Foaming agent for hydraulic composition

Abstract

To provide a foaming agent for hydraulic compositions, a foam-containing hydraulic composition, and a method for producing the same, which enables an increase in the bubble diameter in a foam-containing hydraulic composition having the same specific gravity.SOLUTION: Provided is a foaming agent for hydraulic compositions, comprising the following components (A) and (B), wherein the mass ratio (B) / (A) of the content of component (B) to the content of component (A) is 75 / 25 or more to 99 / 1 or less. Component (A): Olefin sulfonic acid or a salt thereof. Component (B): An anionic surfactant other than component (A).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a foaming agent for a hydraulic composition, a bubble-containing hydraulic composition, and a method for producing the same. [Background technology]

[0002] Air bubbles are introduced into hydraulic compositions using cement or gypsum as a hardening agent to reduce their weight. Usually, a foamed liquid composition containing a foaming agent and water is foamed, and the foam is mixed with the hydraulic composition, or with fine aggregate or various admixtures to produce a lightweight air bubble-containing hydraulic composition.

[0003] Patent Document 1 discloses a mixture for air mortar with stable bubbles, which is characterized by including a hydraulic material containing a cement component consisting of either Portland cement or a blended cement or a combination of these, a foaming agent consisting of a powdered anionic surfactant, and bentonite having a swelling power of 18 ml / 2 g or more. Patent Document 2 discloses a foaming agent for producing lightweight gypsum boards, which is composed of 100 parts of an anionic surfactant selected from an alkali metal salt, ammonium salt, and alkanol ammonium salt of an ethylene oxide adduct of a higher alcohol having 8 and 10 carbon atoms, and 5 to 100 parts of an ethylene oxide 1-2 mole adduct of an alcohol having 1 to 4 carbon atoms, and discloses that the foaming agent for producing lightweight gypsum boards can obtain the required volume with a small amount of use, and has excellent adhesion between the base paper and the gypsum core even in the case of low-density gypsum boards, and shows high core strength. 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. Patent Document 3 discloses a method for producing a lightweight gypsum product in which stable foam characteristics can be obtained, characterized in that when a gypsum slurry containing air bubbles is molded to produce the lightweight gypsum product, an internal olefin sulfonate having 10 to 18 carbon atoms is added to the gypsum slurry. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2020-83663 A [Patent Document 2] Japanese Patent Application Publication No. 7-291761 [Patent Document 3] Japanese Patent Application Laid-Open No. 61-168557 Summary of the Invention [Problem to be solved by the invention]

[0005] The hardened foam of the air-containing hydraulic composition, which uses cement or gypsum as a hardening agent, has environmental (CO) 2 From the standpoint of weight reduction and cost, further weight reduction is required. The bubble-containing hydraulic composition can reduce the specific gravity of the set body of the hydraulic composition by containing bubbles, and thus can be made lighter. However, when the volume (ratio) of bubbles is increased in order to further reduce the weight of the set body of the hydraulic composition, the ratio of the hydraulic composition decreases, and the strength of the set body tends to decrease. On the other hand, as described in paragraph 0004 of JP-A-10-330174, the strength of the set body of the bubble-containing hydraulic composition can be increased by increasing the bubble diameter in the bubble-containing hydraulic composition in a bubble-containing hydraulic composition of the same specific gravity. In addition, when the bubble diameter in the bubble-containing hydraulic composition is increased, the drying time when obtaining the set body of the bubble-containing hydraulic composition is accelerated, which reduces the fuel cost for drying and CO2 emission. 2 In addition, when the bubble diameter in the bubble-containing hydraulic composition is increased, the distance between the bubbles increases, making it difficult for the bubbles to communicate with each other, and improving the heat insulation and sound insulation properties. Therefore, there is a demand for a technology for increasing the bubble diameter in a bubble-containing hydraulic composition having the same specific gravity.

[0006] The present invention provides a foaming agent for hydraulic compositions, a bubble-containing hydraulic composition, and a method for producing the same, which can increase the bubble diameter in a bubble-containing hydraulic composition of the same specific gravity. [Means for solving the problem]

[0007] The present invention relates to a foaming agent for hydraulic compositions, comprising the following components (A) and (B), in which the mass ratio (B) / (A) of the content of the component (B) to the content of the component (A) is 75 / 25 or more and 99 / 1 or less: Component (A): Olefin sulfonic acid or its salt Component (B): Anionic surfactant other than component (A)

[0008] The present invention also relates to a bubble-containing hydraulic composition comprising a hydraulic powder, water, a dispersant, the above-mentioned component (A) and component (B), in which the mass ratio (B) / (A) of the content of the component (B) to the content of the component (A) is 75 / 25 or more and 99 / 1 or less.

[0009] The present invention also relates to 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 a foam. <Process 2> A step of mixing hydraulic powder, water, a dispersant, and the foam obtained in step 1. Effect of the Invention

[0010] According to the present invention, there are provided a foaming agent for hydraulic compositions, a bubble-containing hydraulic composition, and a method for producing the same, which can increase the bubble diameter in a bubble-containing hydraulic composition of the same specific gravity. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The reason why the foaming agent for hydraulic compositions, the bubble-containing hydraulic composition, and the manufacturing method thereof of the present invention can increase the bubble diameter in a bubble-containing hydraulic composition of the same specific gravity is not necessarily clear, but is presumed to be as follows. Conventionally, as disclosed in a prior document (JP Patent Publication No. 2004-529050), for example, attention has been focused on surfactants, and bubble size and the like in a hydraulic composition have been controlled by adjusting foam performance in an aqueous system when a liquid composition containing a foaming agent for hydraulic compositions and water is foamed. However, in the case of a method of controlling only foam performance in an aqueous system by focusing on a surfactant, in order to introduce a certain amount of foam into the hydraulic composition, it is necessary to satisfy a certain level of foam performance such as foaming ability and foam stability, and accordingly, the bubbles become stabilized in the hydraulic composition, coalescence does not proceed, and the bubble diameter is fixed without increasing. Therefore, the present inventors have found that the above-mentioned problems can be solved by controlling the foam performance in an aqueous system and the foam coalescence rate in a hydraulic composition. More specifically, the above-mentioned problem is solved by combining, as component (A), an olefin sulfonic acid or a salt thereof, and, as component (B), an anionic surfactant other than component (A), in a specific mass ratio. The olefin sulfonic acid or its salt, which is component (A) of the present invention, is rapidly adsorbed to the foam film formed by the anionic surfactant, which is component (B), and improves the dynamic stability of the gas-liquid interface, thereby dramatically improving foam performance in aqueous systems. On the other hand, in the hydraulic composition, calcium sulfate, which is one of the main components of the hydraulic powder, strongly interacts with component (A), resulting in a loss of the synergistic effect with component (B), a change in foam performance, and promotion of bubble coalescence, resulting in an increase in the size of bubbles in the hydraulic composition. It is presumed that these actions make it possible to increase the bubble diameter in a bubble-containing hydraulic composition of the same specific gravity. However, the present invention is not limited to the above expression mechanism.

[0012] [Foaming agent for hydraulic composition] <Component (A)> The foaming agent for hydraulic compositions of the present invention contains an olefin sulfonic acid or a salt thereof as component (A). From the viewpoint of increasing the diameter of bubbles in the hydraulic composition, the carbon number of the olefin sulfonic acid of component (A) is preferably 12 or more, more preferably 14 or more, even more preferably 16 or more, and is preferably 20 or less, more preferably 18 or less. The carbon number of the olefin sulfonate represents the carbon number of the olefin to which the sulfonic acid is covalently bonded. The salt of the component (A) may be one or more selected from alkali metal salts such as sodium salts and potassium salts, ammonium salts, and organic ammonium salts.

[0013] From the viewpoints of foaming performance in aqueous systems, particularly foaming ability, enlarging the bubbles in the hydraulic composition, and storage stability of the foaming agent for hydraulic compositions (hereinafter simply referred to as the foaming agent), the (A) component is preferably an internal olefin sulfonic acid having 12 to 20 carbon atoms or a salt thereof.

[0014] An internal olefin sulfonic acid or a salt thereof having 12 to 20 carbon atoms can be obtained by sulfonating, neutralizing, hydrolyzing, and the like an internal olefin having 12 to 20 carbon atoms. The internal olefin refers to an olefin in which a double bond is present inside the 2-position. For example, an internal olefin can be obtained by isomerizing a 1-olefin obtained by dehydrating a 1-alcohol. When an internal olefin is sulfonated, β-sultone is quantitatively produced, and a part of the β-sultone is converted to γ-sultone and olefin sulfonic acid, which are further converted to hydroxyalkanesulfonate (H-form) and olefin sulfonate (O-form) in the neutralization and hydrolysis process (for example, J. Am. Oil Chem. Soc. 69, 39 (1992)). Here, the hydroxy group of the obtained hydroxyalkanesulfonic acid is inside the alkane chain, and the double bond of the olefin sulfonate is inside the olefin chain. The obtained product is mainly a mixture of these, and may contain a small amount of hydroxyalkanesulfonic acid having a hydroxy group at the end of the carbon chain or α-olefinsulfonic acid having a double bond at the end of the carbon chain. In this specification, these products and their mixtures are collectively called internal olefinsulfonic acid. Hydroxyalkanesulfonic acid is also called hydroxyl form of internal olefinsulfonic acid (hereinafter also called HAS), and olefinsulfonic acid is also called olefin form of internal olefinsulfonic acid (hereinafter also called IOS).

[0015] From the viewpoint of increasing the diameter of bubbles in the hydraulic composition, the number of carbon atoms in the internal olefin sulfonate is preferably 12 or more, more preferably 14 or more, even more preferably 16 or more, and preferably 20 or less, more preferably 18 or less. The number of carbon atoms in the internal olefin sulfonate represents the number of carbon atoms in the internal olefin to which the sulfonic acid is covalently bonded.

[0016] The internal olefin sulfonic acid or its salt also includes those containing a small amount of so-called alpha olefin sulfonic acid or its salt (hereinafter also referred to as α-olefin sulfonic acid or its salt), in which the sulfonic acid is at position 1 of the carbon chain. The upper limit of the content of α-olefin sulfonic acid or its salt in the internal olefin sulfonic acid is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, still more preferably 3% by mass or less, and preferably 0.01% by mass or more.

[0017] Internal olefin sulfonic acid or its salt can be obtained by sulfonating an olefin having 12 to 20 carbon atoms and having a double bond at the second or higher position as the main component. When the internal olefin is sulfonated, β-sultone is quantitatively produced, and a part of the β-sultone is converted to γ-sultone and olefin sulfonic acid, which are further converted to hydroxyalkanesulfonic acid and olefin sulfonic acid in the neutralization and hydrolysis process (for example, J. Am.Oil Chem. Soc. 69, 39(1992)). Here, the hydroxy group of the obtained hydroxyalkanesulfonic acid is located inside the alkane chain, and the double bond of the olefin sulfonic acid is located inside the olefin chain. The obtained product is mainly a mixture of these, and some of them may contain a small amount of hydroxyalkanesulfonic acid having a hydroxy group at the end of the carbon chain or olefin sulfonic acid having a double bond at the end of the carbon chain.

[0018] In this specification, these products and mixtures thereof are collectively referred to as internal olefin sulfonic acid or a salt thereof. In addition, hydroxyalkanesulfonic acid or a salt thereof is referred to as hydroxy form of internal olefin sulfonic acid or a salt thereof (HAS), and olefin sulfonic acid or a salt thereof is referred to as olefin form of internal olefin sulfonic acid or a salt thereof (IOS). The mass ratio of the compound in the internal olefin sulfonic acid or a salt thereof can be measured by HPLC-MS peak area.

[0019] The internal olefin sulfonic acid or its salt may contain a hydroxyl form and an olefin form. The mass ratio of the content of the olefin form of the internal olefin sulfonic acid or its salt to the content of the hydroxyl form of the internal olefin sulfonic acid or its salt (olefin form / hydroxyl form) in the internal olefin sulfonic acid or its salt may be 0 / 100 or more, further 5 / 95 or more, and 50 / 50 or less, further 40 / 60 or less, further 30 / 70 or less, further 25 / 75 or less.

[0020] <(B) component> The foaming agent for hydraulic compositions of the present invention contains, as component (B), an anionic surfactant other than component (A).

[0021] Examples of anionic surfactants other than component (A) include sulfonic acid compounds, ether sulfate compounds, carboxylic acid compounds, phosphonic acid compounds, and phosphoric acid compounds having a hydrocarbon group having from 8 to 18 carbon atoms. For example, one or more selected from alkyl or alkenyl sulfate esters having an alkyl or alkenyl group, alkyl or alkenyl sulfonic acids having an alkyl or alkenyl group, polyoxyalkylene alkyl or alkenyl ether sulfate esters having an alkyl or alkenyl group, polyoxyalkylene alkyl or alkenyl ether carboxylic acids having an alkyl or alkenyl group, and salts thereof can be mentioned. Examples of the salts of these anionic surfactants include at least one selected from alkali metal salts such as sodium salts and potassium salts, ammonium salts, and organic ammonium salts.

[0022] From the viewpoint of foaming performance, particularly foaming ability, in aqueous systems, component (B) is preferably at least one selected from alkyl or alkenyl sulfate esters having an alkyl or alkenyl group having from 8 to 18 carbon atoms, alkyl or alkenyl sulfonic acids having an alkyl or alkenyl group having from 8 to 18 carbon atoms, polyoxyalkylene alkyl or alkenyl ether sulfate esters having an alkyl or alkenyl group having from 8 to 18 carbon atoms, and salts thereof. Examples of the salts of these anionic surfactants include one or more selected from alkali metal salts such as sodium salts and potassium salts, ammonium salts, and organic ammonium salts.

[0023] From the viewpoint of foaming ability, particularly among foam performance in aqueous systems, the (B) component is preferably at least one selected from (B1) an alkyl or alkenyl sulfate ester or a salt thereof having an alkyl or alkenyl group having from 8 to 18 carbon atoms (hereinafter referred to as (B1) component), and (B2) a polyoxyalkylene alkyl or alkenyl ether sulfate ester or a salt thereof having an alkyl or alkenyl group having from 8 to 18 carbon atoms (hereinafter referred to as (B2) component).

[0024] From the viewpoint of increasing the diameter of bubbles in the hydraulic composition, the component (B1) preferably has an alkyl or alkenyl group, preferably an alkyl group, having 8 or more carbon atoms, more preferably 10 or more carbon atoms, and preferably 18 or less, more preferably 16 or less, even more preferably 14 or less, and still more preferably 12 or less. Examples of the salt of the component (B1) include one or more salts selected from alkali metal salts such as sodium salts and potassium salts, ammonium salts, and organic ammonium salts.

[0025] Specific examples of the (B1) component include one or more compounds selected from octyl sulfate, decyl sulfate, dodecyl sulfate, tetradecyl sulfate, hexadecyl sulfate, octadecyl sulfate, 2-ethylhexyl sulfate, 2-propylheptyl sulfate, and salts thereof. From the viewpoint of increasing the diameter of bubbles in the hydraulic composition, it is preferable for the component (B1) to contain one or more compounds selected from decyl sulfate, dodecyl sulfate, tetradecyl sulfate, and salts thereof, and it is more preferable for the component (B1) to contain one or more compounds selected from decyl sulfate, dodecyl sulfate, and salts thereof.

[0026] From the viewpoint of foaming performance, particularly foaming ability, in aqueous systems, the component (B) may contain, as the component (B1), two types of alkyl or alkenyl sulfate esters or salts thereof having different numbers of carbon atoms in the alkyl or alkenyl groups.

[0027] From the viewpoint of increasing the diameter of bubbles in the hydraulic composition, the (B2) component preferably has an alkyl or alkenyl group, preferably an alkyl group, having 8 or more carbon atoms, more preferably 10 or more carbon atoms, and preferably 16 or less, more preferably 14 or less, and even more preferably 12 or less carbon atoms. The oxyalkylene group of the component (B2) is an oxyethylene group or an oxypropylene group, and is preferably an oxyethylene group. From the viewpoint of foaming performance, particularly foamability, in an aqueous system, the average number of moles of the oxyalkylene group added is preferably 1 or more, more preferably 2 or more, and from the viewpoint of foaming performance, particularly foamability, in an aqueous system, it is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. Examples of the salt of component (B2) include one or more salts selected from alkali metal salts such as sodium salts and potassium salts, ammonium salts, and organic ammonium salts.

[0028] Specific examples of the component (B2) include 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 sulfate. Examples of the sulfuric acid ester include one or more selected from the group consisting of polyoxyethylene polyoxypropylene tridecyl ether sulfate, polyoxyethylene polyoxypropylene myristyl ether sulfate, polyoxyethylene polyoxypropylene cetyl ether sulfate, polyoxyethylene polyoxypropylene stearyl ether sulfate, and salts thereof. From the viewpoint of increasing the diameter of bubbles in the hydraulic composition, preferred are one or more selected from the group consisting of polyoxyethylene decyl ether sulfate, polyoxyethylene lauryl ether sulfate, polyoxyethylene myristyl ether sulfate, polyoxypropylene decyl ether sulfate, polyoxypropylene lauryl ether sulfate, polyoxypropylene myristyl ether sulfate, polyoxyethylene polyoxypropylene decyl ether sulfate, polyoxyethylene polyoxypropylene lauryl ether sulfate, polyoxyethylene polyoxypropylene myristyl ether sulfate, and salts thereof.

[0029] <Composition, etc.> From the viewpoint of increasing the diameter of bubbles in the hydraulic composition, the foaming agent for hydraulic compositions of the present invention contains the component (A) in an amount of preferably 0.1 mass % or more, more preferably 0.5 mass % or more, even more preferably 1.0 mass % or more, and preferably 25 mass % or less, more preferably 20 mass % or less, even more preferably 10 mass % or less, still more preferably 7.0 mass % or less, and even more preferably 5.0 mass % or less. In the present invention, the mass of the component (A) is expressed as a value converted into a sodium salt.

[0030] From the viewpoint of increasing the diameter of bubbles in the hydraulic composition, the foaming agent for hydraulic compositions of the present invention contains the component (B) in an amount of preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, still more preferably 30% by mass or less, and even more preferably 29.0% by mass or less. In the present invention, the masses of the component (B), and the components (B1) and (B2) contained in the component (B) are expressed in terms of sodium salts.

[0031] In the foaming agent for hydraulic compositions of the present invention, the mass ratio (B) / (A) of the content of the component (B) to the content of the component (A) is 75 / 25 or more, preferably 78 / 22 or more, more preferably 85 / 15 or more, even more preferably 92 / 8 or more, and is 99 / 1 or less, preferably 98 / 2 or less, more preferably 96 / 4 or less, from the viewpoint of increasing the diameter of bubbles in the hydraulic composition.

[0032] The foaming agent for hydraulic compositions of the present invention may contain an aliphatic alcohol as component (C) from the viewpoints of foaming speed and foam stability. From the viewpoints of rapid foaming and foam stability, the component (C) is preferably a monohydric aliphatic alcohol having 6 to 10 carbon atoms. The carbon number of the (C) component is 6 or more and 10 or less, and preferably 8, from the viewpoints of foaming speed and foam stability. From the viewpoints of rapid foaming and foam stability, component (C) is a monohydric alcohol having a straight-chain or branched-chain hydrocarbon group, preferably a straight-chain or branched-chain alkyl group, and more preferably a straight-chain alkyl group.

[0033] Specific examples of the component (C) include one or more selected from hexanol, octanol, decanol, 2-ethylhexanol, and 2-propylheptanol. From the viewpoint of foamability, it is preferable that the component (C) contains one or more selected from octanol and decanol, and more preferably octanol.

[0034] When the foaming agent for hydraulic compositions of the present invention contains component (C), the foaming agent contains component (C) in an amount of preferably 0.5 mass % or more, more preferably 1.0 mass % or more, even more preferably 1.5 mass % or more, and preferably 10 mass % or less, more preferably 5 mass % or less, even more preferably 3 mass % or less, from the viewpoint of increasing the diameter of bubbles in the hydraulic composition.

[0035] The foaming agent for hydraulic compositions of the present invention may contain a nonionic surfactant as component (D) from the viewpoint of lowering the specific gravity of the hydraulic composition and increasing the bubble size. The nonionic surfactant may be one or more selected from alkyl monoglyceryl ether, polyoxyalkylene monoalkyl or alkenyl ether, alkyl glycoside or alkyl polyglycoside (alkyl glycoside type nonionic surfactant), sorbitan-based nonionic surfactant, aliphatic alkanolamide, fatty acid monoglyceride, and sucrose fatty acid ester. Among these, it is preferable to contain an alkyl glycoside type nonionic surfactant from the viewpoint of increasing the diameter of bubbles in the hydraulic composition.

[0036] From the viewpoint of achieving both foam stability, particularly in terms of foam performance in an aqueous system, and enlargement of bubbles in the hydraulic composition, the component (D) is preferably an alkyl glycoside type nonionic surfactant (D1) (hereinafter referred to as component (D1)). Examples of the component (D1) include alkylglycoside-type nonionic surfactants represented by the following general formula (D1). R 1d -(OR 2d ) p G q (D1) [In the formula, R 1d is an alkyl group having 6 to 18 carbon atoms, R 2d is an alkylene group having 2 to 4 carbon atoms, G is a residue derived from a reducing sugar, p is a number of 0 to 10 indicating the average number of moles of oxyalkylene groups added, and p R 2d may be the same or different. q is a number of 1 to 3 indicating the average degree of condensation of G.

[0037] In formula (D1), R 1d From the viewpoint of improving foamability, the number of carbon atoms is preferably 8 or more, more preferably 10 or more, and preferably 14 or less, more preferably 12 or less. R 2d is preferably an ethylene group or a propylene group, more preferably an ethylene group. p is preferably 5 or less, more preferably 2 or less, and may be 0. q is preferably 2.5 or less, more preferably 2 or less. Examples of G include residues derived from monosaccharides such as glucose, galactose, xylose, mannose, lyxose, arabinose, fructose, or mixtures thereof, and examples of disaccharides or higher include residues derived from maltose, xylobiose, isomaltose, cellobiose, gentiobiose, lactose, sucrose, nigerose, turanose, raffinose, gentianose, menzitose, or mixtures thereof. Among these, preferred raw materials are glucose and fructose for monosaccharides and maltose and sucrose for disaccharides or higher, from the viewpoint of availability.

[0038] When the foaming agent for hydraulic compositions of the present invention contains the component (D), from the viewpoints of achieving both foam stability, particularly among foam performances in aqueous systems, and enlargement of bubbles in the hydraulic composition, the foaming agent contains the component (D) in an amount of preferably 0.1 mass % or more, more preferably 0.5 mass % or more, even more preferably 1.0 mass % or more, and preferably 5.0 mass % or less, more preferably 3.0 mass % or less, even more preferably 2.0 mass % or less.

[0039] The foaming agent for hydraulic compositions of the present invention may contain water. The foaming agent for hydraulic compositions of the present invention contains water in an amount of preferably 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less.

[0040] The foaming agent for hydraulic compositions of the present invention may optionally contain a thickener, a chelating agent, a heavy metal scavenger, a rust inhibitor, a preservative, a colorant, a fragrance, a defoamer, a solvent, a dispersant, a flocculant, a water-soluble polymer, etc. However, these do not fall under the category of components (A), (B), (C), and (D).

[0041] The foaming agent for hydraulic compositions of the present invention can be obtained by mixing the component (A), the component (B), and any optional components. During mixing, heating may be performed appropriately to reduce the solution viscosity.

[0042] The foaming agent composition for hydraulic compositions of the present invention is intended for use in the following applications: hydraulic compositions containing air bubbles, such as gypsum slurry, lightweight milk (aerated milk, air milk), lightweight mortar (aerated mortar, air mortar), lightweight concrete (aerated concrete, air concrete), backfilling material, innerfilling material, architectural concrete block, ALC (lightweight aerated concrete), grout material, ceramic porous body, brick, refractory material, lightweight embankment, and pump pressure mortar. In these hydraulic compositions containing air bubbles, the addition of air bubbles is expected to provide functions such as weight reduction, strength improvement, fluidity improvement, heat insulation, heat resistance, viscosity, and fluidity control. Among these foam-containing hydraulic compositions, the foaming agent for hydraulic compositions of the present invention is suitable for use in gypsum slurries.

[0043] [Air-containing hydraulic composition and its manufacturing method] The method for producing a hydraulic composition containing bubbles is preferably a method in which the foaming agent for hydraulic compositions of the present invention is foamed and mixed with a hydraulic substance as foam to make the composition lighter, since this method entrains uniform bubbles. The foaming agent for hydraulic compositions of the present invention or a mixed liquid obtained by diluting it with water may be directly kneaded into paste, slurry, mortar, or concrete containing cement or gypsum as a hydraulic substance. There is no limitation on the method for adding the foaming agent for hydraulic compositions of the present invention to a hydraulic composition, and there is no limitation on the method for foaming the foaming agent for hydraulic compositions of the present invention or a mixed liquid obtained by diluting it with water.

[0044] The present invention provides a bubble-containing hydraulic composition comprising a hydraulic powder, water, a dispersant, component (A), and component (B), in which the mass ratio (B) / (A) of the content of component (B) to the content of component (A) is 75 / 25 or more and 99 / 1 or less. The bubble-containing hydraulic composition of the present invention may further contain component (C). The bubble-containing hydraulic composition of the present invention may further contain component (D). The foaming agent for hydraulic compositions of the present invention can be appropriately applied to the foam-containing hydraulic composition of the present invention. The components (A), (B), (C) and (D) are the same as those described in the foaming agent for hydraulic compositions of the present invention.

[0045] The hydraulic powder is a powder having the physical property of hardening through a hydration reaction, and examples of the powder include cement and gypsum, with gypsum being preferred. Examples of cement include ordinary Portland cement, belite cement, moderate heat cement, high-early-strength cement, ultra-high-early-strength cement, and sulfate-resistant cement. These may also be supplemented with blast furnace slag cement, fly ash cement, or silica fume cement to produce these with the addition of blast furnace slag, fly ash, silica fume, or stone powder (calcium carbonate powder).

[0046] The dispersant may be one or more compounds selected from a naphthalene-based polymer, a polycarboxylic acid-based polymer, a lignin sulfonic acid-based polymer, and a melamine-based polymer. When a polycarboxylic acid polymer is used as a dispersant, the dispersibility is good when producing a bubble-containing hydraulic composition, and water can be reduced, so that the bubble-containing hydraulic composition can be dried quickly when hardened, and fuel costs can be reduced, but there is a disadvantage that the average bubble diameter of the hardened product of the bubble-containing hydraulic composition is smaller than that of the case where a naphthalene polymer is used as a dispersant. The bubble-containing hydraulic composition of the present invention can increase the average bubble diameter of the hardened product of the bubble-containing hydraulic composition even when a polycarboxylic acid polymer is used as a dispersant.

[0047] The naphthalene-based polymer may be, for example, a polymer produced by condensation polymerization. Specifically, for example, a polymer produced by addition condensation of a naphthalene-based compound with an aldehyde, typically formaldehyde condensation, may be used. The naphthalene-based polymer is preferably a condensation polymer produced by an aldehyde, more preferably a formaldehyde condensation polymer.

[0048] As the naphthalene-based polymer, preferably, naphthalene sulfonic acid formaldehyde condensate or its salt can be mentioned. Naphthalene sulfonic acid formaldehyde condensate or its salt is a condensate of naphthalene sulfonic acid and formaldehyde or its salt. Naphthalene sulfonic acid formaldehyde condensate may be co-condensed with aromatic compounds that can be co-condensed with naphthalene sulfonic acid as a monomer, such as, for example, methylnaphthalene, ethylnaphthalene, butylnaphthalene, hydroxynaphthalene, naphthalene carboxylic acid, anthracene, phenol, cresol, creosote oil, tar, melamine, urea, sulfanilic acid and / or their derivatives, as long as the performance is not impaired.

[0049] The naphthalenesulfonic acid formaldehyde condensate or its salt may be, for example, a commercially available product such as Mighty 150, DEMOL N, DEMOL RN, DEMOL MS, DEMOL SN-B, DEMOL SS-L (all manufactured by Kao Corporation), Celluflow 120, Labelin FD-40, Labelin FM-45 (all manufactured by Daiichi Kogyo Co., Ltd.), etc.

[0050] From the viewpoint of improving the fluidity of the hydraulic slurry composition, the naphthalenesulfonic acid formaldehyde condensate or its salt has a weight average molecular weight of preferably 200,000 or less, more preferably 100,000 or less, even more preferably 80,000 or less, even more preferably 50,000 or less, and even more preferably 30,000 or less. From the viewpoint of improving the fluidity of the hydraulic slurry composition, the naphthalenesulfonic acid formaldehyde condensate or its salt has a weight average molecular weight of preferably 1,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, and even more preferably 5,000 or more. The naphthalenesulfonic acid formaldehyde condensate may be in an acid state or a neutralized product.

[0051] The molecular weight of the naphthalenesulfonic acid-formaldehyde condensate or its salt can be measured by gel permeation chromatography under the following conditions. [GPC conditions] Column: G4000SWXL+G2000SWXL (Tosoh) Eluent: 30mM CH 3 COONa / CH 3 CN=6 / 4 Flow rate: 0.7ml / min Detection: UV280nm Sample size: 0.2mg / ml Standard material: Nishio Kogyo Co., Ltd., polystyrene sulfonate sodium conversion (monodisperse polystyrene sulfonate sodium: molecular weight, 206, 1,800, 4,000, 8,000, 18,000, 35,000, 88,000, 780,000) Detector: Tosoh Corporation UV-8020

[0052] As the polycarboxylic acid polymer, a copolymer of a monoester of polyalkylene glycol and (meth)acrylic acid and a carboxylic acid such as (meth)acrylic acid (for example, the compound described in JP-A-8-12397), a copolymer of an unsaturated alcohol having a polyalkylene glycol and a carboxylic acid such as (meth)acrylic acid, a copolymer of an unsaturated alcohol having a polyalkylene glycol and a dicarboxylic acid such as maleic acid, etc. can be used as the polycarboxylic acid dispersant. Here, (meth)acrylic acid means a carboxylic acid selected from acrylic acid and methacrylic acid.

[0053] The polycarboxylic acid polymer may be a copolymer containing, as constituent monomers, a monomer (1e) represented by the following general formula (1e) and a monomer (2e) represented by the following general formula (2e).

[0054] [ka]

[0055] [During the ceremony, R 1e , R 2e , R 3e may be the same or different, and may be a hydrogen atom, a methyl group, or (CH 2 ) r COOM2 and (CH 2 ) r COOM 2 COOM 1 or other (CH 2 ) r COOM 2 and an anhydride may be formed, in which case, M 1 , M 2 does not exist. M 1 , M 2 may be the same or different, and are a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroalkyl group, or an alkenyl group. r: A number between 0 and 2 Indicates the following.

[0056] [ka]

[0057] [During the ceremony, R 4e , R 5e : may be the same or different, hydrogen atom or methyl group R 6e : Hydrogen atom or -COO(AO) n1 X 1 R 7e : Hydrogen atom or an alkyl group having 1 to 4 carbon atoms AO: a group selected from an ethyleneoxy group and a propyleneoxy group n1: the average number of moles of AO added, a number between 1 and 300 q1: A number between 0 and 2 p1: 0 or 1 Indicates the following.

[0058] In general formula (1e), R 1e is preferably a hydrogen atom. In general formula (1e), R 2e is preferably a methyl group. In general formula (1e), R 3eis preferably a hydrogen atom. (CH 2 ) r COOM 2 About COOM 1 or other (CH 2 ) r COOM 2 and an anhydride may be formed, in which case, M 1 , M 2 does not exist. M 1 and M. 2 may be the same or different and are a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroalkyl group, or an alkenyl group. M 1 , M 2 The alkyl group, the hydroalkyl group, and the alkenyl group each preferably have 1 to 4 carbon atoms. M 1 and M. 2 may be the same or different and are preferably a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, or an alkylammonium group, more preferably a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), or an ammonium group, even more preferably a hydrogen atom, an alkali metal, or an alkaline earth metal (1 / 2 atom), and even more preferably a hydrogen atom or an alkali metal. (CH 2 ) r COOM 2 In the formula, r is preferably 0.

[0059] In general formula (2e), R 4e is preferably a hydrogen atom. In general formula (2e), R 5e is preferably a methyl group. In general formula (2e), R 6e is preferably a hydrogen atom. In general formula (2e), R 7e is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. In formula (2e), AO is preferably an ethyleneoxy group. AO preferably contains an ethyleneoxy group. In general formula (2e), n1 is the average number of moles of AO added, and from the viewpoint of initial fluidity, it is preferably 5 or more, more preferably 10 or more, even more preferably 20 or more, and preferably 200 or less, more preferably 150 or less. In the general formula (2e), q1 is preferably 0. In formula (2e), p1 is preferably 1.

[0060] The proportion of monomer (1e) in the total amount of monomer (1e) and monomer (2e) in all constituent monomers of the copolymer is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, still more preferably 40 mol% or more, even more preferably 50 mol% or more, and preferably 99 mol% or less, more preferably 90 mol% or less.

[0061] The proportion of monomer (1e) in all constituent monomers of the copolymer is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, still more preferably 40 mol% or more, even more preferably 50 mol% or more, and preferably 99 mol% or less, more preferably 90 mol% or less.

[0062] Of all the constituent monomers of the copolymer, the total amount of the monomers (1e) and (2e) is preferably 90% by mass or more, more preferably 92% by mass or more, and even more preferably 95% by mass or more and 100% by mass or less. This total amount may be 100% by mass.

[0063] The weight average molecular weight of the copolymer is preferably 1,000 or more, more preferably 5,000 or more, even more preferably 10,000 or more, still more preferably 30,000 or more, and preferably 1,000,000 or less, more preferably 500,000 or less, even more preferably 150,000 or less, still more preferably 100,000 or less.

[0064] The weight average molecular weight of the copolymer was measured by gel permeation chromatography (GPC) under the following conditions. *GPC conditions Equipment: GPC (HLC-8320GPC) manufactured by Tosoh Corporation Column: G4000PWXL+G2500PWXL (Tosoh Corporation) Eluent: 0.2M phosphate buffer / CH 3 CN=9 / 1 Flow rate: 1.0mL / min Column temperature: 40℃ Detection: RI Sample size: 0.2mg / mL Standard substance: Polyethylene glycol equivalent (monodisperse polyethylene glycol with known molecular weight, molecular weight 87,500, 250,000, 145,000, 46,000, 24,000)

[0065] The copolymer may contain, in addition to the monomer (1e) and the monomer (2e), one or more monomers (3e) copolymerizable with the monomer (1e) and / or the monomer (2e). Examples of the monomer (3e) include acrylic acid esters. The copolymer may contain, in all of the structural units, 100% by mass of the total of the monomers (1e) and (2e), or the total of the monomers (1e), (2e), and (3e).

[0066] Examples of the lignin sulfonic acid polymer include lignin sulfonate or its derivatives. Commercially available lignin sulfonate or its derivatives can be used. Examples include Master Pozzolith No. 70 and Master Polyhede 15S series from BASF Japan, Floric S series and Floric R series from Floric, Darlex WRDA from Grace Chemical, Plascrete NC and Plascrete R from Sika Japan, Yamaso 80P, Yamaso 90 series, Yamaso 98 series, Yamaso 02NL-P, Yamaso 02NLR-P, Yamaso 09NL-P, Yamaso NLR-P from Yamaso Chemical, Chupol EX60 series and Chupol LS-A series from Takemoto Oil Co., Ltd., Ligace UA series, Ligace UR series, and Ligace VF series from Ligace.

[0067] Specific examples of lignin sulfonates or derivatives thereof are given below. (I) Alkali metal salts, alkaline earth metal salts, ammonium salts, or amine salts of lignosulfonic acid (II) Lignin derivatives in which an amine compound or an amino group has been introduced into a lignin sulfonate (e.g., JP 2016-108183 A) (III) Lignin derivatives obtained by reacting lignin sulfonate with formaldehyde (e.g., JP 2015-229764 A) (IV) Modified lignins such as oxidized lignin and sulfonated lignin (for example, JP 2003-2714 A) (V) Lignosulfonic acid compound polyol complex (e.g., JP 2007-105899 A) (VI) Lignin sulfonate modified products of 1) to 3) below (for example, JP 2007-261119 A) 1) Lignosulfonate modified product obtained by graft copolymerization of lignosulfonic acid or its salt with an acrylic monomer having a functional group 2) Lignosulfonate modified products obtained by graft copolymerization of lignosulfonic acid or its salt with a vinyl monomer having a functional group 3) Lignosulfonate modified product obtained by adding naphthalenesulfonate-formaldehyde condensate to lignosulfonic acid or its salt (VII) Lignin derivatives in which a polyalkylene glycol compound has been introduced into a lignin sulfonate (for example, JP 2015-193804 A) (VIII) Reaction products of lignin sulfonic acid compounds and water-soluble monomers (e.g., JP 2011-240224 A) Here, examples of lignin sulfonic acid compounds include compounds having a skeleton in which a carbon atom at the α-position of the side chain of the hydroxyphenylpropane structure of lignin is cleaved to introduce a sulfone group. Examples of the water-soluble monomer include compounds having at least one type of ionic functional group, such as a carboxyl group, a hydroxyl group, a sulfone group, a nitroxyl group, a carbonyl group, a phosphate group, an amino group, or an epoxy group, or other polar group. (IX) Lignosulfonic acid derivatives of 4) to 5) below (for example, JP 2015-212216 A) 4) Lignin derivatives obtained by reacting functional groups such as phenolic hydroxyl groups, alcoholic hydroxyl groups, and thiol groups contained in lignin sulfonic acid compounds with at least one water-soluble monomer. 5) A lignin derivative obtained by radical copolymerization of at least one water-soluble monomer with a lignin sulfonic acid compound (usually with the functional group of the compound) using a radical initiator. Here, the lignin sulfonic acid compound is not particularly limited, but examples thereof include those obtained by digesting wood using a sulfite method. Among the water-soluble monomers, examples of the water-soluble monomers that can react with the phenolic hydroxyl groups and / or alcoholic hydroxyl groups contained in the lignin sulfonic acid compounds include alkylene oxides such as ethylene oxide and propylene oxide. Among the water-soluble monomers, examples of the water-soluble monomers that can react with the thiol group contained in the lignin sulfonic acid compound include alkylene oxides such as ethylene oxide and propylene oxide, and alkylene imines such as ethylene imine and propylene imine. Furthermore, examples of the water-soluble monomer used in the radical copolymerization include the monomers described in

[0071] to

[0074] of JP2015-212216A, specifically, 1 to 500 mole adducts of alkylene oxides having 2 to 18 carbon atoms to acrylic acid, methacrylic acid, (meth)acrylic acid, and alkylene oxide adducts obtained by adding 2 to 300 moles of alkylene oxide to allyl alcohol.

[0068] Examples of the melamine-based polymer include melamine sulfonic acid formaldehyde condensates or salts thereof. The melamine sulfonic acid formaldehyde condensates or salts thereof are compounds obtained by reacting melamine with formaldehyde to obtain N-methylolated melamine, reacting it with bisulfite to sulfomethylate a part of the methylol groups, then adding an acid to dehydrate and condense the methylol groups to obtain a formaldehyde condensate, and neutralizing the result with an alkali (see, for example, JP-B-63-37058). Examples of the alkali include hydroxides of alkali metals or alkaline earth metals, ammonia, mono-, di-, and tri-alkyl (carbon number 2-8) amines, and mono-, di-, and trialkanol (carbon number 2-8) amines.

[0069] Commercially available products of melamine sulfonate formaldehyde condensates or salts thereof include Mighty 150V-2 (manufactured by Kao Corporation), SMF-PG (Nissan Chemical Industries, Ltd.), Melflow (Mitsui Chemicals, Inc.), Melment F-10 (Showa Denko K.K.), Super Melamine (manufactured by Nissan Chemical Industries, Ltd.), Floric MS (manufactured by Floric Co., Ltd.), Melment F4000, Melment F10M, and Melment F245 (all manufactured by BASF Japan Ltd.).

[0070] The molecular weight of the melamine sulfonate formaldehyde condensate is preferably 1,000 or more, more preferably 5,000 or more, and preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 20,000 or less (gel permeation chromatography method, polystyrene sulfonic acid equivalent).

[0071] The bubble-containing hydraulic composition of the present invention has 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, and even more preferably 50% by mass or more from the viewpoint of slurry fluidity, and from the viewpoint of hardened body strength, it is 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 70% by mass or less. Here, the water / hydraulic powder ratio is the mass percentage (mass%) of water and hydraulic powder in the hydraulic composition, and is calculated by water / hydraulic powder x 100. The water / hydraulic powder ratio is calculated based on the amount of powder having the physical property of being hardened by hydration reaction. When the powder having the physical property of being hardened by 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 applies to other quantitative relationships of the hydraulic composition regarding the hydraulic powder.

[0072] The bubble-containing hydraulic composition of the present invention contains, from the viewpoint of increasing the diameter of bubbles in the hydraulic composition, preferably 0.00025 parts by mass or more of component (A) per 100 parts by mass of hydraulic powder, more preferably 0.00050 parts by mass or more, even more preferably 0.00075 parts by mass or more, and preferably 0.01 parts by mass or less, more preferably 0.008 parts by mass or less, even more preferably 0.006 parts by mass or less, and even more preferably 0.003 parts by mass or less.

[0073] The bubble-containing hydraulic composition of the present invention contains, relative to 100 parts by mass of hydraulic powder, preferably 0.005 parts by mass or more of component (B) from the viewpoints of increasing the bubble size in the hydraulic composition and reducing the specific gravity of the hardened body, more preferably 0.010 parts by mass or more, even more preferably 0.015 parts by mass or more, still more preferably 0.020 parts by mass or more, and from the viewpoint of the strength of the hardened body, preferably 0.1 parts by mass or less, more preferably 0.08 parts by mass or less, even more preferably 0.06 parts by mass or less, still more preferably 0.04 parts by mass or less, still more preferably 0.028 parts by mass or less.

[0074] In the bubble-containing hydraulic composition of the present invention, the mass ratio (B) / (A) of the content of the component (B) to the content of the component (A) is 75 / 25 or more, preferably 78 / 22 or more, more preferably 85 / 15 or more, even more preferably 92 / 8 or more, and is 99 / 1 or less, preferably 98 / 2 or less, more preferably 96 / 4 or less, from the viewpoint of increasing the diameter of bubbles in the hydraulic composition.

[0075] The bubble-containing hydraulic composition of the present invention contains, from the viewpoint of both improving fluidity and economic efficiency, preferably 0.025 parts by mass or more, more preferably 0.050 parts by mass or more, even more preferably 0.100 parts by mass or more of a dispersant, and preferably 1.0 part by mass or less, more preferably 0.5 part by mass or less, even more preferably 0.3 part by mass or less, per 100 parts by mass of hydraulic powder.

[0076] When the bubble-containing hydraulic composition of the present invention contains component (C), the component (C) is preferably contained in an amount of 0.00050 parts by mass or more, more preferably 0.00100 parts by mass or more, even more preferably 0.00150 parts by mass or more, and preferably 0.015 parts by mass or less, more preferably 0.010 parts by mass or less, even more preferably 0.005 parts by mass or less, per 100 parts by mass of hydraulic powder, from the viewpoint of increasing the diameter of bubbles in the hydraulic composition.

[0077] When the bubble-containing hydraulic composition of the present invention contains component (D), from the viewpoints of achieving both foam stability, particularly foam performance in an aqueous system, and enlargement of bubbles in the hydraulic composition, the bubble-containing hydraulic composition contains component (D) in an amount of preferably 0.00075 parts by mass or more, more preferably 0.00150 parts by mass or more, even more preferably 0.00250 parts by mass or more, and preferably 0.045 parts by mass or less, more preferably 0.030 parts by mass or less, and even more preferably 0.015 parts by mass or less, per 100 parts by mass of hydraulic powder.

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

[0079] The bubble-containing hydraulic composition of the present invention can be dried and cured to give a hardened product. The specific gravity of the hardened body of the bubble-containing hydraulic composition of the present invention is, from the viewpoint of strength, preferably 0.3 or more, more preferably 0.4 or more, and even more preferably 0.5 or more, and from the viewpoint of handleability, is preferably 0.9 or less, more preferably 0.8 or less, and even more preferably 0.7 or less.

[0080] The bubble-containing hydraulic composition of the present invention contains bubbles. The average bubble diameter of the hardened product of the bubble-containing hydraulic composition of the present invention is preferably 220 μm or more, more preferably 250 μm or more, and even more preferably 300 μm or more from the viewpoint of improving the strength of the hardened product, and is preferably 800 μm or less, more preferably 700 μm or less, even more preferably 600 μm or less, still more preferably 500 μm or less, and even more preferably 400 μm or less from the viewpoint of cross-sectional appearance. The average bubble diameter is calculated by preparing a hardened product of the bubble-containing hydraulic composition, arbitrarily cutting the hardened product to prepare a cross section, observing the cross section with a digital microscope, measuring the diameter of 100 random bubble cross sections, and averaging (arithmetic mean) the values. The diameter of the bubble cross section is measured when the bubble cross section is circular, when the bubble cross section is elliptical, and when the bubble cross section is irregular, the diameter is the longest part. The bubble diameter of the hardened product of the bubble-containing hydraulic composition is the same as the bubble diameter of the bubble-containing hydraulic composition before hardening.

[0081] The bubble-containing hydraulic composition of the present invention can be produced by using the foaming agent for hydraulic compositions of the present invention. That is, 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 a foam. <Process 2> A step of mixing hydraulic powder, water, a dispersant, and the foam obtained in step 1. In step 2, a hydraulic composition containing hydraulic powder, water, and a dispersant may be prepared, and the hydraulic composition may be mixed with the foam obtained in step 1.

[0082] The bubble-containing hydraulic composition of the present invention can be prepared by this manufacturing method. The method for producing the bubble-containing hydraulic composition of the present invention can appropriately employ the embodiments described for the foaming agent composition for hydraulic compositions of the present invention and the bubble-containing hydraulic composition of the present invention. In the manufacturing method of the bubble-containing hydraulic composition of the present invention, the contents of the components and their mass ratios described in the bubble-containing hydraulic composition of the present invention can be appropriately applied by replacing the contents of the components with the mixed amounts.

[0083] In step 1, the expansion ratio of the liquid composition varies depending on the application of the hydraulic composition, but from the viewpoint of economy, it is preferably 5 times or more, more preferably 7 times or more, and even more preferably 10 times or more, and 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.

[0084] In step 2, depending on the use of the hydraulic composition, the foam is mixed with the hydraulic composition in an amount of preferably 50% by volume or more, more preferably 100% by volume or more, and even more preferably 150% by volume or more from the viewpoint of reducing the specific gravity of the hardened body, and preferably 400% by volume or less, more preferably 300% by volume or less, and even more preferably 200% by volume or less from the viewpoint of the strength of the hardened body. In this production method, admixtures and admixtures known in the art can be mixed in step 1 and / or step 2.

[0085] After step 2, the following step 3 is further carried out to produce a hardened product of the bubble-containing hydraulic composition. Step 3: A step of forming the bubble-containing hydraulic composition slurry obtained in step 2 and hardening it.

[0086] The specific gravity of the hardened product of the bubble-containing hydraulic composition obtained by the manufacturing method of the bubble-containing hydraulic composition of the present invention is, from the viewpoint of strength, preferably 0.3 or more, more preferably 0.4 or more, even more preferably 0.5 or more, and from the viewpoint of handleability, preferably 0.9 or less, more preferably 0.8 or less, even more preferably 0.7 or less. The average bubble diameter of the hardened body of the bubble-containing hydraulic composition obtained from the bubble-containing hydraulic composition of the present invention is preferably 220 μm or more, more preferably 250 μm or more, and even more preferably 300 μm or more from the viewpoint of improving the strength of the hardened body, and is preferably 800 μm or less, more preferably 700 μm or less, even more preferably 600 μm or less, still more preferably 500 μm or less, and even more preferably 400 μm or less from the viewpoint of cross-sectional appearance.

[0087] [Gas-containing gypsum slurry and its manufacturing method] In the bubble-containing hydraulic composition of the present invention, the hydraulic powder is preferably gypsum. In the present invention, the bubble-containing hydraulic composition in which the hydraulic powder is gypsum is also called a bubble-containing gypsum slurry. That is, the present invention provides a bubble-containing gypsum slurry that contains gypsum, water, a dispersant, component (B), and component (A), and in which the mass ratio (B) / (A) of the content of component (B) to the content of component (A) is 75 / 25 or more and 99 / 1 or less. The bubble-containing gypsum slurry of the present invention is suitable for use in gypsum boards.

[0088] The foaming agent for hydraulic composition of the present invention, the bubble-containing hydraulic composition of the present invention, and the method for producing the bubble-containing hydraulic composition of the present invention can be appropriately applied to the bubble-containing gypsum slurry of the present invention. The air-bubble gypsum slurry of the present invention may further contain component (C). The air-bubble gypsum slurry of the present invention may further contain component (D). The components (A), (B), (C) and (D) are the same as those described in the foaming agent for hydraulic compositions of the present invention. The dispersant is the same as that described in the bubble-containing hydraulic composition of the present invention. In the bubble-containing gypsum slurry of the present invention, the contents of the components and their mass ratios described in the bubble-containing hydraulic composition of the present invention can be appropriately applied by substituting hydraulic powder for gypsum. In the hardened product of the gas bubble-containing gypsum slurry of the present invention, the specific gravity and the average gas bubble diameter are in the same ranges as those described for the gas bubble-containing hydraulic composition of the present invention.

[0089] Any type of gypsum can be used, including high-quality neutralized gypsum, phosphogypsum which is a by-product of phosphoric acid, flue gas desulfurization gypsum generated in thermal power generation, natural gypsum containing various impurities and clay, and mixtures of these. The clay contained in gypsum is mainly composed of hydrated silicate minerals (hereinafter referred to as clay minerals) with a layered structure, and the clay minerals contained as fine particles in this clay include kaolin minerals (kaolinite, dickite, and nacrite), serpentine (lizardite, antigorite, and chrysotile), mica clay minerals (illite, sericite, glauconite, and celadonite), chlorite, vermiculite, and smectite (montmorillonite, beidellite, nontronite, saponite, and hectorite).

[0090] Gypsum includes anhydrous gypsum, hemihydrate gypsum, dihydrate gypsum, etc. As the raw gypsum, natural gypsum, neutralized gypsum, by-product gypsum, or other chemical gypsum can be used alone or in combination of two or more of them. Examples of main chemical gypsum include phosphate gypsum, hydrofluoric gypsum, titanic gypsum, and flue gas desulfurization gypsum. The raw gypsum may also include recycled gypsum. The recycled gypsum may be any recycled gypsum recovered from waste gypsum boards generated by gypsum board manufacturers, waste gypsum boards generated during new construction and demolition, etc. The present invention can be suitably used for any of these raw gypsum, and excellent effects can be obtained for those blended in various ratios.

[0091] The bubble-containing gypsum slurry of the present invention can contain additives used for gypsum boards, etc. Such additives include general-purpose water-reducing agents, defoamers, foam stabilizers, hardening regulators, water repellents, adhesives, retarders, etc. Furthermore, glass fibers, carbon fibers, waste paper, virgin pulp, etc. can be added as reinforcing fibers, or gypsum boards can be produced together with lightweight aggregates such as perlite and foamed steel.

[0092] The foam-containing gypsum slurry of the present invention can be produced using the foaming agent for hydraulic compositions of the present invention. That is, the present invention provides a method for producing an air-bubble gypsum slurry, 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 a foam. <Process 2> A step of mixing gypsum, water, a dispersant, and the foam obtained in step 1. In step 2, a gypsum slurry containing gypsum, water, and a dispersant may be prepared, and the gypsum slurry may be mixed with the foam obtained in step 1.

[0093] This manufacturing method allows the preparation of the air-filled gypsum slurry of the present invention. The method for producing the bubble-containing gypsum slurry of the present invention can be appropriately applied to the aspects described for the foaming agent for hydraulic composition of the present invention, the bubble-containing hydraulic composition and its production method of the present invention, and the bubble-containing gypsum slurry of the present invention. In the manufacturing method of the bubble-containing hydraulic composition of the present invention, the contents of the components and their mass ratios described in the bubble-containing hydraulic composition of the present invention can be appropriately applied by replacing the hydraulic powder with gypsum and further replacing the contents of the components with the mixing amounts. The temperatures of the foam and gypsum slurry used for mixing are preferably 15°C or higher and 40°C or lower, respectively. Steps 1 and 2 can be carried out in accordance with the method for producing the bubble-containing hydraulic composition of the present invention.

[0094] After step 2, the following step 3 is carried out to manufacture a gypsum board. Step 3: A step of forming the air bubble-containing gypsum slurry obtained in step 2 and hardening it. The molding and hardening can be carried out by known methods. For example, the gypsum board can be prepared by referring to "Plaster Board Manufacturing" described on pages 322-324 of "Gypsum Lime Handbook" (edited by the Gypsum Lime Society).

[0095] The specific gravity of the gypsum board obtained by the manufacturing method of the bubble-containing gypsum slurry of the present invention is, from the viewpoint of strength, preferably 0.3 or more, more preferably 0.4 or more, and even more preferably 0.5 or more, and from the viewpoint of handleability, is preferably 0.9 or less, more preferably 0.8 or less, and even more preferably 0.7 or less. The average bubble diameter of the gypsum board obtained by the method for producing a bubble-containing gypsum slurry of the present invention is preferably 220 μm or more, more preferably 250 μm or more, still more preferably 300 μm or more, from the viewpoint of improving the strength of the cured body, and preferably 800 μm or less, more preferably 700 μm or less, still more preferably 600 μm or less, even more preferably 500 μm or less, even more preferably 400 μm or less, from the viewpoint of the cross-sectional appearance.

Examples

[0096] The components used in the examples and comparative examples are shown below. (Component (A)) ·C16IOS: Potassium internal olefin sulfonate having 16 carbon atoms obtained in the following production example <Production Example of C16IOS> C16IOS was obtained by using an internal olefin having 16 carbon atoms and referring to the method described in the production example of JP-A-2014-76988 to obtain an aqueous solution of C16IOS having an active ingredient of 30%. The mass ratio of the olefin form (olefin sulfonic acid potassium) / hydroxy form (hydroxyalkane sulfonic acid potassium) in the obtained potassium internal olefin sulfonate of C16IOS is 17 / 83. The mass ratio of the positional distribution of the sulfonic acid groups of the hydroxy form in C16IOS is 1st / 2nd / 3rd / 4th / 5th / 6-9th = 2.3% / 23.6% / 18.9% / 17.5% / 13.7% / 11.2% / 6.4% / 6.4% / 0% (total 100% by mass). Also, (IO-1S) / (IO-2S) ≒ 1.6 (mass ratio). Note that (IO-1S) / (IO-2S) is the mass ratio of the content of the internal olefin sulfonate [(IO-1S)] in which the sulfonic acid group is present at the 2nd to 4th positions and the content of the internal olefin sulfonate [(IO-2S)] in which the sulfonic acid group is present at the 5th position or higher.

[0097] (Component (B)) ·C10AS: Sodium decyl sulfate (active ingredient 33%)

[0098] (1) Preparation of a foaming agent for a hydraulic composition The foaming agent compositions for hydraulic compositions shown in Table 1 were prepared by the following method. Each raw material was added to a 50 mL screw tube in a specified ratio so that the total amount was 30 g, and the mixture was stirred at 1000 rpm for 30 minutes using a stirrer to prepare a homogeneous and transparent foaming agent for hydraulic compositions. Note that the blending composition of components (A) and (B) shown in Table 1 is based on the active ingredients.

[0099] (2) Preparation of gypsum slurry The foaming agent for hydraulic compositions in Table 1 prepared was mixed with water in an arbitrary ratio to prepare a diluted aqueous solution of the foaming agent for hydraulic compositions. 20 g of the prepared aqueous solution was added to a 1 L disposable cup, and the mixture was stirred at 2000 rpm for 60 seconds using a mixer (EUROSTAR200 control, IKA Japan Co., Ltd.) equipped with a flat 6-blade paddle blade (FP-50, AS ONE Co., Ltd.) to obtain a foam. 200g of calcined gypsum, 4g of dihydrate gypsum, 0.614g of potassium sulfate, 100g of tap water, and 0.4g of dispersant (Mighty 21G-30, polycarboxylic acid polymer, manufactured by Kao Corporation) were added to 20g of the prepared foam, and the mixture was kneaded for 20 seconds at 1150 rpm using the stirrer used for preparing the foam to obtain a gypsum slurry containing bubbles. In addition, the concentration of the diluted aqueous solution of the foaming agent for hydraulic compositions was appropriately adjusted in order to make the specific gravity of the finally obtained gypsum hardened body containing bubbles after drying approximately 0.67. The concentration of the foaming agent for hydraulic compositions in the diluted aqueous solution at that time is described in Table 1 as "required amount added (mass%)". The temperature of the foam and the gypsum slurry used for kneading was 20°C.

[0100] (3) Measurement of the specific gravity and average air bubble diameter of the gypsum hardened body The resulting gypsum slurry containing bubbles was poured into a 10.5 cm square silicone tray to a height of 13 mm and left to stand at room temperature for 1 hour. The hardened gypsum slurry was demolded and left to stand in a thermostatic chamber at 60°C for 24 hours to dry, after which the weight of the gypsum hardened body was measured to calculate the specific gravity of the gypsum hardened body. The specific gravity of each of the obtained gypsum hardened bodies was approximately 0.67. The obtained gypsum hardened body was split horizontally in half to create a cross section of the hardened body. The cross section was observed with a digital microscope (42x magnification), and the diameters of 100 bubble cross sections were measured, starting from the smallest visible bubble, and the average bubble diameter was calculated from the arithmetic mean of these values. When the bubble cross section was circular, the diameter was taken as the diameter; when the bubble cross section was elliptical, the major axis was taken as the diameter; and when the bubble cross section was irregular, the longest part was taken as the diameter. The results are shown in Table 1.

[0101] [Table 1]

[0102] From the results in Table 1, it can be seen that in a gypsum hardened body of the same specific gravity (0.67), by setting the mass ratio (B) / (A) of the (B) component to the (A) component within a specific range, the air bubble diameter in the bubble-containing hydraulic composition of the same specific gravity is larger than when the (B) component or the (A) component is used alone. In other words, it can be said that by setting the mass ratio (B) / (A) of the (B) component to the (A) component within a specific range, the air bubble diameter can be increased without changing the specific gravity of the gypsum hardened body, thereby improving the strength of the hardened body.

Claims

1. A foaming agent for hydraulic compositions, comprising the following components (A) and (B), wherein the mass ratio (B) / (A) of the content of component (B) to the content of component (A) is 75 / 25 or more and 99 / 1 or less. (A) Ingredients: Olefin sulfonic acid or its salt (B) Component: Anionic surfactant other than component (A)

2. The foaming agent for hydraulic compositions according to claim 1, wherein component (B) is one or more selected from alkyl or alkenyl sulfate esters having an alkyl or alkenyl group having 8 to 18 carbon atoms, alkyl or alkenyl sulfonic acid having an alkyl or alkenyl group having 8 to 18 carbon atoms, polyoxyalkylene alkyl or alkenyl ether sulfate esters having an alkyl or alkenyl group having 8 to 18 carbon atoms, and salts thereof.

3. (B) The foaming agent for hydraulic compositions according to claim 1 or 2, wherein component (B) comprises two alkyl or alkenyl sulfate esters or salts thereof having different numbers of carbon atoms in the alkyl or alkenyl group.

4. The foaming agent for hydraulic compositions according to claim 1 or 2, wherein component (B) is one or more selected from (B1) an alkyl or alkenyl sulfate ester or salt thereof having an alkyl or alkenyl group having 8 to 18 carbon atoms, and (B2) a polyoxyalkylene alkyl or alkenyl ether sulfate ester or salt thereof having an alkyl or alkenyl group having 8 to 18 carbon atoms.

5. (A) The foaming agent for hydraulic compositions according to claim 1 or 2, wherein component (A) is an olefin sulfonate having 12 to 20 carbon atoms or a salt thereof.

6. (A) The foaming agent for hydraulic compositions according to claim 1 or 2, wherein component (A) is an internal olefin sulfonate having 12 to 20 carbon atoms or a salt thereof.

7. A foaming agent for hydraulic compositions according to claim 1 or 2, for use with gypsum slurry.

8. A bubble-containing hydraulic composition containing hydraulic powder, water, a dispersant, the following components (A) and (B), wherein the mass ratio (B) / (A) of the content of component (B) to the content of component (A) is 75 / 25 or more and 99 / 1 or less. (A) Ingredients: Olefin sulfonic acid or its salt (B) Component: Anionic surfactant other than component (A)

9. The bubble-containing hydraulic composition according to claim 8, wherein the hydraulic powder is gypsum.

10. The bubble-containing hydraulic composition according to claim 8 or 9, wherein the dispersant is one or more compounds selected from naphthalene polymers, polycarboxylic acid polymers, ligninsulfonic acid polymers, and melamine polymers.

11. 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 described in claim 1 or 2 and water to obtain foam. <Process 2> A step of mixing hydraulic powder, water, a dispersant, and the foam obtained in step 1.

12. A method for producing a bubble-containing hydraulic composition according to claim 11, wherein the hydraulic powder is gypsum.

13. A method for producing a bubble-containing hydraulic composition according to claim 11, wherein the dispersant is one or more compounds selected from naphthalene polymers, polycarboxylic acid polymers, ligninsulfonic acid polymers, and melamine polymers.

14. A method for producing a bubble-containing hydraulic composition according to claim 11, further comprising the following step 3. <Process 3> A step of molding and curing the bubble-containing hydraulic composition slurry obtained in step 2.