 1.19), and 3-pentanol. Alcohol (LogP: 1.21), 2-methyl-1-butanol (logP: 1.29), 2-methyl-2-butanol (LogP: 0.89), 3-methyl-2-butanol (LogP: 1.28), 3-methyl-1-butanol (LogP: 1.16), cyclopentanol (LogP: 0.71), benzyl alcohol (logP: 1.1), 2-hexanol (LogP: 1.76), 3-hexanol (LogP: 1.65), 2- Methyl-1-pentanol (LogP: 1.75), 3-methyl-1-pentanol (LogP: 1.75), 4-methyl-1-pentanol (LogP: 1.75), 2-methyl-2-pentanol (LogP: 1.57), 3-methyl-2-pentanol (LogP: 1.57), 4-methyl-2-pentanol (LogP: 1.57), 2-methyl-3-pentanol (LogP: 1.57), 3-methyl-3-pentanol (LogP: 1.57) The alcohol is selected from one or more of the following: 1.57), 2,2-dimethyl-1-butanol (LogP: 1.57), 2-ethyl-1-butanol (LogP: 1.75), cyclohexanol (logP: 1.23), 1-heptanol (LogP: 2.62), 1-hexanol (logP: 2.03), 2-ethyl-1-hexanol (logP: 2.73), 6-methyl-1-heptanol (LogP: 2.73), and octanol (logP: 3).

[0059] As a glycol ether, a glycol ether having a hydrocarbon group having 7 or fewer carbon atoms is preferred, and one or more of the following can be selected: diethylene glycol monobutyl ether (logP: 0.56), ethylene glycol monobutyl ether (logP: 0.81), ethylene glycol monophenyl ether (logP: 1.16), triethylene glycol monobutyl ether (logP: 0.02), and propylene glycol monobutyl ether (logP: 1.15).

[0060] As an aldehyde, one or more can be selected from butyraldehyde (logP: 0.88), pentanal (logP: 1.31), hexanal (logP: 1.78), pentanal (logP: 2.29), benzaldehyde (logP: 1.48), and cinnamaldehyde (logP: 1.9).

[0061] As a (B) component other than alcohols, glycol ethers, and aldehydes, one or more of the following can be cited: butyl lactate (logP: 0.8), dimethyl ether (logP: 0.1), diethyl ether (logP: 0.89), diisopropyl ether (logP: 1.52), butyl ethyl ether (logP: 2.03), anisole (logP: 2.11), tetrahydrofuran (logP: 0.46), propionic acid (logP: 0.33), butyric acid (logP: 0.79), valeric acid (logP: 1.39), hexanoic acid (logP: 1.92), heptanoic acid (logP: 2.42), and benzoic acid (logP: 1.87).

[0062] From the viewpoint of increasing the diameter of bubbles in the hydraulic composition, component (B) is preferably selected from one or more of acetyl alcohol and octanol. From the viewpoint of the liquid phase stability of the foaming agent composition for hydraulic composition, it is preferably selected from one or more of 1-butanol, benzyl alcohol, benzaldehyde, diethylene glycol monobutyl ether and cyclohexanol, and more preferably from one or more of 1-butanol, benzyl alcohol and benzaldehyde.

[0063] <Composition, etc.>

[0064] In the foaming agent composition for hydraulic compositions of the present invention, from the viewpoint of reducing the amount added to the hydraulic composition, it is preferable to contain 5% or more by mass, more preferably 10% or more by mass, further preferably 15% or more by mass, and even more preferably 20% or more by mass of (A1) component. Moreover, from the viewpoint of the liquid phase stability of the foaming agent composition for hydraulic compositions, it is preferable to contain 60% or less by mass, more preferably 50% or less by mass, further preferably 40% or less by mass, and even more preferably 30% or less by mass of (A1) component.

[0065] In this invention, the mass of component (A1) is specified using a value converted to sodium salt.

[0066] In the foaming agent composition for hydraulic compositions of the present invention, when the (A2) component is present, from the viewpoint of reducing the amount added to the hydraulic composition, it is preferable to contain 1% or more by mass, more preferably 2% or more by mass, and even more preferably 3% or more by mass of the (A2) component. Moreover, from the viewpoint of increasing the diameter of bubbles in the hydraulic composition, it is preferable to contain 10% or less by mass, more preferably 7% or less by mass, and even more preferably 4% or less by mass of the (A2) component.

[0067] In this invention, the mass of the anionic surfactant contained in component (A2) is converted to the value of sodium salt. Furthermore, the mass of the cationic surfactant contained in component (A2) is converted to the value of chloride salt.

[0068] In the foaming agent composition for hydraulic compositions of the present invention, from the viewpoint of reducing the amount added to the hydraulic composition, it is preferable to contain 1% or more by mass, more preferably 3% or more by mass, and even more preferably 5% or more by mass of component (B). Moreover, from the viewpoint of reducing the cost of the foaming agent composition for hydraulic compositions, it is preferable to contain 30% or less by mass, more preferably 20% or less by mass, and even more preferably 10% or less by mass of component (B).

[0069] In the foaming agent composition for hydraulic compositions of the present invention, when containing component (A2), the mass ratio of the content of component (A1) to the total content of components (A1) and (A2) (A1) / [(A1)+(A2)] is preferably 0.5 or more, more preferably 0.6 or more, and even more preferably 0.8 or more, from the viewpoint of reducing the amount added to the hydraulic composition, and is 1 or less, preferably 1.

[0070] In the foaming agent composition for hydraulic compositions of the present invention, the mass ratio (B) / [(A1)+(A2)] of the content of component (B) to the total content of components (A1) and (A2) is 0.05 or more, preferably 0.1 or more, more preferably 0.2 or more, and from the viewpoint of reducing the amount added to the hydraulic composition, it is 0.5 or less, preferably 0.4 or less, more preferably 0.35 or less, and even more preferably 0.3 or less.

[0071] In the foaming agent composition for hydraulic compositions of the present invention, the mass ratio (B) / (A1) of the content of component (B) to the content of component (A1) is preferably 0.05 or more, more preferably 0.1 or more, and even more preferably 0.2 or more, from the viewpoint of reducing the amount added to the hydraulic composition. Moreover, from the viewpoint of reducing the cost of the foaming agent composition for hydraulic compositions, it is preferably 0.5 or less, more preferably 0.4 or less, even more preferably 0.35 or less, and even more preferably 0.3 or less.

[0072] In the foaming agent composition for hydraulic compositions of the present invention, when the (A21) component is present, from the viewpoint of reducing the amount added to the hydraulic composition, it is preferable to contain 1% or more by mass, more preferably 2% or more by mass, further preferably 5% or more by mass, and even more preferably 10% or more by mass of the (A21) component. Moreover, from the viewpoint of increasing the diameter of bubbles in the hydraulic composition, it is preferable to contain 10% or less by mass, more preferably 5% or less by mass, and even more preferably 2% or less by mass of the (A21) component.

[0073] In this invention, the mass of component (A21) is specified using a value converted to sodium salt.

[0074] In the foaming agent composition for hydraulic compositions of the present invention, when the (A21) component is contained, the mass ratio of the content of the (A1) component to the total content of the (A1) component and the (A21) component (A1) / [(A1)+(A21)] is preferably 0.5 or more, more preferably 0.6 or more, and more preferably 0.8 or more, from the viewpoint of reducing the amount added to the hydraulic composition, preferably 1 or less, and more preferably 0.9 or less.

[0075] In the foaming agent composition for hydraulic compositions of the present invention, when containing component (A21), the mass ratio of the content of component (B) to the total content of components (A1) and (A21) (B) / [(A1)+(A21)] is preferably 0.05 or more, more preferably 0.1 or more, and even more preferably 0.2 or more, from the viewpoint of reducing the amount added to the hydraulic composition. Furthermore, from the viewpoint of reducing the cost of the foaming agent composition for hydraulic compositions, it is preferably 0.5 or less, more preferably 0.4 or less, even more preferably 0.35 or less, and even more preferably 0.3 or less.

[0076] The foaming agent composition for hydraulic compositions of the present invention contains water. Preferably, the foaming agent composition for hydraulic compositions of the present invention contains 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and even more preferably 45% by mass or more of water, and preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less of water.

[0077] The foaming agent compositions for hydraulic compositions of the present invention may contain thickeners, chelating agents, heavy metal scavengers, rust inhibitors, preservatives, colorants, fragrances, defoamers, dispersants, coagulants, water-soluble polymers, etc., as other ingredients. They use substances that are not equivalent to ingredients (A1), (A2), and (B).

[0078] The foaming agent composition for hydraulic compositions of the present invention can be obtained by mixing component (A1), optionally component (A2), component (B), and other components. During mixing, heating may be appropriately performed to reduce the viscosity of the solution.

[0079] Examples of applications using the foaming agent composition for hydraulic compositions according to the present invention include gypsum slurry, lightweight emulsions (aerated emulsions, air-filled emulsions), lightweight mortars (aerated mortars, air-filled mortars), lightweight concretes (aerated concrete, air-filled concrete), wall grouting fillers, filling grouting fillers, building concrete blocks, ALC (lightweight aerated concrete), grouting materials, porous ceramics, bricks, refractories, lightweight fill, pump-pressed mortars, and other hydraulic compositions capable of containing air bubbles. In these hydraulic compositions capable of containing air bubbles, by using the foaming agent composition for hydraulic compositions according to the present invention as a foaming agent to mix the air bubbles, it is expected that functions such as lightweighting, increased strength, improved fluidity, thermal insulation, heat resistance, thickening, and fluidity control can be imparted.

[0080] Among these hydraulic compositions capable of containing air bubbles, the hydraulic composition of the present invention with an air-bubbling agent is suitable for use as a gypsum slurry.

[0081] That is, the present invention provides the use of the water-hardening composition foaming agent composition of the present invention as a foaming agent for gypsum slurry.

[0082] The use of the gypsum slurry of the present invention as a foaming agent can be appropriately applied in the manner described in the foaming agent composition for hydraulic compositions of the present invention.

[0083] [Hydraulic compositions containing air bubbles and methods for manufacturing the same]

[0084] Regarding the method for manufacturing the bubble-containing hydraulic composition of the present invention, from the perspective of continuously generating uniform bubbles, a method is preferred in which the hydraulic composition of the present invention is foamed with a foaming agent composition and incorporated into the hydraulic material in foam form to achieve weight reduction. Alternatively, the hydraulic composition of the present invention can be prepared into a mixture using a foaming agent composition or by diluting it with water, and then directly added to pastes, slurries, mortars, and concrete using cement or gypsum as the hydraulic material. There are no limitations on the method of adding the hydraulic composition of the present invention to the hydraulic composition using a foaming agent composition, nor are there limitations on the method of foaming the mixture obtained by diluting the hydraulic composition of the present invention with a foaming agent composition or by diluting it with water.

[0085] The present invention provides a hydraulic composition containing air bubbles, comprising hydraulic powder, water, the above-mentioned component (A1), optional component (A2) and component (B), wherein the mass ratio of the content of component (B) to the total content of components (A1) and (A2) is 0.05 or more and 0.5 or less.

[0086] The water-containing hydraulic compositions of the present invention can be suitably applied to the matters described in the foaming agent compositions of the present invention.

[0087] Components (A1), (A2), and (B) are in the same manner as those described in the foaming agent composition for hydraulic compositions of the present invention.

[0088] Hydraulic powders are powders that harden due to hydration reactions. Examples include cement and gypsum, with gypsum being the preferred material.

[0089] The hydraulic powder preferably contains gypsum. The gypsum content in the hydraulic powder is preferably 80% by mass or more, more preferably 90% by mass or more, and more preferably 100% by mass or less, more preferably 100% by mass.

[0090] In hydraulic powders, the content of clinker fragments is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of minimizing the addition of foaming components. Hydraulic powders preferably do not contain clinker fragments.

[0091] Examples of cement types include ordinary Portland cement, Belite cement, medium-heat cement, fast-drying cement, ultra-fast-drying cement, and sulfuric acid resistant cement. Other types include blast furnace slag cement, fly ash cement, and silica fume cement, which contain blast furnace slag, fly ash cement, and stone powder (calcium carbonate powder).

[0092] In the hydrohardening composition containing air bubbles of the present invention, the water / hydrohardening powder ratio is 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 slurry flowability. Moreover, from the viewpoint of hardened body strength, it is preferably 100% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less.

[0093] Here, the water / hydraulic powder ratio is the mass percentage (mass%) of water to hydraulic powder in the hydraulic composition, calculated by multiplying water / hydraulic powder by 100. The water / hydraulic powder ratio is calculated based on the amount of powder having properties that harden due to hydration. If the powder having properties that harden due to hydration contains a high-strength admixture, the amount of the high-strength admixture is also included in the amount of hydraulic powder. The same applies to the relationships between other amounts in the hydraulic composition related to the hydraulic powder.

[0094] In the hydrohardening composition containing air bubbles of the present invention, from the viewpoint of reducing the specific gravity of the hardened body of the hydrohardening composition containing air bubbles, it is preferable to contain 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and even more preferably 0.01 parts by mass or more of (A1) component relative to 100 parts by mass of hydrohardening powder. Furthermore, from the viewpoint of the strength of the hardened body of the hydrohardening composition containing air bubbles, it is preferable to contain 0.1 parts by mass or less, more preferably 0.06 parts by mass or less, and even more preferably 0.03 parts by mass or less of (A1) component.

[0095] In the hydraulic composition containing air bubbles of the present invention, when containing component (A2), from the viewpoint of reducing the specific gravity of the hardened body of the hydraulic composition containing air bubbles by 100 parts by mass of the hydraulic powder, it is preferable to contain 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, and even more preferably 0.001 parts by mass or more of component (A2). Moreover, from the viewpoint of increasing the diameter of air bubbles in the hardened body of the hydraulic composition containing air bubbles, it is preferable to contain 0.01 parts by mass or less, more preferably 0.006 parts by mass or less, and even more preferably 0.001 parts by mass or less of component (A2).

[0096] In the hydrohardening composition containing bubbles of the present invention, from the viewpoint of reducing the amount of foaming component added, it is preferable to contain 0.00025 parts by mass or more, more preferably 0.00125 parts by mass or more, and even more preferably 0.0025 parts by mass or more of component (B) relative to 100 parts by mass of hydrohardening powder. Moreover, from the viewpoint of reducing costs, it is preferable to contain 0.025 parts by mass or less, more preferably 0.015 parts by mass or less, and even more preferably 0.0075 parts by mass or less of component (B).

[0097] In the hydraulic composition containing air bubbles of the present invention, the mass ratio of the content of component (A1) to the total content of components (A1) and (A2) (A1) / [(A1)+(A2)] is preferably 0.5 or more, more preferably 0.6 or more, and even more preferably 0.8 or more, from the viewpoint of reducing the amount of foaming component added, preferably 1 or less, and more preferably 1.

[0098] In the hydrohardening composition containing bubbles of the present invention, the mass ratio of the content of component (B) to the total content of components (A1) and (A2) (B) / [(A1)+(A2)] is 0.05 or more, preferably 0.1 or more, more preferably 0.2 or more, and from the viewpoint of reducing the amount of foaming component added, it is 0.5 or less, preferably 0.4 or less, more preferably 0.35 or less, and even more preferably 0.3 or less.

[0099] In the hydrohardening composition containing bubbles of the present invention, the mass ratio (B) / (A1) of the content of component (B) to the content of component (A1) is preferably 0.05 or more, more preferably 0.1 or more, and even more preferably 0.2 or more, from the viewpoint of reducing the amount of foaming component added. Moreover, from the viewpoint of reducing costs, it is preferably 0.5 or less, more preferably 0.4 or less, even more preferably 0.35 or less, and even more preferably 0.3 or less.

[0100] In the hydrohardening composition containing air bubbles of the present invention, when component (A21) is included as component (A2), from the viewpoint of reducing the specific gravity of the hardened body of the hydrohardening composition containing air bubbles, it is preferable to contain 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, and even more preferably 0.001 parts by mass or more of component (A21) relative to 100 parts by mass of hydrohardening powder. Moreover, from the viewpoint of increasing the diameter of air bubbles in the hardened body of the hydrohardening composition containing air bubbles, it is preferable to contain 0.01 parts by mass or less, more preferably 0.006 parts by mass or less, and even more preferably 0.001 parts by mass or less of component (A21).

[0101] In the hydrohardening composition containing air bubbles of the present invention, when component (A21) is included as component (A2), the mass ratio of the content of component (A1) to the total content of components (A1) and (A21) (A1) / [(A1)+(A21)] is preferably 0.5 or more, more preferably 0.6 or more, and even more preferably 0.8 or more, from the viewpoint of reducing costs, preferably 1 or less, and more preferably 0.9 or less.

[0102] In the hydrohardening composition containing bubbles of the present invention, when component (A21) is included as component (A2), the mass ratio of the content of component (B) to the total content of components (A1) and (A21) (B) / [(A1)+(A21)] is preferably 0.05 or more, more preferably 0.1 or more, and even more preferably 0.2 or more, from the viewpoint of reducing the amount of foaming component added. Moreover, from the viewpoint of reducing costs, it is preferably 0.5 or less, more preferably 0.4 or less, even more preferably 0.35 or less, and even more preferably 0.3 or less.

[0103] The air-filled hydraulic composition of the present invention may contain fine aggregates and / or coarse aggregates. Additionally, the air-filled hydraulic composition of the present invention may contain additives or blends known in the art.

[0104] Regarding the specific gravity of the hydraulic composition hardener containing air bubbles of the present invention, from the viewpoint of the strength of the hydraulic composition hardener containing air bubbles, it is preferably 0.3 or more, more preferably 0.4 or more, and even more preferably 0.5 or more. Furthermore, from the viewpoint of the operability of the hydraulic composition hardener containing air bubbles, it is preferably 0.9 or less, more preferably 0.8 or less, and even more preferably 0.7 or less.

[0105] The hydraulic composition containing air bubbles of the present invention contains air bubbles. Regarding the average bubble diameter of the hardened body of the hydraulic composition containing air bubbles of the present invention, from the viewpoint of improving the strength of the hardened body, it is preferably 200 μm or more, more preferably 300 μm or more, and even more preferably 350 μm or more. Furthermore, from the viewpoint of aesthetically pleasing cross-section, it is preferably 800 μm or less, more preferably 700 μm or less, even more preferably 650 μm or less, even more preferably 600 μm or less, and even more preferably 550 μm or less.

[0106] The average bubble diameter is calculated as follows: a hardened body containing the hydraulic composition of bubbles is prepared, and the hardened body is arbitrarily cut to form a cross-section. The cross-section is observed using a digital microscope, and the diameter of 100 bubble cross-sections is randomly measured. The average (arithmetic mean) of these values ​​is then used to calculate the diameter. It should be noted that, regarding the measurement of the bubble cross-section diameter, the diameter is measured when the bubble cross-section is circular, the major axis is measured when the bubble cross-section is elliptical, and the longest part is used as the diameter when the bubble cross-section is irregular.

[0107] The hydraulic compositions containing air bubbles of the present invention can be manufactured using the hydraulic compositions of the present invention with air-generating agent compositions.

[0108] That is, the present invention provides a method for manufacturing a water-containing hydraulic composition including the following steps 1 and 2.

[0109] <Process 1>

[0110] A process of foaming a liquid composition containing the hydraulic composition of the present invention with a foaming agent composition and water to obtain foam.

[0111] <Process 2>

[0112] The process involves mixing the foam obtained in step 1 with a hydraulic composition containing hydraulic powder and water to obtain a hydraulic composition containing air bubbles.

[0113] This manufacturing method can be used to prepare the water-filled hydraulic composition of the present invention.

[0114] The method for manufacturing the hydrohardening composition containing air bubbles of the present invention can be appropriately applied to the foaming agent composition for the hydrohardening composition of the present invention and the manner described in the hydrohardening composition containing air bubbles of the present invention.

[0115] In the method for manufacturing the bubble-containing hydraulic composition of the present invention, the content of each component and their mass ratio described in the bubble-containing hydraulic composition of the present invention can be appropriately used by replacing the content of each component with the mixing amount.

[0116] In step 1, the foaming ratio of the liquid composition is determined according to the application of the hydraulic composition, etc. However, from an economic point of view, it is preferably 3 times or more, more preferably 5 times or more, and even more preferably 7 times or more. Moreover, from the point of view of mixing properties, it is preferably 20 times or less, more preferably 15 times or less, and even more preferably 10 times or less.

[0117] In step 2, although the specific steps depend on the intended use of the hydraulic composition, from the viewpoint of reducing the weight of the cured body, it is preferable to mix 50% or more by volume, more preferably 75% or more by volume, and even more preferably 100% or more by volume of foam. Furthermore, from the viewpoint of the strength of the cured body, it is preferable to mix 200% or less by volume, more preferably 150% or less by volume, and even more preferably 100% or less by volume of foam. In this manufacturing method, in steps 1 and / or 2, well-known additives and materials in the art can be mixed.

[0118] After step 2, step 3 is performed to produce a hardened body of the hydraulic composition containing air bubbles.

[0119] Step 3: A step after Step 2 to form and harden the above-mentioned water-bearing hydraulic composition containing air bubbles.

[0120] [Gypsum slurry containing air bubbles and its manufacturing method]

[0121] In the hydraulic composition containing air bubbles of the present invention, the hydraulic powder preferably includes gypsum. In the present invention, the hydraulic composition containing air bubbles and including gypsum hydraulic powder is referred to as a gypsum slurry containing air bubbles.

[0122] The gypsum content in the hydraulic powder is preferably 80% by mass or more, more preferably 90% by mass or more, and more preferably 100% by mass or less, more preferably 100% by mass.

[0123] In hydraulic powders, the content of clinker fragments is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of minimizing the addition of foaming components. Hydraulic powders preferably do not contain clinker fragments.

[0124] That is, the present invention provides a gypsum slurry containing air bubbles, which contains gypsum-containing hydraulic powder, water, the above-mentioned component (A1), optional component (A2) and component (B), wherein the mass ratio of the content of component (B) to the total content of components (A1) and (A2) is 0.05 or more and 0.5 or less.

[0125] The gypsum slurry containing air bubbles of the present invention is suitable for use as gypsum board.

[0126] The gypsum slurry containing air bubbles of the present invention can be suitably applied to the foaming agent composition for hydraulic compositions of the present invention, the hydraulic compositions containing air bubbles of the present invention, and the method for manufacturing the hydraulic compositions containing air bubbles of the present invention.

[0127] Components (A1), (A2), and (B) are in the same manner as those described in the foaming agent composition for hydraulic compositions of the present invention.

[0128] In the gypsum slurry containing air bubbles of the present invention, the range of the content of each component and the range of their mass ratios are the same as those described in the hydraulic composition containing air bubbles of the present invention.

[0129] Gypsum can also be high-quality neutralized gypsum, phosphate gypsum as a byproduct of phosphoric acid, flue gas desulfurization gypsum produced in thermal power generation, natural gypsum containing various impurities, clay, mixtures thereof, and any other type of gypsum.

[0130] The clay contained in gypsum is mainly composed of hydrous silicate minerals with a layered structure (hereinafter referred to as clay minerals). Clay minerals contained in this clay in the form of particulate minerals can be listed as kaolinite minerals (kaolinite, dickite and pearl clay), serpentine (limonite, foliated serpentine, chrysotile), mica clay minerals (illite, sericite, glauconite, chlorite), chlorite, vermiculite, and chlorite (montmorillonite, bedesite, chlorite, saponite, lithium montmorillonite).

[0131] Gypsum includes anhydrous gypsum, hemihydrate gypsum, and dihydrate gypsum. As raw material gypsum, one or more chemical gypsums such as natural gypsum, neutralized gypsum, or by-product gypsum can be used, or a mixture of two or more of them. Examples of main chemical gypsums include phosphate gypsum, fluorophosphate gypsum, titanium gypsum, or flue gas desulfurization gypsum. Furthermore, recycled gypsum can be included in the raw material gypsum. Recycled gypsum can be any recycled gypsum recovered from waste gypsum board generated by gypsum board manufacturers, waste gypsum board generated during construction, or waste gypsum board generated during demolition. This invention can be suitably used with any of these raw material gypsums, and excellent results can also be obtained with gypsum mixed in various proportions.

[0132] The gypsum slurry containing air bubbles of the present invention may contain additives for applications such as gypsum board. Such additives include general-purpose water-reducing agents, defoamers, foam stabilizers, hardening modifiers, hydrophobic agents, adhesives, and delay agents. In addition, glass fiber, carbon fiber, waste paper, virgin pulp, etc. may be added as reinforcing fibers, or the gypsum board may be made together with perlite, foamed steel, etc., as lightweight aggregates.

[0133] Regarding the specific gravity of the hardened gypsum slurry containing air bubbles according to the present invention, from the viewpoint of the strength of the hardened gypsum slurry containing air bubbles, it is preferably 0.3 or more, more preferably 0.4 or more, and even more preferably 0.5 or more. Moreover, from the viewpoint of the operability of the hardened gypsum slurry containing air bubbles, it is preferably 0.9 or less, more preferably 0.8 or less, and even more preferably 0.7 or less.

[0134] The gypsum slurry containing air bubbles of the present invention contains air bubbles. Regarding the average bubble diameter of the hardened body of the gypsum slurry containing air bubbles of the present invention, from the viewpoint of improving the strength of the hardened body, it is preferably 200 μm or more, more preferably 300 μm or more, and even more preferably 350 μm or more. Furthermore, from the viewpoint of aesthetically pleasing cross-section, it is preferably 800 μm or less, more preferably 700 μm or less, even more preferably 650 μm or less, even more preferably 600 μm or less, and even more preferably 550 μm or less.

[0135] That is, the present invention provides a hardened body of gypsum slurry containing air bubbles, which is formed by hardening the gypsum slurry containing air bubbles of the present invention. Regarding the average air bubble diameter, from the viewpoint of improving the strength of the hardened body, it is preferably 200 μm or more, more preferably 300 μm or more, and even more preferably 350 μm or more. Moreover, from the viewpoint of aesthetic cross-section, it is preferably 800 μm or less, more preferably 700 μm or less, even more preferably 650 μm or less, even more preferably 600 μm or less, and even more preferably 550 μm or less.

[0136] The average bubble diameter is calculated as follows: a hardened body containing the hydraulic composition of bubbles is prepared, and the hardened body is arbitrarily cut to form a cross-section. The cross-section is observed using a digital microscope, and the diameter of 100 bubble cross-sections is randomly measured. The average (arithmetic mean) of these values ​​is then used to calculate the diameter. It should be noted that, regarding the measurement of the bubble cross-section diameter, the diameter is measured when the bubble cross-section is circular, the major axis is measured when the bubble cross-section is elliptical, and the longest part is used as the diameter when the bubble cross-section is irregular.

[0137] The present invention provides a method for manufacturing a gypsum slurry containing air bubbles, including the following steps 1 and 2.

[0138] <Process 1>

[0139] A process for obtaining foam by foaming a liquid composition containing a hydraulic composition, a foaming agent composition, and water, wherein the foaming agent composition contains the above-mentioned component (A1), optionally the above-mentioned component (A2), the above-mentioned component (B), and water, and the mass ratio of the content of component (B) to the total content of components (A1) and (A2) (B) / [(A1)+(A2)] is 0.05 or more and 0.5 or less.

[0140] <Process 2>

[0141] The process of mixing the foam obtained in step 1 with a gypsum slurry containing gypsum-containing hydraulic powder and water to obtain a gypsum slurry containing air bubbles.

[0142] This manufacturing method can be used to prepare the gypsum slurry containing air bubbles according to the present invention.

[0143] In step 1, the foaming agent composition for the hydraulic composition described above can be manufactured using the foaming agent composition for the hydraulic composition of the present invention, in the same manner as described in the foaming agent composition for the hydraulic composition of the present invention.

[0144] The method for manufacturing the air-filled gypsum slurry of the present invention can be appropriately applied to the foaming agent composition for the hydraulic composition of the present invention, the air-filled hydraulic composition of the present invention and its manufacturing method, and the manner described in the air-filled gypsum slurry of the present invention.

[0145] In the method for manufacturing the bubble-containing hydraulic composition of the present invention, the content and mass ratio of each component described in the bubble-containing hydraulic composition of the present invention can be appropriately used by replacing the content of each component with the mixing amount. The temperature of the foam and gypsum slurry used in the mixing is preferably 15°C or higher and 40°C or lower.

[0146] Steps 1 and 2 can be carried out according to the manufacturing method of the hydraulic composition containing air bubbles of the present invention.

[0147] After step 2, the following step 3 is carried out to manufacture gypsum board.

[0148] Step 3: The step of shaping and hardening the above-mentioned gypsum slurry containing air bubbles after step 2.

[0149] Molding and hardening can be carried out using well-known methods. For example, gypsum boards can be prepared by referring to the "Gypsum Board Manufacturing" section on pages 322-324 of the "Gypsum and Lime Handbook" (edited by the Gypsum and Lime Society).

[0150] Example

[0151] The following are the ingredients used in the examples and comparative examples.

[0152] (A1)Ingredients

[0153] •C10AS: Sodium decyl sulfate

[0154] • C10-16AS: Sodium alkyl sulfate having alkyl groups with 10 to 16 carbon atoms [mass ratio: carbon number 10 / 12 / 14 / 16 = 62.2 / 24.0 / 8.9 / 4.9, (carbon number 6-10) / (carbon number 11-22) = 1.6]

[0155] (A2) Ingredients

[0156] • AES: Sodium polyoxyethylene alkyl ether sulfate, product name "EMAL D-3-D", manufactured by Kao Corporation, (A21) ingredient

[0157] (B) Ingredients

[0158] • BDG: Diethylene glycol monobutyl ether, LogP: 0.56, manufactured by Tokyo Chemical Industry Co., Ltd.

[0159] • 1-BuOH: 1-Butanol, LogP: 0.88, Fujifilm and Kazumitsu Chemicals Co., Ltd.

[0160] • BnOH: benzyl alcohol, LogP: 1.1, manufactured by Fujifilm and Koizumi Pure Chemicals Co., Ltd.

[0161] • Cyclohexanol: Cyclohexanol, LogP: 1.23, manufactured by Fujifilm and Koei Pure Chemicals Co., Ltd.

[0162] • Benzaldehyde: Benzaldehyde, LogP: 1.48, manufactured by Fujifilm and Kohden Chemical Co., Ltd.

[0163] • C6OH: Hexanol, LogP: 2.03, manufactured by Fujifilm and Koei Pure Chemicals Co., Ltd.

[0164] • C8OH: Octyl alcohol, LogP: 3.0, Product name "KALCOL 0898" manufactured by Kao Corporation

[0165] (B') Component ((B) Component Comparison Component)

[0166] • EtOH: Ethanol, LogP: -0.31, manufactured by Fujifilm and Koizumi Pure Chemicals Co., Ltd.

[0167] Cyclohexane: Cyclohexane, LogP: 3.44, manufactured by Fujifilm and Koujun Pharmaceutical Co., Ltd.

[0168] (1) Preparation of foaming agent composition for hydraulic compositions

[0169] The foaming agent compositions for hydraulic compositions shown in Table 1 were prepared using the following methods.

[0170] Add the raw materials to a 50 mL threaded tube in the given proportions, bringing the total to 30 g. Stir at 1000 rpm for 3 hours using a stir bar. If the solution viscosity is high and the stirring efficiency is poor, heat to 40 °C as appropriate.

[0171] (2) Evaluation of liquid phase stability

[0172] The appearance of each hydraulic composition with foaming agent was evaluated 30 minutes after preparation according to the following criteria. The results are shown in Table 1.

[0173] Uniform and transparent: No phase separation occurs, and no turbidity is observed.

[0174] White turbidity: Although there is no phase separation, turbidity can be observed.

[0175] Separation: Phase separation occurs.

[0176] High-viscosity turbidity: It has high viscosity and turbidity can be observed.

[0177] (2) Preparation of gypsum slurry

[0178] The foaming agent composition for the hydraulic composition prepared in Table 1 was mixed with water in any proportion to prepare a diluted aqueous solution of the foaming agent composition for the hydraulic composition. 25g of the prepared aqueous solution was added to a 1L disposable cup and stirred for 60 seconds at 2000rpm (EUROSTAR 200control, IKA Japan Co., Ltd.) using a flat 6-blade paddle (FP-50, ASONE Co., Ltd.) to obtain foam. It should be noted that in order to make the specific gravity of the dried hardened gypsum slurry containing air bubbles approximately 0.65, the concentration of the diluted aqueous solution of the foaming agent composition for the hydraulic composition was adjusted appropriately. The concentration of the foaming agent composition for the hydraulic composition in the diluted aqueous solution at this time is recorded in Table 1 as "(2) Required addition amount".

[0179] Add 200g of calcined gypsum, 2g of gypsum dihydrate, 150g of water, and 0.8g of water-reducing agent (MIGHTY150, manufactured by Kao Corporation) to a 500mL disposable cup. Use an electric mixer (MK-H4, manufactured by Panasonic Corporation) at speed 3 to mix for 20 seconds to prepare the gypsum slurry before adding the foam.

[0180] Add the entire amount of the prepared gypsum slurry to 25g of foam prepared in a 1L disposable cup. Mix the gypsum slurry in the 1L disposable cup using the aforementioned flat, six-bladed paddle mixer at 1500rpm for 30 seconds to obtain a gypsum slurry containing air bubbles. It should be noted that the water / gypsum ratio in the gypsum slurry is 75% by mass. The temperature of both the foam and the gypsum slurry used in the mixing process is 20°C.

[0181] (3) Determination of the average bubble diameter in gypsum

[0182] The resulting gypsum slurry containing air bubbles was poured into a cylindrical sample mold (made by Plamold or Nifco) with a diameter of 5 cm and a height of 10 cm, and left to stand at room temperature for more than 1 hour.

[0183] The hardened gypsum slurry was removed from the mold box used for cylindrical specimens and dried in a constant temperature bath at 60°C for 24 hours. A section 5 cm high was then cut to obtain a cross-section of the hardened body. This cross-section was observed using a digital microscope, and the diameters of 100 randomly selected bubble sections were measured. The average bubble diameter was calculated based on the arithmetic mean of these values. It should be noted that in determining the diameter of the bubble section, the diameter was measured when the bubble section was circular, the major axis was measured when the bubble section was elliptical, and the longest part was used as the diameter when the bubble section was irregular. The results for "(1) Average bubble diameter in gypsum" are shown in Table 1.

[0184] In addition, the specific gravity of the hardened body of each gypsum slurry is approximately 0.65.

[0185] In addition, Table 1 shows the ratio (1) ÷ (2) of the average bubble diameter in (1) gypsum to the required amount of foaming agent composition for (2) hydraulic compositions. Regarding the average bubble diameter in (1) gypsum and the required amount of foaming agent composition for (2) hydraulic compositions, if the average bubble diameter in (1) gypsum is increased, the required amount of foaming agent composition for (2) hydraulic compositions needs to be increased, which is not economical, and there is a trade-off. The average bubble diameter in gypsum in the examples of this specification is only the result of the test under the conditions described in this specification, and it is easy to change if the manufacturing conditions are changed. However, the relationship that (1) ÷ (2) of the present invention is larger than that of existing products is the same regardless of the manufacturing conditions. That is, the bubble diameter described in the examples of this specification is not very important, what is important is that (1) ÷ (2) is large. For example, compared with Comparative Example 4, Example 1 has a smaller average bubble diameter in (1) gypsum. However, if the manufacturing conditions are changed, the average bubble diameter in gypsum will change. If the average bubble diameter in gypsum is the same, Example 1 has a larger (1) ÷ (2) compared with Comparative Example 4. Therefore, the necessary amount of foaming agent composition to be added to the hydraulic composition can be less. Therefore, in order to achieve the desired average bubble diameter in gypsum with a low addition amount that is economically advantageous, the value of (1) ÷ (2) becomes an important indicator.

[0186] It should be noted that in Comparative Examples 2 and 4, the liquid phase of the water-hardening composition and the foaming agent composition separated, making it difficult to take uniform samples. Therefore, the evaluations in (2) and (3) were not performed.

[0187] [Table 1]

[0188]

[0189] In (1)÷(2), which is an evaluation that combines (1) the average bubble diameter in the gypsum and (2) the necessary amount of addition, Examples 1 to 7 scored higher than Comparative Examples 1, 3 and 5.

[0190] Specifically, it is known that, compared with Comparative Examples 1 and 5, the necessary amount of foaming agent composition used in (2) the hydraulic composition for obtaining gypsum slurry containing air bubbles of the same specific gravity in Examples 1-7 is the same, and the average bubble diameter in (1) gypsum is larger. Furthermore, it can be considered that by increasing the bubble diameter in gypsum, the strength of the hardened body can be improved. Additionally, it is known that, compared with Comparative Example 3, the necessary amount of foaming agent (2) used in Examples 1-7 for obtaining gypsum slurry containing air bubbles of the same specific gravity is approximately half.

Claims

1. A gypsum slurry containing air bubbles, It contains hydraulic powder including gypsum, water, component A1 below, optional component A2 below, and component B below, wherein the mass ratio of component B to the total content of components A1 and A2 (B) / [(A1)+(A2)] is 0.05 or more and 0.5 or less; A1 component: alkyl or alkenyl sulfates or their salts; A2 component: One or more surfactants selected from those other than A1 component; Component B: Nonionic compounds with LogP values ​​above 0 and below 3.

0.

2. The gypsum slurry containing air bubbles according to claim 1, wherein, The gypsum content in the hydraulic powder is above 80% by mass.

3. The gypsum slurry containing air bubbles according to claim 1 or 2, wherein, A1 is an alkyl or alkenyl sulfate or its salt having an alkyl or alkenyl group with 8 or more carbon atoms and 16 or fewer carbon atoms.

4. The gypsum slurry containing air bubbles according to claim 1 or 2, wherein, Ingredient A1 contains: Alkyl or alkenyl sulfates or their salts having an alkyl or alkenyl group having 6 or more but less than 10 carbon atoms, and Alkyl or alkenyl sulfates or their salts having an alkyl or alkenyl group having 11 or more but less than 22 carbon atoms.

5. The gypsum slurry containing air bubbles according to any one of claims 1 to 4, wherein, The mass ratio of the content of component A1 to the total content of components A1 and A2 (A1) / [(A1)+(A2)] is 0.6 or more and 1 or less.

6. The gypsum slurry containing air bubbles according to any one of claims 1 to 5, wherein, Ingredient A1 contains alkyl or alkenyl sulfates or their salts having 10 carbon atoms, either alkyl or alkenyl groups.

7. The gypsum slurry containing air bubbles according to claim 6, wherein, In component A1, the content of alkyl or alkenyl sulfates having 10 carbon atoms or their salts is 60% or more by mass.

8. The gypsum slurry containing air bubbles according to any one of claims 1 to 7, wherein, Component A2 is selected from one or more anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants other than component A1.

9. The gypsum slurry containing air bubbles according to any one of claims 1 to 8, wherein, Component B is a nonionic compound selected from one or more alcohols, glycol ethers, and aldehydes.

10. The gypsum slurry containing air bubbles according to any one of claims 1 to 8, wherein, The nonionic compound of component B is selected from one or more of monohydric alcohols, glycol ethers having a hydrocarbon group with 7 or fewer carbon atoms, and aldehydes.

11. The gypsum slurry containing air bubbles according to any one of claims 1 to 8, wherein, The nonionic compound of component B is selected from one or more of the following: acetyl alcohol, octanol, 1-butanol, benzyl alcohol, benzaldehyde, diethylene glycol monobutyl ether, and cyclohexanol.

12. The gypsum slurry containing air bubbles according to any one of claims 1 to 11, wherein, The water / hydraulic powder ratio is 20% by mass or more and 100% by mass or less.

13. The gypsum slurry containing air bubbles according to any one of claims 1 to 12, wherein, The water-hardening powder contains 0.001 parts by weight and less than 0.1 parts by weight of A1 component relative to 100 parts by weight of water-hardening powder.

14. The gypsum slurry containing air bubbles according to any one of claims 1 to 13, wherein, The water-hardening powder contains 0.00025 parts by weight and less than 0.025 parts by weight of component B, relative to 100 parts by weight of water-hardening powder.

15. The gypsum slurry containing air bubbles according to any one of claims 1 to 14, wherein, Hydraulic powders do not contain pulverized clinker.

16. The gypsum slurry containing air bubbles according to any one of claims 1 to 15, wherein, The hardened body of the gypsum slurry containing air bubbles has an average air bubble diameter of 300 μm or more and 800 μm or less.

17. The gypsum slurry containing air bubbles according to any one of claims 1 to 16, wherein, The specific gravity of the hardened gypsum slurry containing air bubbles is 0.3 or more and 0.9 or less.

18. A method for manufacturing a gypsum slurry containing air bubbles, comprising the following steps 1 and 2: <Process 1> A process for foaming a liquid composition containing a hydraulic composition, a foaming agent composition, and water to obtain foam, wherein the hydraulic composition contains component A1, optionally component A2, component B, and water, and the mass ratio of component B to the total content of components A1 and A2 (B) / [(A1)+(A2)] is 0.05 or more and 0.5 or less; A1 component: alkyl or alkenyl sulfates or their salts; A2 component: One or more surfactants selected from those other than A1 component; Component B: Nonionic compounds with LogP values ​​greater than 0 and less than 3.0; <Process 2> The process of mixing the foam obtained in step 1 with a gypsum slurry containing gypsum-containing hydraulic powder and water to obtain a gypsum slurry containing air bubbles.

19. The method for manufacturing gypsum slurry containing air bubbles according to claim 18, wherein, The gypsum content in the hydraulic powder is above 80% by mass.

20. The method for manufacturing gypsum slurry containing air bubbles according to claim 18 or 19, wherein, Ingredient A1 contains: alkyl or alkenyl sulfates or their salts having an alkyl or alkenyl group having 6 or more but fewer than 10 carbon atoms, and... Alkyl or alkenyl sulfates or their salts having an alkyl or alkenyl group having 11 or more but less than 22 carbon atoms.

21. The method for manufacturing gypsum slurry containing air bubbles according to any one of claims 18 to 20, wherein, The mass ratio of the content of component A1 in the foaming agent composition of the hydraulic composition to the total content of components A1 and A2 (A1) / [(A1)+(A2)] is 0.6 or more and 1 or less.

22. The method for manufacturing gypsum slurry containing air bubbles according to any one of claims 18 to 21, wherein, In component A1, the content of alkyl or alkenyl sulfates having 10 carbon atoms or their salts is 60% or more by mass.

23. The method for manufacturing gypsum slurry containing air bubbles according to any one of claims 18 to 22, wherein, The foaming agent composition of the hydraulic composition contains 5% by mass and 60% by mass of A1 component.

24. The method for manufacturing gypsum slurry containing air bubbles according to any one of claims 18 to 23, wherein, The foaming agent composition of the hydraulic composition contains 1% by mass and less than 30% by mass of component B.

25. The method for manufacturing gypsum slurry containing air bubbles according to any one of claims 18 to 24, wherein, The foaming agent composition of the hydraulic composition contains 10% by mass and less than 90% by mass of water.

26. A method for manufacturing gypsum board, wherein the manufacturing method further comprises, in any one of claims 18 to 25, the method for manufacturing gypsum slurry containing air bubbles, the following step 3: <Process 3> The process following step 2 involves shaping and hardening the gypsum slurry containing air bubbles.

27. A hardened body of a gypsum slurry containing air bubbles, which is formed by hardening the gypsum slurry containing air bubbles according to any one of claims 1 to 17, wherein the average bubble diameter is 200 μm or more and 800 μm or less.

28. The hardened body of the gypsum slurry containing air bubbles according to claim 27, wherein, The specific gravity of the hardened body is above 0.3 and below 0.

9.

29. The use of a hydraulic composition with a foaming agent composition as a foaming agent for gypsum slurry. The foaming agent composition for the hydraulic composition contains component A1, optionally component A2, component B, and water, and the mass ratio of component B to the total content of components A1 and A2 (B) / [(A1)+(A2)] is 0.05 or more and 0.5 or less. A1 component: alkyl or alkenyl sulfates or their salts; A2 component: One or more surfactants selected from those other than A1 component; Component B: Nonionic compounds with LogP values ​​above 0 and below 3.0.

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