Foaming agent for hydraulic composition
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- KAO CORP
- Filing Date
- 2023-09-08
- Publication Date
- 2026-06-29
Abstract
Description
[Technical Field]
[0001] The present invention relates to a foaming agent for hydraulic compositions, a foam-containing hydraulic composition, and a method for producing the same. [Background technology]
[0002] Air bubbles are introduced into hydraulic compositions that use cement or gypsum as a hardening agent to reduce their weight. Typically, lightweight air-bubble hydraulic compositions are produced by foaming a liquid composition containing a foaming agent and water, and mixing the foam with the hydraulic composition, or with fine aggregate or various admixtures.
[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 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 alkali metal salts, ammonium salts, and alkanolammonium salts of sulfates of ethylene oxide adducts of higher alcohols 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. It is disclosed that this foaming agent for producing lightweight gypsum boards can obtain the required volume with a small amount of use, and that even in the case of low-density gypsum boards, it exhibits excellent adhesion between the base paper and the gypsum core and high core strength. In the examples, the foaming agent contains 35% by mass of alkyl ether sulfate and 17% by mass of ethylene glycol monobutyl ether. Patent Document 3 discloses a method for producing a lightweight gypsum product, which is characterized by adding an internal olefin sulfonate having 10 to 18 carbon atoms to a gypsum slurry containing air bubbles to produce the lightweight gypsum product, thereby obtaining stable foam characteristics. [Prior art documents] [Patent documents]
[0004] [Patent Document 1] Japanese Patent Publication No. 2020-83663 [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] There is a demand for further weight reduction in hardened foam-containing hydraulic compositions that use cement or gypsum as a hardening agent, from the viewpoints of cost and environmental (CO2) reduction effects due to production, transportation, and raw material procurement. Air-bubble hydraulic compositions using cement or gypsum as a hardening agent can reduce their specific gravity and weight by incorporating air bubbles, but this weight reduction also results in reduced strength. As described in paragraph 0004 of JP 10-330174 A, increasing the air bubble diameter in the air-bubble hydraulic composition is considered a way to prevent strength loss, but there is a limit to how much air bubble diameter can be increased. Furthermore, achieving weight reduction requires the introduction of highly stable foams, which results in a tendency for the air bubble diameter in the air-bubble hydraulic composition to be small. Therefore, there is a need for a technology that increases the air bubble diameter in a cured product of an air-bubble hydraulic composition with a low specific gravity, or at least prevents the air bubble diameter from becoming smaller, thereby achieving both weight reduction and strength. Furthermore, from the perspectives of reducing chemical costs, reducing the environmental impact during transportation, and ease of regeneration (reducing chemical carryover of recycled gypsum), it is necessary to add a small amount of foaming agent composition, which is the source of foam, to the air-bubble hydraulic composition.
[0006] The present invention provides a foaming agent for hydraulic compositions that can produce a bubble-containing hardened hydraulic composition having a low specific gravity with the same amount of foaming component without reducing the diameter of the bubbles, as well as a bubble-containing hydraulic composition and a method for producing the same that can produce a bubble-containing hardened hydraulic composition having a low specific gravity with the same amount of foaming component without reducing the diameter of the bubbles. In the present invention, the foaming component refers to the components (A) and (B) contained in the foaming agent for hydraulic compositions described below. [Means for solving the problem]
[0007] The present invention relates to a foaming agent for hydraulic compositions, which contains the following components (A) and (B), and the mass ratio (B) / (A) of the content of component (B) to the content of component (A) is 15 / 85 or more and 80 / 20 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 hydraulic powder, water, a dispersant, the aforementioned 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 15 / 85 or more and 80 / 20 or less.
[0009] The present invention also relates to a method for producing a bubble-containing hydraulic composition, which comprises 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. [Effects of the Invention]
[0010] According to the present invention, there are provided a foaming agent for hydraulic compositions that can produce a bubble-containing hardened hydraulic composition having a low specific gravity with the same amount of foaming component without reducing the diameter of the bubbles, as well as a bubble-containing hydraulic composition and a method for producing the same that can produce a bubble-containing hardened hydraulic composition having a low specific gravity with the same amount of foaming component without reducing the diameter of the bubbles.
[0011] The foaming agent for hydraulic compositions of the present invention can provide a bubble-containing hardened hydraulic composition having a small specific gravity with the same amount of foaming agent added, without reducing the size of the bubbles. In other words, the foaming agent for hydraulic compositions of the present invention can provide a bubble-containing hardened hydraulic composition having the same specific gravity with a small amount of foaming agent added, without reducing the size of the bubbles. DETAILED DESCRIPTION OF THE INVENTION
[0012] The foaming agent for hydraulic compositions of the present invention can produce a bubble-containing hardened hydraulic composition having a small specific gravity at the same addition amount without reducing the size of the bubbles, and the bubble-containing hydraulic composition and its manufacturing method of the present invention can produce a bubble-containing hardened hydraulic composition having a small specific gravity at the same foaming component amount without reducing the size of the bubbles. The reason for this is not entirely clear, but is presumed to be as follows. Conventionally, as disclosed in a prior document (JP-A-2004-529050), for example, attention has been focused on surfactants, and the bubble size and the like in hydraulic compositions have been controlled by adjusting the 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 that focuses on surfactants and controls only foam performance in an aqueous system, it is necessary to satisfy a certain level of foam performance such as foaming ability and foam stability in order to introduce a certain amount of foam into the hydraulic composition, and as a result, the bubbles become stabilized in the hydraulic composition, coalescence does not proceed, and the bubbles become fixed without increasing in diameter. Therefore, the present inventors have found that the above-mentioned problems can be solved by controlling the foaming 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, component (A) of the present invention, rapidly adsorbs to the foam film formed by the anionic surfactant, component (B), and improves the dynamic stability of the gas-liquid interface. This dramatically improves foam performance in aqueous systems. Therefore, compared to conventional foaming agent compositions, the amount of foam obtained with the same amount added can be increased, making it possible to efficiently reduce the specific gravity of the foam-containing hydraulic composition cured body. In other words, the amount of foam required to achieve the same specific gravity can be obtained with a smaller amount of foaming agent composition added. On the other hand, in the hydraulic composition, component (A) quickly adsorbs to calcium sulfate, one of the main components of the hydraulic powder, due to a strong interaction, which causes the synergistic effect with component (B) to be lost, the foam performance to change, and the coalescence of bubbles to be promoted, thereby suppressing the reduction in the size of bubbles in the hydraulic composition. It is presumed that these actions enable the production of a bubble-containing hydraulic composition hardened body having a low specific gravity without reducing the diameter of the bubbles, even when the foaming agent composition is added in the same amount. However, the present invention is not limited to the above-mentioned mechanism of expression.
[0013] [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 achieving both a reduction in the amount of foaming agent added and suppression of the reduction in the size 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 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 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.
[0014] The component (A) is preferably an internal olefin sulfonic acid having from 12 to 20 carbon atoms or a salt thereof, from the viewpoints of foaming performance in aqueous systems, particularly foaming ability, suppression of bubble size reduction in the hydraulic composition, reduction in the amount of foaming agent added, and storage stability.
[0015] Internal olefin sulfonic acids or their salts having 12 to 20 carbon atoms can be obtained by sulfonating, neutralizing, and hydrolyzing an internal olefin having 12 to 20 carbon atoms. The term "internal olefin" refers to an olefin in which the double bond is located inside the 2-position. For example, internal olefins can be obtained by isomerizing 1-olefins obtained by dehydrating 1-alcohols. Sulfonation of internal olefins quantitatively produces β-sultone, and a portion of the β-sultone is converted to γ-sultone and olefin sulfonic acid. These are then further converted to hydroxyalkanesulfonate (H-form) and olefin sulfonate (O-form) in the neutralization and hydrolysis steps (e.g., J. Am. Oil Chem. Soc. 69, 39 (1992)). The hydroxy group of the resulting hydroxyalkanesulfonic acid is located within the alkane chain, while the double bond of the olefin sulfonate is located within the olefin chain. The resulting product is primarily a mixture of these compounds, and may contain trace amounts 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 referred to as internal olefinsulfonic acid. Hydroxyalkanesulfonic acid is referred to as the hydroxy form of internal olefinsulfonic acid (hereinafter also referred to as HAS), and olefinsulfonic acid is referred to as the olefin form of internal olefinsulfonic acid (hereinafter also referred to as IOS).
[0016] From the viewpoint of achieving both a reduction in the amount of foaming agent added and suppression of the reduction in 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.
[0017] The internal olefin sulfonic acid or a salt thereof also includes those containing a trace amount of so-called alpha olefin sulfonic acid or a salt thereof (hereinafter also referred to as α-olefin sulfonic acid or a salt thereof), in which the sulfonic acid is located at position 1 of the carbon chain. The upper limit of the content of α-olefin sulfonic acid or a salt thereof 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.
[0018] Internal olefin sulfonic acid or its salt can be obtained by sulfonating an olefin having 12 to 20 carbon atoms and a double bond at or above the second position as the main component. Sulfonation of the internal olefin quantitatively produces β-sultone, and a portion of the β-sultone is converted to γ-sultone and olefin sulfonic acid. These are then converted to hydroxyalkanesulfonic acid and olefin sulfonic acid in the neutralization and hydrolysis steps (e.g., J. Am. Oil Chem. Soc. 69, 39 (1992)). The hydroxy group of the resulting hydroxyalkanesulfonic acid is located within the alkane chain, while the double bond of the olefin sulfonic acid is located within the olefin chain. The resulting product is primarily a mixture of these, and some of the product may contain trace amounts of hydroxyalkanesulfonic acid with a hydroxy group at the terminal of the carbon chain or olefin sulfonic acid with a double bond at the terminal of the carbon chain.
[0019] In this specification, these products and mixtures thereof are collectively referred to as internal olefin sulfonic acid or a salt thereof. Furthermore, hydroxyalkanesulfonic acid or a salt thereof is referred to as a hydroxy form of internal olefin sulfonic acid or a salt thereof (HAS), and olefin sulfonic acid or a salt thereof is referred to as an 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.
[0020] 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, or further 25 / 75 or less.
[0021] <(B) component> The foaming agent for hydraulic compositions of the present invention contains, as component (B), an anionic surfactant other than component (A).
[0022] Examples of anionic surfactants other than component (A) include sulfonic acid compounds, ether sulfate ester compounds, carboxylic acid compounds, phosphonic acid compounds, and phosphoric acid compounds, each having a hydrocarbon group having from 8 to 18 carbon atoms. Examples include 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. 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.
[0023] 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 with 8 to 18 carbon atoms, alkyl or alkenyl sulfonic acids having an alkyl or alkenyl group with 8 to 18 carbon atoms, polyoxyalkylene alkyl or alkenyl ether sulfate esters having an alkyl or alkenyl group with 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.
[0024] From the viewpoint of foaming ability, particularly foaming performance, in aqueous systems, the component (B) 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 component (B1)), 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 component (B2)).
[0025] From the viewpoint of achieving both a reduction in the amount of foaming agent for hydraulic compositions (hereinafter simply referred to as foaming agent) added and suppression of the reduction in 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. The salt of component (B1) may be one or more selected from alkali metal salts such as sodium salts and potassium salts, ammonium salts, and organic ammonium salts.
[0026] Specific examples of component (A1) 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 both reducing the amount of foaming agent added and suppressing the reduction in the size of bubbles in the hydraulic composition, it is preferable for the component (A1) 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 (A1) to contain one or more compounds selected from decyl sulfate, dodecyl sulfate, and salts thereof.
[0027] From the viewpoint of foaming performance, particularly foaming ability, in aqueous systems, component (B) may contain, as component (B1), two types of alkyl or alkenyl sulfate esters or salts thereof, which differ in the number of carbon atoms in the alkyl or alkenyl group.
[0028] From the viewpoint of achieving both a reduction in the amount of foaming agent added and suppression of the reduction in the size of bubbles in the hydraulic composition, the component (B2) 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 component (B2) is an oxyethylene group or an oxypropylene group, preferably an oxyethylene group. From the viewpoint of foaming performance, particularly foamability, in aqueous systems, the average number of moles of oxyalkylene groups added is preferably 1 or more, more preferably 2 or more, and from the viewpoint of foaming performance, particularly foamability, in aqueous systems, it is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. The salt of component (B2) may be one or more selected from alkali metal salts such as sodium salts and potassium salts, ammonium salts, and organic ammonium salts.
[0029] Specific examples of 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, polyoxyethylene polyoxypropylene lauryl ether sulfate, polyoxyethylene Examples of suitable foaming agents include one or more selected from the group consisting of ethylene 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 both reducing the amount of foaming agent added and suppressing the reduction in the size 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.
[0030] <Composition, etc.> The foaming agent for hydraulic compositions of the present invention contains component (A) in an amount of preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, still more preferably 20% by mass or less, and still more preferably 17% by mass or less, from the viewpoints of suppressing the reduction in the diameter of bubbles in the hydraulic composition, reducing the amount of foaming agent added, and reducing the specific gravity of the set hydraulic composition. In the present invention, the mass of component (A) is expressed as a value converted into the sodium salt.
[0031] The foaming agent for hydraulic compositions of the present invention contains component (B) in an amount of preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, still more preferably 13% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, still more preferably 25% by mass or less, still more preferably 23% by mass or less, and still more preferably 20% by mass or less, from the viewpoints of suppressing the reduction in the diameter of bubbles in the hydraulic composition, reducing the amount of foaming agent added, and reducing the specific gravity of the set hydraulic composition. In the present invention, the mass of component (B), and components (B1) and (B2) contained in component (B) are expressed as values converted into sodium salts.
[0032] 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 15 / 85 or more, preferably 25 / 75 or more, more preferably 35 / 65 or more, and even more preferably 45 / 55 or more, and is 80 / 20 or less, preferably 75 / 25 or less, and more preferably 65 / 35 or less, from the viewpoints of suppressing the reduction in the size of bubbles in the hydraulic composition, reducing the amount of foaming agent added, and reducing the specific gravity of the set hydraulic composition.
[0033] The foaming agent for hydraulic compositions of the present invention may contain an aliphatic alcohol as component (C) from the viewpoints of rapid foaming and foam stability. From the viewpoint 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 component (C) is 6 or more and 10 or less, preferably 8, from the viewpoint of rapid foaming and foam stability. From the viewpoint 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.
[0034] Specific examples of component (C) include one or more selected from hexanol, octanol, decanol, 2-ethylhexanol, and 2-propylheptanol. From the viewpoint of foaming properties, it is preferable that the component (C) contains one or more selected from octanol and decanol, and more preferably octanol.
[0035] When the foaming agent for hydraulic compositions of the present invention contains component (C), from the viewpoint of achieving both a reduction in the amount of foaming agent added and suppression of the reduction in the diameter of bubbles in the hydraulic composition, the foaming agent contains component (C) in an amount of preferably 0.5% by mass or more, more preferably 1.0% by mass or more, even more preferably 1.5% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less.
[0036] 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 ethers, polyoxyalkylene monoalkyl or alkenyl ethers, alkyl glycosides or alkyl polyglycosides (alkyl glycoside-type nonionic surfactants), sorbitan-based nonionic surfactants, aliphatic alkanolamides, fatty acid monoglycerides, and sucrose fatty acid esters. 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.
[0037] From the viewpoint of achieving both foam stability, particularly in terms of foam performance in aqueous systems, and enlarging the 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, and q is a number of 1 to 3 indicating the average degree of condensation of G.
[0038] In formula (D1), R 1d From the viewpoint of improving foaming properties, 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 G include residues derived from disaccharides or higher such as 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.
[0039] When the foaming agent for hydraulic compositions of the present invention contains component (D), from the viewpoint of achieving both foam performance in aqueous systems, particularly foam stability, and enlarged bubbles in the hydraulic composition, the foaming agent contains component (D) in an amount of preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, and preferably 5.0% by mass or less, more preferably 3.0% by mass or less, even more preferably 2.0% by mass or less.
[0040] 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.
[0041] The foaming agent for hydraulic compositions of the present invention may optionally contain thickeners, chelating agents, heavy metal scavengers, rust inhibitors, preservatives, colorants, fragrances, defoamers, solvents, dispersants, flocculants, water-soluble polymers, etc. However, these do not fall under the category of components (A), (B), (C), and (D).
[0042] The foaming agent for hydraulic compositions of the present invention can be obtained by mixing component (A), component (B), and any optional components. During mixing, heating may be performed as appropriate to reduce the solution viscosity.
[0043] Target applications of the foaming agent composition for hydraulic compositions of the present invention include hydraulic compositions containing air bubbles, such as gypsum slurry, lightweight milk (aerated milk, aerated milk), lightweight mortar (aerated mortar, aerated mortar), lightweight concrete (aerated concrete, aerated concrete), backfilling material, core filling material, architectural concrete blocks, ALC (lightweight aerated concrete), grout material, porous ceramics, brick, refractory material, lightweight embankment, and mortar for pumping. In these hydraulic compositions containing air bubbles, the addition of air bubbles is expected to impart functions such as weight reduction, improved strength, improved fluidity, thermal 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.
[0044] [Bubble-containing hydraulic composition and its manufacturing method] A preferred method for producing a foamed hydraulic composition is to foam the foaming agent for hydraulic compositions of the present invention and incorporate the foam into a hydraulic substance to achieve blending and weight reduction, since this method entrains uniform bubbles. The foaming agent for hydraulic compositions of the present invention or a mixed solution obtained by diluting it with water may be directly kneaded into paste, slurry, mortar, or concrete containing cement or gypsum as the hydraulic substance. There are no limitations on the method for adding the foaming agent for hydraulic compositions of the present invention to a hydraulic composition, nor on the method for foaming the foaming agent for hydraulic compositions of the present invention or a mixed solution obtained by diluting it with water.
[0045] The present invention provides a bubble-containing hydraulic composition comprising 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 15 / 85 or more and 80 / 20 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 applied to the foam-containing hydraulic composition of the present invention as appropriate. The components (A), (B), (C), and (D) are the same as those described in the foaming agent for hydraulic compositions of the present invention.
[0046] The hydraulic powder is a powder that has the physical property of hardening through a hydration reaction, and examples thereof 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 used to form blast furnace slag cement, fly ash cement, silica fume cement, or silica fume cement, which may contain blast furnace slag, fly ash, silica fume, stone powder (calcium carbonate powder), or the like.
[0047] The dispersant may be one or more compounds selected from naphthalene-based polymers, polycarboxylic acid-based polymers, lignin sulfonic acid-based polymers, and melamine-based polymers. When a polycarboxylic acid polymer is used as a dispersant, it has good dispersibility when producing a bubble-containing hydraulic composition and can reduce water, which has the advantage of accelerating drying when curing the bubble-containing hydraulic composition and reducing fuel costs, but it has the disadvantage that the average bubble diameter of the set body of the bubble-containing hydraulic composition is smaller than when 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 set body of the bubble-containing hydraulic composition even when a polycarboxylic acid polymer is used as a dispersant.
[0048] Examples of naphthalene-based polymers include polymers obtained by condensation polymerization. Specifically, examples include polymers obtained by addition condensation of naphthalene-based compounds with aldehydes, typically formaldehyde condensation. The naphthalene-based polymer is preferably a condensation polymer with aldehydes, and more preferably a formaldehyde condensation polymer.
[0049] The naphthalene-based polymer is preferably a naphthalenesulfonic acid-formaldehyde condensate or a salt thereof. The naphthalenesulfonic acid-formaldehyde condensate or a salt thereof is a condensate of naphthalenesulfonic acid and formaldehyde or a salt thereof. The naphthalenesulfonic acid-formaldehyde condensate may be co-condensed with an aromatic compound capable of co-condensing with naphthalenesulfonic acid, such as methylnaphthalene, ethylnaphthalene, butylnaphthalene, hydroxynaphthalene, naphthalenecarboxylic acid, anthracene, phenol, cresol, creosote oil, tar, melamine, urea, sulfanilic acid, and / or derivatives thereof, as long as the performance is not impaired.
[0050] As the naphthalenesulfonic acid formaldehyde condensate or a salt thereof, commercially available products such as Mighty 150, Demol N, Demol RN, Demol MS, Demol SN-B, and Demol SS-L (all manufactured by Kao Corporation), Celflow 120, Labelin FD-40, and Labelin FM-45 (all manufactured by Daiichi Kogyo Co., Ltd.) can be used.
[0051] 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, still more preferably 50,000 or less, and still 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 still more preferably 5,000 or more. The naphthalenesulfonic acid formaldehyde condensate may be in an acid state or a neutralized product.
[0052] 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 CH3COONa / CH3CN=6 / 4 Flow rate: 0.7ml / min Detection: UV280nm Sample size: 0.2mg / ml Standard material: Nishio Kogyo Co., Ltd., sodium polystyrene sulfonate (monodisperse sodium polystyrene sulfonate: molecular weight: 206, 1,800, 4,000, 8,000, 18,000, 35,000, 88,000, 780,000) Detector: Tosoh Corporation UV-8020
[0053] Examples of polycarboxylic acid polymers that can be used as polycarboxylic acid dispersants include copolymers of monoesters of polyalkylene glycol and (meth)acrylic acid with carboxylic acids such as (meth)acrylic acid (e.g., compounds described in JP-A-8-12397), copolymers of unsaturated alcohols containing polyalkylene glycol with carboxylic acids such as (meth)acrylic acid, and copolymers of unsaturated alcohols containing polyalkylene glycol with dicarboxylic acids such as maleic acid. Here, (meth)acrylic acid means a carboxylic acid selected from acrylic acid and methacrylic acid.
[0054] Examples of the polycarboxylic acid polymer include 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):
[0055] [ka]
[0056] [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 (CH2) r COOM 2 and (CH2) r COOM2 COOM 1 or other (CH2) r COOM 2 and an anhydride may be formed, in which case the M 1 , M 2 does not exist. M 1 , M 2 may be the same or different, and may be 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.]
[0057] [ka]
[0058] [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 : a 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 of 1 to 300 q1: A number between 0 and 2 p1: 0 or 1 indicates.]
[0059] 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 3e is preferably a hydrogen atom. (CH2) r COOM 2About COOM 1 or other (CH2) r COOM 2 and an anhydride may be formed, in which case the 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 still more preferably a hydrogen atom or an alkali metal. (CH2) in general formula (1e) r COOM 2 r is preferably 0.
[0060] 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, more preferably a methyl group. In the general formula (2e), AO is preferably an ethyleneoxy group, and 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 the general formula (2e), p1 is preferably 1.
[0061] 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, still more preferably 50 mol% or more, and preferably 99 mol% or less, more preferably 90 mol% or less.
[0062] The proportion of the monomer (1e) in all the 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, still more preferably 50 mol% or more, and preferably 99 mol% or less, more preferably 90 mol% or less.
[0063] 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.
[0064] 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.
[0065] The weight average molecular weight of the copolymer was measured by gel permeation chromatography (GPC) under the following conditions. *GPC conditions Apparatus: GPC (HLC-8320GPC) manufactured by Tosoh Corporation Column: G4000PWXL + G2500PWXL (Tosoh Corporation) Eluent: 0.2M phosphate buffer / CH3CN=9 / 1 Flow rate: 1.0mL / min Column temperature: 40℃ Detection: RI Sample size: 0.2 mg / mL Standard substance: Polyethylene glycol equivalent (monodisperse polyethylene glycol with known molecular weight, molecular weight 87,500, 250,000, 145,000, 46,000, 24,000)
[0066] 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 structural units, 100% by mass of the total of the monomers (1e) and (2e), or the total of the monomers (1e), (2e), and (3e).
[0067] Examples of lignin sulfonic acid polymers include lignin sulfonates and derivatives thereof. Commercially available lignin sulfonates and derivatives thereof can be used. Examples include Master Pozzolith No. 70 and Master Polyhede 15S series from BASF Japan, the Floric S series and Floric R series from Floric Corporation, Darlex WRDA from Grace Chemical Company, 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, and Yamaso NLR-P from Yamaso Chemical, the Tupol EX60 series and Tupol LS-A series from Takemoto Oil & Fat Co., Ltd., and the LiguAce UA series, LiguAce UR series, and LiguAce VF series from LiguAce Corporation.
[0068] Specific examples of lignin sulfonates or derivatives thereof are listed 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 sulfonates 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 is introduced into lignin sulfonate (e.g., JP 2015-193804 A) (VIII) Reaction products of lignosulfonic 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 water-soluble monomers 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 at least one water-soluble monomer with functional groups such as phenolic hydroxyl groups, alcoholic hydroxyl groups, and thiol groups contained in lignosulfonic acid compounds. 5) Lignin derivatives 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 lignosulfonic acid compound is not particularly limited, but examples thereof include those obtained by cooking wood by the sulfite method. Among the water-soluble monomers, examples of 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 water-soluble monomers used in radical copolymerization include the monomers described in
[0071] to
[0074] of JP 2015-212216 A, specifically, adducts of 1 to 500 moles of alkylene oxide 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.
[0069] Examples of melamine-based polymers include melamine sulfonic acid formaldehyde condensates and their salts. Melamine sulfonic acid formaldehyde condensates and their salts are compounds obtained by reacting melamine with formaldehyde to obtain N-methylolated melamine, then reacting the resulting melamine with a bisulfite to sulfomethylate some of the methylol groups, and then adding an acid to dehydrate and condense the methylol groups to form a formaldehyde condensate, followed by neutralization with an alkali (see, for example, Japanese Patent Publication No. 63-37058). Examples of alkalis include hydroxides of alkali metals or alkaline earth metals, ammonia, mono-, di-, or tri-alkylamines (having 2 to 8 carbon atoms), and mono-, di-, or trialkanolamines (having 2 to 8 carbon atoms).
[0070] Commercially available products of melamine sulfonate formaldehyde condensates or salts thereof include Mytei 150V-2 (manufactured by Kao Corporation), SMF-PG (Nissan Chemical Industries, Ltd.), Melflow (Mitsui Chemicals, Inc.), Melment F-10 (manufactured by 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.).
[0071] 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).
[0072] 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 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 from the viewpoint of hardened body strength. Here, the water / hydraulic powder ratio is the mass percentage (mass%) of water to hydraulic powder in the hydraulic composition, and is calculated by multiplying water / hydraulic powder by 100. The water / hydraulic powder ratio is calculated based on the amount of powder that has the physical property of hardening by hydration reaction. When the powder that has the physical property of hardening 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.
[0073] The bubble-containing hydraulic composition of the present invention contains component (A) in an amount of preferably 0.0005 parts by mass or more, more preferably 0.001 parts by mass or more, even more preferably 0.003 parts by mass or more, still more preferably 0.006 parts by mass or more, and preferably 0.050 parts by mass or less, more preferably 0.020 parts by mass or less, even more preferably 0.015 parts by mass or less, still more preferably 0.013 parts by mass or less, and still more preferably 0.010 parts by mass or less, per 100 parts by mass of hydraulic powder, from the viewpoints of suppressing the reduction in the bubble diameter in the hydraulic composition, reducing the amount of foaming component added, and reducing the specific gravity of the set body.
[0074] The bubble-containing hydraulic composition of the present invention contains component (B) in an amount of preferably 0.002 part by mass or more, more preferably 0.005 part by mass or more, and even more preferably 0.008 part by mass or more, per 100 parts by mass of hydraulic powder, from the viewpoints of inhibiting the bubble diameter in the hydraulic composition from becoming smaller, reducing the amount of foaming component added, and reducing the specific gravity of the set body; and from the viewpoint of the strength of the set body, preferably 0.1 part by mass or less, more preferably 0.05 part by mass or less, even more preferably 0.02 part by mass or less, still more preferably 0.015 part by mass or less, still more preferably 0.012 part by mass or less, and even more preferably 0.011 part by mass or less.
[0075] In the bubble-containing hydraulic composition of the present invention, the mass ratio (B) / (A) of the content of component (B) to the content of component (A) is 15 / 85 or more, preferably 25 / 75 or more, more preferably 35 / 65 or more, and even more preferably 45 / 55 or more, and is 80 / 20 or less, preferably 75 / 25 or less, and more preferably 65 / 35 or less, from the viewpoints of suppressing the reduction in the size of bubbles in the hydraulic composition, reducing the amount of foaming component added, and reducing the specific gravity of the set body.
[0076] The bubble-containing hydraulic composition of the present invention contains, from the viewpoint of both improving fluidity and achieving 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.
[0077] When the bubble-containing hydraulic composition of the present invention contains component (C), from the viewpoint of increasing the diameter of bubbles in the hydraulic composition, the component (C) is preferably contained in an amount of at least 0.00050 parts by mass, more preferably at least 0.00100 parts by mass, even more preferably at least 0.00150 parts by mass, and preferably at most 0.015 parts by mass, more preferably at most 0.010 parts by mass, even more preferably at most 0.005 parts by mass, relative to 100 parts by mass of hydraulic powder.
[0078] When the bubble-containing hydraulic composition of the present invention contains component (D), from the viewpoint of achieving both foam stability, particularly foam performance in aqueous systems, and enlarged bubble diameters in the hydraulic composition, the bubble-containing hydraulic composition of the present invention preferably contains component (D) in an amount of 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, even more preferably 0.015 parts by mass or less, per 100 parts by mass of the hydraulic powder.
[0079] The bubble-containing hydraulic composition of the present invention may contain fine aggregate and / or coarse aggregate, and may also contain admixtures or additives known in the art.
[0080] The bubble-containing hydraulic composition of the present invention can be dried and cured to give a hardened product. The specific gravity of the set body of the bubble-containing hydraulic composition of the present invention is preferably 0.3 or more, more preferably 0.4 or more, and even more preferably 0.5 or more, from the viewpoint of strength, and is preferably 0.9 or less, more preferably 0.8 or less, even more preferably 0.7 or less, still more preferably 0.6 or less, and even more preferably 0.55 or less, from the viewpoint of handleability.
[0081] The bubble-containing hydraulic composition of the present invention contains bubbles. From the viewpoint of improving the strength of the cured product, the average bubble diameter of the cured product of the bubble-containing hydraulic composition of the present invention is preferably 180 μm or more, more preferably 200 μm or more, and from the viewpoint of cross-sectional appearance, it 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 still more preferably 400 μm or less. The average bubble diameter is calculated by preparing a cured product of a bubble-containing hydraulic composition, cutting the cured product at random to prepare a cross section, observing the cross section with a digital microscope, measuring the diameter of 100 randomly selected bubble cross sections, and averaging (arithmetic mean) these values. The diameter of the bubble cross section is measured when the bubble cross section is circular; when the bubble cross section is elliptical, the diameter is measured along the major axis; and when the bubble cross section is irregular, the diameter is measured along the longest part. The bubble diameter of a cured product of a bubble-containing hydraulic composition is the same as the bubble diameter of the bubble-containing hydraulic composition before hardening.
[0082] The foam-containing hydraulic composition 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 a bubble-containing hydraulic composition, which comprises 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 and the foam obtained in step 1 may be mixed.
[0083] The bubble-containing hydraulic composition of the present invention can be prepared by this manufacturing method. The foaming agent composition for hydraulic compositions of the present invention and the aspects described for the foaming agent composition for hydraulic compositions of the present invention and the foaming hydraulic composition of the present invention can be applied as appropriate to the method for producing the bubble-containing hydraulic composition of the present invention. In the method for producing the bubble-containing hydraulic composition of the present invention, the contents of the components and their mass ratios described for the bubble-containing hydraulic composition of the present invention can be appropriately applied by replacing the contents of the components with the mixing amounts.
[0084] 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.
[0085] 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 weight of the set 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 set body. In this production method, admixtures and additives known in the art can be mixed in step 1 and / or step 2.
[0086] 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 molding the bubble-containing hydraulic composition slurry obtained in step 2 and hardening it.
[0087] The specific gravity of the set product of the bubble-containing hydraulic composition obtained by the method for producing a bubble-containing hydraulic composition of the present invention is preferably 0.3 or more, more preferably 0.4 or more, and even more preferably 0.5 or more, from the viewpoint of strength, and is preferably 0.9 or less, more preferably 0.8 or less, even more preferably 0.7 or less, still more preferably 0.6 or less, and even more preferably 0.55 or less, from the viewpoint of handleability. The average bubble diameter of the set body of the bubble-containing hydraulic composition obtained by the method for producing a bubble-containing hydraulic composition of the present invention is preferably 180 μm or more, more preferably 200 μm or more, from the viewpoint of improving the strength of the set 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.
[0088] [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, a 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 containing gypsum, water, a dispersant, component (A), and component (B), wherein the mass ratio (B) / (A) of the content of component (B) to the content of component (A) is 15 / 85 or more and 80 / 20 or less. The bubble-containing gypsum slurry of the present invention is suitable for use in gypsum boards.
[0089] The foaming agent for hydraulic compositions of the present invention, the foam-containing hydraulic composition of the present invention, and the method for producing the foam-containing hydraulic composition of the present invention can be applied as appropriate to the foam-containing gypsum slurry of the present invention. The bubble-containing gypsum slurry of the present invention may further contain component (C). The bubble-containing gypsum slurry of the present invention may further contain component (D). The components (A), (B), (C), and (D) are the same as those described for the foaming agent for hydraulic compositions of the present invention. The dispersant is the same as that described for the foam-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 for the bubble-containing hydraulic composition of the present invention can be appropriately applied by substituting the hydraulic powder for gypsum. In the hardened product of the gas-bubble-containing gypsum slurry of the present invention, the ranges of specific gravity and average gas bubble diameter are the same as those described for the gas-bubble-containing hydraulic composition of the present invention.
[0090] 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 plants, natural gypsum containing various impurities and clay, and mixtures of these. The clay contained in gypsum is mainly composed of hydrous silicate minerals (hereinafter referred to as clay minerals) with a layered structure, and examples of 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).
[0091] Examples of gypsum include anhydrous gypsum, hemihydrate gypsum, and dihydrate gypsum. As the raw gypsum, natural gypsum, neutralized gypsum, by-product gypsum, or other chemical gypsum can be used alone, or a mixture of two or more of these can be used. Examples of major 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 board generated in-house by gypsum board manufacturers, waste gypsum board generated during new construction and demolition, and the like. The present invention can be suitably used with any of these raw gypsums, and excellent effects can be obtained with blends of these gypsums in various ratios.
[0092] 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, antifoaming agents, foam stabilizers, hardening regulators, water repellents, adhesives, retarders, etc. Furthermore, gypsum boards can be produced by adding reinforcing fibers such as glass fiber, carbon fiber, waste paper, virgin pulp, etc., or by adding lightweight aggregates such as perlite or foamed steel.
[0093] 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, which includes 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.
[0094] The gas bubble-containing gypsum slurry of the present invention can be prepared by this manufacturing method. The method for producing the bubble-containing gypsum slurry of the present invention can be appropriately applied to the embodiments described for the foaming agent for hydraulic compositions 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 method for producing the bubble-containing hydraulic composition of the present invention, the contents and mass ratios of the components described for 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.
[0095] After step 2, the following step 3 is further carried out to manufacture a gypsum board. Step 3: A step of molding and curing the air bubble-containing gypsum slurry obtained in Step 2. Molding and curing can be performed by known methods. For example, by referring to "Manufacture of Gypsum Board" described on pages 322 to 324 of the "Gypsum and Lime Handbook" (edited by the Gypsum and Lime Society), a gypsum board can be prepared.
[0096] From the perspective of strength, the specific gravity of the gypsum board obtained by the method for producing an air bubble-containing gypsum slurry of the present invention is preferably 0.3 or more, more preferably 0.4 or more, still more preferably 0.5 or more; and from the perspective of handleability, it is preferably 0.9 or less, more preferably 0.8 or less, still more preferably 0.7 or less, even more preferably 0.6 or less, and even more preferably 0.55 or less. Also, from the perspective of improving the strength of the cured body, the average bubble diameter of the gypsum board obtained by the method for producing an air bubble-containing gypsum slurry of the present invention is preferably 180 μm or more, more preferably 200 μm or more; and from the perspective of the cross-sectional appearance, it is 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, and even more preferably 400 μm or less.
Examples
[0097] 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 prepared using an internal olefin having 16 carbon atoms, and a C16IOS aqueous solution with an active content of 30% was prepared by following the method described in the Preparation Examples of JP 2014-76988 A. The mass ratio of the olefin (potassium olefin sulfonate) to the hydroxyl (potassium hydroxyalkanesulfonate) in the resulting internal potassium olefin sulfonate salt of C16IOS was 17 / 83. The mass distribution of the sulfonic acid groups of the hydroxyl groups in C16IOS was 1 / 2 / 3 / 4 / 5 / 6-9 = 2.3% / 23.6% / 18.9% / 17.5% / 13.7% / 11.2% / 6.4% / 6.4% / 0% (total 100% by mass). The mass ratio of (IO-1S) / (IO-2S) was approximately 1.6. (IO-1S) / (IO-2S) is the mass ratio of the content of internal olefin sulfonate salts [(IO-1S)] in which the sulfonic acid group is located at the 2nd to 4th position and the content of internal olefin sulfonate salts [(IO-2S)] in which the sulfonic acid group is located at the 5th position or higher.
[0098] (B) Component C10AS: Sodium decyl sulfate (active ingredient 33%)
[0099] (1) Preparation of foaming agent for 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 the specified ratio so that the total weight was 30 g, and the mixture was stirred at 1000 rpm for 30 minutes using a stirrer to prepare a homogeneous, transparent foaming agent for hydraulic compositions. The blending compositions of components (A) and (B) shown in Table 1 are based on the active ingredients.
[0100] (2) Preparation of gypsum slurry The foaming agent for hydraulic compositions prepared in Table 1 was mixed with water in an arbitrary ratio to prepare a diluted aqueous solution of foaming agent for hydraulic compositions at a concentration of 0.60% by mass. 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, manufactured by IKA Japan Co., Ltd.) equipped with a flat six-paddle blade (FP-50, manufactured by AS ONE Corporation) to obtain a foam. To 20 g of the prepared foam, 200 g of calcined gypsum, 4 g of gypsum dihydrate, 0.614 g of potassium sulfate, 100 g of tap water, and 0.4 g of a dispersant (Mighty 21G-30, a polycarboxylic acid polymer, manufactured by Kao Corporation) were added, and the mixture was kneaded for 20 seconds at 1,150 rpm using the stirrer used when preparing the foam, to obtain a gypsum slurry containing air bubbles.
[0101] (3) Measurement of the specific gravity and average bubble diameter of the gypsum hardened body The resulting bubble-containing gypsum slurry was poured into a 10.5 cm square silicone tray to a height of 13 mm and allowed to stand at room temperature for 1 hour. The hardened gypsum slurry was demolded and allowed to stand in a 60°C thermostatic chamber for 24 hours to dry. The weight of the gypsum hardened body was then measured to calculate the specific gravity of the gypsum hardened body. The results are shown in Table 1. The obtained gypsum hardened body was then split horizontally in half to create a cross-section of the hardened body. The cross-section was observed using a digital microscope (42x magnification), and the diameters of 100 bubbles were measured, starting with the smallest visible bubbles. The average bubble diameter was calculated from the arithmetic mean of these values. When measuring the diameter of a bubble's cross-section, the diameter was taken as the diameter if the bubble's cross-section was circular; the major axis was taken as the diameter if the bubble's cross-section was elliptical; and the longest part was taken as the diameter if the bubble's cross-section was irregular. The results are shown in Table 1.
[0102] [Table 1]
[0103] It can be seen that in Examples 1 to 6, where the mass ratio (B) / (A) of the (B) component to the (A) component is within the specified range of the present invention, a gypsum hardened body with a lower specific gravity can be obtained without a decrease in the average air bubble diameter in the gypsum hardened body at the same addition amount of foaming agent for hydraulic compositions, compared to Comparative Examples 1 and 3, where either the (A) component or the (B) component is used alone. Also, it can be seen that in Comparative Example 2, where the mass ratio (B) / (A) of the (B) component to the (A) component is outside the specified range of the present invention, a decrease in the average air bubble diameter in the gypsum hardened body can be suppressed, but a gypsum hardened body with a lower specific gravity cannot be obtained compared to Examples 1 to 6.
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 15 / 85 or more and 80 / 20 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 comprising 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 15 / 85 or more and 80 / 20 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.