KR100858858B1 - Set accelerating agent for spraying, spraying material, and spraying method using the same - Google Patents

Abstract

Provided is a fastener capable of providing excellent durability and high durability while reducing the amount of alkali used, and a spraying method using the fastener.

As a jetting accelerator containing calcium aluminate, gypsum and alkali metal aluminate, the calcium aluminate has a vitrification rate of 80% or more, a CaO / Al ₂ O ₃ molar ratio of 1.9 to 3.0, and the alkali Content of the metal aluminate salt is 1.5-10 denier in 100 parts of spraying accelerators, The spraying agent for injections characterized by the above-mentioned.

Description

Spraying agent for spraying, spraying material, and spraying method using the same {SET ACCELERATING AGENT FOR SPRAYING, SPRAYING MATERIAL, AND SPRAYING METHOD USING THE SAME}

The present invention relates to a spray grade for use in injecting fastening concrete onto exposed acidic surfaces in tunnels such as roads, railways, raceways, and the like. It relates to a settlement, spraying material, sprayed concrete, and a spraying method using the same.

In addition, concrete referred to in the present invention is a generic term for cement paste, mortar, or concrete.

Conventionally, in order to prevent the collapse of the exposed acid in tunnel excavation work etc., the method of spraying the quickening concrete which mixed the quickener of powder with concrete is used.

It is known to contain calcium aluminate, gypsum, and an alkali metal aluminate as a quickener used by such a spraying method (refer patent documents 1-3).

Patent Document 1 is a calcium aluminate, a tube in the invention class payment which comprises the the sodium aluminate, sulphate and Na ₂ O / Al ₂ O ₃ molar ratio is 1.00 to 1.30 in. There, the use of specific sodium aluminate solves the problems of long-term preservation and quickness (paragraph), concrete that does not show a decrease in physical properties even in long-term storage compared with the use of conventional sodium aluminate It can be obtained (paragraph [0035]). It is not intended to reduce the amount of sodium aluminate used here.

Patent Literature 1 also describes the following. As calcium aluminate, CaO is C, Al ₂ O ₃ When A is A, calcium aluminate heat treated materials represented by mineral compositions such as C ₃ A, C ₁₂ A ₇ , CA, and CA ₂ may be mentioned, and one or two or more thereof may be used in combination. Moreover, these may be pulverized, and as other components, calcium aluminate in which some alkali metals such as sodium, potassium and lithium are dissolved may be used. Among them, in view of the reaction activity, amorphous calcium aluminate is preferred, and amorphous calcium aluminate in which the heat treatment material corresponding to the C ₁₂ A ₇ composition is quenched is more preferable (paragraph). In addition, the embodiment discloses a fastener comprising calcium aluminate, gypsum and sodium aluminate (paragraphs [0020] to [0034]). However, CaO / Al ₂ O ₃ of calcium aluminate The molar ratio is not disclosed.

Patent Document 2 is selected from the group consisting of calcium aluminate, sodium aluminate, sulfate having a molar ratio of Na ₂ O / Al ₂ O ₃ of 1.0 to 1.3, and a water reducing agent, thickener, ultra fine powder, and fibrous material. The invention relates to a fastener comprising one or two or more kinds of admixtures. As in Patent Document 1, the use of specific sodium aluminate solves the problems of long-term preservation and quickness (paragraphs [0006] to [0007]), and also in long-term storage as compared with the use of conventional sodium aluminate. It is said that a quick spraying cement concrete can be obtained which does not exhibit deterioration of physical properties (paragraph [0090]). However, there is no intention of reducing the amount of sodium aluminate used there, either.

In addition, as for calcium aluminate, amorphous calcium aluminate is preferred in terms of reaction activity, and it is described that amorphous calcium aluminate in which the heat treatment material corresponding to the C ₁₂ A ₇ composition is quenched is more preferable (paragraph [0013]). ). In addition, the embodiment discloses a fastener comprising calcium aluminate, gypsum and sodium aluminate (paragraphs [0051] to [0089]), but discloses a CaO / Al ₂ O ₃ molar ratio of calcium aluminate. It is not.

Patent document 3 is a fastener containing calcium aluminate, sulfate, and sodium aluminate having a Na ₂ O / Al ₂ O ₃ (molar ratio) of less than 1.0, wherein the amount of Na ₂ O in the fastener is from 2.0 to 10.0 mass%. The invention relates to a fastener for sprayed concrete, characterized in that. Its purpose is to provide fastening property, express strength well, and improve fluidity and adhesion as a calcium aluminate-sulfate-sodium aluminate type fastener. This enables continuous static weighing in the fastener supply device and quantitatively supplies the base concrete mixture to reduce the quenching properties of the sprayed concrete and the long-term strength to stabilize the quality. There is provided a fastener for sprayed concrete that can (paragraph [0010]).

In addition, patent document 3 describes as follows. When calcium aluminate is less than 30 mass%, quickness becomes small, and when it exceeds 80 mass%, intensity | strength developability falls, and neither case is unpreferable. In addition, when the sulfate is less than 10% by mass, the strength developability is lowered. When the sulfate is more than 60% by mass, the fastening property is reduced, which is not preferable in any case. And when sodium aluminate is less than 10 mass%, quickness becomes small, and when it exceeds 30 mass%, intensity | strength developability falls, and neither case is unpreferable. The blending ratio of the preferred raw material exhibiting better quenchability and strength developability is in the range of 40 to 60 mass% of calcium aluminate, 20 to 48 mass% of sulfate, and 12 to 20 mass% of sodium aluminate. (Paragraph [0018]). For this reason, the invention of patent document 3 uses a large amount of sodium aluminate, and since it is strong alkaline, there exists a problem of impairing the long-term strength of concrete.

In addition, in patent document 3, calcium aluminate can use either crystalline or amorphous. In consideration of rapidity and the like, there is a substrate called amorphous calcium aluminate having a CaO / Al ₂ O ₃ (molar ratio) of 1.6 to 2.5 (paragraph). However, in the examples, only the fact that CaO / Al ₂ O ₃ (molar ratio) = 1.8 is shown (paragraph), the vitrification rate is not obvious, CaO / Al ₂ O ₃ (molar ratio) is larger than 1.8 It is not specifically disclosed to use a thing having a high vitrification rate.

The problem that the fastener used in the spraying process as described above contains a large amount of alkali impairs the long-term strength of the concrete. In contrast, the alkali-free fastener has an initial fastening performance compared to the fastener containing a large amount of alkali. This lowers the cost, resulting in a high rebound rate at the time of spraying, resulting in a problem that the environmental load increases due to the increase in the material used. In order to solve these problems, a cement composition for a spray material containing calcium aluminate and gypsum and a fastening aid are developed (see Patent Documents 4 and 5).

The invention of Patent Literature 4 discloses, "The cement composition for spraying materials and the spraying which exhibit excellent quenching spraying effect with a considerably small amount of use even when using alkali-free quickening material with low quickening performance or alkali containing quickening material are used. To provide a construction method ”(paragraph [0007]). In addition, the invention of Patent Document 5 discloses that "by mixing with a cement composition in advance before a fastening material, it does not require an alkali component, or provides the quickening auxiliary material which exhibits the outstanding quick spraying effect with the alkali addition amount substantially smaller than before. (Paragraph [0007]). For this reason, neither does it reduce the alkali content of a quick setting material (fast setting material) itself.

Further, Patent Document 4 and 5, in particular anodized in acid calcium, 3CaO and Al ₂ O _3, 12CaO and 7Al ₂ O _3, CaO and Al ₂ O _3, 3CaO and 3Al ₂ O ₃ and CaSO _4, 11CaO and 7Al ₂ O ₃ · CaF _2, and their two or more mixture of the relatively high content of CaO and Al ₂ O _3, is at least a molar ratio of CaO / Al ₂ O ₃ 1, the superior performance with high activity among the calcium aluminate It is described as preferred (Patent Document 4 paragraph, Patent Document 5 paragraph [0019]). However, the combination of calcium aluminate (calcium aluminate) having a large molar ratio of CaO / Al ₂ O ₃ with gypsum and a small amount of alkali metal aluminate is not specifically disclosed.

Patent Document 1: Japanese Patent Application Laid-Open No. 11-12008

Patent Document 2: Japanese Patent Application Laid-Open No. 11-130498

Patent Document 3: Japanese Unexamined Patent Publication No. 2003-12356

Patent document 4: Unexamined-Japanese-Patent No. 11-130499

Patent Document 5: Japanese Patent Application Laid-Open No. 11-130500

Disclosure of the Invention

Problems to be Solved by the Invention

The present invention solves the problems of the prior art and reduces the amount of alkali, while providing a fastener capable of providing high durability and excellent fastness and strength expression, and a spraying method using the quickener. It is to make it a task.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, the present inventors reached | attained invention which makes the following structure the summary. In addition, the part and% in this invention are a mass reference | standard unless there is particular notice.

(1) A spraying filler containing calcium aluminate, gypsum and alkali metal aluminate, wherein the calcium aluminate has a vitrification rate of 80% or more, and a CaO / Al ₂ O ₃ molar ratio of 1.9 to 3.0, Moreover, content of the said alkali metal aluminate is 1.5-10 denier in 100 parts of spraying accelerators, The spraying agent for injections characterized by the above-mentioned.

(2) The calcium aluminate, glass rate is less than 90%, and minutes using the rapid setting agent of the above (1), characterized in that the CaO / Al ₂ O ₃ molar ratio is 2.0 to 2.3.

(3) the alkali metal aluminate in the R ₂ O / Al ₂ O ₃ molar ratio minutes using the rapid setting agent of (1) or (2), characterized in that (R = alkali metal) is 0.8 to 1.2.

(4) The content in 100 parts of the spraying agent for injection is 30 to 60 parts of calcium aluminate, 30 to 60 parts of gypsum, and 1.5 to 10 denier of alkali metal aluminate, characterized in that any of the above (1) to (3) A one shot jetting agent.

(5) The spraying agent for spraying (4) above, wherein the content in 100 parts of the spraying agent for spraying is 40 to 60 parts of calcium aluminate, 40 to 60 parts of gypsum and 2 to 5 deniers of alkali metal aluminate.

(6) An injection material comprising the jetting agent for injection according to any one of (1) to (5) above, and cement having a C ₃ A content of 5 parts or more in 100 parts of cement.

(7) An injection material comprising the jetting agent for injection according to any one of (1) to (5) and blast furnace cement.

(8) An injection material comprising the jetting agent for injection according to any one of the above (1) to (5), and blast furnace slag content of 5 to 70 denier cement in 100 parts of cement.

(9) The spraying method comprising spraying the sprayed concrete containing the spraying material according to any one of the above (6) to (8) to a tunnel or a localized surface of a normal surface.

(10) First, when calcium aluminate having a vitrification rate of 80% or more and a CaO / Al ₂ O ₃ molar ratio of 1.9 to 3.0, alkali metal aluminate, and gypsum are added to the sprayed concrete as a fastener component, the gypsum is initially Then, the spray method, characterized in that the injection by adding calcium aluminate and alkali metal aluminate.

(11) The spray method according to the above (10), wherein the molar ratio (R is an alkali metal) of R ₂ O / Al ₂ O _{3 in} the alkali metal aluminate salt is 0.8 to 1.2.

(12) The spraying method according to the above (10) or (11), wherein the use ratio of the fastener component is 40 to 60 parts of calcium aluminate, 40 to 60 parts of gypsum, and 1 to 15 deniers of the alkali metal aluminate. .

(13) The spraying method according to any one of (10) to (12), wherein the sprayed concrete contains a cement containing 5 parts by weight of 3CaOAl ₂ O ₃ in 100 parts of cement.

(14) The spraying method according to any one of (10) to (12), wherein the sprayed concrete contains blast furnace cement.

(15) The spraying method according to any one of (10) to (12), wherein the sprayed concrete contains cement containing 5 to 70 parts of blast furnace slag in 100 parts of cement.

(16) The spraying method according to any one of (10) to (15), which is sprayed on a tunnel or a ground of a normal surface.

Effects of the Invention

By using the spraying fastener and the spraying material of the present invention, even if the amount of alkali used is smaller than that of the conventional fastening agent, the effect is excellent in quickness and strength development.

Implement the invention  Best form for

Hereinafter, the present invention will be described in detail.

The fastener of the present invention contains calcium aluminate, gypsum and alkali metal aluminate having at least 80% vitrification rate and a CaO / Al ₂ O ₃ molar ratio of 1.9 to ₃ in the fastener.

Calcium aluminate is obtained by pulverizing a mixture of calcia raw materials, alumina raw materials, and the like, followed by heat treatment such as firing in a kiln, melting in an electric furnace, and grinding.

After melting in an electric furnace, quenching and vitrification are preferable, and the vitrification ratio is preferably 80% or more, and more preferably 90% or more. If the vitrification ratio is less than 80%, excellent quickness may not be obtained in some cases.

Calcium aluminate of CaO / Al ₂ O ₃ according to the, and from 1.9 to 3.0 by molar ratio, is preferably from 1.9 to 2.5, more preferably 2.0 to 2.3 a. If the molar ratio is outside this range, excellent fastness may not be obtained in some cases.

The main components of calcium aluminate are CaO and Al ₂ O _3, but it is also possible to contain SiO ₂ , CaF ₂ , Mg, Si, or the like as a mineralizer.

It is also possible to solidify less than 5% of the alkali metal element in calcium aluminate for the purpose of further improving the quickness.

Although the particle size of calcium aluminate and its distribution are not specifically limited, From a viewpoint of quickness, a brain value is preferable 4000 cm <2> / g or more, and 6000 cm <2> / g or more is more preferable.

Although content of calcium aluminate is not specifically limited, 30-60 parts is preferable in 100 parts of fasteners. If it is less than 30 parts, excellent quickness may not be obtained, and if it exceeds 60 parts, long-term strength developability may be impaired.

Examples of the gypsum used in the present invention include anhydrous gypsum, hemihydrate gypsum, dihydrate gypsum, and the like, and one or two or more thereof can be used. Anhydrous gypsum includes hydrofluoric acid byproduct gypsum or natural anhydrous gypsum.

It is preferable that the pH at the time of immersing gypsum in water is weak alkali or acidic with pH 8 or less. When pH is high, the solubility of a gypsum component may become high and the initial strength developability may be inhibited. The pH here means the pH of the diluted slurry at 20 ° C diluted with ion-exchanged water at a ratio of gypsum / ion-exchanged water = 1 g / 100g using an ion exchange electrode or the like.

As for the particle size of gypsum, 3000 cm <2> / g or more is preferable at a brain value, and 5000 cm <2> / g or more is preferable from a viewpoint of intensity | strength expression.

Although the usage-amount of gypsum is not specifically limited, Among 100 parts of fasteners, 30-60 parts are preferable and 40-60 parts are especially preferable. When it is less than 30 parts, long-term strength expressability may be impaired, and when it exceeds 60 parts, excellent quickness may not be obtained.

The alkali metal aluminate used in the present invention is obtained by mixing an alumina raw material and an alkali metal raw material, and examples of the alkali metal include lithium, sodium, potassium, and the like.

Alkali metal aluminate R ₂ O (R = alkali metal element) / Al ₂ O ₃ molar ratio of in the can, it is preferable, more preferably 0.9 to 1.1 is 0.8 to 1.2. If it is less than 0.8, excellent quickness may not be obtained, and if it exceeds 1.2, long-term strength developability may be impaired. The particle size of the alkali metal aluminate is preferably equal to or greater than calcium aluminate or gypsum in view of improving fastness.

The usage-amount of alkali metal aluminate is 1.5-10 parts in 100 parts of fasteners, Preferably it is 1.5-5 parts, More preferably, it is 2-5 parts. If it is less than 1.5 parts, excellent quickness may not be obtained, and if it exceeds 10 parts, quickness may be saturated and strength developability may be impaired.

In addition to these materials, the fastener of the present invention may contain alkali metal carbonate, alkali metal sulfate, quicklime, calcined lime, aluminum hydroxide and the like.

Cement used in the present invention is not particularly limited, 3CaO one of the minerals that make up the cement and _{Al 2 O 3 (C 3 A} ) content is preferably, 5 parts or more of 100 parts of cement, particularly preferably 6 It is -15 denial. If it is less than 5 parts, sufficient fastness may not be obtained. As the cement, blast furnace cement is also preferable, and among them, blast furnace cement containing 5 to 70 parts of fine blast furnace slag powder is particularly preferable among 100 parts of cement. The blast furnace slag fine powder is a fine powder composed mainly of aluminosilicate obtained by pulverizing, pulverizing and classifying the molten slag produced by quenching by-products when making pig iron from steel stone in the blast furnace with water or air. It is preferable to be prescribed in. The blast furnace slag contains CaO, SiO ₂ , Al ₂ O ₃ , MgO and the like, and CaO / SiO ₂ = 1.15 to 1.25, (CaO + MgO) / (SiO ₂ + Al ₂ O ₃ ) = 0.90 to 1.05, Al ₂ O It is preferable that ₃ is less than 15 parts and MgO is less than 5 parts. As for the particle size of blast furnace slag, 3000 cm <2> / g or more is preferable at a brain value from a viewpoint of intensity | strength expression. Cement mixed with blast furnace slag is not particularly limited.

In the present invention, additives such as pH adjusters, dispersants, stabilizers, cryoprotectants, water-soluble accelerators, AE agents, water reducing agents, AE water reducing agents, coagulation retardants, thickeners, fibers, and fine powders do not substantially impair the object of the present invention. It is possible to use together in the range which does not.

As for the usage-amount of the quickening agent of this invention, 5-15 parts are preferable with respect to 100 parts of cement, Especially 6-12 parts are preferable. If the amount of use is less than 5 parts, excellent quenchability may not be obtained. If the amount is more than 15 parts, the construction cost is large, which is not preferable. It is not necessary to add all of the structural components with respect to cement or concrete, and the fastener of this invention may divide and add a structural component as needed. For example, gypsum can be added in two portions, calcium aluminate and alkali metal aluminate. In this case, first, gypsum is added to the cement or concrete, and then calcium aluminate and alkali metal aluminate are more preferable because they improve quickness.

It is preferable to use 3-10 parts with respect to 100 parts of cement which consists of calcium aluminate and alkali metal aluminate. If the amount of use is less than 3 parts, quickness may not be obtained. If the amount is more than 10 parts, the cost of construction becomes large, which is not preferable. Further, gypsum is added from 3 to 10, and likewise, more preferably from 4 to 7 parts relative to 100 parts of the cement, the amount of SO ₃ in the cement is preferably 3-7 and more preferably 2 to 10 parts denied.

In the present invention, the amount of the cement used in the sprayed concrete is preferably 330 to 500 kg / m 3, and the water / cement ratio is preferably 40 to 65%. In addition, the slump and the flow value of the sprayed concrete are not particularly limited.

As a spraying method in this invention, the wet spraying method and the dry spraying method which are generally performed can be used. Examples of the wet method include a method of mixing the fastener of the present invention with sprayed cement concrete, and the dry spray method includes a method of mixing water and the fastener of the present invention with a composition of cement, sand, and gravel. And a method of mixing water with cement, sand, gravel, and the fastener of the present invention.

As a method of mixing the fastener of the present invention with sprayed concrete, it is preferable to mix immediately before spraying using a Y-shaped tube or the like. Specifically, the fastener of the present invention is added to the conveyed concrete, or the fastener component of the present invention is divided into two, for example, gypsum, calcium aluminate and alkali metal aluminate, as described above. There is a method of adding. In the present invention, the time from the addition of the fastener to the injection of the sprayed concrete is preferably 10 seconds or less, more preferably 2 seconds or less. The fastener of the present invention can further reduce dust by using a mixture of water and slurry. In the case of slurrying, it is possible to improve the slurry characteristics by using less than 3% of oxycarboxylic acids as the fastener. Slurryed fasteners can be mixed with sprayed concrete using Y-shaped tubes, or mixed with shower tubes.

Moreover, it is also possible to spray the sprayed concrete which is the spraying material in this invention in the place where the frame frame | skeleton is arrange | positioned in addition to the acid of a tunnel directly to the acid of a normal surface. Here, the frame skeleton is fixed to the wall by combining a wire mesh, rebar, steel frame, etc., and sprays the present sprayed concrete on the frame skeleton to form a reinforcing steel-containing concrete frame.

Hereinafter, the present invention will be described in more detail based on examples. In addition, the meaning of the following symbol is as follows, respectively.

C: Cement, S: Sand, W: Water, C ₃ S: Alite, C ₂ S: Bilite, C ₄ AF: Calcium Alumino Ferrite, C ₃ A: Tricalcium Aluminate

Example 1-1

Mortar using C / S (cement / sand ratio) = 1/3 and W / C (water / cement ratio) = 50% mortar using a polycarboxylic acid-based water reducing agent in C × 1.0% was used.

In 100 parts of fasteners, 10 parts of fasteners containing 55 parts of calcium aluminate, 40 parts of gypsum and 5 parts of alkali metal aluminate shown in Table 1 were used with respect to 100 parts of cement, and the proctor penetration resistance was measured. The test environment temperature is 20 ° C.

The results are written together in Table 1-1.

<Material used>

Cement: C ₃ S = 54%, C ₂ S = 21%, SO ₃ = 3%, C ₄ AF = 9%, C ₃ A = 9%

Calcium Aluminate:

  A compound obtained by mixing a calcia raw material and an alumina raw material at a predetermined ratio, melting at 1600 ° C. in an electric furnace, and controlling various cooling rates to synthesize various kinds of vitrification rates (%), brain 10000 cm 2 / g

Gypsum: Natural anhydrous gypsum, brain 5000㎠ / g

Alkali Metal Aluminate:

Sodium aluminate, Na ₂ O / Al ₂ O ₃ molar ratio 1.1, brain 6000 cm 2 / g

Water: Tap Water

Water reducing agent: polycarboxylic acid type water reducing agent

Sand: Himekawa River, Niigata Prefecture, density 2.62 g / cm 3

<Measurement method>

Procutter penetration resistance (coagulation property): Complies with ASTM C 403 "Method for testing the setting time of concrete by penetration resistance". The coagulation properties of 1 minute and 3 minutes after mixing the mortar and the fastener were evaluated.

From Table 1-1, the rapid setting agent of Experiment No.1-1-3 to Experiment No.1-1-6 using calcium aluminate having a CaO / Al ₂ O ₃ molar ratio of 2.0 to 2.3 and a vitrification rate of 80% or more. It can be seen that the protruder penetration resistance is large and the fastening property is excellent. As in Experiment No.1-1-2 and 1-1-1, as the CaO / Al ₂ O ₃ molar ratio of calcium aluminate is lowered to 1.7 and 1.6, the proctor penetration resistance becomes smaller, and therefore, the quickness becomes worse. The molar ratio of CaO / Al ₂ O ₃ is set to 1.9 or more. Calcium aluminate having a CaO / Al ₂ O ₃ molar ratio of up to 3.0 can be used, but when CaO / Al ₂ O ₃ molar ratio is 2.6 or more, as in Experiment Nos. Since becomes small, Preferably you may be up to 2.5.

As in experiment No.1-1-7 and 1-1-10, when the vitrification rate of calcium aluminate is 75% or less, the proctor penetration resistance becomes small and the fastening property deteriorates, so the vitrification rate is 80% or more. do.

Example 1-2

Among 100 parts of fasteners, a fastener comprising 55 parts of calcium aluminate shown in Experiment No.1-1-4, 40 parts of gypsum, and 5 parts of alkali metal aluminate shown in Table 2 was used with respect to 100 parts of cement. The test was carried out in the same manner as in Example 1-1 except that the protruder penetration resistance was measured using the negative electrode.

The results are written together in Table 1-2.

<Material used>

Alkali Metal Aluminate:

Synthesized using NaOH and Al (OH) ₃ of the 1st reagent, Brain 6000cm 2 / g

From Table _{1-2, R 2 O / Al 2} O 3 mole ratio experiment with an alkaline metal aluminate (R = alkali metal) is 0.8~1.2 No.1-2-2~1-2-5, 1- It can be seen that the fastening agent of 1-4 has a large proctor penetration resistance value and is excellent in fastening property.

Example 1-3

In 100 parts of fasteners, the calcium aluminate, gypsum, and alkali metal aluminate shown in Experiment No.1-1-4 were used as the amounts (parts) shown in Table 1-3, respectively. The test was carried out in the same manner as in Example 1-1 except that 10 parts were used and the proctor penetration resistance and the 24 hour compressive strength were measured.

The results are written together in Table 1-3.

<Test method>

Compressive strength: Tested with 4 × 4 × 16 cm prismatic specimens.

From Table 1-3, the fastener whose usage-amount of calcium aluminate, gypsum, and alkali metal aluminate exists in the range of this invention is Experiment No.1-3-2, 1-3-3, 1-1-4. , 1-3-6, and 1-3-11, it is understood that even when the alkali metal aluminate is less than 2 to 5 parts in 100 parts of the fastener, the proctor penetration resistance is large and the fastening property is excellent. As in experiment No. 1-3-9 and 1-3-8, when the amount of alkali metal aluminate used decreases, the fastness deteriorates, so in 100 parts of the fastener, the alkali metal aluminate is 1.5 parts (experimental) No.1-3-10) or more.

As in Experiment No. 1-3-13 and 1-3-14, when the alkali metal aluminate is increased in excess of 10 parts (Experiment No. 1-3-12) in 100 parts of the fastener, the proctor penetration resistance value, 24 Since time intensity | strength becomes small, quickness is saturated, and strength expressability is impaired, alkali metal aluminate shall be 10 parts or less.

When the amount of gypsum used or the amount of calcium aluminate used is small, as in Experiment No. 1-3-1 and 1-3-7, the injector penetration resistance decreases, and Experiment No. 1-3-4, 1 If the amount of gypsum used or the amount of calcium aluminate used is large, such as -3-5 and 1-3-14, the strength decreases for 24 hours. Therefore, in 100 parts of the fastener, gypsum is 30 to 60 parts, calcium It is preferable to make aluminate into 30-60 parts.

Example 1-4

Among 100 parts of fasteners, a fastener comprising 55 parts of calcium aluminate, 40 parts of gypsum and 5 parts of alkali metal aluminate shown in Experiment No.1-1-4 is shown in Table 1-4 for 100 parts of cement. It tested like Example 1-1 except having measured the promoter penetration resistance using the quantity shown.

The results are written together in Table 1-4.

From Table 1-4, in order to increase the prompter penetration resistance and exhibit the fastening property, as shown in Experiment Nos. 1-4-2 to 1-4-4 and 1-1-4, the fastening agent was applied to 100 parts of cement. It can be seen that it is preferable to add 5% or more.

Example 1-5

Among 100 parts of fasteners, a fastener comprising 55 parts of calcium aluminate, 40 parts of gypsum and 5 parts of alkali metal aluminate shown in Experiment No.1-1-4 was added to 100 parts of cement of the kind shown in Table 5. The test was carried out in the same manner as in Example 1-1, except that 10 parts were used and the proctor penetration resistance was measured.

The results are written together in Table 1-5.

<Material used>

Cement (A): C ₃ S = 58%, C ₂ S = 23%, SO ₃ = 3%, C ₄ AF = 9%, C ₃ A = 3%

Cement (B): C ₃ S = 56%, C ₂ S = 23%, SO ₃ = 3%, C ₄ AF = 9%, C ₃ A = 5%

Cement (C): C ₃ S = 54%, C ₂ S = 21%, SO ₃ = 3%, C ₄ AF = 9%, C ₃ A = 9%

Cement (D): C ₃ S = 51%, C ₂ S = 21%, SO ₃ = 3%, C ₄ AF = 9%, C ₃ A = 12%

It can be seen from Table 1-5 that when C ₃ A = 5% or more of cements (B) to (D), the spraying material has a large protruder penetration resistance and excellent in quickness.

Example 2-1

Mortar using C / S (cement / sand ratio) = 1/3 and W / C (water / cement ratio) = 50% mortar using a polycarboxylic acid-based water reducing agent in C × 1.0% was used.

In 100 parts of fasteners, 10 parts of fasteners containing 55 parts of calcium aluminate, 40 parts of gypsum, and 5 parts of alkali metal aluminate shown in Table 2-1 were used with respect to 100 parts of cement, and the proctor penetration resistance was measured. . The test environment temperature is 20 ° C.

The results are written together in Table 2-1.

<Material used>

cement:

Commercially available commercially available Portland cement and blast furnace slag (Shin-Nitetsu Koro Co., Ltd., brain 4000 cm 2 / g) in a weight ratio of 55:45

Calcium Aluminate:

  A compound obtained by mixing a calcia raw material and an alumina raw material at a predetermined ratio and melting at 1600 ° C. in an electric furnace, and having various vitrification rates by controlling the cooling rate, and the brain 10000 cm 2 / g

Gypsum: Natural anhydrous gypsum, brain 5000㎠ / g

Alkali Metal Aluminate:

Sodium aluminate, Na ₂ O / Al ₂ O ₃ molar ratio 1.1, brain 6000 cm 2 / g

Water: Tap Water

Water reducing agent: polycarboxylic acid type water reducing agent

Sand: Himekawa River, Niigata Prefecture, density 2.62 g / cm 3

<Measurement method>

Proctor penetration resistance (coagulation property): It evaluated according to Example 1-1.

From Table 2-1, the caking agent of Experiment No. 2-1-3 to 2-1-6 using calcium aluminate having a CaO / Al ₂ O ₃ molar ratio of 2.0 to 2.3 and a vitrification rate of 80% or more, is a It can be seen that the penetration resistance is large and the fastening property is excellent. As in Experiment No. 2-1-2 and 2-1-1, as the CaO / Al ₂ O ₃ molar ratio of calcium aluminate is lowered to 1.7 and 1.6, the protruder penetration resistance becomes smaller, and therefore, the quickness becomes worse. The molar ratio of CaO / Al ₂ O ₃ is set to 1.9 or more. Calcium aluminate having a CaO / Al ₂ O ₃ molar ratio of up to 3.0 can be used, but when CaO / Al ₂ O ₃ molar ratio is 2.6 or more, as in Experiment Nos. Since becomes small, Preferably you may be up to 2.5.

As in experiment No. 2-1-7 and 2-1-10, when the vitrification rate of calcium aluminate is 75% or less, the proctor penetration resistance becomes small and the fastening property deteriorates, so the vitrification rate is 80% or more. do.

Example 2-2

Among 100 parts of fasteners, a fastener comprising 55 parts of calcium aluminate shown in Experiment No. 2-1-4, 40 parts of gypsum, and 5 parts of alkali metal aluminate shown in Table 2 was used with respect to 100 parts of cement. The test was carried out in the same manner as in Example 2-1 except that the protruder penetration resistance was measured using the negative electrode.

The results are written together in Table 2-2.

<Material used>

Alkali Metal Aluminate:

Synthesized using NaOH and Al (OH) ₃ of the 1st reagent, Brain 6000cm 2 / g

From Table 2-2, Experiment No. 2-2-2 to 2-2-5, 2- using alkali metal aluminate having a R ₂ O / Al ₂ O ₃ molar ratio (R is an alkali metal) of 0.8 to 1.2 It can be seen that the fastening agent of 1-4 has a large proctor penetration resistance value and is excellent in fastening property.

Example 2-3

Of 100 parts of fasteners, the amounts (parts) of calcium aluminate, gypsum, and alkali metal aluminate shown in Experiment No. 2-1-4 are shown in Table 3, respectively, and this fastener was added to 100 parts of cement. The test was carried out in the same manner as in Example 2-1, except that 10 parts were used, and the proctor penetration resistance and the 24-hour compressive strength were measured.

The results are written together in Table 2-3.

<Test method>

Compressive strength: tested with 4 × 4 × 16 cm prismatic specimens.

From Table 2-3, the fastener whose usage-amount of calcium aluminate, gypsum, and alkali metal aluminate exists in the range of this invention is Experiment No. 2-3-2, 2-3-3, 2-1-4. , 2-3-6 and 2-3-11, even if the alkali metal aluminate is less than 2 to 5 parts in 100 parts of the fastener, it can be seen that the proctor penetration resistance is large and the fastening property is excellent. As in the case of experiment No. 2-3-9 and 2-3-8, when the usage-amount of alkali metal aluminate becomes smaller, quickness worsens, Alkali metal aluminate of 1.5 parts ( Experiment No. 2-3-10) or more. As in Experiment No. 2-3-13 and 2-3-14, in 100 parts of the fastener, when the alkali metal aluminate is increased to more than 10 parts (Experiment No. 2-3-12), the promoter penetration resistance is small. Since the quickness is impaired, alkali metal aluminate is 10 parts or less.

When the amount of gypsum used or the amount of calcium aluminate used is small, as in Experiment No. 2-3-1 and 2-3-7, the injector penetration resistance becomes small, and Experiment No. 2-3-4, 2 If the amount of gypsum used or the amount of calcium aluminate used is large, as in -3-5, since strength decreases for 24 hours, among 100 parts of fasteners, 30 to 60 parts of gypsum and 30 to 60 of calcium aluminate are used. It is preferable to make it negative.

Example 2-4

Among 100 parts of fasteners, a fastener comprising 55 parts of calcium aluminate, 40 parts of gypsum and 5 parts of alkali metal aluminate shown in Experiment No. 2-1-4 is given in Table 2-4 for 100 parts of cement. It tested like Example 2-1 except having measured the promoter penetration resistance using the quantity shown.

The results are written together in Table 2-4.

From Table 2-4, in order to exhibit the fastening property by increasing the protruder penetration resistance value, as shown in Experiment Nos. 2-4-2 to 2-4-4 and 2-1-4, the fastening agent was applied to 100 parts of cement. It can be seen that it is preferable to add 5% or more.

Example 2-5

Among 100 parts of fasteners, a fastener comprising 55 parts of calcium aluminate, 40 parts of gypsum, and 5 parts of alkali metal aluminate shown in Experiment No. 2-1-4 was added to 100 parts of cement of the kind shown in Table 10. The test was carried out in the same manner as in Example 2-1, except that 10 parts were used and the proctor penetration resistance was measured.

The results are written together in Table 2-5.

<Material used>

Cement (A): A mixture of commercially available commercial portland cement and blast furnace slag (manufactured by Shinnitetsu Koro Co., Ltd., brain 4000 cm 2 / g) in a weight ratio of 95: 5.

Cement (B): A mixture of commercially available commercially available Portland cement and blast furnace slag (manufactured by Shinnitetsu Koro Co., Ltd., brain 4000 cm2 / g) in a weight ratio of 80:20.

Cement (C): A mixture of commercially available commercially available Portland cement and blast furnace slag (manufactured by Shinnitetsu Koro Co., Ltd., brain 4000 cm 2 / g) in a weight ratio of 55:45.

Cement (D): A mixture of commercially available commercially available Portland cement and blast furnace slag (manufactured by Shinnitetsu Koro Co., Ltd., brain 4000 cm 2 / g) in a weight ratio of 30:70.

From Table 2-5, when blast furnace slag content increases, it turns out that the pronger penetration resistance value in 3 minutes is large and it is excellent in quickness.

Example 3-1

Mortar using 1.0 parts of polycarboxylic acid-based water reducing agents with respect to 100 parts of cement was used for mortar of C / S (cement / sand ratio) = 1/3 and W / C (water / cement ratio) = 50%. As a fastener component, it is used in the ratio of 55 parts of calcium aluminates shown in Table 3-1, 5 parts of alkali metal aluminates, and 40 parts of gypsum, The gypsum was mixed in 4 parts with respect to 100 parts of cement at the time of mortar preparation, and calcium A mixture of aluminate and alkali metal aluminate was used in the prepared mortar for 6 parts with respect to 100 parts of cement to measure the proctor penetration resistance. The test environment temperature is 20 ° C. The results are written together in Table 3-1.

<Material used>

Cement: C ₃ S = 54%, C ₂ S = 21%, SO ₃ = 3%, C ₄ AF = 9%, C ₃ A = 9%

Calcium Aluminate:

  A compound obtained by mixing a calcia raw material and an alumina raw material at a predetermined ratio, melting at 1600 ° C. in an electric furnace, and controlling various cooling rates to synthesize various kinds of vitrification rates (%), brain 10000 cm 2 / g

Gypsum: Natural anhydrous gypsum, brain 5000㎠ / g

Alkali Metal Aluminate:

Sodium aluminate, Na ₂ O / Al ₂ O ₃ molar ratio 1.1, brain 6000 cm 2 / g

Water: Tap Water

Water reducing agent: polycarboxylic acid type water reducing agent

Sand: Himekawa River, Niigata Prefecture, density 2.62 g / cm 3

<Measurement method>

Proctor penetration resistance (coagulation property): It evaluated according to Example 1-1.

Example 3-2

As a quickening component, it uses at the ratio of 5 parts of alkali metal aluminates shown in Table 3-2, 55 parts of calcium aluminates used by experiment No.3-1-4, and 40 parts of gypsum, and cements gypsum before mortar preparation. The test was carried out in the same manner as in Example 3-1, except that 4 parts of 100 parts were mixed, and 6 parts of a fastener containing alkali metal aluminate and calcium aluminate were used for 100 parts of cement to measure the protruder penetration resistance. It was. The results are written together in Table 3-2.

<Material used>

Aluminate: Synthesized using NaOH and Al (OH) ₃ of the primary reagent, Brain 6000 cm 2 / g

Example 3-3

As the fastener component, calcium aluminate, gypsum, and alkali metal aluminate shown in Experiment No. 3-1-4 are used in the proportions (parts) shown in Table 3-3, respectively, and these fastener components are cement 100 Ten parts were used for the part. However, gypsum was mixed with mortar in advance and prepared. The test was carried out in the same manner as in Example 3-1 except that the proctor penetration resistance and the 24-hour compressive strength were measured. The results are written together in Table 3-3.

<Test method>

Compressive strength: tested with 4 × 4 × 16 cm prismatic specimens.

Example 3-4

As a fastener component, it is used by the ratio of 55 parts of calcium aluminates, 40 parts of gypsum, and 5 parts of alkali metal aluminates shown in Experiment No.3-1-4, and prepares mortar using C * 4 parts of gypsum beforehand. The test was carried out in the same manner as in Example 3-1, except that C x 6 parts of a fastener made of calcium aluminate and alkali metal aluminate was used to measure the protruder penetration resistance. The results are written together in Table 3-4.

<Material used>

Cement (A): C ₃ S = 58%, C ₂ S = 23%, SO ₃ = 3%, C ₄ AF = 9%, C ₃ A = 3%

Cement (B): C ₃ S = 56%, C ₂ S = 23%, SO ₃ = 3%, C ₄ AF = 9%, C ₃ A = 5%

Cement (C): C ₃ S = 54%, C ₂ S = 21%, SO ₃ = 3%, C ₄ AF = 9%, C ₃ A = 9%

Cement (D): C ₃ S = 51%, C ₂ S = 21%, SO ₃ = 3%, C ₄ AF = 9%, C ₃ A = 12%

It is also possible to spray the injection concrete which is the injection material in this invention to the place which arrange | positioned the frame frame | skeleton directly in the acid of a normal surface besides the acid of a tunnel.

In addition, all the content of the JP Patent application 2004-177507, the claim, drawing, and the abstract for which it applied on June 15, 2004 is referred here, and it introduces as a content of this specification.

Claims (16)

As a jetting accelerator containing calcium aluminate, gypsum and alkali metal aluminate, the calcium aluminate has a vitrification rate of 80% or more, a CaO / Al ₂ O ₃ molar ratio of 1.9 to 3.0, and the alkali Content of the metal aluminate salt is 1.5-10 denier in 100 parts of spraying accelerators, The spraying agent for injections characterized by the above-mentioned. The method of claim 1, The calcium aluminate has a vitrification rate of 90% or more and a CaO / Al ₂ O ₃ molar ratio of 2.0 to 2.3. The method according to claim 1 or 2, A molar ratio of R ₂ O / Al ₂ O ₃ (R is an alkali metal) in the alkali metal aluminate salt is 0.8 to 1.2, wherein the spraying agent for injection is used. The method according to claim 1 or 2, Each content in 100 parts of spray fasteners is 30-60 parts of calcium aluminates, 30-60 parts of gypsum, and 1.5-10 deniers of alkali metal aluminates, The spraying agent for injections characterized by the above-mentioned. delete An injection material comprising the jetting agent for injection according to claim 1 or 2 and cement having a content of 3CaO.Al ₂ O ₃ of 5 parts or more in 100 parts of cement. An injection material comprising the jetting agent for injection according to claim 1 or 2 and blast furnace cement. The spraying material according to claim 1 or 2, and the blast furnace slag content in 100 parts of cement contains 5-70 denier cement, The spraying material characterized by the above-mentioned. The spraying method containing the spraying material of Claim 6 is sprayed directly in the tunnel, the mountain of the surface, or the place which frame frame is arrange | positioned, The spraying method characterized by the above-mentioned. When calcium aluminate having a vitrification rate of 80% or more and a CaO / Al ₂ O ₃ molar ratio of 1.9 to 3.0, an alkali metal aluminate, and gypsum are added to the sprayed concrete as a fastener component, the gypsum is first A spraying method characterized by spraying by adding calcium aluminate and alkali metal aluminate. The method of claim 10, A molar ratio (R is an alkali metal) of R ₂ O / Al ₂ O _{3 in} the alkali metal aluminate is 0.8 to 1.2. The method of claim 10 or 11, The spraying method characterized by the use rate of a quickener component being 30-60 parts of calcium aluminates, 30-60 parts of gypsum, and 1-15 deniers of alkali metal aluminates. The method of claim 10 or 11, The sprayed concrete includes a cement containing 5 parts or more of 3CaO.Al ₂ O ₃ in 100 parts of cement. The method of claim 10 or 11, Spraying method characterized in that the sprayed concrete contains blast furnace cement. The method of claim 10 or 11, The spraying concrete method includes a cement containing 5 to 70 parts of blast furnace slag in 100 parts of cement. The method of claim 10 or 11, A spraying method, which is sprayed directly on a tunnel or a local hill, or a place where a frame skeleton is arranged.