Foaming agent for hydraulic components

Abstract

To provide a foaming agent for hydraulic compositions in which solidification of the foaming agent is suppressed under atmospheric exposure. [Solution] A foaming agent for hydraulic compositions, comprising (A) one or more surfactants selected from anionic surfactants, cationic surfactants, and amphoteric surfactants having hydrocarbon groups with 8 to 30 carbon atoms, and (B) an organic compound having a LogP of -5.0 or more and less than 0, and a molecular weight of 50 to 500.

Description

Technical Field

[0001] The present invention relates to a foaming agent for hydraulic compositions and a bubble-containing hydraulic composition.

Background Art

[0002] In the hardened body of a bubble-containing hydraulic composition using cement or gypsum as a curing agent, further weight reduction is required from the viewpoints of environmental (CO2) reduction effects and costs due to manufacturing, transportation, and raw material procurement. In order to increase the amount of air in the hydraulic composition, it is known to incorporate a surfactant to introduce bubbles into the hydraulic composition.

[0003] Patent Document 1 discloses a bubble-containing gypsum slurry containing a hydraulic powder containing gypsum, water, (A1) an alkyl or alkenyl sulfate ester or a salt thereof, optionally one or more selected from surfactants other than the (A1) component), and (B) a nonionic compound having a LogP of 0 or more and 3.0 or less, wherein 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. Patent Document 2 discloses a foaming agent composition for construction work containing (A) an alkyl ether sulfate salt having a hydrocarbon group with 12 to 24 carbon atoms, (B) an alcohol with 12 or more carbon atoms, and as the (C) component, one or more components selected from an anionic surfactant having a hydrocarbon group with 11 or less carbon atoms, a fatty acid with 11 or less carbon atoms or a salt thereof, an alcohol with 11 or less carbon atoms, and a water-soluble nonionic surfactant, wherein the proportion of (A) in all the anionic surfactants in the composition is 70% by mass or more, and the mass ratio (C) / (A) of the content of the (A) component to the content of the (C) component is 0.1 or more and 5 or less. Patent Document 3 discloses a foaming agent composition for hydraulic compositions, which contains (A1): one or more selected from alkyl or alkenyl sulfate esters having an alkyl or alkenyl group having 8 to 10 carbon atoms, and salts thereof; (A2): one or more selected from surfactants other than component (A1); and (B): a monohydric alcohol having 6 to 10 carbon atoms, wherein the mass ratio (A1) / [(A1)+(A2)] of the content of component (A1) to the total content of components (A1) and (A2) is 0.8 or more and 1 or less. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2023 / 18047 [Patent Document 2] Japanese Patent Publication No. 2021-32053 [Patent Document 3] Japanese Patent Publication No. 2023-70662 [Overview of the project] [Problems that the invention aims to solve]

[0005] Generally, foaming agents for hydraulic compositions are introduced into a mixer from a storage tank via piping, measuring machines, and hoppers, and then blended into the hydraulic composition. The equipment that the foaming agent comes into contact with, such as storage tanks, piping, measuring machines, and hoppers, is often not sealed and is exposed to the atmosphere. The foaming agent adhering to the inside of this equipment tends to solidify upon drying. Therefore, a problem arises in that the hydraulic composition containing the solidified foaming agent is difficult to wash away.

[0006] The present invention provides a foaming agent for hydraulic compositions in which solidification of the foaming agent is suppressed, for example, overnight or even for a day, under atmospheric exposure. In the present invention, "solidification" refers to a state in which the constituent components of the foaming agent of the present invention have precipitated, and in the present invention, "adhesion" refers to a state in which the precipitated components or the foaming agent of the present invention containing the precipitated components have been fixed in contact with each other. [Means for solving the problem]

[0007] The present invention relates to a foaming agent for hydraulic compositions, in one embodiment, to (A) one or more surfactants selected from anionic surfactants, cationic surfactants, and amphoteric surfactants having hydrocarbon groups with 8 to 30 carbon atoms [hereinafter referred to as component (A)], and (B) an organic compound having a LogP of -5.0 or more and less than 0, and a molecular weight of 50 to 500 [hereinafter referred to as component (B)].

[0008] In another embodiment, the present invention relates to a bubble-containing hydraulic composition containing hydraulic powder, water, component (A), and component (B). [Effects of the Invention]

[0009] The present invention provides a foaming agent for hydraulic compositions in which solidification of the foaming agent is suppressed, for example, overnight or even for a full day under atmospheric exposure. [Modes for carrying out the invention]

[0010] The reason why the foaming agent for hydraulic compositions of the present invention (hereinafter also referred to as the foaming agent of the present invention) and the bubble-containing hydraulic composition (hereinafter also referred to as the hydraulic composition of the present invention) can suppress solidification of the foaming agent under atmospheric exposure is not entirely clear, but it is presumed to be as follows: Among organic compounds having a predetermined LogP value, component (B) of the present invention, which has a specific molecular weight, can be distributed in a predetermined amount to both water and the micelles formed by component (A) of the present invention, improving the water solubility of the micelles formed by component (A), and suppressing solidification of the foaming agent of the present invention even when water volatilizes and the gas-liquid interface becomes highly concentrated. Furthermore, among organic compounds having a predetermined LogP value, component (B) of the present invention having a specific molecular weight can achieve both a decrease in the thermal mobility of component (A) and an improvement in the water solubility of the micelles formed by component (A), thereby further enhancing the solidification-inhibiting effect of the foaming agent of the present invention when the amount of solid matter increases (for example, when hydraulic powder is mixed into the foaming agent of the present invention, or when a hydraulic composition containing the foaming agent of the present invention dries). However, the present invention is not limited to the above-described mechanism of action.

[0011] [Foaming agent for hydraulic composition] <(A) component> The bubble-containing hydraulic composition of the present invention contains, as component (A), one or more surfactants selected from anionic surfactants, cationic surfactants, and amphoteric surfactants having hydrocarbon groups with 8 to 30 carbon atoms.

[0012] Specific examples of anionic surfactants having a hydrocarbon group with 8 to 30 carbon atoms include one or more selected from sulfate ester salts, sulfonates, and carboxylates, each having a hydrocarbon group with 8 to 30 carbon atoms.

[0013] Examples of sulfate ester salts include alkyl sulfate ester salts having an alkyl group with 8 to 30 carbon atoms, alkenyl sulfate ester salts having an alkenyl group with 8 to 30 carbon atoms, polyoxyalkylene alkyl ether sulfate ester salts having an alkyl group with 8 to 30 carbon atoms, polyoxyalkylene alkenyl ether sulfate ester salts having an alkenyl group with 8 to 30 carbon atoms, and polyoxyalkylene alkylphenyl ether sulfate ester salts having an alkyl group with 8 to 30 carbon atoms.

[0014] The average number of moles of oxyalkylene groups added to a sulfate ester salt having an oxyalkylene group, for example, the average number of moles of oxyethylene groups added, may preferably be 1 to 10 from the viewpoint of suppressing solidification of the foaming agent and foaming ability.

[0015] Examples of sulfonates include alkyl sulfonates having an alkyl group with 8 to 30 carbon atoms, α-olefin sulfonates having 8 to 30 carbon atoms, alkylbenzene sulfonates having an alkyl group with 8 to 30 carbon atoms, alkyl sulfosuccinate ester salts having an alkyl group with 8 to 30 carbon atoms, and alkyl sulfosuccinate ester salts of polyoxyalkylene (preferably polyoxyethylene, with an average addition mole of 1 or more, preferably 5 or less) having an alkyl group with 8 to 30 carbon atoms.

[0016] Examples of carboxylate salts include higher fatty acid salts having 8 to 30 carbon atoms.

[0017] The salts of the aforementioned anionic surfactants include, from the viewpoint of suppressing solidification of the foaming agent and foaming ability, inorganic salts such as sodium salts and potassium salts, and organic salts such as ammonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, and morpholine salts, and preferably one or more selected from sodium salts, potassium salts, and triethanolamine salts.

[0018] Specific examples of cationic surfactants having a hydrocarbon group with 8 to 30 carbon atoms include one or more selected from alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylammonium salts, benzalkonium salts, benzethonium salts, imidazolium salts, and pyridinium salts, all of which have an alkyl group with 8 to 30 carbon atoms. Salts of the cationic surfactant include halogen salts of the cationic surfactant.

[0019] Specific examples of the amphoteric surfactant having a hydrocarbon group with 8 to 30 carbon atoms include betaine-type surfactants, amine oxide-type surfactants, etc. For example, alkyl sulfobetaine having an alkyl group with 8 to 30 carbon atoms, alkyl hydroxysulfobetaine having an alkyl group with 8 to 30 carbon atoms, alkyl amide hydroxysulfobetaine having an alkyl group with 8 to 30 carbon atoms, long-chain alkyl (8 to 30 carbon atoms) dimethylaminoacetic acid betaine, alkyl (8 to 30 carbon atoms) carboxymethylhydroxyethylimidazolium betaine, alkyl (8 to 30 carbon atoms) amidopropyl betaine, and one or more selected from alkyl dimethylamine oxide having an alkyl group with 8 to 30 carbon atoms can be mentioned.

[0020] In addition, as long as it does not prevent the manifestation of the effects of the present invention, nonionic surfactants may be included as other surfactants. Examples of the nonionic surfactant having a hydrocarbon group with 8 to 30 carbon atoms include, for example, amine oxide-type surfactants having a hydrocarbon group with 8 to 30 carbon atoms, glycoside-type nonionic surfactants having a hydrocarbon group with 8 to 30 carbon atoms, polyoxyalkylene monoalkyl (8 to 30 carbon atoms) or alkenyl (8 to 30 carbon atoms) ether-type nonionic surfactants, polyhydric alcohol fatty acid ester-type or polyhydric alcohol alkyl ether-type nonionic surfactants derived from fatty acids (8 to 30 carbon atoms) or aliphatic alcohols (8 to 30 carbon atoms), and one or more selected from fatty acid alkanolamide-type nonionic surfactants having 8 to 30 carbon atoms in the fatty acid part (acyl group) of fatty acid alkanolamides can be mentioned. Incidentally, the polyhydric alcohol fatty acid ester-type or polyhydric alcohol alkyl ether-type nonionic surfactant may include a glycoside-type nonionic surfactant.

[0021] (Component (A) may preferably be an anionic surfactant having a hydrocarbon group with 8 to 30 carbon atoms from the viewpoints of suppressing solidification of the foaming agent and foamability. Moreover, from the viewpoints of suppressing solidification of the foaming agent and foamability, the component (A) may be an anionic surfactant containing one or more selected from (A1) an alkyl or alkenyl sulfate ester having an alkyl or alkenyl group with 12 to 18 carbon atoms or a salt thereof [hereinafter, the component (A1)], and (A2) one or more selected from anionic surfactants having a hydrocarbon group with 8 to 30 carbon atoms other than the component (A1) [hereinafter, the component (A2)].

[0022] (A) component, the total content of anionic surfactants having a hydrocarbon group with 8 to 30 carbon atoms, preferably the total content of the component (A1) and the component (A2), may be preferably 80% by mass or more, more preferably 90% by mass or more, and preferably 100% by mass or less, and substantially 100% by mass is preferable, in the component (A).

[0023] [[ID=�]] (A1) component may be preferably one or more selected from an alkyl or alkenyl sulfate ester having an alkyl or alkenyl group with 12 to 18 carbon atoms or a salt thereof, and more preferably has an alkyl or alkenyl group, preferably an alkyl group, with 12 to 14 carbon atoms. Examples of the salt of the component (A1) include one or more selected from alkali metal salts such as sodium salt and potassium salt, ammonium salts, and organic ammonium salts, and from the viewpoints of suppressing solidification of the foaming agent and foamability, it may be preferably one or more selected from sodium salt, ammonium salts, and organic ammonium salts.

[0024] Specific examples of the component (A1) include one or more selected from dodecyl sulfate ester, tetradecyl sulfate ester, hexadecyl sulfate ester, octadecyl sulfate ester, and salts thereof, and from the viewpoints of suppressing solidification of the foaming agent and foamability, it may be preferably one or more selected from dodecyl sulfate ester, tetradecyl sulfate ester, hexadecyl sulfate ester, and salts thereof.

[0025] Component (A1) may contain (A11) an alkyl or alkenyl sulfate ester having a C12 alkyl or alkenyl group, or a salt thereof [hereinafter referred to as component (A11)], preferably dodecyl sulfate ester or a salt thereof, from the viewpoint of suppressing solidification of the foaming agent and foaming properties. The salt of component (A11) may be one or more selected from alkali metal salts such as sodium salts and potassium salts, ammonium salts, and organic ammonium salts, and from the viewpoint of suppressing solidification of the foaming agent and foaming properties, it may preferably be one or more selected from sodium salts, ammonium salts, and organic ammonium salts.

[0026] When component (A1) contains component (A11), from the viewpoint of suppressing solidification of the foaming agent and foaming ability, the content of component (A11) is preferably 30% by mass or more, more preferably 40% by mass or more, of component (A1), and from the viewpoint of suppressing solidification of the foaming agent and foaming ability, it may be preferably 90% by mass or less, more preferably 80% by mass or less. In the present invention, the mass of component (A11) shall be the value converted to the sodium salt.

[0027] Component (A2) may be one or more anionic surfactants having hydrocarbon groups with 8 to 30 carbon atoms other than component (A1), and from the viewpoint of suppressing solidification of the foaming agent and foaming properties, it may preferably contain one or more selected from (A21) alkyl or alkenyl sulfate esters or salts thereof having alkyl or alkenyl groups with 8 to less than 12 carbon atoms [hereinafter, component (A21)], (A22) polyoxyalkylene alkyl or alkenyl sulfate esters or salts thereof having alkyl or alkenyl groups with 8 to 30 carbon atoms [hereinafter, component (A22)], and (A23) fatty acid salts having alkyl or alkenyl groups with 8 to 30 carbon atoms [hereinafter, component (A23)].

[0028] The total content of anionic surfactants having hydrocarbon groups with 8 to 30 carbon atoms, other than component (A1), in component (A2), preferably the total content of components (A21), (A22), and (A23), is preferably 80% by mass or more, more preferably 90% by mass or more, and preferably 100% by mass or less, and substantially 100% by mass is preferred.

[0029] Component (A21) preferably has an alkyl group or alkenyl group, preferably an alkyl group, having 8 or more carbon atoms, preferably less than 12 carbon atoms, and more preferably 10 or fewer carbon atoms, from the viewpoint of suppressing solidification of the foaming agent and foaming properties. The salt of component (A21) may be one or more selected from alkali metal salts such as sodium salts and potassium salts, ammonium salts, and organic ammonium salts. From the viewpoint of suppressing solidification of the foaming agent and foaming properties, it may preferably be one or more selected from sodium salts, ammonium salts, and organic ammonium salts.

[0030] (A21) Specifically, the component may be one or more selected from octyl sulfate, decyl sulfate, 2-ethylhexyl sulfate, 2-propylheptyl sulfate, and salts thereof. From the viewpoint of suppressing solidification of the foaming agent and foaming ability, it is preferably one or more selected from decyl sulfate or its salts, and more preferably one or more selected from decyl sulfate or its salts.

[0031] When component (A2) contains component (A21), from the viewpoint of suppressing solidification of the foaming agent and foaming ability, the content of component (A21) is preferably 5% by mass or more, more preferably 10% by mass or more, and from the viewpoint of suppressing solidification of the foaming agent and foaming ability, preferably 90% by mass or less, more preferably 70% by mass or less, and may be 100% by mass. In the present invention, the mass of component (A21) shall be the value converted to the sodium salt.

[0032] Component (A22) preferably has an alkyl group or alkenyl group having 10 or more carbon atoms, more preferably 12 or more carbon atoms, and more preferably 22 or fewer carbon atoms, and more preferably 18 or fewer carbon atoms, from the viewpoint of suppressing solidification of the foaming agent and foaming properties. (A22) From the viewpoint of suppressing solidification of the foaming agent and foaming properties, the average number of moles of oxyalkylene groups, preferably oxyethylene groups, added to component (A22) may be preferably 1 or more and 10 or less. The salt of component (A22) can be one or more selected from alkali metal salts such as sodium salts and potassium salts, ammonium salts, and organic ammonium salts. From the viewpoint of suppressing solidification of the foaming agent and foaming properties, sodium salts, ammonium salts, and organic ammonium salts are preferred.

[0033] When component (A2) contains component (A22), from the viewpoint of suppressing solidification of the foaming agent and foaming properties, the content of component (A22) is preferably 5% by mass or more, more preferably 10% by mass or more, and from the viewpoint of suppressing solidification of the foaming agent and foaming properties, preferably 90% by mass or less, more preferably 70% by mass or less, and may be 100% by mass. In the present invention, the mass of component (A22) shall be the value converted to sodium salt.

[0034] Component (A23) preferably has an alkyl group or alkenyl group having 8 or more carbon atoms, more preferably 10 or more carbon atoms, and more preferably 20 or fewer carbon atoms, more preferably 18 or fewer carbon atoms, from the viewpoint of suppressing solidification of the foaming agent and foaming properties. The salt of component (A23) can be one or more selected from alkali metal salts such as sodium salts and potassium salts, ammonium salts, and organic ammonium salts. From the viewpoint of suppressing solidification of the foaming agent and foaming properties, potassium salts, sodium salts, and organic ammonium salts are preferred.

[0035] When component (A2) contains component (A23), from the viewpoint of suppressing solidification of the foaming agent and foaming ability, the content of component (A23) is preferably 5% by mass or more, more preferably 10% by mass or more, of component (A2), and from the viewpoint of suppressing solidification of the foaming agent and foaming ability, it may be 90% by mass or less, more preferably 70% by mass or less, and may be 100% by mass. In the present invention, the mass of component (A23) shall be the value converted to sodium salt.

[0036] When component (A) contains component (A1), from the viewpoint of suppressing solidification of the foaming agent and foaming properties, the content of component (A1) is preferably 40% by mass or more, more preferably 45% by mass or more, and from the viewpoint of suppressing solidification of the foaming agent and foaming properties, it may be 98% by mass or less, more preferably 95% by mass or less, and may be 100% by mass. In the present invention, the mass of component (A1) shall be the value converted to sodium salt.

[0037] When component (A) contains component (A2), from the viewpoint of suppressing solidification of the foaming agent and foaming ability, the content of component (A2) is preferably 2% by mass or more, more preferably 5% by mass or more, of component (A), and from the viewpoint of suppressing solidification of the foaming agent and foaming ability, it may be preferably 90% by mass or less, more preferably 70% by mass or less. In the present invention, the mass of component (A2) shall be the value converted to the sodium salt in the case of anionic surfactants, and the value converted to the compound excluding the counterion in the case of cationic surfactants.

[0038] When component (A) contains component (A2), the mass ratio of the content of component (A1) to the content of component (A2) [(A1) / (A2)] is preferably 0.01 or more, more preferably 0.5 or more, even more preferably 0.8 or more, and also preferably 500 or less, more preferably 200 or less, even more preferably 50 or less, from the viewpoint of suppressing solidification of the foaming agent and foaming ability.

[0039] <(B) component> The foaming agent for hydraulic compositions of the present invention contains, as component (B), an organic compound having a LogP of -5.0 or more and less than 0, and a molecular weight of 50 or more and 500 or less.

[0040] In this invention, the LogP value is a coefficient that indicates 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 at the partition equilibrium when a trace amount of the compound is dissolved as a solute in a two-phase solvent of 1-octanol and water, and is generally expressed in the form of its logarithm LogP with respect to base 10. LogP values ​​for many compounds have been reported, and many values ​​are listed in databases available from Daylight Chemical Information Systems, Inc. (Daylight CIS), ICSC database, etc., so they can be referred to. If there is no measured LogP value, it can be calculated using a program such as "CLogP" available from Daylight CIS. If a measured LogP value is available, this program outputs the "calculated LogP (CLogP)" value calculated by Hansch, Leo's fragment approach along with the measured LogP value. The fragment approach is based on the chemical structure of the compound, taking into account the number of atoms and the type of chemical bonds (cf. A. Leo, Comprehensive Medicinal Chemistry, Vol.4, C. Hansch, PGSammens, JBTaylor and CA Ramsden, Eds., p.295, Pergamon Press, 1990). This CLogP value can be used in place of the measured LogP value when selecting a compound. In this invention, if a measured LogP value is available, that is used; otherwise, the CLogP value calculated by the program CLOGP v4.01 is used. The LogP value of polymers is calculated by determining the chemical structure from the degree of polymerization calculated from the average molecular weight.

[0041] Component (B) may be an organic compound having a LogP of -5.0 or higher, preferably -3.0 or higher, more preferably -2.5 or higher from the viewpoint of inhibiting solidification of the foaming agent and foaming ability, and a LogP of less than 0, preferably -0.1 or lower, more preferably -0.2 or lower from the viewpoint of inhibiting solidification of the foaming agent and foaming ability, a molecular weight of 50 or higher, preferably 80 or higher from the viewpoint of inhibiting solidification of the foaming agent and foaming ability, and a molecular weight of 500 or lower, preferably 200 or lower from the viewpoint of inhibiting solidification of the foaming agent and foaming ability. Component (B) may also be an organic compound having a LogP within the above range and a molecular weight within the above range, preferably having one or more, more preferably two or more, preferably 10 or fewer, more preferably five or fewer hydroxyl groups.

[0042] (B) Specifically, the following organic compounds are examples of components. The information in parentheses following each compound indicates "(abbreviation) (LogP value, (weight-average) molecular weight)". Examples include propylene glycol (PG) (-0.92, 76), dipropylene glycol (DPG) (-1.17, 134), polyethylene glycol 400 (PEG400) (-0.69, weight-average molecular weight 400), 1,3-butanediol (1,3-BG) (-0.74, 90), 2,2-dimethyl-1,3-propanediol (NPG) (-0.84, 104), 1,6-hexanediol (1,6-HG) (-0.11, 118), 1,2-hexanediol (1,2-HG) (-0.58, 118), 2-aminoethanol (MEA) (-1.31, 61), diethanolamine (DEA) (-1.43, 105), and triethanolamine (TEA) (-2.3, 149).

[0043] Component (B) may preferably be one or more selected from dipropylene glycol, 1,3-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 2-aminoethanol, diethanolamine, and triethanolamine, from the viewpoint of suppressing solidification of the foaming agent and foaming properties, and more preferably dipropylene glycol.

[0044] Furthermore, component (B) may be a mixture of the organic compounds listed above, and from the viewpoint of suppressing solidification of the foaming agent and foaming properties, it is preferably a mixture of organic compounds containing dipropylene glycol, and more preferably a mixture of dipropylene glycol, ethyl alcohol, 2-aminoethanol, diethanolamine, and triethanolamine (-1.9 to -2.3).

[0045] <(C) component> Component (C) may contain a nonionic compound with a LogP of 0 or more and 7.0 or less. Component (C) may preferably be a nonionic compound with a LogP of 1 or more, preferably 5.0 or less, more preferably 4 or less, and even more preferably 3.5 or less, from the viewpoint of suppressing solidification of the foaming agent and foaming ability. The method for calculating the LogP value of component (C) is the same as the method for calculating the LogP value of component (B) described above.

[0046] (C) The components are specifically 1-propyl alcohol (LogP: 0.25), 2-propyl alcohol (LogP: 0.05), 1-butyl alcohol (LogP: 0.88), 2-butyl alcohol (LogP: 0.61), 2-methyl-1-propyl alcohol (LogP: 0.76), 2-methyl-2-propyl alcohol (LogP: 0.35), 1-pentyl alcohol (LogP: 1.51), 2-pentyl alcohol (LogP: 1.19), 3-pentyl alcohol (LogP: 1.21), and 2-methyl-1-butyl alcohol. Coal (LogP: 1.29), 2-methyl-2-butyl alcohol (LogP: 0.89), 3-methyl-2-butyl alcohol (LogP: 1.28), 3-methyl-1-butyl alcohol (LogP: 1.16), cyclopentyl alcohol (LogP: 0.71), benzyl alcohol (LogP: 1.1), 2-hexyl alcohol (LogP: 1.76), 3-hexyl alcohol (LogP: 1.65), 2-methyl-1-pentyl alcohol (LogP: 1.75), 3-methyl-1-pentyl alcohol (LogP: 1. 75), 4-methyl-1-pentyl alcohol (LogP: 1.75), 2-methyl-2-pentyl alcohol (LogP: 1.57), 3-methyl-2-pentyl alcohol (LogP: 1.57), 4-methyl-2-pentyl alcohol (LogP: 1.57), 2-methyl-3-pentyl alcohol (LogP: 1.57), 3-methyl-3-pentyl alcohol (LogP: 1.57), 2,2-dimethyl-1-butyl alcohol (LogP: 1.57), 2-ethyl-1-butyl alcohol (LogP: 1.75), cyclohexyl One or more alcohols selected from 1-Heptyl alcohol (LogP: 1.23), 1-Heptyl alcohol (LogP: 2.62), 1-Hexyl alcohol (LogP: 2.03), 2-Ethyl-1-Hexyl alcohol (LogP: 2.73), 6-Methyl-1-Heptyl alcohol (LogP: 2.73), 1-Octyl alcohol (LogP: 3), 1-Decyl alcohol (LogP: 4.23), 1-Dodecanol (LogP: 5.13), 1-Tetradecanol (LogP: 5.5), and 1-Hexadecanol (LogP: 6.7) are examples.

[0047] Component (C) may preferably be one or more selected from 2-hexyl alcohol, 3-hexyl alcohol, 1-octyl alcohol (C8OH), benzyl alcohol (BnOH), 1-decanol, and 1-dodecanol, from the viewpoint of suppressing solidification of the foaming agent and foaming properties, and preferably one or more selected from 2-hexyl alcohol, 3-hexyl alcohol, 1-octyl alcohol, and benzyl alcohol.

[0048] Furthermore, component (C) may be a mixture of the nonionic compounds listed above, and from the viewpoint of suppressing solidification of the foaming agent and foaming properties, it may preferably be a mixture of nonionic compounds containing at least one selected from 1-octyl alcohol and benzyl alcohol.

[0049] <Composition, etc.> The foaming agent for hydraulic compositions of the present invention may contain component (A) in an amount preferably 10% by mass or more, more preferably 20% by mass or more, preferably 50% by mass or less, and more preferably 40% by mass or less, from the viewpoint of suppressing solidification of the foaming agent and foaming properties. In the present invention, the mass of component (A) shall be the value converted to the sodium salt in the case of anionic surfactants, and the value converted to the compound excluding the counterion in the case of cationic surfactants.

[0050] The foaming agent for hydraulic compositions of the present invention, when containing component (A1) as component (A), may contain component (A1) in an amount of preferably 5% by mass or more, more preferably 10% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of suppressing solidification of the foaming agent and foaming properties. In the present invention, the mass of component (A1) shall be the value converted to sodium salt.

[0051] The foaming agent for hydraulic compositions of the present invention, when containing component (A11) as component (A), may contain component (A1) in an amount of preferably 5% by mass or more, more preferably 7% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of suppressing solidification of the foaming agent and foaming properties. In the present invention, the mass of component (A11) shall be the value converted to sodium salt.

[0052] The foaming agent for hydraulic compositions of the present invention, when containing component (A2) as component (A), may contain component (A2) in an amount of preferably 0.2% by mass or more, more preferably 1% by mass or more, preferably 40% by mass or less, and more preferably 30% by mass or less, in the foaming agent, from the viewpoint of suppressing solidification of the foaming agent and foaming properties. In the present invention, the mass of component (A2) shall be the value converted to sodium salt.

[0053] The foaming agent for hydraulic compositions of the present invention may contain component (B) in an amount preferably 1% by mass or more, more preferably 3% by mass or more, preferably 20% by mass or less, and more preferably 15% by mass or less, from the viewpoint of suppressing solidification of the foaming agent and foaming properties.

[0054] If the foaming agent for hydraulic compositions of the present invention contains component (C), from the viewpoint of suppressing solidification of the foaming agent and foaming properties, it may contain preferably 1% by mass or more, more preferably 2.5% by mass or more, and preferably 10% by mass or less, and more preferably 6% by mass or less in the foaming agent.

[0055] In the foaming agent for hydraulic compositions of the present invention, the content of component (A) relative to the content of component (B) is preferably 0.03 or more, more preferably 0.1 or more, in mass ratio [(B) / (A)] from the viewpoint of suppressing solidification of the foaming agent and foaming ability, and preferably 1.5 or less, more preferably 1.0 or less. In the present invention, the content of component (A) is used as a value converted to sodium salt, and in the case of a cationic surfactant, the value converted to the compound excluding the counterion is used.

[0056] In the present invention, when the foaming agent for hydraulic compositions contains component (A1) as component (A), the mass ratio of the content of component (A1) to the content of component (B) in the foaming agent, [(B) / (A1)], is preferably 0.03 or more, more preferably 0.1 or more, from the viewpoint of suppressing solidification of the foaming agent and foaming ability, and preferably 2.0 or less, more preferably 1.5 or less. In the present invention, the content of component (A1) shall be the value converted to sodium salt.

[0057] In the present invention, when the foaming agent for hydraulic compositions contains component (A11) as component (A), the mass ratio of component (A11) to the content of component (B) in the foaming agent is preferably 0.03 or more, more preferably 0.1 or more, and preferably 4.0 or less, more preferably 2.0 or less, from the viewpoint of suppressing solidification and foaming properties of the foaming agent. In the present invention, the content of component (A11) is calculated using the value converted to sodium salt.

[0058] If the foaming agent for hydraulic compositions of the present invention contains component (C), the mass ratio of the content of component (B) to the content of component (C), [(B) / (C)], is preferably 0.25 or more, more preferably 0.5 or more, from the viewpoint of suppressing solidification of the foaming agent and foaming ability, and preferably 10 or less, more preferably 5 or less.

[0059] The foaming agent for hydraulic compositions of the present invention, when it contains component (C), may have a mass ratio of [[(B)+(C)] / (A)] of component (A) to the total amount of component (B) and component (C), which is preferably 0.05 or more, more preferably 0.1 or more, and preferably 2.5 or less, more preferably 2.0 or less, from the viewpoint of suppressing solidification and foaming properties of the foaming agent.

[0060] The foaming agent for hydraulic compositions of the present invention may contain water. The foaming agent for hydraulic compositions of the present invention may contain water in an amount of preferably 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 85% by mass or less.

[0061] The foaming agent for hydraulic compositions of the present invention may optionally contain water-reducing agents, thickeners, chelating agents, heavy metal scavenging agents, rust inhibitors, preservatives, colorants, fragrances, defoaming agents, solvents, dispersants, flocculants, water-soluble polymers, etc. However, those used are those that do not fall under components (A1), (A2), (B), and (C).

[0062] The dispersant contained in the foaming agent for hydraulic compositions of the present invention may, for example, preferably be one or more compounds selected from naphthalene polymers, polycarboxylic acid polymers, ligninsulfonic acid polymers, melamine polymers, polymers containing phosphate groups in their structure, and polymers containing aromatics having polyalkylene oxy groups, more preferably one or more compounds selected from naphthalene polymers, polycarboxylic acid polymers, ligninsulfonic acid polymers, polymers containing phosphate groups in their structure, and polymers containing aromatics having polyalkylene oxy groups.

[0063] The foaming agent for hydraulic compositions of the present invention is obtained by mixing component (A), component (B), component (C), and the aforementioned optional component. During mixing, heating may be appropriate to reduce the viscosity of the solution.

[0064] Applications of the foaming agent for hydraulic compositions of the present invention include hydraulic compositions containing bubbles, such as freeze-resistant concrete, gypsum slurry, lightweight milk (bubble milk, air milk), lightweight mortar (bubble mortar, air mortar), lightweight concrete (bubble concrete, air concrete), backfill materials, inter-fill materials, concrete blocks for construction, ALC (autoclaved lightweight concrete), grout materials, porous ceramics, bricks, refractories, lightweight embankments, mortar for pumping, sprayed concrete, and sprayed mortar. In these bubble-containing hydraulic compositions, it is expected that the mixing of bubbles will impart functions such as weight reduction, strength improvement, fluidity improvement, heat insulation, heat resistance, viscosity imparting, and fluidity control. Among the hydraulic compositions containing these bubbles, the foaming agent for hydraulic compositions of the present invention is suitable for use in freeze-thaw resistant concrete, gypsum slurry, and lightweight concrete.

[0065] The foaming agent for hydraulic compositions of the present invention may be used as a mixed solution obtained by diluting it with water, and the mixed solution may be foamed and kneaded into the hydraulic substance, or the mixed solution may be kneaded into the hydraulic substance as is. The present invention does not limit the method of adding the foaming agent for hydraulic compositions to a hydraulic composition, nor does it limit the method of foaming the foaming agent for hydraulic compositions or a mixture obtained by diluting it with water. In this invention, the term "hydraulic substance" refers to pastes, slurries, mortars, and concretes prepared as hydraulic powders from one or more substances selected from cement, gypsum, and mixtures thereof.

[0066] [Bubble-containing hydraulic composition, and method for producing the same] In one embodiment, the present invention provides a bubble-containing hydraulic composition containing a hydraulic powder, water, component (A), component (B), and component (C). In another embodiment, the present invention provides a bubble-containing hydraulic composition containing a hydraulic powder, water, and the foaming agent for the hydraulic composition of the present invention described above. The foam-containing hydraulic composition of the present invention may appropriately apply the matters described in the foaming agent for hydraulic compositions of the present invention. Components (A), (B), (C), and optional components used in the foam-containing hydraulic composition of the present invention may be the same as those described in the foaming agent for hydraulic compositions of the present invention.

[0067] Hydraulic powder refers to powder that has the property of hardening through a hydration reaction, and examples include cement and gypsum, preferably cement, gypsum, and mixtures thereof.

[0068] Examples of cements include ordinary Portland cement, rapid-hardening Portland cement, ultra-rapid-hardening Portland cement, sulfate-resistant Portland cement, low-heat Portland cement, moderate-heat Portland cement, white Portland cement, alumina cement, and eco-cement (e.g., JIS R 5214). Blast furnace slag cement, fly ash cement, silica fume cement, metakaolin cement, LC3 cement, etc., which are made by adding blast furnace slag, fly ash, silica fume, stone powder (calcium carbonate powder), metakaolin, calcined clay, etc., to these cements are also acceptable.

[0069] Any type of gypsum can be used, including high-quality neutralized gypsum, phosphate gypsum (a by-product of phosphoric acid), flue gas desulfurization gypsum generated from thermal power plants, natural gypsum containing various impurities and clay, and mixtures thereof. The clay contained in gypsum may mainly consist of hydrated silicate minerals with a layered structure (hereinafter referred to as clay minerals), and examples of clay minerals contained as fine-grained minerals in this clay include kaolin minerals (kaolinite, dickite, and nacrite), serpentine (lizardite, antigorite, chrysotile), mica clay minerals (illite, sericite, erythrolite, celadonite), chlorite, vermiculite, and smectite (montmorillonite, beidelite, nontronite, saponite, hectorite).

[0070] Examples of gypsum include anhydrous gypsum, hemihydrate gypsum, and dihydrate gypsum, and preferably hemihydrate gypsum (calcined gypsum). As raw material gypsum, natural gypsum, neutralized gypsum, or chemical gypsum such as by-product gypsum can be used alone or as a mixture of two or more of these. Examples of major chemical gypsums include phosphate gypsum, hydrofluoric acid gypsum, titanium gypsum, or flue gas desulfurization gypsum. Furthermore, recycled gypsum may be included in the raw material gypsum. Recycled gypsum can be any recycled gypsum recovered from waste gypsum boards generated in-house by gypsum board manufacturers, or from waste gypsum boards generated during new construction and demolition. The present invention can be suitably used with any of these raw material gypsums, and excellent effects can also be obtained with blends in various proportions.

[0071] The hydraulic powder may contain cement and other hydraulic powders. For example, preferably ordinary Portland cement may be included in the hydraulic powder at a concentration of 25% by mass or more, more preferably 35% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, and preferably 95% by mass or less, more preferably 92% by mass or less, even more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0072] The bubble-containing hydraulic composition of the present invention may have a water / hydraulic powder ratio of preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, and even more preferably 65% ​​by mass or more, from the viewpoint of slurry fluidity, and preferably 100% by mass or less, more preferably 90% by mass or less, even more preferably 80% by mass or less, and even more preferably 75% by mass or less, from the viewpoint of hardened product strength. Here, the water / hydraulic powder ratio is the mass percentage (mass%) of water and hydraulic powder in the hydraulic composition, and is calculated as water / hydraulic powder × 100. The water / hydraulic powder ratio is calculated based on the amount of powder that has properties that harden through a hydration reaction. If the powder that hardens through a hydration reaction contains a high-strength admixture, the amount of the high-strength admixture is also included in the amount of hydraulic powder. The same may apply to other quantitative relationships of the hydraulic composition with respect to the hydraulic powder.

[0073] The bubble-containing hydraulic composition of the present invention may contain component (A) in an amount of preferably 0.0005 parts by mass or more, more preferably 0.0006 parts by mass or more, preferably 0.2 parts by mass or less, and more preferably 0.1 parts by mass or less, per 100 parts by mass of hydraulic powder, from the viewpoint of suppressing solidification of the foaming agent and foaming properties.

[0074] In the present invention, if component (A) contains component (A1), component (A1) may be contained in an amount of preferably 0.0005 parts by mass or more, more preferably 0.0006 parts by mass or more, preferably 0.2 parts by mass or less, and more preferably 0.1 parts by mass or less, per 100 parts by mass of the hydraulic powder, from the viewpoint of suppressing solidification of the foaming agent and foaming properties.

[0075] In the present invention, if component (A) contains component (A2), component (A2) may be contained in an amount of preferably 0.0005 parts by mass or more, more preferably 0.0006 parts by mass or more, preferably 0.2 parts by mass or less, and more preferably 0.1 parts by mass or less, per 100 parts by mass of the hydraulic powder, from the viewpoint of suppressing solidification of the foaming agent and foaming properties.

[0076] The bubble-containing hydraulic composition of the present invention may contain component (B) in an amount of preferably 0.0000005 parts by mass or more, more preferably 0.000001 parts by mass or more, preferably 0.1 parts by mass or less, and more preferably 0.05 parts by mass or less, per 100 parts by mass of hydraulic powder, from the viewpoint of suppressing solidification of the foaming agent and foaming properties.

[0077] If the bubble-containing hydraulic composition of the present invention contains component (C), component (C) may be contained in an amount of preferably 0.0000005 parts by mass or more, more preferably 0.000001 parts by mass or more, preferably 0.06 parts by mass or less, and more preferably 0.03 parts by mass or less, per 100 parts by mass of hydraulic powder, from the viewpoint of suppressing solidification of the foaming agent and foaming properties.

[0078] The bubble-containing hydraulic composition of the present invention may contain fine aggregate and / or coarse aggregate. Furthermore, the bubble-containing hydraulic composition of the present invention may contain admixtures and admixtures known in the industry.

[0079] Examples of methods for producing a hydraulic composition containing bubbles include (I) a method of foaming the foaming agent for hydraulic compositions of the present invention and incorporating it into a hydraulic substance as foam, and (II) a method of preparing a hydraulic composition by incorporating the foaming agent for hydraulic compositions of the present invention into a hydraulic substance, and then foaming the hydraulic composition.

[0080] The bubble-containing hydraulic composition of the present invention yields a hardened body by drying and curing. The specific gravity of the cured body of the bubble-containing hydraulic composition of the present invention is preferably 0.3 or higher, more preferably 0.4 or higher, and even more preferably 0.5 or higher from the viewpoint of the strength of the hardened body of the hydraulic composition, and may be preferably 2.5 or lower, more preferably 2.0 or lower, and even more preferably 1.5 or lower from the viewpoint of ease of handling.

[0081] The hardened body of the bubble-containing hydraulic composition of the present invention contains bubbles. The average bubble diameter of the cured body of the bubble-containing hydraulic composition of the present invention is preferably 100 μm or more, more preferably 150 μm or more, from the viewpoint of the strength of the cured hydraulic composition, and preferably 400 μm or less, more preferably 300 μm or less, from the viewpoint of the aesthetic appearance of the hydraulic composition. The average bubble diameter is calculated by preparing a hardened body of the bubble-containing hydraulic composition, cutting out a cross-section from the hardened body, observing the cross-section with a digital microscope, and measuring the diameter of, for example, 100 bubble cross-sections. The average value (arithmetic mean) of these measurements is then used to calculate the average bubble diameter. When measuring the diameter of a bubble cross-section, the diameter is measured if the cross-section is circular, the major axis if the cross-section is elliptical, and the longest part if the cross-section is irregularly shaped. The bubble diameter of the hardened body of the bubble-containing hydraulic composition is the same as the bubble diameter of the bubble-containing hydraulic composition before hardening.

[0082] The bubble-containing hydraulic composition of the present invention can be manufactured using the foaming agent for hydraulic compositions of the present invention. In other words, the present invention provides a method for producing a bubble-containing hydraulic composition, comprising the following steps 1 and 2. <Process 1> A step of foaming a liquid composition containing the foaming agent for hydraulic compositions of the present invention and water to obtain foam. <Process 2> A step of mixing hydraulic powder, water, and the foam obtained in step 1. Alternatively, in step 2, a hydraulic composition containing hydraulic powder and water may be prepared, and the hydraulic composition may be mixed with the foam obtained in step 1.

[0083] This manufacturing method allows for the preparation of the bubble-containing hydraulic composition of the present invention. The method for producing the bubble-containing hydraulic composition of the present invention can be appropriately applied to the embodiments described in the foaming agent composition for the hydraulic composition of the present invention and the bubble-containing hydraulic composition of the present invention. In the method for producing 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 applied by replacing the content of each component with the amount of mixture.

[0084] In step 1, from the viewpoint of aerating the liquid composition, the content (solid content) of the foaming agent for hydraulic compositions of the present invention in the liquid composition is preferably 0.01% by mass or more, more preferably 0.015% by mass or more, and preferably 5% by mass or less, and more preferably 2% by mass or less.

[0085] In step 1, the foaming ratio (bubbling ratio) of the liquid composition depends on the intended use of the hydraulic composition, but from an economic standpoint, it is preferably 5 times or more, more preferably 7 times or more, and even more preferably 10 times or more. From the viewpoint of kneadability, it is preferably 30 times or less, more preferably 25 times or less, and even more preferably 20 times or less.

[0086] In step 2, depending on the intended use of the hydraulic composition, foam is mixed with the hydraulic composition in an amount of 50% or more by volume, more preferably 100% or more by volume, and even more preferably 150% or more by volume, from the viewpoint of reducing the specific gravity of the hardened body, and preferably 400% or less by volume, more preferably 300% or less by volume, and even more preferably 200% or less by volume, from the viewpoint of the strength of the hardened hydraulic composition. In this manufacturing method, admixtures and additives known in the industry can be mixed in step 1 and / or step 2.

[0087] After step 2, step 3 is performed to produce a hardened body of the bubble-containing hydraulic composition. Step 3: A step of molding and curing the bubble-containing hydraulic composition slurry obtained in Step 2.

[0088] Furthermore, the bubble-containing hydraulic composition of the present invention can be manufactured using the foaming agent for hydraulic compositions of the present invention. In other words, the present invention provides a method for producing a bubble-containing hydraulic composition, comprising the following steps 1' and 2'. <Process 1'> A step of obtaining a liquid composition containing a foaming agent for hydraulic compositions of the present invention and water. <Process 2'> A step of mixing a hydraulic powder with the liquid composition obtained in step 1' to obtain a hydraulic composition containing a foaming agent. <Step 3'> A step to obtain a foam-containing hydraulic composition slurry by foaming the foaming agent-containing hydraulic composition obtained in the previous step.

[0089] This manufacturing method allows for the preparation of the bubble-containing hydraulic composition of the present invention. The method for producing the bubble-containing hydraulic composition of the present invention can be appropriately applied to the embodiments described in the foaming agent composition for the hydraulic composition of the present invention and the bubble-containing hydraulic composition of the present invention. In the method for producing 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 applied by replacing the content of each component with the amount of mixture.

[0090] In step 1', from the viewpoint of aerating the liquid composition, the content (solid content) of the foaming agent for hydraulic compositions of the present invention in the liquid composition is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, and preferably 5% by mass or less, more preferably 2% by mass or less.

[0091] In step 2', the hydraulic powder and the liquid composition obtained in step 1' may be mixed using mixing methods known in the industry. In this manufacturing method, admixtures and additives known in the industry may be mixed in step 1' and / or step 2'.

[0092] In step 3', the foaming agent-containing hydraulic composition obtained in the previous step may be foamed using a mixing mixer such as a pan-type forced mixer, a twin-screw forced mixer, a tiltable mixer, a Hobart mixer, a rotary mixer, a Hobart mixer, a W-type mixer, a V-type mixer, a drum-type mixer, a conical screw-type mixer, a ribbon mixer, a tumbler mixer, a double-cone mixer, a mill mixer, a juicer mixer, a hand mixer, or a Nauta mixer, preferably at a foaming ratio of 1.01 or higher, more preferably 1.03 or higher, and from the viewpoint of hardened body strength, preferably at a foaming ratio of 5 or lower, more preferably 3 or lower.

[0093] After step 3', step 4' below can be performed to produce a hardened body of the bubble-containing hydraulic composition. Step 4': A step to mold and harden the bubble-containing hydraulic composition slurry obtained in Step 3'.

[0094] The specific gravity of the cured body of the bubble-containing hydraulic composition obtained by the method for producing the bubble-containing hydraulic composition of the present invention is preferably 0.3 or higher, more preferably 0.4 or higher, and even more preferably 0.5 or higher from the viewpoint of strength of the cured body of the hydraulic composition, and may be preferably 2.5 or lower, more preferably 2.0 or lower, and even more preferably 1.5 or lower from the viewpoint of ease of handling.

[0095] The average bubble diameter of the cured body of the bubble-containing hydraulic composition obtained by the method for producing the bubble-containing hydraulic composition of the present invention is preferably 100 μm or more, more preferably 150 μm or more, from the viewpoint of the strength of the cured hydraulic composition, and preferably 400 μm or less, more preferably 300 μm or less, from the viewpoint of the aesthetic appearance of the hydraulic composition. [Examples]

[0096] The components used in the examples and comparative examples are shown below. <(A) component> (A1) component C12 / 14 / 16AS·Na: Sodium alkyl sulfate salt (molar ratio: 12 / 14 / 16 carbon atoms = 74 / 22 / 4, manufactured by Kao Corporation) C12 / 14 / 16AS·TEA: Alkyl sulfate triethanolamine salt (molar ratio: 12 / 14 / 16 carbon atoms = 74 / 22 / 4, manufactured by Kao Corporation) (A2) Component (A21)C10AS·Na: Decyl sulfate sodium salt, manufactured by Kao Corporation (A22) C12 / 14AES·Na: Polyoxyethylene (average number of added moles 2) alkyl sulfate sodium salt (molar ratio: 12 / 14 carbon atoms = 74 / 26), manufactured by Kao Corporation. (A23) Fatty Acids / TEA: Fatty acid triethanolamine salt (molar ratio: 12 / 14 / 16 / 18 / 18 unsaturated / 28 unsaturated = 13 / 3 / 6 / 1 / 70 / 7), manufactured by Kao Corporation. Fatty Acids·Na: Sodium fatty acid salt (molar ratio: 12 / 14 / 16 / 18 saturated / 18 unsaturated / 28 unsaturated = 13 / 3 / 6 / 1 / 70 / 7), manufactured by Kao Corporation.

[0097] <((B') component)> • EtOH: Ethanol (LogP: -0.31, Molecular weight 46) (Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0098] <(B) component> • PEG400: Polyethylene glycol (LogP: -0.69, weight-average molecular weight 400) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) • DPG: Dipropylene glycol (LogP: -1.17, Molecular weight 134) (Manufactured by Fujifilm Wako Pure Chemical Corporation) • 1,3-BG: 1,3-butanediol (LogP: -0.74, molecular weight 90) (manufactured by Fujifilm Wako Pure Chemical Corporation) • NPG: 2,2-dimethyl-1,3-propanediol (LogP: -0.84, Molecular weight 104) (Manufactured by Fujifilm Wako Pure Chemical Corporation) • TEA: Triethanolamine (LogP: -2.3, Molecular weight 149) (Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) • 1,6-HG: 1,6-Hexanediol (LogP: -0.11, Molecular weight 118) (Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) • 1,2-HG: 1,2-Hexanediol (LogP: -0.58, Molecular weight 118) (Manufactured by Fujifilm Wako Pure Chemical Corporation) • PG: Propylene glycol (LogP: -0.92, molecular weight 76) (manufactured by Fujifilm Wako Pure Chemical Corporation) • Organic compound (B1) (LogP: -2.3 to -1.91, mixture of DPG / TEA / DEA / MEA = 50 / 28.6 / 14.2 / 7.2 (mass ratio), molecular weight of DPG 134, molecular weight of TEA 149, molecular weight of DEA: diethanolamine 105, molecular weight of MEA: monoethanolamine 61), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0099] <(C) component> • C8OH: 1-Octyl alcohol (LogP: 3, molecular weight 130) (Product name "Calcol 0898", manufactured by Kao Corporation) • BnOH: Benzyl alcohol (LogP: 1.1, Molecular weight 108) (Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0100] Example 1 (Table 1), Example 2 (Table 2) Each of the components shown in Tables 1 and 2 was stirred with a magnetic stirrer while being heated to 40°C in a 200g beaker scale to the content shown in Tables 1 and 2, thereby preparing the foaming agents for hydraulic compositions shown in Tables 1 to 3.

[0101] (1) Drying test 40 g of the obtained foaming agent for hydraulic compositions was measured into a 100 mL disposable cup (AS ONE Corporation, model number 1-4659-01). The 100 mL cup containing the foaming agent was stored open in a 40°C constant temperature chamber (Advantec Toyo Co., Ltd., forced-air constant temperature drying oven DRM620DB). After 14.5 hours and 26 hours, the top surface of the foaming agent was visually inspected, and the presence or absence of solid matter in the foaming agent was evaluated according to the evaluation criteria shown in Tables 1 and 2. The results are shown in Tables 1 and 2.

[0102] <<Evaluation Criteria for the Suppression of Solid Matter Generation (Visual Evaluation)>> 1: The precipitated solids cover the entire top surface of the foaming agent. 2: Precipitated solids occupy 70% of the top surface of the foaming agent. 3. The precipitated solids occupy half of the top surface of the foaming agent. 4. Precipitated solids account for 30% of the top surface of the foaming agent. 5. No solid matter is generated on the surface of the foaming agent.

[0103] [Table 1]

[0104] [Table 2]

[0105] In the table, component (A) represents the apparent amount (mass%) based on the effective amount. The value in parentheses next to the amount indicates the value converted to sodium salt. In addition, the content (mass%), content ratio (mass%), and mass ratio marked with *1 indicate the value of the (A) component used converted to sodium salt. In the foaming agents for hydraulic compositions in the table, all components other than those listed in the table are water.

[0106] The foaming agents for hydraulic compositions in Examples 1 and 2 were confirmed not to solidify even after exposure to air for 14.5 hours and 26 hours, respectively. In Examples 1-8, the molecular weight of component (B) was relatively small, and in Examples 1-6, the distance between hydroxyl groups in component (B) was large. It is presumed that these factors made it difficult to obtain an improvement in the water solubility of the micelles formed by component (A), resulting in the difference in solidification inhibition effect between 14.5 hours and 26 hours.

[0107] (2) Evaluation of bubble-containing hydraulic compositions (2-1) Preparation of hydraulic composition slurry The foaming agent for hydraulic compositions prepared in Table 1 was mixed with water in a mass ratio of 0.3 to 99.7 to prepare an aqueous solution with a concentration (in form) of 0.3% by mass of the foaming agent for hydraulic compositions. 49.5 g of the prepared aqueous solution was added to a 1 L disposable cup, and the mixture was stirred by hand for 60 seconds at 2000 rpm (EUROSTAR200 control, IKA Japan Co., Ltd.) using a flat 6-blade paddle (FP-50, manufactured by AS ONE Corporation), while rotating the container by hand. After setting the container down, the mixture was stirred for another 30 seconds to obtain foam. 60g of calcined gypsum (Sakura brand calcined gypsum grade A, manufactured by Yoshino Gypsum Co., Ltd.), 240g of ordinary Portland cement (two-type mixture: Taiheiyo Cement / Sumitomo Osaka Cement = 1 / 1, mass ratio), 115.5g of tap water, and 0.48g of water-reducing agent (methacrylic acid / ω-methoxypolyethylene glycol (23 mol) monomethacrylate = 73 / 27 mol%) were added to a 500mL disposable cup, and the mixture was stirred for 5 seconds at setting 3 using a hand mixer (MK-H4, manufactured by Panasonic Corporation) to prepare a hydraulic composition slurry before foam addition. The entire amount of the prepared hydraulic composition slurry was added to 49.5g of foam prepared in a 1L disposable cup, and the mixture was kneaded in the 1L disposable cup at 1150 rpm for 10 seconds using the flat 6-blade paddle blade to obtain a hydraulic composition slurry containing air bubbles. The temperature of both the foam and the hydraulic composition slurry used for mixing was 20°C.

[0108] (2-2) Measurement of air content in hydraulic composition slurry The obtained hydraulic composition slurry containing air bubbles was poured into a mold (Plamold, manufactured by Nifco Corporation) for a cylindrical specimen with a diameter of 5 cm and a height of 10 cm, and its weight was measured. The specific gravity of the hardened hydraulic composition was calculated by dividing the weight of the poured hydraulic composition slurry by the volume of the mold. In addition, the amount of air (volume %) in the hydraulic composition slurry obtained above was measured in accordance with JIS A1128:2019. The results are shown in Table 3. Furthermore, assuming that the amount of air in the hydraulic composition slurry is approximately equal to the amount of air in the hardened hydraulic composition, the values ​​shown in Table 3 are considered to be the "amount of air in the hardened hydraulic composition."

[0109] (2-3) Production of hardened bodies of hydraulic compositions The resulting water-hardening composition slurry containing air bubbles was poured into a mold (Plamold, manufactured by Nifco Corporation) with a diameter of 5 cm and a height of 10 cm, and left to stand at 20°C for 3 hours. The hardened water-hardening composition was demolded from the mold.

[0110] (2-4) Measurement of the average bubble diameter in the hardened hydraulic composition A cross-section of the hardened hydraulic composition was created by making an incision at a height of 5 cm. The cross-section was photographed with a digital microscope (DSX1000, OLYMPUS Corporation, 42x magnification), and the diameters of 100 randomly selected bubble cross-sections were measured. The average bubble diameter was calculated from the arithmetic mean of these values. For measuring the diameter of the bubble cross-section, the diameter was used if the bubble cross-section was circular, the major axis if the bubble cross-section was elliptical, and the longest part if the bubble cross-section was irregular in shape. The results are shown in Table 3. The coefficient of variation was calculated by dividing the standard deviation of the calculated bubble diameters by the average bubble diameter.

[0111] [Table 3]

Claims

1. (A) One or more surfactants selected from anionic surfactants, cationic surfactants, and amphoteric surfactants having a hydrocarbon group with 8 to 30 carbon atoms [hereinafter, component (A)] (B) Organic compounds with a LogP of -5.0 or higher and less than 0, and a molecular weight of 50 or higher and 500 or lower [hereinafter, component (B)] A foaming agent for hydraulic compositions containing [the specified ingredient].

2. The foaming agent for hydraulic compositions according to claim 1, wherein component (A) is an anionic surfactant having a hydrocarbon group with 8 to 30 carbon atoms.

3. The foaming agent for hydraulic compositions according to claim 1, wherein component (A) contains an alkyl or alkenyl sulfate ester or a salt thereof having an alkyl or alkenyl group having 12 or more carbon atoms and 18 carbon atoms.

4. Furthermore, the foaming agent for hydraulic compositions according to claim 1 or 2, further comprising (C) a nonionic compound having a LogP of 0 or more and 7.0 or less [hereinafter, component (C)].

5. The foaming agent for hydraulic compositions according to claim 1 or 2, wherein component (B) is an organic compound having one to ten hydroxyl groups.

6. A bubble-containing hydraulic composition comprising: hydraulic powder; water; (A) one or more surfactants selected from anionic surfactants, cationic surfactants, and amphoteric surfactants having hydrocarbon groups with 8 to 30 carbon atoms; and (B) an organic compound having a LogP of -5.0 or more and less than 0, and a molecular weight of 50 to 500.

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