TW201945314A - Preparation of water-reducing composition, water-reducing composition and hydraulic composition - Google Patents

Abstract

A water-reducing composition is obtained by a method for preparing the water-reducing composition, the method including stirring a water-reducing agent, a water-soluble cellulose ether, a gum and a defoamer by a high speed stirrer, in which the water-reducing agent has a solid component concentration of 10 to 25% by weight and an Na<SP>+</SP> ion concentration of 8,500 ppm or higher, and in which a stirring element in the high speed stirrer has a peripheral speed of 8.50 m/s or higher, and the water-reducing composition has a sedimentation volume of 80% by volume or higher after being left standing for 72 hours from immediately after preparing the water-reducing composition, or being dispersion.

Description

Manufacturing method of water reducing agent composition, water reducing agent composition and hydraulic setting composition

The present invention relates to a method for manufacturing a water reducing agent composition, a water reducing agent composition, and a hydraulic composition.

A hydraulic composition is a composition containing at least a hydraulic material such as cement, an aggregate such as fine aggregate and / or a coarse aggregate, and water. It is an aggregate of inorganic materials having different specific gravity, grain shape, and particle size. Compositions that are prone to material separation, so some people try to improve them by using water-soluble polymers. For example, water-soluble cellulose ethers are used in hydraulic compositions with very few nonionic water-soluble polymers that can increase viscosity even in highly alkaline hydraulic compositions with a pH of 12 or higher.

However, because water-soluble cellulose ether is generally used as a powder, compared with other liquid kneading agents, it has poor handling properties, and is easy to agglomerate when added, or it scatters when added in a small amount, and it is difficult to add a desired amount. .

In order to solve these problems, a water-reducing agent composition (one-liquid water-reducing agent) prepared by mixing a water-soluble cellulose ether, an antifoaming agent, a gum, and a water-reducing agent in advance is proposed (Japanese Patent Laid-Open No. 2016-056081 (Patent Document 1)).

However, in Patent Document 1, attempts are made to improve the storage stability of the water reducing agent composition through the use of gums. When the water reducing agent has a high solid content concentration or a high Na ⁺ ion concentration, the storage stability of the water reducing agent composition is stable. Sex is sometimes poor and there is room for improvement. As long as a superplasticizer with a high solid content concentration or a high Na ⁺ ion concentration can be blended in the superplasticizer composition, there is no need to dilute the superplasticizer to stabilize the superplasticizer composition, so the superplasticizer composition is hydraulically resistant. It is sufficient to add a small amount of the composition, and there are advantages such that the type of the water reducing agent, the solid content concentration, and the like are not easily limited, and the water reducing agent which can be used as a water reducing agent composition has a wider application range.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2016-056081

[Problems to be Solved by the Invention]

The present invention has been made in view of the above-mentioned facts, and therefore provides a water reducing agent having a high solid content concentration and capable of improving a water reducing agent, a water-soluble cellulose ether, a gum, and a defoaming agent having a high Na ⁺ ion concentration. The manufacturing method of the storage stability water-reducing agent composition of a composition, a water-reducing agent composition, and a hydraulic composition containing the same are aimed at.

[Means for solving problems]

In the water-reducing agent composition, if the solid content concentration or Na ⁺ ion concentration of the water-reducing agent exceeds a certain limit concentration, the water-soluble cellulose ether cannot be dissolved, and precipitation phenomenon (salting out) occurs, and stability and sedimentation cannot be achieved. In Patent Document 1, in order to suppress sedimentation of the water-soluble cellulose ether particles subjected to salting out, gums are added to increase the viscosity of the water reducing agent composition. However, due to this limitation, when the solid content concentration in the superplasticizer reaches 10% by mass or more and the Na ⁺ ion concentration exceeds 8500ppm, the water-soluble cellulose ether component will settle, leading to the storage stability of the superplasticizer composition. Worse.
In order to solve this problem, the inventors of the present case have made research on the manufacturing conditions of the water reducing agent composition. As a result, water reducing agents, water-soluble cellulose ethers, gums, and antifoaming agents having high solid content concentration and high Na ⁺ ion concentration have been researched. When the water reducing agent composition was produced by stirring, it was unexpectedly found that the storage stability of the water reducing agent composition could be improved by rotating the stirring rod of the high-speed mixer to a certain speed or more. That is, in order to prevent sedimentation of water-soluble cellulose ether, dispersion of the water-soluble cellulose having a hydrophilic group and a lipophilic group is generally performed by dispersing the rotation of a stirrer of a high-speed stirrer to a certain speed or more. The water-reducing agent composition of ether and water-reducing agent is sufficiently dispersed and stabilized. Therefore, even if the rotation number of the mixer is increased for salting out of water-soluble cellulose ether, it is difficult to determine that the salting-out can be avoided, and a liquefaction (uniformity) is easily achieved. Dispersion) and stable. However, according to the experimental results, it is known that by making the rotation of the stirrer of the high-speed mixer more than a certain peripheral speed, it is not only easy to achieve a liquefaction (uniform dispersion), but also a liquefied state (uniform dispersion state) for a long time. stable.
Based on this knowledge, the inventor of the present case made further efforts to complete the research and finally completed the present invention.

That is, the present invention provides a method for producing a water reducing agent composition, a water reducing agent composition, and a hydraulic composition described below.
1.
A method for manufacturing a water reducing agent composition, which is a method for manufacturing a water reducing agent composition including a step of stirring a water reducing agent, a water-soluble cellulose ether, a gum, and a defoaming agent by a high-speed mixer. The partial concentration is 10 to 25% by mass, the Na ⁺ ion concentration of the water reducing agent is 8,500 ppm or more, and the peripheral speed of the stirrer in the high-speed stirrer is 8.50 m / s or more.
2.
The method for producing a water reducing agent composition according to 1, wherein the water reducing agent is a polycarboxylic acid type water reducing agent.
3.
The manufacturing method of the water reducing agent composition according to 1 or 2, wherein the aforementioned high-speed mixer is a rotor-stator type mixer or a cylindrical wall rotary mixer.
4.
A water reducing agent composition comprising a water reducing agent, a water-soluble cellulose ether, a gum, and a defoaming agent composition, wherein the solid content concentration of the water reducing agent is 10 to 25% by mass, and The Na ⁺ ion concentration was 8,500 ppm or more, and the sedimentation volume of the water reducing agent composition immediately after the production was 72 hours after being left to stand was 80% by volume or more.
5.
A hydraulic composition comprising a water reducing agent composition such as 4, a hydraulic substance and water.

[Effect of the invention]

According to the present invention, even when a water reducing agent composition having a predetermined solid content concentration and ion concentration of a water reducing agent is used, its storage stability can still be improved. When used in a hydraulic composition, the effect of suppressing exudation or preventing aggregates, etc. The effect of material separation is expected.

[Form of Implementing Invention]

The method for producing the water reducing agent composition, the water reducing agent composition, and the hydraulic composition of the present invention will be described below. In addition, the numerical range "A to B" referred to herein is a value including both ends, and means A to B.

[Manufacturing method of water reducing agent composition]
The manufacturing method of the water-reducing agent composition of the present invention is a method for manufacturing a water-reducing agent composition comprising the steps of stirring the water-reducing agent, water-soluble cellulose ether, gums, and defoaming agent by a high-speed mixer, characterized in that: The solid content concentration of the water reducing agent is 10 to 25% by mass, and the Na ⁺ ion concentration of the water reducing agent according to ion chromatography is 8,500 ppm or more, and the peripheral speed of the stirrer in the high-speed stirrer is 8.50 m / s or more.
In addition, the water reducing agent composition means a kneading agent (one-liquid type water reducing agent) for a hydraulic composition containing at least a water reducing agent, a water-soluble cellulose ether, a gum, and an antifoaming agent.

Here, examples of the water reducing agent include polycarboxylic acid based water reducing agents, lignin based water reducing agents, and melamine based water reducing agents.

Among them, specific examples of the polycarboxylic acid-based water reducing agent include polycarboxylic acid ether compounds, composites of polycarboxylic acid ether compounds and crosslinked polymers, and composites of polycarboxylic acid ether compounds and alignment polymers. Polymer, polycarboxylic acid-based compound and highly modified polymer, polyethercarboxylic acid-based polymer compound, maleic acid copolymer, maleate copolymer, maleic acid derivative copolymer, carboxyl group-containing Polyether-based compounds, polycarboxylic acid-containing multipolymers with terminal sulfo groups, polycarboxylic acid-based graft copolymers, polycarboxylic acid-based polymers, and the like.
Specific examples of the lignin-based water reducing agent include lignin sulfonate and derivatives thereof.
Specific examples of the melamine-based water reducing agent include a melamine sulfonic acid formaldehyde condensate, a melamine sulfonate condensate, a melamine sulfonate polyol condensate, and the like.
Among these, from the viewpoint of versatility, a polycarboxylic acid-based water reducing agent is preferably used.

The water reducing agent may be used alone or in combination of two or more depending on the purpose, and a commercially available product may also be used.

The solid content concentration of the water reducing agent is 10 to 25% by mass, preferably 12 to 22.5% by mass, and more preferably 13 to 20% by mass. When it is less than 10% by mass, the water reducing agent composition may not exhibit good storage stability regardless of the present invention. When it exceeds 25% by mass, it is difficult to achieve a single liquefaction (uniform dispersion).

The solid content concentration of the water reducing agent can be measured as follows.
First, take about 5g of water-reducing agent into a 16ml weighing bottle and measure its mass, that is, the mass (g) of the water-reducing agent before drying. Then, it was dried with a dryer at 105 ° C. to a constant weight value, and the mass (g) of the water reducing agent after drying was measured.
Using the measured masses of the water reducing agent before and after drying, the solid content concentration was calculated according to the following formula.
Solid content concentration (% by mass) = (mass of water reducing agent after drying (g) / mass of water reducing agent before drying (g)) × 100

The Na ⁺ ion concentration of the water reducing agent is 8,500 ppm or more, preferably 9,000 to 14,000 ppm, more preferably 9,000 to 13,000 ppm, and even more preferably 9,000 to 12,000 ppm. When it is less than 8,500 ppm, the water reducing agent composition may not exhibit good storage stability regardless of the present invention.

The Na ⁺ ion concentration of the water reducing agent is a value measured by an ion chromatography method. The details are described in the examples.

In the water-reducing agent composition, the water-reducing agent reaches a reference amount (for example, 100 parts by mass), and a water-soluble cellulose ether, a gum, and an antifoaming agent are added to the water-reducing agent at a predetermined ratio. In addition, when the hydraulic composition is prepared, the amount of the water reducing agent is preferably 0.1 based on the fluidity of the concrete, resistance to material separation, retardation, etc., relative to the unit cement amount (kg / m ³ ). The water-reducing agent composition is used in an amount of -3.0% by mass, more preferably 0.5-2.0% by mass.

The water-soluble cellulose ether is preferably nonionic, and examples thereof include alkyl celluloses such as methyl cellulose; hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose; and hydroxypropyl methyl A hydroxyalkyl alkyl cellulose such as cellulose, hydroxyethyl methyl cellulose, and hydroxyethyl ethyl cellulose. The water-soluble cellulose ether may be used alone or in combination of two or more kinds depending on the purpose. Moreover, a commercially available thing can be used for a water-soluble cellulose ether, and the thing manufactured by a well-known method can also be used.

Among the above-mentioned alkyl celluloses, the degree of substitution (DS) of methoxy groups in methyl cellulose is preferably 1.00 to 2.20, and more preferably 1.20 to 2.00. In addition, the degree of substitution (DS) of an alkoxy group in an alkyl cellulose can be calculated | required by converting the value which can be measured according to the 17th revision of the substitution degree analysis method of the methylcellulose of the Japanese Pharmacopoeia.

Among the above hydroxyalkyl celluloses, in the hydroxyethyl cellulose, the molar number (MS) of the substituted hydroxyethoxy groups is preferably 0.30 to 3.00, more preferably 0.50 to 2.80; in the hydroxypropyl cellulose, The substituted molar number (MS) of hydroxypropoxy is preferably 0.10 to 3.30, and more preferably 0.30 to 3.00. The molar number of hydroxyalkoxy groups in the hydroxyalkyl cellulose can be determined by converting a value that can be measured in accordance with the 17th revised Japanese Pharmacopoeia hydroxypropyl cellulose substitution degree analysis method.

Among the above hydroxyalkyl alkyl celluloses, the degree of substitution (DS) of the methoxy group in the hydroxypropyl methyl cellulose is preferably 1.00 to 2.20, more preferably 1.30 to 1.90, and the substitution of the hydroxypropoxy group The number of ears (MS) is preferably 0.10 to 0.60, and more preferably 0.10 to 0.50. Further, in the hydroxyethyl methyl cellulose, the degree of substitution (DS) of the methoxy group is preferably 1.00 to 2.20, more preferably 1.30 to 1.90, and the mole number (MS) of the substitution of the hydroxyethoxy group is preferably 0.10 to 0.60, more preferably 0.20 to 0.40. Furthermore, in the hydroxyethyl ethyl cellulose, the degree of substitution (DS) of the methoxy group is preferably 1.00 to 2.20, more preferably 1.20 to 2.00, and the mole number (MS) of the substitution of the hydroxyethoxy group is better. It is 0.05 to 0.60, and more preferably 0.10 to 0.50. In addition, the degree of substitution of alkoxy groups and the number of moles of hydroxyalkoxy groups in hydroxyalkyl alkyl cellulose can be determined by using hypromellose (hydroxypropyl) described in the 17th revision of the Japanese Pharmacopoeia. Methylcellulose) was calculated by converting the value measured by the method of substitution degree analysis method.

In addition, DS stands for degree of substitution, which is the number of alkoxy groups per unit of glucose ring unit in cellulose; MS stands for molar substitution, which is added to cellulose The average mole number of hydroxyalkoxy groups per unit of glucose ring unit.

The water-soluble cellulose ether is preferably a hydroxyalkyl alkyl cellulose such as hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose among the above examples from the viewpoint of imparting resistance to material separation. .

The viscosity of a 1% by mass aqueous solution of a water-soluble cellulose ether at 20 ° C is preferably 30 to 30,000 mPa · s, and more preferably 300 to 25,000 mPa · s, from the viewpoint of imparting predetermined viscosity to a hydraulic composition. , More preferably 500 to 20,000 mPa · s, and particularly preferably 500 to 3,000 mPa · s.
The viscosity of a 1% by mass aqueous solution of a water-soluble cellulose ether at 20 ° C can be measured using a B-type viscometer under the measurement conditions of 12 rpm.

The addition amount of the water-soluble cellulose ether is preferably 0.1 to 5.0% by mass (parts by mass) relative to the water reducing agent (100% by mass (100 parts by mass)) from the viewpoint of imparting predetermined viscosity to the hydraulic composition. And more preferably 0.5 to 3.0% by mass (mass parts).

Examples of the gums include Daibutan gum, vinylon gum, xanthan gum, and gellan gum.

Among these, Deutam gum is composed of D-glucose, D-glucuronic acid, D-glucose, L-rhamnose and 2 L-rhamnose.
Vinylon is based on a main chain formed by bonding D-glucose, D-glucuronic acid, and L-rhamnose in a ratio of 2: 2: 1, and L-rhamnose or L-mannose is bonded. Structure of the side chain.
Xanthan gum is the same as cellulose. The main chain is β-1,4 bond of D-glucose. The side chain is composed of 2 mannose and 1 glucuronic acid.
Gellan gum is a heteropolysaccharide that binds D-glucose, D-glucuronic acid, and L-rhamnose at a ratio of 2: 1: 1, and uses the four sugars that are bonded as repeating units. class.

The gums can also be added in the form of a powder or an aqueous solution.
Glues can be used alone or in combination of two or more depending on the purpose. As the glue, a commercially available product can be used.

When the amount of the gum is added, it is preferably 0.005 to 2% by mass, and more preferably 0.01 to 1% by mass, relative to the water reducing agent (100% by mass (100% by mass)). (Parts by mass), more preferably 0.1 to 0.8% by mass (parts by mass).
In the case of vinylon gum, xanthan gum, and gellan gum, it is preferably 0.01 to 20 mass%, more preferably 0.1 to 10 mass%, relative to the water reducing agent (100 mass% (100 mass parts)). (Parts by mass), more preferably 0.5 to 8% by mass (parts by mass).

Examples of the defoaming agent include an oxyalkylene-based defoamer, a polysiloxane-based defoamer, an alcohol-based defoamer, a mineral oil-based defoamer, a fatty acid-based defoamer, and a fatty acid ester-based defoamer. Agent.

Among these, specific examples of the oxyalkylene-based defoaming agent include polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; diethylene glycol heptyl ether, Polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene 2-ethylhexyl ether, higher alcohols with a carbon number of 8 or more, or oxyethyleneoxypropylenes with a carbon number of 12 to 14 (Poly) oxyalkylene alkyl ethers such as adducts; (poly) oxyalkylene (alkyl) aryl ethers such as polyoxypropylene phenyl ether, polyoxyethylene nonylphenyl ether; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3-methyl-1 -Butyne-3-ol and other acetylene ethers obtained by addition polymerization of alkylene oxide to acetylene alcohol; diethylene glycol oleate, diethylene glycol laurate, ethylene glycol distearate, poly (Poly) oxyalkylene fatty acid esters such as oxyalkylene oleate; (poly) oxyalkylene fatty acids such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan trioleate Sorbitan fatty acid esters; (Poly) oxyalkylenes such as sodium polyoxypropylene methyl ether sulfate, sodium polyoxyethylene lauryl phenol ether sulfate (Aryl) ether sulfates; (poly) oxyalkylene alkyl phosphates such as (poly) oxyethylene stearyl phosphate; (poly) oxyalkylenes such as polyoxyethylene laurylamine Alkyl amines; polyoxyalkylene amines and the like.

Specific examples of the polysiloxane-based defoaming agent include dimethyl silicone oil, silicone paste, silicone emulsion, organic modified polysiloxane (polyorganosiloxane such as dimethylpolysiloxane), and the like. Siloxane), fluorosilicone oil, etc.
Specific examples of the alcohol-based antifoaming agent include octanol, 2-ethylhexyl alcohol, cetyl alcohol, acetylene alcohol, and glycols.
Specific examples of the mineral oil-based defoaming agent include kerosene, flowing paraffin, and the like.
Specific examples of the fatty acid-based defoaming agent include oleic acid, stearic acid, and alkylene oxide adducts thereof.
Specific examples of the fatty acid ester-based defoaming agent include glyceryl monoricinoleate, alkenyl succinic acid derivative, sorbitol monolaurate, sorbitol trioleate, and natural wax.
Among these, from the viewpoint of defoaming performance, an oxyalkylene-based defoamer is preferable.

The addition amount of the defoaming agent is preferably 0.001 to 16% by mass (parts by mass), and more preferably 0.002 to 10% by mass (parts by mass) relative to the water reducing agent (100% by mass (100 parts by mass)).

The antifoaming agent may be used alone or in combination of two or more kinds depending on the purpose. As the defoaming agent, a commercially available product can be used.

The above water reducing agent, water-soluble cellulose ether, gums, and antifoaming agent are stirred by a high-speed mixer, but the order of adding materials during stirring is not particularly limited.

The high-speed mixer used in the present invention is a device including a stirrer (rotating blade) capable of rotating at a high speed and a container capable of mixing the above materials by the rotation of the stirrer, and examples thereof include a homomixer (HM- (310, manufactured by AS ONE), rotor-stator mixers such as high-speed homogeneous mixers (LZB14-HM-1, manufactured by Chuo Rika Co., Ltd.), and thin-film rotary high-speed mixers (FILMIX, manufactured by PRIMIX) Wall rotation mixer, homogenizer (PH91, manufactured by SMT), etc., or high-speed mixer using these principles. Among these, a rotor-stator type mixer or a cylindrical wall rotary mixer is preferred.

Examples of the type of the agitator (rotating blade) in the high-speed mixer include a turbine-stator type, a film rotating type (PC wheel), a dispersion type, and a perforated cage type; based on the stirring efficiency and the storage of the water reducing agent composition From the viewpoint of stability, a turbine-stator type and a thin film rotating type (PC wheel) are preferred.

The peripheral speed of the stirrer in the high-speed mixer is 8.50 m / s or more, preferably 9.00 to 30.0 m / s, and more preferably 9.00 to 25.0 m / s. When it is less than 8.50 m / s, the storage stability of the superplasticizer composition cannot be improved. In addition, the peripheral speed of the stirrer means the speed of the fastest part of the stirrer (rotating blade) rotating in the high-speed stirrer (that is, the outermost periphery of the stirrer). The peripheral speed v (m / s) of the stir bar is obtained from the diameter d (mm) of the stir bar and the rotation speed n (rpm (revolutions per minute)) of the stir bar according to the following formula.
v = π × d × n / 60,000

The size (diameter) of the stirrer (rotating blade) is preferably from 10 to 500 mm from the viewpoint of manufacturing and processing of the high-speed stirrer.

The rotation speed of the stirrer (rotating blade) in the high-speed mixer is preferably from 325 rpm or more, more preferably from 1,200 to 50,000 rpm, more preferably from 3,500 to 20,000 rpm from the viewpoint of dispersibility.

The stirring time of the high-speed mixer is the time after the stirrer reaches the target peripheral speed, preferably 30 seconds or more, and more preferably 1 minute or more. The upper limit of the stirring time is not particularly limited, but from the viewpoint of effective productivity, it is preferably 60 minutes or less, and more preferably 10 minutes or less.

[Water reducing agent composition]
The water-reducing agent composition of the present invention is obtained according to the above-mentioned method for producing a water-reducing agent composition of the present invention, and it contains at least a water-reducing agent, a water-soluble cellulose ether, a gum, and an antifoaming agent, and preferably is a water-reducing agent. A water-reducing agent composition composed of water-soluble cellulose ether, gums, and a defoaming agent, characterized in that the solid content concentration of the aforementioned water-reducing agent is 10 to 25% by mass, and Na of the water-reducing agent according to the ion chromatography method is Na ^{The +} ion concentration is 8500 ppm or more, and the sedimentation volume of the water reducing agent composition immediately after being manufactured (one liquefaction) to 72 hours after standing is 80% by volume or more.
In addition, according to the present invention, the sedimentation volume of the water reducing agent composition immediately after production (one liquefaction) to 168 hours may be 70% by volume or more.

In addition, when the sedimentation volume of the water reducing agent composition is less than 80% by volume, the required amount of water-soluble solvent cannot be added even if the water reducing agent composition is added to the hydraulic composition due to the separation of the water-soluble cellulose ether. Cellulose ether without material separation.

The sedimentation volume referred to here refers to a measuring cylinder with a predetermined amount (for example, 100 ml) of the water-reducing agent composition just after stirring is injected into a predetermined measuring cylinder with a predetermined outer diameter (for example, 32 mm), and is allowed to stand at room temperature (20 ± 3 ° C) for a certain period The volume ratio (suspension maintenance ratio) of the suspension layer (water reducing agent composition layer) to the entire liquid observed at time. In addition, the amount of the superplasticizer composition immediately after stirring and the size (outer diameter and height) of the measuring cylinder used, as long as the height of the suspension layer (superplasticizer composition layer) in the entire liquid can be clearly confirmed visually during the above observation. (That is, the boundary position of the upper liquid and the suspension layer in the whole liquid) is not specifically defined.

[Hydraulic composition]
The hydraulic composition of the present invention is characterized by including at least the aforementioned water reducing agent composition of the present invention, a hydraulic substance, and water.

Specific applications of the hydraulic composition include concrete, mortar, and cement slurry.

The concrete hydraulic composition system includes the water reducing agent composition, hydraulic material (cement), water, fine aggregate (sand) and coarse aggregate (gravel) of the present invention. Examples of the type include ordinary concrete and medium flow concrete. , High flow concrete, non-separable concrete in water and sprayed concrete.

The mortar hydraulic composition contains the water reducing agent composition, hydraulic material (cement), water, and fine aggregate (sand) of the present invention. Examples of the type include mortar for tiled tiles, repair mortar, and self-leveling materials. .

The cement slurry hydraulic composition system includes the water reducing agent composition, hydraulic material (cement), and water of the present invention, and examples thereof include adhesives for ceramic tile-based inorganic construction materials, and grouting materials for filling members and the empty walls of the members.

The content of the water-reducing agent composition in the hydraulic composition of the present invention is from the viewpoint of imparting resistance to material separation. When the hydraulic composition is used for concrete, it is preferably 0.10 to 2.0% by mass, and more preferably 0.5 to 1.5. Mass%; when the hydraulic composition is for mortar, it is preferably 0.05 to 1.5% by mass, more preferably 0.10 to 1.0% by mass; when the hydraulic composition is for cement slurry, it is preferably 0.02 to 1.0% by mass , More preferably 0.05 to 0.8% by mass.

Examples of hydraulic materials include ordinary Portland cement, early-strength Portland cement, medium-temperature Portland cement, blast furnace cement, silica cement, fly ash cement, high-alumina cement, and ultra-early-strength Portland cement. And other hydraulic cement.

From the viewpoint of ensuring the strength of the content of the hydraulic substance (cement), when the hydraulic composition is used for concrete, it is preferably 270 to 800 kg per 1 m ^{3 of the} concrete.
When the hydraulic composition is for mortar, it is preferably 300 to 1,000 kg per 1 m ^{3 of the} mortar.
When the hydraulic composition is used for cement slurry, it is preferably 500 to 1600 kg per 1 m ^{3 of the} cement slurry.

Examples of water include tap water and sea water. From the viewpoint of salt damage, tap water is preferred.

The water / cement ratio (W / C) in the hydraulic composition is preferably from 30 to 75% by mass, and more preferably from 45 to 65% by mass from the viewpoint of material separation.

The hydraulic composition further includes an aggregate depending on its use. Examples of the aggregate include fine aggregate and coarse aggregate.

As for the fine aggregate, river sand, mountain sand, land sand, crushed sand and the like are preferred. The particle diameter (maximum particle diameter) of the fine aggregate is preferably 5 mm or less.

In terms of coarse aggregate, river gravel, mountain gravel, land gravel, crushed rock, and the like are preferred. The particle size (maximum particle size) of the coarse aggregate is larger than that of the fine aggregate, and is preferably 40 mm or less, and more preferably 25 mm or less.

On fine aggregate content, when the composition of a hydraulic concrete, concrete per 1m ³ press is preferably 400 ~ 1,100kg, more preferably 500 ~ 1,000kg; When the composition is a hydraulic mortar, mortar press It is preferably 500 to 2,000 kg per 1 m ³ , and more preferably 600 to 1,600 kg.

Regarding the coarse aggregate content, when the hydraulic composition is used for concrete, it is preferably 600 to 1,200 kg, and more preferably 650 to 1,150 kg per 1 m ^{3 of} concrete.

The fine aggregate ratio (volume percentage) in the aggregate is preferably from 30 to 55 vol%, more preferably from 35 to 55 vol% from the viewpoint of maintaining fluidity or sufficient strength when the hydraulic composition is used for concrete. %, More preferably 35 to 50% by volume. In addition, the ratio of fine aggregate (volume%) = volume of fine aggregate / (volume of fine aggregate + volume of coarse aggregate) × 100.

In the hydraulic composition, a kneading material may be added as needed in order to suppress heat generation during curing and improve durability after curing. Examples of the kneading material include blast furnace slag and fly ash.

In the hydraulic composition, in order to ensure a predetermined amount of air and obtain the durability of the hydraulic composition, an AE agent (Air Entraining Agent) may be used in combination as required. Examples of the AE agent include anion surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and rosin surfactants.
Examples of the anionic surfactant type include a carboxylic acid type, a sulfate type, a sulfonic acid type, and a phosphate type.
Examples of the cationic surfactant system include amine salt type, primary amine salt type, secondary amine salt type, tertiary amine salt type, and quaternary amine salt type.
Examples of the nonionic surfactant include an ester type, an ester / ether type, an ether type, and an alkanolamine type. Examples of the amphoteric surfactant system include an amino acid type and a sulfobetaine type.
Examples of the rosin-based surfactant include abietic acid, neo-rosinic acid, oleoresinic acid, pimaric acid, isopimaric acid, and dehydroabietic acid.

In the hydraulic composition, in order to obtain the strength of the hydraulic composition, an antifoaming agent may be added as required. Examples of the defoaming agent include the same as those described above.
From the viewpoint of dispersibility, the amount of the defoaming agent to be added is preferably 1 to 50% by mass based on the water-soluble cellulose ether.

In addition, in the hydraulic composition of the present invention, in order to manage the physical properties of the hydraulic composition (fresh concrete, fresh mortar, or fresh cement slurry) immediately after mixing, calcium chloride, lithium chloride, Accelerators such as calcium formate, or retarders such as sodium citrate and sodium gluconate.

In addition, in the hydraulic composition of the present invention, in order to prevent shrinkage cracking caused by hardening and drying, and cracks caused by temperature stress caused by the heat of hydration reaction of cement, bluestone or Lime-based swelling material.

The hydraulic composition described above can be produced by a common method. For example, first add the water-reducing agent composition, hydraulic material (cement) and aggregates (fine aggregate and coarse aggregate), antifoaming agent of the present invention to the forced biaxial kneading mixer, and dry-knead. . Thereafter, water was added and kneaded to obtain a hydraulic composition.

As described above, it is possible to provide a water reducing agent, a water-soluble cellulose ether, a gum, and a defoamer which include at least a solid content concentration of 10 to 25% by mass and a Na ⁺ ion concentration of 8,500 ppm or more by ion chromatography. A water reducing agent composition capable of improving storage stability at the same time, a manufacturing method thereof, and a hydraulic composition.

[Example]

Examples and comparative examples are given below to describe the present invention more specifically, but the present invention is not limited by these examples.

[Examples 1 to 12, Comparative Example 1]
The amount of water reducing agent, water-soluble cellulose ether, gums, and defoaming agent shown below are measured in the manner shown in Table 1 below. For these materials, the following high-speed mixer is used to stir the conditions (peripheral speed) shown in Table 1. And rotation speed) and agitated to prepare a water reducing agent composition.
In addition, the stirring time is set to 1 minute after adding all the materials of the water reducing agent, water-soluble cellulose ether, gums, and defoaming agent. The gums are added in a powder state.

＜ Materials used ＞
(1) Water reducing agent: Polycarboxylic acid type water reducing agent (CHUPOL HP-11, made by Takemoto Oil)
(Solid content concentration; 24.3%, Na ⁺ ion concentration; 16,000 ppm)
The water reducing agent is diluted with pure water as required, and adjusted to the solid content concentration and Na ⁺ ion concentration shown in Table 1 (that is, 14.0% by mass and 9,200ppm, 16.0% by mass and 10,500ppm, 17.0% by mass and 11,200ppm and 20.0% by mass And 13,200ppm (4 levels).

The Na ⁺ ion concentration in the water reducing agent was measured by the following method.
The sample of the water-reducing agent supplied to the water-reducing agent composition was diluted with pure water to a concentration of 1 / 10,000, and filtered through a 0.2 μm filter (trade name: Ekiclodisk (made of PTFE), manufactured by Thermo Fisher Scientific). The filtrate was measured by an ion chromatograph (DIONEX ICS-1600, manufactured by Thermo Fisher Scientific) under the following measurement conditions.

(Measurement conditions)
Protection column; CG14 (manufactured by Thermo Fisher Scientific)
Main column; CS14 (manufactured by Thermo Fisher Scientific)
Suppressor; CERS-500-4mm (manufactured by Thermo Fisher Scientific)
Column temperature; 30 ℃
Fluid volume; 1ml / min
Injection volume; 25μm
Eluent; 10mM-MSA (methanesulfonic acid)
The eluent was prepared by diluting 2 mol of methanesulfonic acid with pure water to 10 mmol.

(2) Water-soluble cellulose ether:
・ Hydroxypropyl methylcellulose (HPMC)
(DS; 1.40, MS; 0.20, viscosity of a 1% by mass aqueous solution at 20 ° C; 2,200 mPa · s)
・ Hydroxyethyl methyl cellulose (HEMC)
(DS; 1.50, MS; 0.20, viscosity of a 1% by mass aqueous solution at 20 ° C; 2,100 mPa · s)
・ Hydroxyethyl cellulose (HEC)
(DS; viscosity of 2.50, 1% by mass aqueous solution at 20 ° C; 2,100mPa · s)

(3) glue:
・ Daitan (DG) (KELCO-CRETE DG-F, CP Kelco)
・ Vellon (WG) (KELCO-CRETE WG, CP Kelco)
・ Xanthan Gum (XG) (KELTROL, CP Kelco)

(4) Defoaming agent: Oxyalkylene-based defoaming agent (SN DEFOAMER 14-HP, manufactured by SAN NOPCO)

＜ High Speed Mixer ＞
(1) Homogeneous mixer (HM-310, manufactured by AS ONE)
(Kind of stirrer: turbine-stator type, size (diameter) of stirrer (rotary blade): 29mm)
(2) Film Rotary High Speed Mixer (FILMIX, manufactured by PRIXIX)
(Type of agitator: film rotation type (PC wheel type), size (diameter) of agitator (rotary blade): 52mm)

＜ Evaluation method ＞
About the obtained water reducing agent composition, the sedimentation volume was measured by the following method.

(Measurement of sedimentation volume)
Take 100ml of the water-reducing agent composition just after being manufactured, that is, just after liquefaction (dispersion), into a measuring cylinder with a plug (outer diameter 32mm, capacity 100ml, made by IWAKI), and place (stand still) at room temperature (20 ± 3 ℃) ), Press immediately after taking (0 hours), after 24 hours, after 72 hours, after 168 hours, visually observe the interface with Shangchengye. The volume ratio (suspension maintenance ratio) of the suspension layer (superplasticizer composition layer) to the entire liquid was calculated from the scale corresponding to the boundary as the sedimentation volume. For example, when the boundary with the upper liquid is 0mL, the sedimentation volume is 100% by mass; when the boundary with the upper liquid is 90mL, the sedimentation volume is 90% by mass; when the boundary with the upper liquid is 50mL, the sedimentation volume is 50% by mass.

The above results are shown in Table 1.
As a result, it was found that at the time of manufacturing a water-reducing agent composition containing a water-reducing agent having a solid content concentration of 10.0 to 25.0% by mass and a Na ⁺ ion concentration of 8,500 ppm or more, a water-soluble cellulose ether, a gum, and a defoaming agent, By setting the peripheral speed of the high-speed mixer to 8.50 m / s or more, the storage stability of the superplasticizer composition can be improved.

・ PC: Polycarboxylic acid, HPMC: Hydroxypropyl methylcellulose,
HEMC: hydroxyethyl methyl cellulose, HEC: hydroxy ethyl cellulose,
DG: Dayan gum, WG: Vinylon gum, XG: Xanthan gum,
OA series: oxyalkylene series

In addition, the present invention has been described so far using the above embodiment, but the present invention is not limited by this embodiment. Other embodiments, additions, changes, deletions, and the like can be changed within the scope that can be considered by the practitioner. As long as the effects of the present invention can be exerted, any aspect is included in the scope of the present invention.

Claims (5)

A manufacturing method of a water reducing agent composition, which is a method for manufacturing a water reducing agent composition including a step of stirring a water reducing agent, a water-soluble cellulose ether, a gum, and a defoaming agent by a high-speed mixer. The partial concentration is 10 to 25% by mass, the Na ⁺ ion concentration of the water reducing agent is 8,500 ppm or more, and the peripheral speed of the stirrer in the high-speed stirrer is 8.50 m / s or more. The method for producing a water reducing agent composition according to claim 1, wherein the water reducing agent is a polycarboxylic acid type water reducing agent. The method for manufacturing a water reducing agent composition according to claim 1 or 2, wherein the aforementioned high-speed mixer is a rotor-stator type mixer or a cylindrical wall rotary mixer. A water reducing agent composition comprising a water reducing agent, a water-soluble cellulose ether, a gum, and a defoaming agent composition, wherein the solid content concentration of the water reducing agent is 10 to 25% by mass, and The Na ⁺ ion concentration was 8,500 ppm or more, and the sedimentation volume of the water reducing agent composition immediately after the production was 72 hours after being left to stand was 80% by volume or more. A hydraulic composition comprising the water reducing agent composition according to claim 4, a hydraulic substance, and water.