JP2001172070A - Cement admixture, cement concrete, method for producing cement concrete, and spray working method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cement admixture capable of diminishing rebound rate and/or dust emission in cement concrete spray working operation and to be used in such spray works for tunnels and the like, to provide a method for spray work using the above admixture, and to provide a method for modifying the workability of a cement composition subject to decline in slump characteristics. SOLUTION: This cement admixture essentially comprises a polyethylene oxide esp. 1000,000-5000,000 in average molecular weight, an esp. 1-4C alkylnaphthalenesulfonic acid-formaldehyde condensate >=105% in sulfonation rate and a lignosulfonate and/or urea esp. with the pH of its 5% aqueous solution of >=7.0. A cement composition is obtained by including the above admixture and cement. The 2nd objective cement concrete contains the above admixture. The 3rd objective spray working method comprises, in particular mixing part of the essential components, e.g. an alkylnaphthalenesulfonic acid- formaldehyde condensate >=105% in sulfonation rate with a quick-setting cement mixture just before spraying operation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention provides a method for modifying the workability of cement compositions, ie, reducing the slump properties. Furthermore, the present invention provides a cement admixture used when spraying cement concrete containing a quick setting agent on an exposed ground surface in a tunnel such as a road, a railway, and a headrace, and a cement concrete using the same. The present invention relates to a manufacturing method and a spraying method using the cement concrete. In the present invention, parts and percentages are based on mass unless otherwise specified. Further, the cement concrete referred to in the present invention is a general term for those containing cement and the cement admixture of the present invention, and the cement composition is a general term for those containing admixtures other than cement and the cement admixture of the present invention. Yes, the cement mixture contains cement and a part of the cement admixture of the present invention.

[0002]

2. Description of the Related Art Conventionally, a method for modifying the slump characteristics of cement or mortar has been proposed (Japanese Patent Publication No. Hei 06-511228). However, for applications such as shotcrete for concrete, the effect was not always sufficient. Also, in order to prevent collapse of exposed ground due to tunnel excavation or the like, a quick-setting concrete spraying method in which a quick-setting agent is mixed with concrete has been performed (Japanese Patent Publication No. Sho 60-004149). In this spraying method, a concrete is usually prepared by mixing cement, aggregate, and water in a mixing and mixing plant installed at an excavation site, transported by an agitator truck, and pumped by a concrete pump, and This is a method of mixing with a quick-setting agent pumped from the other side and spraying it as a quick-setting concrete on the ground surface to a predetermined thickness.

[0003] The quick setting agent used at this time is a simple or mixture of calcium aluminate, alkali metal aluminate, alkali metal carbonate and the like, and an alkali-aggregate reaction suppressing quick setting for permanent structures. Agents are known (JP-A-64-051351, JP-B-56-027457, JP-A-61-026538, JP-A-63-210050, and JP-A-08-048553. Gazette). However, when the conventional quick-setting admixture is used, there has been a problem that a rebound rate and a generated amount of dust at the time of spraying are large.

The inventor of the present invention has conducted various studies to solve the above-mentioned problems. As a result, the use of a specific cement admixture rapidly reduced the slump of cement concrete,
The inventors have found that the rebound rate and the amount of dust at the time of spraying can be reduced, and have completed the present invention.

[0005]

That is, the present invention relates to polyethylene oxides, in particular, polyethylene oxides having an average molecular weight of 1,000,000 to 5,000,000, celluloses, and formalin alkylnaphthalenesulfonate having a sulfonation ratio of 105% or more. Condensates, in particular, alkylnaphthalenesulfonic acid formalin condensates having an alkyl group having 1 to 4 carbon atoms and a sulfonation ratio of 105% or more, lignin sulfonate,
In particular, a cement admixture containing lignin sulfonate having a pH of 7.0 or more in a 5% aqueous solution and urea as an active ingredient, a cement composition containing cement, a cement concrete containing the cement admixture, Two to five types of active ingredients in the cement admixture, in particular, polyethylene oxides or polyethylene oxides and celluloses and the cement composition, at different points in the cement concrete production, mixed into a cement mixture, cement concrete Immediately before the outlet of the construction equipment, the sulfonation rate
Cement concrete mixed with alkylnaphthalenesulfonic acid formalin condensate of 105% or more, or alkylnaphthalenesulfonic acid formalin condensate of 105% or more, ligninsulfonate and / or urea, and cement mixture Production method, a quick-setting cement composition comprising a cement composition and a quick-setting agent,
Quick-setting cement concrete mixed with the cement admixture, and a spraying method using the quick-setting cement concrete, particularly a part of an effective component of the cement admixture, immediately before spraying. Part of the active ingredient of the cement admixture, which is mixed with the quick-setting cement mixture, particularly immediately before spraying, is mixed with the quick-setting cement mixture. A spraying method comprising condensates or alkylnaphthalenesulfonic acid formalin condensates having a sulfonation ratio of 105% or more and ligninsulfonate and / or urea.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The polyethylene oxides (hereinafter referred to as PEOs) used in the present invention have a sulfonation rate of 105%.
When the above-mentioned alkyl naphthalene sulfonic acid formalin condensates, lignin sulfonate, and the interaction with urea quickly reduce the slump of cement concrete, impart viscosity to the cement concrete, and spray the cement concrete, This prevents the cement concrete from dripping from the spraying surface immediately after spraying, and reduces the rebound rate and the amount of dust. PEO of the present invention
The class includes polyethylene oxide and those containing a mercaptan, phenyl group, epoxy group, hydroxyl group, carboxyl group and the like in the molecule of polyethylene oxide. The average molecular weight of PEOs is 1,000,000 to 5 by weight average.
One million is preferred. If it is less than 1 million, the slump of cement concrete may not be reduced quickly or the rebound rate may be large.If it exceeds 5 million, the workability and workability of cement concrete will be reduced, and cement and quick-setting agent will be contained. Pumpability of the resulting quick-setting cement concrete may be reduced. The amount of PEO used is cement
0.001 to 0.5 part is preferable for 100 parts. If the amount is less than 0.001 part, the effect of reducing the slump of cement concrete and the effect of reducing the rebound rate of sprayed cement concrete may not be sufficient.If the amount exceeds 0.5 part, the pumpability of the cement mixture or cement concrete may be impaired, and the economy may be reduced. It is also not preferable.

The alkyl naphthalene sulfonic acid formalin condensates (hereinafter referred to as ANS) used in the present invention.
Is an alkyl group added to the naphthalene ring, for example,
Alkyl naphthalene sulfonic acid formalin condensate having 1 to 4 carbon atoms such as methyl naphthalene sulfonic acid formalin condensate, ethyl naphthalene sulfonic acid formalin condensate, propyl naphthalene sulfonic acid formalin condensate, and butyl naphthalene sulfonic acid formalin condensate The active ingredient is generally used. In the present invention, the sulfonation rate of ANSs needs to be 105% or more, and preferably 120% or more. If it is less than 105%, the slump of cement concrete, which is the object of the present invention, cannot be rapidly reduced, and the rebound rate and dust amount at the time of spraying may not be reduced in some cases. In addition, industrially produced ANSs are often alkali metal salts, alkaline earth metal salts, ammonium salts or organic amine salts. The amount of ANS used is 0.1 parts per 100 parts of cement.
~ 5 parts are preferred. If it is less than 0.1 part, the effect of reducing the slump of cement concrete and the effect of reducing the rebound of sprayed cement concrete may not be sufficient, and if it exceeds 5 parts, the strength development of the cement concrete may be adversely affected.

The lignin sulfonic acid salt (hereinafter referred to as LNG) used in the present invention includes sodium, potassium and calcium salts of lignin sulfonic acid, of which sodium salt is usually used and commercial products are used. It is possible. Among them, those having an average molecular weight of 10,000 or more and a pH of a 5% aqueous solution of 7.0 or more are preferable. Outside this range,
In some cases, the rebound rate and dust amount at the time of spraying are not sufficiently reduced. The amount of LNG used is preferably 0.1 to 5 parts with respect to 100 parts of cement. Outside this range, the slump reduction effect and rebound reduction effect of the cement concrete may be insufficient, or the effect of the quick-setting agent used in the quick-setting cement concrete may be adversely affected.

[0010] Urea (hereinafter referred to as UR) used in the present invention is considered to interact with PEOs through hydrogen bonding, and when used in combination with ANSs, the rebound rate and dust amount of sprayed cement concrete are reduced by synergistic action. Reduce. The amount of UR used is 0.1 to 5 per 100 parts of cement.
Parts are preferred. Outside this range, the effect of reducing rebound and dust may be insufficient, or the effect of the quick-setting agent used for quick-setting cement concrete may be adversely affected.

In the present invention, celluloses can be used in combination depending on the conditions of use such as cement concrete mixing. As the celluloses, hydroxyalkylcellulose such as methylcellulose, carboxymethylcellulose, and hydroxypropylcellulose can be used, and commercially available products are easily available. Cellulose P
When used in place of EOs, the amount of PEOs used
Substitution up to about 10% is preferred. Above that, the workability and workability of the cement concrete may be impaired.

[0012] The cement used in the present invention is not particularly limited, and various types of portland cement which are usually used, such as ordinary, fast, super fast and low heat, and blast furnace slag, Fly ash, limestone fine powder, or various mixed cements mixed with silica, etc., further, alumina cement, expanded cement,
And colloid cement can be used.

The quick-setting agent used in the present invention is not particularly limited, and alkali metal aluminates, alkali metal carbonates, silicates, and the like are used as inorganic salts, and cement minerals are used as cement minerals. Calcium aluminates, calcium sulfoaluminates, and the like, and examples of the organic system include triethanolamine and glycerin, which can be used in any state of powder, slurry, or liquid. The amount of the quick-setting agent used is appropriately determined depending on the material used.
Approximately 5 to 5 parts is preferable, and a large amount thereof is a calcium mineral calcium sulfoaluminate, preferably about 8 to 15 parts based on 100 parts of cement. If the amount of the quick-setting agent is less than this, the quick-setting force is insufficient and rebound may be extremely large, and even if the amount of the quick-setting agent is used more than this, the effect corresponding to it is not obtained, Not economically favorable.

In the present invention, it is preferable to use a fibrous material in order to improve the impact resistance and elasticity of the hardened cement concrete. As the fibrous material, any of inorganic and organic materials can be used. Examples of the inorganic fiber include glass fiber, carbon fiber, rock wool, asbestos, ceramic fiber, and metal fiber. Examples of the organic fiber include vinylon fiber, polyethylene fiber, polypropylene fiber, polyacryl fiber, and cellulose. Fiber, polyvinyl alcohol fiber, polyamide fiber, pulp, hemp, and the like. Among these, metal fibers and vinylon fibers are preferable from the viewpoint of the effect. The length of the fibrous material is preferably 50 mm or less, and more preferably 30 mm or less, from the viewpoint of pumpability and mixing properties. If it exceeds 50 mm, the pumping pipe may be blocked. The amount of fiber used is preferably 0.5 to 10 parts by volume with respect to 100 parts by volume of cement concrete. If the amount is less than 0.5 part by volume, there may be no effect, and if it exceeds 10 parts by volume, the fluidity of cement concrete may be significantly impaired.

In the present invention, in addition to the above-mentioned materials, aggregates such as sand and gravel, a setting modifier, an AE agent, an antifoaming agent, a thickener, a cement expanding agent, a rust preventive, an antifreeze, an SBR, Polymer emulsions such as polyacrylates, calcium compounds such as calcium oxide and calcium hydroxide, aluminum sulfate, sulfates such as alkali metal sulfates, alkali metal sulfites and alkali metal bisulfites, clay minerals such as bentonite, zeolites , Hydrotalcite, and ion exchangers such as hydrocalmite, inorganic phosphate, and one or more of boric acid and the like may be used in combination within a range that does not substantially inhibit the object of the present invention. It is possible.

The method of mixing and kneading the cement admixture of the present invention is not particularly limited, and a conventional method can be applied. When the cement admixture of the present invention is mixed with the cement composition, the consistency of the cement concrete is reduced. Therefore, a part of the active ingredient of the cement admixture is previously mixed with the cement composition to form a cement mixture, and a cement concrete construction device It is preferable to use the remaining active ingredients in a mixture immediately before the outlet of the active ingredient. In the present invention, as a device for mixing cement, aggregate, water, and the like, an existing stirring device can be used. For example, a tilting mixer, an omni mixer, a V-type mixer, a Henschel mixer,
And Nauta mixer can be used.

In the present invention, from the aspect of modifying the slump characteristics of the cement concrete, two to five kinds of active ingredients of the cement admixture are mixed with the cement composition at different points in the cement concrete production. preferable. In particular, PEOs or PEOs and celluloses are mixed with a cement composition to form a cement mixture, and ANSs and a cement mixture or ANSs, and LNG and / or U, immediately before an outlet of a cement concrete construction device.
R and a method of mixing a cement mixture are preferred. In the present invention, when spraying in combination with a quick setting agent,
It is preferable to mix S or ANS with LNG and / or UR immediately before spraying, for example, at a spray nozzle, with a quick-setting cement mixture in which PEO or PEO and cellulose are previously mixed. When all of the active ingredients of the cement admixture are mixed with the cement composition, the pumpability is rapidly reduced. Therefore, when all the active ingredients are added at locations other than the spray nozzle, clogging and pulsation may occur.

Examples of the method of mixing the quick-setting admixture include a method in which the cement mixture or the cement composition and the powder quick-setting admixture are separately pneumatically fed and mixed together, or a method in which the cement mixture or the cement composition and the quick-setting admixture are mixed. Are mixed with a cement mixture or a cement composition, or the like.

As the spraying method of the present invention, a dry spraying method or a wet spraying method can be used. The dry spray method is, for example, a method in which cement and aggregate are mixed and pneumatically fed, and water and a quick-setting agent are mixed and sprayed in a wet state, and the wet spray method is, for example, This is a method in which cement, aggregate, and water are mixed in advance to form a cement composition, which is then air-pneumatically fed, mixed and mixed with a quick-setting agent, and sprayed. Of these, the dry spraying method may increase the amount of dust, so it is preferable to use the wet spraying method. In the spraying method of the present invention, conventional spraying equipment and the like can be used. The spraying equipment is not particularly limited as long as the spraying is sufficiently performed. For example, for the pumping of a cement mixture or a cement composition, "Ariba 280" (trade name, manufactured by Ariba) may be used. "Natom Cleat" manufactured by Chiyoda Manufacturing Co., Ltd., and "Ankomat Pump" manufactured by Putzmeister Co., Ltd. can be used for pumping the quick-setting agent slurry. A common water pump can be used to add water to the powder quick-setting admixture, and a method of adding water together with compressed air is possible. Further, the pressure of the compressed air for pumping the quick-setting admixture is set so that the cement mixture or cement composition in a wet state does not enter the pumping tube of the quick-setting adsorber and block the inside of the pumping tube. It is preferable that the pressure is higher by about 0.01 to 0.3 MPa than the pressure. Further, the pumping speed of the cement mixture or the cement composition is preferably 4 to 20 m ³ / h. Furthermore, the junction of the quick-setting agent and the cement mixture or the cement composition can be a structure in which the shape of the pipe or the inner wall is liable to be spiral or turbulent in order to improve the mixing property.

[0020]

The present invention will be described below in detail based on experimental examples.

[0021] The unit amount of Experimental Example 1 each material, a cement composition was prepared as a cement 450 kg / m ^3, water 180 kg / m ^3, fine aggregates 1,104kg / m ^3, and coarse aggregate 597kg / m ^3, Further, 1 part by volume of fiber was added to 100 parts by volume of the cement composition. In addition, P shown in Table 1
The EOs were previously mixed with the cement composition to form a cement mixture, and the mixture was pumped under the conditions of a pumping speed of 4 m ³ / h and a pumping pressure of 0.4 MPa using Ariba “Ariba 280”. ANS type e and quick setting agent α shown in Table 1 for 100 parts of cement
Was blown with compressed air from one of the Y-shaped tubes at the spray nozzle using a “Natom Cleat” to obtain a quick-setting cement concrete, and the rebound rate, the amount of dust, and the compressive strength were measured. The results are also shown in Table 1. Note that AN
The sulfonation ratio (%) of S was calculated based on the amount of sulfuric acid actually consumed by neutralization titration based on the amount of sulfuric acid necessary for converting alkylnaphthalene into monosulfonic acid. .

<Materials Used> Cement: ordinary Portland cement, commercial product, Blaine value 3,200 cm ² / g, specific gravity 3.16 Fine aggregate: Oigawa river sand, surface water ratio 4.0%, specific gravity 2.64 Coarse aggregate: Ome crushed stone, Surface dry state, specific gravity 2.70, maximum dimension 10mm Quick setting agent α: calcium aluminate, commercially available PEOs a: polyethylene oxide, average molecular weight 2,000,000, commercially available ANSs e: methyl naphthalene sulfonic acid formalin condensate, sulfonated Rate: 120%, average molecular weight: 20,000 Fiber: steel fiber, length 30mm, specific gravity 7.8, commercial product

<Measurement method> Rebound rate: Rapid-setting cement concrete was formed into an arched shape with an iron plate at a pumping speed of 4 m ³ / h for 15 minutes and a height of 3.5.
m, a 2.5m wide mock tunnel. After spraying, measure the amount of quick-setting cement concrete and fiber that have bounced off, and calculate from (bounced quick-setting cement concrete or fiber) / (sprayed quick-setting cement concrete or fiber). Calculated. Dust amount: Measured with a dust meter at a position 3 m from the spray surface. Compressive strength: The prepared quick-setting cement concrete was sprayed on a formwork. Compressive strength of 3 hours of age, using a 25 cm wide x 25 cm long pull-out mold specimen, cover the pin from the surface of the pull-out mold with quick-setting cement concrete, and pull out the pin from the back side of the mold Then, the pull-out strength at that time was obtained, and (compression strength) = (pull-out strength) × 4 /
It was calculated from the formula of (sample contact area). The compressive strength after 1 day of material was measured using a specimen having a diameter of 5 cm and a length of 10 cm collected from a mold having a width of 50 cm, a length of 50 cm and a thickness of 20 cm.

[0024]

[Table 1]

EXPERIMENTAL EXAMPLE 2 100 parts of cement were mixed with PEOs shown in Table 2 in advance in a cement composition to form a cement mixture, and 100 parts of cement were mixed with ANSs and LNG shown in Table 2 for 100 parts of cement.
行 っ and UR were used in the same manner as in Experimental Example 1 except that UR was used. The results are also shown in Table 2.

<Materials used> LNG ヲ: Lignin sulfonate, commercial product, pH of 5% aqueous solution pH 10.0, average molecular weight 15,000 URW: urea, commercial product

[0027]

[Table 2]

EXPERIMENTAL EXAMPLE 3 0.3 parts of PEOs and 100 parts of cement were mixed in advance with a cement composition to obtain a cement mixture, and 3 parts of ANS and 3 parts of LNG ヲ per 100 parts of cement.
UR was used in the same manner as in Experimental Example 1 except that 3 parts of UR wax were used and the quick setting agent shown in Table 3 was used. The results are also shown in Table 3.

<Materials used> Quick setting agent β: calcium sulfoaluminate, commercially available Quick setting agent γ: mixture of potassium aluminate and potassium carbonate, commercially available

[0030]

[Table 3]

Experimental Example 4 0.3 parts of PEO shown in Table 4 and 100 parts of cement were mixed in advance with a cement composition to prepare a cement mixture, and 3 parts of LNG ヲ 100 parts of cement and 3 parts of U
The experiment was performed in the same manner as in Experimental Example 1 except that Rwa and ANSs shown in Table 4 were used. The results are also shown in Table 4.

<Materials> PEOs b: polyethylene oxide, average molecular weight 100
10,000, commercially available PEOs C: polyethylene oxide, average molecular weight 500
10,000, PEOs: polyethylene glycol, average molecular weight 300
ANS: Commercially available ANS: ethyl naphthalene sulfonic acid formalin condensate, sulfonation rate 120%, average molecular weight 20,000 ANS: propyl naphthalene sulfonic acid formalin condensate, sulfonation rate 120%, average molecular weight 20,000 ANS H: butyl naphthalene sulfonic acid formalin condensate, sulfonation rate 120%, average molecular weight 20,000 ANS: methyl naphthalene sulfonic acid formalin condensate, sulfonation rate 135%, average molecular weight 20,000 ANS: methyl naphthalene sulfonic acid Formalin condensate, sulfonation rate 105%, average molecular weight 20,000 ANS: methyl naphthalenesulfonic acid formalin condensate, sulfonation rate 100%, average molecular weight 20,000 Cellulose: main component methylcellulose, commercial product

[0033]

[Table 4]

[0034]

The use of the cement admixture of the present invention makes it possible to reduce the amount of rebound and the amount of dust generated during spraying of quick-setting cement concrete.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C04B 103: 30 C04B 103: 30

Claims (13)

[Claims] 1. A cement admixture comprising polyethylene oxides and an alkylnaphthalenesulfonic acid formalin condensate having a sulfonation ratio of 105% or more as active ingredients. 2. A cement admixture containing polyethylene oxides, alkylnaphthalenesulfonic acid formalin condensates having a sulfonation ratio of 105% or more, and ligninsulfonic acid salts and / or urea as active ingredients. 3. The polyethylene oxide having an average molecular weight of 1,000,000 to 5,000,000.
The cement admixture described. 4. The cement admixture according to claim 1, wherein a part of the amount of the polyethylene oxides is replaced by celluloses. 5. The p of a 5% aqueous solution of ligninsulfonate
The cement admixture according to any one of claims 2 to 4, wherein H is 7.0 or more. 6. The alkylnaphthalenesulfonic acid formalin condensate having a sulfonation ratio of 105% or more, wherein the alkyl group has 1 to 4 carbon atoms. Cement admixture. 7. A cement composition containing cement,
A cement concrete comprising the cement admixture according to claim 1. 8. The method according to claim 1, wherein two to five active ingredients in the cement admixture according to claim 1 are mixed with the cement composition at different points in the cement concrete production. To produce cement concrete. 9. An alkylnaphthalene sulfonic acid having a sulfonation rate of 105% or more immediately before an outlet of a cement concrete construction device, wherein polyethylene oxides or polyethylene oxides and celluloses are mixed with a cement composition to form a cement mixture. Cement concrete characterized by mixing a formalin condensate with a cement mixture or an alkylnaphthalenesulfonic acid formalin condensate having a sulfonation ratio of 105% or more, a cement mixture, and a lignin sulfonate and / or urea Manufacturing method. 10. A quick-setting cement obtained by mixing a quick-setting cement composition containing a cement composition and a quick-setting agent with the cement admixture according to any one of claims 1 to 6. concrete. 11. A quick setting cement composition containing a cement composition and a quick setting agent, and a cement admixture according to any one of claims 1 to 6, mixed and sprayed. Spraying method characterized by the following. 12. The cement-admixture according to claim 1, wherein a part of the active ingredient of the cement admixture is mixed with the quick-setting cement mixture immediately before spraying.
The spraying method described. 13. Immediately before spraying, a part of the active ingredient of the cement admixture to be mixed with the quick-setting cement mixture is an alkylnaphthalenesulfonic acid formalin condensate having a sulfonation ratio of 105% or more, or sulfonation. An alkylnaphthalenesulfonic acid formalin condensate having a ratio of 105% or more,
13. The spraying method according to claim 12, wherein the method is lignin sulfonate and / or urea.