JP6650262B2 - Surface aesthetic improver composition for hydraulic composition - Google Patents

Description

  The present invention relates to a method for producing a surface aesthetic improver composition for a hydraulic composition, a hydraulic composition, a method for producing a cured product, and a method for improving the appearance of a cured product of a hydraulic composition.

  Various admixtures have been used to improve the physical properties of hydraulic compositions such as concrete. In particular, AE agents, water reducing agents, and AE water reducing agents are frequently used from the viewpoint of improving the fluidity and dispersibility of uncured concrete. These are useful in that they have high water-reducing properties and can reduce slump loss, but have the problem that the amount of air entrained in the concrete tends to be large. When the amount of air entrained in the concrete increases, coarse air bubbles are likely to be generated, leading to uneven filling and eventually a decrease in the strength of the cured body, and furthermore to form voids (air bubble traces) on the surface of the cured body, which is a factor that impairs aesthetic appearance. .

  Conventionally, from the viewpoint of effective use of industrial waste, fly ash, a by-product of coal-fired power generation, silica fume, a by-product of silicon alloy production, and blast furnace slag, a by-product of steel refining, are used for concrete. Considered as a material. However, fly ash contains a large amount of unburned carbon fine powder in large amounts, and when used as hydraulic powder for concrete, it precipitates and disperses on the concrete surface after curing, and significantly impairs the appearance of the cured product surface. there were.

Patent Document 1 discloses a hydraulic composition containing hydrophobic black particles, cement, a dispersant, and an antifoaming agent.
Patent Document 2 discloses a hydraulic composition containing a water-soluble polymer composed of a specific polyalkylene oxide derivative, a high-performance water reducing agent, an antifoaming agent, and a hydraulic powder.
US Pat. No. 5,049,086 discloses a cement composition comprising a water-insoluble defoamer, an amine solubilizer capable of solubilizing the water-insoluble defoamer in an acidic medium, and optionally a dispersant for a cement composition. An admixture composition is disclosed.

JP-A-2002-3264 JP-A-9-156981 JP 2006-511418 A

  However, the techniques disclosed in Patent Documents 1 to 3 do not always satisfy the surface aesthetics depending on the composition used.

  The present invention provides an aesthetic enhancer composition for a hydraulic composition, from which a cured product of the hydraulic composition having an excellent surface appearance can be obtained.

The present invention provides (A) a compound represented by the following general formula (A1), a compound represented by the following general formula (A2), a compound represented by the following general formula (A3), and a compound represented by the following general formula (A4) One or more compounds selected from the compounds represented by
(B) a compound in which a mixture obtained by adding 0.1% by mass to water becomes turbid or separated at 20 ° C;
(C) a cement dispersant;
The present invention relates to a surface beauty improver composition for a hydraulic composition, comprising:

[Wherein, R is a hydrophobic group containing a carbon atom,
AO is an alkyleneoxy group having 2 to 4 carbon atoms,
Y is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
p is the average number of moles of AO added, and is a number from 1 to 100,
q and r are the same or different and are each an average number of added moles of AO, are 0 or more, q + r is 1 or more and 100 or less,
M, M ¹ and M ² are the same or different and are each a counter ion;
X ¹ and X ² are the same or different and are each a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]

Also, the present invention
Hydraulic powder,
water and,
(A) a compound represented by the general formula (A1), a compound represented by the general formula (A2), a compound represented by the general formula (A3), and a compound represented by the general formula (A4) One or more compounds selected from compounds,
(B) a compound in which a mixture obtained by adding 0.1% by mass to water becomes turbid or separated at 20 ° C;
(C) a cement dispersant;
And a hydraulic composition containing:

Further, the present invention provides a hydraulic powder, water, (A) a compound represented by the general formula (A1), a compound represented by the general formula (A2), and a compound represented by the general formula (A3). Of the compound represented by formula (A4) and one or more compounds selected from the compounds represented by formula (A4), and (B) a mixture obtained by adding 0.1% by mass to water is cloudy at 20 ° C. Or a step of mixing a compound to be separated and (C) a cement dispersant to prepare a hydraulic composition,
Filling the prepared hydraulic composition in a mold, and curing, and
Demolding the cured hydraulic composition,
The present invention relates to a method for producing a cured product having:

Further, the present invention provides (A) a compound represented by the general formula (A1), a compound represented by the general formula (A2), a compound represented by the general formula (A3), and a compound represented by the general formula (A3). One or more compounds selected from the compounds represented by A4),
(B) a compound in which a mixture obtained by adding 0.1% by mass to water becomes turbid or separated at 20 ° C;
(C) A method for improving the aesthetics of a cured product of a hydraulic composition, which cures a hydraulic composition obtained by adding and kneading a cement dispersant with cement and water.

Hereinafter, (A) a compound represented by the general formula (A1), a compound represented by the general formula (A2), a compound represented by the general formula (A3), and a compound represented by the general formula (A4) One or more compounds selected from the above compounds will be described as the component (A).
Hereinafter, the compound (B) in which the mixture obtained by adding 0.1% by mass to water becomes turbid or separated at 20 ° C. will be described as the component (B).
Hereinafter, the (C) cement dispersant will be described as the (C) component.

  ADVANTAGE OF THE INVENTION According to this invention, the aesthetic enhancer composition for hydraulic compositions which is excellent in surface aesthetics, for example, the hardened | cured material of a hydraulic composition in which black spots and air bubbles were reduced is provided.

Factors for judging the surface appearance of the cured product of the hydraulic composition include black spots, traces of surface air bubbles, peeling residue on a mold, and the like.Techniques that can suppress all of these are conventionally known. I didn't. The present inventors have improved the dispersibility of the component (B) by using the compound of the component (A) and the compound of the component (B) in combination with the component (C), and have improved the black spots, traces of surface bubbles, It has been found that peeling residue on a mold can be suppressed, and that a reduction in strength does not occur.
The cured product of the hydraulic composition containing the aesthetic enhancer composition for a hydraulic composition of the present invention has such an aesthetic appearance that it does not need to be subjected to a decorative treatment as a building or the like (so-called “punching-out” method or the like). Because of the provision, it is possible to expand the structure to a variety of uses other than the use of the structure requiring strength.

[Surface beauty improver composition for hydraulic composition]
<(A) component>
The component (A) includes a compound represented by the general formula (A1), a compound represented by the general formula (A2), a compound represented by the general formula (A3), and a compound represented by the general formula (A4). One or more compounds selected from the compounds represented.
The component (A) has a structure in which a hydrophobic group containing a carbon atom and a (poly) alkyleneoxy group are linked by an oxygen atom or a nitrogen atom, and when linked by an oxygen atom, the terminal of the (poly) alkyleneoxy group is terminated. It is a compound in which a sulfuric ester group or a hydrogen atom or an alkyl having 1 to 4 carbon atoms is linked, and when linked by a nitrogen atom, the terminal of the (poly) alkyleneoxy group is a sulfuric ester group or a hydroxyl group or an ether group. .

In the general formulas (A1), (A2), (A3) and (A4), R is a hydrophobic group containing a carbon atom. Here, with respect to R, the hydrophobic group refers to a group in which the compound having RH has an HLB of 2.25 or less.
R is a monovalent group.
In other words, R is a group obtained by removing one hydrogen atom from a compound containing a carbon atom, represented by RH, and having an HLB of 2.25 or less.

The HLB of RH is based on the Davis method.
The HLB of RH is preferably 2.25 or less, more preferably 1.30 or less, still more preferably -1.55 or less, and preferably -5.83 or more, from the viewpoint of suppressing black spot formation. Preferably it is -4.40 or more, more preferably -3.45 or more.
Further, the HLB of RH is preferably 2.25 or less, more preferably 1.30 or less, still more preferably 0.35 or less, and preferably -3.45 or more from the viewpoint of suppressing surface bubble formation. , More preferably -2.50 or more, and still more preferably -1.55 or more.

The HLB of RH is considered to be a factor involved in the strength of the hydrophobic interaction of the compound represented by the general formula (A1), (A2), (A3) or (A4) having the corresponding R. Can be
For example, since a surfactant is stably present in water, a hydrophilic group is formed on the water side and a hydrophobic group is formed on the inside to form micelles or the like, so that an area where the hydrophobic group comes into contact with water is reduced as much as possible. I do. The aromatic ring such as a naphthalene ring in the compound of the component (B) and the cement dispersant as the component (C) has a structure with a very high hydrophobicity. When the HLB of -H is 2.25 or less, the structure becomes very hydrophobic. Therefore, in water, the groups R of the component (B), the component (C), and the component (A) are intricately assembled with each other by hydrophobic groups in order to reduce the contact area with water. It is considered that an aggregate suitable for expressing the effect of is formed. In the present invention, each of the component (B) and the component (C) is associated with the component (A) by including the group R in which the HLB of RH is 2.25 or less in the component (A). As a result, it was not obtained only by the component (B), the component (C), or the component (A). It is presumed that black spots, traces of surface bubbles, and peeling residue on a mold can be suppressed because the “property of dispersing particles such as black particles” is developed.

In the general formulas (A1), (A2), (A3) and (A4), R is a group selected from a hydrocarbon group and a hydrocarbon group containing a substituent.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an aralkyl group, an aryl group, and an aryl group in which one, two, or three hydrogen atoms of a hydrocarbon are substituted. The hydrocarbon group is preferably a group selected from an alkyl group and an alkenyl group.

  The substituent is an atom or an atomic group introduced in place of the hydrogen atom of the most basic organic compound (Chemical Dictionary, First Edition, Seventh Printing, Tokyo Chemical Dojin, April 2003) 1 day). The hydrocarbon containing a substituent may be a derivative of a hydrocarbon. Derivatives are compounds that have been modified to the extent that they do not significantly alter the structure or properties of the parent, such as the introduction of a functional group, oxidation, reduction, or substitution of atoms when a certain hydrocarbon is considered as the parent.

  The carbon number of R can be selected from preferably 10 or more, more preferably 12 or more, and preferably 27 or less, more preferably 26 or less, and further preferably 24 or less.

The alkyl group for R is preferably an aliphatic alkyl group, more preferably a straight-chain aliphatic alkyl group, and still more preferably a straight-chain primary aliphatic alkyl group.
The alkenyl group for R is preferably an aliphatic alkenyl group, more preferably a linear aliphatic alkenyl group, and still more preferably a linear primary aliphatic alkenyl group.

R is preferably an alkyl group from an economic viewpoint.
R is preferably an alkenyl group from the viewpoint of easy dissolution in water.
The alkyl group or the alkenyl group includes, for example, a decyl group, a lauryl group, a myristyl group, a palmityl group, a stearyl group, a behenyl group, an isostearyl group, and an oleyl group.From the viewpoint of improving the surface appearance, preferably a lauryl group, a myristyl group. Group, palmityl group, stearyl group, behenyl group, isostearyl group, oleyl group, more preferably lauryl group, myristyl group, palmityl group, stearyl group, oleyl group.

Specific examples of R are preferably a hydrocarbon group having 10 or more carbon atoms, more preferably 12 or more carbon atoms, and preferably 27 or less, more preferably 26 or less, and still more preferably 24 or less. Examples include a group selected from hydrocarbon groups in which a hydrogen atom has been substituted with a substituent.
Other specific examples of R are preferably an alkyl group or alkenyl group having 10 or more carbon atoms, more preferably 12 or more carbon atoms, and preferably 27 or less, more preferably 26 or less, and still more preferably 24 or less. And a group selected from a group in which a hydrogen atom of the alkyl group or the alkenyl group is substituted with a substituent.
Among them, preferably an aliphatic alkyl group, more preferably a linear aliphatic alkyl group, still more preferably a linear primary aliphatic alkyl group, and preferably 10 or more carbon atoms, more preferably 12 or more, and preferably Is selected from alkenyl groups of 27 or less, more preferably 26 or less, even more preferably 24 or less, preferably aliphatic alkenyl groups, more preferably linear aliphatic alkenyl groups, and still more preferably linear primary aliphatic alkenyl groups. Groups.

  In the general formulas (A1), (A2), (A3) and (A4), AO is an alkyleneoxy group having 2 to 4 carbon atoms, preferably an alkyleneoxy group having 2 or 3 carbon atoms. AO preferably contains an alkyleneoxy group having 2 carbon atoms.

In the general formulas (A1) and (A2), p is the average number of moles of AO added, and is preferably 1 or more, preferably 5 or more, more preferably 10 or more, and still more preferably 20 from the viewpoint of improving the surface appearance. As described above, the number is more preferably 50 or more, and from an economic viewpoint, the number is 100 or less, preferably 90 or less, more preferably 80 or less.
In the general formulas (A3) and (A4), q and r are the same or different and are each an average addition mole number of AO, and are 0 or more. From the viewpoint of improving the surface appearance, q + r is 1 or more, preferably 2 or more, more preferably 5 or more, still more preferably 10 or more, still more preferably 20 or more, and still more preferably 50 or more, and economical. From the viewpoint, the number is 100 or less, preferably 90 or less, more preferably 80 or less.

In the general formula (A1), Y is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
In the general formulas (A2) and (A4), M, M ¹ and M ² are the same or different and are each a counter ion, and are a hydrogen ion, an alkali metal ion, or an alkaline earth metal ion (１ ／ atom). ), Ammonium ion and the like.
M, M ¹ and M ² are preferably ammonium ions from the viewpoint of easy production of the compound. M, M ¹ and M ² are preferably an alkali metal ion, more preferably an alkali metal ion selected from a sodium ion and a potassium ion, from the viewpoint of the odor of the compound.

In Formula (A3), X ¹ and X ² are the same or different and are each a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. The hydrocarbon group is preferably an alkyl group. X ¹ and X ² are each preferably a hydrogen atom.

The surface beauty improver composition for a hydraulic composition of the present invention contains the component (A) in a solid content of preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably from the viewpoint of improving the surface beauty. Is at least 5% by mass, more preferably at least 10% by mass, even more preferably at least 15% by mass, even more preferably at least 25% by mass, and preferably at most 95% by mass, more preferably at least 75% by mass. The content is more preferably 50% by mass or less, even more preferably 45% by mass or less.
In addition, about the surface appearance enhancer composition for hydraulic compositions, a solid content means components other than water.

<(B) component>
The component (B) is a compound in which a mixture (0.1 mass% water mixture) when 0.1 mass% is added to water (B) becomes cloudy or separates at 20 ° C.
The component (B) is incompatible with water because the water mixture becomes turbid or separates even in a small amount. However, the action of the component (A) enhances the interaction with the component (C) and enhances the black color. It is considered to promote the dispersion of substances and the like (for example, particles contained in fly ash, aggregates having irregularities) recognized in the above.

  The component (B) is a water-insoluble compound. Regarding the component (B), the term "water-insoluble" means that the solubility in water is 0.1% by mass or less at 20 ° C.

  As the component (B), a compound which becomes turbid or separates at 20 ° C. when the mixture is added to water at 0.1% by mass, and is a compound having a mineral functional oil, a vegetable oil, an oil or fat, a fatty acid, a fatty acid ester, or a hydroxyl functional group. And amides, phosphates, metal soaps, silicones, oxyalkylenes, propylene oxide group-containing polymers, hydrocarbons, and one or more compounds selected from acetylene-type diols.

  The component (B) is preferably polysiloxane, polyoxyethylene polyoxypropylene, polyoxypropylene, acetylene glycol, polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene alkylamide, trialkyl phosphate, alcohol And one or more compounds selected from these derivatives.

  Examples of the polysiloxane include polysiloxane, dimethylpolysiloxane, and polyhydroxymethylsiloxane.

  Examples of the polyoxyethylene polyoxypropylene include a polyoxyethylene polyoxypropylene random polymer and a polypropylene oxide-polyethylene oxide-polypropylene oxide block polymer.

  Examples of the polypropylene oxide and its derivatives include polyoxypropylene glyceryl ether and polyoxypropylene.

  As acetylene glycol and its derivatives, acetylenol E00 and acetylenol E13 (all from Kawaken Fine Chemical Co., Ltd.), DYNOL (registered trademark) 604, SURFYNOL (registered trademark) 440, SURFYNOL (registered trademark) 104, SURFYNOL (registered trademark) Commercial products such as 2502, SURFYNOL (registered trademark) 420, and SURFYNOL (registered trademark) DF-75 (all manufactured by Air Products and Chemicals Co., Ltd.). Derivatives of acetylene glycol include alkylene oxide adducts of acetylene glycol.

  Examples of the polyoxyalkylene fatty acid ester include an alkylene oxide adduct of a fatty acid having 4 to 22 carbon atoms.

  Examples of the polyoxyalkylene alkyl ether include an alkylene oxide adduct of an alcohol having 4 to 22 carbon atoms.

  Examples of the polyoxyalkylene alkylamide include an amine oxide adduct of an amide of a fatty acid having 4 to 22 carbon atoms with an amine such as monoethanolamine and diethanolamine.

  Examples of the trialkyl phosphate include tributyl phosphate and triisobutyl phosphate.

  Examples of the alcohol include alcohols having 4 to 22 carbon atoms, preferably monohydric alcohols having 4 to 22 carbon atoms.

Suitable examples of the water-insoluble compound useful as component (B) for improving the surface appearance include:
As polysiloxane, SAGTEX DSA (trademark),
As a polyoxyalkylene fatty acid ester, a polyoxyalkylene alkyl ether, or a polyoxyalkylene alkylamide, SN Deformer 260 (trademark), SN Deformer 265 (trademark), SN Deformer 466 (trademark) (all Sannopco Corporation), defoaming Agent NO. 21 (trademark), defoamer NO. 8 (trademark) (both by Kao Corporation),
As acetylene glycol, DYNOL (registered trademark) 604, SURFYNOL (registered trademark) 440,
As trialkyl phosphate, tributyl phosphate, triisobutyl phosphate,
As alcohols, 2-ethylhexanol, polyoxyethylene polyoxypropylene, Newpol PE-61 (trademark), Newpol PE-71 (trademark) (both from Sanyo Chemical Co., Ltd.), and polyoxypropylene having a molecular weight of 2000 It contains a polypropylene glycol of not less than 100,000 and not more than 100,000.

Component (B) is preferably from the viewpoint of stability when component (A), component (B), and component (C) are mixed,
As polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl ether, or polyoxyalkylene alkylamide, SN Deformer 260 (trademark), SN Deformer 265 (trademark), SN Deformer 466 (trademark), defoamer NO. 21 (trademark), defoamer NO. 8 (trademark),
As acetylene glycol, DYNOL (registered trademark) 604, SURFYNOL (registered trademark) 440,
As trialkyl phosphate, tributyl phosphate, triisobutyl phosphate,
2-ethylhexanol as the alcohol,
As polyoxyethylene polyoxypropylene, Newpol PE-61 (trademark), Newpol PE-71 (trademark), and as polyoxypropylene, one or more compounds selected from polypropylene glycol having a molecular weight of 2,000 to 100,000. is there.

Alternatively, the component (B) is preferably from the viewpoint of economy,
As polysiloxane, DK Q1-1183 (trademark),
As polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl ether, or polyoxyalkylene alkylamide, SN Deformer 260 (trademark), SN Deformer 265 (trademark), SN Deformer 466 (trademark), defoamer NO. 21 (trademark), defoamer NO. 8 (trademark),
As trialkyl phosphate, tributyl phosphate, triisobutyl phosphate,
As alcohol, 2-ethylhexanol Polyoxyethylene Polyoxypropylene is selected from Newpol PE-61 (trademark), Newpol PE-71 (trademark), and polyoxypropylene is selected from polypropylene glycol having a molecular weight of 2,000 to 100,000. One or more compounds.

<(C) component>
The component (C) is a cement dispersant. Examples of the dispersant that can be used include a naphthalene-based polymer, a melamine-based polymer, a phenol-based polymer, and a lignin-based polymer. From the viewpoint of shortening the time required for the cured product of the hydraulic composition to reach the required strength, a cement dispersant comprising a polymer having an aromatic ring is preferred.

  As the naphthalene-based polymer, a naphthalene sulfonic acid formaldehyde condensate and a salt thereof, for example, Mighty 150 manufactured by Kao Corporation can be used. As the melamine-based polymer, a melaminesulfonic acid formaldehyde condensate and a salt thereof, for example, Mighty 150-V2 manufactured by Kao Corporation can be used. As the phenolic polymer, a phenolsulfonic acid formaldehyde condensate and a salt thereof, for example, compounds described in JP-A-49-104919 can be used. As lignin polymers, lignin sulfonic acid and salts thereof, for example, Bolegard Ultrazine NA, Borregaard Co., Ltd. Can be used.

  The component (C) is preferably a cement dispersant comprising a polymer compound having a monomer unit containing a naphthalene ring.

  Further, the component (C) preferably includes a naphthalenesulfonic acid formaldehyde condensate or a salt thereof. The naphthalene sulfonic acid formaldehyde condensate or a salt thereof is a condensate of naphthalene sulfonic acid and formaldehyde or a salt thereof. Naphthalenesulfonic acid formaldehyde condensate, as long as the performance is not impaired, as a monomer, for example, methylnaphthalene, ethylnaphthalene, butylnaphthalene, hydroxynaphthalene, naphthalenecarboxylic acid, anthracene, phenol, cresol, creosote oil, tar, melamine, It may be co-condensed with an aromatic compound which can be co-condensed with naphthalene sulfonic acid, such as urea, sulfanilic acid and / or derivatives thereof.

  The naphthalenesulfonic acid formaldehyde condensate or a salt thereof may be, for example, Mighty 150, Demol N, Demol RN, Demol MS, Demol SN-B, Demol SS-L (all manufactured by Kao Corporation), Cell Flow 120, Labelin FD-40 And a commercially available product such as Labelin FM-45 (all manufactured by Dai-ichi Kogyo Co., Ltd.).

  The naphthalenesulfonic acid formaldehyde condensate or a salt thereof has a weight average molecular weight of preferably 200,000 or less, more preferably 100,000 or less, and still more preferably 80, from the viewpoint of improving the surface appearance of the cured product of the hydraulic composition. 5,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. The naphthalenesulfonic acid formaldehyde condensate or a salt thereof has a weight average molecular weight of preferably 1,000 or more, more preferably 3,000 or more, and still more preferably, from the viewpoint of improving the surface appearance of the cured product of the hydraulic composition. Is 4,000 or more, more preferably 5,000 or more. The naphthalenesulfonic acid formaldehyde condensate may be in an acid state or a neutralized product.

The molecular weight of the naphthalenesulfonic acid formaldehyde condensate or a salt thereof can be measured using gel permeation chromatography under the following conditions.
[GPC conditions]
Column: G4000SWXL + G2000SWXL (Tosoh Corporation)
Eluent: 30 mM CH ₃ COONa / CH ₃ CN = 6/4
Flow rate: 0.7ml / min
Detection: UV 280 nm
Sample size: 0.2mg / ml
Standard substance: manufactured by Nishio Industry Co., Ltd. in terms of sodium polystyrene sulfonate (sodium monodisperse polystyrene sulfonate: molecular weight, 206, 1,800, 4,000, 8,000, 18,000, 35,000, 88,000, 780,000)
Detector: Tosoh Corporation UV-8020

  Examples of a method for producing a naphthalenesulfonic acid formaldehyde condensate or a salt thereof include a method of obtaining a condensate by a condensation reaction between naphthalenesulfonic acid and formaldehyde. The condensate may be neutralized. In addition, water insolubles by-produced by the neutralization may be removed. Specifically, in order to obtain naphthalenesulfonic acid, a sulfonated product is obtained by reacting at 1.2 to 1.4 mol of sulfuric acid with respect to 1 mol of naphthalene at 150 to 165 ° C for 2 to 5 hours. Next, formalin is added dropwise at 85 to 95 ° C over 3 to 6 hours so that the amount of formaldehyde becomes 0.95 to 0.99 mole per 1 mole of the sulfonate, and after the addition, condensation is performed at 95 to 105 ° C. Perform the reaction. Further, from the viewpoint of suppressing the metal corrosion of a storage tank or the like since the aqueous solution of the obtained condensate has a high acidity, water and a neutralizing agent are added to the obtained condensate, and the neutralization step is performed at 80 to 95 ° C. be able to. The neutralizing agent is preferably added in an amount of 1.0 to 1.1 mole times with respect to naphthalenesulfonic acid and unreacted sulfuric acid, respectively. In addition, water-insoluble matter generated by the neutralization can be removed, and the method is preferably separation by filtration. Through these steps, an aqueous solution of a water-soluble salt of a naphthalenesulfonic acid formaldehyde condensate is obtained. This aqueous solution can be used as it is as an aqueous solution of the component (C). Further, if necessary, the aqueous solution is dried and powdered to obtain a powdery salt of a naphthalenesulfonic acid formaldehyde condensate, which can be used as a powdery dispersant. Drying and pulverization can be performed by spray drying, drum drying, freeze drying, or the like.

  The surface beauty improver composition for a hydraulic composition of the present invention contains the component (C) in a solid content, preferably 5% by mass or more, more preferably 25% by mass or more, from the viewpoint of improving the surface appearance of the cured product. , More preferably 50% by mass or more, even more preferably 55% by mass or more, and preferably 99% by mass or less, more preferably 97% by mass or less, still more preferably 95% by mass or less, and still more preferably 90% by mass or less. The content is more preferably 85% by mass or less, even more preferably 75% by mass or less.

When the component (C) is a cement dispersant comprising a polymer compound having a monomer unit containing a naphthalene ring [hereinafter referred to as the component (C ')], and further, a naphthalenesulfonic acid formaldehyde condensate or a salt thereof, From the viewpoint of obtaining a hydraulic composition excellent in surface aesthetics of a cured product, the component (A) with respect to the monomer unit containing a naphthalene ring in the component (C ′), Is preferably 1% or more and 30% or less. From the same viewpoint, the molar ratio is preferably 3% or more, more preferably 5% or more, still more preferably 7% or more, and preferably 16% or less, more preferably 13% or less, and further preferably 11% or less. It is as follows. This molar ratio is calculated based on the total amount of the monomer units containing a naphthalene ring in the component (C ′) and the total amount of the component (A). Specifically, it is calculated by the following equation.
Molar ratio (%) = [[total amount (mol) of component (A)] / [total amount (mol) of monomer unit containing naphthalene ring in component (C ′)]] × 100

When the component (C ′) is a naphthalenesulfonic acid formaldehyde condensate or a salt thereof, the monomer unit containing a naphthalene ring is a monomer unit formed by a dehydration-condensation reaction between naphthalenesulfonic acid or a salt thereof and formaldehyde. When the component (C ′) is a sodium salt of a naphthalenesulfonic acid formaldehyde condensate, the total amount (mol) of a monomer unit containing a naphthalene ring in the compound is calculated by the following formula. In the formula, the sodium salt of a naphthalenesulfonic acid formaldehyde condensate is referred to as NSF.
Total amount (mol) of monomer units containing naphthalene rings in NSF = [total amount of mass of monomer units containing naphthalene rings in NSF] / [molecular weight of monomer units containing naphthalene rings in NSF]

When the component (C ′) is a condensate of naphthalenesulfonic acid or a salt thereof and formaldehyde, the total amount of the mass of the monomer unit containing a naphthalene ring in the component (C ′) is the total mass of the compound.
The total amount of the mass of the monomer unit containing a naphthalene ring in the component (C ′) is the condensate of the component (C ′) containing naphthalenesulfonic acid or a salt thereof, formaldehyde, and another monomer not containing a naphthalene ring. In the case of, the mass is obtained by removing the mass of the monomer unit derived from formaldehyde and the other monomer not containing the naphthalene ring from the total mass of the compound.
The mass of the monomer unit derived from the other monomer not containing the naphthalene ring may be calculated using a general analyzer that can determine a copolymer mass ratio such as a nuclear magnetic resonance spectrometer, or may be synthesized. It may be calculated from the charged amount at the time. .

  When the component (C ′) is a sodium salt of a naphthalenesulfonic acid formaldehyde condensate, the molecular weight of the sodium unit of the naphthalenesulfonic acid formaldehyde condensate is determined by the molecular weight (230.2) of sodium naphthalenesulfonic acid and the formaldehyde. It can be determined as a value obtained by subtracting water (18.0) which is a by-product of the condensation reaction from the sum of (30.0), that is, 242.2.

In the surface beauty improver composition for a hydraulic composition of the present invention, for example, when the component (C ′) is a sodium salt of a naphthalenesulfonic acid formaldehyde condensate and the component (A) is a polyoxyethylene alkyl ether sulfate ammonium salt, The molar ratio of the total amount of the component (A) to the monomer unit containing a naphthalene ring in the component C ′) is determined by separating the component (A) from the component (C ′) by a general method such as a reprecipitation method or a liquid separation method. Then, the mass ratio can be measured and calculated.
The structure of the component (A) and the component (C ′) in the surface beauty improver composition for a hydraulic composition can be determined by a general method such as a reprecipitation method or a liquid separation method. ') The components can be separated and analyzed using a general analyzer such as a nuclear magnetic resonance spectrometer or liquid chromatography.

The surface beauty improver composition for a hydraulic composition of the present invention essentially has a proportion in the composition according to the molar ratio of the monomer unit having a naphthalene ring in the component (C ′) and the component (A). Although it is preferable to determine, for example, the following mass ratio can be defined.
From the viewpoint of improving the surface appearance of the cured product, the mass ratio of the component (A) to the component (C ′) is (C ′) / (A). , Preferably 0.08 or more, more preferably 0.50 or more, further preferably 0.70 or more, even more preferably 0.90 or more, and preferably 70 or less, more preferably 50 or less, and still more preferably Is 30 or less, still more preferably 15 or less, still more preferably 8.0 or less, still more preferably 5.0 or less, and still more preferably 3.0 or less.

<Other components, composition, etc.>
The surface aesthetic improver composition for hydraulic composition of the present invention is a conventional cement dispersant, water-soluble polymer compound, air entrainer, cement wetting agent, expanding agent, retarder, quick setting agent, thickener, Components such as a flocculant, a strength enhancer, a curing accelerator, and a preservative can be contained.

  The surface appearance enhancer composition for a hydraulic composition of the present invention may be in any form of a liquid or a solid. When the surface beauty improver composition for a hydraulic composition of the present invention is a liquid, it preferably contains water.

  The content of water when the surface beauty enhancer composition for a hydraulic composition is a liquid containing water is preferably 10% from the viewpoint of workability in preparing the hydraulic composition. It is at least 30% by mass, more preferably at least 30% by mass, further preferably at least 50% by mass, and from the viewpoint of economy, preferably at most 90% by mass, more preferably at most 60% by mass.

  The content of the component (A) in the case where the surface beauty improver composition for a hydraulic composition is a liquid containing water contains, from the viewpoint of improving the surface beauty of the cured product of the hydraulic composition, It is preferably at least 1% by mass, more preferably at least 6% by mass, still more preferably at least 11% by mass, and preferably at most 83% by mass, more preferably at most 60% by mass, still more preferably at most 45% by mass. is there.

  When the surface beauty improver composition for hydraulic composition is a liquid containing water, the content of the component (B) is preferably from the viewpoint of improving the surface beauty of the cured product of the hydraulic composition. It is preferably at least 0.0001% by mass, more preferably at least 0.001% by mass, even more preferably at least 0.005% by mass, and preferably at most 10% by mass, more preferably at most 5% by mass, even more preferably. Is 2% by mass or less.

  When the surface beauty improver composition for a hydraulic composition is a liquid containing water, the content of the component (C) is preferably from the viewpoint of improving the surface beauty of a cured product of the hydraulic composition. It is preferably at least 7% by mass, more preferably at least 10% by mass, still more preferably at least 15% by mass, and preferably at most 89% by mass, more preferably at most 84% by mass, even more preferably at most 79% by mass. is there.

  The total content of the component (A) and the component (C) when the surface beauty enhancer composition for a hydraulic composition is a liquid containing water is determined from the viewpoint of improving the surface beauty of the cured product of the hydraulic composition. From the composition, it is preferably at least 10% by mass, more preferably at least 20% by mass, even more preferably at least 30% by mass, and preferably at most 90% by mass, more preferably at most 70% by mass, Preferably it is 50% by mass or less.

(Hydraulic composition)
The present invention provides a hydraulic composition containing hydraulic powder, water, component (A), component (B), and component (C).

  The hydraulic powder used in the hydraulic composition of the present invention is a powder having physical properties to be hardened by a hydration reaction, such as cement and gypsum. Preferred are cements such as ordinary Portland cement, belite cement, moderate heat cement, early-strength cement, ultra-high-strength cement, and sulfate-resistant cement. Blast furnace slag cement, fly ash cement, silica fume cement, etc. obtained by adding powder having a posolan effect and / or latent hydraulic property, such as blast furnace slag, fly ash, silica fume, and the like, or stone powder (calcium carbonate powder) to cement, etc. May be.

The hydraulic composition of the present invention has a water / hydraulic powder ratio [mass percentage (mass%) of water and hydraulic powder in the slurry, usually abbreviated as W / P. , W / C. Is 10% by mass or more, or 15% by mass or more, and 500% by mass or less, or 400% by mass or less, or 200% by mass or less, or 100% by mass or less, or 70% by mass or less, or 60% by mass % Or less, or 50% by mass or less.
The water / hydraulic powder ratio is preferably 10% by mass or more, more preferably 15% by mass or more from the viewpoint that fluidity can be expressed even with a small amount of water, and high strength such as cement milk for ground improvement. From the viewpoint that it can be used for applications where is not required, the content is preferably 500% by mass or less, more preferably 400% by mass or less, further preferably 200% by mass or less, and still more preferably 100% by mass or less.
The water / hydraulic powder ratio is preferably 10% by mass or more, more preferably 15% by mass or more, since the fluidity can be expressed even with a small amount of water. From the viewpoint of being able to meet the required use, the content is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.

  Specific examples and preferred embodiments of the component (A), the component (B), and the component (C) used in the hydraulic composition of the present invention are described in the surface beauty improver composition for a hydraulic composition of the present invention, respectively. Is the same as

  In the hydraulic composition of the present invention, the component (A) is preferably at least 0.0001 part by mass, more preferably at least 0.001 part by mass, even more preferably at least 0.1 part by mass, based on 100 parts by mass of the hydraulic powder. 01 parts by mass or more, even more preferably 0.04 parts by mass or more, even more preferably 0.10 parts by mass or more, even more preferably 0.20 parts by mass or more, and preferably 10 parts by mass or less, more preferably It is contained in an amount of 5 parts by mass or less, more preferably 1 part by mass or less, still more preferably 0.40 parts by mass or less, still more preferably 0.35 parts by mass or less, and still more preferably 0.28 parts by mass or less.

  The hydraulic composition of the present invention contains the component (B) with respect to 100 parts by mass of the hydraulic powder, preferably at least 0.00001 part by mass, more preferably at least 0.00005 part by mass, even more preferably at least 0.1 part by mass. 0001 parts by mass or more, more preferably 0.0005 parts by mass or more, still more preferably 0.0007 parts by mass or more, even more preferably 0.001 parts by mass or more, and preferably 0.05 part by mass or less. Preferably 0.07 parts by mass or less, more preferably 0.1 parts by mass or less, even more preferably 0.2 parts by mass or less, even more preferably 0.5 parts by mass or less, even more preferably 1.0 parts by mass. It contains below.

  In the hydraulic composition of the present invention, the component (C) is preferably at least 0.001 part by mass, more preferably at least 0.01 part by mass, even more preferably at least 0.1 part by mass, based on 100 parts by mass of the hydraulic powder. 1 part by mass or more, still more preferably 0.15 part by mass or more, still more preferably 0.22 part by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 2 parts by mass. The content is more preferably 1.5 parts by mass or less, even more preferably 1.0 part by mass or less.

  In the hydraulic composition of the present invention, the total of the component (A) and the component (C) is preferably at least 0.001 part by mass, more preferably 0.01 part by mass, based on 100 parts by mass of the hydraulic powder. Or more, more preferably 0.1 or more parts, even more preferably 0.2 or more parts, and preferably 20 parts or less, more preferably 10 parts or less, even more preferably 3 parts or less. More preferably, the content is 0.9 parts by mass or less.

  The hydraulic composition of the present invention preferably contains an aggregate. Examples of the aggregate include aggregates selected from fine aggregate and coarse aggregate. Examples of the fine aggregate include those defined by the number 2311 in JIS A0203-2014. As fine aggregate, river sand, land sand, mountain sand, sea sand, lime sand, silica sand and their crushed sand, blast furnace slag fine aggregate, ferronickel slag fine aggregate, lightweight fine aggregate (artificial and natural) and recycled Fine aggregate and the like. In addition, as the coarse aggregate, those defined by the number 2312 in JIS A0203-2014 can be mentioned. For example, coarse aggregate includes river gravel, land gravel, mountain gravel, sea gravel, lime gravel, crushed stone, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural) and recycled. Coarse aggregate and the like can be mentioned. Different types of fine aggregate and coarse aggregate may be used as a mixture, or a single type may be used.

When the hydraulic composition is concrete, the amount of coarse aggregate is used, the strength of the hydraulic composition is reduced, the amount of hydraulic powder such as cement used is reduced, and the filling property to a mold or the like is improved. From the viewpoint, the bulk volume is preferably at least 50%, more preferably at least 55%, even more preferably at least 60%, and preferably at most 100%, more preferably at most 90%, even more preferably at most 80%. is there. Bulk volume is the proportion of coarse aggregate volume in concrete 1 m ³ (including the voids).
When the hydraulic composition is concrete, the amount of the fine aggregate is preferably 500 kg / m ³ or more, more preferably 600 kg / m ³ or more, from the viewpoint of improving the filling property into a mold or the like. Preferably it is 700 kg / m ³ or more, and preferably 1000 kg / m ³ or less, more preferably 900 kg / m ³ or less.
When the hydraulic composition is mortar, the amount of fine aggregate used is preferably 800 kg / m ³ or more, more preferably 900 kg / m ³ or more, even more preferably 1000 kg / m ³ or more, and preferably 2000 kg / m ³ or more. / M ³ or less, more preferably 1800 kg / m ³ or less, still more preferably 1700 kg / m ³ or less.

  Examples of the hydraulic composition include concrete and the like. Among them, concrete using cement is preferable. The hydraulic composition of the present invention may be any of self-leveling, refractory, plaster, lightweight or heavy concrete, AE, repair, prepacked, trammy, ground improvement, grouting, cold weather, etc. It is also useful in the field of.

  The hydraulic composition of the present invention may further contain other components. For example, an AE agent, a retarder, a foaming agent, a thickener, a foaming agent, a fluidizing agent, and the like can be used.

(Production method of hydraulic composition)
The present invention provides a method for producing a hydraulic composition, which comprises mixing hydraulic powder, water, component (A), component (B), and component (C). In the present invention, the component (A) and the component (B) may be separately mixed with a hydraulic powder to produce a hydraulic composition, but the component (A), the component (B) and the component (C) may be prepared in advance. It is preferable to mix the component (A) with the hydraulic powder. In the production of a hydraulic composition, it is more preferable to use the surface beauty enhancer composition for a hydraulic composition of the present invention.

Specific examples and preferred embodiments of the component (A), the component (B), and the component (C) used in the method for producing a hydraulic composition of the present invention are respectively the surface beauty improver for a hydraulic composition of the present invention. Same as described for the composition.
Specific examples and preferred embodiments of the hydraulic powder used in the method for producing a hydraulic composition of the present invention are the same as those described for the hydraulic composition of the present invention.
Further, the matters described in the surface beauty improver composition for a hydraulic composition of the present invention and the hydraulic composition can be appropriately applied to the method for producing the hydraulic composition of the present invention.

  In the method for producing a hydraulic composition of the present invention, the component (A) is preferably at least 0.001 part by mass, more preferably at least 0.005 part by mass, and still more preferably 100 parts by mass of the hydraulic powder. Is at least 0.01 part by mass, more preferably at least 0.04 part by mass, even more preferably at least 0.10 part by mass, even more preferably at least 0.20 part by mass, and preferably at least 2.0 parts by mass. Or less, more preferably 1.5 parts by mass or less, still more preferably 1 part by mass or less, still more preferably 0.40 parts by mass or less, still more preferably 0.35 parts by mass or less, even more preferably 0.28 parts by mass. Mix below.

  In the method for producing a hydraulic composition of the present invention, the component (B) is preferably at least 0.00001 part by mass, more preferably at least 0.00005 part by mass, and still more preferably 100 parts by mass of the hydraulic powder. Is 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, still more preferably 0.0007 parts by mass or more, still more preferably 0.001 parts by mass or more, and preferably 0.05 part by mass. Or less, more preferably 0.07 parts by mass or less, further preferably 0.1 parts by mass or less, still more preferably 0.2 parts by mass or less, still more preferably 0.5 parts by mass or less, and still more preferably 1. Mix 0 parts by mass or less.

  In the method for producing a hydraulic composition of the present invention, the component (C) is preferably at least 0.01 part by mass, more preferably at least 0.05 part by mass, and still more preferably 100 parts by mass of the hydraulic powder. Is at least 0.1 part by mass, more preferably at least 0.15 part by mass, even more preferably at least 0.22 part by mass, and preferably at most 4 parts by mass, more preferably at most 3 parts by mass, still more preferably 1 part by mass or less, more preferably 0.50 part by mass or less, even more preferably 0.40 part by mass or less.

  In the method for producing a hydraulic composition of the present invention, the total of the components (A) and (C) is preferably 0.01 parts by mass or more, more preferably 0 parts by mass, per 100 parts by mass of the hydraulic powder. 0.05 parts by mass or more, further preferably 0.1 parts by mass or more, still more preferably 0.2 parts by mass or more, and preferably 4 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 2 parts by mass. Below, even more preferably 0.9 parts by mass or less.

  In the method for producing a hydraulic composition of the present invention, from the viewpoint of smoothly mixing the components (A), (B) and (C) with the hydraulic powder such as cement, the components (A) and (B) It is preferable that the component (C) and the component (C) are mixed in advance with water and mixed with the hydraulic powder. The water-containing surface beauty improver composition for a hydraulic composition of the present invention can be used.

  In addition, in the method for producing a hydraulic composition of the present invention, a method of mixing a hydraulic powder such as cement and a surface beauty improving agent composition for a hydraulic composition of the present invention is preferable. The surface beauty improver composition for a hydraulic composition of the present invention may be a powder or a liquid. The surface beauty improver composition for a hydraulic composition of the present invention is added to the hydraulic powder so that the component (A), the component (B), and the component (C) are in the above-described amounts. Preferably. Specifically, as a mass part of the solid content of the surface beauty improver composition for a hydraulic composition of the present invention, based on 100 parts by mass of the hydraulic powder, preferably 0.001 part by mass or more, more preferably 0.005 parts by mass or more, further preferably 0.01 parts by mass or more, still more preferably 0.05 parts by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 3 parts by mass. Parts by weight, more preferably 0.9 parts by weight or less.

  The mixing of the hydraulic powder, water, the component (A), the component (B), and the component (C) can be performed using a mixer such as a mortar mixer or a forced twin-screw mixer. In addition, mixing is preferably performed for 1 minute or more, more preferably 2 minutes or more, and preferably 5 minutes or less, and more preferably 3 minutes or less. In preparing the hydraulic composition, the materials and agents described for the hydraulic composition and their amounts can be used.

  In the obtained hydraulic composition, the hydraulic composition is further filled into a mold, cured, and cured. Examples of the form include a form of a building and a form for a concrete product. Examples of the method of filling the mold include a method of directly charging the mixture from a mixer, a method of pumping the hydraulic composition with a pump, and introducing the composition into the mold.

  During the curing of the hydraulic composition, the composition may be cured by heating to promote the curing, and the curing may be promoted. Here, the heat curing can promote curing by holding the hydraulic composition at a temperature of 40 ° C. or more and 80 ° C. or less.

(Production method of cured product of hydraulic composition)
According to the present invention,
A step of preparing a hydraulic composition by mixing hydraulic powder, water, the component (A), the component (B), and the component (C). The prepared hydraulic composition is placed in a mold. Filling, curing, curing, and
Demolding the cured hydraulic composition,
A method for producing a cured product having:
The matters described in the surface aesthetic improver composition for a hydraulic composition, the hydraulic composition, and the method for producing the hydraulic composition of the present invention can also be applied to the method for producing the cured product.

  As a cured product of a hydraulic composition using a mold that is a concrete product, for civil engineering products, concrete piles, concrete poles, various block products for revetment, box culvert products, segment products used for tunnel construction, etc. Examples of bridge pier girder products include architectural products such as curtain wall products, columns, beams, and building member products used for floorboards.

(How to improve surface aesthetics)
The present invention provides a cured product of a hydraulic composition, which cures a hydraulic composition obtained by adding and kneading the component (A), the component (B), and the component (C) with cement and water. Provide a way to improve
Specific examples and preferred embodiments of the component (A), the component (B), and the component (C) used in the method for improving surface aesthetics of the present invention will be described in the description of the aesthetic enhancer composition for hydraulic compositions of the present invention, respectively. Is the same as
Specific examples and preferred embodiments of the hydraulic powder used in the method for improving the surface appearance of the present invention are the same as those described for the hydraulic composition of the present invention.
In addition, the items described in the method for producing an aesthetic enhancer composition for a hydraulic composition, the hydraulic composition, and the hydraulic composition of the present invention can be appropriately applied to the method for improving the surface appearance of the present invention. .

<Example 1 and Comparative Example 1>
(1) Preparation of mortar Cement (C), fly ash (FA), and fine aggregate (S) are charged and emptied using a mortar mixer (universal mixing stirrer manufactured by Dalton Co., Ltd., model: 5DM-03-γ). The kneading was performed at a low speed (63 rpm) of a mortar mixer for 10 seconds, and kneading water (W) containing the components (A) and (B) was added. Then, the mixture was fully kneaded for 120 seconds at a low speed rotation (63 rpm) of a mortar mixer to prepare a mortar.
The mixing conditions of the mortar were as shown in Table 1 below.

In the table, W / C is the mass ratio between the amount of water and the amount of cement, and is determined by [the amount of water / the amount of cement] × 100 (% by mass) (the same applies hereinafter).
In the table, W / P is the mass ratio of the amount of water and the amount of hydraulic powder (cement and fly ash), and is expressed as [water amount / (cement compound amount + fly ash). )] X 100 (% by mass) (the same applies hereinafter).

The components used in Table 1 are as follows.
・ Water (W): Tap water (water temperature 20 ° C)
Cement (C): Ordinary Portland cement (Two kinds: Ordinary Portland cement manufactured by Taiheiyo Cement Co., Ltd./Ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd. = 1/1, mass ratio) Density 3.16 g / cm ³
Fly ash (FA): Chubu Electric Power Co., Ltd., fine aggregate (S): Chengyang production Mountain sand Density 2.55g / cm ³

The components used in Table 2 are as follows.
Component (A): polyoxyethylene (30) ammonium oleyl ether sulfate (the number in parentheses is the average number of moles of ethylene oxide added), R in the general formula (A2) is an oleyl group, p is 30, and M is Compound which is an ammonium ion. Component (B): SN Deformer 466, Sannopco Co., Ltd., effective component 100% by mass, polyether-based antifoaming agent (a mixed solution in which 0.1% by mass is added to water becomes cloudy at 20 ° C.) Do)
Component (C) NSF: Naphthalenesulfonic acid formaldehyde condensate sodium salt, weight average molecular weight 15,000
-PCE: polycarboxylic acid-based dispersant synthesized in Production Example 1 below

Production Example 1 (Production of polycarboxylic acid-based dispersant)
114 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. 300 g of an aqueous solution of 60% by mass of ω-methoxy polyethylene glycol monomethacrylate (average number of moles of ethylene oxide 120: ester purity 100%), 11.5 g of methacrylic acid (reagent: manufactured by Wako Pure Chemical Industries, Ltd.), and 3-mercapto An aqueous solution obtained by mixing and dissolving 1.2 g of propionic acid and an aqueous solution obtained by dissolving 1.9 g of ammonium persulfate in 45 g of water were each dropped into the above reaction vessel over 1.5 hours. Thereafter, the mixture was aged at 80 ° C. for 1 hour, and an aqueous solution obtained by dissolving 0.8 g of ammonium persulfate in 15 g of water was added dropwise over 30 minutes, followed by aging at 80 ° C. for 1.5 hours. After completion of the ripening, the mixture was cooled to 40 ° C. or lower and neutralized with 9.6 g of a 48% aqueous sodium hydroxide solution to obtain a copolymer (polycarboxylic acid-based dispersant) having a weight average molecular weight of 54,000 (neutralization degree: 0. 7). Thereafter, the solid content was adjusted to 40% by mass with water to obtain a 40% by mass aqueous solution of a polycarboxylic acid-based dispersant. The molar ratio of ω-methoxy polyethylene glycol monomethacrylate / methacrylic acid is 20/80.

(2) Form Filling and Curing Process According to JIS A 1132, three cylindrical molds (bottom diameter: 5 cm, height 10 cm) are each filled with mortar by a two-layer filling method at 25 ° C. Cured in air (25 ° C.) in the room. The specimen hardened 24 hours after the preparation of the mortar was released from the mold to obtain a specimen. Three of these specimens were used to measure the compressive strength after 24 hours.
The 24-hour strength of the test specimen was measured based on JIS A1108, and the average value of three test specimens was obtained.
In addition, one of the test specimens was arbitrarily taken out and evaluated for black spots, surface bubbles, and releasability according to the following criteria.
* Black spot Rank C: Four or more black spots were present in 9 cm ² .
Rank B: One to three black spots existed in 9 cm ² .
Rank A: There was no black spot in 9 cm ² .
* Surface bubbles Rank C: Four or more holes having a diameter of 2 mm or more were present in 9 cm ² .
Rank B: One to three holes having a diameter of 2 mm or more were present in 9 cm ² .
Rank A: No hole having a diameter of 2 mm or more was present in 9 cm ² .
* Peelability 1: A peeled material having a size of 5 cm ² or more per one adhered to the mold.
2: Peeling of magnitude of less than one per 1 cm ² or more 5 cm ² is adhered to the mold.
3: Exfoliated material having a size of less than 1 cm ² per one piece adhered to the mold.
Table 2 shows the results.

* 1 HLB of RH: HLB of a compound in which R in formula (A1), (A2), (A3) or (A4) is RH (the same applies to the following Examples and Comparative Examples).
* 2 Addition amount: Addition amount (parts by mass) of component (A), component (B) or component (C) in terms of effective component based on 100 parts by mass of cement (the same applies to the following examples and comparative examples)

  From the results in Table 2, it can be seen that the effects of the components (A) and (B) are remarkable for the cement dispersant having a naphthalene ring of the component (C).

<Example 2 and Comparative Example 2>
The composition of the mortar was as shown in Table 3, and the mortar was prepared in the same manner as in Example 1 and Comparative Example 1 using the component (A) in Table 4 in the amounts shown in Table 4, and the same evaluation was performed. Table 4 shows the results. In addition, regarding the component (A) in the table, the number in parentheses of the compound is the average addition mole number of ethylene oxide, and is p in the general formula (A1) or the general formula (A2), or p in the general formula (A3) or the general formula (A3). It shows q + r in the formula (A4). In Table 4, compounds not corresponding to the component (A) are also shown in the column of the component (A) for convenience.

<Example 3 and Comparative Example 3>
The composition of the mortar was as shown in Table 5, and the mortar was prepared in the same manner as in Example 1 and Comparative Example 1 using the components (B) in Table 6 in the amounts shown in Table 6, and the same evaluation was performed. Table 6 shows the results. In Table 6, POE of the component (A) is an abbreviation for polyoxyethylene. In Table 6, compounds not corresponding to the component (B) are also shown in the column of the component (B) for convenience.

* 1 Transparency: Neither turbidity nor separation occurred, and it was transparent and uniform.
* 2 Separation: Separation in the form of oil droplets had occurred.

Claims (8)

(A) a compound represented by the following general formula (A1), a compound represented by the following general formula (A2), a compound represented by the following general formula (A3), and a compound represented by the following general formula (A4) One or more compounds selected from compounds,
(B) a compound in which a mixture obtained by adding 0.1% by mass to water becomes turbid or separated at 20 ° C;
(C) a cement dispersant comprising a polymer compound having a monomer unit containing a naphthalene ring;
A surface beauty improver composition for a hydraulic composition containing
(B) from polysiloxane, polyoxyethylene polyoxypropylene, polyoxypropylene, acetylene glycol, polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene alkylamide, trialkyl phosphate, and derivatives thereof Ri one or more compounds der selected,
The mass ratio of the cement dispersant composed of a polymer compound having a monomer unit containing a naphthalene ring of the compound of (A) and (C) is, in (C) / (A), 1 or more, 7 or less, Ru der , A surface beauty improver composition for hydraulic compositions.

[Wherein, R is a hydrophobic group containing a carbon atom,
AO is an alkyleneoxy group having 2 to 4 carbon atoms,
Y is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
p is the average number of moles of AO added, and is a number from 1 to 100,
q and r are the same or different and are each an average number of added moles of AO, are 0 or more, q + r is a number of 1 or more and 100 or less, and M, M ¹ , and M ² are The same or different, each being a counter ion,
X ¹ and X ² are the same or different and are each a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ] (B) is one or two selected from polysiloxane, polyoxyethylene polyoxypropylene, polyoxypropylene, acetylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene alkylamide, trialkyl phosphate, and derivatives thereof The composition according to claim 1, wherein the composition is at least one compound . Hydraulic powder,
water and,
(A) a compound represented by the following general formula (A1), a compound represented by the following general formula (A2), a compound represented by the following general formula (A3), and a compound represented by the following general formula (A4) One or more compounds selected from compounds,
(B) a compound in which a mixture obtained by adding 0.1% by mass to water becomes turbid or separated at 20 ° C;
(C) a cement dispersant comprising a polymer compound having a monomer unit containing a naphthalene ring;
A hydraulic composition containing
(B) is derived from polysiloxane, polyoxyethylene polyoxypropylene, polyoxypropylene, acetylene glycol, polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene alkylamide, trialkyl phosphate, and derivatives thereof. Ri one or more compounds der selected,
The mass ratio of the cement dispersant composed of a polymer compound having a monomer unit containing a naphthalene ring of the compound of (A) and (C) is, in (C) / (A), 1 or more, 7 or less, Ru der , Hydraulic compositions.

[Wherein, R is a hydrophobic group containing a carbon atom,
AO is an alkyleneoxy group having 2 to 4 carbon atoms,
Y is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
p is the average number of moles of AO added, and is a number from 1 to 100,
q and r are the same or different and are each an average number of added moles of AO, are 0 or more, q + r is 1 or more and 100 or less,
M, M ¹ and M ² are the same or different and are each a counter ion;
X ¹ and X ² are the same or different and are each a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ] (B) is one or two selected from polysiloxane, polyoxyethylene polyoxypropylene, polyoxypropylene, acetylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene alkylamide, trialkyl phosphate, and derivatives thereof 4. The hydraulic composition of claim 3, which is at least one compound . Hydraulic powder, water, (A) a compound represented by the following general formula (A1), a compound represented by the following general formula (A2), a compound represented by the following general formula (A3), and One or more compounds selected from the compounds represented by the general formula (A4), and (B) a compound in which a mixture obtained by adding 0.1% by mass to water becomes turbid or separated at 20 ° C. (C) mixing a cement dispersant comprising a polymer compound having a monomer unit containing a naphthalene ring with a cement dispersant to prepare a hydraulic composition,
Filling the prepared hydraulic composition in a mold, and curing, and
Demolding the cured hydraulic composition,
A method for producing a cured product having
(B) from polysiloxane, polyoxyethylene polyoxypropylene, polyoxypropylene, acetylene glycol, polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene alkylamide, trialkyl phosphate, and derivatives thereof Ri one or more compounds der selected,
The mass ratio of the cement dispersant composed of a polymer compound having a monomer unit containing a naphthalene ring of the compound of (A) and (C) is, in (C) / (A), 1 or more, 7 or less, Ru der , A method for producing a cured product.

[Wherein, R is a hydrophobic group containing a carbon atom,
AO is an alkyleneoxy group having 2 to 4 carbon atoms,
Y is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
p is the average number of moles of AO added, and is a number from 1 to 100,
q and r are the same or different and are each an average number of added moles of AO, are 0 or more, q + r is 1 or more and 100 or less,
M, M ¹ and M ² are the same or different and are each a counter ion;
X ¹ and X ² are the same or different and are each a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ] (B) is one or two selected from polysiloxane, polyoxyethylene polyoxypropylene, polyoxypropylene, acetylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene alkylamide, trialkyl phosphate, and derivatives thereof The method for producing a cured product according to claim 5, which is a compound of at least one kind . (A) a compound represented by the following general formula (A1), a compound represented by the following general formula (A2), a compound represented by the following general formula (A3), and a compound represented by the following general formula (A4) One or more compounds selected from compounds,
(B) a compound in which a mixture obtained by adding 0.1% by mass to water becomes turbid or separated at 20 ° C;
(C) A cement dispersant comprising a polymer compound having a monomer unit containing a naphthalene ring, and a cement and water are added and kneaded to cure a hydraulic composition, and the cured product of the hydraulic composition has an aesthetic appearance. Improvement method,
(B) is derived from polysiloxane, polyoxyethylene polyoxypropylene, polyoxypropylene, acetylene glycol, polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene alkylamide, trialkyl phosphate, and derivatives thereof. Ri one or more compounds der selected,
The mass ratio of the cement dispersant composed of a polymer compound having a monomer unit containing a naphthalene ring of the compound of (A) and (C) is, in (C) / (A), 1 or more, 7 or less, Ru der , A method for improving the aesthetic appearance of a cured product of a hydraulic composition.

[Wherein, R is a hydrophobic group containing a carbon atom,
AO is an alkyleneoxy group having 2 to 4 carbon atoms,
Y is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
p is the average number of moles of AO added, and is a number from 1 to 100,
q and r are the same or different and are each an average number of added moles of AO, are 0 or more, q + r is 1 or more and 100 or less,
M, M ¹ and M ² are the same or different and are each a counter ion;
X ¹ and X ² are the same or different and are each a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ] (B) is one or two selected from polysiloxane, polyoxyethylene polyoxypropylene, polyoxypropylene, acetylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene alkylamide, trialkyl phosphate, and derivatives thereof The method for improving the beauty of a cured product of the hydraulic composition according to claim 7, which is a compound of at least one kind .