JP3107604B2 - Concrete composition for self-filling - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a self-compacting concrete composition which does not require compaction. More specifically, it increases the viscosity and fluidity of concrete used as a building material and secondary product material, has excellent resistance to separation of aggregate, cement, and water, and does not require compaction by vibration of a vibrator or the like The present invention relates to a concrete composition for self-filling.

[0002]

2. Description of the Related Art Conventionally, as a method of applying a concrete composition, it has been general practice to put concrete into a formwork with reinforcing bars and compact it by vibrating a vibrator. It is. But,
In recent years, noise pollution by vibrators at the time of casting and shortage of manpower in the concrete industry have become problems. In response to these problems, research on concrete with self-compacting properties that does not require vibration compaction has begun, but at present the technology has not yet reached practical use.

In general, when the fluidity of concrete is increased, aggregates are separated, coarse aggregates are entangled with each other, and not only the filling property is deteriorated, but also the strength is reduced because uniform concrete cannot be obtained. In addition, in the case of a concrete mixture containing a large amount of a thickening agent such as underwater concrete, the separation of aggregates is suppressed but the viscosity is significantly increased (for example, the concrete composition for underwater construction disclosed in Japanese Patent Publication No. 62-35984). In the material, the viscosity of the concrete mixing water is 500
~ 5000cps. ), Not only the filling work becomes difficult, but also the development of the initial strength due to the delay of the curing time, which is the property of the thickener, is slow, so that it is difficult to apply it to construction and civil engineering, especially secondary products. .

In recent years, reports have been made under the name of hyper-performance concrete [Concrete Engineering Annual Reports, 63-68]
P. (1989)] is a concrete composition that does not require compaction, in which a large amount of fine powder such as blast furnace slag or fly ash is added, and a thickener is further added. Although the curing time has been improved, the large amount of powder requires a large amount of water and the water / cement ratio is as high as 100%, making it difficult to use for secondary products that require early demolding. is there.

[0005]

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 concrete composition containing a high-performance water reducing agent and a water-soluble polymer, wherein the water-soluble polymer is a monohydric alcohol having 12 or more carbon atoms in the molecule, a monohydric mercaptan or an alkylphenol of an alkylphenol. A self-compacting concrete, characterized by using a product obtained by reacting a compound having at least one epoxy group with an adduct of 20 mol or more of oxide and having a slump flow value of 50 cm or more according to JIS A 1101 of the concrete. Composition.

The present invention is a concrete composition to which both a high-performance water reducing agent and the above-mentioned water-soluble polymer are added. The concrete composition satisfies the conflicting performance of separation resistance and high fluidity, and satisfies early strength. Things. In the concrete composition of the present invention, a high-performance water reducing agent added in order to obtain high fluidity (slump flow value specified in JIS A 1101 is 50 cm or more),
It is preferable to add about 0.3 to 3.0% by weight as an active ingredient to cement.

As a high-performance water reducing agent, a naphthalene sulfonate formaldehyde condensate (trade name: Mighty 150)
Manufactured by Kao Corporation, or a melamine sulfonate formaldehyde condensate [for example, trade name Matey 150V-2, manufactured by Kao Corporation] or a substance having a water reducing ability equivalent to or higher than these. Further, as a high-performance water reducing agent, melamine, urea, phenol or aniline methylolates and sulfonates of one or more selected from formaldehyde monocondensates or cocondensates, for example, phenolsulfonic acid formaldehyde condensates (Patent No. 1097647
Phenol / sulfanilic acid formaldehyde co-condensate (compounds described in JP-A-1-113419) and phenol / melamine methylolated sulfonate co-condensate (JP-A-56-13647) Urea / melamine methylolated sulfonic acid cocondensates (compounds described in JP-B-52-13991).

[0008] The water-soluble polymer used in the concrete composition of the present invention may be a monohydric alcohol having 12 or more carbon atoms in the molecule, a monohydric mercaptan or an adduct of alkylphenol of alkylphenol of 20 mol or more with an epoxy group. The main component is a product obtained by reacting a compound having at least one compound.

In the present invention, typical examples of the monohydric alcohol, monohydric mercaptan or alkylphenol having 12 or more carbon atoms in the molecule include octylphenol, nonylphenol, dodecylphenol, diamylphenol and dioctylphenol. Or alkylphenols such as dinonylphenol, dodecyl alcohol, tridecyl alcohol, hexadecyl alcohol,
A monohydric aliphatic alcohol such as 2-hexyldecyl alcohol or octadecyl alcohol, an alicyclic monohydric alcohol such as abiethyl alcohol, or a monovalent aliphatic mercaptan such as dodecyl mercaptan; Mixtures of more than one species may be used.

Alkylene oxide adducts suitable for use in the present invention include monohydric alcohols having 12 or more carbon atoms, monohydric mercaptans or alkylphenols as described above and ethylene oxide alone, or both ethylene oxide and propylene oxide. Is added randomly or in a block form to 20 mol or more. The addition molar ratio of both ethylene oxide and propylene oxide is preferably at least 80 mol% of ethylene oxide and at most 20 mol% of propylene oxide, and the number of added moles is preferably about 100 to 250 mol in terms of performance.

Examples of the compound having one epoxy group useful in the present invention include glycidol, epihalohydrin, butyl glycidyl ether and the like. The compound having two epoxy groups is β, α-epoxypropyl ether 1,2-bis (β, γ-epoxypropoxy) ethane, 1,3-bis (β, γ-epoxypropoxy) propane, 1,4-bis (β, γ-epoxypropoxy) butane, 1,2- Bis (β-methyl-β, γ-epoxypropoxy) ethane, 1,2-bis (2, β-epoxy-γ-methoxy) ethane, 1,6-bis (epoxyethyl) hexane, 1,4-bis ( β, γ-epoxypropoxy) benzene, 2,2-bis [p- (β, γ-epoxypropoxy) phenyl] propane, 1-epoxyethyl-
3,4-epoxycyclohexane (common name: vinylcyclohexene diepoxide), α-limonene diepoxide, etc., among which 2,2-bis [p- (β, γ-epoxypropoxy) phenyl] propane, 1-epoxyethyl 3,4
-Epoxycyclohexane (common name: vinylcyclohexene diepoxide), diepoxide such as α-limonene diepoxide, etc., and preferably the number of epoxy groups is two.

In order to obtain the water-soluble polymer of the present invention, the compound having one or more epoxy groups and the above-mentioned alkylene oxide adduct are reacted in the presence of an alkali catalyst at a reaction temperature of 50 to 200 ° C., preferably 100 ° C. Reaction time at ~ 150 ° C
It can be obtained by reacting for 10 minutes to 10 hours, preferably 30 minutes to 3 hours. When the number of carbon atoms in the molecule of the monohydric alcohol, monohydric mercaptan, or alkylphenol, which is the starting component of the alkylene oxide adduct used for synthesizing the water-soluble polymer of the present invention, is less than 12, no viscosity increase is exhibited. If the number of moles of the alkylene oxide added is less than 20, the reaction product with the compound having one or more epoxy groups becomes insoluble in water and cannot be used as a separation reducing agent. The reaction ratio between the compound having one or more epoxy groups and the alkylene oxide adduct is suitably about 0.5 to 5 equivalents of the compound having one or more epoxy groups per 1 equivalent of hydroxy of the alkylene oxide adduct. is there.

The amount of the water-soluble polymer to be added is suitably 0.01 to 0.2% based on the cement. Although the concrete composition of the present invention is mainly composed of cement, fine aggregate and coarse aggregate, various admixture materials such as various cements, blast furnace slag and fly ash can be used. Further, various admixtures can be added to the composition of the present invention. For example, an AE (air entraining) agent, an antifoaming agent, a quick strengthening agent, a retarding agent, a surfactant and the like can be mentioned.

[0014] The concrete composition of the present invention is used for molded concrete. The concrete compact is not particularly limited, and is usually a compact compacted by a vibrator. Further, the concrete composition of the present invention can be used for secondary products requiring initial strength. That is, according to the steam curing method specified in JIS A5338, paragraph 4-4-2, the strength of 100 kg / cm ² or more required for demolding the secondary product can be obtained in a short time. Although the concrete composition of the present invention does not require compaction by vibration using a vibrator, compaction in an extremely small vibration region (for example, a normal vibration frequency of 1/10 to 1/3) is also possible. .

[0015]

[Product name Mighty 150, manufactured by Kao Corporation]

 (B) Melamine sulfonate formaldehyde condensate [Matey 150V-2, manufactured by Kao Corporation]Comparative general water reducing agent  (C) Lignin sulfonate [trade name: Sun extract, manufactured by Sanyo Kokusaku Pulp Co., Ltd.]Water-soluble polymer  (A) Manufacturing Example (1) (b) Manufacturing Example (2) (c) Manufacturing Example (3) (d) Manufacturing Example (4) (e) Production Example (5) (F) Production Example (6) (G) Production Example (7) (H) Production Example (8)Comparative water-soluble polymer  (I) Methylcellulose [CMC Daicel 1170, Daicel Chemical Industries, Ltd.
The basic mix and use of concrete tested in the examples
The contents of the materials are shown below.Concrete mix  -Cement / water ratio (W / C) = 45.0%-Sand / [sand + gravel] ratio (s / a) = 50.0%-Cement amount (C) = 370 kg / m^Three Materials used  ・ Cement: Normal Portland cement Specific gravity = 3.16 ・ Sand: Kinokawa river sand Specific gravity = 2.56 ・ Gravel: Takarazuka crushed stone Specific gravity = 3.60 Results of slump flow, separation resistance and self-filling properties are shown in Table 1.
Shown in

[0016]

[Table 1]

The contents of Table 1 are shown below.・ Addition amount: Solid content% to cement ・ Slump flow: Slump according to JIS A 1101
Flow value (cm)-Separation resistance: Evaluate visually (visually)
went. The evaluation criteria are as follows. ○; No separation of aggregate and water × ×: Separation of aggregate and water ・ Self-filling property: φ10 after kneading concrete
cm of concrete in a cylindrical formwork,
The state of packing on the cleat surface was visually observed. Evaluation criteria are
It is as follows. O: 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. Examples of the production of the used water-soluble polymer are shown below.Production Example-1  Product name Calcol 86 [manufactured by Kao Corporation, stearyl alcohol
Mixture of ethanol and cetanol, hydroxyl number 200
Addition of 200 moles of ethylene oxide using Lucari catalyst
85g of vinylcyclohexene diepoxide
2.4 g of (epoxy equivalent: 76) and react at 140 ° C for 3 hours
After that, it was neutralized with acetic acid.

[0018]Production Example-2  Abitol (Hercules) synthesized according to Production Example-1
Powder, tetrahydroabiethyl alcohol and di
Mixture with hydroabiethyl alcohol)
150 g of 100 moles of oxide and vinylcyclohexene
12 g reaction product of diepoxide (epoxy equivalent 76).

[0019]Production Example-3  Ethyle of nonylphenol synthesized according to Production Example-1
Oxide and propylene oxide (molar ratio 10:
1) Random adduct (20 moles of ethylene oxide added)
0, propylene oxide addition mole number 20) 100 g and vinyl
3.3 g of cyclohexene diepoxide (epoxy equivalent 76)
Reaction product.

[0020]Production Example-4  Polyethylene glycol synthesized according to Production Example-1
Uryl ether (50 moles of ethylene oxide added) 70
g and vinylcyclohexene diepoxide (epoxy equivalent
76) 12 g of reaction product.

[0021]Production Example-5  Polyethylene glycol di synthesized according to Production Example-1
Nonylphenyl ether (ethylene oxide addition mole
40 g) of 70 g of vinylcyclohexene diepoxide (Epo
Xyl equivalent 76) 8 g of reaction product.

[0022]Production Example-6  Dodecyl mercaptan ethyl synthesized according to Production Example-1
100 g of lenoxide adduct (100 moles added) and vinyl
6.6 g of cyclohexene diepoxide (epoxy equivalent: 76)
Reaction product.

[0023]Production Example-7  Polyethylene glycol synthesized according to Production Example-1
Kutadecyl ether (ethylene oxide addition mole number 22
0) Reaction of 100 g with α-limonene diepoxide 4.4 g
object.

[0024]Production Example-8  Polyethylene glycol synthesized according to Production Example-1
Kutadecyl ether (ethylene oxide addition mole number 22
0) 100 g and trade name Epicoat 828 [Showa Shell Sekiyu
Co., Ltd., bisphenol A-epichlorohydrin initial
Condensate] 2.8 g of reaction product.

[0025]Production Example-9  Polyethylene glycol synthesized according to Production Example-1
Uryl ether (mol of ethylene oxide added 220) 1
00g and 15g of epichlorohydrin (epoxy equivalent 92)
Reaction product.

From the results shown in Table 1, it can be seen that the concrete composition of the present invention satisfies the fluidity, the separation resistance and the self-filling property, while the comparative product cannot satisfy both the performances of the flowability and the separation resistance. It can be seen that the self-filling property is lacking and that many surface voids are generated.

Next, fluidity, self-filling property, separation resistance, and compressive strength were evaluated using the high-performance water reducing agent and the general water reducing agent shown in Table 2 in the above-mentioned concrete formulation and the above-mentioned water-soluble polymer. Table 3 shows the results.

[0028]

[Table 2]

[0029]

[Table 3]

The methods for measuring fluidity, self-filling property and separation resistance are the same as described above. After compressing the concrete, concrete is packed in a cylindrical form of φ10cm, left standing for 2 hours, heated at a rate of 20 ° C for 1 hour, kept at 65 ° C for 4 hours, and then left to cool for steam curing. The strength after 24 hours was measured according to JIS A 1108. From the results shown in Table 3, the concrete composition of the present invention satisfies the required properties such as fluidity, separation resistance, and self-compacting property, and has a compressive strength of 130 kg / cm.
It turns out that expression of ^two or more intensities is possible.

[0031]

The use of the self-compacting concrete composition of the present invention makes it possible to ensure high fluidity, separation resistance and initial strength. Improved, especially in the production of concrete products, has a large ripple effect on noise reduction and production rationalization.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI // C04B 103: 32 111: 62 (56) References JP-A-4-331754 (JP, A) JP-A-4-198050 ( JP, A) JP-A-1-294556 (JP, A) JP-A-61-186253 (JP, A) JP-A-60-27637 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , (DB name) C04B 28/02 C04B 24/22 C04B 24/30 C04B 24/32

Claims (4)

(57) [Claims] 1. A concrete composition containing a high-performance water reducing agent and a water-soluble polymer, wherein the water-soluble polymer is a monohydric alcohol having 12 or more carbon atoms in its molecule, a monohydric mercaptan or an alkylphenol, and an alkylene. A self-catalyst characterized by using a reaction product of an alkylene oxide adduct to which at least 20 mol of oxide is added and a compound having at least one epoxy group, and having a slump flow value of 50 cm or more according to JIS A 1101 of concrete. Concrete composition for filling. 2. The concrete composition for self-filling according to claim 1, wherein the compound having one or more epoxy groups has two epoxy groups. 3. The self-compacting concrete composition according to claim 1, wherein the high-performance water reducing agent is a naphthalene sulfonate formaldehyde condensate or a melamine sulfonate formaldehyde condensate. 4. The high-performance water reducing agent is melamine, phenol,
The self-consolidating concrete composition according to claim 1 or 2, which is one or more formaldehyde monocondensates or cocondensates selected from methylolates and sulfonates of a compound selected from the group consisting of urea and aniline. .