JPH0873250A - Hydraulic composition - Google Patents

Abstract

(57) [Summary] [Structure] Monohydric alcohol having 6 to 30 carbon atoms in the molecule, monohydric mercaptan having 6 to 30 carbon atoms in the molecule, 6 to 30 carbons in the molecule Water containing an alkylphenol having an atom, an amine having 6 to 30 carbon atoms in the molecule, a carboxylic acid having 6 to 30 carbon atoms in the molecule, and a polyalkylene oxide derivative having 10 to 1000 moles of alkylene oxide added A hydraulic composition containing a water-soluble polymer, a high-performance water reducing agent, and a hydraulic powder. [Effects] High fluidity, resistance to separation of aggregates, and securing of strength have made it possible to dramatically improve the method of using concrete and the method of constructing concrete. In particular, noise elimination and production in the production of concrete products. The ripple effect on rationalization is great.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compaction-free hydraulic composition having high fluidity and a method for producing the same. More specifically, it enhances the viscosity and fluidity of concrete, mortar and paste used as building materials and secondary product materials, and imparts excellent properties to the separation resistance of aggregates, cement and water. The present invention relates to a hydraulic composition that does not require compaction.

[0002]

2. Description of the Related Art Conventionally, as a method of constructing a concrete composition, it has been generally practiced to put concrete into a form frame having reinforcing bars and to perform compaction by vibrating a vibrator. Is. But,
In recent years, noise pollution caused by a vibrator when placing concrete and shortage of manpower in the concrete industry have become problems. In order to address these problems, research on concrete with self-filling properties that does not require vibration compaction has begun, but the current situation is that it has not yet been put into practical use technically.

Generally, when the fluidity of concrete is increased, aggregates are separated, coarse aggregates are entangled with each other to deteriorate the filling property, and uniform concrete cannot be obtained, resulting in a decrease in strength. Further, in a concrete mixture containing a large amount of a thickening agent such as underwater concrete, aggregate separation is suppressed but the viscosity becomes extremely high (for example, underwater construction concrete composition disclosed in Japanese Patent Publication No. 62-35984). For concrete, the viscosity of mixing water of concrete is 500 ~
It is 5000 cps. ) However, not only the filling work becomes difficult, but the initial strength is delayed due to the delay of the curing time, which is the property of the thickener, so it is difficult to apply it to construction and civil engineering, especially secondary products. .

In recent years, the name of hyper-performance concrete has been reported [Concrete Engineering Annual Report, 63-68]
Page (1989)] is a compaction-free concrete composition in which a large amount of fine powder such as blast furnace slag and fly ash is added, and a thickener is further added. Although the curing time has been improved, it requires a large amount of water due to the large amount of powder, and since it is a raw material with a water / cement ratio of 100%, it is used for secondary products that require early demolding. Is a difficult situation.

[0005]

[Means for Solving the Problems] The inventors of the present invention are keen to obtain a self-compacting concrete composition having a high fluidity, a large separation resistance, a self-compacting property, and a small effect on the strength due to retardation of curing. As a result of examination, the present invention has been completed.

That is, the present invention relates to a monohydric alcohol having 6 to 30 carbon atoms in the molecule, a monohydric mercaptan having 6 to 30 carbon atoms in the molecule, and 6 to 30 carbon atoms in the molecule. Alkylphenol having 6 to 30 in the molecule
A water-soluble polymer (a) comprising a polyalkylene oxide derivative obtained by adding 10 to 1000 moles of alkylene oxide to an amine having 6 carbon atoms or a carboxylic acid having 6 to 30 carbon atoms in the molecule, and high performance water reduction A hydraulic composition comprising the agent (b) and the hydraulic powder (c).

When the hydraulic composition of the present invention is used as compaction-free concrete, it requires a slump flow value of 50 cm or more in the slump test specified in JIS A 1101. A slump flow value of 50 to 70 cm is preferable in order to ensure sufficient filling properties. If the slump flow value is less than 50 cm, sufficient filling properties cannot be secured. When the slump flow value exceeds 70 cm, the cement paste and the gravel are separated from each other, and the reinforcing bars are clogged with the gravel, and as a result, sufficient filling properties cannot be obtained.

As the hydraulic powder in the present invention, cement or a mixture of fine powder having a fineness of 3,000 cm ² / g or more and cement is preferable. As the fine powder having a fineness of 3,000 cm ² / g or more, one or more fine powders selected from the group of blast furnace slag, fly ash, silica fume, stone powder, etc. are used, but cost and supply Considering the above, blast furnace slag, fly ash and stone powder are preferable. The fineness of the fine powder is better as the specific surface area is higher from the viewpoint of separation resistance. For example, in the case of blast furnace slag, it is preferably 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.

In the present invention, a monohydric alcohol having 6 to 30 carbon atoms in the molecule, a monohydric mercaptan having 6 to 30 carbon atoms in the molecule, or 6 to 30 carbon atoms in the molecule Representative examples of the alkylphenols include octylphenol, nonylphenol, dodecylphenol, diamylphenol, alkylphenols such as dioctylphenol or dinonylphenol, dodecyl alcohol, tridecyl alcohol, hexadecyl alcohol, 2-hexyldecyl alcohol and octadecyl alcohol. Monohydric aliphatic alcohols, alicyclic monohydric alcohols such as abiethyl alcohol or monohydric aliphatic mercaptans such as dodecyl mercaptan and stearyl mercaptan, etc., and one or two of these It may be used the above mixture.

Typical examples of amines having 6 to 30 carbon atoms in the molecule include dodecylamine, nonylamine, stearylamine and the like.
Representative examples of carboxylic acids having -30 carbon atoms include lauric acid (dodecanoic acid), nonanoic acid, stearic acid and the like. Any of these may use one kind or a mixture of two or more kinds.

The alkylene oxide adduct suitable for use in the present invention as the component (a) is 6 in the molecule as described above.
A monohydric alcohol having 30 to 30 carbon atoms, a monohydric mercaptan having 6 to 30 carbon atoms, an alkylphenol having 6 to 30 carbon atoms, an amine having 6 to 30 carbon atoms in the molecule, or Carboxylic acid having 6 to 30 carbon atoms in the molecule, ethylene oxide alone,
Alternatively, both ethylene oxide and propylene oxide are randomly or block-wise added in an amount of 10 to 1000 moles (average number of moles added).

As the alkylene oxide, ethylene oxide and propylene oxide are suitable, and the addition molar ratio of both is 80 mol% or more of ethylene oxide and 20 mol% or less of propylene oxide, and the average number of added mols is about 100 to 500 mol. Is preferable in terms of performance. It should be noted that the alkylene oxide suitable for use in the present invention does not cause a problem in performance even if it contains a polyalkylene oxide produced as a by-product during production.

The optimum amount of the water-soluble polymer (a) to be added depends on the length of the alkylene oxide in the molecule,
0.01 to the amount of water required when producing a hydraulic composition
10.0% by weight is suitable.

In the hydraulic composition of the present invention, in order to obtain high fluidity (slump flow value: 50 cm or more), the high-performance water reducing agent (b) is added to the cement in an effective amount of 0.3 to 3.0% by weight. To do. As the high-performance water reducing agent that can be used in the present invention, those shown in the following (1) to (3) are particularly preferable.

(1) naphthalene, melamine, phenol,
Examples thereof include formaldehyde condensates of one or more compounds selected from the group of methylolated products and sulfonated products of urea and aniline (hereinafter referred to as copolymer A), for example, naphthalenesulfonic acid metal salt formaldehyde condensation. [For example, Mighty 150: Kao Corporation], melamine sulfonic acid metal salt formaldehyde condensate [for example, Mighty 150-V2: Kao Corporation],
Phenolsulfonic acid formaldehyde compound (Patent N
No. 1097647) and phenol / sulfanilic acid formaldehyde co-condensates (the compounds described in JP-A No. 1-113419) and the like.

(2) A polymer or copolymer obtained by polymerizing one or more monomers selected from the group consisting of unsaturated monocarboxylic acids and their derivatives, unsaturated dicarboxylic acids and their derivatives ( Japanese Patent Publication No. 2-7901, JP-A-3-75252
And the compounds described in JP-B-2-8983) (hereinafter referred to as copolymer B).

(3) A monomer represented by the following general formula (1) (C
-1) and a copolymer obtained by polymerizing one or more kinds of monomers (C-2) selected from the compounds represented by the following general formulas (2) and (3) (hereinafter , Called copolymer C)
Is mentioned.

[0018]

[Chemical 3]

[Wherein R ₁ and R _{2 are} hydrogen and a methyl group m ₁ is an integer of 0 to 2 AO: an oxyalkylene group having 2 to 3 carbon atoms n is an integer of 2 to 300 X: hydrogen or 1 carbon atom] 3 represents an alkyl group. ]

[0020]

[Chemical 4]

[Wherein R ₃ , R ₄ , R ₅ : hydrogen, methyl group, (CH ₂ ) m ₂ COOM ₂ R ₆ : hydrogen, methyl group M _1, M ₂ , Y: hydrogen, alkali metal, alkali Earth metal,
Ammonium, alkylammonium or substituted alkylammonium m ₂ represents an integer of 0 to 2. In the copolymer (C) of the present invention, examples of the monomer (C-1) represented by the general formula (1) include methoxy polyethylene glycol, methoxy polyethylene polypropylene glycol, ethoxy polyethylene glycol, ethoxy polyethylene polypropylene glycol, Esterification products of polyalkylene glycols capped with one terminal alkyl such as propoxyethylene glycol, propoxy polyethylene polypropylene glycol, etc. and dehydrogenation (oxidation) reaction of acrylic acid, methacrylic acid or fatty acid, and dehydrogenation (oxidation of acrylic acid, methacrylic acid or fatty acid ) An ethylene oxide or propylene oxide adduct to the reaction product is used.

The repeating of the polyalkylene glycol monomer includes ethylene oxide, propylene oxide,
Random, block, or alternating ethylene oxide and propylene oxide can be used. When the repeating mole number of the polyalkylene glycol monomer is 110 to 300, shortening of curing delay, high fluidity,
It is particularly preferable in terms of high packing property and high separation reduction property.

Examples of the compound represented by the general formula (2) include acrylic acid, methacrylic acid, crotonic acid and metal salts thereof. Further, as the unsaturated dicarboxylic acid-based monomer, maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, fumaric acid, or their alkali metal salts, alkaline earth metal salts, ammonium Salts, amine salts, substituted amine salts are used.

As the compound represented by the general formula (3), allyl sulfonic acid, methallyl sulfonic acid, or their alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts and substituted amine salts can be used. used.

The reaction units of the monomer (C-1) and the monomer (C-2) constituting the copolymer (C) of the present invention are monomer (C-1) / monomer ( C-2) = 0.1 / 100 to 100/10
The range of 0 (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 exceeds 100/100, the separation resistance tends to decrease.

The copolymer (C) of the present invention can be produced by a known method. For example, JP-A-59-16216
No. 3, Special Fair 2-11542, Special Fair 2-7901, Special Fair 2-78
A solvent polymerization method such as No. 97 is mentioned. Examples of the solvent used in the solvent polymerization method include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, benzene, toluene, xylene, cyclohexane, n-hexane, aliphatic hydrocarbons, ethyl acetate, acetone and methyl ethyl ketone. Water and primary to quaternary alcohols are preferable in consideration of handling and reaction equipment.

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

It is also possible to use sodium bisulfite, mercaptoethanol or an amine compound as an accelerator in combination with the polymerization initiator, and these polymerization initiators or accelerators can be appropriately selected and used. .

Weight average molecular weight of the copolymer (C) of the present invention
The (gel permeation chromatography method / polystyrene sulfonic acid conversion) is preferably in the range of 3,000 to 1,000,000, and more preferably 5,000 to 100,000. 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 (C) in the present invention is
You may react with another copolymerizable monomer within the range which does not impair the effect of this invention. For example, acrylonitrile,
Examples thereof include acrylic acid ester, acrylamide, methacrylamide, styrene, styrene sulfonic acid and the like.

The above-mentioned copolymers (A) to (C) which are the high-performance water reducing agent (b) can be used in combination at any ratio, but (A) and (B) are used in combination. In this case, the effective substance is preferably (B) / (A) = 60/40 to 99/1.

In the hydraulic composition of the present invention, the weight ratio of the water-soluble polymer (a) to the superplasticizer (b) is water-soluble polymer / superplasticizer = 95/5 to 5/95. 90 / 10-preferably
30/70 is more preferable.

The hydraulic composition of the present invention is used for concrete moldings. The concrete compact is not particularly limited, and a compact compacted by a vibrator is usually targeted.

The method of adding the superplasticizer in the present invention to the cement composition may be either an aqueous solution or a powder, and the addition timing may be dry blending with cement, dissolution in kneading water, or It is possible to add the cement mixture at the start of kneading, that is, at the same time as or immediately after water injection to the cement until the end of kneading of the cement mixture, and it is also possible to add it to the cement mixture once kneaded. is there. In addition, it is possible to use either a method of adding the entire amount at a time or a method of adding the total amount in several times.

When a known dispersant is used in combination, ligninsulfonic acid or a salt thereof, oxycarboxylic acid or a salt thereof, polycarboxylic acid or a salt thereof, and polyalkylcarboxylic anhydride or a salt thereof (for example, Japanese Patent Publication No. 63- 5346
No. 1, JP-A-62-83344, JP-A No. 1-270550) and the like, or one of them may be mixed with cement or a cement mixture, or one of them may be cement or a cement mixture. Alternatively, the other may be blended after kneading.

Further, other cement additives (materials) such as sustained-release dispersant, AE water-reducing agent, superplasticizer, high-performance water-reducing agent, retarder, early strengthening agent, accelerator, foaming agent, foaming agent. Agents, defoamers, water retention agents, thickeners, self-leveling agents, waterproofing agents, rust inhibitors, colorants, mildew-proofing agents, crack reducing agents, polymer emulsions, other surfactants, and other highly water-soluble agents. molecule,
A swelling agent (material), glass fiber and a combination of a plurality of these are also possible.

[0037]

EFFECTS OF THE INVENTION According to the hydraulic composition of the present invention, since it is possible to secure high fluidity, aggregate separation resistance and strength, the method of using concrete and the method of constructing concrete are dramatically improved. In particular, in the production of concrete products, it has a great ripple effect on noise reduction and production rationalization.

[0038]

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. Unless otherwise specified, “%” in the following examples is “% by weight”, and the number of moles of alkylene oxide added is the average number of moles added.

Example 1 <Material> Water (W): Tap water Cement (C): Normal Portland cement (specific gravity 3.1
7) Fine aggregate (S): Kinokawa sand (specific gravity 2.57) Coarse aggregate (G): Takarazuka crushed stone (specific gravity 2.62) Fine powder (F) Blast furnace slag: Specific surface area 8,000 cm ² / g, specific gravity 2.90 Fly ash : Specific surface area 3,600 cm ² / g, specific gravity 2.90 Stone powder: Specific surface area 3,500 cm ² / g, specific gravity 2.70 <Mixing method of concrete> Cement dispersant is previously mixed and dissolved in water. After mixing 50 liters of concrete for 3 minutes using a barrel mixer, slump flow and aggregate separation resistance were measured. Tables 1 to 3 show the composition of the concrete composition prepared using the above materials, the water reducing agent and the water-soluble polymer used.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

Production Example 1 200 mol of ethylene oxide was added to Calcole 86 (a mixture of stearyl alcohol and cetanol, manufactured by Kao Corporation) under a nitrogen atmosphere at 140 ° C. using an alkali catalyst.

Production Example 2 Nonylphenol ethylene oxide and propylene oxide (molar ratio 10: 1) were randomly added according to Production Example 1 (number of ethylene oxide addition moles: 200).
, The number of moles of propylene oxide added 20).

Production Example 3 According to Production Example 1, 450 mol of ethylene oxide was added to dodecyl mercaptan.

Production Example 4 According to Production Example 1, 750 mol of ethylene oxide was added to palmityl alcohol.

Production Example 5 According to Production Example 1, 20 mol of ethylene oxide was added to abiethyl alcohol.

<Evaluation items> 1. Slump flow JIS S 1101 slump flow value (cm) 2. Separation resistance Visual (visual) evaluation was performed. The evaluation criteria are as follows. ○ No separation of aggregate and separation of water × Separation of aggregate and separation of water 3. Self-filling property After the concrete is mixed, it is packed into a cylinder form of φ10 cm, and after hardening and demolding, the filling state of the concrete surface is visually observed. Observed at. The evaluation criteria are as follows. ○ No void of 3 mm or more was generated. △ Void of 3 mm or more was slightly generated. × Many voids of 3 mm or more were generated. The above measurement results are shown in Table 4.

[0049]

[Table 4]

From the above results, it can be seen that the hydraulic composition of the present invention exhibits a high fluidity with a slump flow value of 50 cm or more and has good separation resistance, and thus has excellent self-filling property. On the other hand, in the case of the comparative product, when the water reducing agent is used, the separation resistance is satisfied, but even if 5% of the water reducing agent is added, the slump flow value is about 45 cm, so that sufficient self-filling property is not obtained. In addition, when a water-soluble polymer such as methyl cellulose is used, the fluidity is significantly reduced,
It can be seen that excellent self-filling property cannot be obtained.

Example 2 The ratio of the high-performance water-reducing agent used in Example 1, the water-soluble polymer used in Example 1, and the water-soluble polymers obtained in the following Production Examples 7 to 12 are shown in Table 5, respectively. The same test as in Example 1 was performed.

Production Example 7 85 g of a product of Calcole 86 (a product of Kao Corporation, a mixture of stearyl alcohol and cetanol) to which 200 mol of ethylene oxide was added using an alkali catalyst was added to 85 g of vinylcyclohexene diepoxide (epoxy equivalent: 76). )
2.4 g was added, and the mixture was reacted at 140 ° C. for 3 hours and then neutralized with acetic acid (water-soluble polymer No. 7).

Production Example 8 Ethylene oxide and propylene oxide of nonylphenol synthesized according to Production Example 7 (molar ratio 10:
1) Random adducts (ethylene oxide addition mole number 20)
0, propylene oxide addition mole number 20) 100 g and vinylcyclohexene diepoxide (epoxy equivalent 76) 3.3 g
Reaction product (water-soluble polymer No. 8).

Production Example 9 Reaction product of 100 g of dodecyl mercaptan ethylene oxide adduct (addition mole number 100) synthesized according to Production Example 7 and 6.6 g of vinylcyclohexene diepoxide (epoxy equivalent 76) (water-soluble polymer No. .9).

Production Example 10 To 100 g of an ethylene oxide adduct of abiethyl alcohol (the number of added moles: 20) produced according to Production Example 7, 0.6 g of diphenylmethane diisocyanate was added and reacted at 110 ° C. for 3 hours (high water solubility). Molecule No.10).

Production Example 11 Ethylene oxide and propylene oxide of ethylene glycol synthesized according to Production Example 1 (molar ratio 10:
2) Random adduct (Ethylene oxide addition mole number 30
0, 100 g of propylene oxide added mole number of 60) and 4.1 g of behenic acid were reacted in chloroform under reflux condition for 5 hours using a solid catalyst (water-soluble polymer No. 11).

Production Example 12 100 g of polyethylene glycol (average molecular weight 10,000) and vinylcyclohexene diepoxide (epoxy equivalent 76) 0.2
After reacting g with an alkali catalyst at 140 ° C. for 3 hours,
8.5 g of polyoxyethylene lauryl alcohol glycidyl ether (epoxy equivalent 952) was added, and the mixture was reacted at 140 ° C. for 3 hours and neutralized with acetic acid (water-soluble polymer No. 12).

[0058]

[Table 5]

Example 3 The following Production Example using the monomers C-1 to C-6 shown below
Copolymer (C) was prepared as in 13-22. In addition, water-soluble polymers as in Production Examples 23 to 24 were also produced. However, EO represents ethylene oxide, PO represents propylene oxide, and the number of added moles means the average number of added moles. C-1: Methanol EO / methacrylic acid monoester (EO
Addition mol number = 115) C-2: Methanol EO / acrylic acid monoester (EO addition mol number = 220) C-3: Methanol EO / methacrylic acid monoester (EO)
Addition mol number = 280) C-4: acrylic acid EO adduct (EO addition mol number = 130) C-5: acrylic acid PO / EO block adduct (PO addition mol number = 10, EO addition mol number = 135) C-6: Acrylic acid EO / PO block adduct (EO addition mole number = 135, PO addition mole number = 5) The production examples of the copolymer (C) and the water-soluble polymer are shown below.
The average molecular weight of the copolymer (C) is determined from the molecular weight by gel permeation chromatography method / sodium polystyrene sulfonate conversion.

Production Example 13 10 mol of water was charged into a reaction vessel equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C. in a nitrogen atmosphere. C-1
0.09 mol and acrylic acid 1 mol (molar ratio = 9/100), water
A mixture of 7.5 mol, 0.01 mol of 20% ammonium persulfate aqueous solution, and 4-g of 2-mercaptoethanol
Each of the three is simultaneously added dropwise to the reaction system over 2 hours. Next, 0.03 mol of 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, the temperature is raised to 95 ° C., 12 g of 35% hydrogen peroxide is added dropwise over 1 hour, and aging is performed 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 22,000 (water reducing agent C-1).

Production Example 14 A reaction vessel equipped with a stirrer was charged with 8 mol of water, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C. in a nitrogen atmosphere. C-2
0.05 mol and 1 mol of methacrylic acid (molar ratio = 5/100), water
A mixture of 8.5 mol, 0.01 mol of a 20% ammonium persulfate aqueous solution, and 3 g of 2-mercaptoethanol.
Each of the three is simultaneously added dropwise to the reaction system over 2 hours. Next, 0.03 mol of 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, the temperature is raised to 95 ° C., 9 g of 35% hydrogen peroxide is added dropwise over 1 hour, and aging is performed at the same temperature (95 ° C.) for 2 hours. After completion of the aging, 0.7 mol of 48% sodium hydroxide was added for neutralization to obtain a copolymer having a molecular weight of 85,000 (water reducing agent C-2).

Production Example 15 In a reaction vessel equipped with a stirrer, 5 mol of water was charged, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 95 ° C. in a nitrogen atmosphere. C-3
20 with a mixture of 0.002 mol, 1 mol of maleic acid monosodium salt (molar ratio = 0.2 / 100), and 15 mol of 90 ° C warm water
% Ammonium persulfate aqueous solution (0.01 mol) and 2-mercaptoethanol (3 g) are simultaneously added dropwise to the reaction system over 2 hours. Next, 0.03 mol of 20% ammonium persulfate aqueous solution was added dropwise over 30 minutes, and the temperature (95
Aging). After aging, 1% of 9% of 35% hydrogen peroxide at 95 ℃
The mixture is added dropwise over a period of time and 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 (water reducing agent C-3).

Production Example 16 A reaction vessel equipped with a stirrer was charged with 10 mol of water, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C. in a nitrogen atmosphere. C-4
A mixture of 0.01 mol, 0.9 mol of acrylic acid, 0.1 mol of sodium methallyl sulfonate (molar ratio = 1/90/10) and 7.5 mol of water and dissolved, and a 20% ammonium persulfate aqueous solution 0.01
Mol and 2-mercaptoethanol (4 g) are simultaneously added dropwise to the reaction system over 2 hours. Then 20%
0.03 mol of an aqueous ammonium persulfate solution is added dropwise over 30 minutes, and the mixture is aged at the same temperature (75 ° C) for 1 hour. After aging, the temperature was raised to 95 ° C, and 12 g of 35% hydrogen peroxide was added dropwise over 1 hour.
Aging at the same temperature (95 ℃) for a certain period of time. 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 (water reducing agent C-4).

Production Example 17 10 mol of water was charged into a reaction vessel equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C. in a nitrogen atmosphere. C-5
0.01 mol and 1 mol of methacrylic acid (molar ratio = 1/100), water
A mixture of 7.5 mol, 0.01 mol of 20% ammonium persulfate aqueous solution, and 1 g of 2-mercaptoethanol
Each of the three is simultaneously added dropwise to the reaction system over 2 hours. Next, 0.03 mol of 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, the temperature is raised to 95 ° C., 5 g of 35% hydrogen peroxide is added dropwise over 1 hour, and aging is performed at the same temperature (95 ° C.) for 2 hours. After completion of aging, 0.7 mol of 48% sodium hydroxide was added to neutralize and obtain a copolymer having a molecular weight of 105,000 (water reducing agent C-5).

Production Example 18 A reaction vessel equipped with a stirrer was charged with 10 mol of water, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C. in a nitrogen atmosphere. C-6
0.01 mol and 1 mol of sodium acrylate (molar ratio = 1 /
100), 7.5 mol of water mixed and dissolved, 0.01 mol of 20% ammonium persulfate aqueous solution, and 2 g of 2-mercaptoethanol are simultaneously added dropwise to the reaction system over 2 hours. Next, 0.03 mol of 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, the temperature is raised to 95 ° C., 9 g of 35% hydrogen peroxide is added dropwise over 1 hour, and aging is performed 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 77,000 (water reducing agent C-6).

Production Example 19 In a reaction vessel equipped with a stirrer, 23 mol of water was charged, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C. in a nitrogen atmosphere. C-2
0.045 mol and acrylic acid 0.3 mol (molar ratio = 15/100),
A mixture of 10 mol of water, 0.003 mol of 20% ammonium persulfate aqueous solution, and 2-mercaptoethanol
1.2 g of each of the three substances are dropped simultaneously into the reaction system over 2 hours. Next, 0.009 mol of a 20% ammonium persulfate aqueous solution is added dropwise over 30 minutes, followed by aging at the same temperature (75 ° C) for 1 hour. After aging, the temperature is raised to 95 ° C., 4 g of 35% hydrogen peroxide is added dropwise over 1 hour, and aging is performed at the same temperature (95 ° C.) for 2 hours. After the aging was completed, 0.21 mol of 48% sodium hydroxide was added for neutralization to obtain a copolymer having a molecular weight of 51,000 (water reducing agent C-7).

Production Example 20 A reaction vessel equipped with a stirrer was charged with 23 mol of water, and the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C. in a nitrogen atmosphere. C-1
0.08 mol and acrylic acid 0.2 mol (molar ratio = 40/100),
A mixture of 12 moles of water, 0.002 moles of 20% ammonium persulfate aqueous solution, and 2-mercaptoethanol
0.6 g of each of the three substances is dropped simultaneously into the reaction system over 2 hours. Next, 0.006 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, the temperature is raised to 95 ° C., 3 g of 35% hydrogen peroxide is added dropwise over 1 hour, and aging is performed at the same temperature (95 ° C.) for 2 hours. After completion of the aging, 0.14 mol of 48% sodium hydroxide was added to neutralize and obtain a copolymer having a molecular weight of 56,000 (water reducing agent C-8).

Production Example 21 18 mol of water was charged into a reaction vessel equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C. in a nitrogen atmosphere. C-1
0.06 mol and acrylic acid 0.1 mol (molar ratio = 60/100),
A mixture of 8 mol of water, 0.001 mol of 20% ammonium persulfate aqueous solution, and 2-mercaptoethanol
0.3 g of each of the three substances is dropped simultaneously into the reaction system over 2 hours. Next, 0.003 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, the temperature is raised to 95 ° C., 2 g of 35% hydrogen peroxide is added dropwise over 1 hour, and aging is performed at the same temperature (95 ° C.) for 2 hours. After completion of aging, 0.07 mol of 48% sodium hydroxide was added for neutralization to obtain a copolymer having a molecular weight of 45,000 (water reducing agent C-9).

Production Example 22 In a reaction vessel equipped with a stirrer, 30 mol of water was charged, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C. in a nitrogen atmosphere. C-1
0.1 mol and acrylic acid 0.1 mol (molar ratio = 100/100), water
A mixture of 13 mol and dissolved, 0.001 mol of 20% ammonium persulfate aqueous solution, and 2-mercaptoethanol 0.3
g of each of the three is simultaneously added dropwise to the reaction system over 2 hours. Next, 0.003 mol of 20% ammonium persulfate aqueous solution is added to 30%.
Drop over a period of minutes and age for 1 hour at the same temperature (75 ° C). After aging, the temperature is raised to 95 ° C., 2 g of 35% hydrogen peroxide is added dropwise over 1 hour, and aging is performed at the same temperature (95 ° C.) for 2 hours. After completion of aging, 0.07 mol of 48% sodium hydroxide was added for neutralization to obtain a copolymer having a molecular weight of 72,000 (water reducing agent C-10).

Production Example 23 According to Production Example 1 of Example 1, 320 mol of ethylene oxide was added to dodecylamine (water-soluble polymer No. 1).
3).

Production Example 24 In the same manner as in Production Example 1 of Example 1, 260 mol of ethylene oxide was added to lauric acid (water-soluble polymer No. 14).

<Evaluation> Using the water reducing agent or water-soluble polymer as described above and the water reducing agent or water-soluble polymer shown in Tables 7 and 8, the same evaluation as in Example 1 was performed. Moreover, the curing time and the compression strength were measured by the following methods. -Curing time-Measurement of setting time by proctor penetration resistance test of JIS A 6204-Compressive strength-Compressive strength test of JIS A 1123 Table 6 shows concrete mix and materials used in this example.

[0073]

[Table 6]

[0074]

[Table 7]

[0075]

[Table 8]

<Evaluation of Results> As is clear from Tables 7 and 8, the admixture of the present invention shows fluidity at a low addition amount, has a large material separation resistance, and has a high self-filling property as compared with the comparative product. It can be seen that it is excellent and the curing time is short. These results show that the concrete construction method is dramatically improved, and in the production of concrete structures, it is expected to be effective in eliminating noise, streamlining the production, and shortening the construction period.

From the above results, it can be seen that the hydraulic composition of the present invention has a high slump flow value of 50 cm or more and high separation resistance, and thus has excellent self-filling property.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C04B 24/30 Z 28/02 // (C04B 28/02 7:19 7:26 24:22 C 24:32) A 103: 32 103: 44 111: 62 (72) Inventor Keisho Tadokoro 1334 Minato Minato, Wakayama, Wakayama Kao Research Institute

Claims (8)

[Claims] 1. A compound having 6 to 30 carbon atoms in the molecule
Polyhydric alcohol, having 6 to 30 carbon atoms in the molecule 1
Valenic mercaptans, alkylphenols having 6 to 30 carbon atoms in the molecule, amines having 6 to 30 carbon atoms in the molecule, or carboxylic acids having 6 to 30 carbon atoms in the molecule with alkylene oxides. Water-soluble polymer (a) consisting of polyalkylene oxide derivative with 10 to 1000 mol added, high-performance water reducing agent (b) and hydraulic powder (c)
A hydraulic composition comprising: 2. The high-performance water reducing agent is a formaldehyde condensate (A) of one or more compounds selected from the group of methylol compounds and sulfonate compounds of naphthalene, melamine, phenol, urea and aniline. The hydraulic composition according to claim 1. 3. A polymer obtained by polymerizing a high-performance water-reducing agent with one or more monomers selected from the group consisting of unsaturated monocarboxylic acids and their derivatives, unsaturated dicarboxylic acids and their derivatives. Alternatively, the hydraulic composition according to claim 1, which is a copolymer (B). 4. A high-performance water reducing agent comprising a monomer (C-1) represented by the following general formula (1) and the following general formulas (2) and (3):
The hydraulic composition according to claim 1, which is a copolymer (C) obtained by polymerizing one or more kinds of monomers (C-2) selected from the compounds represented by: Embedded image [Wherein R ₁ and R _{2 are} hydrogen and a methyl group m ₁ is an integer of 0 to 2 AO: an oxyalkylene group having 2 to 3 carbon atoms n: an integer of 2 to 300 X: hydrogen or a carbon number of 1 to 3] Represents an alkyl group. ] [Chemical 2] [In the formula, R ₃ , R ₄ , R ₅ : hydrogen, methyl group, (CH ₂ ) m ₂ COOM ₂ R ₆ : hydrogen, methyl group M _1, M ₂ , Y: hydrogen, alkali metal, alkaline earth metal ,
Ammonium, alkylammonium or substituted alkylammonium m ₂ represents an integer of 0 to 2. ] 5. The superplasticizer is a combination of (A) and (B), wherein (A) is selected from the group of methylolated and sulfonated compounds of any of naphthalene, melamine, phenol, urea and aniline. Formaldehyde condensate of one or more compounds, (B) is obtained by polymerizing one or more monomers selected from the group consisting of unsaturated monocarboxylic acids and their derivatives, unsaturated dicarboxylic acids and their derivatives. The hydraulic composition according to claim 1, which is a polymer or a copolymer obtained as described above. 6. The high-performance water reducing agent is a combination of (A) and (B), and the weight ratio (B) / (A) of (A) and (B) is 60/40 to 99/1 as an effective substance. The range of 5
The hydraulic composition described. 7. The weight ratio (a) / (b) of the water-soluble polymer (a) and the superplasticizer (b) is in the range of 95/5 to 5/95. The composition according to item 1. 8. The hydraulic composition according to claim 1, having a slump flow value in a range of 50 to 70 cm in a slump test specified in JIS A 1101.