JP7018036B2 - Admixture composition for hydraulic composition - Google Patents

Description

The present invention relates to an admixture composition for a hydraulic composition, a hydraulic composition, a method for producing a hydraulic composition, and a method for producing a cured product of a hydraulic composition.

Hydraulic powders such as cement and blast furnace slag have the property of reacting with water and hardening, and are called mortar when mixed with sand and concrete when mixed with gravel. These materials have been used in various structures because their morphology can be easily changed before curing. Further, by adding a chemical agent to concrete or the like before hardening, it is possible to improve the workable time and workability. Most of the chemical agents use surfactants, and in some cases, excessive bubbles are generated, which causes a decrease in strength. Therefore, many of these chemicals contain antifoaming agents.

Patent Document 1 describes (A) a water reducing agent containing a polycarboxylic acid or a salt or derivative thereof, and (B) a tertiary amine system having an average molecular weight of 100 or more and 1500 or less represented by a specific structural formula. Disclosed is an admixture system for modifying a hydrated cement composition comprising a defoaming agent.

Patent Document 2 describes a defoaming agent for a cement composition comprising a salt of an organic amine having an alkyl group or an alkenyl group having 6 to 24 carbon atoms of an unsubstituted or hydroxyl group or halogen substituted which may be mediated by an amide bond. Is disclosed.

Japanese Patent Publication No. 2005-500232 Japanese Unexamined Patent Publication No. 2000-247704

A polycarboxylic acid-based dispersant is known as a dispersant for hydraulic compositions. The polycarboxylic acid-based dispersant is a dispersant having excellent fluidity, fluidity retention, etc., and whose performance can be easily designed. Some polycarboxylic acid-based dispersants use an acid catalyst in the manufacturing process. There is no problem even if the acid catalyst remains in the polycarboxylic acid-based dispersant as long as it does not adversely affect the hydraulic composition.
On the other hand, it is desirable to obtain a one-component preparation by blending a polycarboxylic acid-based dispersant and an amine-based defoaming agent in terms of workability and the like. In that case, it is desired to have excellent storage stability and defoaming property.

However, if an amine-based defoaming agent is combined with a polycarboxylic acid-based dispersant using a sulfonic acid-based acid catalyst in the manufacturing process to form a one-component preparation, phase separation or crystal precipitation may occur. It has been found that the storage stability of the obtained preparation may be impaired.

There is also an ether-based defoaming agent as the defoaming agent, but if the ether-based defoaming agent and the polycarboxylic acid-based dispersant are used as a one-component preparation, creaming occurs on the upper part of the product and the storage stability is inferior.

The present invention provides an admixture composition for a hydraulic composition having excellent storage stability and defoaming properties.

The present invention comprises (A) a polycarboxylic acid-based dispersant [hereinafter referred to as (A) component], and (B) a third amine having one hydrocarbon group having 9 or more and 12 or less carbon atoms and two methyl groups. The present invention relates to an admixture composition for a water-hard composition containing a compound [hereinafter referred to as (B) component] and (C) sulfonic acid or a salt thereof [hereinafter referred to as (C) component].

The present invention also relates to a hydraulic composition containing the admixture composition for a hydraulic composition of the present invention, a hydraulic powder, an aggregate, and water.

The present invention also relates to a method for producing a hydraulic composition, which comprises mixing the admixture composition for a hydraulic composition of the present invention, a hydraulic powder, an aggregate, and water.

Further, the present invention comprises mixing the admixture composition for a hydraulic composition of the present invention, a hydraulic powder, an aggregate and water to produce a hydraulic composition, and the hydraulic composition is produced. The present invention relates to a method for producing a cured product of a hydraulic composition.

According to the present invention, there is provided an admixture composition for a hydraulic composition having excellent storage stability and defoaming property. The admixture composition for a hydraulic composition of the present invention is particularly excellent in storage stability at low temperatures.

The component (B) of the present invention is a component that mainly contributes to the development of defoaming property. The defoaming property of the component (B) is brought about by improving the orientation to the foam film by improving the hydrophobicity in the water-hard composition slurry system in which the component (B) is basic, and promoting defoaming. Is considered to be. From the viewpoint of this hydrophobicity (defoaming property), it is preferable that the compound of the component (B) is an amine compound having a long-chain hydrocarbon group, and the hydrocarbon group has a certain number of carbon atoms or more. .. On the other hand, when a polycarboxylic acid-based dispersant and an amine-based defoaming agent are combined, a one-component type is formed by mixing a sulfonic acid salt, for example, a sulfonic acid salt used as a catalyst in the process of synthesizing the polycarboxylic acid. The stability of the formulation tends to decrease. However, in the present invention, the storage stability of the composition is also improved by using the component (B). This is because the hydrocarbon group of the component (B) has a certain number of carbon atoms or less, so that the crystallization of the sulfonate of the component (B) is suppressed, and the component (B) is stable in the admixture composition. It is thought that this is because it can exist. From this point of view, in the present invention, as the component (B), a third amine compound having a hydrocarbon group having 9 or more and 12 or less carbon atoms is used.

[Micible composition for hydraulic composition]
<Ingredient (A)>
The component (A) is a polycarboxylic acid-based dispersant.
As the polycarboxylic acid-based dispersant, a copolymer containing the monomer (1a) represented by the following general formula (1a) as a constituent monomer is preferable from the viewpoint of initial fluidity.
The polycarboxylic acid-based dispersant contains a monomer (1a) represented by the following general formula (1a) and a monomer (2a) represented by the following general formula (2a) as constituent monomers. Coalescence is more preferred.

[In the formula,
R ^1a , R ^2a : may be the same or different, hydrogen atom or methyl group R ^3a : hydrogen atom or -COO (AO) _n1 X ¹
R ^4a : Hydrogen atom or alkyl group having 1 or more and 4 or less carbon atoms AO: Group selected from ethyleneoxy group and propyleneoxy group n1: Average number of moles of AO, 1 or more and 300 or less q: 0 or more and 2 The following numbers p: 0 or 1
Is shown. ]

[In the formula,
R ^5a , R ^6a , R ^7a : may be the same or different, a hydrogen atom, a methyl group or (CH ₂ ) _r COM ² , and (CH ₂ ) _r COM ² is COM ¹ or another (CH ₂ ). ) _R COM2 may form anhydrate, in which case M ¹ and M ² of those groups ^are absent.
M ¹ , M ² : Can be the same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroalkyl group or Alkali group r: Indicates a number of 0 or more and 2 or less. ]

In the general formula (1a), R ^1a is preferably a hydrogen atom from the viewpoint of flow retention.
In the general formula (1a), R ^2a is preferably a methyl group from the viewpoint of fluid retention.
In the general formula (1a), R ^3a is preferably a hydrogen atom from the viewpoint of flow retention.
In the general formula (1a), R ^4a is preferably a hydrogen atom or a methyl group, and more preferably a methyl group, from the viewpoint of fluid retention.
In the general formula (1a), ethyleneoxy group is preferable for AO from the viewpoint of flow retention. The AO preferably contains an ethyleneoxy group.
In the general formula (1a), n1 is the average number of moles of substance added of AO, and is 1 or more, preferably 5 or more, more preferably 7 or more, and 300 or less, preferably 250 or less, from the viewpoint of flow retention. It is more preferably 200 or less, still more preferably 150 or less, still more preferably 100 or less, still more preferably 70 or less, still more preferably 50 or less, still more preferably 30 or less.
In the general formula (1a), q is preferably 0 from the viewpoint of flow retention.
In the general formula (1a), p is preferably 1 from the viewpoint of flow retention.

Sulfonic acid may be used as an acid catalyst in the production of the monomer (1a). For example, Japanese Patent Application Laid-Open No. 2008-214638 describes such a method. When producing the component (A) of the present invention, a mixture containing the monomer (1a) produced by such a method and a sulfonic acid can be used as it is as long as the effect of the present invention is not impaired. ..

In the general formula (2a), a hydrogen atom is preferable for ^R5a from the viewpoint of flow retention.
In the general formula (2a), R ^6a is preferably a methyl group from the viewpoint of flow retention.
In the general formula (2a), a hydrogen atom is preferable for R ^7a from the viewpoint of flow retention.
For (CH ₂ ) _r COMM ² , anhydrate may be formed with COOM ¹ or another (CH ₂ ) _r COMM ² , in which case M ¹ and M ² of those groups are absent.
M ¹ and M ² may be the same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroalkyl group or It is an alkenyl group.
The alkyl group, hydroalkyl group, and alkenyl group of M ¹ and M ² each preferably have 1 or more carbon atoms and 4 or less carbon atoms.
M ¹ and M ² may be the same or different, preferably a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, or an alkylammonium group, and a hydrogen atom, an alkali metal, or an alkaline soil. A metal like metal (1/2 atom) or an ammonium group is more preferable, a hydrogen atom, an alkali metal or an alkaline earth metal (1/2 atom) is more preferable, and a hydrogen atom or an alkali metal is further preferable.
From the viewpoint of flow retention, the r of (CH ₂ ) _r COMM ² in the general formula (2a) is preferably 1.

From the viewpoint of flow retention, the total amount of the monomers (1a) in the constituent monomers of the copolymer containing the monomer (1a) is preferably 90% by mass or more. It is preferably 92% by mass or more, more preferably 95% by mass or more, and preferably 100% by mass or less. This total amount may be 100% by mass.
The copolymer containing the monomer (1a) and the monomer (2a) as a constituent monomer is the monomer (1a) and the monomer (1a) in the constituent monomer from the viewpoint of flow retention. The total amount of 2a) is preferably 90% by mass or more, more preferably 92% by mass or more, further preferably 95% by mass or more, and preferably 100% by mass or less. This total amount may be 100% by mass.

The copolymer containing the monomer (1a) and the monomer (2a) as a constituent monomer is the monomer (2a) in the total of the monomer (1a) and the monomer (2a). From the viewpoint of fluid retention of the water-hard composition, the ratio is preferably 40 mol% or more, preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less.

A polycarboxylic acid-based dispersant, a copolymer containing a monomer (1a) as a constituent monomer, and a copolymer containing a monomer (1a) and a monomer (2a) as a constituent monomer. The weight average molecular weight of the water-hard composition is preferably 20,000 or more, more preferably 30,000 or more, still more preferably 40,000 or more, and preferably 100,000 or less, from the viewpoint of fluid retention of the water-hard composition. It is more preferably less than 100,000, still more preferably 80,000 or less.

A polycarboxylic acid-based dispersant, a copolymer containing a monomer (1a) as a constituent monomer, and a polymer containing a monomer (1a) and a monomer (2a) as a constituent monomer. The weight average molecular weight and the number average molecular weight of the above are measured by the gel permeation chromatography (GPC) method under the following conditions, respectively.
* GPC conditions Equipment: GPC (HLC-8320GPC) manufactured by Tosoh Corporation Column: G4000PWXL + G2500PWXL (manufactured by Tosoh Corporation)
Eluent: 0.2M phosphate buffer / CH ₃ CN = 9/1
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detection: RI
Sample size: 0.2 mg / mL
Standard substance: Polyethylene glycol equivalent (monodisperse polyethylene glycol with known molecular weight, molecular weight 87,500, 250,000, 145,000, 46,000, 24,000)

From the viewpoint of initial fluidity and fluid retention, the water-hard composition of the present invention contains a polycarboxylic acid-based dispersant, preferably 0.1 part by mass or more, more preferably 100 parts by mass with respect to 100 parts by mass of the water-hard powder. Is contained in an amount of 0.2 parts by mass or more, preferably 3.5 parts by mass or less, and more preferably 2 parts by mass or less.

As the polycarboxylic acid-based dispersant, two or more kinds of dispersants having different average number of moles of AO added and ratio of monomer (1a) and monomer (2a) can also be used.

<Ingredient (B)>
The component (B) is a third amine compound having one hydrocarbon group having 9 or more and 12 or less carbon atoms and two methyl groups. That is, one of the three groups bonded to the nitrogen atom is a hydrocarbon group having 9 or more and 12 or less carbon atoms, and two are a tertiary amine compound having a methyl group. Here, the hydrocarbon group preferably has 10 or more carbon atoms. Examples of the hydrocarbon group include an alkyl group and an alkenyl group, and an alkyl group is preferable.

The component (B) is preferably a compound represented by the following general formula (b1).

[In the formula, R ^1b represents a hydrocarbon group having 9 or more and 12 or less carbon atoms, preferably an alkyl group or an alkenyl group, and more preferably an alkyl group. ]

Examples of the component (B) include N, N-dimethyldecylamine and N, N-dimethyldodecylamine.
In the present invention, N, N-dimethyldecylamine and N, N-dimethyldodecylamine can be used in combination as the component (B). In this case, the mass ratio of N, N-dimethyldecylamine / N, N-dimethyldodecylamine is preferably 10/90 or more, more preferably 20/80 or more, preferably 99/1 or less, more preferably 90 /. It is 10 or less.

<Ingredient (C)>
The component (C) is sulfonic acid or a salt thereof.
The sulfonic acid is preferably a sulfonic acid having a total carbon number of 1 or more and 9 or less.
The sulfonic acid is preferably an aromatic sulfonic acid having a total carbon number of 1 or more and 9 or less.
Examples of the salt include alkali metal salts such as sodium and potassium, alkanolamine salts, amine salts and ammonium salts. The salt is preferably an alkali metal salt.

The component (C) is preferably an alkylbenzene sulfonic acid having an alkyl group having 1 or more and 3 or less carbon atoms or a salt thereof.
The component (C) is more preferably one or more compounds selected from toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid and salts thereof.
The component (C) is more preferably p-toluenesulfonic acid or a salt thereof.
The component (C) is more preferably p-toluenesulfonic acid or an alkali metal salt thereof.

<Composition, optional ingredients, etc.>
In the admixture composition for a water-hardening composition of the present invention, the component (A) is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 60% by mass. Hereinafter, it is more preferably contained in an amount of 50% by mass or less, still more preferably 40% by mass or less.

In the admixture composition for a water-hardening composition of the present invention, the component (B) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.10% by mass or more, and It is preferably contained in an amount of 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less.

In the admixture composition for a water-hardening composition of the present invention, the component (C) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.10% by mass or more, and , Preferably 0.40% by mass or less, more preferably 0.35% by mass or less, still more preferably 0.23% by mass or less, still more preferably 0.22% by mass or less, still more preferably 0.21% by mass. It contains the following.

The admixture composition for a water-hardening composition of the present invention has a mass ratio (A) / (B) of the component (A) to the component (B) preferably 10 or more from the viewpoint of defoaming property and dispersibility. , More preferably 20 or more, still more preferably 30 or more, and preferably 4000 or less, more preferably 3900 or less, still more preferably 3800 or less, still more preferably 2000 or less, still more preferably 1000 or less, still more preferably. It is 500 or less, more preferably 350 or less.

The admixture composition for a water-hardening composition of the present invention has a mass ratio (A) / (C) of the component (A) to the component (C) preferably 15 or more, more preferably 15 or more, from the viewpoint of dispersibility. 25 or more, more preferably 50 or more, still more preferably 100 or more, and preferably 6000 or less, more preferably 5900 or less, still more preferably 5800 or less, still more preferably 3000 or less, still more preferably 2000 or less, and more. It is more preferably 1000 or less, still more preferably 500 or less.

The admixture composition for a water-hardening composition of the present invention preferably has a mass ratio (B) / (C) of the component (B) to the component (C) from the viewpoint of storage stability of the one-component preparation. 0.02 or more, more preferably 0.05 or more, still more preferably 0.10 or more, still more preferably 0.15 or more, and preferably 500 or less, more preferably 450 or less, still more preferably 400 or less, more. It is more preferably 200 or less, still more preferably 100 or less, still more preferably 50 or less, still more preferably 30 or less, still more preferably 10 or less, still more preferably 5 or less.

The admixture composition for a hydraulic composition of the present invention can further contain (D) a polyoxyalkylene alkyl ether represented by the general formula (d1) [hereinafter referred to as a component (D)]. The component (D) is a preferable component from the viewpoint of storage stability and defoaming property of the one-component preparation.
R ^1d- (AO) _m -H (d1)
[In the formula,
R ^1d : Alkyl group having 4 or more and 20 or less carbon atoms AO: Group m selected from ethyleneoxy group and propyleneoxy group m: The average number of moles of AO added, representing a number of 1 or more and 300 or less. ]

In the general formula (d1), the carbon number of R ^1d is preferably 6 or more, more preferably 8 or more, and preferably 22 or less, more preferably 20 or less.
In the general formula (d1), the AO is preferably a copolymer of an ethyleneoxy group and a propyleneoxy group. It is preferable that AO contains a propyleneoxy group.
In the general formula (d1), m is the average number of moles of substance added of AO, preferably 5 or more, more preferably 10 or more, and preferably 40 or less, more preferably 35 or less.

When the admixture composition for a water-hardening composition of the present invention contains the component (D), the composition contains the component (D) in an amount of preferably 0.001% by mass or more, more preferably 0.01% by mass. The above, and preferably 1% by mass or less, more preferably 0.1% by mass or less.

The admixture composition for a water-hardening composition of the present invention has, as optional components, a water-soluble polymer compound, an air entraining agent, a cement wetting agent, a swelling agent, a waterproofing agent, a retarding agent, a quick-setting agent, a thickener, and an agglomerate. It can contain components such as an agent, a drying shrinkage reducing agent, a strength enhancer, a curing accelerator, and a preservative [excluding those corresponding to the components (A) to (D)].

The admixture composition for a hydraulic composition of the present invention preferably contains water. Water is a component constituting the rest of the composition, and is used in an amount such that the total of the component (A), the component (B), the component (C) and the optional component is 100% by mass.

When the admixture composition for a hydraulic composition of the present invention contains water, the pH at 20 ° C. is 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, and 10 or less, 9 or less. You can select from 8 or less, 7 or less, or 6 or less. From the viewpoint of storage stability of the admixture composition for hydraulic composition, the pH is preferably 1 or more, more preferably 2 or more, and preferably 6 or less. Admixture for water-hard composition Adjusting the pH of the composition to the acidic side (pH 6 or less) improves the hydrogen ion concentration in the composition and reduces the degree of separation of the component (C) in the acid separation equilibrium, resulting in a decrease. , It is considered that the storage stability of the composition is further improved because the salt with the component (B) is less likely to be formed.

The present invention simply comprises (C) a monomer containing the monomer (1a) in the presence of sulfonic acid or a salt thereof, and further containing the monomer (1a) and the monomer (2a). Reacting the weights to obtain a mixture containing (A) a polycarboxylic acid-based dispersant and (C) a sulfonic acid or a salt thereof.
The mixture is mixed with (B) a third amine compound having one hydrocarbon group having 9 or more and 12 or less carbon atoms and two methyl groups to obtain an admixture composition for a water-hard composition.
To provide a method for producing an admixture composition for a hydraulic composition. The reaction in this production method is a synthesis of a polycarboxylic acid-based dispersant according to a known method, for example, Japanese Patent No. 3212399, Japanese Patent No. 3184698, Japanese Patent No. 3600100, Japanese Patent No. 2774445, and the like. It can be carried out with reference to the method. The matters described in the admixture composition for hydraulic composition of the present invention can be appropriately applied to this production method. At that time, the content in the composition can be replaced with a mixed amount or a blending amount.

[Hydraulic composition]
The hydraulic composition of the present invention is a hydraulic composition containing the admixture composition for a hydraulic composition of the present invention, a hydraulic powder, an aggregate, and water. The hydraulic composition of the present invention is a hydraulic composition obtained by blending the admixture composition for a hydraulic composition of the present invention, a hydraulic powder, an aggregate, and water.

Preferred embodiments of the component (A), the component (B), and the component (C) used in the hydraulic composition of the present invention are the same as those of the admixture composition of the present invention.

Examples of the aggregate include aggregates selected from fine aggregates and coarse aggregates. 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 of these, 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.

The mass ratio of the component (A) to the component (B) in the water-hardening composition of the present invention (A) / (B), and the mass ratio of the component (A) to the component (C) (A) / (C). ), The mass ratio (B) / (C) of the component (B) to the component (C) can be selected from the ranges described in the admixture composition for a water-hard composition of the present invention, respectively.

From the viewpoint of dispersibility and strength development, the water-hardening composition of the present invention contains the component (A) in an amount of 0.01 parts by mass or more, more preferably 0 parts by mass, based on 100 parts by mass of the water-hardening powder. It contains 05 parts by mass or more, more preferably 0.10 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 2 quality parts or less.

From the viewpoint of dispersibility and defoaming property, the water-hardening composition of the present invention contains the component (B) in an amount of 0.0001 part by mass or more, more preferably 0. It contains 0003 parts by mass or more, more preferably 0.0007 parts by mass or more, preferably 0.5 parts by mass or less, more preferably 0.25 parts by mass or less, still more preferably 0.10 parts by mass or less.

From the viewpoint of dispersibility and storage stability of the one-component preparation, the water-hard composition of the present invention contains the component (C) in an amount of 0.0001 part by mass or more, preferably 0.0001 part by mass or more, based on 100 parts by mass of the water-hard powder. More preferably 0.0003 parts by mass or more, further preferably 0.0007 parts by mass or more, and preferably 0.020 parts by mass or less, more preferably 0.015 parts by mass or less, still more preferably 0.01 parts by mass or less. contains.

Further, in the water-hardening composition of the present invention, the ratio (mass ratio) of the water / water-hardening powder is preferably 0.15 or more, more preferably 0.2 or more, and preferably preferably 0.2 or more, from the viewpoint of workability. It is 2 or less, more preferably 1 or less.

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 such as cement, and improves the filling property into the formwork 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. be. 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 formwork or the like. It is preferably 700 kg / m ³ or more, preferably 1,000 kg / m ³ or less, and more preferably 900 kg / m ³ or less.
When the water-hard composition is a mortar, the amount of the fine aggregate used is preferably 800 kg / m ³ or more, more preferably 900 kg / m ³ or more, still more preferably 1,000 kg / m ³ or more, and preferably 1,000 kg / m 3 or more. 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.

The water-hardening composition of the present invention can contain, as optional components, a retarder, a curing accelerator, an AE agent, a leavening agent, a foaming agent, a thickener, a fluidizing agent, a foaming agent, a waterproofing agent and the like. ..

[Method for producing hydraulic composition]
The method for producing a hydraulic composition of the present invention is a method for producing a hydraulic composition in which the admixture composition for a hydraulic composition of the present invention, a hydraulic powder, an aggregate, and water are mixed. Is. Mixing of these components can be carried out by a known method.

Preferred embodiments of the component (A), the component (B), the component (C), the hydraulic powder, and the aggregate used in the method for producing a hydraulic composition of the present invention are the same as those of the admixture composition of the present invention.

In the method for producing a water-hardening composition of the present invention, the components (A), (B), and (C) are mass ratios of the component (A) and the component (B) (A) / (B), (. The mass ratio (A) / (C) of the component (A) to the component (C) and the mass ratio (B) / (C) of the component (B) to the component (C) are the water-hardening compositions of the present invention, respectively. The admixture for physical use can be mixed so as to be in the range described in the composition.

In the method for producing a hydraulic composition of the present invention, the components (A), (B), and (C) are contained in the range described in the hydraulic composition of the present invention with respect to the hydraulic powder, respectively. Can be mixed so as to be.

Further, in the method for producing a water-hard composition of the present invention, from the viewpoint of workability, the water / water-hard composition has a water / water-hard composition ratio (mass ratio) of preferably 0.15 or more. It is more preferably 0.2 or more, preferably 2 or less, and more preferably 1 or less.

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 such as cement, and improves the filling property into the formwork 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. be. 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 formwork or the like. It is preferably 700 kg / m ³ or more, preferably 1,000 kg / m ³ or less, and more preferably 900 kg / m ³ or less.
When the water-hard composition is a mortar, the amount of the fine aggregate used is preferably 800 kg / m ³ or more, more preferably 900 kg / m ³ or more, still more preferably 1,000 kg / m ³ or more, and preferably 1,000 kg / m 3 or more. 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.

[Method for producing a cured product of hydraulic composition]
The method for producing a cured product of the hydraulic composition of the present invention is a method of mixing the admixture composition for a hydraulic composition of the present invention, a hydraulic powder, an aggregate, and water to form a hydraulic composition. Is a method for producing a cured product of a hydraulic composition, wherein the hydraulic composition is cured.
In the step of producing the hydraulic composition, the method for producing the hydraulic composition of the present invention can be adopted. The preferred embodiment described in the method for producing a hydraulic composition of the present invention can be appropriately applied to this step.
As a step of curing the hydraulic composition, a known method for curing the hydraulic composition can be adopted. The step of curing the hydraulic composition can be carried out in consideration of the use, shape and the like of the cured product.

<Examples 1 to 4 and Comparative Example 1>
(1) Preparation of admixture composition Tap water, the following (A) component, the following (B) component, the following (C) component, and if necessary, the following (D) component, the contents in the table (the rest is water supply) Water), and the mixture was stirred at 20 ° C. for 10 minutes using a magnetic stirrer to prepare an admixture composition. More specifically, the admixture compositions in Tables 1 to 7 are described in Marum screw tube No. The component (A), the component (B) and the component (C) were added to No. 7, and the mixture was prepared by vigorously stirring with a magnetic stirrer for 5 minutes. The pH of the admixture composition was measured at 20 ° C. according to item 8.3 of JIS K 3362; 2008, and if necessary, a 48% aqueous sodium hydroxide solution (manufactured by Wako Pure Chemical Industries, Ltd.), 2 mol / L. Adjusted using hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.). The component (C) was added so that the content in the final admixture composition was as shown in the table in consideration of the method for synthesizing the copolymer. The content of each component in the table is mass% based on the effective component (the same applies hereinafter).

<Ingredient (A)>
Copolymer 1: Methacrylic acid / methoxypolyethylene glycol (average number of moles added 25) Monomethacrylate = 75 mol / 25 mol, weight average molecular weight = 50,000
Polymer 2: Acrylic acid / polyethylene glycol (average number of moles added 50) isoprenyl ether = 75 mol / 25 mol, weight average molecular weight = 60,000
Copolymer 3: Methacrylic acid / methoxypolyethylene glycol (average number of moles added: 10) Monomethacrylate = 50 mol / 50 mol, weight average molecular weight = 50,000
Copolymer 4: Methacrylic acid / methoxypolyethylene glycol (average number of moles added 120) monomethacrylate = 80 mol / 20 mol, weight average molecular weight = 50,000
The copolymers 1, 3 and 4 were synthesized by referring to the method described in Japanese Patent No. 3184698, if necessary. In the copolymers 1 and 3, a monomer prepared using sodium p-toluenesulfonate was used.
Further, the copolymer 2 was synthesized by referring to the method described in Japanese Patent No. 3683176 as necessary. In the copolymer 2, a monomer produced without using sodium p-toluenesulfonate was used. Copolymer 2 was also used for evaluation to confirm the effect of the content of p-toluenesulfonate sodium.

<Ingredient (B)>
・ N, N-dimethyldecylamine, manufactured by Kao Corporation ・ N, N-dimethyldodecylamine, manufactured by Kao Corporation

<(B') component (comparative compound of (B) component)>
・ N, N-dimethyloctylamine, manufactured by Kao Corporation ・ N, N-dimethyltetradecylamine, manufactured by Tokyo Chemical Industry Co., Ltd.

<Ingredient (C)>
・ Sodium p-toluenesulfonate, manufactured by Tokyo Chemical Industry Co., Ltd.

<(D) component>
-D-1: Polyoxypropylene (average number of added moles 5) Alkyl (carbon number 12-14) ether, manufactured by Kao Co., Ltd.-d-2: Polyoxyethylene (average number of added moles 2) Polyoxypropylene (average number of added moles) Mol number 6) Alkyl (carbon number 18) ether, manufactured by Kao Co., Ltd.

(2) Storage stability test 50 g of miscible composition, Marum screw tube No. It was sampled at 7 and stored at 5 ° C. The appearance of the admixture composition was visually observed over time, and the period during which a uniform state could be maintained was measured. After storage, evaluation was performed up to 6 months, and if the condition was uniform at that time, it was described as "6 months or more" in the table.

It can be seen that a miscible composition having excellent storage stability can be obtained by combining the component (B) of the present invention with the components (A) and (C) as in the examples. On the other hand, in Comparative Example 1-1 in which the component (B') is used instead of the component (B), it can be seen that the storage stability is significantly reduced.

<Example 5 and Comparative Example 5>
(1) Preparation of mortar A mortar was prepared at 20 ° C. with the following mortar formulation. For the mortar, use the mortar mixer specified in JIS R5201 to put about half of the fine aggregate, cement, and the remaining fine aggregate into the mortar mixer in this order, and then perform empty kneading (60 rpm, 10 seconds). , A uniform mixture of the admixture composition prepared in advance and tap water was added thereto, and the mixture was kneaded (60 rpm, 120 seconds) to prepare. All test materials used were stored at 20 ° C.

<Mortar combination>
-Cement: 400 g (1: 1 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)
-Fine aggregate: 700 g (sand, from Joyo, Kyoto Prefecture, dry surface, surface dry specific density 2.50)
-Micible composition: prepared by the method described in Example 1 and the like at the ratio shown in Table 5 (the components used are the same as those in Example 1 and the like).
-Tap water: 160 g (total mass with the above admixture composition)

(2) Evaluation of mortar fluidity The mortar immediately after kneading prepared in (1) is 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 is measured. It was used as an index of mortar liquidity. The results are shown in Table 5.

(3) Measurement of mortar air volume As an index of the mortar air volume immediately after kneading prepared in (1), a mortar air volume test was conducted using a steel container with a capacity of 400 mL JIS A 1171: 2000 (polymer). The test method for cement mortar) was used as a reference. The results are shown in Table 5. This amount of air is an index of defoaming property, and the smaller the value, the better the defoaming property.

The storage stability of the admixture composition was evaluated in the same manner as in Example 1. The results are shown in Table 5.

* 1 Addition amount: Addition amount per 100 parts by mass of cement (same below)

As shown in Table 5, it can be seen that the admixture composition of the present invention has excellent storage stability and a small amount of mortar air, that is, excellent defoaming property. On the other hand, it can be seen that Comparative Examples 5-2 and 5-4, which do not contain the component (B) and contain the component (D) corresponding to the ether-based defoaming agent, are inferior in storage stability.

<Example 6 and Comparative Example 6>
(1) Preparation of concrete Concrete was prepared at 20 ° C. with the following concrete composition. A coarse aggregate, about half of the fine aggregate, cement, calcium carbonate fine powder, and the remaining fine aggregate were put into a forced biaxial mixer (manufactured by KYC) in this order, and kneaded for 10 seconds. Then, a uniform mixture of the admixture composition prepared in advance, tap water and an air entraining agent blended if necessary was added thereto, and the mixture was kneaded for 120 seconds to obtain concrete. All test materials used were stored at 20 ° C.

<Concrete composition (30L / bat)>
-Cement: 12.7 kg (1: 1 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)
-Calcium carbonate fine powder: 5.4 kg (manufactured by Shimizu Kogyo Co., Ltd., specific density 2.71)
・ Fine aggregate: 20.0 kg (sand, from Joyo, Kyoto Prefecture, dry surface, surface dry specific density 2.50)
・ Coarse aggregate: 25.7 kg (gravel, from Nishijima, Hyogo prefecture, dry surface, surface dry specific density 2.63)
-Micible composition: prepared by the method described in Example 1 and the like at the ratio shown in Table 6 (the components used are the same as those in Example 1 and the like).
-Air entraining agent: Mighty AE-03 manufactured by Kao Corporation (the amount added in Table 6 (100 parts by mass with respect to cement) was added to tap water and used).
-Tap water: 5.0 kg (total mass of the above admixture composition and air entraining agent)

(2) Evaluation of concrete fluidity The concrete slump flow immediately after kneading prepared in (1) was measured and evaluated based on JIS A 1101 and JIS A 1150. The results are shown in Table 6.

(3) Measurement of the amount of air in concrete The amount of air in the concrete immediately after kneading prepared in (1) was measured based on JIS A 1128 after being re-kneaded with a scoop immediately before the measurement. The results are shown in Table 6. This amount of air is an index of defoaming property, and the smaller the value, the better the defoaming property.

The storage stability of the admixture composition was evaluated in the same manner as in Example 1. The results are shown in Table 6.

From Examples 6-2 to 6-4, it can be seen that the amount of air can be adjusted by adjusting the amount of the air entraining agent added. Therefore, in Example 6-2, it is easy to change the design when it is desired to secure the amount of air.
On the other hand, it can be seen that Comparative Examples 6-1 and 6-2, which do not contain the component (B) and contain the component (D) corresponding to the ether-based defoaming agent, are inferior in storage stability.

<Example 7 and Comparative Example 7>
(1) Preparation of concrete Concrete was prepared at 20 ° C. with the following concrete composition. A coarse aggregate, about half of the fine aggregate, cement, and the remaining fine aggregate were put into a forced biaxial mixer (manufactured by KYC) in this order, and kneaded for 10 seconds. Then, a uniform mixture of the admixture composition prepared in advance, tap water and an air entraining agent blended if necessary was added thereto, and the mixture was kneaded for 90 seconds to obtain concrete. All test materials used were stored at 20 ° C.

<Concrete composition (30L / bat)>
-Cement: 10.2 kg (1: 1 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)
・ Fine aggregate: 24.9 kg (sand, from Joyo, Kyoto Prefecture, dry surface, surface dry specific density 2.50)
-Coarse aggregate: 27.8 kg (gravel, surface dry state, surface dry specific density 2.63)
-Micible composition: prepared by the method described in Example 1 and the like at the ratio shown in Table 7 (the components used are the same as those in Example 1 and the like).
-Air entraining agent: Mighty AE-03 manufactured by Kao Corporation (the amount added in Table 7 (100 parts by mass with respect to cement) was added to tap water and used).
-Tap water: 5.1 kg (total mass of the above admixture composition and air entraining agent)

(2) Evaluation of fluidity and fluidity retention of concrete For the concrete immediately after kneading prepared in (1), concrete slumps were measured based on JIS A 1101 and JIS A 1150. In addition, cover the concrete after evaluation with a vinyl sheet to prevent it from drying, and leave it in a dark place at 20 ° C for 20 minutes, 40 minutes, and 60 minutes after kneading. Concrete slumps were measured and evaluated in the same manner as above. The results are shown in Table 7.

(3) Evaluation of the amount of air in the concrete The amount of air in the concrete prepared in (1) immediately after kneading and after standing at 20 ° C in a dark place for 20 minutes, 40 minutes, and 60 minutes after kneading. Was re-kneaded with a scoop immediately before the measurement, and then measured based on JIS A 1128. The results are shown in Table 7. This amount of air is an index of defoaming property, and the smaller the value, the better the defoaming property.

The storage stability of the admixture composition was evaluated in the same manner as in Example 1. The results are shown in Table 7.

As shown in Table 7, it can be confirmed that the admixture composition of the present invention is excellent not only in defoaming property immediately after kneading concrete but also in defoaming property after a certain period of time, that is, in foam suppressing property. can. On the other hand, it can be seen that Comparative Example 7-1, which does not contain the component (B) and contains the component (D) corresponding to the ether-based defoaming agent, is inferior in storage stability.

Claims (16)

(A) Polycarboxylic acid-based dispersant [hereinafter referred to as (A) component], and (B) a third amine compound having one hydrocarbon group having 9 or more and 12 or less carbon atoms and two methyl groups [hereinafter, An admixture composition for a water-hard composition containing (referred to as a component (B)] and (C) a sulfonic acid or a salt thereof [hereinafter referred to as a component (C)].
The component (A) is a copolymer containing the monomer (1a) represented by the following general formula (1a) and the monomer (2a) represented by the following general formula (2a) as constituent monomers. the law of nature,
An admixture composition for a hydraulic composition, wherein the mass ratio (A) / (C) of the component (A) to the component (C) is 15 or more and 6000 or less .

[In the formula,
R ^1a , R ^2a : may be the same or different, hydrogen atom or methyl group R ^3a : hydrogen atom or -COO (AO) _n1 X ¹
R ^4a : Hydrogen atom or alkyl group having 1 or more and 4 or less carbon atoms AO: Group selected from ethyleneoxy group and propyleneoxy group n1: Average number of moles of AO, 1 or more and 300 or less q: 0 or more and 2 The following numbers p: 1
Is shown. ]

[In the formula,
R ^5a , R ^6a , R ^7a : may be the same or different, a hydrogen atom, a methyl group or (CH ₂ ) _r COM ² , and (CH ₂ ) _r COM ² is COM ¹ or another (CH ₂ ). ) _R COM2 may form anhydrate, in which case M ¹ and M ² of those groups ^are absent.
M ¹ , M ² : Can be the same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroalkyl group or Alkali group r: Indicates a number of 0 or more and 2 or less. ] The water-hard composition according to claim 1, wherein the copolymer has a total amount of the monomer (1a) and the monomer (2a) in the constituent monomer of 90% by mass or more and 100% by mass or less. For admixture composition. The copolymer according to claim 1 or 2, wherein the ratio of the monomer (2a) in the total of the monomer (1a) and the monomer (2a) is 40 mol% or more and 90 mol% or less. Mixture composition for water-hardening composition. The admixture composition for a hydraulic composition according to any one of claims 1 to 3, which contains the component (A) in an amount of 5% by mass or more and 60% by mass or less. The admixture composition for a hydraulic composition according to any one of claims 1 to 4, which contains the component (B) in an amount of 0.01% by mass or more and 5% by mass or less. The admixture composition for a water-hard composition according to any one of claims 1 to 5, wherein the component (C) is an alkylbenzene sulfonic acid having an alkyl group having 1 or more and 3 or less carbon atoms or a salt thereof. The mixture for a water-hard composition according to any one of claims 1 to 6, wherein the component (C) is one or more compounds selected from toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid and salts thereof. Agent composition. The admixture composition for a hydraulic composition according to any one of claims 1 to 7, wherein the component (C) is p-toluenesulfonic acid or a salt thereof. The admixture composition for a hydraulic composition according to any one of claims 1 to 8, which contains the component (C) in an amount of 0.01% by mass or more and 0.40% by mass or less. The admixture composition for a hydraulic composition according to any one of claims 1 to 9, wherein the mass ratio (A) / (B) of the component (A) to the component (B) is 10 or more and 4000 or less. The admixture composition for a hydraulic composition according to any one of claims 1 to 10 , wherein the mass ratio (B) / (C) of the component (B) to the component (C) is 0.02 or more and 500 or less. thing. The admixture composition for a hydraulic composition according to any one of claims 1 to 11 , further comprising (D) a polyoxyalkylene alkyl ether represented by the general formula (d1).
R ^1d- (AO) _m -H (d1)
[In the formula,
R ^1d : Alkyl group having 4 or more and 20 or less carbon atoms AO: Group m selected from ethyleneoxy group and propyleneoxy group m: The average number of moles of AO added, representing a number of 1 or more and 300 or less. ] The admixture composition for a hydraulic composition according to any one of claims 1 to 12 , wherein the pH at 20 ° C. is 1 or more and 10 or less. A hydraulic composition containing the admixture composition for a hydraulic composition according to any one of claims 1 to 13 , a hydraulic powder, an aggregate, and water. A method for producing a hydraulic composition, which comprises mixing the admixture composition for a hydraulic composition according to any one of claims 1 to 13 , a hydraulic powder, an aggregate, and water. A hydraulic composition is produced by mixing the admixture composition for a hydraulic composition according to any one of claims 1 to 13 , a hydraulic powder, an aggregate, and water to produce the hydraulic composition. A method for producing a cured product of a hydraulic composition, which cures the composition.