WO2024172052A1 - 水硬性組成物用表面美観向上剤 - Google Patents

水硬性組成物用表面美観向上剤 Download PDF

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WO2024172052A1
WO2024172052A1 PCT/JP2024/004942 JP2024004942W WO2024172052A1 WO 2024172052 A1 WO2024172052 A1 WO 2024172052A1 JP 2024004942 W JP2024004942 W JP 2024004942W WO 2024172052 A1 WO2024172052 A1 WO 2024172052A1
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present
hydraulic composition
mass
hydraulic
surfactant
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English (en)
French (fr)
Japanese (ja)
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悠登 名越
博行 川上
恒平 島田
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Kao Corp
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Kao Corp
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Priority to EP24756894.2A priority Critical patent/EP4667436A1/en
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients

Definitions

  • the present invention relates to a surfactant for use as a surface aesthetic improver for hydraulic compositions, a surface aesthetic improver for hydraulic compositions, a hydraulic composition, a method for producing a hardened product of a hydraulic composition, a method for improving the surface aesthetic of a hardened product of a hydraulic composition, use of a surfactant as a surface aesthetic improver for hydraulic compositions, and a kit for improving surface aesthetics.
  • Hydraulic compositions such as concrete can be manufactured, for example, by filling a formwork with the unhardened hardening composition, then hardening it in a later process by drying or through a chemical reaction to obtain a hardened body.
  • One of the factors that determines the value of a hardened body is the aesthetic appearance of the surface. This literally means the beauty of the surface of the hardened body, and the more aesthetically pleasing the surface is, the more the product value tends to be evaluated highly.
  • JP 2019-196282 A discloses a surface aesthetics enhancer for hydraulic compositions that contains a specific fatty acid alkanolamide, a polycarboxylic acid-based dispersant, and a specific solvent.
  • JP 2019-26506 A discloses a resin emulsion used in a cement additive that contains a specific emulsion resin, an aqueous solvent, and a nonionic emulsifier (polyoxyethylene alkyl ether) used in the emulsion polymerization of the resin, and discloses that the use of a cement additive containing the resin emulsion can improve the surface aesthetics of the hardened product of the cement composition.
  • JP 2018-130957 A discloses a formwork release agent containing a specific fatty acid alkanolamide.
  • the present invention aims to provide a surface aesthetics improver for hydraulic compositions that can better control the behavior of air bubbles in a hydraulic composition, which are the cause of air bubble marks on the surface of the hardened hydraulic composition, and improve the surface aesthetics of the hardened hydraulic composition.
  • the present invention provides a surface aesthetic improver for hydraulic compositions, which contains a surfactant that, when measured by the bubble pressure method (20°C), has a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms.
  • the present invention also provides a surfactant for use as a surface aesthetic enhancer for hydraulic compositions, which, when a measurement aqueous solution obtained by adding a surfactant at a concentration of 0.05% by mass to bleeding water of the hydraulic composition described below is measured by the bubble pressure method (20°C), has a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms.
  • the present invention also provides a hydraulic composition containing the above-mentioned surface aesthetic improver for hydraulic compositions, hydraulic powder, and water.
  • the present invention also provides a method for producing a hardened hydraulic composition, comprising the steps of: mixing a surface aesthetic improver for hydraulic compositions, which has a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms, when measured by the bubble pressure method (20°C), with hydraulic powder and water to prepare a hydraulic composition; filling a formwork with the prepared hydraulic composition and hardening it; and demolding the hardened hydraulic composition.
  • a surface aesthetic improver for hydraulic compositions which has a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms, when measured by the bubble pressure method (20°C), with hydraulic powder and water to prepare a hydraulic composition; filling a formwork with the prepared hydraulic composition and harden
  • the present invention also provides a method for improving the surface appearance of a hardened body of a hydraulic composition, which comprises adding a surfactant to a hydraulic composition containing hydraulic powder and water, the surfactant having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms, as measured by the bubble pressure method (20°C).
  • the present invention also provides the use of a surfactant as a surface aesthetic improver for a hydraulic composition, the surfactant having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms when a measurement aqueous solution obtained by adding a surfactant at a concentration of 0.05 mass % to the bleeding water of the hydraulic composition is measured by the bubble pressure method (20°C).
  • the present invention also provides a kit for improving the surface aesthetics of a hardened hydraulic composition, which combines the above-mentioned aqueous solution ⁇ containing a surfactant for improving the surface aesthetics of a hydraulic composition with the aqueous solution ⁇ containing the following cement dispersant.
  • [Cement dispersant] A copolymer containing, as constituent monomers, a monomer (1b) represented by the following general formula (1b) and a monomer (2b) represented by the following general formula (2b).
  • R 1b , R 2b , R 3b may be the same or different and are a hydrogen atom, a methyl group or (CH 2 ) r COOM 2 , in which case (CH 2 ) r COOM 2 may form an anhydride with COOM 1 or another (CH 2 ) r COOM 2 , in which case M 1 and M 2 in those groups do not exist.
  • M 1 and M 2 may be the same or different and each represents 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 represents a number of 0 to 2.
  • R 4b and R 5b may be the same or different and are a hydrogen atom or a methyl group.
  • R 6b a hydrogen atom or -COO(AO) n1
  • R 7b R7b a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • AO an oxyalkylene group having 2 to 4 carbon atoms
  • n1 the average number of moles of AO added, which is a number of 4 to 200
  • q1 a number of 0 to 2
  • p1 0 or 1 Indicates that.
  • a specific surfactant that satisfies the dynamic surface tension described above adsorbs to air bubbles in the hydraulic composition, particularly coarse bubbles of several centimeters that are noticeable as air bubble marks, making it possible to peel the air bubbles off the formwork.
  • the number of air bubbles between the hydraulic composition and the formwork is reduced, and the surface air bubble marks on the hardened body of the hydraulic composition are reduced, improving the surface aesthetics.
  • the reason for the manifestation of such an effect is presumed to be as follows. For example, a hydraulic composition such as concrete is applied to a metal formwork with release oil, and is filled into the formwork by pouring and vibrating, and then hardened.
  • the plasticity of the concrete is released due to the dilatant property, but once the plasticity is released, the air bubbles that have formed and adhered to the formwork are held down by the concrete, and cannot be peeled off by the action of the surfactant. Therefore, it is desirable to peel off the air bubbles before the time of about 1000 ms when the plasticity is released. It is known that many general-purpose release oils have a dynamic surface tension of approximately 25 to 35 mN/m at the gas interface.
  • a surfactant has a dynamic surface tension of 35 mN/m or less at the gas-liquid interface for a bubble film life of 1000 ms, it is assumed that it will be able to adsorb and peel off bubbles that appear at the part where the hydraulic composition and the formwork come into contact with each other via the release oil, especially large bubbles that are noticeable as bubble marks (several centimeters in size).
  • the specific surfactant of the present invention has a dynamic surface tension of 55 mN/m or more at a bubble film life of 10 ms, and is adsorbed to bubbles relatively slowly (compared to other surfactants).
  • the surfactant is not bound to the surface of fine bubbles (which have an extremely large surface area) and a sufficient amount of free surfactant remains in the water, allowing it to be adsorbed to the surface of the original target, coarse bubbles. Therefore, the specific surfactant of the present invention is considered to have a high effect of modifying coarse bubbles.
  • the present invention relates to a surfactant for surface aesthetic improver for hydraulic composition (hereinafter referred to as "surfactant of the present invention”), which has a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms when a measuring aqueous solution obtained by adding a surfactant at a concentration of 0.05 mass % to bleeding water of the following hydraulic composition is measured by a bubble pressure method (20°C).
  • surfactant of the present invention a surfactant for surface aesthetic improver for hydraulic composition
  • the ordinary Portland cement does not have to be of a specific manufacturer, place of origin, or brand, and any ordinary Portland cement can be used.
  • the dynamic interfacial tension at the gas-liquid interface in the present invention is dominated by the surfactant of the present invention, and is hardly affected by the ionic species present in the cement particles or the bleeding water, or by other optional components.
  • the reason for this is unclear, but is presumed to be as follows.
  • the surfactant of the present invention is rather strongly hydrophobic, and it is presumed that it does not diffuse much in water, and that most of it is coordinated to the gas-liquid interface. Therefore, it is presumed that it is not affected by dissolved ion species, cement particles, cement dispersants, and other soluble polymeric compounds.
  • the dynamic surface tension of the surfactant of the present invention is measured using a measurement aqueous solution prepared by adding a surfactant at a concentration of 0.05% by mass to the bleeding water of the hydraulic composition described above, for example, using a KRUSS BP100 at 20°C, capillary diameter: 0.2 to 0.3 mm, measurement time: 10 ms to 10,000 ms.
  • the surfactant of the present invention is added to the bleeding water of the hydraulic composition at a concentration of 0.05 mass % to obtain a measurement aqueous solution, and the measurement aqueous solution is measured by the bubble pressure method (20°C).
  • the dynamic surface tension ( ⁇ 1) at a bubble film life of 10 ms is 55 mN/m or more, and from the viewpoint of the effect of reducing the amount of bubble traces on the surface of the hardened hydraulic composition, the dynamic surface tension ( ⁇ 2) is 35 mN/m or less, and from the viewpoint of the effect of reducing the amount of bubble traces on the surface of the hardened hydraulic composition, the dynamic surface tension ( ⁇ 2) at a bubble film life of 1000 ms is 35 mN/m or less, and from the viewpoint of the effect of reducing the amount of bubble traces on the surface of the hardened hydraulic composition, the dynamic surface tension ( ⁇ 2) is 33 mN/m or less, and from the viewpoint of the effect of reducing the amount of bubble traces on the surface of the hardened hydraulic composition, the dynamic surface tension ...
  • the surfactant of the present invention has a dynamic surface tension ( ⁇ 3) of 55 mN/m or more at a bubble film life of 10 ms when the surfactant aqueous solution having a concentration of 0.3% by mass is measured by the bubble pressure method (20°C), and from the viewpoint of the effect of reducing the amount of air bubbles on the surface of the hardened body of the hydraulic composition, the dynamic surface tension ( ⁇ 4) of 35 mN/m or less at a bubble film life of 1000 ms is preferably 33 mN/m or less, more preferably 31 mN/m or less, even more preferably 29 mN/m or less, and even more preferably 28 mN/m or less from the viewpoint of the effect of reducing the amount of air bubbles on the surface of the hardened body of the hydraulic composition.
  • the surfactant of the present invention is preferably a surfactant in which the ⁇ 1 is 55 mN/m or more and the ⁇ 2 is 35 mN/m or less, specifically, a nonionic surfactant in which the ⁇ 1 is 55 mN/m or more and the ⁇ 2 is 35 mN/m or less, more specifically, one or more nonionic surfactants selected from polyoxyalkylene alkyl ethers, alkyl alkanolamides, and polyoxyethylene alkyl amines in which the ⁇ 1 is 55 mN/m or more and the ⁇ 2 is 35 mN/m or less are more preferred, and from the viewpoint of the effect of reducing the amount of air bubble traces on the surface of the hardened body of the hydraulic composition, more specifically, a polyoxyalkylene alkyl ether in which the ⁇ 1 is 55 mN/m or more and the ⁇ 2 is 35 mN/m or less is even more preferred.
  • a polyoxyalkylene alkyl ether can be used in which the average carbon number of the alkyl group is preferably 9 or more, more preferably 10 or more, and preferably 12 or less, more preferably 11 or less.
  • the average carbon number of the alkyl groups is the weight average carbon number calculated from the content ratio of all polyoxyalkylene ethers contained in the surfactant of the present invention and the number of carbon atoms in the alkyl groups in each polyoxyalkylene alkyl ether.
  • the surfactant of the present invention is a nonionic surfactant in which ⁇ 1 is 55 mN/m or more and ⁇ 2 is 35 mN/m or less
  • the alkylene oxide is preferably ethylene oxide or propylene oxide, and more preferably ethylene oxide, and a polyoxyalkylene alkyl ether can be used.
  • the surfactant of the present invention is a polyoxyethylene alkyl ether in which ⁇ 1 is 55 mN/m or more and ⁇ 2 is 35 mN/m or less
  • the average number of moles of ethylene oxide added is preferably 1 or more, more preferably 2 or more, and is preferably 6 or less, more preferably 5 or less.
  • the surfactant of the present invention is a polyoxypropylene alkyl ether in which ⁇ 1 is 55 mN/m or more and ⁇ 2 is 35 mN/m or less, from the viewpoint of the effect of reducing the amount of air bubble traces on the surface of the hardened hydraulic composition, the average number of moles of propylene oxide added is preferably 0 or more, and is preferably 6 or less, and more preferably 4 or less.
  • the average number of moles of alkylene oxide added is the weight average value of the content of all polyoxyethylene alkyl ethers contained in the surfactant of the present invention and the average number of moles of ethylene oxide added in each polyoxyethylene alkyl ether.
  • a polyoxyethylene alkyl ether can be used in which the average carbon number of the alkyl group is preferably 9 or more and preferably 12 or less, and the average number of moles of ethylene oxide added is preferably 1 or more and preferably 6 or less.
  • the surfactant of the present invention when the surfactant of the present invention is a polyoxyethylene alkyl ether in which the ⁇ 1 is 55 mN/m or more and the ⁇ 2 is 35 mN/m or less, the polyoxyethylene alkyl ether may be a polyoxyethylene alkyl ether in which the number of moles of added oxyethylene groups is 0, that is, an alkyl alcohol having an alkyl group that is a raw material for the polyoxyethylene alkyl ether.
  • the alkyl alcohol having the alkyl group is regarded as part of the polyoxyethylene alkyl ether.
  • the content of the alkyl alcohol having the alkyl group in the polyoxyethylene alkyl ether is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 5% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less.
  • the surfactant of the present invention is a nonionic surfactant having ⁇ 1 of 55 mN/m or more and ⁇ 2 of 35 mN/m or less, from the viewpoint of the effect of reducing the amount of air bubble traces on the surface of the hardened hydraulic composition
  • the HLB of the nonionic surfactant is preferably 5 or more, more preferably 7 or more, and is preferably 14 or less, more preferably 12 or less, and even more preferably 11 or less.
  • HLB Hydrophile Lipophile Balance
  • HLB is an abbreviation for Hydrophile Lipophile Balance, and is an index to know whether a compound is hydrophilic or lipophilic.
  • the value ranges from 0 to 20. The smaller the HLB value, the stronger the lipophilicity.
  • HLB is calculated, for example, by the Griffin method.
  • HLB (sum of molecular weights of hydrophilic parts of formulas/molecular weight) x 20
  • the surfactant of the present invention is a polyoxyalkylene alkyl ether or further a polyoxyethylene alkyl ether having ⁇ 1 of 55 mN/m or more and ⁇ 2 of 35 mN/m or less
  • the HLB of the polyoxyalkylene alkyl ether or further a polyoxyethylene alkyl ether is preferably 5 or more, more preferably 7 or more, and preferably 14 or less, more preferably 12 or less, and even more preferably 11 or less.
  • HLB value [(molecular weight of polyoxyalkylene group portion in nonionic surfactant)/(molecular weight of nonionic surfactant)] ⁇ 20
  • the molecular weight of the polyoxyalkylene group portion in the nonionic surfactant is calculated using the average number of moles of polyoxyalkylene groups added.
  • the surfactant of the present invention is preferably one or more selected from polyoxyethylene (5) lauryl ether, polyoxyethylene (2) decyl ether, and polyoxyethylene (3) decyl ether, and from the viewpoint of the effect of reducing the amount of air bubble traces on the surface of the hardened hydraulic composition, one or more selected from polyoxyethylene (5) lauryl ether and polyoxyethylene (2) decyl ether is more preferable.
  • the present invention provides a method for using, as a surface aesthetic improver for a hydraulic composition, a surfactant having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms when a measurement aqueous solution obtained by adding a surfactant at a concentration of 0.05% by mass to the bleeding water of the hydraulic composition is measured by a bubble pressure method (20°C).
  • a surfactant having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms when a measurement aqueous solution obtained by adding a surfactant at a concentration of 0.05% by mass to the bleeding water of the hydraulic composition is measured by a bubble pressure method (20°C).
  • the surfactants having the ⁇ 1 and ⁇ 2 can be the same as the specific examples and preferred aspects of the surfactants of the present invention described above.
  • the present invention provides a method for selecting a surfactant to be used in a surface aesthetic enhancer for a hydraulic composition, the method including selecting a surfactant having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms, as measured by a bubble pressure method (20°C).
  • the surfactants having the ⁇ 1 and ⁇ 2 can be the same as the specific examples and preferred aspects of the surfactants of the present invention described above.
  • the present invention provides a method for selecting a surfactant to be applied to a surface aesthetic improver for a hydraulic composition, which includes selecting a surfactant (e.g., a nonionic surfactant, e.g., a polyoxyalkylene alkyl ether, e.g., a polyoxyethylene alkyl ether) having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms when a measurement aqueous solution obtained by adding a surfactant at a concentration of 0.05 mass% to the bleeding water of the hydraulic composition is measured by a bubble pressure method (20°C).
  • a surfactant e.g., a nonionic surfactant, e.g., a polyoxyalkylene alkyl ether, e.g., a polyoxyethylene alkyl ether
  • the surfactants e.g., nonionic surfactants, e.g., polyoxyalkylene alkyl ethers, e.g., polyoxyethylene alkyl ethers
  • the surfactants having the ⁇ 1 and ⁇ 2 can be the same as the specific examples and preferred aspects of the surfactants of the present invention described above.
  • the surfactant of the present invention can be used to prepare a surface aesthetic improver for hydraulic compositions, which will be described later. That is, in an exemplary embodiment of the present invention, the present invention provides a surface aesthetic improver for hydraulic compositions, which contains a surfactant (also referred to as the "surfactant of the present invention") that has a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms, as measured by the bubble pressure method (20°C).
  • a surfactant also referred to as the "surfactant of the present invention
  • the present invention provides a surface aesthetic improver for a hydraulic composition (hereinafter also referred to as the "aesthetic improver of the present invention"), which has a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a foam film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a foam film life of 1000 ms, as measured by a bubble pressure method (20°C).
  • the aesthetic appearance improver of the present invention refers to an agent that reduces air bubble marks on the surface of a hardened hydraulic composition and improves the aesthetic appearance of the surface of the hardened hydraulic composition.
  • the aesthetic enhancer of the present invention has a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms when measured by the bubble pressure method (20°C), preferably 58 mN/m or more, more preferably 60 mN/m or more from the viewpoint of the effect of reducing the amount of bubble traces on the surface of the hardened hydraulic composition, and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms, preferably 33 mN/m or less, more preferably 31 mN/m or less, and even more preferably 29 mN/m or less from the viewpoint of the effect of reducing the amount of bubble traces on the surface of the hardened hydraulic composition.
  • ⁇ 1 of 55 mN/m or more at a bubble film life of 10 ms when measured by the bubble pressure method (20°C)
  • a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms,
  • the present invention provides a surface aesthetic improver for hydraulic compositions containing a surfactant, the surface aesthetic improver for hydraulic compositions having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms when a measurement aqueous solution obtained by adding a surfactant at a concentration of 0.05% by mass to the bleeding water of the hydraulic composition is measured by a bubble pressure method (20°C).
  • the aesthetic appearance enhancer of the present invention includes the above two surface aesthetic enhancers for hydraulic compositions.
  • the surfactant when the aesthetic enhancer of the present invention contains a surfactant, can be the surfactant for surface aesthetic enhancers for hydraulic compositions of the present invention described above (hereinafter also referred to as "surfactant of the present invention” and also referred to as component (A)).
  • the dynamic surface tension ( ⁇ 1) at a bubble film life of 10 ms when the aesthetic enhancer of the present invention contains the surfactant of the present invention, is 55 mN/m or more, and from the viewpoint of the effect of reducing the amount of bubble traces on the surface of the hardened body of the hydraulic composition, it is preferably 58 mN/m or more, more preferably 60 mN/m or more, and the dynamic surface tension ( ⁇ 2) at a bubble film life of 1000 ms is 35 mN/m or less, and from the viewpoint of the effect of reducing the amount of bubble traces on the surface of the hardened body of the hydraulic composition, it is preferably 33 mN/m or less, more preferably 31 mN/m or less, and even more preferably 29 mN/m or less.
  • the content of the surfactant of the present invention is preferably 0.05% by mass or more, more preferably 0.5% by mass or more, and even more preferably 2.0% by mass or more, from the viewpoint of the effect of reducing the amount of air bubble traces on the surface of the hardened hydraulic composition, and from the viewpoint of the storage stability of the surface aesthetic enhancer, it is preferably 8.0% by mass or less, and more preferably 4.0% by mass or less.
  • the content of the surfactant in which ⁇ 1 is 55 mN/m or more and ⁇ 2 is 35 mN/m or less is preferably 0.05 mass% or more, more preferably 0.5 mass% or more, and even more preferably 2.0 mass% or more from the viewpoint of the effect of reducing the amount of air bubble traces on the surface of the hardened hydraulic composition, and from the viewpoint of the storage stability of the surface aesthetic enhancer, it is preferably 8.0 mass% or less, and more preferably 4.0 mass% or less.
  • the content of the polyoxyethylene alkyl ether is preferably 0.05% by mass or more, more preferably 0.5% by mass or more, and even more preferably 2.0% by mass or more, from the viewpoint of the effect of reducing the amount of air bubble traces on the surface of the hardened hydraulic composition, and is preferably 8.0% by mass or less, and more preferably 4.0% by mass or less, from the viewpoint of the storage stability of the surface aesthetic enhancer.
  • the surface aesthetics enhancer for hydraulic compositions of the present invention is preferably in liquid form from the viewpoint of ease of handling. Therefore, the surface aesthetics enhancer for hydraulic compositions of the present invention is preferably used in liquid form such as a homogeneous solution, and a solution containing water, and even more preferably an aqueous solution, is used. That is, in an exemplary embodiment of the present invention, an aqueous solution containing the surfactant of the present invention can be used as the surface aesthetics enhancer for hydraulic compositions of the present invention.
  • the surface aesthetics enhancer for hydraulic compositions of the present invention exhibits excellent surface aesthetics enhancement even with a small amount of the surfactant of the present invention, and in one specific embodiment, it can contain a cement dispersant, a product stabilizer, an antifoaming agent, etc.
  • the surface aesthetic improver for hydraulic compositions of the present invention may further contain (B) a cement dispersant (hereinafter also referred to as component (B)).
  • the component (B) of the present invention includes one or more cement dispersants selected from lignin sulfonic acid polymers, polycarboxylic acid polymers, naphthalene polymers, melamine polymers, and phenolic polymers.
  • one or more cement dispersants selected from lignin sulfonic acid polymers, polycarboxylic acid polymers, and naphthalene polymers are preferred, and from the viewpoint of fluidity retention of the hydraulic composition, polycarboxylic acid dispersants are more preferred.
  • the polycarboxylic acid polymer used as component (B) of the present invention may be, for example, a copolymer of a monoester of polyalkylene glycol and (meth)acrylic acid and a carboxylic acid such as (meth)acrylic acid (such as the compound described in JP-A-8-12397), a copolymer of an unsaturated alcohol having polyalkylene glycol and a carboxylic acid such as (meth)acrylic acid, or a copolymer of an unsaturated alcohol having polyalkylene glycol and a dicarboxylic acid such as maleic acid.
  • (meth)acrylic acid means a carboxylic acid selected from acrylic acid and methacrylic acid.
  • the component (B) of the present invention is preferably a polycarboxylic acid-based dispersant containing a copolymer containing, as constituent monomers, a monomer (1b) represented by the following general formula (1b) and a monomer (2b) represented by the following general formula (2b), and more preferably a polycarboxylic acid-based dispersant that is the copolymer.
  • R 1b , R 2b , R 3b may be the same or different and are a hydrogen atom, a methyl group or (CH 2 ) r COOM 2 , in which case (CH 2 ) r COOM 2 may form an anhydride with COOM 1 or another (CH 2 ) r COOM 2 , in which case M 1 and M 2 in those groups do not exist.
  • M 1 and M 2 may be the same or different and each represents 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; and r represents a number of 0 to 2.
  • R 4b and R 5b may be the same or different and are a hydrogen atom or a methyl group.
  • R 6b a hydrogen atom or -COO(AO) n1
  • R 7b R7b a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • AO an alkyleneoxy group having 2 to 4 carbon atoms
  • n1 the average number of moles of AO added, which is a number of 4 to 200
  • q1 a number of 0 to 2
  • p1 0 or 1.
  • R 1b , R 2b , and R 3b may be the same or different, and at least one is preferably a methyl group and the remaining is a hydrogen atom, and more preferably R 1b is a hydrogen atom, R 2b is a methyl group, and R 3b is a hydrogen atom.
  • (CH 2 ) r COOM 1 may form an anhydride with COOM 1 or another (CH 2 ) r COOM 1 , and in that case, M 1 and M 2 of those groups do not exist.
  • M 1 and 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 hydroxyalkyl group, or an alkenyl group, and the alkyl group, hydroxyalkyl group, and alkenyl group of M 1 and M 2 each preferably have 1 to 4 carbon atoms.
  • M1 and M2 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, further preferably a hydrogen atom, an alkali metal, or an alkaline earth metal (1/2 atom), and even further preferably a hydrogen atom or an alkali metal.
  • r in ( CH2 ) rCOOM1 is preferably 1.
  • R 4b and R 5b may be the same or different and may be a hydrogen atom or a methyl group, with R 4b being preferably a hydrogen atom and R 5b being preferably a methyl group from the viewpoint of improving the aesthetic appearance of the surface.
  • R 6b may be a hydrogen atom or -COO(AO) n1 R 7b , with a hydrogen atom being preferred from the viewpoint of improving the aesthetic appearance of the surface.
  • R 7b may be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, with a methyl group being preferred.
  • AO may be an alkyleneoxy group having 2 to 4 carbon atoms, with an ethyleneoxy group being preferred. It is preferred that AO contains an ethyleneoxy group.
  • n1 is the average number of moles of AO added, and may be 4 or more, preferably 5 or more, more preferably 10 or more, even more preferably 20 or more, from the viewpoint of the viscosity and dispersibility of the hydraulic composition, and may be 200 or less, preferably 150 or less, more preferably 120 or less, even more preferably 60 or less.
  • q1 may be a number of 0 or more and 2 or less, preferably 0.
  • p1 may be 0 or 1, preferably 1.
  • the copolymer used as component (B) of the present invention has a total amount of monomer (1b) and monomer (2b) in the constituent monomers of 90% by mass or more, more preferably 92% by mass or more, even more preferably 95% by mass or more, and 100% by mass or less. This total amount may be 100% by mass.
  • the copolymer used as component (B) of the present invention has a ratio of monomer (1b) in the total of monomer (1b) and monomer (2b) of preferably 1 mass% or more, more preferably 2 mass% or more, even more preferably 3 mass% or more, even more preferably 5 mass% or more, and preferably 50 mass% or less, more preferably 40 mass% or less, even more preferably 30 mass% or less, and even more preferably 25 mass% or less, from the viewpoint of dispersibility of the hydraulic composition.
  • the copolymer used as component (B) of the present invention has a weight average molecular weight of preferably 10,000 or more, more preferably 20,000 or more, even more preferably 30,000 or more, even more preferably 35,000 or more, and preferably 100,000 or less, more preferably 90,000 or less, and even more preferably 80,000 or less, from the viewpoint of dispersibility in the hydraulic composition.
  • the weight average molecular weight of the copolymer used as component (B) of the present invention is measured by gel permeation chromatography (GPC) under the following conditions:
  • GPC HPC 8320GPC
  • G4000PWXL + G2500PWXL manufactured by Tosoh Corporation
  • Flow rate 1.0mL/min
  • the copolymer used as the component (B) of the present invention may be, for example, one or more selected from the following copolymers.
  • the polycarboxylic acid copolymers 1, 2, and 3 listed above when used in combination as the component (B) of the present invention, they can be used in a mass ratio of, for example, 50/25/25 for the copolymer 1/copolymer 2/copolymer 3.
  • the average number of moles of ethylene oxide added to each polycarboxylic acid copolymer is calculated by taking the mass average at the blending ratio of the copolymers, and this is regarded as the average number of moles of ethylene oxide added in the (combined) polycarboxylic acid copolymers.
  • the content of the component (B) of the present invention in the aesthetic enhancer of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, and is preferably 60% by mass or less, more preferably 50% by mass or less, from the viewpoint of the fluidity retention of the hydraulic composition.
  • the surface aesthetics improver for hydraulic compositions of the present invention may further contain (C) a product stabilizer (hereinafter also referred to as component (C)).
  • C a product stabilizer
  • component (C) of the present invention include polyoxyethylene alkyl ether sulfate or a salt thereof, polyoxyethylene polyoxypropylene alkyl ether sulfate or a salt thereof; polyoxyethylene alkyl ether (excluding component (A) of the present invention), sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, etc.
  • the component (C) of the present invention is preferably one or more compounds selected from compounds represented by the following general formula (c) [hereinafter referred to as component (c-1)].
  • R 1c represents a hydrocarbon group having an average carbon number of 4 to 20
  • EO represents an ethyleneoxy group
  • PO represents a propyleneoxy group
  • n represents the average number of moles of EO added which is a number of 1 to 50
  • m represents a number of PO
  • the average number of moles of EO and PO added is 0 to 10, and EO and PO may be bonded in blocks or randomly.
  • M represents a counter cation.
  • R 1c may be a hydrocarbon group having an average carbon number of 4 to 20, and from the viewpoints of compatibility with surfactants and solubility in water, it is preferably 8 or more, more preferably 10 or more, even more preferably 12 or more, even more preferably 16 or more, and is preferably 20 or less, and more preferably 18 or less.
  • R 1c is preferably a linear or branched alkyl group or a linear or branched alkenyl group, and more preferably a linear or branched alkenyl group.
  • n is the average number of moles of EO added and may be a number between 1 and 50, and from the viewpoint of one-component stability, it is preferably 2 or more, more preferably 10 or more, even more preferably 15 or more, even more preferably 20 or more, and preferably 40 or less, more preferably 35 or less, even more preferably 30 or less, and even more preferably 25 or less. Since excessive air entrainment into the hydraulic composition causes a decrease in the strength of the hardened hydraulic composition, it is preferable that the air entrainment of the component (C) of the present invention into the hydraulic composition is small.
  • m is the average number of moles of PO added and may be a number between 0 and 10, and from the viewpoints of compatibility with the surfactant and solubility in water, it is preferably 5 or less, more preferably 3 or less, and even more preferably 1 or less.
  • EO and PO may be bonded in blocks or randomly, and from the viewpoint of manufacturability, block addition is preferred. From the viewpoints of compatibility with the surfactant of the present invention and air entrainment in the hydraulic composition, m is preferably 0.
  • M can be an inorganic ion selected from sodium ion, ammonium ion, potassium ion, calcium ion, magnesium ion, etc., or an organic ammonium ion selected from monoethanolammonium ion, diethanolammonium ion, triethanolammonium ion, morpholinium ion, etc., with the sodium ion being preferred from the viewpoint of availability.
  • the component (c-1) of the present invention may be, for example, sodium polyoxyethylene alkyl ether sulfate (average carbon number: 18, average number of polyoxyethylene added moles: 23), etc.
  • the component (C) of the present invention may be a combination of the component (c-1) and a component other than the component (c-1) [hereinafter referred to as component (c-2)].
  • component (c-2) include phenyl glycol, phenyl diglycol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether; octyl dimethylamine, decyl dimethylamine, etc.
  • the component (C) of the present invention is preferably one or more selected from (c-1) polyoxyethylene alkyl ether sulfate or a salt thereof, and (c-2) phenyl glycol, and more preferably (c-1) polyoxyethylene alkyl ether sulfate or a salt thereof, and (c-2) phenyl glycol, and more preferably (c-1) polyoxyethylene alkyl ether sulfate or a salt thereof having an average carbon number of 18 and an average number of moles of ethylene oxide added of 23, and (c-2) phenyl glycol.
  • the mass ratio (c-2)/(c-1) of the content of the (c-1) component to the content of the (c-2) component in the total content of the (c-1) component and the (c-2) component is preferably 0.050 or more, more preferably 0.10 or more, from the viewpoint of product stability, and is preferably 1.0 or less, more preferably 0.50 or less, and specifically 0.125 is particularly preferred, from the viewpoint of cost reduction.
  • the product stabilizer preferably has an alkali metal salt such as sodium as a counter cation.
  • the content of component (C) in the aesthetic enhancer of the present invention is preferably 1.0 mass% or more, more preferably 5.0 mass% or more, from the viewpoint of product stability, and is preferably 15 mass% or less, more preferably 10 mass% or less, from the viewpoint of cost reduction.
  • the aesthetic enhancer of the present invention may further contain (D) an antifoaming agent (hereinafter also referred to as component (D)).
  • D an antifoaming agent
  • the (D) component of the present invention includes an antifoaming agent having an HLB of less than 3.
  • the (D) component of the present invention includes polyalkylene glycol alkyl ether-based antifoaming agents (excluding the (A) component of the present invention), polyalkylene glycol alkyl ester-based antifoaming agents, polyol polyether-based antifoaming agents, polyalkylene glycol block polymer-based antifoaming agents, silicone-based antifoaming agents, and among these, antifoaming agents having an HLB of less than 3.
  • the (D) component of the present invention is preferably one or more selected from polyalkylene glycol alkyl ether-based antifoaming agents having an HLB of less than 3 (excluding the (A) component of the present invention), polyalkylene glycol alkyl ester-based antifoaming agents having an HLB of less than 3, and silicone-based antifoaming agents having an HLB of less than 3, from the viewpoint of adjusting the amount of air in the hydraulic composition and the viewpoint of the storage stability of the surface aesthetic improving agent, and more preferably a polyalkylene glycol alkyl ether-based antifoaming agent having an HLB of less than 3.
  • the HLB value of the antifoaming agent is calculated using the Griffin method.
  • the content of the component (D) of the present invention in the aesthetic enhancer of the present invention is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, from the viewpoint of adjusting the amount of air in the hydraulic composition, and is preferably 0.5 mass% or less, more preferably 0.1 mass% or less, from the viewpoint of the storage stability of the surface aesthetic enhancer.
  • the aesthetic enhancer of the present invention may contain, as a more specific embodiment, the components (A), (B), (C) and (D).
  • the content of component (A) in the total content of components (A), (B), (C) and (D) as the aesthetic enhancer of the present invention is preferably 1.0% by mass or more, more preferably 3.0% by mass or more, from the viewpoint of the effect of reducing the amount of air bubble traces on the surface of the hardened body of the hydraulic composition, and is preferably 15% by mass or less, more preferably 10% by mass or less, from the viewpoint of the storage stability of the surface aesthetic enhancer.
  • the content of component (B) in the total content of components (A), (B), (C), and (D) is preferably 60% by mass or more, more preferably 70% by mass or more, and is preferably 90% by mass or less, more preferably 85% by mass or less, from the viewpoint of the fluidity retention of the hydraulic composition.
  • the content of component (C) in the total content of components (A), (B), (C), and (D) of the aesthetic enhancer of the present invention is preferably 1% by mass or more, more preferably 5% by mass or more, from the viewpoint of product stability, and is preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoint of cost reduction.
  • the content of component (D) in the total content of components (A), (B), (C) and (D) as the aesthetic enhancer of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of adjusting the amount of air in the hydraulic composition, and is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, from the viewpoint of the storage stability of the surface aesthetic enhancer.
  • the mass ratio (A)/(B) of the components (A) and (B) of the aesthetic enhancer of the present invention is preferably 0.01 or more, more preferably 0.05 or more, from the viewpoint of the effect of reducing the amount of air bubble traces on the surface of the cured body of the hardening composition, and is preferably 1.0 or less, more preferably 0.5 or less, from the viewpoint of cost reduction.
  • the mass ratio (A)/(D) of the (A) component to the (D) component of the aesthetic enhancer of the present invention is preferably 10 or more, more preferably 15 or more, from the viewpoint of product stability, and is preferably 100 or less, more preferably 50 or less, from the viewpoint of adjusting the amount of air in the hydraulic composition.
  • the aesthetic enhancer of the present invention can be blended into the mixing water used when preparing the hydraulic composition.
  • the aesthetic enhancer of the present invention can be added so that the content of component (C) in the kneading water is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 0.5% by mass or less, and more preferably 0.1% by mass or less, within the above range.
  • the content of component (D) in the mixing water is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, and preferably 0.01% by mass or less, more preferably 0.005% by mass or less, and the aesthetic enhancer of the present invention can be added so that the content falls within the above range.
  • the aesthetic enhancer of the present invention may further contain at least one type of (poly)glycoside having an alkyl group having 8 to 20 carbon atoms or an alkenyl group having 8 to 20 carbon atoms and a sugar condensation degree of 1 to 5 (hereinafter also referred to as the (poly)glycoside of the present invention).
  • the mass ratio of the content of the (poly)glycoside to the content of the surfactant of the present invention having the dynamic surface tension described above, i.e., (poly)glycoside/(A) component (mass ratio) is preferably 0 or more, and preferably 0.05 or less, more preferably 0.01 or less.
  • the aesthetic enhancer of the present invention is preferably 0 in terms of the strength expression of the hydraulic composition hardened body.
  • the (poly)glycoside used in the present invention is at least one type of (poly)glycoside having an alkyl group having 8 to 20 carbon atoms or an alkenyl group having 8 to 20 carbon atoms and a sugar condensation degree of 1 to 5.
  • the (poly)glycoside used in the present invention preferably has an alkyl or alkenyl group with 8 or more carbon atoms, and preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and even more preferably 12 or less.
  • the (poly)glycoside of the present invention preferably has an alkyl group with 8 to 20 carbon atoms.
  • the sugar condensation degree of the (poly)glycoside used in the present invention is preferably 1 or more from the viewpoint of water solubility, and more preferably 5 or less, even more preferably 4 or less, even more preferably 3 or less, and even more preferably 2 or less.
  • the sugars constituting the (poly)glycosides used in the present invention include, specifically, glucose, maltose, and sucrose.
  • the (poly)glycosides used in the present invention are preferably at least one type of (poly)glucoside having an alkyl group with 8 to 20 carbon atoms or an alkenyl group with 8 to 20 carbon atoms and a sugar condensation degree of 1 to 5, and more preferably at least one type of (poly)glucoside having an alkyl group with 8 to 20 carbon atoms and a sugar condensation degree of 1 to 5.
  • a hydraulic composition containing a surface aesthetic improver for hydraulic compositions, hydraulic powder, and water, in which the dynamic surface tension ( ⁇ 1) at a bubble film life of 10 ms is 55 mN/m or more and the dynamic surface tension ( ⁇ 2) at a bubble film life of 1000 ms is 35 mN/m or less when measured by a bubble pressure method (20°C).
  • a hydraulic composition containing a surfactant, hydraulic powder, and water in which when a measurement aqueous solution obtained by adding a surfactant at a concentration of 0.05% by mass to the bleeding water of the hydraulic composition is measured by a bubble pressure method (20°C), the dynamic surface tension ( ⁇ 1) at a bubble film life of 10 ms is 55 mN/m or more and the dynamic surface tension ( ⁇ 2) at a bubble film life of 1000 ms is 35 mN/m or less.
  • the specific examples and preferred aspects of the surfactant for the hydraulic composition of the present invention can be the same as the surfactant for the surface aesthetic improver for hydraulic composition of the present invention described above [hereinafter also referred to as the "surfactant of the present invention” and also referred to as component (A)].
  • the hydraulic composition of the present invention includes the above two hydraulic compositions.
  • the hydraulic powder used in the present invention includes cement.
  • cement used in the present invention include ordinary Portland cement, early strength Portland cement, ultra-early strength Portland cement, sulfate-resistant Portland cement, low-heat Portland cement, white Portland cement, and ecocement (e.g., JIS R5214, etc.).
  • the preferred cements for use in the present invention are ordinary Portland cement, sulfate-resistant Portland cement, and white Portland cement, with ordinary Portland cement being more preferred.
  • the cement used in the present invention may include blast furnace slag, fly ash, silica fume, etc., and may also include non-hydraulic limestone fine powder, etc.
  • the hydraulic powder used in the present invention may be silica fume cement or blast furnace cement mixed with cement.
  • the aesthetic enhancer of the present invention is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, even more preferably 0.010 parts by mass or more, even more preferably 0.03 parts by mass or more, and is preferably 10 parts by mass or less, more preferably 3.0 parts by mass or less, even more preferably 2.5 parts by mass or less, even more preferably 2.0 parts by mass or less, and even more preferably 1.0 parts by mass or less, relative to 100 parts by mass of hydraulic powder, from the viewpoint of the effect of reducing the amount of air bubble traces on the surface of the hardened body of the hydraulic composition.
  • the content of the surfactant of the present invention in the hydraulic composition of the present invention is, from the viewpoint of the effect of reducing the amount of air bubble traces on the surface of the hardened body of the hydraulic composition, preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, even more preferably 0.010 parts by mass or more, even more preferably 0.03 parts by mass or more, and preferably 10 parts by mass or less, more preferably 3.0 parts by mass or less, even more preferably 2.5 parts by mass or less, even more preferably 2.0 parts by mass or less, and even more preferably 1.0 parts by mass or less, relative to 100 parts by mass of the hydraulic powder.
  • the hydraulic composition of the present invention may contain a (B) cement dispersant (hereinafter also referred to as component (B)) in addition to the aesthetic enhancer of the present invention or the surfactant of the present invention.
  • component (B) cement dispersant
  • specific examples and preferred aspects of the cement dispersant of the hydraulic composition of the present invention may be the same as the (B) cement dispersant contained in the aesthetic enhancer of the present invention described above.
  • the content of component (B) is preferably 0.10 parts by mass or more, and more preferably 0.20 parts by mass or more, relative to 100 parts by mass of hydraulic powder from the viewpoint of improving the fluidity of the hydraulic composition, and is preferably 1.0 part by mass or less, and more preferably 0.50 part by mass or less, from the viewpoint of durability of the hardened body of the hydraulic composition.
  • the total content of component (B) in the hydraulic composition of the present invention is preferably 0.10 parts by mass or more, more preferably 0.20 parts by mass or more, relative to 100 parts by mass of hydraulic powder, from the viewpoint of improving the fluidity of the hydraulic composition, and is preferably 1.0 part by mass or less, more preferably 0.50 part by mass or less, from the viewpoint of durability of the hardened body of the hydraulic composition.
  • the hydraulic composition of the present invention may further contain (C) a product stabilizer [hereinafter also referred to as component (C)] in addition to the aesthetic enhancer of the present invention or the surfactant of the present invention.
  • component (C) a product stabilizer [hereinafter also referred to as component (C)] in addition to the aesthetic enhancer of the present invention or the surfactant of the present invention.
  • component (C) a product stabilizer [hereinafter also referred to as component (C)] in addition to the aesthetic enhancer of the present invention or the surfactant of the present invention.
  • the content of component (C) is preferably 0.01 part by mass or more, and more preferably 0.02 part by mass or more, per 100 parts by mass of hydraulic powder from the viewpoint of product stability, and is preferably 1.0 part by mass or less, and more preferably 0.1 part by mass or less, from the viewpoint of cost reduction.
  • the content of the component (c-1) is preferably 0.01 part by mass or more, and more preferably 0.02 part by mass or more, relative to 100 parts by mass of the hydraulic powder from the viewpoint of product stability, and is preferably 1.0 part by mass or less, and more preferably 0.1 part by mass or less, from the viewpoint of cost reduction.
  • the hydraulic composition of the present invention may further contain (D) an antifoaming agent (hereinafter also referred to as component (D)) in addition to the aesthetic enhancer of the present invention or the surfactant of the present invention.
  • component (D) an antifoaming agent
  • specific examples and preferred aspects of the antifoaming agent of the hydraulic composition of the present invention may be the same as the (D) antifoaming agent contained in the aesthetic enhancer of the present invention described above.
  • the content of the (D) component is preferably 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, and is preferably 1.0 part by mass or less, more preferably 0.5 part by mass or less, per 100 parts by mass of the hydraulic powder, from the viewpoint of durability of the hardened body of the hydraulic composition.
  • the total content of component (D) in the hydraulic composition of the present invention is preferably 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, and is preferably 1.0 part by mass or less, more preferably 0.5 part by mass or less, per 100 parts by mass of hydraulic powder, from the viewpoint of durability of the hardened body of the hydraulic composition.
  • the hydraulic composition of the present invention may further contain an air entraining agent in addition to the aesthetic enhancer of the present invention or the surfactant of the present invention.
  • the hydraulic composition of the present invention contains an air entraining agent
  • the hydraulic composition of the present invention when the hydraulic composition of the present invention contains an air entraining agent, specific examples include rosin acid, alkyl sulfate or a salt thereof, polyoxyethylene alkyl ether sulfate or a salt thereof (excluding component (c-1) of the present invention), polyoxyethylene alkyl ether phosphate or a salt thereof, etc.
  • the air entraining agent used in the hydraulic composition of the present invention is preferably polyoxyethylene alkyl ether sulfate or a salt thereof (excluding component (c-1) of the present invention) from the viewpoint of improving the durability of the hardened body of the hydraulic composition.
  • the content of the air entraining agent is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 1.0 part by mass or less, more preferably 0.5 part by mass or less, per 100 parts by mass of hydraulic powder, from the viewpoint of durability of the hardened body of the hydraulic composition.
  • the hydraulic composition of the present invention may contain, as a specific embodiment, the (A) component, the (B) component, the (C) component, the (D) component, hydraulic powder, and water.
  • the hydraulic composition of the present invention may contain the (A) component, the (B) component, the (D) component, hydraulic powder, and water.
  • the mass ratio (A)/(B) of the (A) component to the (B) component of the hydraulic composition of the present invention is preferably 0.01 or more, more preferably 0.05 or more, from the viewpoint of the effect of reducing the amount of air bubble traces on the surface of the hardened hydraulic composition, and is preferably 1.0 or less, more preferably 0.5 or less, from the viewpoint of cost reduction.
  • the mass ratio (A)/(D) of the (A) component to the (D) component of the hydraulic composition of the present invention is preferably 10 or more, more preferably 15 or more, from the viewpoint of product stability, and is preferably 100 or less, more preferably 50 or less, from the viewpoint of adjusting the amount of air in the hydraulic composition.
  • the water/hydraulic powder ratio [water and hydraulic powder in the hydraulic composition (mass of water/mass of hydraulic powder x 100), usually abbreviated as W/P, and when the hydraulic powder is cement, abbreviated as W/C] of the hydraulic composition of the present invention is preferably 20% or more, more preferably 30% or more, and is preferably 95% or less, more preferably 80% or less.
  • the amount of air contained in the hydraulic composition of the present invention is not particularly limited, but from the viewpoint of durability of the set body of the hydraulic composition, it is preferably 0% or more and more preferably 3.0% or less.
  • the amount of the defoamer added as component (D) of the present invention can be adjusted so that the amount of air in the hydraulic composition of the present invention is within the above range.
  • the hydraulic composition of the present invention may further contain aggregate.
  • aggregate examples include fine aggregate and coarse aggregate, and the fine aggregate is preferably mountain sand, land sand, river sand, or crushed sand, and the coarse aggregate is preferably mountain gravel, land gravel, river gravel, or crushed stone.
  • lightweight aggregate may be used.
  • aggregate is taken from "Concrete Overview" (published by Gijutsu Shoin on June 10, 1998).
  • the aggregate can be used in the usual range used in the preparation of concrete, mortar, etc.
  • the amount of coarse aggregate used is preferably 50% or more by bulk volume, more preferably 55% or more, even more preferably 60% or more, and preferably 100% or less, more preferably 90% or less, and even more preferably 80% or less, from the viewpoint of the properties of the concrete.
  • the bulk volume is the ratio of the volume (including voids) of the coarse aggregate in 1 m3 of concrete.
  • the amount of fine aggregate used is preferably 500 kg/m3 or more, more preferably 600 kg/ m3 or more, even more preferably 700 kg/ m3 or more, and preferably 1000 kg/m3 or less, and preferably 900 kg/ m3 or less , from the viewpoint of improving the filling property into a formwork, etc.
  • the amount of fine aggregate used is preferably 800 kg/ m3 or more, more preferably 900 kg/ m3 or more, even more preferably 1000 kg/ m3 or more, and is preferably 2000 kg/ m3 or less, more preferably 1800 kg/ m3 or less, even more preferably 1700 kg/ m3 or less.
  • the hydraulic composition of the present invention may contain other components in addition to the above components.
  • examples include retarders, thickeners, waterproofing agents, fluidizing agents, and early strengthening agents.
  • the early-strengthening agent contained in the hydraulic composition of the present invention includes a compound selected from the group consisting of hydrochlorides, sulfates, nitrates, nitrites, cyanates, thiocyanates, thiosulfates, and formates of alkali metals and alkaline earth metals, or an organic compound selected from the group consisting of alkanolamines, glycerin derivatives, formaldehyde derivatives, and catechol derivatives, and nanoparticles of hydration products of Portland cement (C-S-H, and calcium hydroxide).
  • a compound selected from the group consisting of hydrochlorides, sulfates, nitrates, nitrites, cyanates, thiocyanates, thiosulfates, and formates of alkali metals and alkaline earth metals or an organic compound selected from the group consisting of alkanolamines, glycerin derivatives, formaldehyde
  • the hydraulic composition of the present invention can be used for concrete or mortar.
  • the hydraulic composition of the present invention is useful in any field, such as for self-leveling, refractories, plaster, light or heavy concrete, air entrainment, repair, prepacked, trame, ground improvement, grout, and cold weather use.
  • a method for producing a hydraulic composition which is prepared by mixing a surface aesthetic improver for a hydraulic composition (hereinafter also referred to as the "aesthetic improver of the present invention") having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms, as measured by a bubble pressure method (20°C), with hydraulic powder and water.
  • a surface aesthetic improver for a hydraulic composition hereinafter also referred to as the "aesthetic improver of the present invention” having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms, as measured by a bubble pressure method (20°C), with hydraulic powder and water.
  • the present invention provides a method for producing a hydraulic composition by mixing a surfactant for surface aesthetics improver for hydraulic compositions of the present invention (hereinafter also referred to as "surfactant of the present invention” and also referred to as component (A)), hydraulic powder, and water, and the surfactant has a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms when a measurement aqueous solution obtained by adding a surfactant at a concentration of 0.05 mass% to the bleeding water of the hydraulic composition is measured by a bubble pressure method (20°C).
  • surfactant of the present invention also referred to as “surfactant of the present invention” and also referred to as component (A)
  • the surfactant has a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇
  • specific examples and preferred aspects of the aesthetic enhancer of the present invention used in the method for producing a hydraulic composition of the present invention can be the same as those of the surface aesthetic enhancer for a hydraulic composition of the present invention.
  • specific examples and preferred aspects of the surfactant and optional components of the present invention used in the method for producing a hydraulic composition of the present invention can be the same as those of the surfactant and optional components described in the surface aesthetic enhancer for a hydraulic composition of the present invention.
  • specific examples and preferred aspects of the hydraulic powder used in the method for producing a hydraulic composition of the present invention can be the same as those of the hydraulic composition of the present invention.
  • the matters described in the surface aesthetic enhancer for a hydraulic composition of the present invention and the hydraulic composition of the present invention can be appropriately applied to the method for producing a hydraulic composition of the present invention.
  • the method for producing the hydraulic composition of the present invention can be to prepare the hydraulic composition by mixing the surfactant of the present invention, hydraulic powder, and water. Also, in an exemplary embodiment of the present invention, the method for producing the hydraulic composition of the present invention can be to prepare the hydraulic composition by mixing the surfactant of the present invention, optional components, hydraulic powder, and water.
  • the hydraulic composition of the present invention can be prepared by mixing the surfactant of the present invention and the optional components described above separately with a hydraulic powder.
  • the surfactant of the present invention and the optional components are mixed in advance, there is no need to install a new tank, and the integrated product can be mixed with the hydraulic powder.
  • the hydraulic composition of the present invention can be produced by mixing the aesthetic enhancer of the present invention with the hydraulic powder.
  • the mixed amounts of each component, hydraulic powder, and water used in the method for producing the hydraulic composition of the present invention can be applied by replacing the contents of each component, hydraulic powder, and water described in the hydraulic composition of the present invention with the mixed amounts.
  • the method for producing the hydraulic composition of the present invention in order to smoothly mix the surfactant and optional components of the present invention with hydraulic powder such as cement, can be such that the surfactant of the present invention, optional components, and water are mixed in advance, and then mixed with the hydraulic powder.
  • the method for producing the hydraulic composition of the present invention in order to smoothly mix the surfactant and optional components of the present invention with hydraulic powder such as cement, can be such that the aesthetic enhancer of the present invention containing water, (optional components used in the hydraulic composition as necessary), and water are mixed in advance, and then mixed with the hydraulic powder.
  • the method for producing the hydraulic composition of the present invention can include adding the aesthetic enhancer of the present invention to a hydraulic powder such as cement and mixing it.
  • the aesthetic enhancer of the present invention is preferably added to the hydraulic powder so that the surfactant and optional components of the present invention are added in the above-mentioned amounts (contents).
  • the amount of the aesthetic enhancer of the present invention added, as parts by mass of solid content, relative to 100 parts by mass of hydraulic powder is preferably 0.001 parts by mass or more from the viewpoint of improving the aesthetic appearance of the surface, more preferably 0.005 parts by mass or more, even more preferably 0.01 parts by mass or more, even more preferably 0.03 parts by mass or more, and from the viewpoint of improving the aesthetic appearance of the surface by ensuring high fluidity, is preferably 10 parts by mass or less, more preferably 3.0 parts by mass or less, even more preferably 2.5 parts by mass or less, even more preferably 2.0 parts by mass or less, even more preferably 1.0 parts by mass or less.
  • the hydraulic composition of the present invention can be produced by mixing using a mixer such as a mortar mixer or a forced twin-shaft mixer.
  • the mixing time is preferably 1 minute or more, more preferably 2 minutes or more, and preferably 5 minutes or less, more preferably 3 minutes or less.
  • the materials and chemicals described in the hydraulic composition and their amounts can be used.
  • a surface aesthetic improver for hydraulic compositions (hereinafter also referred to as “aesthetic improver of the present invention”) having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms, as measured by a bubble pressure method (20°C), a method for producing a hardened body of a hydraulic composition (hereinafter also referred to as "method for producing a hardened body of the present invention”), the method comprising the steps of mixing a hydraulic powder with water to prepare a hydraulic composition, filling the prepared hydraulic composition into a formwork and hardening it, and demolding the hardened hydraulic composition.
  • a method for producing a hardened product of a hydraulic composition comprising the steps of mixing a surface aesthetic improver for hydraulic compositions, hydraulic powder, and water to prepare a hydraulic composition, filling a formwork with the prepared hydraulic composition and hardening it, and demolding the hardened hydraulic composition, wherein the surface aesthetic improver for hydraulic compositions (hereinafter also referred to as the "aesthetic improver of the present invention”) is a surfactant (hereinafter also referred to as the "surfactant of the present invention” or component (A)) having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms when a measurement aqueous solution obtained by adding a surfactant at a concentration of 0.05 mass% to the bleeding water of the hydraulic composition is measured by a bubble pressure method
  • the specific examples and preferred aspects of the surfactant and optional components of the present invention used in the manufacturing method of the hardened body of the hydraulic composition of the present invention can be the same as those of the surface aesthetic improver for hydraulic composition of the present invention.
  • the specific examples and preferred aspects of the aesthetic improver of the present invention used in the manufacturing method of the hydraulic composition of the present invention can be the same as those of the surface aesthetic improver for hydraulic composition of the present invention.
  • the specific examples and preferred aspects of the hydraulic powder used in the manufacturing method of the hardened body of the hydraulic composition of the present invention can be the same as those of the hydraulic composition of the present invention.
  • the matters described in the surface aesthetic improver for hydraulic composition of the present invention and the hydraulic composition used in the manufacturing method of the hardened body of the hydraulic composition of the present invention can be appropriately applied to the manufacturing method of the hardened body of the hydraulic composition of the present invention.
  • the process for preparing the hydraulic composition included in the method for producing a hardened product of the hydraulic composition of the present invention can be the same as the method for producing the hydraulic composition of the present invention.
  • the hydraulic composition obtained by the preparation of the hydraulic composition included in the method for producing a hardened body of the hydraulic composition of the present invention is further filled into a formwork, cured, and hardened.
  • the formwork used in the process of filling and hardening the hydraulic composition in the formwork which is included in the method of producing a hardened product of the hydraulic composition of the present invention, includes a formwork for a building, a formwork for a concrete product, etc.
  • Methods of filling the formwork include a method of directly pouring the hydraulic composition from a mixer, and a method of pumping the hydraulic composition into the formwork.
  • the form used in the process of filling and hardening the hydraulic composition in a form, which is included in the method of producing a hardened hydraulic composition of the present invention is preferably coated with a release agent from the viewpoint of the releasability of the hardened hydraulic composition when demolded.
  • the release agent may be (1) mineral oil such as kerosene, diesel, spin oil, transformer oil, machine oil, etc.; (2) synthetic oil such as polyalkylene glycol; (3) vegetable oil such as rapeseed, coconut, palm, soybean oil, etc.; (4) fats and oils; (5) fatty acid esters, etc.; and may be either an "oil-based release agent” that is applied as is or an "aqueous-based release agent” that is emulsified in water.
  • the process for filling a form with the hydraulic composition and hardening it which is included in the method for producing a hardened product of the hydraulic composition of the present invention, can include heat curing to promote hardening during curing of the hydraulic composition.
  • heat curing can promote hardening by maintaining the hydraulic composition at a temperature of 40°C or higher and 80°C or lower.
  • the hardened hydraulic composition can be demolded to obtain a hardened hydraulic composition.
  • the hardened hydraulic composition has sufficient compressive strength.
  • the compressive strength at the time of demolding is preferably equal to or greater than the strength described in, for example, "2023 Japan Society of Civil Engineers Standard Specifications [Construction Section] Commentary Table 8.8.1.”
  • examples of hardened hydraulic compositions using a form for a concrete product obtained by the method for producing a hardened hydraulic composition of the present invention include civil engineering products such as concrete piles, concrete poles, various block products for revetments, box culvert products, segment products used in tunnel construction, and girder products for bridge piers, and examples of architectural products include curtain wall products, and architectural component products used for columns, beams, and floor panels.
  • the time from contacting the hydraulic powder with water to demolding is preferably 16 hours or more and 72 hours or less from the viewpoint of obtaining the strength required for demolding and improving the production cycle.
  • a method for improving the surface appearance of a hardened body of a hydraulic composition which comprises adding a surfactant (hereinafter also referred to as the "surfactant of the present invention") having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms, as measured by a bubble pressure method (20°C), to a hydraulic composition containing hydraulic powder and water.
  • the present invention provides a method for improving the aesthetic appearance of a hardened body of a hydraulic composition, which includes adding a surfactant of the present invention to a hydraulic composition containing hydraulic powder and water, and the surfactant has a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms when the measurement aqueous solution obtained by adding a surfactant at a concentration of 0.05% by mass to the bleeding water of the hydraulic composition is measured by a bubble pressure method (20°C) (hereinafter, also referred to as the "surfactant of the present invention").
  • the present invention provides a method for improving the surface aesthetics of a hardened body of a hydraulic composition, which comprises adding a surface aesthetics improver for hydraulic compositions of the present invention (hereinafter also referred to as the "aesthetics improver of the present invention") to a hydraulic composition containing hydraulic powder and water, the aesthetics improver having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms (hereinafter also referred to as the "aesthetics improver of the present invention”).
  • ⁇ 1 surface aesthetics improver for hydraulic compositions of the present invention
  • ⁇ 2 dynamic surface tension
  • specific examples and preferred aspects of the surfactant and optional components of the present invention used in the aesthetic improvement method of the present invention can be the same as those described in the surfactant for the surface aesthetic improver for hydraulic composition of the present invention.
  • specific examples and preferred aspects of the aesthetic improver and optional components of the present invention used in the aesthetic improvement method of the present invention can be the same as those described in the surface aesthetic improver for hydraulic composition of the present invention.
  • specific examples and preferred aspects of the hydraulic powder used in the aesthetic improvement method of the present invention can be the same as those described in the hydraulic composition of the present invention.
  • the matters described in the aesthetic improver, hydraulic composition, and method for producing the hardened product thereof of the present invention can be appropriately applied to the aesthetic improvement method of the present invention.
  • the present invention provides a surface aesthetic improvement kit for a hardened body of a hydraulic composition, which is a combination of a first agent containing the surfactant of the present invention and a second agent containing the cement dispersant described above.
  • the present invention provides a surface aesthetic improvement kit for a hardened body of a hydraulic composition, which is a combination of a first agent containing a surfactant (hereinafter also referred to as “surfactant of the present invention”) having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms when the surfactant is added at a concentration of 0.05 mass% to the bleeding water of the hydraulic composition and the aqueous solution for measurement is measured by a bubble pressure method (20°C), and a second agent containing the cement dispersant (hereinafter also referred to as "cement dispersant of the present invention”).
  • a surfactant of the present invention having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a
  • the present invention provides a surface aesthetic improvement kit for a hardened body of a hydraulic composition, which is a combination of an aqueous solution ⁇ containing the surfactant of the present invention and an aqueous solution ⁇ containing the cement dispersant described above.
  • the present invention provides a surface aesthetic improvement kit for a hardened body of a hydraulic composition, which is a combination of an aqueous solution ⁇ containing a surfactant (hereinafter also referred to as the "surfactant of the present invention") having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms when the measurement aqueous solution obtained by adding a surfactant at a concentration of 0.05 mass% to the bleeding water of the hydraulic composition is measured by a bubble pressure method (20°C), and an aqueous solution ⁇ containing the cement dispersant (hereinafter also referred to as the "cement dispersant of the present invention”).
  • a surfactant of the present invention having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35
  • the aesthetic improvement kit of the present invention includes the above two aesthetic improvement kits.
  • the aesthetic improvement kit of the present invention is specifically composed of an aqueous solution ⁇ containing the surfactant of the present invention and an aqueous solution ⁇ containing the cement dispersant of the present invention described above, in a separated state.
  • the aesthetic improvement kit of the present invention can be appropriately applied to the first agent containing the surfactant of the present invention, preferably the aqueous solution ⁇ , and the second agent containing the above-mentioned cement dispersant of the present invention, preferably the aqueous solution ⁇ , as described above, with respect to the surfactant for surface aesthetic improvement agent for hydraulic composition of the present invention, the surface aesthetic improvement agent for hydraulic composition, the hydraulic composition, the method for manufacturing a hydraulic composition, the method for manufacturing a hardened body of a hydraulic composition, and the method for improving the surface aesthetic of a hardened body of a hydraulic composition.
  • the aesthetic improvement kit of the present invention can be stored in containers that allow the components to be stored separately and mixed at the time of use.
  • a kit is preferred in which a first agent containing a surfactant of the present invention, preferably the aqueous solution ⁇ , and a second agent containing a cement dispersant of the present invention, preferably the aqueous solution ⁇ , are filled in separate containers that hold them.
  • the amount of the surfactant of the present invention in the first agent, preferably in the aqueous solution ⁇ is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass or more, and is preferably 100% by mass or less, more preferably 50% by mass or less, and even more preferably 20% by mass or less.
  • the cement dispersant of the present invention is preferably a copolymer containing, as constituent monomers, a monomer (1b) represented by the general formula (1b) and a monomer (2b) represented by the general formula (2b), and the amount of the cement dispersant of the present invention is such that the content of the copolymer in the second agent, preferably the aqueous solution ⁇ , is preferably 10% by mass or more, more preferably 20% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less.
  • the aesthetic improvement kit of the present invention preferably contains an optional product stabilizer in at least one of the first agent containing the surfactant of the present invention, preferably the aqueous solution ⁇ , and the second agent containing the cement dispersant of the present invention, preferably the aqueous solution ⁇ .
  • the aesthetic improvement kit of the present invention preferably contains an optional defoaming agent or air entraining agent in at least one of the first agent containing the surfactant of the present invention, preferably the aqueous solution ⁇ , and the second agent containing the cement dispersant of the present invention, preferably the aqueous solution ⁇ .
  • the aesthetic improvement kit of the present invention preferably contains an optional defoaming agent in at least one of the first agent containing the surfactant of the present invention, preferably the aqueous solution ⁇ , and the second agent containing the cement dispersant of the present invention, preferably the aqueous solution ⁇ , from the viewpoint of the air entrainment of the hydraulic composition, and preferably contains an optional air entraining agent in at least one of the first agent containing the surfactant of the present invention, preferably the aqueous solution ⁇ , and the second agent containing the cement dispersant of the present invention, preferably the aqueous solution ⁇ , from the viewpoint of the air entrainment of the hydraulic composition.
  • the aesthetic improvement kit of the present invention comprises a first agent containing the surfactant of the present invention, preferably the aqueous solution ⁇ , and a second agent containing the cement dispersant of the present invention, preferably the aqueous solution ⁇ , in which the mass ratio of the surfactant of the present invention and the cement dispersant of the present invention, preferably the copolymer which is the cement dispersant of the present invention, "surfactant/cement dispersant" is preferably 10/90 or more and preferably 90/10 or less, from the viewpoint of the effect of reducing the amount of air bubble marks on the surface of the hardened hydraulic composition, and is mixed within the above range.
  • a first agent containing the surfactant of the present invention and a second agent containing the cement dispersant of the present invention are used by mixing with water, and the total content of the surfactant of the present invention and the cement dispersant of the present invention, preferably the above-mentioned copolymer which is the cement dispersant of the present invention, is preferably 0.1 parts by mass or more, more preferably 0.15 parts by mass or more, and is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, per 100 parts by mass of water, from the viewpoint of the effect of reducing the amount of air bubble traces on the surface of the hardened body of the hydraulic composition.
  • the present invention also includes the following aspects:
  • a surface aesthetic improver for hydraulic compositions comprising a surfactant having a dynamic surface tension ( ⁇ 3) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 4) of 28 mN/m or less at a bubble film life of 1000 ms when a 0.3 mass% aqueous surfactant solution is measured by a bubble pressure method (20°C).
  • a surfactant for use as a surface aesthetic improver for hydraulic compositions which has a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms, as measured by a bubble pressure method (20°C).
  • a surfactant for improving the surface appearance of a hydraulic composition which, when a measuring aqueous solution obtained by adding a surfactant at a concentration of 0.05% by mass to bleeding water of the following hydraulic composition is measured by a bubble pressure method (20°C), has a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms.
  • ⁇ 1 dynamic surface tension
  • ⁇ 2 dynamic surface tension
  • a surfactant for surface aesthetics improver for hydraulic compositions having a concentration of 0.05% by mass relative to the bleeding water of the hydraulic composition, the bleeding aqueous solution being adjusted so that the following (B) is 0.82% by mass, the following (C) is 0.15% by mass, and the following (D) is 0.0033% by mass, when the surfactant is measured by a bubble pressure method (20°C), the dynamic surface tension ( ⁇ 1) at a foam film life of 10 ms is 55 mN/m or more, and the dynamic surface tension ( ⁇ 2) at a foam film life of 1000 ms is 35 mN/m or less.
  • a surface appearance improver for a hydraulic composition comprising the surfactant for a surface appearance improver for a hydraulic composition according to ⁇ 3>.
  • ⁇ 6> The surface appearance improver for hydraulic composition according to any one of ⁇ 1> to ⁇ 2> or ⁇ 4> to ⁇ 5>, wherein the surfactant for the surface appearance improver for hydraulic composition according to ⁇ 3> is a polyoxyethylene alkyl ether having an average carbon number of 9 or more and 12 or less, and an average added mole number of ethylene oxide of 1 or more and 6 or less.
  • a surface aesthetic improver for a hydraulic composition comprising the following (i) and (ii), the content of (ii) being 20 mass % or more and 50 mass % or less based on the surface aesthetic improver for a hydraulic composition: (i): A surface aesthetic improver for a hydraulic composition, which, when measured by a bubble pressure method (20°C), has a dynamic surface tension ( ⁇ 1) of 55 mN/m or more after a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less after a bubble film life of 1000 ms.
  • a cement dispersant which is a copolymer containing, as constituent monomers, a monomer (1b) represented by the following general formula (1b) and a monomer (2b) represented by the following general formula (2b):
  • R 1b hydrogen atom
  • R 2b methyl group
  • R 3b hydrogen atom
  • M 1 and M 2 may be the same or different and each represents a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), Indicates that.
  • R 4b is a hydrogen atom
  • R 5b is a methyl group
  • R 6b is a hydrogen atom
  • R 7b is an alkyl group having 1 carbon atom
  • AO is an alkyleneoxy group having 2 carbon atoms
  • n1 is the average number of moles of AO added and is a number of 20 to 60
  • q1 is 0, and p1 is 1.
  • a surface aesthetic improver for a hydraulic composition comprising the following (iii) and (ii), wherein the content of (ii) is 20 mass % or more and 50 mass % or less based on the surface aesthetic improver for a hydraulic composition.
  • a surfactant for surface aesthetic improvers for hydraulic compositions in which, when a measuring aqueous solution obtained by adding a surfactant at a concentration of 0.05% by mass to bleeding water of the following hydraulic composition is measured by a bubble pressure method (20°C), the dynamic surface tension ( ⁇ 1) at a bubble film life of 10 ms is 55 mN/m or more and the dynamic surface tension ( ⁇ 2) at a bubble film life of 1000 ms is 35 mN/m or less.
  • a cement dispersant which is a copolymer containing, as constituent monomers, a monomer (1b) represented by the following general formula (1b) and a monomer (2b) represented by the following general formula (2b):
  • R 1b is a hydrogen atom
  • R 2b is a methyl group
  • R 3b is a hydrogen atom
  • M 1 and M 2 may be the same or different and each represents a hydrogen atom, an alkali metal, or an alkaline earth metal (1/2 atom).
  • R 4b is a hydrogen atom
  • R 5b is a methyl group
  • R 6b is a hydrogen atom
  • R 7b is an alkyl group having 1 carbon atom
  • AO is an alkyleneoxy group having 2 carbon atoms
  • n1 is the average number of moles of AO added and is a number of 20 to 60
  • q is the average number of moles of AO added and is a number of 20 to 60
  • a surface aesthetic improver for a hydraulic composition comprising the following (iv) and (ii), wherein the content of (ii) is 20 mass % or more and 50 mass % or less based on the surface aesthetic improver for a hydraulic composition.
  • a surface appearance improver for a hydraulic composition which is at least one member selected from polyoxyethylene (2) decyl ether, polyoxyethylene (3) decyl ether, and polyoxyethylene (5) lauryl ether.
  • a cement dispersant which is a copolymer containing, as constituent monomers, a monomer (1b) represented by the following general formula (1b) and a monomer (2b) represented by the following general formula (2b): [In the formula, R 1b is a hydrogen atom, R 2b is a methyl group, R 3b is a hydrogen atom, M 1 and M 2 may be the same or different and are each a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), Indicates that.
  • R 4b is a hydrogen atom
  • R 5b is a methyl group
  • R 6b is a hydrogen atom
  • R 7b is an alkyl group having 1 carbon atom
  • AO is an alkyleneoxy group having 2 carbon atoms
  • n1 is the average number of moles of AO added and is a number of 20 to 60
  • q1 is 0, and p1 is 1.
  • a surface aesthetics improver for a hydraulic composition comprising the following (i), (ii), (v), and (vi), wherein the content of (ii) is 20% by mass or more and 50% by mass or less relative to the surface aesthetics improver for a hydraulic composition, the content of (v) is 5% by mass or more and 10% by mass or less relative to the surface aesthetics improver for a hydraulic composition, and the content of (vi) is 0.01% by mass or more and 0.1% by mass or less relative to the surface aesthetics improver for a hydraulic composition.
  • a surface aesthetic improver for a hydraulic composition which, when measured by a bubble pressure method (20°C), has a dynamic surface tension ( ⁇ 1) of 55 mN/m or more after a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less after a bubble film life of 1000 ms.
  • a cement dispersant which is a copolymer containing, as constituent monomers, a monomer (1b) represented by the following general formula (1b) and a monomer (2b) represented by the following general formula (2b):
  • R 1b is a hydrogen atom
  • R 2b is a methyl group
  • R 3b is a hydrogen atom
  • M 1 and M 2 may be the same or different and each represents a hydrogen atom, an alkali metal, or an alkaline earth metal (1/2 atom).
  • R 4b is a hydrogen atom
  • R 5b is a methyl group
  • R 6b is a hydrogen atom
  • R 7b is an alkyl group having 1 carbon atom
  • AO is an alkyleneoxy group having 2 carbon atoms
  • n1 is the average number of moles of AO added and is a number of 20 to 60
  • q1 is 0, and p1 is 1.
  • (v) A product stabilizer containing one or more compounds selected from the compounds
  • a surface aesthetic improver for a hydraulic composition comprising the following (iii), (ii), (v), and (vi), wherein the content of (ii) is 20% by mass or more and 50% by mass or less, based on the surface aesthetic improver for a hydraulic composition, the content of (v) is 5% by mass or more and 10% by mass or less, based on the surface aesthetic improver for a hydraulic composition, and the content of (vi) is 0.01% by mass or more and 0.1% by mass or less, based on the surface aesthetic improver for a hydraulic composition.
  • a surfactant for surface aesthetic improvers for hydraulic compositions in which, when a measuring aqueous solution obtained by adding a surfactant at a concentration of 0.05% by mass to bleeding water of the following hydraulic composition is measured by a bubble pressure method (20°C), the dynamic surface tension ( ⁇ 1) at a bubble film life of 10 ms is 55 mN/m or more and the dynamic surface tension ( ⁇ 2) at a bubble film life of 1000 ms is 35 mN/m or less.
  • a cement dispersant which is a copolymer containing, as constituent monomers, a monomer (1b) represented by the following general formula (1b) and a monomer (2b) represented by the following general formula (2b):
  • R 1b is a hydrogen atom
  • R 2b is a methyl group
  • R 3b is a hydrogen atom
  • M 1 and M 2 may be the same or different and each represents a hydrogen atom, an alkali metal, or an alkaline earth metal (1/2 atom).
  • R 4b is a hydrogen atom
  • R 5b is a methyl group
  • R 6b is a hydrogen atom
  • R 7b is an alkyl group having 1 carbon atom
  • AO is an alkyleneoxy group having 2 carbon atoms
  • n1 is the average number of moles of AO added and is a number of 20 to 60
  • q is the average number of moles of AO added and is a number of 20 to 60
  • a surface aesthetics improver for a hydraulic composition comprising the following (iv), (ii), (v), and (vi), wherein the content of (ii) is 20% by mass or more and 50% by mass or less, based on the surface aesthetics improver for a hydraulic composition, the content of (v) is 5% by mass or more and 10% by mass or less, based on the surface aesthetics improver for a hydraulic composition, and the content of (vi) is 0.01% by mass or more and 0.1% by mass or less, based on the surface aesthetics improver for a hydraulic composition.
  • a surface appearance improver for a hydraulic composition which is at least one member selected from polyoxyethylene (2) decyl ether, polyoxyethylene (3) decyl ether, and polyoxyethylene (5) lauryl ether.
  • a cement dispersant which is a copolymer containing, as constituent monomers, a monomer (1b) represented by the following general formula (1b) and a monomer (2b) represented by the following general formula (2b): [In the formula, R 1b is a hydrogen atom, R 2b is a methyl group, R 3b is a hydrogen atom, and M 1 and M 2 may be the same or different and each represents a hydrogen atom, an alkali metal, or an alkaline earth metal (1/2 atom).] [In the formula, R 4b is a hydrogen atom, R 5b is a methyl group, R 6b is a hydrogen atom, R 7b is an alkyl group having 1 carbon atom, AO is an alkyleneoxy group having 2 carbon
  • a hydraulic composition comprising the following (i), (ii), (v), and (vi), water, and a hydraulic powder, wherein the content of (i) is from 0.01 to 1 part by mass relative to 100 parts by mass of the hydraulic powder, the content of (ii) is from 0.2 to 0.5 parts by mass relative to 100 parts by mass of the hydraulic powder, the content of (v) is from 0.02 to 0.1 parts by mass relative to 100 parts by mass of the hydraulic powder, and the content of (vi) is from 0.0005 to 0.5 parts by mass relative to 100 parts by mass of the hydraulic powder.
  • a surface aesthetic improver for a hydraulic composition which, when measured by a bubble pressure method (20°C), has a dynamic surface tension ( ⁇ 1) of 55 mN/m or more after a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less after a bubble film life of 1000 ms.
  • a cement dispersant which is a copolymer containing, as constituent monomers, a monomer (1b) represented by the following general formula (1b) and a monomer (2b) represented by the following general formula (2b):
  • R 1b is a hydrogen atom
  • R 2b is a methyl group
  • R 3b is a hydrogen atom
  • M 1 and M 2 may be the same or different and each represents a hydrogen atom, an alkali metal, or an alkaline earth metal (1/2 atom).
  • R 4b is a hydrogen atom
  • R 5b is a methyl group
  • R 6b is a hydrogen atom
  • R 7b is an alkyl group having 1 carbon atom
  • AO is an alkyleneoxy group having 2 carbon atoms
  • n1 is the average number of moles of AO added and is a number of 20 to 60
  • q1 is 0, and p1 is 1.
  • (v) A product stabilizer containing one or more compounds selected from the compounds
  • the composition comprises the following (iii), (ii), (v), (vi), water, and hydraulic powder,
  • the content of (iii) is 0.01 parts by mass or more and 1 part by mass or less relative to 100 parts by mass of the hydraulic powder
  • the content of (ii) is 0.2 parts by mass or more and 0.5 parts by mass or less relative to 100 parts by mass of the hydraulic powder
  • the content of (v) is 0.02 parts by mass or more and 0.1 parts by mass or less relative to 100 parts by mass of the hydraulic powder
  • the content of (vi) is 0.0005 parts by mass or more and 0.5 parts by mass or less relative to 100 parts by mass of the hydraulic powder
  • Hydraulic composition Hydraulic composition.
  • a surfactant for surface aesthetic improvers for hydraulic compositions which, when a measuring aqueous solution obtained by adding a surfactant at a concentration of 0.05% by mass to bleeding water of the following hydraulic composition is measured by a bubble pressure method (20°C), has a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms.
  • ⁇ 1 dynamic surface tension
  • ⁇ 2 dynamic surface tension
  • a cement dispersant which is a copolymer containing, as constituent monomers, a monomer (1b) represented by the following general formula (1b) and a monomer (2b) represented by the following general formula (2b):
  • R 1b is a hydrogen atom
  • R 2b is a methyl group
  • R 3b is a hydrogen atom
  • M 1 and M 2 may be the same or different and each represents a hydrogen atom, an alkali metal, or an alkaline earth metal (1/2 atom).
  • R 4b is a hydrogen atom
  • R 5b is a methyl group
  • R 6b is a hydrogen atom
  • R 7b is an alkyl group having 1 carbon atom
  • AO is an alkyleneoxy group having 2 carbon atoms
  • n1 is the average number of moles of AO added and is a number of 20 to 60
  • q is the average number of moles of AO added and is a number of 20 to 60
  • the composition comprises the following (iv), (ii), (v), and (vi), water, and a hydraulic powder
  • the content of (iv) is 0.01 parts by mass or more and 1 part by mass or less relative to 100 parts by mass of the hydraulic powder
  • the content of (ii) is 0.2 parts by mass or more and 0.5 parts by mass or less relative to 100 parts by mass of the hydraulic powder
  • the content of (v) is 0.02 parts by mass or more and 0.1 parts by mass or less relative to 100 parts by mass of the hydraulic powder
  • the content of (vi) is 0.0005 parts by mass or more and 0.5 parts by mass or less relative to 100 parts by mass of the hydraulic powder
  • Hydraulic composition Hydraulic composition
  • a surface appearance improver for a hydraulic composition which is at least one member selected from polyoxyethylene (2) decyl ether, polyoxyethylene (3) decyl ether, and polyoxyethylene (5) lauryl ether.
  • a cement dispersant which is a copolymer containing, as constituent monomers, a monomer (1b) represented by the following general formula (1b) and a monomer (2b) represented by the following general formula (2b): [In the formula, R 1b is a hydrogen atom, R 2b is a methyl group, R 3b is a hydrogen atom, and M 1 and M 2 may be the same or different and each represents a hydrogen atom, an alkali metal, or an alkaline earth metal (1/2 atom).] [In the formula, R 4b is a hydrogen atom, R 5b is a methyl group, R 6b is a hydrogen atom, R 7b is an alkyl group having 1 carbon atom, AO is an alkyleneoxy group having 2 carbon
  • a method for producing a hardened product of a hydraulic composition comprising the steps of: mixing a surface appearance improver for a hydraulic composition, which contains a surfactant having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms, with hydraulic powder and water to prepare a hydraulic composition; filling the prepared hydraulic composition into a formwork and hardening it; and demolding the hardened hydraulic composition.
  • a surface appearance improver for a hydraulic composition which contains a surfactant having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms
  • a method for improving the surface appearance of a hardened body of a hydraulic composition comprising adding a surfactant having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms, when measured by a bubble pressure method (20°C), to the hydraulic composition containing hydraulic powder and water.
  • a surfactant having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms, when measured by a bubble pressure method (20°C), to the hydraulic composition containing hydraulic powder and water.
  • a surfactant as a surface aesthetic improver for a hydraulic composition, the surfactant having a dynamic surface tension ( ⁇ 1) of 55 mN/m or more at a bubble film life of 10 ms and a dynamic surface tension ( ⁇ 2) of 35 mN/m or less at a bubble film life of 1000 ms when a measuring aqueous solution obtained by adding a surfactant at a concentration of 0.05 mass % to bleeding water of the hydraulic composition described below is measured by a bubble pressure method (20°C).
  • a bubble pressure method (20°C).
  • a surface aesthetic improving kit for a hardened body of a hydraulic composition comprising an aqueous solution ⁇ containing the surfactant for a surface aesthetic improving agent for a hydraulic composition according to the above item ⁇ 4> and an aqueous solution ⁇ containing a cement dispersant as described below.
  • cement dispersant A copolymer containing, as constituent monomers, a monomer (1b) represented by the following general formula (1b) and a monomer (2b) represented by the following general formula (2b).
  • R 1b , R 2b , R 3b may be the same or different and are a hydrogen atom, a methyl group or (CH 2 ) r COOM 2 , in which case (CH 2 ) r COOM 2 may form an anhydride with COOM 1 or another (CH 2 ) r COOM 2 , in which case M 1 and M 2 in those groups do not exist.
  • M 1 and M 2 may be the same or different and each represents 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 represents a number of 0 to 2.
  • R 4b and R 5b may be the same or different and are a hydrogen atom or a methyl group.
  • R 6b a hydrogen atom or -COO(AO) n1
  • R 7b R7b a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • AO an oxyalkylene group having 2 to 4 carbon atoms
  • n1 the average number of moles of AO added, which is a number of 4 to 200
  • q1 a number of 0 to 2
  • p1 0 or 1 Indicates that.
  • the formulation of the hydraulic composition is shown in Table 1, and the evaluation results are shown in Table 2.
  • the compounds in the table are as follows.
  • the numbers in parentheses indicate the average number of moles of ethylene oxide added.
  • the HLB of component (A) is the HLB measured by the Griffin method.
  • Palm kernel oil fatty acid diethanolamide Product name "Aminone PK02-S", manufactured by Kao Corporation
  • the mass ratio of water to hydraulic powder was 30 parts by mass of water to 100 parts by mass of hydraulic powder.
  • the amount of fine aggregate was 115 parts by mass to 100 parts by mass of hydraulic powder.
  • the components used were as follows. ⁇ W: Mixing water (tap water (Wakayama City tap water)) C: Ordinary Portland cement (manufactured by Taiheiyo Cement Corporation, density 3.16 g/cm 3 ) S: Fine aggregate (mountain sand produced in Joyo, Kyoto Prefecture, density 2.50 g/cm 3 ) G: Coarse aggregate (andesite crushed stone from Nishijima, Hyogo Prefecture (a mixture of crushed stone with a diameter of 10-20 mm and crushed stone with a diameter of 5-10 mm at a mass ratio of 1:1), density 2.63 g/cm 3 )
  • the mixing water contained the surfactant shown in Table 2, the following component (B), the following component (C), and the following component (D), and the concentrations of each component in the mixing water were adjusted to 0.05% by mass of the surfactant shown in Table 2, 0.82% by mass of the following component (B), 0.15% by mass of the following component (C) (the mass ratio of the following component (c-2) to the following component (c-1), (c-2)/(c-1), in the above-mentioned component (C), was 0.125), and 0.0033% by mass of the following component (D).
  • Dynamic Surface Tension Measurement (2-1) Dynamic Surface Tension Measurement of Surfactant A 0.3% by mass concentration aqueous solution of the surfactant was measured for dynamic surface tension ( ⁇ 3 and ⁇ 4) by the bubble pressure method (20° C., capillary diameter: 0.2 to 0.3 mm, measurement time: 10 ms to 10,000 ms) using a bubble pressure type dynamic surface tensiometer (product name: BP100) manufactured by KRUSS.
  • BP100 bubble pressure type dynamic surface tensiometer
  • Examples 1 to 3 confirmed that the hardened hydraulic composition using the surface aesthetics improver for hydraulic compositions of the present invention had few air bubble marks on its surface, less than 1%, making it very difficult to determine the number of air bubbles.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
PCT/JP2024/004942 2023-02-14 2024-02-14 水硬性組成物用表面美観向上剤 Ceased WO2024172052A1 (ja)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0812397A (ja) 1994-06-30 1996-01-16 Kao Corp 自己充填性コンクリート混和剤
JP2018130957A (ja) 2017-02-13 2018-08-23 花王株式会社 型枠離型剤
WO2018199055A1 (ja) * 2017-04-26 2018-11-01 花王株式会社 水硬性組成物用混和剤組成物
JP2019026506A (ja) 2017-07-28 2019-02-21 株式会社日本触媒 セメント添加剤用樹脂エマルション
JP2019196282A (ja) 2018-05-09 2019-11-14 花王株式会社 水硬性組成物用水和発熱抑制剤
JP2022134514A (ja) * 2021-03-03 2022-09-15 花王株式会社 起泡剤
JP2022176809A (ja) * 2021-05-17 2022-11-30 東邦化学工業株式会社 重縮合物及び水硬性組成物用添加剤

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0812397A (ja) 1994-06-30 1996-01-16 Kao Corp 自己充填性コンクリート混和剤
JP2018130957A (ja) 2017-02-13 2018-08-23 花王株式会社 型枠離型剤
WO2018199055A1 (ja) * 2017-04-26 2018-11-01 花王株式会社 水硬性組成物用混和剤組成物
JP2019026506A (ja) 2017-07-28 2019-02-21 株式会社日本触媒 セメント添加剤用樹脂エマルション
JP2019196282A (ja) 2018-05-09 2019-11-14 花王株式会社 水硬性組成物用水和発熱抑制剤
JP2022134514A (ja) * 2021-03-03 2022-09-15 花王株式会社 起泡剤
JP2022176809A (ja) * 2021-05-17 2022-11-30 東邦化学工業株式会社 重縮合物及び水硬性組成物用添加剤

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Concrete Handbook", 10 June 1998, GIJUTSU SHOIN COMPANY, LIMITED

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