JP2020075840A - Dispersant composition for hydraulic composition - Google Patents

Abstract

To provide a dispersant composition for a hydraulic composition that provides a hydraulic composition having excellent initial fluidity, and a hydraulic composition having excellent initial fluidity and a method for producing the same.SOLUTION: The dispersant composition for a hydraulic composition contains a polymer (A) having a weight-average molecular weight of 1,000 or more and 1,000,000 or less (excluding the following components (B)), and a polymer (B) containing a monomer unit having a polyalkylene oxy group having an average addition molar number of an alkyleneoxy group of 5 or more and 300 or less, and an aromatic ring. The polymer (A) comprises a monomer unit having a group selected from the group consisting of a carboxylic acid group and a phosphoric acid group, and a monomer unit having a polyalkylene oxy group.SELECTED DRAWING: None

Description

  The present invention relates to a dispersant composition for hydraulic composition and a hydraulic composition.

  A dispersant for a hydraulic composition is a chemical admixture used to disperse cement particles to reduce the amount of unit water required to obtain a required slump and improve workability of the hydraulic composition. Is. As the dispersant, conventionally, a naphthalene-based dispersant such as naphthalenesulfonic acid formaldehyde condensate, 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.

Patent Document 1 describes a cement dispersant containing a formaldehyde cocondensation product of an aromatic compound (A) having an oxyalkylene group introduced therein and an aromatic compound (B) having a carboxyl group as an essential component. Has been done.
In Patent Document 2, an aromatic compound as an optional component selected from the group consisting of A) a specific aromatic compound or heteroaromatic compound having an oxyethylene and / or oxypropylene group, and B) a specific aminoplast-forming agent. A polycondensation product containing an aldehyde selected from the group consisting of a group compound, C) formaldehyde, glyoxylic acid, and benzaldehyde, or a mixture thereof as an admixture used in an aqueous suspension of an inorganic binder such as cement paste. It is described to be used.

JP-A-8-12401 Japanese Patent Publication No. 2008-517080

  The present invention provides a dispersant composition for a hydraulic composition, which gives a hydraulic composition with excellent initial fluidity, a hydraulic composition with excellent initial fluidity, and a method for producing the same.

  The present invention includes (A) a monomer unit having a group selected from a carboxylic acid group and a phosphoric acid group, and a monomer unit having a polyalkyleneoxy group, and a weight average molecular weight of 1,000 or more and 1,000,000 or less. (But excluding the following component (B)) (hereinafter referred to as the component (A)), and (B) a polyalkyleneoxy group having an average addition mole number of alkyleneoxy groups of 5 to 300, and an aromatic ring. The present invention relates to a dispersant composition for a hydraulic composition, which contains a polymer (hereinafter, referred to as a component (B)) containing a monomer unit (hereinafter, referred to as a monomer unit (B1)) having

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

  The present invention also relates to a method for producing a hydraulic composition, which comprises mixing the component (A), the component (B), the hydraulic powder and water.

ADVANTAGE OF THE INVENTION According to this invention, the dispersant composition for hydraulic compositions which can obtain the hydraulic composition excellent in initial fluidity, the hydraulic composition excellent in initial fluidity, and its manufacturing method are provided.
By producing a hydraulic composition using the dispersant composition for a hydraulic composition of the present invention, initial fluidity, for example, hydraulic fluid having excellent fluidity after 3 minutes from contact with water during preparation of the hydraulic composition. A composition can be obtained.

[Dispersant composition for hydraulic composition]
Although details of the mechanism of effect expression of the present invention are unknown, it is presumed as follows.
When a general polycarboxylic acid-based dispersant is added to a hydraulic composition, the polycarboxylic acid-based dispersant adsorbs to agglomerates such as inorganic particles that have agglomerated to some extent to fluidize the hydraulic composition. However, the polycarboxylic acid-based dispersant has low adsorbability to the aggregate in the hydraulic composition and is adsorbed over time, thereby suppressing slump loss of the hydraulic composition. Therefore, it is known that a polycarboxylic acid-based dispersant having particularly low adsorptivity does not contribute to the initial dispersibility of the hydraulic composition. However, the component (B) of the present invention has a high adsorptivity to the inorganic particles and the like in the hydraulic composition, and is adsorbed before the inorganic particles and the like agglomerate and suppresses the agglomeration, thereby reducing the bound water. We believe that it suppresses and consequently suppresses slump loss. Thus, it is presumed that a hydraulic composition having excellent initial dispersibility can be obtained by using the two components (A) and (B) of the present invention having different adsorption properties in combination.

<(A) component>
The component (A) contains a monomer unit having a group selected from a carboxylic acid group and a phosphoric acid group and a monomer unit having a polyalkyleneoxy group, and has a weight average molecular weight of 1,000 or more and 1,000,000 or less. It is a polymer. However, the component (A) does not include the component (B).
In the present invention, the “monomer unit” means a “repeating unit” in the polymer.

  The polymer in the component (A) is a compound obtained by addition polymerization or condensation polymerization. Examples of the addition polymerization include radical polymerization and ionic polymerization, which are methods of reacting a monomer having an unsaturated bond. Examples of the condensation polymerization include addition condensation with aldehydes, which is typified by formaldehyde condensation of aromatic compounds.

The carboxylic acid group of the component (A) is a group represented by -COOM ⁰ (M ⁰ represents a counter ion). The carboxylic acid group is a group selected from a carboxy group and a carboxy group which is a salt, and includes a carboxy group which forms an anhydride with another carboxy group.

The phosphate group of the component (A) is a group represented by —OPO (OM ¹ ) (OM ² ) (M ¹ and M ² are the same or different and each represents a counter ion). The phosphoric acid group is a group selected from a phosphoric acid group and a salt-forming phosphoric acid group.
Here, examples of M ⁰ , M ¹ , and M ² include a hydrogen ion, an alkali metal ion, an alkaline earth metal ion (1/2 atom), an ammonium ion, and an amine.

  Examples of the polyalkyleneoxy group as the component (A) include a polyethyleneoxy group and a polypropyleneoxy group.

  The component (A) is preferably a polymer selected from a polymer containing a carboxylic acid group-containing monomer unit and a polymer containing a carboxylic acid group-containing monomer unit and a phosphoric acid group-containing monomer unit. A polymer containing a monomer unit having is more preferable.

  As the component (A), for example, an addition polymer of a phosphoric acid group and / or a carboxylic acid compound having an unsaturated bond and a compound having a monomer unit having a polyalkyleneoxy group having an unsaturated bond, a carboxylic acid group And a condensation polymer of a compound having a monomer unit having a group selected from a phosphoric acid group and a monomer unit having a polyalkyleneoxy group and formaldehyde.

  The weight average molecular weight of the component (A) is 1,000 or more, preferably 5,000 or more, more preferably 10,000 or more, further preferably 30,000 or more, from the viewpoint of improving the fluidity of the hydraulic composition. And it is 1,000,000 or less, preferably 500,000 or less, more preferably 150,000 or less, and further preferably 100,000 or less. This weight average molecular weight is measured by gel permeation chromatography (GPC) using polyethylene glycol as a standard substance.

For example, as the component (A),
(1) From alkoxypolyalkylene glycol mono (meth) acrylate, (meth) acrylic acid, (meth) acrylic acid ester having 1 to 3 carbon atoms which may have a hydroxyl group, and phosphoric acid ester having an unsaturated group A copolymer obtained by copolymerizing at least one selected from
(2) a copolymer obtained by copolymerizing an ether compound of polyalkylene glycol and an unsaturated alcohol, and one or more kinds selected from dicarboxylic acids and dicarboxylic acid anhydrides,
Is mentioned. Here, (meth) acrylate means acrylate or methacrylate, and (meth) acrylic acid means acrylic acid or methacrylic acid.

  Examples of the monomer unit having a carboxylic acid group include a monomer unit derived from at least one monomer selected from a monocarboxylic acid having an addition-polymerizable unsaturated bond and a dicarboxylic acid having an addition-polymerizable unsaturated bond. .. For example, a monomer unit derived from one or more kinds of monomers selected from acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid may be mentioned. 1 selected from methacrylic acid and acrylic acid Monomer units derived from more than one monomer are preferred. It may be a monomer unit having an anhydride compound such as maleic anhydride or a half ester such as maleic acid monoester as a monomer.

  The monomer unit having a group selected from phosphoric acid groups is derived from at least one monomer selected from a phosphoric acid compound having an addition-polymerizable unsaturated bond and a phosphoric acid compound having a condensation-polymerizable aromatic functional group. And a monomer unit to be used. For example, phosphoric acid di-[(2-hydroxyethyl) methacrylic acid] ester, phosphoric acid di-[(2-hydroxyethyl) acrylic acid] ester, phosphoric acid mono (2-hydroxyethyl) methacrylic acid ester, phosphoric acid monoester. Examples thereof include monomer units derived from one or more kinds of monomers selected from (2-hydroxyethyl) acrylic acid ester and polyalkylylene glycol mono (meth) acrylate acid phosphoric acid ester, and phosphoric acid di-[(2- A monomer unit derived from one or more kinds of monomers selected from hydroxyethyl) methacrylic acid] ester and phosphoric acid mono (2-hydroxyethyl) methacrylic acid ester is preferable. Further, any one or more of these alkali metal salts, alkaline earth metal salts, ammonium salts, and amine salts may be used.

  Examples of the monomer unit having a polyalkyleneoxy group include a monomer unit derived from a compound having an unsaturated bond capable of addition polymerization and a polyalkyleneoxy group. Examples thereof include a monomer unit derived from one or more kinds of monomers selected from alkoxypolyalkylene glycol mono (meth) acrylate and ether compounds of polyalkylene glycol and unsaturated alcohol. Specific examples of the monomer unit having a polyoxyalkylene group include methoxy polyethylene glycol, methoxy polyethylene polypropylene glycol, ethoxy polyethylene glycol, ethoxy polyethylene polypropylene glycol, propoxy polyethylene glycol, propoxy polyethylene polypropylene glycol, and the like. Esterification product of glycol and acrylic acid or methacrylic acid, ethylene oxide and / or propylene oxide adduct of allyl alcohol, ethylene oxide and / or propylene oxide adduct of isoprenol, ethylene oxide and / or propylene oxide adduct of vinyl alcohol, Examples thereof include monomer units derived from monomers selected from ethylene oxide and / or propylene oxide adducts of acrylic acid, and ethylene oxide and / or propylene oxide adducts of methacrylic acid.

  In the monomer unit having a polyalkyleneoxy group as the component (A), the average addition mole number of alkyleneoxy groups per the monomer unit is preferably 5 or more, more preferably 10 or more, further preferably from the viewpoint of dispersibility. It is 20 or more, and preferably 200 or less, more preferably 150 or less, and further preferably 100 or less.

  From the viewpoint of improving the fluidity of the hydraulic composition, the component (A) comprises a monomer (A1) represented by the following general formula (A1) and a monomer (A2) represented by the following general formula (A2). A copolymer containing it as a monomer [hereinafter referred to as a copolymer (A)] is preferable.

[In the formula,
R ^1a and R ^2a : may be the same or different, and are a hydrogen atom or a methyl group R ^3a : hydrogen atom or — (CO) _q O (AO) _n X
X: an alkyl group having 1 to 4 carbon atoms AO: a group selected from an ethyleneoxy group and a propyleneoxy group n: an average number of moles of AO added, which is 1 or more and 300 or less p: 0 or more and 2 or less q : Indicates the number of 0 or 1. ]

[In the formula,
R ^4a , R ^5a , R ^6a : which may be the same or different, are a hydrogen atom, a methyl group or (CH ₂ ) _r COOM ⁴ , and (CH ₂ ) _r COOM ⁴ is COOM ³ or another (CH _2). ) An anhydride may be formed with _r COOM ⁴ , in which case M ³ and M ⁴ of those groups are not present.
M ³ and M ^4, which may be the same or different, are a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, an alkylammonium group or a substituted alkylammonium group r: a number of 0 or more and 2 or less Indicates. ]

In formula (A1), R ^1a is preferably a hydrogen atom.
In general formula (A1), R ^2a is preferably a methyl group.
In formula (A1), R ^3a is preferably a hydrogen atom.
In general formula (A1), X is preferably a methyl group.
In general formula (A1), AO is preferably an ethyleneoxy group. AO preferably contains an ethyleneoxy group.

  In general formula (A1), n is the average number of moles of AO added, and is 1 or more and 300 or less. From the viewpoint of initial fluidity, n is preferably a number of 5 or more, more preferably 10 or more, still more preferably 20 or more, and preferably 200 or less, more preferably 150 or less, still more preferably 100 or less.

In general formula (A1), p is preferably 0.
In general formula (A1), q is preferably 1.

In formula (A2), R ^4a is preferably a hydrogen atom.
In general formula (A2), R ^5a is preferably a methyl group or a hydrogen atom.
In general formula (A2), R ^6a is preferably a hydrogen atom.
For (CH ₂ ) _r COOM ^4, it may form an anhydride with COOM ³ or another (CH ₂ ) _r COOM ⁴ , in which case M ³ , M ⁴ of those groups are absent.
Regarding the copolymer (A), in the general formula (A2), M ³ and M ⁴ may be the same or different and each is preferably a hydrogen atom.
R in the general formula (A2) in the _{(CH 2)} r COOM ⁴ is 1 are preferred.

  From the viewpoint of improving fluidity, the copolymer (A) has a total amount of the monomers (A1) and (A2) in the constituent monomers of 90% by mass or more, preferably 92% by mass or more, and more preferably It is 95 mass% or more and 100 mass% or less. This total amount may be 100% by weight.

  In the copolymer (A), the ratio of the monomer (A2) to the total of the units (A1) and (A2) is preferably 10 mol% or more, more preferably 20 mol% or more, from the viewpoint of improving fluidity. More preferably 30 mol% or more, still more preferably 40 mol% or more, even more preferably 50 mol% or more, and preferably 99 mol% or less, more preferably 90 mol% or less, further preferably 80 mol% or less. Is.

The weight average molecular weight of the copolymer (A) is 1,000 or more, preferably 5,000 or more, more preferably 10,000 or more, further preferably 30,000 or more, and 1,000,000 or less, preferably Is 500,000 or less, more preferably 150,000 or less, and further preferably 100,000 or less. This weight average molecular weight is measured by gel permeation chromatography (GPC) under the following conditions.
* GPC conditions Device: GPC (HLC-8320GPC) Tosoh Corporation Column: G4000PWXL + G2500PWXL (Tosoh Corporation)
Eluent: 0.2 M phosphate buffer / CH ₃ CN = 9/1
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detection: RI
Sample size: 0.2mg / mL
Standard material: Polyethylene glycol equivalent (monodisperse polyethylene glycol: molecular weight 87,500, 250,000, 145,000, 46,000, 24,000)

<(B) component>
The component (B) is a polymer containing a polyalkyleneoxy group having an average addition mole number of alkyleneoxy groups of 5 or more and 300 or less and a monomer unit (B1) having an aromatic ring.

  The polymer in the component (B) is, for example, a compound obtained by addition polymerization or condensation polymerization. Examples of the addition polymerization include radical polymerization and ionic polymerization, which are methods of reacting a monomer having an unsaturated bond. Examples of the condensation polymerization include addition condensation with aldehydes, which is typified by formaldehyde condensation of aromatic compounds. The component (B) is preferably a condensation polymer of aldehydes, more preferably a formaldehyde condensation polymer.

As the monomer unit (B1), a benzene compound having a polyalkyleneoxy group, which may have a substituent other than the polyalkyleneoxy group, and a polyalkyleneoxy group having a substituent other than the polyalkyleneoxy group From a benzene compound having a polyalkyleneoxy group, which may have a substituent other than the polyalkyleneoxy group. The resulting monomer units are preferred.
Examples of the substituent other than the polyalkyleneoxy group include at least one selected from an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a hydroxyl group, and a halogeno group.

In the monomer unit (B1), the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 3 carbon atoms, and more preferably an ethyleneoxy group.
In the monomer unit (B1), the average addition mole number of alkyleneoxy groups is 5 or more, preferably 10 or more, more preferably 20 or more, still more preferably 35 or more, still more preferably 37 or more, from the viewpoint of dispersibility. More preferably 42 or more, still more preferably 50 or more, still more preferably 70 or more, and 300 or less, preferably 200 or less, more preferably 150 or less, still more preferably 110 or less, still more preferably 90 or less. is there.
In the monomer unit (B1), the average number of moles of alkyleneoxy groups added is 5 or more, preferably 10 or more, more preferably 20 or more, still more preferably 30 or more, still more preferably 35 or more, from the viewpoint of initial strength. And it is 300 or less, preferably 200 or less, more preferably 150 or less, further preferably 110 or less, even more preferably 90 or less, even more preferably 70 or less, still more preferably 50 or less.

  From the viewpoint of dispersibility, the monomer unit (B1) is preferably a monomer unit obtained from a compound represented by the following general formula (B1).

[In formula, AO is an alkyleneoxy group, m is an average addition mole number of an alkyleneoxy group, and is a number of 5 or more and 300 or less. Y ¹ is an arbitrary substituent of the benzene ring, and is at least one selected from an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a hydroxyl group, and a halogeno group. ]

In general formula (B1), AO is preferably an alkyleneoxy group having 2 to 3 carbon atoms, and more preferably an ethyleneoxy group.
In the general formula (B1), m is 5 or more, preferably 10 or more, more preferably 20 or more, still more preferably 35 or more, still more preferably 37 or more, still more preferably 42 or more, from the viewpoint of dispersibility. Still more preferably 50 or more, still more preferably 70 or more, and 300 or less, preferably 200 or less, more preferably 150 or less, still more preferably 110 or less, still more preferably 90 or less. , M are 5 or more, preferably 10 or more, more preferably 20 or more, still more preferably 30 or more, still more preferably 35 or more, and 300 or less, preferably 200 or less, more preferably from the viewpoint of initial strength. It is 150 or less, more preferably 110 or less, even more preferably 90 or less, even more preferably 70 or less, even more preferably 50 or less.
In the general formula (B1), when Y ¹ is contained, Y ¹ is preferably one or more selected from an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms. Further, Y ¹ may not be included.

  Examples of the monomer unit (B1) include a monomer unit obtained from one or more compounds selected from polyoxyalkylene phenyl ether and polyoxyalkylene naphthyl ether. Specifically, the raw material compound of the monomer unit (B1) is a compound obtained by adding 5 to 300 mol of an oxyalkylene group on average to phenol, cresol, nonylphenol, naphthalene, methylnaphthalene, butylnaphthalene, bisphenol and the like.

  From the viewpoint of dispersibility, the component (B) is preferably a polymer further containing a monomer unit having a carboxylic acid group and an aromatic ring (hereinafter referred to as the monomer unit (B2)). That is, the component (B) is preferably a polymer containing the monomer unit (B1) and the monomer unit (B2). Further, the component (B) is more preferably a formaldehyde condensation polymer containing a monomer unit (B1) and a monomer unit (B2).

The aromatic compound having a carboxylic acid group of the monomer unit (B2) has a carboxylic acid group and may have a substituent other than the carboxylic acid group, and a carboxylic acid group having a carboxylic acid group. There may be mentioned a monomer unit obtained from one or more compounds selected from naphthalene compounds which may have a substituent other than a group, which has a carboxylic acid group and may have a substituent other than the carboxylic acid group. Monomer units obtained from benzene compounds are preferred.
The carboxylic acid group is a group selected from a carboxy group and a carboxy group which is a salt, and includes a carboxy group which forms an anhydride with another carboxy group.
Examples of the substituent other than the carboxylic acid group include at least one selected from an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a hydroxyl group, and a halogeno group.

  From the viewpoint of dispersibility, the monomer unit (B2) is preferably a monomer unit obtained from a compound represented by the following general formula (B2).

[In the formula, Z ¹ is a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, an alkylammonium group or a substituted alkylammonium group. Y ² is an arbitrary substituent of the benzene ring, and is at least one selected from an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a hydroxyl group, and a halogeno group. ]

In general formula (B2), Z ¹ is preferably a hydrogen atom or an alkali metal, more preferably a hydrogen atom.
In the general formula (B2), when Y ² is contained, Y ² is preferably one or more selected from a hydroxyl group and an alkyl group having 1 to 20 carbon atoms, and more preferably a hydroxyl group. Further, Y ² may not be included.

  The monomer unit (B2) is a benzene or naphthalene derivative, specifically, a monomer unit obtained from one or more compounds selected from hydroxybenzoic acid, benzoic acid, isophthalic acid, oxynaphthoic acid, and isomers thereof. From the viewpoint of fluidity, a monomer unit obtained from hydroxybenzoic acid and one or more compounds selected from benzoic acid is preferable, and a monomer unit obtained from hydroxybenzoic acid is more preferable.

  The component (B) may be a polymer that further contains a monomer unit having a sulfonic acid group and an aromatic ring (hereinafter referred to as the monomer unit (B3)) from the viewpoint of fluidity retention. That is, the component (B) may be a polymer containing the monomer unit (B1), the monomer unit (B2) and the monomer unit (B3). The component (B) may be a formaldehyde condensation polymer containing the monomer unit (B1), the monomer unit (B2) and the monomer unit (B3).

Examples of the aromatic compound having a sulfonic acid group of the monomer unit (B3) include a benzene compound having a sulfonic acid group and optionally having a substituent other than the sulfonic acid group, and a sulfonic acid group having a sulfonic acid group. Examples thereof include a monomer unit obtained from one or more compounds selected from naphthalene compounds that may have a substituent other than a group, have a sulfonic acid group, and may have a substituent other than a sulfonic acid group. Monomer units obtained from benzene compounds are preferred.
The sulfonic acid group is a group selected from a sulfo group and a sulfo group forming a salt.
Examples of the substituent other than the sulfonic acid group include at least one selected from an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a hydroxyl group, and a halogeno group.

  The monomer unit (B3) is preferably a monomer unit obtained from a compound represented by the following general formula (B3), from the viewpoint of fluidity retention.

[In the formula, Z ² is a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, an alkylammonium group or a substituted alkylammonium group. Y ³ is an arbitrary substituent of the benzene ring, and is at least one selected from an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a hydroxyl group, and a halogeno group. ]

In general formula (B3), Z ² is preferably a hydrogen atom or an alkali metal, more preferably a hydrogen atom.
In the general formula (B3), if having a Y ^3, Y ³ represents a hydroxyl group, and preferably one or more selected from alkyl groups of 1 to 20 carbon atoms, a hydroxyl group is more preferable. Further, Y ³ may not be included.

  The monomer unit (B3) is a benzene or naphthalene derivative, specifically, one or more selected from benzenesulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, alkylnaphthalenesulfonic acid, naphtholsulfonic acid, and isomers thereof. A monomer unit obtained from a compound is mentioned, and from the viewpoint of fluidity retention, a monomer unit obtained from one or more compounds selected from benzenesulfonic acid and phenolsulfonic acid is preferable, and a monomer unit obtained from phenolsulfonic acid is more preferable. preferable.

  The component (B) may have, in addition to the monomer unit (B1), the monomer unit (B2), and the monomer unit (B3), other polymerizable monomer units as long as the effects of the present invention are not impaired. .. Examples of the monomer unit other than the monomer unit (B1), the monomer unit (B2), and the monomer unit (B3) include a monomer unit obtained from an alkylphenol such as phenol and cresol, a phosphate group such as phenoxyethanol phosphate, and an aromatic ring. And a monomer unit obtained from the compound having.

When the component (B) contains the monomer unit (B2), the molar ratio (B2) / (B1) of the monomer unit (B1) and the monomer unit (B2) in the component (B) is from the viewpoint of fluidity retention. , Preferably 5/95 or more, more preferably 10/90 or more, still more preferably 15/85 or more, even more preferably 20/80 or more, even more preferably 30/70 or more, even more preferably 40/60 or more. , More preferably 50/50 or more, still more preferably 60/40 or more, even more preferably 70/30 or more, even more preferably 72/28 or more, and preferably 95/5 or less, more preferably 90. / 10 or less, more preferably 80/20 or less, still more preferably 77/23 or less.
The molar ratio (B2) / (B1) of the monomer unit (B1) and the monomer unit (B2) in the component (B) is preferably 5/95 or more, more preferably 10/90 or more from the viewpoint of initial strength. , More preferably 15/85 or more, even more preferably 20/80 or more, even more preferably 30/70 or more, even more preferably 40/60 or more, even more preferably 50/50 or more, even more preferably 60. / 40 or more, more preferably 70/30 or more, even more preferably 72/28 or more, even more preferably 77/23 or more, and preferably 95/5 or less, more preferably 90/10 or less, further preferably Is 82/18 or less.
The molar ratio (B2) / (B1) between the monomer unit (B1) and the monomer unit (B2) in the component (B) is a raw material compound which becomes the monomer unit (B1) when the component (B) is produced, It may be calculated from the charging ratio of the raw material compound to be the monomer unit (B2).

When the component (B) contains the monomer unit (B2) and the monomer unit (B3), the molar ratio of the total of the monomer unit (B1) and the monomer unit (B2) in the component (B) to the monomer unit (B3) ( From the viewpoint of flow retention, (B1) + (B2)) / (B3) is preferably 99.999 / 0.001 or more, more preferably 99.99 / 0.01 or more, and further preferably 99.9. /0.1 or more, more preferably 99/1 or more, even more preferably 95/5 or more, and preferably 60/40 or less, more preferably 70/30 or less, still more preferably 80/20 or less, more It is more preferably 85/15 or less, still more preferably 90/10 or less.
The molar ratio ((B1) + (B2)) / (B3) of the total of the monomer unit (B1) and the monomer unit (B2) in the component (B) and the monomer unit (B3) is the same as that of the component (B). It may be calculated from the charging ratio of the raw material compound to be the monomer unit (B1), the raw material compound to be the monomer unit (B2), and the raw material compound to be the monomer unit (B3).

  When the component (B) contains the monomer unit (B2), the total amount of the monomer unit (B1) and the monomer unit (B2) in all the monomer units of the component (B) is 70 mol% or more, preferably 80 mol%. The above content is more preferably 90 mol% or more and 100 mol% or less. This total amount may be 100 mol%. When the component (B) is a condensation polymer, the total amount of the monomer unit (B1) and the monomer unit (B2) in the constituent monomer of the component (B) is the same as that of the constituent monomer of the component (B). , Shall be calculated assuming that aldehydes such as formaldehyde used in the condensation polymerization reaction are not included.

  When the component (B) contains a monomer unit (B2) and a monomer unit (B3), the total amount of the monomer unit (B1), the monomer unit (B2), and the monomer unit (B3) in all the monomer units of the component (B). Is 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, and 100 mol% or less. This total amount may be 100 mol%. When the component (B) is a condensation polymer, the total amount of the monomer unit (B1), the monomer unit (B2) and the monomer unit (B3) in the constituent monomers of the component (B) is It is assumed that the constituent monomer (1) does not include aldehydes such as formaldehyde used in the condensation polymerization reaction.

From the viewpoint of dispersibility, the weight average molecular weight of the component (B) is preferably 5,000 or more, more preferably 8,000 or more, further preferably 10,000 or more, and preferably 150,000 or less, more preferably Is 100,000 or less, more preferably 50,000 or less. This weight average molecular weight is measured by gel permeation chromatography (GPC) under the following conditions.
* GPC conditions Device: GPC (HLC-8320GPC) manufactured by Tosoh Corporation Column: G4000SWXL + G2000SWXL + guard column SWXL (manufactured by Tosoh Corporation)
_{Eluent: 30mM CH 3 COONa / CH 3} CN = 6/4
Flow rate: 0.7 mL / min
Column temperature: room temperature Detection: RI
Sample size: 0.2mg / mL
Standard material: Sodium polystyrene sulfonate conversion (Molecular weight 1,690, 7,540, 16,000, 68,300, 126,700, 587,600)

  The component (B) can be produced by using a known method. For example, when the component (B) is an aldehyde condensation polymer, it can be produced by using the method described in JP-A-8-12401.

<Composition of Dispersant Composition for Hydraulic Composition, etc.>
From the viewpoint of improving fluidity, the dispersant composition for hydraulic composition of the present invention preferably contains the component (A) in the solid content in an amount of preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more. It is contained in an amount of not less than 95% by mass, preferably not more than 95% by mass, more preferably not more than 90% by mass, further preferably not more than 85% by mass. In the hydraulic composition, the solid content means a component other than water.

  From the viewpoint of retention, the dispersant composition for hydraulic composition of the present invention contains the component (B) in the solid content of preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass. % Or more, and preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less.

In the dispersant composition for hydraulic compositions of the present invention, the mass ratio (A) / (B) between the content of the component (A) and the content of the component (B) is the initial fluidity and the fluidity retention. From the viewpoint of satisfying both, preferably 5/95 or more, more preferably 10/90 or more, still more preferably 20/80 or more, still more preferably 30/70 or more, still more preferably 40/60 or more, and preferably Is 95/5 or less, more preferably 90/10 or less, still more preferably 80/20 or less, even more preferably 70/30 or less, still more preferably 60/40 or less.
Further, in the dispersant composition for hydraulic composition of the present invention, the mass ratio (A) / (B) between the content of the component (A) and the content of the component (B) is preferably from the viewpoint of initial strength. Is 5/95 or more, more preferably 10/90 or more, even more preferably 20/80 or more, even more preferably 30/70 or more, even more preferably 40/60 or more, and preferably 95/5 or less, It is preferably 90/10 or less, more preferably 80/20 or less, still more preferably 70/30 or less, still more preferably 60/40 or less.

  The dispersant composition for a hydraulic composition of the present invention preferably further contains (C) an antifoaming agent [hereinafter referred to as (C) component] from the viewpoint of strength development.

  As the component (C), a nonionic surfactant-based defoaming agent is preferable. The component (C) is preferably a silicone-based defoaming agent, a fatty acid ester-based defoaming agent, or an ether-based defoaming agent, more preferably dimethylpolysiloxane for the silicone-based defoaming agent, and polyalkylene for the fatty acid ester-based defoaming agent. A glycol fatty acid ester is more preferable, and a polyalkylene glycol alkyl ether is more preferable as the ether antifoaming agent. As the component (C), an antifoaming agent having an oxypropylene group is preferable.

  The component (C) and the HLB (Davis method) of the nonionic surfactant antifoaming agent are preferably less than 0. Further, the component (C) and the HLB (Griffin method) of the nonionic surfactant-based defoaming agent are preferably 8 or less. Further, the 1% by mass aqueous suspension of the component (C) is preferably visually separated or clouded. Further, the turbidity of the 1% by mass aqueous suspension of the component (C) is preferably 100 NTU or more. Further, the component (C) preferably has no foaming property. The turbidity of the 1% by mass aqueous suspension can be measured using a portable turbidimeter TN100IR (manufactured by Nikko Hansen Co., Ltd.).

  As the component (C), a fatty acid ester-based defoaming agent is preferable from the viewpoint of suppressing the decrease in strength.

  The silicone antifoaming agent is preferably an emulsifying type that is compatible with water. Examples of such emulsifying type include KM-70, KM-73A (both Shin-Etsu Silicone Co., Ltd.), TSA series (momentive performance). -Materials Japan GK), FS Antifoam series [Toray Dow Corning Co., Ltd.], Antifoam E-20 [Kao Co., Ltd.], and other commercial products.

  Examples of the polyalkylene glycol fatty acid ester among the fatty acid ester-based defoaming agents include commercially available products such as Rheodor TW-L120 [Kao Corporation], Nicofix, and Folex Rex [both are Nichika Chemical Co., Ltd.].

  As the polyalkylene glycol alkyl ether among the ether-based defoamers, defoamer No. Defoaming agent No. 1 Examples thereof include commercially available products such as No. 5 [all Kao Corporation] and ADEKA Pluronic series [ADEKA Corporation].

  The dispersant composition for hydraulic composition of the present invention, from the viewpoint of strength development, the component (C) in the solid content is preferably 0.000001 mass% or more, more preferably 0.00005 mass% or more, The content is more preferably 0.00025 mass% or more, and preferably 1 mass% or less, more preferably 0.075 mass% or less, still more preferably 0.05 mass% or less.

  The dispersant composition for hydraulic composition of the present invention is a conventional cement dispersant, a water-soluble polymer compound, an air entraining agent, a cement wetting agent, an expanding material, a waterproofing agent, a retarding agent, an accelerator, a thickener. , A coagulant, a drying shrinkage reducing agent, a strength enhancer, a curing accelerator, a preservative and the like (excluding those corresponding to the components (A) to (C)) can be further contained.

  The form of the dispersant composition for hydraulic composition of the present invention may be liquid or solid. When the dispersant composition for a hydraulic composition of the present invention is a liquid, it preferably contains water.

  When the dispersant composition for hydraulic composition is a liquid, the content of water in the composition is preferably 20% by mass or more, more preferably 40% by mass or more, from the viewpoint of easy handling. The content is more preferably 50% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less from the viewpoint of improving the fluidity of the hydraulic composition.

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

  The hydraulic powder used in the hydraulic composition of the present invention is a powder having physical properties of being hardened by a hydration reaction, and examples thereof include cement and gypsum. Preferred are normal Portland cement, belite cement, moderate heat cement, early strength cement, ultra early strength cement, sulfate resistant cement and the like. Also, blast furnace slag cement, fly ash cement, silica fume cement, etc. to which powder such as blast furnace slag, fly ash, silica fume and the like having pozzolanic action and / or latent hydraulic property, or stone powder (calcium carbonate powder) is added to cement etc. But it's okay.

  The hydraulic composition of the present invention has a water / hydraulic powder ratio [mass percentage of water and hydraulic powder in slurry (mass%), usually abbreviated as W / P, but when the powder is cement. , W / C. ], From the viewpoint of initial fluidity, strength development, and workability, preferably 10 mass% or more, more preferably 15 mass% or more, further preferably 20 mass% or more, and preferably 80 mass% or less, It is more preferably 70% by mass or less, still more preferably 60% by mass or less.

  Specific examples and preferred embodiments of the component (A) and the component (B) used in the hydraulic composition of the present invention are the same as those described in the dispersant composition for hydraulic composition of the present invention.

  From the viewpoint of fluidity, the hydraulic composition of the present invention preferably contains the component (A) in an amount of 0.01 part by mass or more, more preferably 0.05 part by mass or more, relative to 100 parts by mass of the hydraulic powder. , More preferably 0.1 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 5 parts by mass or less, even more preferably 2 parts by mass or less, still more preferably 1 part by mass. It is contained in an amount of at most 0.5 part by mass, more preferably at most 0.5 part by mass.

  The hydraulic composition of the present invention preferably contains the component (B) in an amount of 0.01 parts by mass or more, and more preferably 0.05 parts by mass, with respect to 100 parts by mass of the hydraulic powder, from the viewpoint of flow retention. Or more, more preferably 0.1 part by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, further preferably 5 parts by mass or less, still more preferably 2 parts by mass or less, still more preferably It is contained in an amount of 1 part by mass or less, more preferably 0.5 part by mass or less.

  In the hydraulic composition of the present invention, the total content of the component (A) and the component (B) is preferably 0.02 parts by mass or more based on 100 parts by mass of the hydraulic powder from the viewpoint of initial fluidity. , More preferably 0.1 parts by mass or more, further preferably 0.2 parts by mass or more, and preferably 20 parts by mass or less, more preferably 16 parts by mass or less, still more preferably 10 parts by mass or less, still more preferably It is 4 parts by mass or less, more preferably 2 parts by mass or less, still more preferably 1 part by mass or less.

In the hydraulic composition of the present invention, the mass ratio (A) / (B) between the content of the component (A) and the content of the component (B) is from the viewpoint of both initial fluidity and fluidity retention. , Preferably 5/95 or more, more preferably 10/90 or more, even more preferably 20/80 or more, even more preferably 30/70 or more, even more preferably 40/60 or more, and preferably 95/5 or less. , More preferably 90/10 or less, still more preferably 80/20 or less, still more preferably 70/30 or less, still more preferably 60/40 or less.
In the hydraulic composition of the present invention, the mass ratio (A) / (B) between the content of the component (A) and the content of the component (B) is preferably 5/95 or more from the viewpoint of initial strength. , More preferably 10/90 or more, still more preferably 20/80 or more, even more preferably 30/70 or more, even more preferably 40/60 or more, and preferably 95/5 or less, more preferably 90/10. The ratio is preferably 80/20 or less, more preferably 70/30 or less, still more preferably 60/40 or less.

  The hydraulic composition of the present invention may contain the component (C). Specific examples and preferred embodiments of the component (C) are the same as those described in the dispersant composition for hydraulic composition of the present invention.

  When the hydraulic composition of the present invention contains the component (C), the component (C) is preferably added in an amount of 0.0001 mass with respect to 100 parts by mass of the hydraulic powder from the viewpoint of strength development and workability. Parts or more, more preferably 0.001 parts by mass or more, further preferably 0.01 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, further preferably 0.1 parts by mass. Contains below.

  The hydraulic composition of the present invention preferably contains an aggregate. Examples of aggregates include aggregates selected from fine aggregates and coarse aggregates. Examples of the fine aggregate include those specified by No. 2311 in JIS A0203-2014. As fine aggregate, river sand, land sand, mountain sand, sea sand, lime sand, silica sand and crushed sand of these, blast furnace slag fine aggregate, ferronickel slag fine aggregate, lightweight fine aggregate (artificial and natural) and recycled Fine aggregates and the like can be mentioned. Further, as the coarse aggregate, one specified by the number 2312 in JIS A0203-2014 can be mentioned. For example, as coarse aggregate, river gravel, land gravel, mountain gravel, sea gravel, lime gravel, crushed stone of these, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural) and recycled Examples include coarse aggregate. Fine aggregates and coarse aggregates may be used by mixing different types, or may be used by a single type.

When the hydraulic composition is concrete, the amount of coarse aggregate used reduces the expression of the strength of the hydraulic composition and the amount of hydraulic powder such as cement, and improves the filling property into the formwork etc. 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, further preferably 80% or less. Is. The bulk volume is the ratio of the volume (including voids) of coarse aggregate in 1 m ^{3 of} concrete.
Further, when the hydraulic composition is concrete, the amount of the fine aggregate used 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 the mold and the like. It is preferably 700 kg / m ³ or more, and preferably 1,000 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 800 kg / ^{m 3} or more, more preferably 900 kg / ^{m 3} or more, more preferably 1,000kg / ^{m 3} or more, and preferably Is 2,000 kg / m ³ or less, more preferably 1,800 kg / m ³ or less, still more preferably 1,700 kg / m ³ or less.

  Concrete examples of the hydraulic composition include concrete. Among them, concrete using cement is preferable. The hydraulic composition of the present invention is for self-leveling, for refractories, for plaster, for light or heavy concrete, for AE, for repair, for prepacked, for traymy, for ground improvement, for grout, in the cold, 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 waterproofing agent, a fluidizing agent and the like (excluding those corresponding to the components (A) to (C)) can be mentioned.

[Method for producing dispersant composition for hydraulic composition]
The present invention provides a method for producing a dispersant composition for a hydraulic composition, which comprises mixing the component (A) and the component (B).

Specific examples and preferred embodiments of the component (A) and the component (B) used in the method for producing a dispersant composition for a hydraulic composition of the present invention are respectively the dispersant composition for a hydraulic composition of the present invention. Same as mentioned. In addition to component (A) and component (B), it is mixed with component (C) to produce a dispersant composition for hydraulic composition containing component (A), component (B), and component (C). You can also do it. Specific examples and preferred embodiments of the component (C) are the same as those described in the dispersant composition for hydraulic composition of the present invention.
Moreover, the matters described in the dispersant composition for hydraulic composition of the present invention can be appropriately applied to the method for producing the dispersant composition for hydraulic composition of the present invention. In the method for producing a dispersant composition for a hydraulic composition of the present invention, the mixing amount of each component is applied by replacing the content of each component of the dispersant composition for a hydraulic composition of the present invention with the mixing amount. be able to.

In the method for producing a dispersant composition for a hydraulic composition of the present invention, the mass ratio (A) / (B) between the content of the component (A) and the content of the component (B) is the initial fluidity, and From the viewpoint of compatibility of fluidity retention, preferably 5/95 or more, more preferably 10/90 or more, further preferably 20/80 or more, still more preferably 30/70 or more, still more preferably 40/60 or more, And it is preferably 95/5 or less, more preferably 90/10 or less, still more preferably 80/20 or less, still more preferably 70/30 or less, still more preferably 60/40 or less.
Further, in the method for producing a hydraulic composition of the present invention, the mass ratio (A) / (B) between the content of the component (A) and the content of the component (B) is preferably 5 from the viewpoint of initial strength. / 95 or more, more preferably 10/90 or more, still more preferably 20/80 or more, even more preferably 30/70 or more, even more preferably 40/60 or more, and preferably 95/5 or less, more preferably It is 90/10 or less, more preferably 80/20 or less, still more preferably 70/30 or less, still more preferably 60/40 or less.

  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.

  Examples of the method for producing the dispersant composition for a hydraulic composition of the present invention include a method for producing a dispersant composition for a hydraulic composition in which the component (A), the component (B) and water are mixed. In this case, the component (A), the component (B) and water can be mixed by any method as long as the performance is not deteriorated. For example, a method in which water or warm water is charged into a mixing tank in advance, and then the molten component (A) is charged to form an aqueous solution, and then the component (B) is charged and mixed with a stirrer, or the component (A) and (B) are mixed. Each of the components) is dissolved in water and the aqueous solution of the component (A) and the aqueous solution of the component (B) are mixed.

[Method for producing hydraulic composition]
The present invention provides a method for producing a hydraulic composition in which component (A), component (B), hydraulic powder, and water are mixed.

Specific examples and preferred embodiments of the component (A) and the component (B) used in the method for producing a hydraulic composition of the present invention are the same as those described in the dispersant composition for hydraulic composition of the present invention. Is.
The 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 for the hydraulic composition of the present invention.
Furthermore, in addition to the hydraulic powder, water, the component (A), and the component (B), the component (C) is mixed to obtain the component (A), the component (B), the component (C), and the hydraulic property. It is also possible to produce a hydraulic composition containing powder and water. Specific examples and preferred embodiments of the component (C) are the same as those described in the dispersant composition for hydraulic composition of the present invention.
Moreover, the matters described in the dispersant composition for hydraulic composition and the hydraulic composition of the present invention can be appropriately applied to the method for producing the hydraulic composition of the present invention. In the method for producing a hydraulic composition of the present invention, the mixing amount of each component can be applied by replacing the content of each component described in the hydraulic composition of the present invention with the mixing amount.

In the method for producing a hydraulic composition of the present invention, the mass ratio (A) / (B) of the mixing amount of the (A) component and the mixing amount of the (B) component is compatible with initial fluidity and fluidity retention. From the viewpoint of, preferably 5/95 or more, more preferably 10/90 or more, still more preferably 20/80 or more, still more preferably 30/70 or more, still more preferably 40/60 or more, and preferably 95. / 5 or less, more preferably 90/10 or less, still more preferably 80/20 or less, still more preferably 70/30 or less, still more preferably 60/40 or less.
In the method for producing a hydraulic composition of the present invention, the mass ratio (A) / (B) of the mixed amount of the component (A) and the mixed amount of the component (B) is preferably 5 from the viewpoint of initial strength. / 95 or more, more preferably 10/90 or more, still more preferably 20/80 or more, even more preferably 30/70 or more, even more preferably 40/60 or more, and preferably 95/5 or less, more preferably It is 90/10 or less, more preferably 80/20 or less, still more preferably 70/30 or less, still more preferably 60/40 or less.

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

  In the method for producing a hydraulic composition of the present invention, the water / hydraulic powder ratio is preferably 10% by mass or more, and more preferably 15% by mass from the viewpoint of initial fluidity, strength development and workability. % Or more, more preferably 20% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less, it is preferable to produce a hydraulic composition. It is preferable to use water and hydraulic powder so as to have such a water / hydraulic powder ratio.

  The obtained hydraulic composition is filled with a hydraulic composition in a mold and cured and cured. Examples of the formwork include a formwork for buildings and a formwork for concrete products. Examples of the method of filling the mold include a method of directly charging from a mixer and a method of pumping the hydraulic composition with a pump to introduce it into the mold.

  During curing of the hydraulic composition, it may be cured by heating to accelerate the curing. Here, the heat curing can hold the hydraulic composition at a temperature of 40 ° C. or higher and 80 ° C. or lower to accelerate the curing.

According to the present invention,
Step of mixing component (A), component (B), hydraulic powder and water to prepare hydraulic composition Step of filling, curing and curing the prepared hydraulic composition in a mold ,as well as,
A step of demolding the cured hydraulic composition,
There is provided a method for producing a cured product having: The matters described in the dispersant composition for hydraulic composition of the present invention, the hydraulic composition, the method for producing the dispersant composition for hydraulic composition, and the method for producing the hydraulic composition are the production of this cured product. It can also be applied to the method.

  As a hardened product of a hydraulic composition using a form that is a concrete product, in civil engineering products, various block products for revetment, box culvert products, segment products used for tunnel construction, bridge girder products, etc. Examples of the building products include curtain wall products, pillars, beams, and building member products used for floor boards.

(1) Preparation of mortar Using a mortar mixer (Dalton Co., Ltd. universal mixing stirrer model: 5DM-03-γ), the following cement (C) and fine aggregate (S) are added and mortar mixer is used. 10 seconds at low speed rotation (63 rpm), and kneading water (W) containing the component (A) or the component (A ′) (comparative component of the component (A)) and the component (B) shown in Table 2 is added. added. Then, main kneading was carried out for 2 minutes by low-speed rotation (63 rpm) of a mortar mixer to prepare a mortar containing each component shown in Table 2. The mortar was prepared at an ambient temperature of 20 ° C.
The mixing conditions of the mortar were 140 g of water, 400 g of cement, 700 g of fine aggregate, and the water / cement ratio (W / C) was 35% by mass.

・ Water (W): Tap water (water temperature 20 ° C)
Cement (C): ordinary Portland cement (mixture of two: Taiheiyo Cement / Sumitomo Osaka Cement = 1/1, mass ratio), density 3.14 g / cm ^3.
・ Fine aggregate (S): Mountain sand from Joyo Density 2.55 g / cm ³

The components used are as follows.
Component (A)-(A-1): Copolymer (A) containing monomer (A1) and monomer (A2) as constituent monomers, monomer (A2) / monomer (A1) = methacrylic acid / methoxy polyethylene Glycol (23) monomethacrylate (average number of moles added in parentheses) = 73 moles / 27 moles, the total amount of the monomers (A1) and (A2) in the constituent monomers is 100% by mass, and the weight average molecular weight is 50,000.
-(A-2): Copolymer (A) containing monomer (A1) and monomer (A2) as constituent monomers, monomer (A2) / monomer (A1) = methacrylic acid / methoxy polyethylene glycol (9) Monomethacrylate (average number of moles added in parentheses) = 47 moles / 53 moles, total amount 100% by weight of monomer (A1) and monomer (A2) in constituent monomers, weight average molecular weight 70,000

(A ') component (comparative component of (A) component)
-(A'-1): naphthalene dispersant, MY150, manufactured by Kao Corporation

Component (B)-(B-1): Formaldehyde condensation polymer composed of monomer units (B1) and monomer units (B2), monomer unit (B2) / monomer unit (B1) = p-hydroxybenzoic acid Monomer unit obtained from acid / monomer unit obtained from polyoxyethylene (40) phenyl ether (average number of moles added in parentheses) = 80 moles / 20 moles (charge ratio), monomer unit (B1) in all monomer units And the total amount of the monomer units (B2) are 100% by mass, and the weight average molecular weight is 18,000.
The condensation polymer (B-1) was synthesized by the following method. A reactor with stirring was charged with 0.2 mol of polyoxyethylene (40) phenyl ether, 0.8 mol of p-hydroxybenzoic acid, 0.5 mol of sulfuric acid and 5 mol of water, and 37% formaldehyde was added dropwise. After the dropping, the mixture was reacted at 105 ° C. for 9 hours, then cooled, 48% sodium hydroxide was added to adjust the pH to 10 or more, water was added to adjust the solid content, and a condensation polymer having a weight average molecular weight of 18,000. Got

-(B-2): a formaldehyde condensation polymer composed of a monomer unit (B1) and a monomer unit (B2), or a monomer unit (B2) / monomer unit (B1) = p-hydroxybenzoic acid. Monomer unit / monomer unit obtained from polyoxyethylene (60) phenyl ether (average number of moles added in parentheses) = 80 moles / 20 moles (charge ratio), monomer units (B1) and monomer units (in all monomer units) B2) total amount 100% by mass, weight average molecular weight 30,000
The condensation polymer (B-2) was synthesized by the following method. A reactor with stirring was charged with 0.2 mol of polyoxyethylene (60) phenyl ether, 0.8 mol of p-hydroxybenzoic acid, 0.5 mol of sulfuric acid and 5 mol of water, and 37% formaldehyde was added dropwise. After dropping, after reacting for 15 hours at 105 ° C., cooling, 48% sodium hydroxide was added to adjust pH to 10 or more, water was added to adjust solid content, and a condensation polymer having a weight average molecular weight of 30,000. Got

-(B-3): a formaldehyde condensation polymer composed of the constituent monomers of the monomer unit (B1) and the monomer unit (B2), obtained from monomer unit (B2) / monomer unit (B1) = p-hydroxybenzoic acid Monomer unit / monomer unit obtained from polyoxyethylene (80) phenyl ether (average number of added moles in parentheses) = 80 moles / 20 moles (charge ratio), monomer unit (B1) and monomer unit (in all monomer units) B2) total amount 100 mass%, weight average molecular weight 21,000
The method for synthesizing the condensation polymer of (B-3) was as follows. A reactor with stirring was charged with 0.2 mol of polyoxyethylene (80) phenyl ether, 0.8 mol of p-hydroxybenzoic acid, 0.5 mol of sulfuric acid and 5 mol of water, and 0.9% of 37% formaldehyde. Mol drop. After the dropwise addition, the mixture was reacted at 105 ° C. for 25 hours, cooled, 48% sodium hydroxide was added to adjust the pH to 10 or higher, water was added to adjust the solid content, and a condensation polymer having a weight average molecular weight of 21,000 was added. Got

-(B-4): a formaldehyde condensation polymer composed of the constituent monomers of the monomer unit (B1) and the monomer unit (B2), obtained from monomer unit (B2) / monomer unit (B1) = p-hydroxybenzoic acid Monomer unit / monomer unit obtained from polyoxyethylene (100) phenyl ether (average number of moles added in parentheses) = 80 moles / 20 moles (charge ratio), the monomer unit (B1) and the monomer unit (in all monomer units) B2) total amount 100 mass%, weight average molecular weight 20,000
The condensation polymer (B-4) was synthesized by the following method. In a reactor with stirring, 0.2 mol of polyoxyethylene (100) phenyl ether, 0.8 mol of p-hydroxybenzoic acid, 0.5 mol of sulfuric acid and 5 mol of water were charged, and 37% formaldehyde was added to 0.9 mol. Mol drop. After the dropping, the mixture is reacted at 105 ° C. for 27 hours, cooled, 48% sodium hydroxide is added to adjust the pH to 10 or more, water is added to adjust the solid content, and a condensation polymer having a weight average molecular weight of 20,000. Got

(B-5): Formaldehyde condensation polymer composed of monomer units (B1), monomer units (B2) and monomer units (B3), monomer units (B2) / monomer units (B1) / monomer units (B3) = monomer unit obtained from p-hydroxybenzoic acid / monomer unit obtained from polyoxyethylene (40) phenyl ether (average number of moles added in parentheses) / monomer unit obtained from phenolsulfonic acid = 70 mol / 20 mol / 10 mol (charge ratio), the total amount of the monomer units (B1) and monomer units (B2) and the monomer units (B3) in all the monomer units is 100% by mass, and the weight average molecular weight is 24,000.
The condensation polymer (B-5) was synthesized by the following method. In a reactor with stirring, 0.2 mol of polyoxyethylene (40) phenyl ether, 0.7 mol of p-hydroxybenzoic acid, 0.1 mol of phenolsulfonic acid, 0.5 mol of sulfuric acid, 5 mol of water. After charging, 0.9 mol of 37% formaldehyde was added dropwise. After dropping, react at 105 ° C for 4.5 hours, cool, add 48% sodium hydroxide to adjust pH to 10 or more, add water to adjust solid content, and condense weight average molecular weight of 24,000. A polymer was obtained.

(B-6): Formaldehyde condensation polymer composed of monomer units (B1), monomer units (B2) and monomer units (B3), monomer units (B2) / monomer units (B1) / monomer units (B3) = monomer unit obtained from p-hydroxybenzoic acid / monomer unit obtained from polyoxyethylene (100) phenyl ether (average number of moles in parentheses) / monomer unit obtained from phenolsulfonic acid = 70 mol / 20 mol / 10 mol (charge ratio), the total amount of the monomer units (B1), the monomer units (B2) and the monomer units (B3) in all the monomer units is 100% by mass, the weight average molecular weight is 24,000
The method for synthesizing the condensation polymer (B-6) was as follows. In a reactor with stirring, 0.2 mol of polyoxyethylene (100) phenyl ether, 0.7 mol of p-hydroxybenzoic acid, 0.1 mol of phenolsulfonic acid, 0.5 mol of sulfuric acid, 5 mol of water. Charge and add 0.9 mol of 37% formaldehyde dropwise. After dripping, after reacting at 105 ° C. for 19 hours, it was cooled, 48% sodium hydroxide was added to adjust the pH to 10 or more, water was added to adjust the solid content, and a condensation polymer having a weight average molecular weight of 24,000. Got

(B-7): Formaldehyde condensation polymer composed of monomer unit (B1) and monomer unit (B2) constituting monomer, monomer unit (B2) / monomer unit (B1) = obtained from p-hydroxybenzoic acid Monomer units / monomer units obtained from polyoxyethylene (40) phenyl ether (average number of moles added in parentheses) = 75 moles / 25 moles (charge ratio), monomer units (B1) and monomer units (in all monomer units) B2) total amount 100% by mass, weight average molecular weight 20,000
The method for synthesizing the condensation polymer (B-7) was as follows. A reactor with stirring was charged with 0.25 mol of polyoxyethylene (40) phenyl ether, 0.75 mol of p-hydroxybenzoic acid, 0.5 mol of sulfuric acid and 5 mol of water, and 0.9% of 37% formaldehyde. Mol drop. After dropping, after reacting at 105 ° C. for 14 hours, cooled, 48% sodium hydroxide was added to adjust pH to 10 or more, water was added to adjust solid content, and a condensation polymer having a weight average molecular weight of 20,000. Got

(B-8): Formaldehyde condensation polymer composed of monomer units (B1) and monomer units (B2), monomer unit (B2) / monomer unit (B1) = obtained from p-hydroxybenzoic acid Monomer units / monomer units obtained from polyoxyethylene (40) phenyl ether (average number of moles added in parentheses) = 70 moles / 30 moles (charge ratio), monomer units (B1) and monomer units (in all monomer units) B2) total amount 100 mass%, weight average molecular weight 20,000
The condensation polymer (B-8) was synthesized by the following method. In a reactor with stirring, 0.3 mol of polyoxyethylene (40) phenyl ether, 0.7 mol of p-hydroxybenzoic acid, 0.5 mol of sulfuric acid and 5 mol of water were charged, and 37% formaldehyde was added to 0.9 mol. Mol drop. After the dropping, the mixture is reacted at 105 ° C. for 15 hours, then cooled, 48% sodium hydroxide is added to adjust the pH to 10 or more, water is added to adjust the solid content, and a condensation polymer having a weight average molecular weight of 20,000 is obtained. Got

-(B-9): Formaldehyde condensation polymer composed of monomer unit (B1) and constituent monomers of other monomer unit, monomer unit (B1) / other monomer unit = obtained from polyoxyethylene (20) phenyl ether Monomer units (average number of moles in parentheses) / monomer units obtained from phenoxyethanol phosphate = 50 moles / 50 moles (charge ratio), the total amount of the monomer units (B1) and the other monomer units in all the monomer units 100 mass%, weight average molecular weight 12,500
The condensation polymer (B-9) was synthesized by the following method. Charge 0.5 mol of polyoxyethylene (20) phenyl ether, 0.5 mol of phenoxyethanol phosphate, 0.27 mol of water, 0.4 mol of sulfuric acid, and 1.1 mol of 37% formaldehyde into a reactor with stirring. Dropped. After dropping, after reacting at 105 ° C. for 14 hours, it was cooled, 48% sodium hydroxide was added to adjust the pH to 10 or more, water was added to adjust the solid content, and a condensation polymer having a weight average molecular weight of 12,500. Got

  Table 1 shows a summary of the composition and molecular weight of the component (B).

(2) Evaluation of fluidity The flow of the prepared mortar was measured according to the test method of JIS R5201. However, the operation to give the drop motion was not performed. The mortar flow was measured for each mortar at 3, 30, and 60 minutes after mortar preparation. Here, the preparation of the mortar was started at the time when water first contacted the cement. Table 2 shows the mortar flow of each mortar after 3 minutes. Table 2 shows the fluidity retention rate after 30 minutes (%) and the fluidity retention rate after 60 minutes (%) calculated from the following formulas.
Flowability retention rate (%) after 30 minutes = 100 × (mortar flow value after 30 minutes) / (mortar flow value after 3 minutes)
Flowability retention rate (%) after 60 minutes = 100 × (mortar flow value after 60 minutes) / (mortar flow value after 3 minutes)

(3) Strength Evaluation of Hardened Mortar The strength of the hardened mortar after 24 hours was evaluated for the prepared mortars in Table 2 according to the test method described below. The results are shown in Table 2.
Based on JIS A 1132, a plastic concrete specimen molding form (Plastic mold, Marui Co., Ltd., cylindrical mold, bottom diameter 5 cm, height 10 cm) is filled with mortar by a two-layer packing method. Then, it was cured in air (20 ° C.) in a room at 20 ° C. and cured to prepare a sample. After 24 hours from the preparation of the mortar, the cured specimen was removed from the mold.
The compressive strength was measured based on JIS A 1108. The time from the preparation of the mortar was based on the point of time when the water first came into contact with the cement during the preparation of the mortar.

In Table 2, the addition amount of the component (A) or the component (B) is the addition amount (parts by mass) of each component to 100 parts by mass of cement.
Further, in Table 2, (A) / (B) (mass ratio) is the ratio (mass ratio) between the content of the component (A) and the content of the component (B) in the hydraulic composition.
Further, in Comparative Example 1 in which the result of mortar flow in Table 2 is described as "separation", since water was separated immediately after the preparation of the mortar, the fluidity and the compression strength were not evaluated.
Further, in Table 2, the component (A ') is described in the column of the component (A) for convenience.

Claims (16)

  (A) A polymer containing a monomer unit having a group selected from a carboxylic acid group and a phosphoric acid group and a monomer unit having a polyalkyleneoxy group and having a weight average molecular weight of 1,000 or more and 1,000,000 or less ( However, the following (excluding the component (B)) (hereinafter referred to as the component (A)), and (B) a monomer having a polyalkyleneoxy group having an average addition mole number of alkyleneoxy groups of 5 or more and 300 or less, and an aromatic ring. A dispersant composition for a hydraulic composition, comprising a polymer (hereinafter referred to as a component (B)) containing a unit (hereinafter referred to as a monomer unit (B1)).   The hydraulic composition according to claim 1, wherein the monomer unit (B1) is a monomer unit obtained from a polyoxyalkylene phenyl ether having a polyalkyleneoxy group having an average addition mole number of alkyleneoxy groups of 5 or more and 300 or less. Dispersant composition.   The dispersant composition for a hydraulic composition according to claim 1 or 2, wherein the component (B) is a formaldehyde condensation polymer.   The water according to any one of claims 1 to 3, wherein the component (B) is a polymer further containing a monomer unit having a carboxylic acid group and an aromatic ring (hereinafter referred to as the monomer unit (B2)). A dispersant composition for a hard composition.   The dispersant composition for a hydraulic composition according to claim 4, wherein the monomer unit (B2) is a monomer unit obtained from hydroxybenzoic acid.   The water according to claim 4 or 5, wherein the molar ratio (B2) / (B1) of the monomer unit (B1) and the monomer unit (B2) in the component (B) is 5/95 or more and 95/5 or less. A dispersant composition for a hard composition.   The mass ratio (A) / (B) of the content of the (A) component and the content of the (B) component is 5/95 or more and 95/5 or less, In any one of Claims 1-6. A dispersant composition for a hydraulic composition as described above.   (A) A polymer containing a monomer unit having a group selected from a carboxylic acid group and a phosphoric acid group and a monomer unit having a polyalkyleneoxy group and having a weight average molecular weight of 1,000 or more and 1,000,000 or less ( However, the following (excluding the component (B)) (hereinafter referred to as the component (A)), and (B) a monomer having a polyalkyleneoxy group having an average addition mole number of alkyleneoxy groups of 5 or more and 300 or less, and an aromatic ring. A hydraulic composition comprising a polymer containing a unit (hereinafter referred to as a monomer unit (B1)) (hereinafter referred to as a component (B)), a hydraulic powder, and water.   The hydraulic composition according to claim 8, wherein the monomer unit (B1) is a monomer unit obtained from a polyoxyalkylene phenyl ether having a polyalkyleneoxy group having an average addition mole number of alkyleneoxy groups of 5 or more and 300 or less. ..   The hydraulic composition according to claim 8 or 9, wherein the component (B) is a formaldehyde condensation polymer.   The water according to any one of claims 8 to 10, wherein the component (B) is a polymer further containing a monomer unit having a carboxylic acid group and an aromatic ring (hereinafter referred to as the monomer unit (B2)). Hard composition.   The hydraulic composition according to claim 11, wherein the monomer unit (B2) is a monomer unit obtained from hydroxybenzoic acid.   The hydraulic composition according to claim 11 or 12, wherein the molar ratio (B2) / (B1) of the monomer unit (B1) and the monomer unit (B2) is 5/95 or more and 95/5 or less.   The mass ratio (A) / (B) of the content of the (A) component and the content of the (B) component is 5/95 or more and 95/5 or less, In any one of Claims 8-13. The hydraulic composition described.   The total content of the component (A) and the component (B) is 0.02 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the hydraulic powder, according to any one of claims 8 to 14. The hydraulic composition described. (A) A polymer containing a monomer unit having a group selected from a carboxylic acid group and a phosphoric acid group and a monomer unit having a polyalkyleneoxy group and having a weight average molecular weight of 1,000 or more and 1,000,000 or less ( However, (excluding the following component (B)), (B) a polymer containing a monomer unit having an average addition mole number of alkyleneoxy groups of 5 to 300 and an aromatic ring, and a hydraulic property A method for producing a hydraulic composition, which comprises mixing powder and water.