Surface aesthetic appearance improver for hydraulic compositions

Abstract

To provide a surface aesthetic appearance improver for a hydraulic composition that is capable of controlling the behavior of bubbles in the hydraulic composition, which causes bubble marks on a surface of a hardened body of the hydraulic composition, thereby improving the surface aesthetic appearance of the hardened body.SOLUTION: A surface aesthetic appearance improver for a hydraulic composition contains a surfactant (A) satisfying specific requirements (i) and (ii).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a surface appearance improver for a hydraulic composition, a hydraulic composition, a method for producing a hardened product of the hydraulic composition, and a method for improving the surface appearance of a hydraulic composition. [Background technology]

[0002] Hydraulic compositions, such as concrete, can be produced, for example, by filling a formwork with an unhardened hardening composition, followed by hardening through drying or chemical reaction in a post-process to obtain a hardened body. One of the factors that influence 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 beautiful the surface is, the higher the value of the product tends to be evaluated.

[0003] One of the causes of the deterioration of the surface appearance of the cured body is the traces of air bubbles exposed on the surface of the cured body. To address this problem, measures have been taken to add a repair process to hide the traces of air bubbles after curing, but this is not desirable from the standpoint of cost and labor.

[0004] Patent Document 1 discloses a surface appearance improver for a hydraulic composition, which contains a specific fatty acid alkanolamide, a polycarboxylic acid-based dispersant, and a specific solvent. Patent Document 2 discloses a resin emulsion used as a cement additive, which contains a specific emulsion resin, an aqueous solvent, and a nonionic emulsifier (polyoxyethylene alkyl ether) used in emulsion polymerization of the resin, and discloses that the use of a cement additive containing the resin emulsion can improve the aesthetic surface appearance of a hardened product of a cement composition.

[0005] In addition, measures have been taken to reduce the number of bubbles that form at the interface between the composition and the form before the composition is completely hardened by applying a release agent to the form used when hardening the hydraulic composition, thereby promoting the rise of bubbles in the composition. For example, Patent Document 3 discloses a form release agent containing a specific fatty acid alkanolamide. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2019-196282 A [Patent Document 2] JP 2019-26506 A [Patent Document 3] JP 2018-130957 A Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a surface appearance improver for a hydraulic composition, which can better control the behavior of air bubbles in a hydraulic composition, which cause air bubble marks on the surface of a hardened body of the hydraulic composition, and can improve the surface appearance of the hardened body. [Means for solving the problem]

[0008] The present invention provides a surface appearance improver for a hydraulic composition, which contains (A) a surfactant [hereinafter, component (A)] that satisfies the following requirements (i) and (ii), for use in combination with (B) an air-entraining agent [hereinafter, component (B)]:

[0009] [Requirement (i)] When a 0.3% by mass aqueous solution of component (A) is measured by a bubble pressure method (20°C), the dynamic surface tension (σa1) of the aqueous solution of component (A) at a bubble film lifetime of 10 ms and the dynamic surface tension (σb) of the aqueous solution of component (B) satisfy the relationship σb≦σa1. [Requirement (ii)] When a 0.3% by mass aqueous solution of component (A) is measured by the bubble pressure method (20°C), the dynamic surface tension (σa2) at a bubble film life of 1000 ms is 28 mN / m or less.

[0010] The present invention also provides a hydraulic composition comprising (A) a surfactant satisfying the above requirements (i) and (ii), (B) an air entraining agent, a hydraulic powder, and water.

[0011] The present invention also provides a method for producing a hardened product of a hydraulic composition, comprising the steps of: mixing (A) a surfactant satisfying the above requirements (i) and (ii), (B) an air-entraining agent, a 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.

[0012] The present invention also provides a method for improving the surface appearance of a hydraulic composition, which comprises adding (A) a surfactant satisfying the above requirements (i) and (ii), and (B) an air-entraining agent. Effect of the Invention

[0013] By using the surface aesthetics improver for hydraulic compositions of the present invention, it is possible to control the behavior of bubbles in the hydraulic composition, which cause bubble marks on the surface of the hardened body of the hydraulic composition, and to improve the surface aesthetics of the hardened body of the hydraulic composition. [Brief description of the drawings]

[0014] [Figure 1] (a) Photograph of the surface of the hardened hydraulic composition of Comparative Example 2-3 (b) Photograph of the surface of the hardened hydraulic composition of Example 2-3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The present inventors have found that a surfactant satisfying the above-mentioned dynamic surface tension (hereinafter referred to as the present surfactant (A)) adsorbs to bubbles in a hydraulic composition, particularly coarse bubbles of several centimeters that are noticeable as bubble marks, and enables the bubbles to be peeled off from a formwork. As a result, the number of bubbles between the hydraulic composition and the formwork is reduced, and the surface bubble marks of the hardened hydraulic composition are reduced, improving the surface aesthetics. Although not wishing to be bound by a particular theory, the reason for the manifestation of such an effect is presumed to be as follows.

[0016] A hydraulic composition such as concrete is, for example, applied with release oil to a metal formwork, poured and vibrated to fill the formwork, and then hardened. During hardening, the concrete's dilatant properties cause the concrete to lose its plasticity, but once the plasticity is released, 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 a surfactant. Therefore, it is desirable to peel off the bubbles before the time of about 1000 ms when the plasticization is released. It is known that many general-purpose release oils have a dynamic surface tension of up to about 28 mN / m at the gas interface. Therefore, it is presumed that if the surfactant (A) has a dynamic surface tension of 28 mN / m or less at the gas-liquid interface during the bubble film life of 1000 ms, it can adsorb and peel off the bubbles that appear at the part where the hydraulic composition and the formwork come into contact with each other through the release oil, especially the coarse bubbles that are noticeable as bubble marks (several centimeters).

[0017] In addition, fine air bubbles are introduced into hydraulic compositions such as concrete using an air entraining agent. In this case, when the present surfactant (A) is used, the air entraining agent acts as a sacrificial adsorbent for the fine air bubbles, and can prevent the present surfactant (A) from being deactivated on the surfaces of the fine air bubbles.

[0018] Due to such an action mechanism, when a hydraulic composition containing the surface aesthetics improver for hydraulic compositions of the present invention is filled into a formwork coated with a release agent, air bubbles appearing at the site where the hydraulic composition comes into contact with the release agent sequentially move into the hydraulic composition, reducing air bubble marks on the surface and improving the surface aesthetics.

[0019] <Surface appearance improver for hydraulic compositions> The present invention relates to a surface appearance improver for a hydraulic composition, which contains (A) a surfactant (hereinafter, component (A)) that satisfies the following requirements (i) and (ii), and is to be used in combination with (B) an air-entraining agent (hereinafter, component (B)):

[0020] [Requirement (i)] When a 0.3% by mass aqueous solution of component (A) is measured by a bubble pressure method (20°C), the dynamic surface tension (σa1) of the aqueous solution of component (A) at a bubble film lifetime of 10 ms and the dynamic surface tension (σb) of the aqueous solution of component (B) satisfy the relationship σb≦σa1.

[0021] [Requirement (ii)] When a 0.3% by mass aqueous solution of component (A) is measured by the bubble pressure method (20°C), the dynamic surface tension (σa2) at a bubble film life of 1000 ms is 28 mN / m or less.

[0022] The dynamic surface tension in the present invention can be measured, for example, by using a BP100 manufactured by KRUSS, at 20° C., capillary diameter: 0.2 to 0.3 mm, and measurement time: 10 ms to 10,000 ms.

[0023] The component (A) satisfies the following requirement (i): when a 0.3 mass% aqueous solution of the component (A) is measured by the bubble pressure method (20°C), the dynamic surface tension (σa1) of the aqueous solution of the component (A) at a bubble film life of 10 ms and the dynamic surface tension (σb) of the aqueous solution of the component (B) satisfy the relationship σb≦σa1. The concentration of the aqueous solution of the component (B) used in combination with the surface aesthetic improver for hydraulic compositions is not particularly limited, but the σb measured for the aqueous solution must be equal to or less than the σa1.

[0024] The component (A) satisfies the above-mentioned requirement (ii). That is, when an aqueous solution of the component (A) having a concentration of 0.3% by mass is measured by a bubble pressure method (20°C), the dynamic surface tension (σa2) at a bubble film life of 1000 ms is 28 mN / m or less, and from the viewpoint of the effect of reducing the number of bubble marks on the surface of the hardened body of the hydraulic composition, it is preferably 27 mN / m or less, and more preferably 25 mN / m or less.

[0025] It is preferable that the component (A) further satisfies the following requirement (iii).

[0026] [Requirement (iii)] The diffusion coefficient (Da) of component (A) and the diffusion coefficient (Db) of component (B) satisfy the relationship Da < Db.

[0027] The diffusion coefficient D quantitatively represents the ease of diffusion of components (A) and (B) (solutes) in the hydraulic composition (solvent). According to Fsinerman et. al. Colloids and Surfaces, 1994, A, 87, 61 - 75., strictly speaking, the diffusion coefficient D is calculated by (the slope of the change in surface tension at a foam film lifetime of 0 - 10 ms) × (a constant). However, since both (the surface tension of the aqueous solution at a foam film lifetime of 0 ms, 72.4 mN / m) and (the constant) are constant regardless of the type of surfactant, in the present invention, the difference between [the surface tension of the aqueous solution at a foam film lifetime of 0 ms, 72.4 mN / m] and [the surface tension value of the aqueous solution at a foam film lifetime of 10 ms], that is, the change amount of the dynamic surface tension of the solute in the solvent, is defined as the diffusion coefficient D. Therefore, as one aspect of the calculation method of the diffusion coefficient D, the diffusion coefficient (Da) of component (A) in the present invention corresponds to the difference between 72.4 mN / m and [the dynamic surface tension at a foam film lifetime of 10 ms] when the aqueous solution of component (A) with a concentration of 0.3 mass% is measured by the bubble pressure method (20°C). The diffusion coefficient (Db) of component (B) in the present invention corresponds to, for example, the difference between 72.4 mN / m and [the dynamic surface tension at a foam film lifetime of 10 ms] when the aqueous solution of component (B) with an aqueous solution concentration satisfying requirement (i) is measured by the bubble pressure method (20°C).

[0028] In the surface appearance improver for the hydraulic composition of the present invention, by using component (A) with a smaller diffusion coefficient Da than the diffusion coefficient Db of component (B) used in combination, it is considered that component (B) diffuses more easily than component (A) and adsorbs quickly to fine bubbles.

[0029] Component (A) satisfies the above requirements (i), (ii), and, if necessary, requirement (iii). As a specific aspect, the following components (A) can be mentioned.

[0030] The component (A) is preferably a nonionic surfactant satisfying the above requirements (i) and (ii), and examples thereof include nonionic surfactants such as polyoxyethylene alkyl ethers, alkyl alkanolamides, and polyoxyethylene alkyl amines. 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, polyoxyethylene alkyl ethers are preferred.

[0031] When the component (A) is a nonionic surfactant satisfying the requirements (i) and (ii), from the viewpoint of the effect of reducing the number of air bubble traces on the surface of the hardened body of the hydraulic composition, the component (A) may contain a polyoxyethylene alkyl ether in which the number of carbon atoms in the alkyl group is preferably 8 or more, more preferably 9 or more, and preferably 12 or less, and more preferably 11 or less. Also, when the component (A) is a nonionic surfactant satisfying the requirements (i) and (ii), from the viewpoint of the effect of reducing the number of air bubble traces on the surface of the hardened body of the hydraulic composition, the component (A) may contain a polyoxyethylene alkyl ether in which the average number of moles of ethylene oxide added is preferably 1 or more, more preferably 2 or more, and preferably 6 or less, and more preferably 5 or less.

[0032] That is, when the surface appearance improver for a hydraulic composition of the present invention is a nonionic surfactant satisfying the above requirements (i) and (ii) as component (A), it can contain a polyoxyethylene alkyl ether having an alkyl group carbon number of 8 or more and 12 or less and an average added mole number of ethylene oxide of 1 or more and 6 or less.

[0033] In the surface aesthetic improver for hydraulic composition of the present invention, the content of the component (A) of the present invention is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1.0 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 from the viewpoint of the storage stability of the surface aesthetic improver, it is preferably 8.0 mass% or less, more preferably 5.0 mass% or less, and even more preferably 4.0 mass%.

[0034] The surface appearance improver for hydraulic compositions of the present invention containing such component (A) is used in combination with an air entraining agent (B). As a specific embodiment, the following component (B) can be mentioned.

[0035] The component (B) used in combination with the surface appearance improver for hydraulic compositions of the present invention is not particularly limited, and examples thereof include resin soap, saturated or unsaturated fatty acid, lauryl sulfate, alkylbenzenesulfonic acid or a salt thereof, alkane sulfonate, polyoxyalkylene alkyl (or alkylphenyl) ether, polyoxyalkylene alkyl (or alkylphenyl) ether sulfate or a salt thereof, polyoxyalkylene alkyl (or alkylphenyl) ether phosphate or a salt thereof, protein material, alkenyl succinic acid, α-olefin sulfonate, and the like.

[0036] The component (B) used in combination with the surface appearance improver for hydraulic composition of the present invention is preferably a resin soap such as rosin acid, or an anionic surfactant such as polyoxyethylene alkyl ether sulfate, from the viewpoints of the effect of reducing the amount of air bubble traces on the surface of the hardened hydraulic composition and the durability of the hardened hydraulic composition.

[0037] The component (B) used in combination with the surface appearance improver for hydraulic composition of the present invention includes resin soaps such as rosin acid and rosin acid esters, and from the viewpoints of the effect of reducing the amount of air bubble traces on the surface of the hardened hydraulic composition and the durability of the hardened hydraulic composition, rosin acid is preferred.

[0038] In addition, the component (B) used in combination with the surface appearance improver for hydraulic compositions of the present invention includes anionic surfactants such as polyoxyethylene alkyl ether sulfates and polyoxyethylene alkyl ether phosphates, and from the viewpoints of the effect of reducing the amount of air bubble traces on the surface of the hardened hydraulic composition and the durability of the hardened hydraulic composition, polyoxyethylene alkyl ether sulfates are preferred.

[0039] When the component (B) used in combination with the surface appearance improver for hydraulic composition of the present invention is a polyoxyethylene alkyl ether sulfate, for example, from the viewpoint of the effect of reducing the number of air bubble traces on the surface of the hardened hydraulic composition, the average number of moles of ethylene oxide added is preferably 1 or more, more preferably 2 or more, and from the viewpoint of the durability of the hardened hydraulic composition, the average number of moles of ethylene oxide added is preferably 4 or less, more preferably 3 or less, from the viewpoint of the effect of reducing the number of air bubble traces on the surface of the hardened hydraulic composition, the number of carbon atoms in the alkyl group is preferably 10 or more, more preferably 12 or more, and from the viewpoint of the durability of the hardened hydraulic composition, the average number of carbon atoms is preferably 22 or less, more preferably 20 or less.

[0040] The (B) component used in combination with the surface aesthetic improver for hydraulic compositions of the present invention can be combined in such a content that the mass ratio to the content of the (A) component in the surface aesthetic improver for hydraulic compositions of the present invention falls within the following range: That is, the (A) component in the surface aesthetic improver for hydraulic compositions of the present invention and the (B) component used in combination with the surface aesthetic improver for hydraulic compositions of the present invention are such that the mass ratio (A) / (B) of the content of the (A) component to the content of the (B) component is preferably 0.005 or more, more preferably 0.01 or more, from the viewpoint of the effect of reducing the number of air bubbles on the surface of the hardened body of the hydraulic composition, and is preferably 10 or less, more preferably 1.0 or less, and even more preferably 0.2 or less, from the viewpoint of the durability of the hardened body of the hydraulic composition.

[0041] The surface aesthetic improver for hydraulic compositions of the present invention is preferably in a liquid form from the viewpoint of handling. Therefore, the surface aesthetic improver for hydraulic compositions of the present invention is preferably used in a liquid form such as a homogeneous solution, and more preferably contains water, and further preferably is an aqueous solution. That is, an aqueous solution containing component (A) can be used as the surface aesthetic improver for hydraulic compositions of the present invention.

[0042] The present invention can also provide a surface aesthetic improver for hydraulic compositions, which contains (A) a surfactant satisfying the above requirements (i) and (ii) and (B) an air entraining agent. In the surface aesthetic improver for hydraulic compositions of the present invention, specific examples and preferred aspects of the (A) component, the (B) component and optional components can be the same as those of the above-mentioned surface aesthetic improver for hydraulic compositions of the present invention.

[0043] The present invention can also provide a method for selecting a surfactant in a surface aesthetic improver for hydraulic compositions to be used in combination with an air entraining agent, comprising selecting a surfactant in which the dynamic surface tension (σa1) of a 0.3% by mass aqueous surfactant solution at a foam film life of 10 ms and the dynamic surface tension (σb) of the air entraining agent satisfy the relationship σb≦σa1, and the dynamic surface tension (σa2) of a 0.3% by mass aqueous surfactant solution at a foam film life of 1000 ms is 28 mN / m or less. In the method for selecting a surfactant in a surface aesthetic improver for hydraulic compositions of the present invention, specific examples and preferred aspects of the surfactant, air entraining agent and optional components can be the same as those of the surface aesthetic improver for hydraulic compositions of the present invention described above.

[0044] The surface appearance improver for hydraulic compositions of the present invention exhibits excellent improvement in surface appearance even with a small amount of component (A), and in a specific embodiment, it may contain a cement dispersant, a product stabilizer, an antifoaming agent, etc.

[0045] The surface appearance improver for hydraulic composition of the present invention may further contain a cement dispersant. The cement dispersant may be one or more cement dispersants selected from lignin sulfonic acid polymers, polycarboxylic acid polymers, naphthalene polymers, melamine polymers, and phenolic polymers. From the viewpoint of dispersibility, 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 preferred.

[0046] Examples of polycarboxylic acid polymers that can be used include copolymers of monoesters of polyalkylene glycol and (meth)acrylic acid and carboxylic acids such as (meth)acrylic acid (e.g., compounds described in JP-A-8-12397), copolymers of unsaturated alcohols having polyalkylene glycol and carboxylic acids such as (meth)acrylic acid, copolymers of unsaturated alcohols having polyalkylene glycol and dicarboxylic acids such as maleic acid, etc. Here, (meth)acrylic acid means a carboxylic acid selected from acrylic acid and methacrylic acid.

[0047] As the cement dispersant, a polycarboxylic acid-based dispersant containing a copolymer containing, as constituent monomers, a monomer (1c) represented by the following general formula (1c) and a monomer (2c) represented by the following general formula (2c):

[0048] [ka]

[0049] [During the ceremony, R 1c , R 2c , R 3c may be the same or different, and may be a hydrogen atom, a methyl group, or (CH2)rCOOM 2 and (CH2)rCOOM2 is COOM 1 Or it may form an anhydride with another (CH2)rCOOM2, in which case, M of those groups 1 , M 2 does not exist. M 1 , M 2 may be the same or different, and are a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroalkyl group, or an alkenyl group. r: A number between 0 and 2.

[0050] [ka]

[0051] [During the ceremony, R 4c , R 5c : may be the same or different, hydrogen atom or methyl group R 6c : Hydrogen atom or -COO(AO) n1 R 7c R 7c : 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, a number between 4 and 200 q1: A number between 0 and 2 p1: 0 or 1.

[0052] In the general formula (1c), R 1c , R 2c , R 3c may be the same or different, at least one of which is preferably a methyl group and the rest being hydrogen atoms; R 1c is a hydrogen atom, R 2c is a methyl group, R 3c is more preferably a hydrogen atom. 1 About COOM 1 or other (CH2)rCOOM 1 and an anhydride may be formed, in which case, M 1 , M 2 does not exist.

[0053] In the general formula (1c), M 1 , M 2 may be the same or different and are a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. 1 , M 2 The alkyl group, hydroxyalkyl group, and alkenyl group each preferably have 1 to 4 carbon atoms. 1, M 2 may be the same or different, and are preferably a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, or an alkylammonium group, more preferably a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), or an ammonium group, 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. 1 In the above formula, r is preferably 1.

[0054] In the general formula (2c), R 4c , R 5c may be the same or different and are a hydrogen atom or a methyl group. From the viewpoint of improving the surface appearance, R 4c is a hydrogen atom, R 5c In the general formula (2c), R is preferably a methyl group. 6c is a hydrogen atom or -COO(AO) n1 R 7c From the viewpoint of improving the appearance of the surface, a hydrogen atom is preferable. 7c is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a methyl group. In the general formula (2c), AO is an alkyleneoxy group having 2 to 4 carbon atoms, preferably an ethyleneoxy group. It is preferable that AO contains an ethyleneoxy group. In the general formula (2c), n1 is the average number of moles of AO added, and from the viewpoint of the viscosity and dispersibility of the hydraulic composition, it is 4 or more, preferably 5 or more, more preferably 10 or more, even more preferably 20 or more, and is 200 or less, preferably 150 or less, and more preferably 120 or less. In the general formula (2c), q1 is a number of 0 to 2, preferably 0. In the general formula (2c), p1 is 0 or 1, preferably 1.

[0055] The copolymer contained in the cement dispersant has a total content of monomer (1c) and monomer (2c) in the constituent monomers of preferably 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 content may be 100% by mass.

[0056] In the copolymer contained in the cement dispersant, the proportion of monomer (1c) in the total of monomer (1c) and monomer (2c) is preferably 2 mol% or more, more preferably 4 mol% or more, even more preferably 5 mol% or more, still more preferably 10 mol% or more, and is preferably 98 mol% or less, more preferably 95 mol% or less, and even more preferably 90 mol% or less, from the viewpoint of dispersibility of the hydraulic composition.

[0057] The weight average molecular weight of the copolymer contained in the cement dispersant is 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 is preferably 100,000 or less, more preferably 90,000 or less, and even more preferably 80,000 or less, from the viewpoint of dispersibility of the hydraulic composition.

[0058] The weight average molecular weight of the copolymer contained in the cement dispersant was measured by gel permeation chromatography (GPC) under the following conditions. *GPC conditions Equipment: GPC (HLC-8320GPC) manufactured by Tosoh Corporation Column: G4000PWXL+G2500PWXL (Tosoh Corporation) Eluent: 0.2M phosphate buffer / CH3CN=9 / 1 Flow rate: 1.0mL / min Column temperature: 40℃ Detection: RI Sample size: 0.2mg / mL Standard substance: Polyethylene glycol equivalent (monodisperse polyethylene glycol with known molecular weight, molecular weight 87,500, 250,000, 145,000, 46,000, 24,000)

[0059] The cement dispersant used in the surface appearance improver for hydraulic composition of the present invention may be, for example, one or more types selected from the following cement dispersants. Polycarboxylic acid dispersant 1; methacrylic acid / methoxypolyethylene glycol (23) monomethacrylate = 75 mol / 25 mol, weight average molecular weight = 50,000 (the number in parentheses is the average number of moles of ethylene oxide added) Polycarboxylic acid dispersant 2: methacrylic acid / methoxypolyethylene glycol (120) monomethacrylate = 80 moles / 20 moles, weight average molecular weight = 50,000 (the number in parentheses is the average number of moles of ethylene oxide added) Polycarboxylic acid dispersant 3: acrylic acid / polyethylene glycol (50) isoprenyl ether = 75 mol / 25 mol, weight average molecular weight = 50,000 (the number in parentheses is the average number of moles of ethylene oxide added)

[0060] When the polycarboxylic acid-based dispersants 1, 2, and 3 listed above are used in combination, they can be used in a mass ratio of, for example, 50 / 25 / 25, of the dispersant 1 / the dispersant 2 / the dispersant 3. When a plurality of cement dispersants are used in this manner, the average number of moles of AO added of each dispersant is calculated by taking the mass average at the blending ratio of the dispersants, and this is the average number of moles of AO added of the (combined) dispersants.

[0061] In the surface appearance improver for hydraulic composition of the present invention, the content of the cement dispersant is preferably 10 mass% or more, more preferably 20 mass% or more, from the viewpoint of fluidity retention of the hydraulic composition, and is preferably 60 mass% or less, more preferably 50 mass% or less.

[0062] The surface aesthetic improver for hydraulic compositions of the present invention may further contain a product stabilizer. Specific examples thereof include polyoxyethylene alkyl ether sulfate or its salt, polyoxyethylene polyoxypropylene alkyl ether sulfate or its salt; polyoxyethylene alkyl ether (excluding the specific surfactant of the present invention), sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, etc. Specific examples thereof include phenyl glycol, phenyl diglycol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether; octyl dimethylamine, decyl dimethylamine, etc. Among these, from the viewpoint of product stability and cost reduction, polyoxyethylene alkyl ether sulfate or its salt, and phenyl glycol are preferred, and more specifically, polyoxyethylene alkyl ether sulfate or its salt, and phenyl glycol, which have an average carbon number of 18 and an average added mole number of ethylene oxide of 23, are more preferred.

[0063] The product stabilizer used in the surface appearance improver for hydraulic composition of the present invention may contain one or more compounds selected from the compounds represented by the following general formula (d) [hereinafter referred to as component (d-1)].

[0064] R 1d -O-[(EO) n (PO) m ]-SO3M (d) [In the formula, R 1d is a hydrocarbon group having 4 to 20 carbon atoms, EO is an ethyleneoxy group, PO is a propyleneoxy group, n is the average number of moles of EO added and is a number of 1 to 50, m is the average number of moles of PO added and is a number of 0 to 10, and EO and PO may be bonded in blocks or randomly.

[0065] In the general formula (d), R 1dis a hydrocarbon group having 4 to 20 carbon atoms, and from the viewpoint of one-liquid stability, it is preferably 8 or more, more preferably 12 or more, even more preferably 16 or more, and preferably 20 or less, and more preferably 18 or less. In the general formula (d), n is the average number of moles of EO added, and is a number of 1 to 50, and from the viewpoint of one-liquid stability, it is preferably 10 or more, more preferably 15 or more, even more preferably 20 or more, and preferably 35 or less, more preferably 30 or less, and even more preferably 25 or less. In the general formula (d), m is the average number of moles of PO added, and is a number of 0 to 10, and from the viewpoint of one-liquid stability, it is preferably 5 or less, more preferably 3 or less, and even more preferably 1 or less.

[0066] The component (d-1) may be, for example, sodium polyoxyethylene alkyl ether sulfate (average carbon number: 18, average number of moles of polyoxyethylene added: 23).

[0067] The product stabilizer may be a combination of the above-mentioned component (d-1) and a component other than the above-mentioned component (d-1) [hereinafter referred to as component (d-2)]. Specific examples of the component (d-2) include phenyl glycol, phenyl diglycol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, octyldimethylamine, and decyldimethylamine.

[0068] From the viewpoints of product stability and cost reduction, the product stabilizer is preferably one or more selected from (d-1) polyoxyethylene alkyl ether sulfate or a salt thereof and (d-2) phenyl glycol, and more preferably (d-1) polyoxyethylene alkyl ether sulfate or a salt thereof, and (d-2) phenyl glycol. Specifically, (d-1) polyoxyethylene alkyl ether sulfate having an average carbon number of 18 and an average number of ethylene oxide added of 23, or a salt thereof, and (d-2) phenyl glycol are more preferable.

[0069] The product stabilizer containing the (d-1) component has a mass ratio (d-2) / (d-1) of the content of the (d-1) component to the content of the (d-2) component in the total content of the (d-1) component and the (d-2) component, which is preferably 0.050 mass% or more, more preferably 0.10 mass% or more, from the viewpoint of product stability, and preferably 1.0 mass% or less, more preferably 0.50 mass% or less, particularly preferably 0.125, from the viewpoint of cost reduction. The product stabilizer preferably has an alkali metal salt such as sodium as a counter cation.

[0070] In the surface appearance improver for hydraulic composition of the present invention, the content of the product stabilizer 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.

[0071] The surface appearance improver for hydraulic composition of the present invention may further contain an antifoaming agent. Examples of the antifoaming agent include antifoaming agents having an HLB value of less than 3. Specifically, examples of the antifoaming agent include polyalkylene glycol alkyl ether-based antifoaming agents (excluding the specific surfactant 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 value of less than 3 are included. From the viewpoint of adjusting the amount of air in the hydraulic composition and the viewpoint of the storage stability of the surface appearance improver, polyalkylene glycol alkyl ether-based antifoaming agents (excluding the specific surfactant of the present invention), polyalkylene glycol alkyl ester-based antifoaming agents, and silicone-based antifoaming agents are preferred, and polyalkylene glycol alkyl ether-based antifoaming agents are more preferred. The HLB value of the antifoaming agent is calculated using the Griffin method. The Griffin method is calculated from the following formula. HLB = 20 × sum of hydrophilic moieties formula weight / molecular weight

[0072] The content of the defoaming agent in the surface aesthetic improver for hydraulic composition 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 storage stability of the surface aesthetic improver.

[0073] As a further specific embodiment, the surface aesthetic improver for hydraulic compositions of the present invention may contain the component (A) of the present invention, a cement dispersant (C) [hereinafter, component (C)], a product stabilizer (D) [hereinafter, component (D)], and an antifoaming agent (E) [hereinafter, component (E)].

[0074] In the surface aesthetic improver for hydraulic composition of the present invention, the content of the component (A) in the total content of the components (A), (C), (D) and (E) is preferably 1.0 mass% or more, more preferably 3.0 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 is preferably 10 mass% or less, more preferably 5.0 mass% or less, from the viewpoint of the storage stability of the surface aesthetic improver.

[0075] In the surface appearance improver for hydraulic composition of the present invention, the content of the component (C) in the total content of the components (A), (C), (D) and (E) is preferably 60 mass% or more, more preferably 70 mass% or more, and is preferably 90 mass% or less, more preferably 85 mass% or less, from the viewpoint of the fluidity retention of the hydraulic composition.

[0076] In the surface appearance improver for hydraulic compositions of the present invention, the content of the component (D) in the total content of the components (A), (C), (D) and (E) is preferably 1 mass % or more, more preferably 5 mass % or more, from the viewpoint of product stability, and is preferably 30 mass % or less, more preferably 20 mass % or less, from the viewpoint of cost reduction.

[0077] In the surface aesthetic improver for hydraulic composition of the present invention, the content of the component (E) in the total content of the components (A), (C), (D) and (E) is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, from the viewpoint of adjusting the air content in the hydraulic composition, and is preferably 1.0 mass% or less, more preferably 0.5 mass% or less, from the viewpoint of the storage stability of the surface aesthetic improver.

[0078] In the surface appearance improver for hydraulic compositions of the present invention, the mass ratio (A) / (C) of the component (A) to the component (C) 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 body of the hydraulic composition, and is preferably 1.0 or less, more preferably 0.5 or less, from the viewpoint of cost reduction.

[0079] In the surface appearance improver for hydraulic composition of the present invention, the mass ratio (A) / (E) of the component (A) to the component (E) 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.

[0080] The surface appearance improver for a hydraulic composition of the present invention can be blended with mixing water used when preparing a hydraulic composition.

[0081] The content of the component (A) in the mixing water is preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and the surface appearance improver for hydraulic composition of the present invention can be blended so that the content falls within the above range.

[0082] The content of the component (C) in the mixing water is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and is preferably 2.0% by mass or less, more preferably 1.0% by mass or less. The surface appearance improver for hydraulic compositions of the present invention can be blended so that the content falls within the above range.

[0083] The content of the (D) component in the mixing water is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and the surface appearance improver for hydraulic composition of the present invention can be blended so that the content falls within the above range.

[0084] The content of the (E) component in the mixing water is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, and is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and the surface appearance improver for hydraulic compositions of the present invention can be blended so that the content falls within the above range.

[0085] <Hydraulic composition> The hydraulic composition of the present invention contains (A) a surfactant satisfying the above requirements (i) and (ii) [hereinafter, component (A)], (B) an air-entraining agent [hereinafter, component (B)], hydraulic powder, and water. In the hydraulic composition of the present invention, specific examples and preferred aspects of component (A), component (B) and optional components can be the same as those of the surface aesthetic improver for hydraulic composition of the present invention.

[0086] The hydraulic powder may be cement. Examples of cement include ordinary Portland cement, high-early-strength Portland cement, ultra-high-early-strength Portland cement, sulfate-resistant Portland cement, low-heat Portland cement, white Portland cement, and ecocement (e.g., JIS R5214, etc.). Among these, ordinary Portland cement, sulfate-resistant Portland cement, and white Portland cement are preferred, and ordinary Portland cement is more preferred.

[0087] The cement may contain blast furnace slag, fly ash, silica fume, etc., and may also contain non-hydraulic limestone fine powder, etc. Silica fume cement or blast furnace cement mixed with cement can be used.

[0088] In the hydraulic composition of the present invention, the content of component (A) is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and is preferably 1.0 part by mass or less, more preferably 0.1 part 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.

[0089] In the hydraulic composition of the present invention, the content of the (B) component is preferably 0.001 part by mass or more, and more preferably 0.01 part by mass or more, relative to 100 parts by mass of the 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, and is preferably 1.0 part by mass or less, and more preferably 0.1 part by mass or less, from the viewpoint of the durability of the hardened body of the hydraulic composition.

[0090] In the hydraulic composition of the present invention, the mass ratio (A) / (B) of the content of the component (A) to the content of the component (B) is preferably 0.005 or more, more preferably 0.01 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 10 or less, more preferably 1.0 or less, and even more preferably 0.2 or less, from the viewpoint of the durability of the hardened body of the hydraulic composition.

[0091] The hydraulic composition of the present invention may further contain a cement dispersant. When the hydraulic composition of the present invention contains the dispersant, the content of the dispersant is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more, relative to 100 parts by mass of the 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 0.5 part by mass or less, from the viewpoint of durability of the hardened body of the hydraulic composition.

[0092] The hydraulic composition of the present invention may further contain a product stabilizer. When the hydraulic composition of the present invention contains a product stabilizer, the content of the product stabilizer is, from the viewpoint of product stability, preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 1.0 part by mass or less, more preferably 0.1 part by mass or less, relative to 100 parts by mass of the hydraulic powder.

[0093] The hydraulic composition of the present invention may further contain a defoaming agent. When the hydraulic composition of the present invention contains an antifoaming agent, the amount of the antifoaming agent is preferably 0.00001 part by mass or more, more preferably 0.0001 part by mass or more, and is preferably 1.0 part by mass or less, more preferably 0.5 part by mass or less, relative to 100 parts by mass of the hydraulic powder, from the viewpoint of durability of the hardened body of the hydraulic composition.

[0094] As a specific embodiment, the hydraulic composition of the present invention may contain the surface aesthetic improver for hydraulic compositions of the present invention, hydraulic powder, and water. As a further specific embodiment, the hydraulic composition of the present invention may contain the (A) component, the (B) component, the (C) cement dispersant [hereinafter referred to as the (C) component], the (D) product stabilizer [hereinafter referred to as the (D) component], the (E) defoamer [hereinafter referred to as the (E) component], hydraulic powder, and water.

[0095] In the hydraulic composition of the present invention, the content of the (A) component in the total content of the (A), (B), (C), (D) and (E) components is preferably 0.1 mass% or more, more preferably 1.0 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 mass% or less, more preferably 10 mass% or less, from the viewpoint of the storage stability of the surface aesthetic improver.

[0096] In the hydraulic composition of the present invention, the content of the (B) component in the total content of the (A), (B), (C), (D) and (E) components is preferably 1.0 mass% or more, more preferably 10 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 75 mass% or less, more preferably 60 mass% or less, from the viewpoint of the durability of the hardened body of the hydraulic composition.

[0097] In the hydraulic composition of the present invention, the content of the component (C) in the total content of the components (A), (B), (C), (D) and (E) is preferably 1.0 mass% or more, more preferably 10 mass% or more, and is preferably 95 mass% or less, more preferably 80 mass% or less, from the viewpoint of the fluidity retention of the hydraulic composition.

[0098] In the hydraulic composition of the present invention, the content of the component (D) in the total content of the components (A), (B), (C), (D) and (E) is preferably 1.0 mass% or more, and more preferably 5.0 mass% or more, from the viewpoint of product stability, and is preferably 20 mass% or less, and more preferably 15 mass% or less, from the viewpoint of cost reduction.

[0099] In the hydraulic composition of the present invention, the content of the component (E) in the total content of the components (A), (B), (C), (D) and (E) 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 5.0% by mass or less, more preferably 1.0% by mass or less, from the viewpoint of the storage stability of the surface aesthetic improver.

[0100] In the hydraulic composition of the present invention, the mass ratio of the (A) component to the (D) component, (A) / (D), is preferably 0.01 or more, more preferably 0.05 or more, from the viewpoint of the effect of reducing the number of air bubble traces on the surface of the hardened body of the hydraulic composition, and is preferably 1.0 or less, more preferably 0.1 or less, from the viewpoint of cost reduction.

[0101] In the hydraulic composition of the present invention, the mass ratio (A) / (E) of the (A) component to the (E) component is preferably 1.0 or more, more preferably 10 or more, from the viewpoint of adjusting the amount of air in the hydraulic composition, and is preferably 100 or less, more preferably 50 or less, from the viewpoint of storage stability.

[0102] From the viewpoint of workability and economy, the hydraulic composition of the present invention has a water / hydraulic powder ratio [the mass ratio of water to hydraulic powder in the hydraulic composition (mass of water / mass of hydraulic powder×100), usually abbreviated as W / P, and when the hydraulic powder is cement, abbreviated as W / C] of preferably 20% or more, more preferably 30% or more, and more preferably 95% or less, more preferably 80% or less.

[0103] The hydraulic composition of the present invention is not particularly limited with respect to the amount of air contained in the hydraulic composition, but from the viewpoint of durability of the set body of the hydraulic composition, it is preferably 0% or more and more preferably 6.0% or less. The amounts of the (B) air entraining agent and the (d) defoaming agent added can be adjusted so that the amount of air in the hydraulic composition of the present invention falls within the above range.

[0104] The hydraulic composition of the present invention may further contain aggregate. Examples of aggregate 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. Depending on the application, lightweight aggregate may be used. The term aggregate is based on "Concrete Overview" (published by Gijutsu Shoin on June 10, 1998).

[0105] The aggregate may be used in the usual range used in preparing concrete, mortar, etc. When the hydraulic composition is concrete, 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, even more preferably 80% or less, from the viewpoint of the properties of the concrete. The bulk volume is the amount of coarse aggregate per 1 m of concrete. 3 In addition, when the hydraulic composition is concrete, the amount of fine aggregate used is 500 kg / m from the viewpoint of improving the filling property into the formwork, etc. 3 More than 600kg / m is preferable. 3 More preferably, 700 kg / m 3 More preferably, 1000 kg / m 3 Less than 900kg / m is preferable. 3When the hydraulic composition is mortar, the amount of fine aggregate used is preferably 800 kg / m 3 More than 900kg / m is preferable. 3 More preferably, 1000kg / m 3 More preferably, 2000 kg / m 3 Less than 1800kg / m is preferable. 3 Less than 1700kg / m is more preferable. 3 The following is even more preferred:

[0106] The hydraulic composition of the present invention may further contain other components in addition to the above components. Examples of such components include retarders, thickeners, waterproofing agents, fluidizing agents, and early strength agents. Examples of early strength agents include compounds selected from hydrochlorides, sulfates, nitrates, nitrites, cyanates, thiocyanates, thiosulfates, and formates of alkali metals and alkaline earth metals, organic compounds selected from alkanolamines, glycerin derivatives, formaldehyde derivatives, and catechol derivatives, and nanoparticles of Portland cement hydration products (CSH and calcium hydroxide).

[0107] The hydraulic composition of the present invention can be used for concrete and mortar. The hydraulic composition of the present invention is useful in any field such as self-leveling, refractory, plaster, light or heavy concrete, air entrainment, repair, prepacked, trame, ground improvement, grout, and cold weather.

[0108] <Method for producing hydraulic composition> The present invention provides a method for producing a hydraulic composition by mixing component (A), component (B), an optional component, hydraulic powder, and water. The present invention also provides a method for producing a hydraulic composition by mixing a surface aesthetic improver for hydraulic compositions containing component (A), component (B), hydraulic powder, and water. In this production method, specific examples and preferred aspects of component (A), component (B), and optional components can be the same as those of the surface aesthetic improver for hydraulic compositions of the present invention. In addition, in the production method for a hydraulic composition of the present invention, specific examples and preferred aspects of the hydraulic powder can be the same as those of the hydraulic composition of the present invention. In addition, the matters described for the surface aesthetic improver for hydraulic compositions and the hydraulic composition of the present invention can be appropriately applied to the production method for a hydraulic composition of the present invention.

[0109] <Method for producing a hardened product of a hydraulic composition> The present invention provides a method for producing a hardened product of a hydraulic composition, comprising the steps of: preparing a hydraulic composition by mixing a surface appearance improver for hydraulic compositions containing component (A), component (B), hydraulic powder, and water; filling a formwork with the prepared hydraulic composition and hardening it; and demolding the hardened hydraulic composition.

[0110] In the method for producing a hardened product of the hydraulic composition of the present invention, specific examples and preferred aspects of the (A) component, the (B) component and the optional components can be the same as those of the surface aesthetic improver for hydraulic composition of the present invention. In addition, in the method for producing a hardened product of the hydraulic composition of the present invention, specific examples and preferred aspects of the hydraulic powder can be the same as those of the hydraulic composition of the present invention. In addition, the matters described in the surface aesthetic improver for hydraulic composition and the hydraulic composition of the present invention can be appropriately applied to the method for producing a hardened product of the hydraulic composition of the present invention.

[0111] In the process of preparing the hydraulic composition, the hydraulic composition is prepared by mixing the (A) component, the (B) component, the hydraulic powder, and water. In the process of preparing the hydraulic composition, the (A) component, the (B) component, the optional component, the hydraulic powder, and water may be mixed to prepare the hydraulic composition. In the present invention, the (A) component, the (B) component, and the optional component may be mixed separately with the hydraulic powder to prepare the hydraulic composition, but if the (A) component, the (B) component, and the optional component are mixed in advance, there is no need to add a new tank, and it is preferable to mix the integrated product with the hydraulic powder, that is, to mix the surface aesthetic improver for hydraulic composition of the present invention with the hydraulic powder. In the process of preparing the hydraulic composition, the mixing amounts of each component, hydraulic powder, and water 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 mixing amounts.

[0112] In the process of preparing the hydraulic composition, from the viewpoint of smoothly mixing the (A) component, the (B) component, and the optional components with the hydraulic powder such as cement, it is preferable to previously mix the (A) component, the (B) component, the optional components, and water, and then mix the mixture with the hydraulic powder. In addition, the surface appearance improver for the hydraulic composition of the present invention, which contains water, can be used.

[0113] In addition, in the step of preparing the hydraulic composition, a method of mixing hydraulic powder such as cement, the surface aesthetic improver for hydraulic compositions of the present invention, and component (B) is preferred. The surface aesthetic improver for hydraulic compositions of the present invention is preferably added to the hydraulic powder so that the components (A), (B) and optional components are mixed in the above-mentioned amounts (contents).

[0114] Specifically, the surface aesthetics improver for hydraulic compositions of the present invention, as parts by mass of solids, is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and even more preferably 0.1 part by mass or more, relative to 100 parts by mass of hydraulic powder from the viewpoint of improving surface aesthetics, and from the viewpoint of improving surface aesthetics by ensuring high fluidity, the amount is preferably 3.0 parts by mass or less, 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 part by mass or less.

[0115] The mixing in the process of preparing the hydraulic composition can be carried out 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. In preparing the hydraulic composition, the materials and chemicals described in the hydraulic composition and their amounts can be used.

[0116] The obtained hydraulic composition is further filled into a formwork, cured, and hardened. Examples of the formwork include formwork for buildings, formwork for concrete products, etc. Methods for filling the formwork include a method of directly pouring the composition from a mixer, a method of pumping the hydraulic composition into the formwork, etc.

[0117] When the hydraulic composition is cured, the composition can be cured by heating to accelerate the hardening. Here, the heat curing can be performed by maintaining the hydraulic composition at a temperature of 40° C. or more and 80° C. or less to accelerate the hardening.

[0118] Examples of hardened bodies of hydraulic compositions using formwork, which is a concrete product, 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 the like, girder products for bridge piers, and the like, and examples of architectural products include curtain wall products, and architectural component products used for columns, beams, and floor panels.

[0119] In the present invention, the time from contacting the hydraulic powder with water in the preparation of the hydraulic composition 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.

[0120] <Method for improving the surface appearance of hydraulic composition> The method for improving the surface appearance of a hydraulic composition of the present invention is a method for improving the surface appearance of a hydraulic composition by adding component (A) and component (B) to a hydraulic composition containing hydraulic powder and water. The method for improving the surface appearance of a hydraulic composition of the present invention can also use a method in which a surface appearance improver for hydraulic compositions containing component (A) and component (B) are added when preparing a hydraulic composition by mixing hydraulic powder and water.

[0121] Specific examples and preferred aspects of the (A) component, the (B) component and the optional components used in the method for improving the surface appearance of a hydraulic composition of the present invention can be the same as those described in the surface appearance improver for a hydraulic composition of the present invention. Specific examples and preferred aspects of the hydraulic powder used in the method for improving the surface appearance of a hydraulic composition of the present invention can be the same as those described in the hydraulic composition of the present invention. Furthermore, the matters described in the surface appearance improver for a hydraulic composition of the present invention, the hydraulic composition and the method for producing the hardened product thereof can be appropriately applied to the method for improving the surface appearance of a hydraulic composition of the present invention. EXAMPLES

[0122] 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.

[0123] Polyoxyethylene (2) octyl ether; surfactant obtained in Production Example 1 Polyoxyethylene (2) decyl ether; surfactant obtained in Production Example 2

[0124] [Production Example 1] Preparation of polyoxyethylene (2) octyl ether 860g (6.71 mol) of octyl alcohol and 4.36g (0.067 mol) of potassium hydroxide (86% pure content) were charged into a 2L autoclave equipped with a stirrer, thermometer, and EO inlet tube, and after replacing with nitrogen, dehydration was performed for 30 minutes at 110°C and -0.101 MPa. Then, 590g (13.4 mol) of ethylene oxide was supplied to the above mixture and reacted at 155±5°C with an initial nitrogen pressure of 0.005 MPa. Then, 4.095g (0.068 mol) of acetic acid was added to neutralize. The average number of moles of EO added in the obtained product was 1 When confirmed by 1 H-NMR, the average number of moles of EO added was 2 moles.

[0125] [Production Example 2] Preparation of polyoxyethylene (2) decyl ether 1060g (6.71 mol) of decyl alcohol and 4.36g (0.067 mol) of potassium hydroxide (86% pure content) were charged into a 2L autoclave equipped with a stirrer, thermometer, and EO inlet tube, and after replacing with nitrogen, dehydration was performed for 30 minutes at 110°C and -0.101 MPa. Then, 590g (13.4 mol) of ethylene oxide was supplied to the mixed reaction product at an initial nitrogen pressure of 0.005 MPa and 155±5°C to react. Then, 4.095g (0.068 mol) of acetic acid was added to neutralize. The average number of moles of EO added in the obtained product was 1 When confirmed by 1 H-NMR, the average number of moles of EO added was 2 moles.

[0126] <Optional ingredients> (B-1) Air entraining agent, "Vinsol W", manufactured by Yamaso Chemical Co., Ltd. (B-2) Air entraining agent, sodium polyoxyethylene alkyl ether sulfate (average carbon number: 12, average number of moles of ethylene oxide added: 2) (C) Polycarboxylic acid dispersant; methacrylic acid / methoxypolyethylene glycol (23) monomethacrylate copolymer (the number in parentheses is the average number of moles of ethylene oxide added) (D) (d-1) Compound represented by the above general formula (d); sodium polyoxyethylene alkyl ether sulfate (in the above general formula (d), R 1d is a hydrocarbon group with 18 carbon atoms, n is 23, and m is 0), (d-2): Phenoxyethanol · Defoamers; Silicone-based defoamers

[0127] [Table 1]

[0128] The mass ratio of water to hydraulic powder (W / C) was 30% (30 parts by mass of water for 100 parts by mass of hydraulic powder). The amount of fine aggregate was 115 parts by mass for 100 parts by mass of hydraulic powder. The ingredients 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 (yamasand from Joyo, Kyoto Prefecture, density 2.50g / cm 3 ) G: Coarse aggregate (andesite crushed stone from Nishijima, Hyogo Prefecture (10-20 mm diameter crushed stone / 5-10 mm diameter crushed stone mixed at a mass ratio of 1 / 1), density 2.63 g / cm 3 )

[0129] (1) Preparation of hydraulic composition Under the mixing conditions shown in Table 1, coarse aggregate (G), half of the fine aggregate (S), half of the cement (C), and the remaining half of the fine aggregate (S) were charged in this order into a forced twin-shaft mixer (manufactured by IHI Corporation) and dry-mixed for 15 seconds. Then, mixing water of the following composition was charged and mixed for 90 seconds to prepare a hydraulic composition. The mixing water contained component (A), component (B), polycarboxylic dispersant, product stabilizer, antifoaming agent, and product stabilizer, and the concentrations of each component in the mixing water were adjusted to be 0.05 mass% of component (A), 0.84 mass% (Table 2) or 0.28 mass% (Table 3), 0.82 mass% of polycarboxylic dispersant, 0.15 mass% of product stabilizer, and 0.0033 mass% of antifoaming agent, as shown in Tables 2 and 3.

[0130] (2) Dynamic surface tension measurement of components (A) and (B) (2-1) Examples, Comparative Examples 1-2 to 1-8, and Comparative Examples 2-2 to 2-5 The components (A) and (B) shown in Tables 2 and 3 were dissolved in tap water to obtain an aqueous solution of component (A) (concentration 0.3% by mass) and an aqueous solution of component (B) (concentration 4.5% by mass (Table 2) or 1.5% by mass (Table 3)). The aqueous solutions obtained were measured by the bubble pressure method (20°C, capillary diameter: 0.2-0.3 mm, measurement time: 10 ms-10,000 ms) using a bubble pressure dynamic surface tensiometer (product name: BP100) manufactured by KRUSS. The results are shown in Tables 2 and 3.

[0131] (2-2) Comparative Example 1-1 and Comparative Example 2-1 The hydraulic compositions of Comparative Example 1-1 and Comparative Example 2-1 (hydraulic compositions not containing component (A)) were prepared by the above "(1) Preparation of hydraulic composition". The content of component (B) was blended in an amount that would result in the same amount of air as in the examples and other comparative examples. The hydraulic compositions were centrifuged (Kokusan Corporation centrifugal separator, 3000 rpm, 5 min, 20°C), and the supernatant was taken as the free water in the hydraulic composition. The content of component (B) was calculated from the free water, and it was confirmed that the hydraulic composition of Comparative Example 1-1 was 0.5 mass% (B) and the hydraulic composition of Comparative Example 2-1 was 0.2 mass% (B). The dynamic surface tension (σb) was measured in the same manner as in (2-1) and is shown in Tables 2 and 3, respectively.

[0132] (3) Measurement of air content in hydraulic composition For the hydraulic composition obtained above, the air content (volume %) in the hydraulic composition was measured in accordance with JISA1128: 2019. The results are shown in Tables 2 and 3.

[0133] (4) Measurement of air bubble traces in hardened hydraulic compositions (4-1) Preparation of hardened hydraulic composition The hydraulic composition obtained above was filled into a 0.1m x 0.2m x 0.5m steel formwork from the 0.2m x 0.5m surface without vibration, and cured at 20°C to harden. The hardened hydraulic composition was removed from the formwork 24 hours after preparation. An oil-based straight type release agent was applied to the inside of the formwork.

[0134] (4-2) Measurement of air bubble traces in hardened hydraulic composition The surface of one side (0.2m x 0.5m) of the removed hardened body was rubbed with a plastic brush to remove the thin skin, and the image data of the surface was photographed with a smartphone and converted to two colors using ImageJ (areas with air bubble marks were black, and other areas were white). From the ratio of each color, the area ratio of the air bubble marks on the surface of the hardened body was calculated using the following formula, which was used to determine the amount of air bubble marks (%). The results are shown in Tables 2 and 3. Bubble trace amount = Bubble trace area (m 2 ) / 0.2m x 0.5m surface of poured side (m 2 ) x 100

[0135] [Table 2]

[0136] [Table 3]

[0137] From the results of Examples 1 and 2, it was confirmed that the hardened hydraulic composition using the surface aesthetic improver for hydraulic compositions of the present invention in combination with the air entraining agent (B) had less than 1% air bubble marks on its surface, and had few air bubble marks. Figure 1(a) shows a photograph of the hardened hydraulic composition surface of Comparative Example 2-3, and Figure 1(b) shows a photograph of the hardened hydraulic composition surface of Example 2-3. The color of the hardened hydraulic composition surface differs depending on the degree of adhesion of the release agent, but the two hardened hydraulic compositions were prepared under the same conditions except for the difference in components (A) and (B).

Claims

1. A surface appearance improver for a hydraulic composition, to be used in combination with an air-entraining agent (B) [hereinafter, component (B)], containing (A) a surfactant (hereinafter, component (A)] that satisfies the following requirements (i) and (ii): [Requirement (i)] When a 0.3% by mass aqueous solution of component (A) was measured by the bubble pressure method (20°C), the dynamic surface tension (σa １ ) and the dynamic surface tension (σb) of the aqueous solution of component (B) is σb≦σa １ The relationship is as follows: [Requirement (ii)] When a 0.3% by mass aqueous solution of component (A) was measured by the bubble pressure method (20°C), the dynamic surface tension (σa ２ ) is 28 mN / m or less.

2. 2. The surface appearance improver for a hydraulic composition according to claim 1, wherein the component (A) satisfies the following requirement (iii): [Requirement (iii)] The diffusion coefficient (Da) of component (A) and the diffusion coefficient (Db) of component (B) satisfy the relationship Da<Db.

3. 3. The surface appearance improver for hydraulic compositions according to claim 1 or 2, wherein component (A) is a polyoxyethylene alkyl ether having an alkyl group with 8 to 12 carbon atoms and an average number of moles of ethylene oxide added of 1 to 6.

4. 3. The surface aesthetic improver for a hydraulic composition according to claim 1 or 2, wherein the component (B) used in combination is one or more selected from the group consisting of rosin acid, polyethylene glycol alkyl ether sulfate, polyoxyethylene (2) sodium lauryl sulfate, and polyethylene glycol alkyl ether phosphate.

5. The surface appearance improver for a hydraulic composition according to claim 1 or 2, further comprising a cement dispersant.

6. The surface appearance improver for a hydraulic composition according to claim 5, wherein the cement dispersant is a copolymer containing, as constituent monomers, a monomer (1c) represented by the following general formula (1c) and a monomer (2c) represented by the following general formula (2c): 【Chemistry 1】 [During the ceremony, R 1c , R 2c , R 3c may be the same or different, and may be a hydrogen atom, a methyl group, or (CH 2 ) rCOOM 2 and (CH 2 ) rCOOM 2 is COOM 1 or other (CH 2 ) rCOOM2 and may form an anhydride, in which case, M of these groups 1 , M 2 does not exist. M 1 , M 2 may be the same or different, and are a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroalkyl group, or an alkenyl group r: a number between 0 and 2 indicates.] 【Chemistry 2】 [During the ceremony, R 4c , R 5c : may be the same or different, and may be a hydrogen atom or a methyl group R 6c : a hydrogen atom or -COO(AO) n1 R 7c R 7c : a hydrogen atom or an alkyl group having 1 to 4 carbon atoms AO: an alkyleneoxy group having 2 to 4 carbon atoms n1: average number of moles of AO added, a number of 4 or more and 200 or less q1: a number between 0 and 2 p1: 0 or 1 indicates.]

7. The surface appearance improver for a hydraulic composition according to claim 1 or 2, further comprising one or more compounds selected from compounds represented by the following general formula (d): 2 1d --[(5O) n ・(P) m )-39 3 M (d) [In the formula, R 1d represents a hydrocarbon group having from 4 to 20 carbon atoms, EO represents an ethyleneoxy group, PO represents a propyleneoxy group, n represents the average number of moles of EO added and is a number from 1 to 50, and m represents the average number of moles of PO added and is a number from 0 to 10, and EO and PO may be bonded in blocks or randomly.

8. A hydraulic composition comprising: (A) a surfactant satisfying the following requirements (i) and (ii) [hereinafter referred to as component (A)], (B) an air-entraining agent [hereinafter referred to as component (B)], hydraulic powder, and water. [Requirement (i)] When a 0.3% by mass aqueous solution of component (A) was measured by the bubble pressure method (20°C), the dynamic surface tension (σa １ ) and the dynamic surface tension (σb) of the aqueous solution of component (B) is σb≦σa １ The relationship is as follows: [Requirement (ii)] The dynamic surface tension (σa ２ ) is 28 mN / m or less.

9. A step of preparing a hydraulic composition by mixing (A) a surfactant satisfying the following requirements (i) and (ii) [hereinafter referred to as component (A)], (B) an air-entraining agent [hereinafter referred to as component (B)], hydraulic powder, and water; a step of filling the prepared hydraulic composition into a form and hardening it; A step of demolding the hardened hydraulic composition; A method for producing a hardened product of a hydraulic composition comprising the above-mentioned formula (1). [Requirement (i)] When a 0.3% by mass aqueous solution of component (A) was measured by the bubble pressure method (20°C), the dynamic surface tension (σa １ ) and the dynamic surface tension (σb) of the aqueous solution of component (B) is σb≦σa １ The relationship is as follows: [Requirement (ii)] When a 0.3% by mass aqueous solution of component (A) was measured by the bubble pressure method (20°C), the dynamic surface tension (σa ２ ) is 28 mN / m or less.

10. A method for improving the surface appearance of a hydraulic composition, comprising adding (A) a surfactant satisfying the following requirements (i) and (ii) [hereinafter referred to as component (A)], and (B) an air-entraining agent [hereinafter referred to as component (B)]: [Requirement (i)] When a 0.3% by mass aqueous solution of component (A) was measured by the bubble pressure method (20°C), the dynamic surface tension (σa １ ) and the dynamic surface tension (σb) of the aqueous solution of component (B) is σb≦σa １ The relationship is as follows: [Requirement (ii)] When a 0.3% by mass aqueous solution of component (A) was measured by the bubble pressure method (20°C), the dynamic surface tension (σa ２ ) is 28 mN / m or less.

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