JP6804492B2 - Dispersant composition for hydraulic composition - Google Patents

Description

The present invention relates to a dispersant composition for a hydraulic composition, a hydraulic composition, a method for improving dispersion performance, a dispersant composition for an inorganic powder, and a dispersant for a hydraulic composition.

The dispersant for the hydraulic composition is a chemical admixture used to disperse cement particles to reduce the amount of unit water required to obtain the required slump and improve the workability of the hydraulic composition. Is. Conventionally, as the dispersant, a naphthalene-based dispersant such as a formaldehyde condensate of naphthalene sulfonic acid, a polycarboxylic acid-based dispersant such as a copolymer of a monomer having a carboxylic acid and a monomer having an alkylene glycol chain, Melamine-based dispersants such as melamine sulfonic acid formaldehyde condensate are known.

The hydraulic composition has a use as a repair material for repairing and reinforcing various structures, and it is expected that the demand for it will increase in Japan in the future. The repair material is often prepared using, for example, a premix of a hydraulic powder and a powder dispersant. Naphthalene sulfonic acid-based dispersants have been evaluated for their insensitivity to fluctuations in the amount of surface water in aggregates, fluctuations in temperature and humidity in the casting environment, and excellent thixotropy, which affects iron leveling. , Suitable for use in repair materials.

On the other hand, a thickener is added to the hydraulic composition to improve moldability and the like. For example, Patent Document 1 describes an admixture for cement extrusion containing a cellulosic binder, a water reducing agent and / or a nonionic surfactant, a defoaming agent, and a silica powder.
Further, Patent Document 2 describes a predetermined nonionic-cellulose ether (component I), a predetermined nonionic surfactant, a predetermined anionic surfactant, a predetermined cationic surfactant, or naphthalene sulfonic acid / formaldehyde-. Described are thickener combinations for building materials, comprising at least one type of condensation product (Component II).

Japanese Unexamined Patent Publication No. 2006-232651 Japanese Unexamined Patent Publication No. 7-166150

The combined use of a naphthalene sulfonic acid-based dispersant and a polymer thickener was considered desirable in order to impart fluidity and moldability (appropriate viscosity, etc.) to the water-hard composition, but the polymer Among the thickeners, cellulosic thickeners typified by hydroxypropylmethylcellulose, hydroxyethylcellulose, and methylcellulose have poor compatibility with naphthalene sulfonic acid-based dispersants, and when both are used in combination, significant thickening occurs and fluidity occurs. Is not fully expressed.

The present invention provides a dispersant composition for a hydraulic composition from which a hydraulic composition having excellent fluidity can be obtained.

The present invention comprises (A) a polymer compound having a monomer unit containing a naphthalene ring and
(B) Cellulose-based thickener and
(C) A compound represented by the following general formula (C1), a compound represented by the following general formula (C2), a compound represented by the following general formula (C3), and a compound represented by the following general formula (C4). , And one or more compounds selected from the compounds represented by the following general formula (C5).
The present invention relates to a dispersant composition for a hydraulic composition containing.

[In the formula,
R is an alkyl group having 10 to 22 carbon atoms, an alkenyl group having 10 to 22 carbon atoms, a benzylphenyl group having 13 to 27 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. Is the basis and
X is O or COO
Each AO is an alkyleneoxy group having 2 to 4 carbon atoms independently.
n and m are the average number of moles added of AO, which are 20 or more and 200 or less, respectively.
o and p are the average number of moles added of AO, each of which is 0 or more, and o + p is 5 or more and 200 or less.
q and r are the average number of moles added of AO, each of which is 0 or more, and q + r is 5 or more and 200 or less.
Y is an independent hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms.
R ¹ is a residue obtained by removing hydroxyl groups from a multivalent alcohol having 3 or more and 20 or less hydroxyl groups.
t, u are each independently an integer, t + u corresponds to the number of hydroxyl groups in the polyhydric alcohol serving as a R ^1,
s1 and s2 are the average number of moles of AO added, and are numbers of 0 or more such that s1 × t + s2 × u is 5 or more and 200 or less. ]

Further, the present invention comprises a water-hard powder, water, a polymer compound having a monomer unit containing a naphthalene ring, (B) a cellulosic thickener, and (C) the general formula (C1). The compound represented by, the compound represented by the general formula (C2), the compound represented by the general formula (C3), the compound represented by the general formula (C4), and the compound represented by the general formula (C5). The present invention relates to a water-hardening composition containing one or more compounds selected from the represented compounds.

Further, the present invention prepares a water-hard composition by mixing a water-hard powder, water, and a polymer compound having a monomer unit containing (A) a naphthalene ring.
(B) Cellulose-based thickener, (C) the compound represented by the general formula (C1), the compound represented by the general formula (C2), the compound represented by the general formula (C3), the above. The compound represented by the general formula (C4) and one or more compounds selected from the compounds represented by the general formula (C5) are added.
The present invention relates to the method for improving the dispersion performance of the hydraulic powder of (A).

Further, the present invention comprises (A) a polymer compound having a monomer unit containing a naphthalene ring and
(B) Cellulose-based thickener and
(C) The compound represented by the general formula (C1), the compound represented by the general formula (C2), the compound represented by the general formula (C3), and the compound represented by the general formula (C4). , And one or more compounds selected from the compounds represented by the general formula (C5).
The present invention relates to a dispersant composition for an inorganic powder containing.

Further, the present invention comprises (A) a polymer compound having a monomer unit containing a naphthalene ring and
(B) Cellulose-based thickener and
(C) The compound represented by the general formula (C1), the compound represented by the general formula (C2), the compound represented by the general formula (C3), and the compound represented by the general formula (C4). , And one or more compounds selected from the compounds represented by the general formula (C5).
The present invention relates to the use of a composition containing the above as a dispersant for a hydraulic composition.

Hereinafter, (A) a polymer compound having a monomer unit containing a naphthalene ring is a component (A), (B) a cellulosic thickener is a component (B), and (C) a compound represented by the general formula (C1). , The compound represented by the general formula (C2), the compound represented by the general formula (C3), the compound represented by the general formula (C4), and the compound represented by the general formula (C5). One or more selected compounds will be described as the component (C).

According to the present invention, there is provided a dispersant composition for a hydraulic composition capable of obtaining a hydraulic composition having excellent fluidity.
Further, according to the present invention, there is provided a dispersant composition for an inorganic powder that can obtain a slurry having excellent fluidity.
Since the dispersant composition of the present invention can be obtained in powder form, it can be suitably used for premixing with hydraulic powder.

[Dispersant composition for hydraulic composition]
The details of the effect expression mechanism of the present invention are unknown, but it is presumed as follows.
The component (A), for example, a naphthalene sulfonic acid-based dispersant and the cellulosic thickener represented by the component (B), hydroxypropylmethyl cellulose, hydroxyethyl cellulose, and methyl cellulose, are water-soluble polymers but have a hydrophobic structure. Since they are amphipathic molecules having both of these substances and are strongly bound to each other by intermolecular interaction force such as hydrophobic interaction in an aqueous solvent, the fluidity of the component (A) is not sufficiently expressed when used in combination.
When the component (A), the component (B) and the component (C) are combined as in the present invention, the component (A), for example, the naphthalene sulfonic acid-based dispersant is conjugated by the surfactant which is the component (C). It is considered that a state is formed, which alleviates the interaction force between the component (A) and the component (B) and enhances the effect of the component (A) on expressing fluidity. The cellulosic thickener of the component (B) is a thickener that is desirable for obtaining a dispersant composition for a hydraulic composition in combination with the component (A) in terms of balance between economy and performance, handleability, and the like. However, there is a problem of a decrease in fluidity due to excessive thickening as described above. However, the present invention solves such a problem and provides a dispersant composition for a hydraulic composition having excellent fluidity. As described in Patent Document 2, it is known that a high thickening effect is exhibited by combining a nonionic-cellulose ether with a certain surfactant or a naphthalene sulfonic acid / formaldehyde-condensation product. .. However, when the component that brings about such a high thickening effect is used in a specific combination of the component (A), the component (B) and the component (C) as in the present invention, the hydraulic composition becomes excessively thickened. A hydraulic composition having excellent fluidity can be obtained without maintaining an appropriate viscosity. This is an unexpected effect that cannot be predicted by those skilled in the art from the findings of Cited Document 2.

<Ingredient (A)>
The component (A) is a polymer compound having a monomer unit containing a naphthalene ring. The component (A) can be used as a dispersant for a hydraulic composition containing a hydraulic powder such as cement or gypsum, for example.

The component (A) is preferably a naphthalene sulfonic 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. Naphthalene sulfonic acid formaldehyde condensate can be used as monomers as monomers, for example, methylnaphthalene, ethylnaphthalene, butylnaphthalene, hydroxynaphthalene, naphthalenecarboxylic acid, anthracene, phenol, cresol, cleosort oil, tar, melamine, etc. It may be co-condensed with an aromatic compound capable of co-condensing with naphthalene sulfonic acid such as urea, sulfanic acid and / or derivatives thereof.

The naphthalene sulfonic acid formaldehyde condensate or a salt thereof may be, for example, Mighty 150, Demor N, Demor RN, Demor MS, Demor SN-B, Demor SS-L (all manufactured by Kao Corporation), Cellflow 120, Labelin FD-40. , Labelin FM-45 (both manufactured by Daiichi Kogyo Co., Ltd.) and the like can be used.

The naphthalene sulfonic 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, still more preferably 80,000 or less, from the viewpoint of improving the fluidity of the water-hard composition. , More preferably 50,000 or less, even more preferably 30,000 or less. The naphthalene sulfonic 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, still more preferably 4, from the viewpoint of improving the fluidity of the water-hard composition. It is 000 or more, more preferably 5,000 or more. The naphthalene sulfonic acid formaldehyde condensate may be in an acidic state or in a neutralized state.

The molecular weight of the naphthalene sulfonic acid formaldehyde condensate or a salt thereof can be measured by 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: 0.7 ml / min
Detection: UV280nm
Sample size: 0.2 mg / ml
Standard substance: Polystyrene sulfonate soda equivalent manufactured by Nishio Kogyo Co., Ltd. (monodisperse sodium polystyrene sulfonate: molecular weight, 206, 1800, 4,000, 8,000, 18,000, 35,000, 88,000, 780,000)
Detector: Tosoh Corporation UV-8020

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

<Ingredient (B)>
The component (B) is a cellulosic thickener. Examples of the cellulosic thickener include hydroxypropylmethyl cellulose, hydroxyethyl cellulose, methyl cellulose and the like. As the cellulosic thickener, a cellulosic thickener selected from hydroxypropylmethylcellulose and methylcellulose is preferable. As the cellulosic thickener, those in the form of cellulose fibers, cellulose nanofibers, and cellulose nanocrystals can also be used.

The cellulosic thickener preferably has a structure in which the hydroxyl group of the glucose ring of cellulose is substituted with a methoxy group. In that case, from the viewpoint of water solubility and handleability, the cellulosic thickener has a degree of substitution defined by the average number of hydroxyl groups substituted with methoxy groups per glucose ring unit of cellulose, preferably 5 or less. It is more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, preferably 0.01 or more, more preferably 0.1 or more, still more preferably 0.5 or more, still more preferably 1. It is 0 or more.

Further, the cellulosic thickener preferably has a structure in which the hydroxyl group of the glucose ring of cellulose is substituted with a hydroxypropoxy group or a hydroxyethoxy group, such as hydroxypropylmethylcellulose or hydroxyethylcellulose. In that case, the cellulosic thickener has a substitution molar number defined by the average number of moles of hydroxypropoxy groups and / or hydroxyethoxy groups added per glucose ring unit of cellulose from the viewpoint of water solubility and handleability. It is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more. Even more preferably, it is 0.15 or more.

The cellulosic thickener has a structure in which the hydroxyl group of the glucose ring of cellulose is substituted with a methoxy group having a substitution number in the above range and a hydroxypropoxy group and / or a hydroxyethoxy group having a substitution number in the above range. Is more preferable.

<Component (C)>
The component (C) is a compound represented by the general formula (C1) [hereinafter, also referred to as compound (C1)], a compound represented by the general formula (C2) [hereinafter, also referred to as compound (C2)], and the like. The compound represented by the general formula (C3) [hereinafter, also referred to as compound (C3)], the compound represented by the general formula (C4) [hereinafter, also referred to as compound (C4)], and the general formula (C5). ) Is one or more selected from the compounds represented by (hereinafter, also referred to as compound (C5)]. The component (C) is one selected from compound (C1), compound (C2), compound (C3), compound (C4), and compound (C5) from the viewpoint of dispersibility and uniformity of the hydraulic composition. Or two or more compounds. The component (C) is preferably one or two selected from compound (C1), compound (C2), compound (C3), and compound (C4) from the viewpoint of dispersibility and uniformity of the water-hard composition. The above compounds, more preferably one or more compounds selected from compound (C1), compound (C2), and compound (C3), and even more preferably compound (C1) and compound (C2). ) Is one or more compounds selected from.

[Compound (C1)]
The compound (C1) is a compound represented by the general formula (C1).
In the general formula (C1), the alkyl group of R is preferably an aliphatic alkyl group, more preferably a linear aliphatic alkyl group, and even more preferably a linear primary aliphatic alkyl group. From the viewpoint of improving dispersibility, the alkyl group of R has 10 or more carbon atoms, more preferably 12 or more carbon atoms, and 22 or less, more preferably 20 or less carbon atoms. Examples of the alkyl group of R include a decyl group, a lauryl group, a myristyl group, a palmityl group, a stearyl group, a behenyl group, and an isostearyl group.

In the general formula (C1), the alkenyl group of R is preferably an aliphatic alkenyl group, more preferably a linear aliphatic alkenyl group, and further preferably a linear primary aliphatic alkenyl group. From the viewpoint of improving dispersibility, the alkenyl group of R has 10 or more carbon atoms, more preferably 12 or more carbon atoms, and 22 or less, more preferably 20 or less carbon atoms. Examples of the alkenyl group of R include an oleyl group.

In the general formula (C1), the benzylphenyl group of R is a phenyl group substituted with 1 or more and 3 or less benzyl groups. Specific examples thereof include a monobenzylphenyl group, a dibenzylphenyl group, a tribenzylphenyl group, and a combination thereof.

In the general formula (C1), the styrenated phenyl group of R is a phenyl group substituted with 1 or more and 3 or less styrenes. Specific examples thereof include a monostyrenated phenyl group, a distyrenated phenyl group, a tristyrenated phenyl group, and a combination thereof.

R is preferably an alkyl group from an economic point of view.
R is preferably an alkenyl group from the viewpoint of ease of dissolution in water.
R is a benzylphenyl group or a styrenated phenyl group from the viewpoint of developing the strength of the cured product and suppressing foaming of the water-hard composition.
When X in the general formula (C1) is COO, as R, for groups having no ring structure among the above groups, a group obtained by subtracting one carbon number from those groups can be exemplified. it can. For example, an undecylic group is exemplified instead of a lauryl group.

In the general formula (C1), X is O or COO, preferably O, from the viewpoint of fluidity.

In the general formula (C1), AO is an alkyleneoxy group having 2 or more and 4 or less carbon atoms, preferably an alkyleneoxy group having 2 or 3 carbon atoms, from the viewpoint of fluidity. It is preferable that the AO contains an alkyleneoxy group having 2 carbon atoms.

In the general formula (C1), n is the average number of moles added of AO, which is 5 or more and 200 or less from the viewpoint of cement dispersibility. From the viewpoint of improving the fluidity of the hydraulic composition, n is preferably 10 or more, more preferably 15 or more, further preferably 20 or more, even more preferably 25 or more, and interacting with the component (A). From the viewpoint of ease and economy, it is preferably 175 or less, more preferably 150 or less, still more preferably 125 or less, still more preferably 100 or less.

In the general formula (C1), Y is a hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms, and a hydrogen atom is preferable.

Examples of the compound (C1) include polyoxyethylene alkyl ethers such as polyoxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearylethylene, and polyoxyethylene oleyl ether, and polyoxyethylene alkenyl ethers. In addition, polyoxyethylene alkyl esters such as polyoxyethylene monostearate can be mentioned. Examples thereof include polyoxyethylene-substituted aryl ethers such as polyoxyethylene tribenzyl phenyl ether and polyoxyethylene distyrene phenyl ether.

[Compound (C2)]
The compound (C2) is a compound represented by the general formula (C2).
In the general formula (C2), specific examples and preferable examples of R are the same as those of compound (C1).
In the general formula (C2), m is the average number of moles added of AO, which is 5 or more and 200 or less. From the viewpoint of improving the fluidity of the hydraulic composition, n is preferably 10 or more, more preferably 15 or more, further preferably 20 or more, even more preferably 25 or more, and interacting with the component (A). From the viewpoint of ease and economy, it is preferably 175 or less, more preferably 150 or less, still more preferably 125 or less, still more preferably 100 or less.
In the general formula (C2), M is a counter ion, and examples thereof include hydrogen ion, alkali metal ion, alkaline earth metal ion (1/2 atom), and ammonium ion.
From the viewpoint of ease of producing the compound, M is preferably an ammonium ion.
M is an alkali metal ion preferably selected from alkali metal ions, more preferably sodium ions and potassium ions, from the viewpoint of the odor of the compound.
Examples of the compound (C2) include polyoxyethylene alkyl ether sulfate esterified products or salts thereof, polyoxyethylene alkenyl ether sulfate esterified products or salts thereof, and polyoxyethylene substituted aryl ether sulfate esterified products or salts thereof.

[Compound (C3)]
The compound (C3) is a compound represented by the general formula (C3).
In the general formula (C3), specific examples and preferable examples of R are the same as those of compound (C1).
In the general formula (C3), o and p are the average number of moles added of AO, each of which is 0 or more, and o + p is 5 or more and 200 or less. From the viewpoint of cement dispersibility, o + p is preferably 10 or more, more preferably 15 or more, further preferably 20 or more, even more preferably 25 or more, and easy to interact with the component (A) and economically. From this point of view, it is preferably 175 or less, more preferably 150 or less, still more preferably 125 or less, still more preferably 100 or less.
In the general formula (C3), Y is the same or different, and is a hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms, respectively. Each Y is preferably a hydrogen atom.

[Compound (C4)]
The compound (C4) is a compound represented by the general formula (C4).
In the general formula (C4), specific examples and preferable examples of R are the same as those of compound (C1).
In the general formula (C4), q and r are the average number of moles added of AO, each of which is 0 or more, and q + r is 5 or more and 200 or less. From the viewpoint of cement dispersibility, q + r is preferably 10 or more, more preferably 15 or more, still more preferably 20 or more, and preferably 175 from the viewpoint of ease of interaction with the component (A) and economics. Below, it is more preferably 150 or less, still more preferably 125 or less, still more preferably 100 or less.
In the general formula (C2), M is a counter ion, and examples thereof include hydrogen ion, alkali metal ion, alkaline earth metal ion (1/2 atom), and ammonium ion.
From the viewpoint of ease of producing the compound, M is preferably an ammonium ion.
M is an alkali metal ion preferably selected from alkali metal ions, more preferably sodium ions and potassium ions, from the viewpoint of the odor of the compound.
Examples of the compound (C4) include sulfate esterified products of aliphatic amine alkylene oxide adducts such as beef fat amine ethylene oxide adduct sulfate esterified products.

[Compound (C5)]
In the general formula (C5), the carbon number of R is preferably 12 or more, more preferably 14 or more, further preferably 16 or more, and preferably 24 or less, more preferably 22 or less, still more preferably 20 or less. ..
In the general formula (C5), R is preferably an alkenyl group, preferably a linear alkenyl group.
In the general formula (C5), s1 and s2 are the average number of moles of AO added, and are independently 0 or more, preferably 5 or more and 200 or less. Further, s1 and s2 are numbers of 0 or more in which s1 × t + s2 × u is 5 or more and 200 or less. The number of s1 × t + s2 × u is preferably 10 or more, more preferably 15 or more, and preferably 150 or less, more preferably 100 or less.
In the general formula (C5), t, u is an integer independently, t + u corresponds to the number of hydroxyl groups in the polyhydric alcohol to be R ^1. t + u is preferably 3 or more, more preferably 5 or more, and preferably 8 or less, more preferably 7 or less.
Examples of the compound (C5) include polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitol tetraoleic acid ester. Examples of the compound (C5) include ethylene oxide adducts of fats and oils such as polyoxyethylene hydrogenated castor oil.

<Composition of dispersant composition for hydraulic composition, etc.>
From the viewpoint of improving fluidity, the dispersant composition for a water-hard composition of the present invention contains the component (A) in a solid content of preferably 5% by mass or more, more preferably 25% by mass or more, still more preferably 50. Mass% or more, 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, still more preferably 90% by mass or less, still more preferable. Is contained in an amount of 85% by mass or less, more preferably 75% by mass or less.
Regarding the dispersant composition for hydraulic composition, the solid content means a component other than water.

From the viewpoint of improving fluidity, the dispersant composition for a water-hard composition of the present invention contains the component (B) in a solid content of preferably 0.05% by mass or more, more preferably 0.10% by mass or more. More preferably 0.15% by mass or more, still more preferably 0.20% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 2% by mass or less, still more preferably. Contains 1% by mass or less.

From the viewpoint of improving fluidity, the dispersant composition for a water-hard composition of the present invention contains the component (C) in a solid content of preferably 0.05% by mass or more, more preferably 0.10% by mass or more. More preferably 0.15% by mass or more, still more preferably 0.20% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 2% by mass or less, still more preferably. Contains 1% by mass or less.

The dispersant composition for a hydraulic composition of the present invention is a molar of the total amount of the component (C) with respect to the monomer unit containing a naphthalene ring in the component (A) from the viewpoint of obtaining a hydraulic composition having excellent fluidity. The ratio is preferably 0.4% or more and 30% or less. From the same viewpoint, the molar ratio is preferably 1% or more, more preferably 3% or more, still more preferably 5% or more, even more preferably 7% or more, and preferably 16% or less, more preferably 13. % Or less, more preferably 11% or less. This molar ratio is calculated based on the total amount of the monomer units containing the naphthalene ring in the component (A) and the total amount of the component (C). Specifically, it is calculated by the following formula (
The same applies below).
Mole ratio (%) = [[[(C) component total amount (mol)] / [(A) total amount of monomer units containing naphthalene ring in component (mol)]] × 100
When two or more components (A) and (C) are used, the total value of the moles can be used for calculation.

When the component (A) is a naphthalene sulfonic 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 naphthalene sulfonic acid or a salt thereof and formaldehyde. When the component (A) is a sodium salt of a naphthalene sulfonic acid formaldehyde condensate, the total amount (mol) of the monomer unit containing the naphthalene ring in the compound is calculated by the following formula. In the formula, the sodium salt of the naphthalene sulfonic acid formaldehyde condensate is referred to as NSF.
Total amount of monomer units containing naphthalene ring in NSF (mol) = [total mass of monomer unit containing naphthalene ring in NSF] / [molecular weight of monomer unit containing naphthalene ring in NSF]

The total mass of the monomer unit containing the naphthalene ring in the component (A) is the total mass of the compound when the component (A) is a naphthalene sulfonic acid or a condensate of a salt thereof and formaldehyde.
The total mass of the monomer unit containing the naphthalene ring in the component (A) is the case where the component (A) is a condensate of naphthalene sulfonic acid or a salt thereof, formaldehyde, and another monomer not containing the naphthalene ring. , The total mass of the compound minus the mass of the other monomer not containing the naphthalene ring and the monomer unit derived from formaldehyde.
The mass of the monomer unit derived from the other monomer not containing the naphthalene ring may be calculated from the amount charged at the time of synthesis, or the copolymerization mass ratio of a nuclear magnetic resonance spectrum device or the like can be obtained. It may be calculated using an analyzer.

The molecular weight of the monomer unit containing the naphthalene ring in the component (A) is the molecular weight of sodium naphthalene sulfonate (230.2) and formaldehyde (30) when the component (A) is a sodium salt of a formaldehyde condensate of naphthalene sulfonate. It can be determined as the value obtained by subtracting water (18.0), which is a by-product of the condensation reaction, from the sum of 0.0), that is, 242.2.
Further, the molecular weight of the component (C) may be obtained from the sum of the atomic weights constituting the molecule, or may be calculated using software such as ChemBioDraw (manufactured by PerkinElmer).

In the dispersant composition for a hydraulic composition of the present invention, from the viewpoint of the uniformity of the hydraulic composition, the component (A) / component (B), which is the mass ratio of the component (A) to the component (B), is contained. It is preferably 0.1 or more, more preferably 1 or more, still more preferably 10 or more, and preferably 100 or less, more preferably 90 or less, still more preferably 80 or less.

In addition to the components (A), (B), and (C), the dispersant composition for a hydraulic composition of the present invention includes a blast furnace slag fine powder, fine aggregate, a re-emulsified resin powder, a fluidizing agent, and a curing agent. Ingredients such as accelerators and setting retarders can be included. If necessary, these components can also be added to the dispersant composition for inorganic powders and the hydraulic composition of the present invention, which will be described later.

As the blast furnace slag fine powder, the blast furnace slag fine powder specified in JIS A 6206 “Blast furnace slag fine powder for concrete” is preferable. The specific surface area of the brain of the blast furnace slag fine powder is preferably 3000 cm ² / g or more, more preferably 3500 cm ² / g or more, further preferably 4000 cm ² / g or more, and preferably 8000 cm ² / g or less, more preferably. the 6000 cm ² / g or less, still more preferably not more than 5000 cm ² / g. The specific surface area of the brain of the blast furnace slag fine powder is determined according to JIS R 5201.

The fine aggregate preferably has a maximum particle size of 0.85 mm or less and contains less than 5% by mass of coarse particles having a particle size of more than 0.6 mm in 100% by mass of the fine aggregate. As such fine aggregate, sands such as silica sand, river sand, land sand, sea sand, and crushed sand, slag fine aggregate, recycled fine aggregate, and alumina cement clinker can be appropriately selected and used. As the fine aggregate, sands such as silica sand, river sand, land sand, sea sand and crushed sand, and those selected from alumina cement clinker can be preferably used.

The re-emulsified resin powder can be used regardless of its main component composition, whereby the abrasion resistance can be improved. From the viewpoint of weather resistance such as resistance to ultraviolet rays, it is preferably composed mainly of a vinyl acetate / acrylic copolymer. As a result, the surface of the cured product can have better durability and weather resistance.

Examples of the fluidizing agent include commercially available fluidizing agents such as formaldehyde condensate of melamine sulfonic acid, casein, casein calcium, polycarboxylic acid type, polyether type and polyether polycarboxylic acid type, which also have a water reducing effect. Can be used regardless of type.

Examples of the curing accelerator include inorganic lithium salts such as lithium carbonate, lithium chloride, lithium sulfate, lithium nitrate and lithium hydroxide, and organic lithium salts such as lithium oxalate, lithium acetate, lithium tartrate, lithium malate and lithium citrate. Also, sodium aluminate can be mentioned. Lithium carbonate is preferable from the viewpoint of curing acceleration effect, availability and price.

As the setting retarder, known ones can be used. As an example, organic acids such as oxycarboxylic acids, sugars such as glucose, maltose, and dextrin, sodium bicarbonate, sodium phosphate, etc. may be used alone or in combination of two or more components. it can.

The dispersant composition for a hydraulic composition of the present invention may be in any form of liquid or solid, but solid is preferable. The solid is preferably a powder. Here, the powder means solid particles including granules, flakes, pellets, granules and the like. The shape of the powder may be fixed or irregular. When the dispersant composition for a hydraulic composition of the present invention is a powder, the average particle size is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 1 μm or more, and preferably 2000 μm or less. , More preferably 1500 μm or less, still more preferably 1000 μm or less.

The dispersant composition for a hydraulic composition of the present invention has a viscosity of 13,000 mPa · s when 0.8 parts by mass is added to 100 parts by mass of cement to a reference cement paste having the following composition. It can be as follows. Preferably, the dispersant for a water-hard composition of the present invention contains 0.35 parts by mass of the component (A) and 0.30 parts by mass of the component (B) with respect to 100 parts by mass of the cement in the reference cement paste having the following composition. When the parts (C) are added so as to be 0.15 parts by mass by mass, the viscosity of the cement paste can be 13,000 mPa · s or less. Here, the viscosity of the cement paste is 20 ° C., B-type viscometer (VISCOTESTER VT-04, manufactured by Rion Co., Ltd.), rotor No. 1. It was measured under the condition of a rotation speed of 62.5 rpm.
* Composition of standard cement paste-Cement: 400 g, 1: 1 (mass ratio) mixture of ordinary Portland cement manufactured by Taiheiyo Cement Co., Ltd. and ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd., specific gravity 3.16
・ Tap water: 160g

[Dispersant composition for inorganic powder]
Specific examples and preferred embodiments of the component (A), the component (B) and the component (C) used in the dispersant composition for an inorganic powder of the present invention are the dispersant composition for a hydraulic composition of the present invention, respectively. It is the same as that described in.

The inorganic powder is not particularly limited, and examples thereof include the following. Among the inorganic powders, the one used for the hydraulic powder is the dispersant composition for the hydraulic composition of the present invention.
(1) Hydroxide powders such as cement and plaster (2) Powders with posoran action such as fly ash, silica fume, volcanic ash and silicate clay (3) Latent hydrohardness such as coal ash, blast furnace slag and silicate soil Powder (4) Caolin, aluminum silicate, clay, talc, mica, calcium silicate, sericite, bentonite and other silicates (5) Calcium carbonate, magnesium carbonate, barium carbonate, basic lead carbonate and other carbonates (6) Sulfates such as calcium sulfate and barium sulfate (7) Chromates such as strontium chromate and pigment yellow (8) Molybdenate such as zinc molybdenate, zinc molybdate and magnesium molybdenum (9) Alumina, Metal oxides such as antimony oxide, titanium oxide, cobalt oxide, triiron tetroxide, diiron trioxide, trilead tetroxide, lead monoxide, chromium green oxide, tungsten trioxide, yttrium oxide (10) aluminum hydroxide, Metal hydroxides such as magnesium hydroxide, calcium hydroxide, iron hydroxide and metatitanic acid (11) Metal carbides such as silicon carbide, tungsten carbide, boron carbide and titanium carbide (12) Aluminum nitride, silicon nitride, boron nitride, Zirconia, barium titanate, satin white, carbon black, graphite, chrome yellow, mercury sulfide, ultramarine, Paris blue, titanium yellow, chrome vermilion, lithopon, copper acetohydrate, nickel, silver, palladium, zircone titanate Other inorganic powders not classified in (1) to (11) above, such as lead acid acid.

The dispersant composition for inorganic powder of the present invention can be used for an inorganic powder slurry. The inorganic powder slurry is a slurry containing an inorganic powder, water, a component (A), a component (B), and a component (C). When the inorganic powder is a hydraulic powder, the slurry is the hydraulic composition of the present invention.
Specific examples and preferred embodiments of the components (A), (B) and (C) used in the slurry of the present invention are the same as those described in the dispersant composition for a hydraulic composition of the present invention, respectively. is there.

Examples of the inorganic powder slurry include a slurry using blast furnace slag as the inorganic powder (hereinafter referred to as blast furnace slag slurry). The blast furnace slag slurry preferably contains the dispersant composition for inorganic powder of the present invention in an amount of 0.01 parts by mass or more and 5.0 parts by mass with respect to 100 parts by mass of the blast furnace slag. The blast furnace slag slurry contains water, preferably 40 parts by mass or more, more preferably 45 parts by mass or more, and preferably 250 parts by mass, more preferably 230 parts by mass or less, based on 100 parts by mass of blast furnace slag.

[Hydraulic composition]
The present invention provides a hydraulic composition containing a hydraulic powder, water, a component (A), a component (B), and a component (C). As the component (A), the component (B), and the component (C), the hydraulic composition may be prepared by adding the dispersant composition for the hydraulic composition of the present invention, and each of them may be prepared separately. A hydraulic composition may be prepared by adding it to a system containing a hydraulic powder and water.

The hydraulic powder used in the hydraulic composition of the present invention is a powder having physical properties that is cured by a hydration reaction, and examples thereof include cement and gypsum. Preferred are ordinary Portland cement, belite cement, moderate heat cement, early-strength cement, ultra-fast-strength cement, sulfate-resistant cement and the like. In addition, blast furnace slag cement, fly ash cement, silica fume cement, etc. to which powder having pozolan action and / or latent hydrohardness such as blast furnace slag, fly ash, silica fume, etc., and stone powder (calcium carbonate powder) are added to cement, etc. It may be.

The water-hard composition of the present invention has a water / water-hard powder ratio [mass percentage (mass%) of water and water-hard powder in a slurry, usually abbreviated as W / P, but when the powder is cement. , W / C abbreviated. ], However, from the viewpoint that fluidity can be exhibited even with a small amount of water, it is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and preferably 90% by mass or less. It is more preferably 70% by mass or less, still more 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 dispersant composition for the hydraulic composition of the present invention, respectively. Is the same as.

In the water-hardening composition of the present invention, the component (A) is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, still more preferably 0 part by mass, based on 100 parts by mass of the water-hard powder. 3 parts by mass or more, more preferably 0.4 parts by mass or more, still more preferably 0.5 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass. Hereinafter, it is more preferably contained in an amount of 1 part by mass or less.

In the water-hardening composition of the present invention, the component (B) is preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass or more, still more preferably 0. parts by mass, based on 100 parts by mass of the water-hard powder. Containing 15 parts by mass or more, more preferably 0.20 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 2 parts by mass or less, still more preferably 1 part by mass or less. To do.

In the hydraulic composition of the present invention, from the viewpoint of excellent fluidity, the molar ratio of the total amount of the component (C) to the monomer unit containing the naphthalene ring in the component (A) is preferably 0.4% or more and 30% or less. Is. From the same viewpoint, the molar ratio is preferably 1% or more, more preferably 3% or more, still more preferably 5% or more, even more preferably 7% or more, and preferably 16% or less, more preferably 13. % Or less, more preferably 11% or less.

In the water-hardening composition of the present invention, the component (C) is preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass or more, still more preferably 0. parts by mass, based on 100 parts by mass of the water-hard powder. Containing 15 parts by mass or more, more preferably 0.20 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 2 parts by mass or less, still more preferably 1 part by mass or less. To do.

In the water-hardening composition of the present invention, the total of the component (A), the component (B) and the component (C) is preferably 0.05 from the viewpoint of fluidity with respect to 100 parts by mass of the water-hardening powder. More than parts by mass, more preferably 0.10 parts by mass or more, still more preferably 0.15 parts by mass or more, still more preferably 0.20 parts by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass. Hereinafter, the content is more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less.

In the hydraulic composition of the present invention, from the viewpoint of the uniformity of the hydraulic composition, the component (A) / component (B), which is the mass ratio of the component (A) to the component (B), is preferably 0.01. The above is more preferably 0.05 or more, further preferably 0.1 or more, and preferably 100 or less, more preferably 50 or less, still more preferably 10 or less.

The hydraulic composition of the present invention preferably has a viscosity (20 ° C.) of 13,000 mPa · s or less. Here, the viscosity is measured by the method described for the reference cement paste. When the hydraulic composition of the present invention contains an aggregate, the viscosity may be the viscosity of the hydraulic composition having a composition excluding the aggregate.

The hydraulic composition of the present invention preferably contains an aggregate. Examples of the aggregate include an aggregate selected from a fine aggregate and a coarse aggregate. Examples of the fine aggregate include those specified by No. 2311 in JIS A0203-2014. Fine aggregates include 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. Examples include fine aggregates. In addition, examples of the coarse aggregate include those specified by No. 2312 in JIS A0203-2014. For example, coarse aggregates include river gravel, land gravel, mountain gravel, sea gravel, lime gravel, crushed stones, 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. As the fine aggregate and the coarse aggregate, different types may be mixed and used, or a single type may be used.

When the hydraulic composition is concrete, the amount of coarse aggregate used reduces the development of the strength of the hydraulic composition and the amount of hydraulic powder used such as cement, and improves the filling property into the mold and the like. From the viewpoint, the bulk volume is preferably 50% or more, more preferably 55% or more, further preferably 60% or more, and preferably 100% or less, more preferably 90% or less, still more preferably 80% or less. Is. The bulk volume is the ratio of the volume (including voids) of the coarse aggregate in 1 m ^{3 of} concrete.
When the hydraulic composition is concrete, the amount of fine aggregate used is preferably 500 kg / m ³ or more, more preferably 600 kg / m ³ or more, and further, from the viewpoint of improving the filling property into a mold or the like. It is preferably 700 kg / m ³ or more, and preferably 1000 kg / m ³ or less, more preferably 900 kg / m ³ or less.
If the hydraulic composition is mortar, the amount of fine aggregate is preferably from 800 kg / ^{m 3} or more, more preferably 900 kg / ^{m 3} or more, more preferably 1000 kg / ^{m 3} or more, and, preferably 2000kg / 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. Of these, concrete using cement is preferable. The hydraulic composition of the present invention can be used for self-leveling, refractory, plaster, lightweight or heavy concrete, AE, repair, prepacked, traymy, ground improvement, grout, 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, re-emulsifying resin powder, fluidizing agent, curing accelerator, setting retarder, AE agent, foaming agent, foaming agent, waterproofing agent, etc. [excluding those corresponding to components (A) to (C)]. Be done.

[Method for producing dispersant composition for hydraulic composition]
The present invention provides a method for producing a dispersant composition for a hydraulic composition, which mixes a component (A), a component (B), and a component (C).
Specific examples and preferred embodiments of the component (A), the component (B), and the component (C) used in the method for producing a dispersant composition for a hydraulic composition of the present invention are the hydraulic composition of the present invention, respectively. It is the same as that described in the dispersant composition for use.
In addition, the matters described in the dispersant composition for a hydraulic composition of the present invention can be appropriately applied to the method for producing a dispersant composition for a hydraulic composition of the present invention.
The method for producing a dispersant composition for a hydraulic composition of the present invention is suitable as a method for producing a dispersant composition for a hydraulic composition of the present invention.

The method for producing the dispersant composition for a hydraulic composition of the present invention is for a hydraulic composition in which the powder of the component (A), the powder of the component (B), and the powder of the component (C) are mixed. Examples thereof include a method for producing a powder dispersant composition. The mixing amount of each component is preferably an amount corresponding to the preferable content described in the dispersant composition for hydraulic composition of the present invention.

Further, as a method for producing a dispersant composition for a hydraulic composition of the present invention, a liquid composition containing the component (A), the component (B), the component (C), and water is dried and (A). A method for producing a powder dispersant composition for a hydraulic composition, which obtains a powder composition containing the component (B), the component (B), and the component (C). Also in this method, the amount of each component is preferably an amount corresponding to the preferable content described in the dispersant composition for hydraulic composition of the present invention.

[Method for producing hydraulic composition]
The present invention provides a method for producing a hydraulic composition in which a hydraulic powder, water, a component (A), a component (B), and a component (C) are mixed.
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 the dispersant composition for the hydraulic composition of the present invention, respectively. It is the same as that described in.
Further, specific examples and preferred embodiments of the hydraulic powder used in the method for producing the hydraulic composition of the present invention are the same as those described in the hydraulic composition of the present invention.
In addition, the dispersant composition for a hydraulic composition of the present invention and the matters described in the hydraulic composition can be appropriately applied to the method for producing a hydraulic composition of the present invention.

The method for producing a hydraulic composition of the present invention contains (I) a hydraulic powder and one or more components selected from (II) (A) component, (B) component, and (C) component. It is preferable to mix the powder composition to be produced with water.
That is, for example, a powder composition (so-called premix) containing a hydraulic powder, a component (A), a component (B), and a component (C) can be used.
Further, a powder composition containing a hydraulic powder, a component (A), and a component (B) can be used. In this case, it is preferable to mix the powder composition with a liquid composition containing the component (C) and water.
As a method for producing a hydraulic powder of the present invention, a powder containing (I) a hydraulic powder and one or more components selected from (II) (A) component, (B) component, and (C) component. Examples thereof include a method for producing a hydraulic composition in which the composition and water are mixed.

It is also possible to produce a hydraulic composition without using the powder composition as described above. For example, a method of mixing the liquid composition containing the component (C) and water with the hydraulic powder and then mixing the component (B) can be mentioned. Further, a liquid composition containing the component (B), the component (C) and water can be mixed with the hydraulic powder. In these methods, the component (A) can be mixed at any time.

Mixing the hydraulic powder, water, the component (A), the component (B), and the component (C) is performed using a mixer such as a hand mixer, a disc mixer, a mortar mixer, or a forced twin-screw mixer. be able to. Further, the mixture is preferably mixed for 1 minute or longer, more preferably 2 minutes or longer, and preferably 5 minutes or shorter, more preferably 3 minutes or shorter. In preparing the hydraulic composition, the materials and chemicals described in the hydraulic composition and their amounts can be used.

The obtained hydraulic composition is further filled with a hydraulic composition in a mold, or applied to the surface of a structure made of a hydraulic composition such as concrete or mortar, cured, and cured. Examples of formwork include building formwork, formwork for concrete products, and the like. Examples of the filling method into the mold include a method of directly charging from a mixer or a container, a method of pumping a hydraulic composition with a pump, and a method of introducing the hydraulic composition into the mold. Further, as a method of applying to the surface of the structure, a method of using a dragonfly or a trowel for plastering can be mentioned.

When curing the hydraulic composition, it may be heat-cured to promote curing to promote curing. Here, the heat curing can promote the curing by holding the hydraulic composition at a temperature of 40 ° C. or higher and 80 ° C. or lower.

According to the present invention, a hydraulic powder, water, a component (A), a component (B), and a component (C) are mixed to prepare a hydraulic composition, and the hydraulic composition is cured. , A method for producing a cured product is provided.
The method for producing a cured product of the present invention is
A step of preparing a hydraulic composition by mixing a hydraulic powder, water, a component (A), a component (B), and a component (C).
Including a step of applying the prepared hydraulic composition to the surface of a structure or filling a mold, and a step of curing and curing the hydraulic composition, if necessary.
If necessary, a step of removing the cured hydraulic composition,
Can be included. The structure is preferably a structure formed of a hydraulic composition different from the hydraulic composition used for coating.
The matters described in the method for producing a dispersant composition for a hydraulic composition, the hydraulic composition, the method for producing a dispersant composition for a hydraulic composition, and the method for producing a hydraulic composition of the present invention are the production of this cured product. It can also be applied to the method.

As hardened bodies of water-hardening compositions using formwork, which is a concrete product, as civil engineering products, various block products for shore protection, box culvert products, segment products used for tunnel construction, etc., girder products for piers, etc. Examples of building products include curtain wall products, pillars, beams, building member products used for floorboards, and the like.

[Method of improving dispersion performance]
In the present invention, the component (A) is added to the component (B) and the component (C) when the hydraulic powder, water, and the component (A) are mixed to prepare a hydraulic composition. Provide a method for improving the dispersion performance of hydraulic powder. The component (A) is known as a dispersant for hydraulic powders, and its dispersion performance improves the fluidity of the hydraulic composition. However, it is known that when the component (A) and the component (B) are used in combination, the viscosity is remarkably increased and the fluidity of the hydraulic composition is reduced. In the present invention, the addition of the component (C) improves the fluidity of the hydraulic composition as compared with the case where the components (A) and (B) are used. That is, it can be said that the addition of the component (C) improves the dispersion performance of the component (A) with respect to the hydraulic powder.

Specific examples and preferred embodiments of the component (A), the component (B), and the component (C) used in the method for improving the dispersion performance of the present invention are described in the dispersant composition for a hydraulic composition of the present invention, respectively. It is the same as the one.
Further, specific examples and preferred embodiments of the hydraulic powder used in the method for improving the dispersion performance of the present invention are the same as those described in the hydraulic composition of the present invention.
Further, the matters described in the method for producing a dispersant composition for a hydraulic composition, the hydraulic composition, the method for producing a dispersant composition for a hydraulic composition, and the method for producing a hydraulic composition of the present invention are the matters described in the present invention. It can be appropriately applied to a method for improving dispersion performance.

〔use〕
The present invention discloses the use of a composition containing a component (A), a component (B), and a component (C) as a dispersant for a hydraulic composition.
The present invention also discloses the use of a composition containing a hydraulic powder, water, a component (A), a component (B), and a component (C) as a hydraulic composition.
For these uses, the method for producing a dispersant composition for a hydraulic composition, a dispersant composition for an inorganic powder, a hydraulic composition, a dispersant composition for a hydraulic composition, and a hydraulic composition of the present invention. The items described in the manufacturing method and the method for improving the dispersion performance of the above can be appropriately applied.

The present invention also discloses a composition containing a component (A), a component (B), and a component (C) for use in a dispersant for a hydraulic composition.
The present invention also discloses a composition containing a hydraulic powder, water, a component (A), a component (B), and a component (C) for use in a hydraulic composition.
These compositions include, a method for producing a dispersant composition for a hydraulic composition, a dispersant composition for an inorganic powder, a hydraulic composition, a dispersant composition for a hydraulic composition, and a hydraulic composition of the present invention. The matters described in the method for producing a product and the method for improving the dispersion performance can be appropriately applied.

<Example 1 and Comparative Example 1>
(1) Preparation of cement paste Using the following compounding ingredients, a cement paste was prepared with the following composition. The following compounding ingredients were kneaded with a hand mixer (650 rpm, 30 seconds, then 820 rpm for 30 seconds) to prepare a cement paste. In Table 1 (b), all of the cement pastes of Examples 1-2-1 to 1-2-16 have a viscosity (20 ° C.) measured by the method described for the reference cement paste of 13,000 mPa. It was less than or equal to s.

A dry mix containing a powder dispersant [component (A)], a cellulosic thickener [component (B)] and cement was mixed with tap water to prepare a cement paste. Of the surfactants [component (C)], c-1 to c-3 were added to the dry mix. On the other hand, of the surfactants [component (C)], c-4 to c-15 were blended in tap water. Each component was used so that the amount added to cement was as shown in Table 1. The amount added to cement in the table is a part by mass with respect to 100 parts by mass of cement, the component (A) and the component (C) are in terms of pure content, and the component (B) is a tangible amount added.

* Blending ingredients and blending amount [The amount of ingredients (A) to (C) added is shown in the table]
-Cement: 400 g, 1: 1 (mass ratio) mixture of ordinary Portland cement manufactured by Taiheiyo Cement Co., Ltd. and ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd., specific gravity 3.16
-Component (A): Powder dispersant, naphthalene sulfonic acid formaldehyde condensate, Mighty 100 (manufactured by Kao Corporation)

(B) Component b-1: Cellulose-based thickener, hydroxypropylmethylcellulose, Asukaclean D, manufactured by Shin-Etsu Chemical Co., Ltd. b-2: Cellulose-based thickener, hydroxypropylmethylcellulose, Metrose 90SH, Shin-Etsu Chemical Co., Ltd. Made by the company (methoxy group substitution degree: 1.4, hydroxypropoxy group substitution molar number: 0.20)
b-3: Cellulose-based thickener, hydroxypropylmethyl cellulose, hi-Metros 90SH, manufactured by Shin-Etsu Chemical Co., Ltd. b-4: Cellulose-based thickener, hydroxyethyl cellulose, HEC AW-15F, manufactured by Sumitomo Seika Co., Ltd. (Hydroxy) Number of moles substituted with ethoxy group: 1.5 to 2.5)

(C) Component c-1: Polyoxyethylene stearyl ether (average number of moles of ethylene oxide added 50)
c-2: Polyoxyethylene monostearate (average number of moles of ethylene oxide added 150)
c-3: Polyoxyethylene styrenated phenyl ether (average number of moles of ethylene oxide added 64, styrene is a mixture of mono-, di-, and tri-styrene compounds, average degree of styrene substitution: 2 (di styrene))
c-4: Polyoxyethylene oleyl ether sulfate sodium salt (average number of moles of ethylene oxide added 23)
c-5: Polyoxyethylene stearyl ether sulfate ammonium salt (average number of moles of ethylene oxide added 50)
c-6: Polyoxyethylene oleyl ether sulfate ammonium salt (average number of moles of ethylene oxide added 30)
c-7: Polyoxyethylene polyoxypropylene alkyl ether (average ethylene oxide molar addition number 10, propylene oxide average addition mole number 5, alkyl group: lauryl group and myristyl group)
c-8: Polyoxyethylene C11-C15 secondary alkyl ether (average number of moles of ethylene oxide added 9)
c-9: Polyoxyethylene hydrogenated beef tallow amine ether (average number of moles of ethylene oxide added 20)
c-10: Polyoxyethylene styrenated phenyl ether sulfate ammonium salt (ethylene oxide average addition molar number 13, styrene is a mixture of mono-, di- and tri-styrene compounds, average styrene substitution: 2 (di styrene))
c-11: Polyoxyethylene sorbitol tetraoleate (average number of moles of ethylene oxide added 30)
c-12: Polyoxyethylene hardened castor oil (average number of moles of ethylene oxide added 25)
c-13: Polyoxyethylene hydrogenated beef tallow amine ether sulfate ammonium salt (average number of moles of ethylene oxide added 20)
c-14: Polyoxyethylene lauryl ether (average number of moles of ethylene oxide added 47)
c-15: Polyoxyethylene oleyl ether (average number of moles of ethylene oxide added 30)

・ Tap water: 160g

(2) Evaluation (2-1) Evaluation of cement paste fluidity The cement paste immediately after kneading was filled in a flow cone having a diameter of 50 mm and a height of 50 mm, and the paste flow was measured. The results are shown in Table 1.

(2-2) Evaluation of performance when thickener is used in combination For Examples (excluding some), the paste flow improvement rate (%) is calculated from the following formula using the paste flow measured in (2-1). It was calculated and the performance when the component (C) was used in combination was evaluated. The results are shown in Table 1.
Paste flow maintenance rate (%) = (paste flow of example / reference paste flow) × 100
The standard was a comparative example of the composition excluding the component (C) from the composition of the example to be evaluated.

<Example 2 and Comparative Example 2>
(1) Preparation of mortar Using the following compounding ingredients, a mortar was prepared with the following composition. The mortar was prepared by kneading the ingredients (60 rpm, 60 seconds, then 120 rpm, 120 seconds) using a mortar mixer specified in JIS R 5201.
* Blending ingredients and blending amount [The amount of ingredients (A) to (C) added is shown in the table]
-Cement: 800 g, 1: 1 (mass ratio) mixture of ordinary Portland cement manufactured by Taiheiyo Cement Co., Ltd. and ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd., specific gravity 3.16
-Component (A): Powder dispersant, naphthalene sulfonic acid formaldehyde condensate, Mighty 100 (manufactured by Kao Corporation)
-Ingredient (B): 1 g (0.125 parts by mass with respect to 100 parts by mass of cement), cellulosic thickener, hydroxypropyl methylcellulose, Asukaclean D, manufactured by Shin-Etsu Chemical Co., Ltd.-Ingredient (C): Polyoxy Ethylene stearyl ether (average number of moles of ethylene oxide added 50)
・ Fine aggregate: 700g, from Joyo, Kyoto Prefecture, surface dry specific gravity 2.50
・ Tap water: 280g
The powder dispersant [(A) component] and the surfactant [(C)] were used after being dry-mixed in cement in advance so that the amounts added to the cement were as shown in Table 2. The amount added to cement is parts by mass with respect to 100 parts by mass of cement.
Moreover, in some examples, the surface water amount of the fine aggregate was adjusted by the following method.
* Adjustment of surface water amount of fine aggregate The surface water amount is sprayed by spraying on the fine aggregate in a dry surface state, and the surface water amount is measured by the method described in JIS A 1111. The surface water amount is 2% by mass or 5 Mass% fine aggregate was prepared.

(2) Evaluation Evaluation of mortar fluidity The mortar immediately after kneading was filled in a flow cone (upper diameter 70 mm × lower diameter 100 mm × height 60 mm) described in JIS R 5201, and the mortar flow was measured. The results are shown in Table 2.

Claims (10)

(A) Naphthalene sulfonic acid formaldehyde condensate or a salt thereof ,
(B) Cellulose-based thickener and
(C) a compound represented by the following general formula (C2), the following general formula (C3) a compound represented by the following general formula (C4) in one or more selected compounds or we represented Compounds and
Dispersant composition for hydraulic composition containing.

[In the formula,
R is an alkyl group having 10 to 22 carbon atoms, an alkenyl group having 10 to 22 carbon atoms, a benzylphenyl group having 13 to 27 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. Is the basis and
Each AO is an alkyleneoxy group having 2 to 4 carbon atoms independently.
m is the average number of moles added of AO, which is 5 or more and 200 or less.
o and p are the average number of moles added of AO, each of which is 0 or more, and o + p is 5 or more and 200 or less.
q and r are the average number of moles added of AO, each of which is 0 or more, and q + r is 5 or more and 200 or less.
Y is an independent hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms.
M is a counterion independently of each other. ] The dispersant composition for a hydraulic composition according to claim 1, wherein the molar ratio of the total amount of (C) to the monomer unit containing a naphthalene ring in (A) is 0.4% or more and 30% or less. The dispersant composition for a hydraulic composition according to claim 1 or 2 , wherein the form is a powder. A hydraulic powder, and water, (A) naphthalenesulfonic acid formaldehyde condensate or a salt thereof, (B) and cellulose-based thickener, a compound represented by (C) under following general formula (C2), the following formula (C3) a compound represented by, and one or more compounds and hydraulic composition containing the selected compound or al represented by the following general formula (C4).

[In the formula,
R is an alkyl group having 10 to 22 carbon atoms, an alkenyl group having 10 to 22 carbon atoms, a benzylphenyl group having 13 to 27 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. Is the basis and
Each AO is an alkyleneoxy group having 2 to 4 carbon atoms independently.
m is the average number of moles added of AO, which is 5 or more and 200 or less.
o and p are the average number of moles added of AO, each of which is 0 or more, and o + p is 5 or more and 200 or less.
q and r are the average number of moles added of AO, each of which is 0 or more, and q + r is 5 or more and 200 or less.
Y is an independent hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms.
M is a counterion independently of each other. ] The hydraulic composition according to claim 4 , wherein the molar ratio of the total amount of (C) to the monomer unit containing the naphthalene ring in (A) is 0.4% or more and 30% or less. The hydraulic composition according to claim 4 or 5 , which contains 0.001 part by mass or more and 10 parts by mass or less of (A) with respect to 100 parts by mass of the hydraulic powder. When preparing a water-hard composition by mixing a water-hard powder, water, and (A) a formaldehyde condensate of naphthalene sulfonic acid or a salt thereof .
(B) a cellulose-based thickener, compounds represented by the compound represented by (C) under following general formula (C2), the compound represented by the following general formula (C3), and the following general formula (C4) adding the one or more compounds selected ones or al,
(A) Method for improving dispersion performance with respect to hydraulic powder.

[In the formula,
R is an alkyl group having 10 to 22 carbon atoms, an alkenyl group having 10 to 22 carbon atoms, a benzylphenyl group having 13 to 27 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. Is the basis and
Each AO is an alkyleneoxy group having 2 to 4 carbon atoms independently.
m is the average number of moles added of AO, which is 5 or more and 200 or less.
o and p are the average number of moles added of AO, each of which is 0 or more, and o + p is 5 or more and 200 or less.
q and r are the average number of moles added of AO, each of which is 0 or more, and q + r is 5 or more and 200 or less.
Y is an independent hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms.
M is a counterion independently of each other. ] The dispersion performance according to claim 7 , wherein (C) is added so that the molar ratio of the total amount of (C) to the monomer unit containing the naphthalene ring in (A) is 0.4% or more and 30% or less. How to improve. (A) Naphthalene sulfonic acid formaldehyde condensate or a salt thereof ,
(B) Cellulose-based thickener and
Compounds represented by (C) under following general formula (C2), the compound represented by the following general formula (C3), and one or two elements selected compound or al represented by the following general formula (C4) With the above compounds
Use of a composition containing the above as a dispersant for a hydraulic composition.

[In the formula,
R is an alkyl group having 10 to 22 carbon atoms, an alkenyl group having 10 to 22 carbon atoms, a benzylphenyl group having 13 to 27 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. Is the basis and
Each AO is an alkyleneoxy group having 2 to 4 carbon atoms independently.
m is the average number of moles added of AO, which is 5 or more and 200 or less.
o and p are the average number of moles added of AO, each of which is 0 or more, and o + p is 5 or more and 200 or less.
q and r are the average number of moles added of AO, each of which is 0 or more, and q + r is 5 or more and 200 or less.
Y is an independent hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms.
M is a counterion independently of each other. ] The use according to claim 9 , wherein in the composition, the molar ratio of the total amount of (C) to the monomer unit containing a naphthalene ring in (A) is 0.4% or more and 30% or less.