JPH10120451A - Hydraulic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hydraulic composition having high fluidity, large separation resistance and self-packing property and hardly having an effect due to delay of curing on strength by combinedly using a specific water-soluble polymer as a thickener and compounding the water-soluble polymer with a high- performance water reducing agent, hydraulic powder and water. SOLUTION: This hydraulic composition comprises a water-soluble polymer (a1 ) having <10% absorption ratio as absorption characteristics to cement, a water-soluble polymer (a1 ) having >=10% absorption ratio as absorption characteristics to cement, a high-performance water-reducing agent (b), hydraulic powder (c) and water (d). A weight ratio of the water-soluble polymers (a1 ) to (a2 ) is preferably (100/1) to (1/1). The water-soluble polymer (a1 ) include a 6-30C monohydric alcohol, 6-30C monohydric mercaptan, a 6-30C alkylphenol, a polyalkylene oxide to which 10-1,000mol alkylene oxide is added to a 6-30C amine or 6-30C carboxylic acid. The water-soluble polymer (a2 ) includes methylcellulose or PVA.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydraulic composition having high fluidity and requiring no compaction. More specifically, concrete, mortar and paste used as building materials and secondary product materials, which are highly viscous and fluid and have excellent resistance to separation of aggregates, cement, and water, and vibrators and the like. The present invention relates to a hydraulic composition that does not require compaction due to vibration of the hydraulic composition.

[0002]

2. Description of the Related Art Conventionally, concrete has been used for cement, water, fine aggregate, coarse aggregate,
It is manufactured by mixing various additives and the like. In recent years, the development of high fluidity concrete that further enhances the fluidity of fresh concrete before hardening has been actively pursued. High-fluidity concrete has higher fluidity than conventional concrete, has excellent self-filling properties, does not require compaction by vibration of a vibrator or the like, and can improve workability. Although this high fluidity concrete does not yet have an established definition, the slump flow of concrete according to JIS A 1101 is generally 50 cm or more, preferably
It is about 50-70cm.

[0003] If the slump flow is less than 50 cm, sufficient self-filling property cannot be ensured. If the slump flow exceeds 70 cm, material separation between cement paste and gravel or the like is caused, and clogging between rebars by gravel occurs. As a result, sufficient self-filling properties cannot be obtained.

[0004] In the production of concrete, a typical additive conventionally mixed for the purpose of enhancing fluidity and self-filling properties is a water reducing agent mainly having a dispersing action of particles such as cement.
It is an AE agent having an air entraining action and the like. In recent years, a high performance water reducing agent having further enhanced these effects and a high performance AE water reducing agent having an air entraining action and a fluidity maintaining action have been developed. The high-performance water reducing agent and the high-performance AE water reducing agent are generally used in the form of an aqueous solution having a solute concentration of about 20 to 40% by weight.
The fluidity can be imparted to fresh concrete by using the seed or two or more kinds in combination.

[0005] The high fluidity concrete has a high fluidity in the state of fresh concrete, and at the same time,
Non-uniform materials such as cement, water, fine aggregate, coarse aggregate,
It is necessary to have sufficient material separation resistance (hereinafter sometimes abbreviated as separation resistance) so as not to cause separation before and after curing. As a method for increasing the separation resistance, there are a powder-based separation resistance increasing method (hereinafter, referred to as a powder method), a thickener-based separation resistance increasing method (hereinafter, referred to as a thickener method), and a combined method. Separation resistance increase method (hereinafter referred to as combination method)
The following three methods have been proposed.

[0006] The powder method is to mix the admixture materials such as fly ash, limestone fine powder and the like to increase the powder content in the high fluidity concrete and lower the water powder ratio, thereby reducing the plasticity of the high fluidity concrete. This is a method of increasing the viscosity and increasing the material separation resistance. Specifically, at the time of kneading the materials, the admixture material as described above is combined with cement for 500 times.
Mix to about kg / m ³ .

[0007] The thickener method is a method in which a thickener is added at the time of kneading materials to increase the plastic viscosity of high-fluid concrete and increase the material separation resistance.

The combined method is a method of increasing the plastic viscosity of high-fluidity concrete and increasing the material separation resistance by using a powder method for increasing the powder content and a thickener method for adding a thickener. is there.

In the above-mentioned powder method, there is a problem that the fluidity of the produced concrete is apt to change sharply with changes in the unit water amount and the admixture amount. In the thickener method and the combined method using a thickener, fluctuations in fluidity due to changes in the unit water amount and the amount of admixture are lessened than in the powder method, but a large amount of thickener is added as in underwater concrete. In the concrete mix, the viscosity becomes extremely high.
62-35984), in order to impart sufficient fluidity,
It is necessary to add a large amount of a high-performance water reducing agent, and there is a problem that the initial strength is slow due to an increase in cost and a delay in curing time, and it is difficult to apply it to construction and civil engineering, especially to secondary products. In recent years, there has been disclosed a technology capable of satisfying both fluidity and resistance to material separation by using a water-soluble polymer having an adsorption property of 10% or less as an adsorbent for cement as a thickener (Japanese Unexamined Patent Publication (Kokai) No. Heisei (Kokai) No. Heisei (KOKAI) No. Heisei 9 (1994) -207. No. 8-12407). However, such a water-soluble polymer has a small increase in viscosity, and in order to obtain a desired viscosity, a large amount of addition is required, and there has been a problem that the cost is increased and the curing is delayed. In addition, when used in the form of an aqueous solution, the amount used increases, and there is a problem that the existing concrete plant equipment cannot be used unless the amount of kneading is reduced.Therefore, a technology that shows a remarkable effect with a small amount of addition is desired. I was

[0010]

DISCLOSURE OF THE INVENTION The present inventors have been keen to obtain a concrete composition for self-filling which has a high fluidity, a large separation resistance, has a self-compacting property, and has little influence on strength due to retardation of curing. As a result of the study, the present invention has been completed.

That is, the present invention relates to a water-soluble polymer (hereinafter referred to as a non-adsorbing type thickener) (a-1) having an adsorption rate of less than 10% for cement and an adsorption rate of 10% for cement. The above water-soluble polymers (hereinafter referred to as adsorption-type thickeners) (a-2), high-performance water reducing agents (b), hydraulic powders (c) and water
(d) is provided.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION When the hydraulic composition of the present invention is used as compaction-free concrete, a slump flow value of 50 cm in a slump test specified in JISA 1101 is used.
Need more. In order to ensure a sufficient filling property, a slump flow value of 50 to 70 cm is preferable. If the slump flow value is less than 50 cm, sufficient filling properties cannot be secured. If the slump flow value exceeds 70 cm, separation of the cement paste and gravel is caused, and clogging between the reinforcing bars is caused by gravel, and as a result, sufficient filling properties cannot be obtained.

The hydraulic powder (c) used in the hydraulic composition of the present invention is preferably cement or a mixture of fine powder having a specific surface area of not less than 3,000 cm ² / g and cement.
As fine powder with a fineness of 3,000 cm ² / g or more, blast furnace slag,
One or more kinds of fine powders selected from the group of fly ash, silica fume, stone powder and the like are used, but blast furnace slag, fly ash and stone powder are desirable in view of cost and supply. The fineness of the fine powder is better as the separation resistance is higher, for example, in the case of blast furnace slag,
It is preferably from 5,000 to 10,000 cm ² / g. Even if the fineness is less than this range, a predetermined separation resistance can be obtained by increasing the blending amount.

The non-adsorptive type thickener (a-1) used in the hydraulic composition of the present invention has an adsorbing property to cement of an adsorbing rate
It is less than 10%, and preferably has an adsorption rate of 5% or less in consideration of the influence on the fluidity of concrete.

As the non-adsorbing type thickener (a-1) used in the hydraulic composition of the present invention, specifically, 6 to 30 per molecule
Monohydric alcohols with 6 carbon atoms, 6-30 in the molecule
Monovalent mercaptans having 6 carbon atoms in the molecule
Alkyl phenols having 30 carbon atoms, amines having 6 to 30 carbon atoms in the molecule or 6 to 30 carbon atoms in the molecule
And polyalkylene oxide derivatives obtained by adding 10 to 1000 moles of an alkylene oxide to a carboxylic acid having two carbon atoms.

A monohydric alcohol having 6 to 30 carbon atoms in the molecule, a monohydric mercaptan having 6 to 30 carbon atoms in the molecule, an alkylphenol having 6 to 30 carbon atoms in the molecule, Representative examples of amines having 6 to 30 carbon atoms in the molecule or carboxylic acids having 6 to 30 carbon atoms in the molecule include dodecyl alcohol,
Tridecyl alcohol, hexadecyl alcohol, 2-
Monohydric aliphatic alcohols such as hexyldecyl alcohol and octadecyl alcohol; alicyclic monohydric alcohols such as abiethyl alcohol; dodecyl mercaptan;
Monovalent aliphatic mercaptans such as stearyl mercaptan; alkylphenols such as octylphenol, nonylphenol, dodecylphenol, diamylphenol, dioctylphenol, dinonylphenol; monovalent aliphatic amines such as dodecylamine, nonylamine, stearylamine; Examples thereof include monovalent fatty acids such as lauric acid (dodecanoic acid), nonanoic acid, and stearic acid, and one or a mixture of two or more of them can be used.

The alkylene oxide includes ethylene oxide, propylene oxide and butylene oxide. As alkylene oxide,
When two or more of these are used, the addition molar ratio is preferably at least 80 mol% of ethylene oxide.
Further, when the average number of added moles is about 100 to 500 moles, preferable performance can be obtained.

When used in the present invention, there is no problem even if the alkylene oxide contains a polyalkylene oxide by-produced during its production.

In the present invention, the non-adsorbing thickener (a-1)
By using together with the adsorption thickener (a-2), a hydraulic composition having good separation resistance and self-filling property can be obtained with a smaller amount of addition.

The adsorptive thickener (a-2) used in the hydraulic composition of the present invention has an adsorptivity to cement of 10%.
% Or more, and in order to impart sufficient viscosity to concrete, an adsorption rate of 20% or more is preferable. Representative examples of the adsorption-type thickener used in the hydraulic composition of the present invention include saccharide polymers such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, xanthan gum, pullulan and sulfonated polysaccharides, and polyvinyl alcohol. No.

The amount of the non-adsorptive thickener (a-1) to be added is an effective amount based on the amount of water required for producing the hydraulic composition.
0.1-2.0% by weight is suitable.

The amount of the adsorption-type thickener (a-2) to be added is 0.01 to an effective amount with respect to the amount of water required for producing the hydraulic composition.
~ 0.1% by weight is suitable.

The non-adsorption type thickener (a-1) and the adsorption type thickener (a-
The content ratio or addition ratio in the hydraulic composition of 2) is preferably (a-1) / (a-2) = 100/1 to 1/1 by weight.

In order to obtain high fluidity (slump flow value: 50 cm or more) in the hydraulic composition of the present invention, 0.05 to 5.0% by weight of a high-performance water reducing agent (b) is added to cement as an effective component. And more preferably 0.1 to 2.0% by weight.

As the high-performance water reducing agent (b) used in the hydraulic composition of the present invention, one or two selected from the group consisting of methylolates and sulfonates of any of naphthalene, melamine, phenol, urea and aniline are used. Formaldehyde condensate of at least one kind of compound, for example, naphthalene sulfonic acid metal salt formaldehyde condensate [for example, Mighty 150; manufactured by Kao Corporation], melamine sulfonic acid metal salt formaldehyde condensate [for example, Mighty 15
0-V2: manufactured by Kao Corporation], a phenolsulfonic acid formaldehyde compound (such as the compound described in Patent No. 1097647), and a phenol / sulfanilic acid formaldehyde cocondensate (such as the compound described in JP-A-1-113419). ).

As the high-performance water reducing agent (b) used in the hydraulic composition of the present invention, one or more selected from the group consisting of unsaturated monocarboxylic acids and derivatives thereof, and unsaturated dicarboxylic acids and derivatives thereof A polymer or copolymer obtained by polymerizing two or more types of monomers (JP-B-2
-7901, JP-A-3-75252 and JP-B-2-8983).

Further, as a high-performance water reducing agent (b) used in the hydraulic composition of the present invention, a monomer (B-1) represented by the following general formula (1) and a monomer represented by the following general formula (2) ) And one or more monomers selected from the compounds represented by (3) (B-2)
The copolymer (b-1) obtained by polymerizing the above is particularly preferably used.

[0028]

Embedded image

Wherein R ₁ , R ₂ : hydrogen or a methyl group m ₁ : number of 0 to 2 AO: oxyalkylene group having 2 to 3 carbons n: number of 2 to 300 X: hydrogen or 1 carbon atom Represents an alkyl group of ]

[0030]

Embedded image

Wherein R ₃ , R ₄ , R ₅ : hydrogen, methyl group or (CH ₂ ) _m2 COOM ₂ R ₆ : hydrogen or methyl group M ₁ , M ₂ , Y: hydrogen, alkali metal, alkaline earth Kinds of metals,
Ammonium, alkylammonium or substituted alkylammonium m ₂ : represents the number of 0 to 2; The copolymer used in the hydraulic composition of the present invention (b-
In 1), the monomer (B-1) represented by the general formula (1) includes methoxy polyethylene glycol, methoxy polyethylene polypropylene glycol, ethoxy polyethylene glycol, ethoxy polyethylene polypropylene glycol, propoxy polyethylene glycol, and propoxy polyethylene polypropylene glycol. Such as esterified product of an alkyl-blocked polyalkylene glycol at one end with a dehydrogenation (oxidation) reaction product of acrylic acid, methacrylic acid or fatty acid, or ethylene oxide to a dehydrogenation (oxidation) reaction product of acrylic acid, methacrylic acid or fatty acid ,
A propylene oxide adduct is used.

As the repetition of the polyalkylene glycol monomer, any one of ethylene oxide alone, propylene oxide alone, and random, block or alternate addition of ethylene oxide and propylene oxide can be used.

When the number of moles of the polyalkylene glycol monomer is from 110 to 300, it is particularly preferable in view of shortening of curing delay, high fluidity, high filling property and high separation reducing property.

The compound represented by the general formula (2) includes, as unsaturated monocarboxylic acid monomers, acrylic acid, methacrylic acid, crotonic acid, or an alkali metal salt thereof.
Examples include alkaline earth metal salts, ammonium salts, amine salts, and substituted amine salts. Further, as an unsaturated dicarboxylic acid monomer, maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid,
Fumaric acid, or an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an amine salt, or a substituted amine salt thereof.

The compound represented by the general formula (3) includes allyl sulfonic acid, methallyl sulfonic acid, and alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts and substituted amine salts thereof. No.

The monomer (B-1) and the monomer (B-2) constituting the copolymer (b-1) used in the hydraulic composition of the present invention.
Is the reaction unit of monomer (B-1) / monomer (B-2) = 0.1 / 100
The range of 100 to 100 (molar ratio) is particularly excellent in fluidity and separation resistance. When the above molar ratio is less than 0.1 / 100, the fluidity tends to decrease, and when it is more than 100/100, the separation resistance tends to decrease.

The copolymer (b-1) used in the hydraulic composition of the present invention can be produced by a known method. For example, JP-A-59-162163, JP-B-2-1154
No. 2, JP-B-2-7901, JP-B-2-7897, and the like.

The solvent used in the solvent polymerization method includes:
Examples include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, benzene, toluene, xylene, cyclohexane, n-hexane, aliphatic hydrocarbon, ethyl acetate, acetone, methyl ethyl ketone, and the like. Considering handling and reaction equipment, water and methyl alcohol, ethyl alcohol and isopropyl alcohol are preferred.

As the aqueous polymerization initiator, a water-soluble initiator such as ammonium or alkali metal persulfate or hydrogen peroxide is used. Benzoyl peroxide, lauroyl peroxide, or the like is used as a polymerization initiator in solvent polymerization using a solvent other than an aqueous solvent.

It is also possible to use mercaptoethanol as a chain transfer agent or sodium hydrogen sulfite or an amine compound as a polymerization accelerator in combination with the polymerization initiator. Accelerators can be appropriately selected and used.

The weight average molecular weight (gel permeation chromatography / polystyrene sulfonic acid conversion) of the copolymer (b-1) used in the hydraulic composition of the present invention is preferably from 3,000 to 1,000,000, and from 5,000 to 1,000,000. Ten
0,000 is more preferred. If the molecular weight is too large, the fluidity will decrease, and if the molecular weight is too small, the separation resistance will tend to decrease.

Further, the copolymer (b-1) used in the hydraulic composition of the present invention may be reacted with another copolymerizable monomer as long as the effects of the present invention are not impaired. For example, acrylonitrile, acrylate, acrylamide, methacrylamide, styrene, styrenesulfonic acid and the like can be mentioned.

High performance water reducing agent (b) and water-soluble polymer (a) =
The mixing ratio of (a-1) + (a-2) is (b) / (a) = 95 / 5-5 / 95
(Weight ratio) is preferred, and 90/10 to 30/70 is more preferably used.

In the present invention, the mixing ratio of the hydraulic powder (c) in the hydraulic composition is 5 to 40% by weight, and the mixing ratio of the fine powder in the hydraulic powder is 5 to 70% by weight. is there. Also water
(d) is used in an amount of 15 to 100% by weight based on the hydraulic powder (c).

The water-soluble polymers (a-1) and (a-2) in the present invention
The method of adding the high-performance water reducing agent (b) to the cement composition can be either in the form of an aqueous solution or a powder,
The time of addition should be dry blending with cement, dissolution in kneading water, or kneading of the cement mixture, i.e., from the same time as or immediately after water injection into the cement to the end of kneading of the cement mixture. Is also possible,
It is also possible to add to the cement composition once kneaded. It is also possible to use either a method of adding the whole amount at a time or a method of adding it after several decompositions.

When a known dispersant is used in combination, lignin sulfonic acid or a salt thereof, oxycarboxylic acid or a salt thereof, and polyalkyl carboxylic anhydride or a salt thereof (for example, JP-B-63-5346, JP-A-62 -83344, JP-A-1-270550), etc., and kneading after blending one with cement or cement blend, or blending one with cement or cement blend. After that, the other may be blended.

Further, other cement additives (materials), for example, a sustained-release dispersant, an AE water reducing agent, a superplasticizer, a retarder, an early strengthener, an accelerator, a foaming agent, a foaming agent, and an antifoaming agent , Water retention agent, thickener, self-leveling agent, waterproofing agent, rust inhibitor, coloring agent, fungicide, crack reducing agent, polymer emulsion, other surfactant, other water-soluble polymer, swelling agent ( Materials), glass fibers and combinations of a plurality thereof.

According to the hydraulic composition of the present invention, since high fluidity, aggregate separation resistance and strength can be ensured, the method of using concrete and the method of applying concrete are dramatically improved. Particularly in the production of concrete products, there is a great ripple effect on noise reduction and production rationalization.

[0049]

EXAMPLES The present invention will be described below with reference to production examples and examples, but the present invention is not limited to these examples. In the following examples, "EO" represents "ethylene oxide", "PO" represents propylene oxide,
The number of moles added represents the average number of moles added. Unless otherwise specified, “%” is “% by weight”.

Tables 1 to 3 show the non-adsorption type thickener (a-1), the adsorption type thickener (a-2) and the high-performance water reducing agent (b) used.

[0051]

[Table 1]

(Production Example 1) Trade name: Calcol 86 (mixture of stearyl alcohol and cetanol: manufactured by Kao Corporation) was added in an atmosphere of nitrogen at 140 ° C. and 200 mol of ethylene oxide using an alkali catalyst.

(Production Example 2) According to Production Example 1, nonylphenol was randomly added with ethylene oxide and propylene oxide at a molar ratio of 10: 1 (the number of moles of EO added: 200, the number of moles of PO added: 20). .

(Production Example 3) The water-soluble polymer produced in Production Example 1 and polyethylene glycol (molecular weight: 10,000) were mixed at a weight ratio of 8: 2.

(Production Example 4) According to Production Example 1, 320 mol of ethylene oxide was added to dodecyl mercaptan.

(Production Example 5) According to Production Example 1, 260 mol of ethylene oxide was added to lauric acid.

[0057]

[Table 2]

The method for measuring the adsorption rate of the water-soluble polymer (thickener) is as follows. [Method of measuring adsorption properties of water-soluble polymer (thickener) to cement] Using ordinary Portland cement (hereinafter abbreviated as cement), water / cement weight ratio of 100%
Then, the cement is added to a 0.5% by weight aqueous solution of a water-soluble polymer, and the mixture is stirred by hand for 5 minutes and left standing for 25 minutes. Thereafter, the cement paste is centrifuged at 3000 rpm for 15 minutes, and the water-soluble high molecular weight in the separated supernatant is measured by organic carbon content analysis (TOC). The difference between the water-soluble high-molecular weight added first and the water-soluble high-molecular weight in the supernatant is determined, and the difference is defined as the amount of adsorption to cement. Also,
The ratio of the amount of adsorption to the initial amount of addition is defined as the adsorption ratio.

[0059]

[Table 3]

(Production Example 6) A reaction vessel equipped with a stirrer was charged with 10 mol of water, and purged with nitrogen while stirring.
The temperature was raised to 75 ° C. A mixture of 0.09 mol of methanol EO / methacrylic acid monoester (number of moles of added EO = 115), 1 mol of acrylic acid (molar ratio = 9/100), 7.5 mol of water, 0.01 mol of a 20% ammonium persulfate aqueous solution, and 2 -4 g of mercaptoethanol are simultaneously added dropwise to the reaction system over 2 hours. Next, 0.03 mol of a 20% ammonium persulfate aqueous solution was added dropwise over 30 minutes, and the same temperature (75
℃). After aging, the temperature was raised to 95 ° C, 12 g of 35% hydrogen peroxide was added dropwise over 1 hour, and the same temperature (95 ° C) for 2 hours
And mature. After aging, 0.7 mol of 48% sodium hydroxide was added for neutralization to obtain a copolymer having a molecular weight of 22,000.

(Production Example 7) A reaction vessel equipped with a stirrer was charged with 5 mol of water, and the mixture was purged with nitrogen while stirring.
The temperature was raised to 95 ° C. 0.02 mol of methanol EO / methacrylic acid monoester (number of moles of added EO = 23), 1 mol of maleic acid monosodium salt (molar ratio = 2/100), 15 mol of 90 ° C hot water mixed and dissolved, and a 20% ammonium persulfate aqueous solution
0.01 mol and 3 g of 2-mercaptoethanol are simultaneously added dropwise to the reaction system over 2 hours. Then 20
0.03 mol of a 10% aqueous solution of ammonium persulfate is added dropwise over 30 minutes, and the mixture is aged at the same temperature (95 ° C) for 1 hour. 35 at 95 ℃ after aging
9 g of hydrogen peroxide was added dropwise over 1 hour, and the mixture was aged at the same temperature (95 ° C.) for 2 hours. After completion of aging, 0.7 mol of 48% sodium hydroxide was added for neutralization to obtain a copolymer having a molecular weight of 12,000.

(Production Example 8) 10 mol of water was charged into a reaction vessel equipped with a stirrer, and purged with nitrogen while stirring.
The temperature was raised to 75 ° C. Acrylic acid EO / PO block adduct (PO addition mole = 10, EO addition mole = 135) 0.01 mole, acrylic acid 0.9 mole and sodium methallylsulfonate 0.1 mole
Mol (molar ratio = 1/90/10), 7.5 mol of water mixed and dissolved, and 0.01 mol of a 20% aqueous ammonium persulfate solution,
And 4 g of 2-mercaptoethanol are simultaneously added dropwise to the reaction system over 2 hours. Next, 0.03 mol of a 20% ammonium persulfate aqueous solution is added dropwise over 30 minutes, and the mixture is aged at the same temperature (75 ° C.) for 1 hour. After aging, raise the temperature to 95 ° C,
12 g of hydrogen peroxide over 1 hour, and aged at the same temperature (95 ° C.) for 2 hours. After completion of the aging, 0.6 mol of 48% sodium hydroxide was added for neutralization to obtain a copolymer having a molecular weight of 7,200.

<< Evaluation as Hydraulic Composition >> Table 4 shows the mixing conditions of concrete.

[0064]

[Table 4]

The concrete kneading method is as follows. A high-performance water reducing agent and a water-soluble polymer are kneaded in advance and dissolved in water.
Using a 100 liter forced twin-screw mixer, 50 liters of concrete were kneaded for 2 minutes. Then, the following four evaluation items of the following slump flow, aggregate separation resistance, self-filling property, and curing time were measured. Table 5 shows the results.

<Evaluation Items> Slump flow Slump flow value according to JIS A 1101 (cm) 2. Separation resistance Evaluation was made by visual observation (visually). The evaluation criteria are as follows. ：: Aggregate separation and no water separation ×: Aggregate separation and water separation Self-filling property After the concrete was kneaded, the concrete was packed in a cylindrical form having a diameter of 10 cm, and after hardening and demolding, the filling state of the concrete surface was visually observed. The evaluation criteria are as follows. ：: No voids of 3 mm or more were generated. Δ: Voids of 3 mm or more were slightly generated. X: Many voids of 3 mm or more were generated. Curing time Measurement of condensation time by JIS A 6204 proctor penetration resistance test.

[0067]

[Table 5]

<Evaluation of Results> As is clear from Table 5, the hydraulic composition of the present invention has a high fluidity with a slump flow value of 50 cm or more, and has a good separation resistance, so that it has excellent self-filling properties. Has been obtained. On the other hand, in the case of the comparative product, the separation resistance is not satisfied with a small amount of addition, and a sufficient self-filling property is not obtained. In order to obtain sufficient separation resistance, excessive addition of a thickener and a high-performance water reducing agent is necessary, and a problem of curing delay has been recognized. From the above results, it can be seen that the product of the present invention shows fluidity with a low addition of an admixture, has high resistance to material separation, and has excellent self-filling properties. These results show that the construction method of concrete is remarkably improved, and it is expected that in the production of concrete structures, the effects of eliminating noise, streamlining production, and shortening the construction period are expected.

[0069]

According to the hydraulic composition of the present invention, it is possible to secure high fluidity, aggregate separation resistance, and strength, so that the method of using concrete and the method of applying concrete are dramatically improved. In particular, in the production of concrete products, the ripple effect on noise reduction and production rationalization is great.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C04B 28/02 C04B 28/02 // C04B 103: 30 103: 44

Claims (4)

[Claims] 1. Adsorption characteristic for cement is 10%
Less than water-soluble polymer (a-1), water-soluble polymer with an adsorption rate of 10% or more to cement (a-2), high-performance water reducing agent (b), hydraulic powder (c) And a water (d). 2. The water-soluble polymer (a-1) has a molecular weight of 6 to 30.
Monohydric alcohols with 6 carbon atoms, 6-30 in the molecule
Monovalent mercaptans having 6 carbon atoms in the molecule
Alkyl phenols having 30 carbon atoms, amines having 6 to 30 carbon atoms in the molecule or 6 to 30 carbon atoms in the molecule
The hydraulic composition according to claim 1, which is a polyalkylene oxide derivative obtained by adding 10 to 1000 moles of an alkylene oxide to a carboxylic acid having two carbon atoms. 3. A high-performance water reducing agent (b) comprising a monomer (B-1) represented by the following general formula (1) and a compound represented by the following general formulas (2) and (3): 3. A polymer (b-1) obtained by polymerizing at least one selected monomer (B-2).
The hydraulic composition as described in the above. Embedded image [Wherein R ₁ , R ₂ : hydrogen or methyl group m ₁ : number of 0 to 2 AO: oxyalkylene group having 2 to 3 carbons n: number of 2 to 300 X: hydrogen or 1 to 3 carbon atoms Represents an alkyl group. [Chemical formula 2] [Wherein R ₃ , R ₄ , R ₅ : hydrogen, methyl group or (CH ₂ ) _m2 COOM ₂ R ₆ : hydrogen or methyl group M ₁ , M ₂ , Y: hydrogen, alkali metal, alkaline earth metal,
Ammonium, alkylammonium or substituted alkylammonium m ₂ : represents the number of 0 to 2; ] 4. A water-soluble polymer (a-1) and a water-soluble polymer (a-
The content ratio of 2) is (a-1) / (a-2) = 100/1 to 1 by weight.
The hydraulic composition according to any one of claims 1 to 3, which is in a range of 1/1.