Surface appearance-enhancing agent composition for hydraulic composition

Abstract

Provided are a surface appearance-improving agent composition for a hydraulic composition, a hydraulic composition excellent in surface appearance of a hardened body, and a method for improving surface appearance of a hydraulic composition, the surface appearance-improving agent composition being capable of improving the surface appearance of the hardened body by favorably controlling the behavior of bubbles in the hydraulic composition adhering to a mold form or a release agent applied to the surface of the mold form, which causes bubble marks on the surface of the hardened body of the hydraulic composition.SOLUTION: A surface appearance-improving agent composition for a hydraulic composition, comprising the following component (A): A modified silicone having at least one repeating unit selected from a repeating unit (a1) represented by a specific general formula (a1) and a repeating unit (a2) represented by a specific general formula (a2) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a surface appearance improver composition for a hydraulic composition, a 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 by filling a formwork with an unhardened hardenable composition, followed by hardening through drying or chemical reaction in a subsequent process to obtain a hardened product. One of the factors that influences the value of a hardened product is the aesthetic appearance of its surface. This literally refers to the beauty of the surface of the hardened product, and the more aesthetically pleasing the surface is, the more the product tends to be evaluated as having higher value.

[0003] One of the causes of the deterioration of the surface appearance of the cured product is the traces of air bubbles that are exposed on the surface of the cured product. 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 standpoints of cost and labor.

[0004] Patent Document 1 discloses a drying inhibitor for mortar or concrete that has a high initial drying inhibitory effect after spraying, which comprises (A) a nonionic surfactant represented by general formula (I), (B) a surfactant whose 0.1 wt % aqueous solution at 20°C has a surface tension of 10 to 45 mN / m, and (C) water. Patent Document 2 discloses a method for preventing efflorescence in a hardened self-leveling aqueous composition, which comprises pouring a self-leveling aqueous composition containing a base material made of cement and gypsum or a base material made of cement and an expanding material, water, aggregate, a thickener, and an antifoaming agent, and hardening the composition, the method comprising blending 0.00005 to 0.005 parts by weight of polyoxyalkylene-modified silicone with 100 parts by weight of the self-leveling aqueous composition, and using a cement dispersant made of a water-soluble vinyl copolymer obtained by copolymerizing a vinyl monomer containing 50 to 90 mol % of a structural unit represented by formula (1) as a structural unit. Patent Document 3 discloses a dry composition useful for producing, for example, cement-based materials such as mortar, concrete, and plaster, which comprises at least one binder and at least one silicone oil and enables reduction in dust generation. Patent Document 4 discloses a water-repellent composition for treating porous substrates, which comprises an emulsion containing water, at least one surfactant, and a specific siloxane copolymer. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-273765 [Patent Document 2] Japanese Patent Application Publication No. 7-267712 [Patent Document 3] Japanese Patent Application Laid-Open No. 2015-57369 [Patent Document 4] Special Publication No. 2014-531491 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention provides a surface appearance improver composition for a hydraulic composition, which can effectively control the behavior of air bubbles in the hydraulic composition, which cause air bubble marks on the surface of a cured product of the hydraulic composition, adhering to a formwork or a mold release agent applied to the surface of the formwork, thereby improving the surface appearance of the cured product; a hydraulic composition which provides excellent surface appearance of a cured product; and a method for improving the surface appearance of a hydraulic composition.

[0007] In the present invention, improving the surface appearance means reducing the number of bubble traces on the surface of a hardened product of a hydraulic composition to improve the appearance of the surface of the hardened product. [Means for solving the problem]

[0008] The present invention relates to a surface appearance improver composition for a hydraulic composition, which contains the following component (A): Component (A): a modified silicone having one or more repeating units selected from the repeating unit (a1) represented by general formula (a1) and the repeating unit (a2) represented by general formula (a2).

[0009] [ka]

[0010] [In general formula (a1), R 1a is a hydrocarbon group having 1 to 6 carbon atoms, and R 2a is an alkylene group having 1 to 10 carbon atoms, a is 1 or 0, and * is a bonding site. X is -O-(AO) e R 3a and a group selected from the following general formula (a3):

[0011] [ka]

[0012] AO is an alkyleneoxy group having 2 to 4 carbon atoms, e is the average number of moles of AO added, and is a number of 0 to 50, and R 3a is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. 4a are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or -(CO)-R 5a and R 5a is a hydrocarbon group having 1 to 30 carbon atoms; s is an integer of 0 to 3, t is an integer of 0 to 3, and u is an integer of 0 to 20. *-SiR 7a 3-b (R 8a -X) b (a2) [In general formula (a2), R 7a are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 8a are each independently an alkylene group having 1 to 10 carbon atoms, b is an integer of 1 to 3, and * is a bonding site. X is -O-(AO)e R 3a and a group selected from the general formula (a3), where AO is an alkyleneoxy group having 2 to 4 carbon atoms, e is the average number of moles of AO added and is a number of 0 to 50, and R 3a is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. 4a are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or -(CO)-R 5a and R 5a is a hydrocarbon group having 1 to 30 carbon atoms; s is an integer of 0 to 3, t is an integer of 0 to 3, and u is an integer of 0 to 20.

[0013] The present invention also relates to a hydraulic composition containing the component (A), a hydraulic powder, and water.

[0014] The present invention also relates to a method for improving the surface appearance of a hydraulic composition, which comprises mixing the component (A), a hydraulic powder, and water. [Effects of the Invention]

[0015] According to the present invention, there are provided a surface appearance improver composition for hydraulic compositions, which can effectively control the behavior of air bubbles in a hydraulic composition that cause air bubble marks on the surface of a hardened hydraulic composition, in adhering to a formwork or a mold release agent applied to the surface of the formwork, thereby improving the surface appearance of the hardened hydraulic composition; a hydraulic composition that provides excellent surface appearance of a hardened hydraulic composition; and a method for improving the surface appearance of a hydraulic composition. DETAILED DESCRIPTION OF THE INVENTION

[0016] The reason why the surface appearance improver composition for hydraulic compositions of the present invention can better control the behavior of bubbles in a hydraulic composition, which cause bubble marks on the surface of a cured hydraulic composition, and improve the surface appearance of the cured hydraulic composition is not necessarily clear, but is presumed to be as follows. Hydraulic compositions such as concrete are prepared, for example, by applying a release agent to a metal formwork, filling the formwork with the composition and vibrating it, and then hardening. Component (A) contained in the surface appearance improver composition for hydraulic compositions of the present invention has a silicone skeleton with high affinity for air and a skeleton containing many oxygen atoms with high affinity for water. This allows component (A) to act on the interface of bubbles in the hydraulic composition, interposing water between the bubbles and the formwork (or the release agent applied to the formwork), preventing bubbles in the hydraulic composition from adhering to the formwork (or the release agent applied to the formwork), reducing the number of bubble traces on the surface of the hardened hydraulic composition, and presumably improving the appearance of the surface of the hardened hydraulic composition. However, the present invention is not limited to the above-mentioned mechanism of action.

[0017] [Surface appearance improver composition for hydraulic composition] <Component (A)> The surface appearance improver composition for a hydraulic composition of the present invention contains the following component (A): Component (A): a modified silicone having one or more repeating units selected from the repeating unit (a1) represented by general formula (a1) and the repeating unit (a2) represented by general formula (a2).

[0018] [ka]

[0019] [In general formula (a1), R 1a is a hydrocarbon group having 1 to 6 carbon atoms, and R 2a is an alkylene group having 1 to 10 carbon atoms, a is 1 or 0, and * is a bonding site. X is -O-(AO) e R 3a and a group selected from the following general formula (a3):

[0020] [ka]

[0021] AO is an alkyleneoxy group having 2 to 4 carbon atoms, e is the average number of moles of AO added, and is a number of 0 to 50, and R 3a is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. 4a are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or -(CO)-R 5a and R 5a is a hydrocarbon group having 1 to 30 carbon atoms; s is an integer of 0 to 3, t is an integer of 0 to 3, and u is an integer of 0 to 20. *-SiR 7a 3-b (R 8a -X) b (a2) [In general formula (a2), R 7a are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R 8a are each independently an alkylene group having 1 to 10 carbon atoms, b is an integer of 1 to 3, and * is a bonding site. X is -O-(AO) e R 3a and a group selected from the general formula (a3), where AO is an alkyleneoxy group having 2 to 4 carbon atoms, e is the average number of moles of AO added and is a number of 0 to 50, and R 3a is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. 4a are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or -(CO)-R 5a and R 5a is a hydrocarbon group having 1 to 30 carbon atoms; s is an integer of 0 to 3, t is an integer of 0 to 3, and u is an integer of 0 to 20.

[0022] In general formula (a1), R 1a is a hydrocarbon group having 6 or less carbon atoms, preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and even more preferably 1 carbon atom, preferably an alkyl or alkenyl group, more preferably an alkyl group. R 1a is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Examples of the alkyl group include a group selected from the group consisting of butyl, n-butyl, tert-butyl, pentyl, and phenyl. Among these, a methyl group is preferred. In general formula (a1), R 2a The alkylene group has 10 or less carbon atoms, preferably 8 or less, more preferably 5 or less, even more preferably 4 or less, still more preferably 3 or less, and 1 or more carbon atoms. R 2a is, for example, a group selected from a methanediyl group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, an n-propane-1,3-diyl group, and an n-propane-1,2-diyl group. Among these, a group selected from a methanediyl group, an ethane-1,2-diyl group, an n-propane-1,3-diyl group, and an n-propane-1,2-diyl group is preferred, and an n-propane-1,3-diyl group is more preferred.

[0023] In the general formula (a1), X is —O—(AO) e R 3a and a group selected from the general formula (a3), and from the viewpoint of reducing bubble marks in the hydraulic composition, preferably -O-(AO) e R 3a is.

[0024] -O-(AO) e R 3a In the formula, AO is preferably a group selected from an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group, more preferably an ethyleneoxy group, from the viewpoint of improving water solubility. AO preferably contains an ethyleneoxy group. e is the average number of moles of AO added, and from the viewpoint of improving hydrophilicity, it is a number of 0 or more, preferably 2 or more, more preferably 5 or more, and 50 or less, preferably 30 or less, more preferably 15 or less. Furthermore, the AO may be different among the average e repeating units, and may be randomly added, block added, or a mixture of these. It is preferable that 70 mol % or more, more preferably 80 mol % or more, even more preferably 90 mol % or more of EO groups are ethyleneoxy groups (EO groups), and furthermore, all AO groups are EO groups. For example, AO may contain propyleneoxy, butyleneoxy, etc. in addition to EO. R 3a is a hydrogen atom or an alkyl group having 1 or more carbon atoms and 30 or less, preferably 12 or less, and more preferably 3 or less.

[0025] In general formula (a3), R 4a are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, preferably 12 or less, more preferably 8 or less, and even more preferably 3 or less, and —(CO)—R 5a and R 5a is a hydrocarbon group having 1 to 30 carbon atoms, preferably 12 or less, more preferably 8 or less, and even more preferably 3 or less, preferably an alkyl or alkenyl group, and preferably an alkyl group. From the viewpoint of improving hydrophilicity, s is an integer of 0 or more and 3 or less, preferably 2 or less, and more preferably 1 or less. From the viewpoint of improving hydrophilicity, t is an integer of 0 or more and 3 or less, preferably 2 or less, and more preferably 1 or less. From the viewpoint of improving hydrophilicity, u is an integer of 0 or more and 20 or less, preferably 10 or less, and more preferably 5 or less.

[0026] In general formula (a2), R 7a are each independently a hydrocarbon group having 6 or less carbon atoms, preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and even more preferably 1 carbon atom, preferably an alkyl or alkenyl group, more preferably an alkyl group. R 7a is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Examples of the alkyl group include a group selected from the group consisting of butyl, n-butyl, tert-butyl, pentyl, and phenyl. Among these, a methyl group is preferred. In general formula (a2), R 8a The alkylene group has 10 or less carbon atoms, preferably 8 or less, more preferably 5 or less, even more preferably 4 or less, still more preferably 3 or less, and 1 or more carbon atoms. R 8ais, for example, a group selected from a methanediyl group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, an n-propane-1,3-diyl group, and an n-propane-1,2-diyl group. Among these, a group selected from a methanediyl group, an ethane-1,2-diyl group, an n-propane-1,3-diyl group, and an n-propane-1,2-diyl group is preferred, and an n-propane-1,3-diyl group is more preferred.

[0027] In the general formula (a2), X is —O—(AO) e R 3a , a group selected from the general formula (a3), and from the viewpoint of reducing bubble marks in the hydraulic composition, preferably -O-(AO) e R 3a is. -O-(AO) e R 3a In the formula, e, AO, and R 3a are the same as those described above. In general formula (a3), R 4a , s, t, and u are the same as those in the above-described embodiments.

[0028] X is -O- (AO) e R 3a Examples of the modified silicone compound include the following commercially available products. KF6123, KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-640, KF-642, KF-643, KF-644, KF6204, KF-6011, and KF-6043 manufactured by Shin-Etsu Chemical Co., Ltd. SF1188SAfluid, Silsoft840 fluid, Silsoft860 fluid, Silsoft870 fluid, Silsoft875fluid, Silsoft876 fluid, Silsoft895 manufactured by MOMENTIVE. DOWSIL 501W,Additive,DOWSIL FZ-2104,DOWSIL FZ-2123,DOWSIL L-7604,SYLGARD OFX-0309 Fluid,XIAMETER OFX-5211,XIAMETER OFX-0193 Fluid,DOWSIL SH3746 Fluid,DOWSIL8032,DOWSIL manufactured by DOW FZ-2215. Examples of modified silicone compounds in which X is represented by general formula (a3) ​​include the following commercially available products. Shin-Etsu Chemical Co., Ltd. KF-6100, KF-6104

[0029] The kinematic viscosity of the modified silicone of component (A) is preferably 1 mm at 25°C from the viewpoint of improving the surface appearance of the hydraulic composition and improving workability. 2 / s or more, preferably 5 mm 2 / s or more, more preferably 10 mm 2 / s or more, and preferably 1,000,000 mm 2 / s or less, preferably 50,000 mm 2 / s or less, more preferably 10,000 mm 2 / s or less, and even more preferably 5000 mm 2 / s or less, and even more preferably 1000 mm 2 / s or less, and even more preferably 400 mm 2 / s or less, and even more preferably 300 mm 2 / s or less. The kinematic viscosity of the modified silicone may be a catalog value, or may be measured using, for example, a fully automatic micro kinematic viscometer (manufactured by Viscotec Co., Ltd.).

[0030] From the viewpoint of improving the surface appearance of the hydraulic composition and improving mixability, the HLB of the modified silicone of component (A) is preferably 5 or more, more preferably 7 or more, even more preferably 10 or more, and even more preferably 12 or more, and is preferably 17 or less, more preferably 15 or less. In the present invention, HLB is an abbreviation for Hydrophile Lipophile Balance, and serves as an index for determining whether a compound is hydrophilic or lipophilic. The HLB value may be a value found in academic literature or a catalog value, or the HLB value may be calculated. In this case, the HLB value is calculated using the Griffin method represented by the following formula: HLB = (sum of molecular weights of hydrophilic parts / molecular weight) × 20 Examples of the hydrophilic group include a hydroxy group, an ethyleneoxy group, and an oxypropylene group.

[0031] <Composition, etc.> When the surface aesthetics improver composition for hydraulic compositions of the present invention is incorporated into a hydraulic composition to improve the aesthetics of the surface of the hardened hydraulic composition, it is preferable that the surface aesthetics improver composition for hydraulic compositions of the present invention further contains (B) a cement dispersant (hereinafter referred to as component (B)) from the viewpoint of the effect of reducing the number of air bubble traces on the surface of the hardened hydraulic composition.

[0032] The cement dispersant of component (b) may be one or more compounds selected from naphthalene polymers, polycarboxylic acid polymers, lignin sulfonic acid polymers, melamine polymers, polymers containing a phosphate group in the structure, and polymers containing an aromatic having a polyalkyleneoxy group, and from the viewpoint of the effect of reducing the number of bubble traces on the surface of the hardened hydraulic composition, polycarboxylic acid polymers are preferred.

[0033] Examples of polycarboxylic acid polymers that can be used include copolymers of a monoester of polyalkylene glycol and (meth)acrylic acid with a carboxylic acid such as (meth)acrylic acid (for example, compounds described in JP-A-8-12397), copolymers of an unsaturated alcohol having polyalkylene glycol with a carboxylic acid such as (meth)acrylic acid, and copolymers of an unsaturated alcohol having polyalkylene glycol with a dicarboxylic acid such as maleic acid. Here, (meth)acrylic acid refers to a carboxylic acid selected from acrylic acid and methacrylic acid, which may be present in combination.

[0034] Examples of the polycarboxylic acid polymer (hereinafter also referred to as (b1)) include a copolymer containing, as constituent monomers, a monomer (11b) represented by the following general formula (11b) and a monomer (12b) represented by the following general formula (12b):

[0035] [ka]

[0036] [During the ceremony, R 11b , R 12b , R 13b may be the same or different, and may be a hydrogen atom, a methyl group, or (CH2) r COOM 12 and (CH2) r COOM 12 COOM 11 or other (CH2) r COOM 12 and an anhydride may be formed, in which case the M 11 , M 12 does not exist. M 11 , M 12 may be the same or different, and may be a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroalkyl group, or an alkenyl group r: a number between 0 and 2 indicates.]

[0037] [ka]

[0038] [During the ceremony, R 14b , R 15b , R 16b : may be the same or different, and may be a hydrogen atom, a methyl group, (CH2) s COOM 13 , or (CH2) q1 (CO) p1 O(AO)n1 -R 17b R 17b : 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, a number of 4 or more and 200 or less q1: A number between 0 and 2 p1: 0 or 1 M 13 : hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group or alkenyl group s: a number between 0 and 2 indicates.]

[0039] In the general formula (11b), from the viewpoint of availability, R 11b is preferably a hydrogen atom. In the general formula (11b), from the viewpoint of availability, R 12b is preferably a hydrogen atom or a methyl group. In the general formula (11b), from the viewpoint of availability, R 13b is preferably a hydrogen atom. (CH2) r COOM 12 About COOM 11 or other (CH2) r COOM 12 and an acid anhydride may be formed, in which case, M 11 , M 12 does not exist. M 11 and M 12 may be the same or different and are a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroalkyl group, or an alkenyl group. M 11 and M 12 The alkyl group, the hydroalkyl group, and the alkenyl group each preferably have 1 to 4 carbon atoms. M 11 and M 12may be the same or different and are preferably a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, or an alkylammonium group, more preferably a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), or an ammonium group, even more preferably a hydrogen atom, an alkali metal, or an alkaline earth metal (1 / 2 atom), and still more preferably a hydrogen atom or an alkali metal. (CH2) in general formula (11b) r COOM 12 r is preferably 0.

[0040] In general formula (12b), R 14b is preferably a hydrogen atom from the viewpoint of availability. In general formula (12b), R 15b From the viewpoints of availability and dispersibility in the hydraulic composition, is preferably a hydrogen atom or a methyl group, more preferably a methyl group. In general formula (12b), R 16b is preferably a hydrogen atom from the viewpoint of availability. In general formula (12b), R 17b From the viewpoint of availability, is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. In the general formula (12b), AO is preferably a group selected from an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group, more preferably an ethyleneoxy group, from the viewpoint of dispersibility of the hydraulic composition. AO preferably contains an ethyleneoxy group. In general formula (12b), n1 is the average number of moles of AO added, and from the viewpoint of dispersibility of the hydraulic composition, it is preferably 4 or more, more preferably 20 or more, and preferably 150 or less, more preferably 120 or less, even more preferably 80 or less, and even more preferably 40 or less. Furthermore, the AOs in the average n1 repeating units may be different, and may be randomly added, block added, or a mixture of these. It is preferable that 70 mol % or more, more preferably 80 mol % or more, even more preferably 90 mol % or more of EO groups are ethyleneoxy groups (EO groups), and furthermore, all AO groups are EO groups. For example, AO may contain propyleneoxy, butyleneoxy, etc. in addition to EO. In the general formula (12b), q1 is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0, from the viewpoint of dispersibility of the hydraulic composition. In the general formula (12b), p1 is preferably 1 from the viewpoint of dispersibility of the hydraulic composition. In general formula (12b), M 13 is 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. M 13 The alkyl group, the hydroalkyl group, and the alkenyl group each preferably have 1 to 4 carbon atoms. M 13 is preferably a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), an ammonium group, or an alkylammonium group, more preferably a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), or an ammonium group, even more preferably a hydrogen atom, an alkali metal, or an alkaline earth metal (1 / 2 atom), and still more preferably a hydrogen atom or an alkali metal. In the general formula (12b), (CH2) s COOM 13 The s is preferably 0.

[0041] The proportion of the monomer (11b) in the total amount of the monomer (11b) and the monomer (12b) in all the constituent monomers of the copolymer (b1) is, from the viewpoint of dispersibility in the hydraulic composition, preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and still more preferably 20% by mass or less.

[0042] From the viewpoint of dispersibility in the hydraulic composition, the proportion of the monomer (11b) in all the constituent monomers of the copolymer (b1) is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and still more preferably 20% by mass or less.

[0043] The total amount of the monomer (11b) and the monomer (12b) in all the constituent monomers of the copolymer (b1) is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and preferably 100% by mass or less, from the viewpoint of dispersibility in the hydraulic composition. This total amount may be 100% by mass.

[0044] From the viewpoint of dispersibility in the hydraulic composition, the weight average molecular weight of the copolymer (b1) is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 20,000 or more, still more preferably 30,000 or more, still more preferably 40,000 or more, and preferably 100,000 or less, more preferably 80,000 or less, even more preferably 60,000 or less.

[0045] The weight average molecular weight of the copolymer was measured by gel permeation chromatography (GPC) under the following conditions. *GPC conditions Apparatus: GPC (HLC-8320GPC) manufactured by Tosoh Corporation Column: G4000PWXL + G2500PWXL (Tosoh Corporation) Eluent: 0.2M phosphate buffer / CH3CN=9 / 1 Flow rate: 1.0mL / min Column temperature: 40℃ Detection: RI Sample size: 0.2 mg / mL Standard substance: Polyethylene glycol equivalent (monodisperse polyethylene glycol with known molecular weight, molecular weight 250,000, 145,000, 87,500, 46,000, 24,000)

[0046] The copolymer (b1) may contain, in addition to the monomer (11b) and the monomer (12b), one or more monomers (13b) copolymerizable with the monomer (11b) and / or the monomer (12b). Examples of the monomer (13b) include acrylic esters. In the copolymer (b1), the total of the monomer (11b) and the monomer (12b), or the total of the monomer (11b), the monomer (12b), and the monomer (13b), may account for 100% by mass of all structural units.

[0047] When the surface appearance improver composition for hydraulic compositions of the present invention contains the components (A) and (B), the content of the component (A) in the composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and preferably 60% by mass or less, more preferably 30% by mass or less, even more preferably 10% by mass or less, from the viewpoint of the effect of reducing the amount of bubble traces on the surface of the cured hydraulic composition.

[0048] When the surface appearance improver composition for hydraulic compositions of the present invention contains component (B), the content of component (B) in the composition is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, from the viewpoint of the effect of reducing the amount of bubble traces on the surface of the cured hydraulic composition.

[0049] When the surface appearance improver composition for hydraulic compositions of the present invention contains the component (B), the mass ratio (A) / (B) of the content of the component (A) to the content of the component (B) is, from the viewpoint of the effect of reducing the number of bubble traces on the surface of the hydraulic composition cured body, preferably 0.01 or more, more preferably 0.03 or more, even more preferably 0.06 or more, still more preferably 0.10 or more, and preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, still more preferably 5 or less, still more preferably 1 or less, still more preferably 0.5 or less, still more preferably 0.2 or less.

[0050] The surface appearance improver composition for a hydraulic composition of the present invention can contain water. That is, the surface appearance improver composition for a hydraulic composition of the present invention may be in a liquid state, or may even be an aqueous solution. When the surface appearance improver composition for hydraulic compositions of the present invention contains water, the content of water is preferably 0% by mass or more, more preferably 10% by mass or more, and preferably 90% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 30% by mass or less, from the viewpoint of reducing viscosity.

[0051] The surface appearance improver composition for hydraulic compositions of the present invention exhibits an excellent effect of improving the surface appearance of the cured product of the hydraulic composition even in an embodiment containing the component (A), but as a specific embodiment, it can further contain an antifoaming agent. The antifoaming agent is not particularly limited as long as it does not affect the effects of the present invention, and examples thereof include antifoaming agents with an HLB of less than 3 (excluding component (A)). Specific examples of the defoaming agent include polyalkylene glycol alkyl ether-based defoaming agents, polyalkylene glycol alkyl ester-based defoaming agents, polyol polyether-based defoaming agents, polyalkylene glycol block polymer-based defoaming agents, and silicone-based defoaming agents (excluding component (A)). Among these, defoaming agents having an HLB of less than 3 are further included. From the viewpoint of adjusting the amount of air in the hydraulic composition and the storage stability of the surface appearance improver composition for hydraulic composition, for example, the defoaming agent is preferably one or more selected from polyalkylene glycol alkyl ether-based defoaming agents, polyalkylene glycol alkyl ester-based defoaming agents, and silicone-based defoaming agents (excluding component (A)), and more preferably a silicone-based defoaming agent (excluding component (A)).

[0052] The surface appearance improver composition for hydraulic compositions of the present invention may contain, as optional components, components such as water-soluble polymer compounds, air-entraining agents, cement wetting agents, expanding agents, retarders, quick-setting agents, thickeners, flocculants, strength enhancers, hardening accelerators, compatibilizers, and preservatives (however, excluding those corresponding to the above-mentioned components (A) and (B)).

[0053] When the surface appearance improver composition for hydraulic compositions of the present invention is applied to a formwork to improve the surface appearance of the hydraulic composition filled in the formwork after it has hardened, it preferably further contains (C) a mold release agent (hereinafter referred to as component (C)).

[0054] Examples of the release agent for component (C) include (1) mineral oils such as kerosene, diesel, spin oil, transformer oil, machine oil, turbine oil, gear oil, bearing oil, and electrical insulating oil, (2) synthetic oils such as polyalkylene glycol, (3) vegetable oils such as rapeseed, coconut, palm, and soybean oil, (4) fats and oils, and (5) fatty acid esters, and one or more of these can be used. Of these, component (C) is preferably one or more selected from mineral oils, more preferably one or more selected from spin oils and machine oils, and even more preferably machine oil.

[0055] When the surface appearance improver composition for hydraulic compositions of the present invention contains the components (A) and (C), the content of the component (A) in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, from the viewpoint of the effect of reducing the amount of bubble traces on the surface of the cured hydraulic composition.

[0056] When the surface appearance improver composition for hydraulic compositions of the present invention contains component (C), the content of component (C) in the composition is, from the viewpoint of improving releasability, preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and preferably 98% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less.

[0057] When the surface appearance improver composition for hydraulic composition of the present invention contains the component (C), the mass ratio (A) / (C) of the content of the component (A) to the content of the component (C) is preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and preferably 20 or less, more preferably 10 or less, even more preferably 5 or less, from the viewpoint of the effect of reducing the number of bubble traces on the surface of the cured hydraulic composition.

[0058] The surface aesthetics improver composition for hydraulic compositions of the present invention is incorporated into a hydraulic composition, and the hydraulic composition is filled into a form and cured, or is applied to a form and then filled with the hydraulic composition and cured. This effectively controls the behavior of air bubbles in the hydraulic composition, which cause air bubble marks on the surface of a hardened hydraulic composition, adhering to the form or to a release agent applied to the form surface, thereby suppressing the occurrence of air bubble marks on the surface of the hardened hydraulic composition and improving the aesthetics of the surface. That is, the surface appearance improver composition for a hydraulic composition of the present invention may be a surface bubble mark inhibitor composition for a hydraulic composition. The surface bubble mark inhibitor composition for a hydraulic composition of the present invention is the same as the surface aesthetics improver composition for a hydraulic composition of the present invention, and the aspects described for the surface aesthetics improver composition for a hydraulic composition of the present invention can be applied as appropriate.

[0059] [Method for producing a surface appearance improver composition for hydraulic compositions] The present invention provides a method for producing a surface appearance improver composition for a hydraulic composition, which comprises mixing component (A). By this production method, the surface appearance improver composition for a hydraulic composition of the present invention containing component (A) is produced. In the method for producing the surface appearance improver composition for hydraulic compositions of the present invention, component (B) can be further mixed. In the method for producing the surface appearance improver composition for hydraulic compositions of the present invention, water can be further mixed. In the method for producing the surface appearance improver composition for hydraulic compositions of the present invention, component (C) can be further mixed. Specific examples and preferred embodiments of the components (A), (B), and (C) used in the method for producing the surface appearance improver composition for hydraulic compositions of the present invention are the same as those described for the surface appearance improver composition for hydraulic compositions of the present invention. The matters described in relation to the surface appearance improver composition for hydraulic compositions of the present invention can be appropriately applied to the method for producing the surface appearance improver composition for hydraulic compositions of the present invention. In the method for producing the surface appearance improver composition for hydraulic compositions of the present invention, the contents of the components and their mass ratios described in the surface appearance improver composition for hydraulic compositions of the present invention can be appropriately applied by replacing the contents of the components with the mixing amounts.

[0060] [Hydraulic composition] The present invention provides a hydraulic composition containing component (A), hydraulic powder, and water. The hydraulic composition of the present invention may further contain component (B). Specific examples and preferred embodiments of the components (A) and (B) used in the hydraulic composition of the present invention are the same as those described in the surface appearance improver composition for hydraulic composition of the present invention. The matters described in relation to the surface appearance improver composition for hydraulic compositions of the present invention and the method for producing the same can be appropriately applied to the hydraulic composition of the present invention.

[0061] <Hydraulic powder> The hydraulic powder used in the hydraulic composition of the present invention is a powder that hardens when mixed with water. Examples 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). Among these, from the viewpoint of strength development, one or more cements selected from early-strength Portland cement, ordinary Portland cement, sulfate-resistant Portland cement, and white Portland cement are preferred, and one or more cements selected from early-strength Portland cement and ordinary Portland cement are more preferred. The hydraulic powder may also contain blast furnace slag, fly ash, silica fume, anhydrous gypsum, etc., or non-hydraulic limestone fine powder. The hydraulic powder may also contain blast furnace cement, fly ash cement, or silica fume cement, which is a mixture of cement with blast furnace slag, fly ash, silica fume, etc. Clay such as bentonite may also be included. The hydraulic compositions finally obtained by adding sand, sand and gravel as aggregates to these powders are generally called mortar, concrete, etc.

[0062] <Aggregate> The hydraulic composition of the present invention may contain aggregate. Examples of aggregates include one or more types of aggregate selected from fine aggregates and coarse aggregates. Examples of fine aggregates include those specified under No. 2311 in JIS A0203-2014. Examples of fine aggregates include river sand, land sand, mountain sand, sea sand, lime sand, silica sand, and crushed sands thereof, blast furnace slag fine aggregate, ferronickel slag fine aggregate, lightweight fine aggregate (artificial and natural), and recycled fine aggregate. Examples of coarse aggregates include those specified under No. 2312 in JIS A0203-2014. Examples of coarse aggregates include river gravel, land gravel, mountain gravel, sea gravel, lime gravel, crushed stones thereof, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural), and recycled coarse aggregate. Different types of fine aggregates and coarse aggregates may be used in combination, or a single type may be used.

[0063] <Composition, etc.> In the hydraulic composition of the present invention, the content of component (A) is preferably 0.0001 part by mass or more, more preferably 0.001 part by mass or more, even more preferably 0.01 part by mass or more, and preferably 5 parts by mass or less, more preferably 1 part by mass or less, even more preferably 0.5 parts by mass or less, still more preferably 0.1 part by mass or less, and still more preferably 0.05 part by mass or less, per 100 parts by mass of hydraulic powder, from the viewpoint of the effect of reducing the amount of bubble traces on the surface of the hardened body.

[0064] In the hydraulic composition of the present invention, the content of component (A) is preferably 0.00001 part by mass or more, more preferably 0.0001 part by mass or more, even more preferably 0.0005 part by mass or more, and preferably 0.05 part by mass or less, more preferably 0.01 part by mass or less, even more preferably 0.005 part by mass or less, per 100 parts by mass of the hydraulic composition, from the viewpoint of reducing the amount of bubble traces on the surface of the cured product.

[0065] When the hydraulic composition of the present invention contains component (B), the content of component (B) is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and even more preferably 0.10 part by mass or more, relative to 100 parts by mass of the hydraulic powder, from the viewpoint of the fluidity of the hydraulic composition, and is preferably 2.0 parts by mass or less, more preferably 1.0 part by mass or less, even more preferably 0.50 part by mass or more, and even more preferably 0.30 parts by mass or less, from the viewpoint of economy.

[0066] When the hydraulic composition of the present invention contains the component (B), the mass ratio (A) / (B) of the content of the component (A) to the content of the component (B) is, from the viewpoint of the effect of reducing the number of bubble traces on the surface of the cured body, preferably 0.01 or more, more preferably 0.03 or more, even more preferably 0.06 or more, still more preferably 0.10 or more, and preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, still more preferably 5 or less, still more preferably 1 or less, still more preferably 0.5 or less, still more preferably 0.2 or less.

[0067] In the hydraulic composition of the present invention, the mass percentage of the water content to the hydraulic powder content (water / hydraulic powder ratio (W / P)) is preferably 60 mass% or less, more preferably 50 mass% or less, even more preferably 45 mass% or less, and preferably 10 mass% or more, more preferably 20 mass% or more, even more preferably 30 mass% or more, from the viewpoint of the effect of reducing the amount of bubble traces on the surface of the hardened body. Here, the water / hydraulic powder ratio (W / P) is the mass percentage (mass%) of water to hydraulic powder in the hydraulic composition, and is calculated as water / hydraulic powder x 100. The water / hydraulic powder ratio is calculated based on the amount of powder that has the physical property of hardening through a hydration reaction. Furthermore, when the hydraulic powder is cement, W / P may be expressed as W / C. In addition, when the hydraulic powder includes powders selected from powders with pozzolanic action, powders with latent hydraulic properties, and stone powder (calcium carbonate powder) in addition to powders such as cement that harden through hydration, the amounts of these powders are also included in the amount of hydraulic powder in this invention. Furthermore, when the powder that hardens through hydration contains a high-strength admixture, the amount of the high-strength admixture is also included in the amount of hydraulic powder. This also applies to other parts by mass that involve the mass of the hydraulic powder.

[0068] In the hydraulic composition of the present invention, the mass percentage of the hydraulic powder content to the aggregate content (hydraulic powder content / aggregate content x 100) is preferably 60 mass% or less, more preferably 45 mass% or less, even more preferably 30 mass% or less, still more preferably 25 mass% or less, and preferably 5 mass% or more, more preferably 10 mass% or more, even more preferably 15 mass% or more, from the viewpoint of the effect of reducing the amount of bubble traces on the surface of the hardened body.

[0069] 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, for example, preferably 0% or more, more preferably 8.0% or less.

[0070] 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 used per 1 m of concrete. 3 The coarse aggregate ratio is the ratio of the volume (including voids) of the coarse aggregate in the concrete. From the viewpoint of the properties of concrete, the coarse aggregate ratio is preferably 9.0% by mass or less, more preferably 8.0% by mass or less, even more preferably 7.0% by mass or less, and preferably 5.0% by mass or more, more preferably 5.5% by mass or more, and even more preferably 6.0% by mass or more. The coarse aggregate ratio can be measured in accordance with JIS A 1102. When the hydraulic composition is concrete, the amount of fine aggregate used is preferably 500 kg / m from the viewpoint of improving filling properties into forms, etc. 3 More preferably, 600 kg / m 3 More preferably, 700 kg / m 3 or more, and preferably 1000 kg / m 3 Less than or equal to 900 kg / m 3 When the hydraulic composition is mortar, the amount of fine aggregate used is preferably 800 kg / m 3 More preferably, 900 kg / m 3 More preferably, 1000 kg / m 3 or more, and preferably 2000 kg / m 3 or less, more preferably 1800 kg / m 3 or less, more preferably 1700 kg / m 3 The coarse particle ratio of the fine aggregate is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, even more preferably 3.5% by mass or less, from the viewpoint of improving the packing property into forms, etc., and is preferably 1.0% by mass or more, more preferably 1.5% by mass or more, even more preferably 2.0% by mass or more. The coarse particle ratio can be measured in accordance with JIS A 1102.

[0071] The hydraulic composition of the present invention may further contain other components in addition to the above components, such as retarders, thickeners, air-entraining agents, waterproofing agents, fluidizing agents, early strengthening agents, antifoaming agents, compatibilizers, preservatives, etc. (excluding those corresponding to the above components (A) and (B)). Examples of early-strengthening agents include compounds selected from alkali metal and alkaline earth metal hydrochlorides, sulfates, nitrates, nitrites, cyanates, thiocyanates, thiosulfates, and formates, or organic compounds selected from alkanolamines, glycerin derivatives, formaldehyde derivatives, and catechol derivatives, and nanoparticles of Portland cement hydration products (CSH, calcium carbonate and calcium hydroxide).

[0072] The hydraulic composition of the present invention may be used for concrete or mortar. The hydraulic composition of the present invention is useful in any field such as self-leveling, refractories, plaster, lightweight or heavy-duty concrete, air entrainment, repair, prepacked, trame, ground improvement, grout, and cold weather use.

[0073] [Method for producing hydraulic composition] The present invention provides a method for producing a hydraulic composition, which comprises mixing component (A), a hydraulic powder, and water. In the method for producing the hydraulic composition of the present invention, component (B) can be further mixed. In the method for producing the hydraulic composition of the present invention, aggregate can be further mixed. Specific examples and preferred embodiments of the components (A) and (B) used in the method for producing the hydraulic composition of the present invention are the same as those described in the surface appearance improver composition for hydraulic compositions of the present invention, and specific examples and preferred embodiments of the hydraulic powder and aggregate are the same as those described in the hydraulic composition of the present invention. In the method for producing the hydraulic composition of the present invention, the hydraulic powder is mixed so that the W / P ratio falls within the range described for the hydraulic composition of the present invention. The amount of aggregate used (mixed amount) and the mass percentages of the hydraulic powder content and aggregate content are also within the same ranges as described for the hydraulic composition of the present invention. The matters described in relation to the surface appearance improver composition for hydraulic compositions of the present invention, the method for producing the same, and the hydraulic composition of the present invention can be appropriately applied to the method for producing the hydraulic composition of the present invention. In the method for producing the hydraulic composition of the present invention, the contents of the components and their mass ratios described for the hydraulic composition of the present invention can be appropriately applied by replacing the contents of the components with the mixing amounts.

[0074] In the method for producing the hydraulic composition of the present invention, for example, the component (A) of the present invention and the optional component (B) may be mixed separately with a hydraulic powder to prepare the hydraulic composition, or if the component (A) of the present invention and the optional component (B) are mixed in advance, there is no need to install a new tank, and the combined product may be mixed with the hydraulic powder. That is, in the method for producing the hydraulic composition of the present invention, the surface appearance improver composition for hydraulic compositions of the present invention may be mixed with the hydraulic powder.

[0075] Specifically, in the method for producing the hydraulic composition of the present invention, the amount of the surface appearance improver composition for hydraulic compositions of the present invention mixed, in terms of parts by mass of solid content, relative to 100 parts by mass of hydraulic powder is preferably 0.0001 parts by mass or more, more preferably 0.001 parts by mass or more, even more preferably 0.01 parts by mass or more, and preferably 10 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1 part by mass or less, from the viewpoint of the effect of reducing the amount of bubble traces on the surface of the hardened body.

[0076] In the method for producing the hydraulic composition of the present invention, mixing may be carried out using a mixer such as a mortar mixer, a forced twin-screw mixer, etc. The mixing time is, for example, preferably 1 minute or more, more preferably 2 minutes or more, and preferably 5 minutes or less, more preferably 3 minutes or less.

[0077] <Method for producing a hardened product of hydraulic composition> The present invention provides a method for producing a hardened product of a hydraulic composition (hereinafter referred to as method (1) for producing a hardened product of a hydraulic composition of the present invention), which comprises the steps of: preparing a hydraulic composition by mixing component (A), hydraulic powder, and water; filling the prepared hydraulic composition into a formwork or a formwork coated with a release agent of component (C), and hardening the composition; and demolding the hardened hydraulic composition. The present invention also provides a method for producing a hardened product of a hydraulic composition (hereinafter referred to as method for producing a hardened product of a hydraulic composition (2)), which comprises the steps of: preparing a hydraulic composition by mixing hydraulic powder and water; filling the prepared hydraulic composition into a formwork coated with a surface appearance improver composition for hydraulic compositions of the present invention, which contains component (A) and component (C), and hardening the composition; and demolding the hardened hydraulic composition. The matters described in the surface appearance improver composition for hydraulic compositions and the method for producing the same, and the hydraulic composition and the method for producing the same of the present invention can be appropriately applied to the method for producing a cured product of the hydraulic composition of the present invention.

[0078] In the method (1) for producing a hardened product of the hydraulic composition of the present invention, in the step of preparing the hydraulic composition by mixing component (A), hydraulic powder, and water, component (B) can be further mixed. Furthermore, in the step of preparing the hydraulic composition, aggregate can be further mixed. Specific examples and preferred aspects of component (A) and component (B) are the same as those described in the surface appearance improver composition for hydraulic compositions of the present invention, and specific examples and preferred aspects of the hydraulic powder and aggregate are the same as those described in the hydraulic composition of the present invention. In the process of preparing the hydraulic composition, the hydraulic powder is mixed so that the W / P ratio falls within the range described for the hydraulic composition of the present invention. The amount of aggregate used (mixed amount) and the mass percentage of the hydraulic powder content and the aggregate content also fall within the ranges described for the hydraulic composition of the present invention. In the process of preparing the hydraulic composition, the contents of the components and their mass ratios described for the hydraulic composition of the present invention can be appropriately applied by replacing the contents of the components with the mixing amounts. The step of preparing the hydraulic composition included in the method for producing a hardened product of the hydraulic composition of the present invention may be the same as that described in the method for producing the hydraulic composition of the present invention.

[0079] The method (1) for producing a hardened product of the hydraulic composition of the present invention includes, for example, a step of filling a formwork with the hydraulic composition prepared in the previous step and hardening the composition. Examples of the formwork used in the method for producing a hardened product of the hydraulic composition of the present invention include formwork for buildings and formwork for concrete products. Methods for filling the formwork include a method of directly pouring the composition from a mixer and a method of pumping the hydraulic composition into the formwork.

[0080] In the method (1) for producing the hardened product of the hydraulic composition of the present invention, the form used may be preferably coated with a mold release agent (component (C)) from the viewpoint of, for example, the releasability of the hardened product of the hydraulic composition when demolded. Component (C) is the same as that described in the surface appearance improver composition for hydraulic composition of the present invention.

[0081] In the method (2) for producing a hardened product of the hydraulic composition of the present invention, in the step of mixing hydraulic powder and water to prepare the hydraulic composition, component (B) can be further mixed. In the step of preparing the hydraulic composition, aggregate can be further mixed. Specific examples and preferred aspects of component (B) are the same as those described in the surface appearance improver composition for hydraulic compositions of the present invention, and specific examples and preferred aspects of the hydraulic powder and aggregate are the same as those described in the hydraulic composition of the present invention. In the process of preparing the hydraulic composition, the hydraulic powder is mixed so that the W / P ratio falls within the range described for the hydraulic composition of the present invention. The amount of aggregate used (mixed amount) and the mass percentage of the hydraulic powder content and the aggregate content also fall within the ranges described for the hydraulic composition of the present invention. In the process of preparing the hydraulic composition, the contents of the components and their mass ratios described for the hydraulic composition of the present invention can be appropriately applied by replacing the contents of the components with the mixing amounts. The step of preparing the hydraulic composition included in the method for producing a hardened product of the hydraulic composition of the present invention may be the same as that described in the method for producing the hydraulic composition of the present invention.

[0082] In the method (2) for producing a hardened product of the hydraulic composition of the present invention, the surface appearance improver composition for hydraulic composition of the present invention containing component (A) and component (C) is applied to a formwork, and the hydraulic composition is filled into the formwork and hardened. The surface appearance improver composition for hydraulic compositions of the present invention, which contains the component (A) and the component (C), is the same as the surface appearance improver composition for hydraulic compositions of the present invention, and the aspects described for the surface appearance improver composition for hydraulic compositions of the present invention can be applied as appropriate. The surface appearance improver composition for hydraulic compositions of the present invention may be applied to the formwork by spraying with a sprayer, in addition to being applied to the formwork by a brush or a mop. The amount of the surface appearance improver composition for hydraulic compositions of the present invention to be applied to a form is preferably 0.5 g / m from the viewpoints of mold releasability and surface appearance. 2 More preferably, 1 g / m 2 More preferably, 1.5 g / m 2 or more, and preferably 40 g / m 2 Less than 38 g / m 2 More preferably 36 g / m or less 2 The following is the result.

[0083] In the methods (1) and (2) for producing a hardened product of the hydraulic composition of the present invention, for example, when the hydraulic composition of the present invention is filled into a form and cured, heat curing can be carried out to accelerate hardening. Here, heat curing can be carried out by maintaining the hydraulic composition at a temperature of 40°C or higher and 80°C or lower to accelerate hardening, for example.

[0084] The hardened hydraulic composition can be demolded to obtain a hardened product of the hydraulic composition of the present invention. At the time of demolding, it is preferable that the hardened product of the hydraulic composition has sufficient compressive strength. The compressive strength at the time of demolding is preferably equal to or greater than the strength specified in, for example, "2023 Japan Society of Civil Engineers Standard Specifications [Construction Section] Commentary Table 8.8.1."

[0085] Examples of hardened products of hydraulic compositions using formwork for concrete products 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, and girder products for bridge piers, and examples of architectural products include curtain wall products and architectural component products used for columns, beams, and floorboards.

[0086] In the present invention, in the preparation of the hydraulic composition, the time from bringing the hydraulic powder into contact with water to demolding is, for example, 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.

[0087] <Method for improving the surface appearance of hydraulic composition> The present invention provides a method for improving the surface appearance of a hydraulic composition (hereinafter referred to as method (1) for improving the surface appearance of a hydraulic composition of the present invention), which comprises mixing component (A), hydraulic powder, and water. In the method (1) for improving the surface appearance of a hydraulic composition of the present invention, component (B) can be further mixed. In the method (1) for improving the surface appearance of a hydraulic composition of the present invention, aggregate can be further mixed. Specific examples and preferred embodiments of the components (A) and (B) used in the method (1) for improving the surface appearance of a hydraulic composition of the present invention are the same as those described in the surface appearance improver composition for a hydraulic composition of the present invention, and specific examples and preferred embodiments of the hydraulic powder and aggregate are the same as those described in the hydraulic composition of the present invention. In the method for improving the surface appearance of a hydraulic composition of the present invention, the hydraulic powder is mixed so that the W / P ratio falls within the range described for the hydraulic composition of the present invention. The amount of aggregate used (mixed amount) and the mass percentages of the hydraulic powder content and aggregate content are also within the same ranges as described for the hydraulic composition of the present invention. In the method (1) for improving the surface appearance of a hydraulic composition of the present invention, the contents of the components and their mass ratios described for the hydraulic composition of the present invention can be appropriately applied by replacing the contents of the components with the mixing amounts. The matters described in the hydraulic composition surface appearance improver composition and its manufacturing method, the hydraulic composition and its manufacturing method, and the method for manufacturing a cured product of the hydraulic composition of the present invention can be appropriately applied to the hydraulic composition surface appearance improving method (1) of the present invention.

[0088] In the method for improving the surface appearance of a hydraulic composition of the present invention, the preparation of the hydraulic composition may be the same as that described in the method for producing the hydraulic composition of the present invention. Furthermore, the method for producing a hardened product of the hydraulic composition prepared after the hydraulic composition is prepared may be the same as that described in the method for producing a hardened product of the hydraulic composition of the present invention.

[0089] The present invention provides a method for improving the surface appearance of a hydraulic composition (hereinafter referred to as the method for improving the surface appearance of a hydraulic composition of the present invention (2)), which comprises applying a surface appearance improver composition for a hydraulic composition containing components (A) and (C) to a formwork, and filling the formwork with a hydraulic composition containing hydraulic powder and water. The surface appearance improver composition for hydraulic compositions of the present invention, which contains the component (A) and the component (C), is the same as the surface appearance improver composition for hydraulic compositions of the present invention, and the aspects described for the surface appearance improver composition for hydraulic compositions of the present invention can be applied as appropriate. The amount of the surface appearance improver composition for hydraulic compositions of the present invention to be applied to a form is also within the same range as that described in the method (2) for producing a hardened product of the hydraulic composition of the present invention.

[0090] In the method (2) for improving the surface appearance of a hydraulic composition of the present invention, the hydraulic composition containing hydraulic powder and water can further contain component (B). The hydraulic composition can further contain aggregate. Specific examples and preferred aspects of component (B) are the same as those described for the surface appearance improver composition for hydraulic compositions of the present invention, and specific examples and preferred aspects of the hydraulic powder and aggregate are the same as those described for the hydraulic composition of the present invention. The hydraulic powder is contained in the hydraulic composition so that the W / P ratio falls within the range described for the hydraulic composition of the present invention. The amount of aggregate used (mixed amount) and the mass percentage of the hydraulic powder content and the aggregate content also fall within the same ranges as described for the hydraulic composition of the present invention. The content of each component in the hydraulic composition is the same as that described for the hydraulic composition of the present invention. The matters described in the hydraulic composition surface appearance improver composition and its manufacturing method, the hydraulic composition and its manufacturing method, and the method for manufacturing a hardened product of the hydraulic composition of the present invention can be appropriately applied to the hydraulic composition surface appearance improving method (2) of the present invention.

[0091] The methods (1) and (2) for improving the surface appearance of a hydraulic composition of the present invention can effectively control the behavior of air bubbles in the hydraulic composition, which cause air bubble marks on the surface of a hardened hydraulic composition, adhering to a formwork or a release agent applied to the surface of the formwork, thereby reducing air bubble marks on the surface of the hardened hydraulic composition and improving the surface appearance. That is, the method for improving the surface appearance of a hydraulic composition of the present invention may be a method for suppressing bubble marks on the surface of a hydraulic composition. The method for suppressing bubble marks on the surface of a hydraulic composition of the present invention is the same as the method for improving the surface appearance of a hydraulic composition of the present invention, and the matters described in the method for improving the surface appearance of a hydraulic composition of the present invention, the surface appearance improver composition for a hydraulic composition and its manufacturing method of the present invention, the hydraulic composition and its manufacturing method, and the method for manufacturing a hardened product of the hydraulic composition can be appropriately applied to the method for suppressing bubble marks on the surface of a hydraulic composition of the present invention. [Example]

[0092] The components (A) and (B) used in the examples and comparative examples were as follows.

[0093] <Component (A)> A1: Side chain polyether-modified silicone (modified silicone having a repeating unit (a1) represented by general formula (a1) (in general formula (a1), X is -O-(AO) e R 3a , R 2a is an alkylene group with 3 carbon atoms, a is 1, R 1a , R 3a are methyl groups, AO is an ethyleneoxy group, and e is 8.) Kinematic viscosity (25°C) 20mm 2 / s, HLB14) A2: PEG-11 methyl ether dimethicone (side chain polyether modified silicone) (modified silicone having a repeating unit (a1) represented by general formula (a1) (in general formula (a1), X is -O-(AO) e R 3a , R 2a is an alkylene group with 3 carbon atoms, a is 1, R 1a , R 3a are methyl groups, AO is an ethyleneoxy group, and e is 11.) Kinematic viscosity (25°C) 130mm 2 / s, HLB14.5) A3: Polyglyceryl-3 disiloxane dimethicone (modified silicone having a repeating unit (a1) represented by general formula (a1) (X is a group represented by general formula (a3), a is an alkylene group having 3 carbon atoms, R 1a is a methyl group, R 4a is a hydrogen atom, s is 0, t is 1, and u is 3.) Kinematic viscosity (25°C) 40,000 mm 2 / s, HLB5~10) A4: PEG-12 dimethicone (linear polyether-modified silicone) (modified silicone having a repeating unit (a2) represented by general formula (a2) (in general formula (a2), X is -O-(AO) e R 3a , R 8a is an alkylene group with 3 carbon atoms, b is 1, R 3a is a hydrogen atom, R 7ais a methyl group, AO is an ethyleneoxy group, and e is 12.) Kinematic viscosity (25°C) 220mm 2 / s, HLB12.5)

[0094] <(B) component> B1: methacrylic acid / methoxypolyethylene glycol (23) monomethacrylate = 17.3 mass% / 82.7 mass% = 75 mol% / 25 mol%, weight average molecular weight Mw = 60,000 The numbers in parentheses for the above components are the average number of moles of ethyleneoxy groups added.

[0095] The weight average molecular weight of the polycarboxylic acid polymer of component (B) was measured by gel permeation chromatography (GPC) under the following conditions. *GPC conditions Apparatus: GPC (HLC-8320GPC) manufactured by Tosoh Corporation Column: G4000PWXL + G2500PWXL (Tosoh Corporation) Eluent: 0.2M phosphate buffer / CH3CN=9 / 1 Flow rate: 1.0mL / min Column temperature: 40℃ Detection: RI Sample size: 0.2 mg / mL Standard substance: Polyethylene glycol equivalent (monodisperse polyethylene glycol with known molecular weight, molecular weight 250,000, 145,000, 87,500, 46,000, 24,000)

[0096] (1) Preparation of hydraulic composition Coarse aggregate (G), half of the fine aggregate (S), cement (C), and the remaining half of the fine aggregate (S) were charged into a forced twin-shaft mixer (manufactured by IHI Corporation) under the mixing conditions shown in Table 1, and dry-mixed for 10 seconds. Then, mixing water (W) of the following composition was charged, and the mixture was mixed for 90 seconds to prepare a hydraulic composition. The mixing water contained the (A) component, the (B) component, an air-entraining agent (Mighty AE-02, manufactured by Kao Corporation), and an antifoaming agent (Foamlex 797, manufactured by Nicca Chemical Co., Ltd.) shown in Table 2. The concentrations of the components in the mixing water were adjusted so that the blending amounts per 100 parts by mass of cement in the hydraulic composition for components (A) and (B) were the values ​​shown in Table 2, and the blending amounts per 100 parts by mass of cement in the hydraulic composition for the air-entraining agent and the antifoaming agent were 0.03 part by mass and 0.0006 part by mass, respectively. The air content (volume %) in the hydraulic composition obtained above was measured in accordance with JISA1128:2019 and was found to be 4.0 to 5.0%.

[0097] [Table 1]

[0098] The ingredients used in Table 1 are 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 , coarse grain ratio 2.9) G: Coarse aggregate (andesite crushed stone from Nishijima, Hyogo Prefecture (crushed stone with a diameter of 10-20 mm and crushed stone with a diameter of 5-10 mm mixed at a mass ratio of 1:1, density 2.63 g / cm 3 , coarse grain ratio 6.7) In Table 1, W / C is the mass ratio of the amount of water to the amount of cement, and is calculated by [amount of water / amount of cement] x 100 (mass%). Note that the amounts of each component contained in water are minute compared to the amount of hydraulic composition, so these amounts were taken into account when calculating W / C. Furthermore, C / (S+G) is the mass ratio of the amount of cement to the total amount of fine aggregate and coarse aggregate, and is calculated by [amount of cement / total amount of fine aggregate and coarse aggregate] x 100 (mass%).

[0099] (2) Measurement of air bubble traces in hardened hydraulic compositions (2-1) Preparation of hardened hydraulic composition A 0.1 m x 0.2 m x 0.5 m steel form was placed on a table vibrator vibrating at 50 Hz, and the hydraulic composition obtained above was filled in and cured at 20°C. 24 hours after the preparation of the hydraulic composition, the hardened hydraulic composition was removed from the form. An oil-based, straight-type mold release agent, "Parat Mold" (manufactured by Yamaso Chemical Co., Ltd.), was applied to the inside of the form.

[0100] (2-2) Measurement of air bubble traces in hardened hydraulic compositions One surface (0.2 m x 0.5 m) of the removed hardened body was rubbed with a plastic brush to remove the thin skin, and the surface was photographed with a smartphone. Image data was converted to two colors using ImageJ (areas with air bubble traces were black, and other areas were white). The area percentage of the hardened body surface that was occupied by air bubble traces was calculated from the ratio of each color using the following formula, and this was defined as the air bubble trace amount (area %). The results are shown in Table 2. The smaller the air bubble trace amount (area %), the better the surface appearance of the hardened hydraulic composition body. Bubble trace amount (area%) = Bubble trace area (m 2 ) / 0.2m x 0.5m surface area (m 2 ) x 100

[0101] [Table 2]

[0102] In Table 2, the amounts of the (A) and (B) components in each hydraulic composition are the amounts (parts by mass) based on 100 parts by mass of cement (hydraulic powder), and are the amounts of active components (solids). The (A) / (B) (mass ratio) of each hydraulic composition is the mass ratio (A) / (B) of the content of the (A) component to the content of the (B) component in the hydraulic composition.

Claims

1. A surface appearance improver composition for a hydraulic composition, comprising the following component (A): Component (A): a modified silicone having one or more repeating units selected from a repeating unit (a1) represented by general formula (a1) and a repeating unit (a2) represented by general formula (a2). 【Chemistry 1】 [In general formula (a1), R １ａ is a hydrocarbon group having 1 to 6 carbon atoms, and R ２ａ is an alkylene group having 1 to 10 carbon atoms, a is 1 or 0, and * is a bonding site. X is -O-(AO) ｅ R ３ａ and a group selected from the following general formula (a3): 【Chemistry 2】 AO is an alkyleneoxy group having 2 to 4 carbon atoms, e is the average number of moles of AO added, which is a number of 0 to 50, and R ３ａ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ４ａ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or —(CO)—R ５ａ is a group selected from ５ａ is a hydrocarbon group having 1 to 30 carbon atoms, s is an integer of 0 to 3, t is an integer of 0 to 3, and u is an integer of 0 to 20. *-SiR ７ａ ３－ｂ (R ８ａ -X) ｂ (a2) [In general formula (a2), R ７ａ are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R ８ａ are each independently an alkylene group having 1 to 10 carbon atoms, b is an integer of 1 to 3, and * is a bonding site. X is -O-(AO) ｅ R ３ａ and a group selected from the general formula (a3), where AO is an alkyleneoxy group having 2 to 4 carbon atoms, e is the average number of moles of AO added and is a number of 0 to 50, and R ３ａ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ４ａ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or —(CO)—R ５ａ is a group selected from ５ａ is a hydrocarbon group having 1 to 30 carbon atoms, s is an integer of 0 to 3, t is an integer of 0 to 3, and u is an integer of 0 to 20.

2. The surface appearance improver composition for hydraulic compositions according to claim 1, further comprising (B) a cement dispersant.

3. The surface appearance improver composition for a hydraulic composition according to claim 1, further comprising (C) a mold release agent.

4. A hydraulic composition comprising the following component (A), a hydraulic powder, and water: Component (A): a modified silicone having one or more repeating units selected from a repeating unit (a1) represented by general formula (a1) and a repeating unit (a2) represented by general formula (a2). 【Transformation 3】 [In general formula (a1), R １ａ is a hydrocarbon group having 1 to 6 carbon atoms, and R ２ａ is an alkylene group having 1 to 10 carbon atoms, a is 1 or 0, and * is a bonding site. X is -O-(AO) ｅ R ３ａ and a group selected from the following general formula (a3): 【Chemistry 4】 AO is an alkyleneoxy group having 2 to 4 carbon atoms, e is the average number of moles of AO added, which is a number of 0 to 50, and R ３ａ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ４ａ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or —(CO)—R ５ａ is a group selected from ５ａ is a hydrocarbon group having 1 to 30 carbon atoms, s is an integer of 0 to 3, t is an integer of 0 to 3, and u is an integer of 0 to 20. *-SiR ７ａ ３－ｂ (R ８ａ -X) ｂ (a2) [In general formula (a3), R ７ａ are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R ８ａ are each independently an alkylene group having 1 to 10 carbon atoms, b is an integer of 1 to 3, and * is a bonding site. X is -O-(AO) ｅ R ３ａ and a group selected from the general formula (a3), where AO is an alkyleneoxy group having 2 to 4 carbon atoms, e is the average number of moles of AO added and is a number of 0 to 50, and R ３ａ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ４ａ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or —(CO)—R ５ａ is a group selected from ５ａ is a hydrocarbon group having 1 to 30 carbon atoms, s is an integer of 0 to 3, t is an integer of 0 to 3, and u is an integer of 0 to 20.

5. The hydraulic composition according to claim 4, further comprising (B) a cement dispersant.

6. A method for improving the surface appearance of a hydraulic composition, comprising mixing the following component (A), hydraulic powder, and water: Component (A): a modified silicone having one or more repeating units selected from a repeating unit (a1) represented by general formula (a1) and a repeating unit (a2) represented by general formula (a2). 【Transformation 5】 [In general formula (a1), R １ａ is a hydrocarbon group having 1 to 6 carbon atoms, and R ２ａ is an alkylene group having 1 to 10 carbon atoms, a is 1 or 0, and * is a bonding site. X is -O-(AO) ｅ R ３ａ and a group selected from the following general formula (a3): 【Transformation 6】 AO is an alkyleneoxy group having 2 to 4 carbon atoms, e is the average number of moles of AO added, which is a number of 0 to 50, and R ３ａ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ４ａ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or —(CO)—R ５ａ is a group selected from ５ａ is a hydrocarbon group having 1 to 30 carbon atoms, s is an integer of 0 to 3, t is an integer of 0 to 3, and u is an integer of 0 to 20. *-SiR ７ａ ３－ｂ (R ８ａ -X) ｂ (a2) [In general formula (a3), R ７ａ are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R ８ａ are each independently an alkylene group having 1 to 10 carbon atoms, b is an integer of 1 to 3, and * is a bonding site. X is -O-(AO) ｅ R ３ａ and a group selected from the general formula (a3), where AO is an alkyleneoxy group having 2 to 4 carbon atoms, e is the average number of moles of AO added and is a number of 0 to 50, and R ３ａ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ４ａ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or —(CO)—R ５ａ is a group selected from ５ａ is a hydrocarbon group having 1 to 30 carbon atoms, s is an integer of 0 to 3, t is an integer of 0 to 3, and u is an integer of 0 to 20.

7. The method for improving the surface appearance of a hydraulic composition according to claim 6, further comprising mixing (B) a cement dispersant.

8. A method for improving the surface appearance of a hydraulic composition, comprising applying the surface appearance improver composition for hydraulic compositions according to claim 3 to a formwork, and filling the formwork with a hydraulic composition containing hydraulic powder and water.

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