JPH083555A - Injection chemical composition for stabilizing the ground and artificial structure and stabilized and reinforced water-stopping engineering method using the same - Google Patents

Abstract

PURPOSE:To provide a composition for stabilizing the ground or artificial structure, which comprises an aqueous alkali silicate, an organic polyisocyanate and a specific tertiary amine, thus is useful as a water stopper or a solidification stabilizer because it is excellent in the safety, stabilizing and reinforcing effect, durability, solidification strength and the like. CONSTITUTION:This composition comprises (A) an aqueous alkali silicate, (B) an organic polyisocyanate, preferably terminal isocyanate group-containing urethane prepolymer, (C) a tertiary amine of the formula (R is a cycloalkyl or an aralkyl), for example, N,N-dimethyl-cyclohexylamine or N,N- dimethylbenzylamine, and, preferably (D) a polyol ingredient. The ingredient A is in 20-40wt.% on the solid basis, the ingredient B is used at a weight ratio of 20/100-100/20 A/B, the ingredient C is preferably used in an amount of 0.5-15 pts.wt. per 100 pts.wt. of the ingredient B. This composition is applied to base rock or ground by boring them, inserting pouring bolts into the holes and pouring the composition into them.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an injectable liquid chemical composition for stabilizing the ground, artificial structures, etc., and a stable reinforced waterproofing method using the same. More specifically, consolidation and stabilization of rocks with crush zones and unstable soft ground, water leakage, water stoppage and void filling of rocks and ground with spring water, cracks and voids in artificial structures such as concrete. The present invention relates to a method for strengthening, sealing, and stopping water in an existing tunnel or the like, and a highly safe injectable chemical liquid composition used therefor.

[0002]

2. Description of the Related Art Conventionally, inorganic or organic grout has been injected as one of the methods for strengthening unstable rocks and grounds and for filling cracks and voids in artificial structures, and some effects have been achieved.

However, a detailed check of these methods has not always yielded satisfactory results. For example, cement milk, which is commonly used, is a suspension, so its permeability to cracks such as rocks and man-made structures and ground layers such as gravel is poor, and its solidification rate and strength development are slow. The purpose of early and stable strengthening of unstable ground during tunnel excavation and underground ground excavation, which is required to solidify in time and develop strength, cannot be achieved. In addition, the injected cement milk is diluted and washed away when water is leaked or leaked. Also, the water-based two-liquid system grout, which is a typical inorganic grout, has a low solidified body strength of about 3 to 10 kg / cm ² , and when the solidified body comes into contact with water, a change with time occurs and Na ₂ O
There is a problem in that the main components such as SiO ₂ and SiO ₂ are leached out, resulting in alkali contamination and a significant decrease in strength.

On the other hand, organic grouts such as urea also have problems such as insufficient consolidation strength and elution of hardening components and auxiliary components such as sulfuric acid and formalin. Also,
JP-B-63-63687, 63-63688, 63-63688
JP, JP 63-7413 JP, 63-7490 JP, JP
63-7491, 63-8477, 63-35913, etc. describe a method for consolidating rock mass by injecting a fast-curing rigid urethane foam system containing polyol and polyisocyanate as main components. However, according to these construction methods,
Although the solidifying effect can be expected, the raw material is extremely expensive and exhibits flammability, so that improvement in economic efficiency and safety is required.

Further, JP-A-61-9482 and JP-A-55-1
No. 60079 describes an injectable liquid composition prepared by using polyisocyanate and water glass (sodium silicate solution), and blending a specific phenolic tertiary amine as a polyisocyanate trimerization catalyst on the water glass side. Has been done.
However, this composition has a disadvantage that the phenol-based tertiary amine is poorly compatible with polyisocyanate and water glass, so that when they are mixed, they are immediately separated. For example, an expensive agent such as silicone polyol is required in order to increase the compatibility, and there is a problem that the cost increases. Further, when a phenolic tertiary amine is used, formalin is generated due to the heat of reaction, which is not desirable for the health of workers on site, and it is not desirable that the phenol derivative is mixed into groundwater or river. Further, in the case where the injectable liquid chemical composition used is one of the above-mentioned specific phenolic tertiary amines, which is water-insoluble and has a property of scratching the skin remarkably, if it is adhered to the skin or clothes, it is thoroughly washed with water. Since it cannot be removed and is likely to remain, such an injectable liquid composition poses a serious problem in terms of safety.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made by paying attention to the above-mentioned prior art, and it has been difficult to inject a highly safe injectable drug solution composition containing a specific component to form it conventionally. By forming a foamed inorganic-organic composite consolidate, it has a large consolidation strength, is flame retardant, and has excellent safety, stability-enhancing effect, durability, pouring workability, and economic efficiency. The purpose of the present invention is to strengthen the stability of the artificial structure or to stop water.

[0007]

That is, the present invention is
(A) Alkaline silicate aqueous solution, (B) Organic polyisocyanate compound and (C) General formula (I):

[0008]

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The first aspect of the present invention is a stabilizing injectable liquid composition for a ground or artificial structure comprising a tertiary amine represented by the formula (wherein R represents a cycloalkyl group or an aralkyl group). (D) in the injectable liquid composition for medical use
A second invention is to contain a polyol component,
A plurality of holes are formed at a predetermined interval in the rock or the ground, a hollow injection bolt is inserted into the hole, and the stabilizing injection chemical liquid composition is injected into the rock or the ground through the opening of the bolt, and then solidified. A third aspect of the present invention is a stable strengthening and waterproofing method for rock or ground, which is characterized in that it is tied or sealed. Further, an injection pipe is inserted into an artificial structure, and the stabilizing injection liquid chemical composition is provided through the injection pipe. A fourth aspect of the present invention is a method for stabilizing and waterproofing an artificial structure, which is characterized by injecting an object into the artificial structure and / or the back surface thereof to be solidified or sealed.

[0010]

OPERATION AND EXAMPLE As described above, the stabilizing injectable liquid composition (hereinafter referred to as injectable liquid composition) for stabilizing the ground or artificial structure of the present invention is (A) an alkali silicate aqueous solution (hereinafter, (A) component), (B) organic polyisocyanate compound (hereinafter referred to as (B) component) and (C) general formula (I):

[0011]

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(In the formula, R represents a cycloalkyl group or an aralkyl group)
(C) component).

The solidification reaction of the injectable liquid composition of the present invention is not clear because it is extremely complicated, but probably (A).
When the component and the component (B) are mixed, the silanol group in the component (A) reacts with the isocyanate group in the component (B) to form a silicic acid anhydride-urethane complex, and at the same time (B) While the component reacts with water to generate carbon dioxide, a multimer or a silicic acid anhydride-urea cross-linked complex is formed by a urea bond, and part of carbon dioxide produced as a by-product is dissolved in the component (A).
It is presumed that it is based on gelling the alkali silicate in the component (A) to form a silicic acid anhydride gel. Furthermore, when the (D) polyol component (hereinafter referred to as the (D) component) is present, the hydroxyl group in the (D) component reacts with the (B) component to form a urethane resin. Presumed to be based.

Further, carbon dioxide gas generated by the reaction of the component (B) with water and the reaction of the component (A) with the component (B) or the reaction between the component (A) and the component (D) with the component (B). Due to the steam evaporated by the heat of reaction generated during the reaction, the silicic acid anhydride-urethane composite forms a foamed flame-retardant solidified body and increases its volume. At this time,
Foaming occurs, but the foaming pressure at the time of foaming facilitates the silicic acid anhydride-urethane composite to enter into the spaces such as earth and sand, rocks, bricks, coal, and artificial structures.

The injectable liquid composition of the present invention will be described below.

The aqueous solution of alkali silicate which is the component (A) used in the present invention is, as described above, mainly due to the reaction between the silanol group and the isocyanate group of the component (B) which will be described later. It is a component that forms the body.

Examples of the component (A) include those containing an aqueous solution such as potassium silicate or sodium silicate represented by the formula: Na ₂ O.xSiO ₂ as a main component.
Such sodium silicate has, for example, a molar ratio of Na ₂ O and SiO _{2 of} about 3: 1 to 1: 4 (in the above formula, x is about 0.3 to 4).

The solid content concentration of the component (A) is preferably adjusted to 10% by weight or more, particularly 20% by weight or more, 70% or less, and 40% by weight or less.

The organic polyisocyanate compound which is the component (B) used in the present invention includes the above-mentioned components (A) and (C).
The component is a component that uniformly disperses the component or the component (A), the component (C) and, if necessary, the component (D) described below, and emulsifies it to make the reaction uniform.

Examples of the component (B) include diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate (polymeric MDI), liquid diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, trimethylene xylylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, Examples thereof include a single polyisocyanate such as hydrogenated diphenylmethane diisocyanate or a mixture of two or more thereof, and a dimer or trimer obtained by adding a catalyst to the polyisocyanate.

In addition to the above, monools such as methanol, ethanol, propanol, butanol, octanol and lauryl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,3 -Butanediol,
1,4-butanediol, 1,6-hexanediol and other diols, glycerin, trimethylolpropane,
Polyols such as pentaerythritol: In addition, monoethanolamine, diethanolamine, triethanolamine, diglycerin, sorbitol, sucrose, etc., alone or in combination, ethylene oxide, propylene oxide, butylene oxide, styrene oxide and other alkylene oxides, alone or in combination, Monool or polyol obtained by addition polymerization by a known method, and the polyisocyanate, for example, the equivalent ratio of NCO group and OH group (NCO group / OH group) is 1.5 or more, preferably 2.0 or more, Also 100 or less, preferably 50
A urethane prepolymer containing a terminal isocyanate group, which is obtained by reacting by a known method as described below, can also be suitably used as the component (B).

Among these (B) components, the consolidation strength,
From the viewpoints of safety and hygiene and economy, urethane prepolymers containing terminal isocyanate groups are preferable, and those that have a very low volatility at so-called handling environmental temperature, are liquid, and have a consolidation strength and economy preferable.

The blending amount of the component (B) differs depending on, for example, the molar ratio of Na ₂ O and SiO ₂ in the component (A), and therefore cannot be determined unconditionally. If the compounding amount is too large, the cost of the injectable liquid composition becomes high, which is uneconomical, and it tends to be very difficult to control the compounding ratio by the proportional infusion pump. ) Component and (B) component in a mixing ratio ((A) component / (B) component) of 10 by weight.
/ 100 or more, especially 20/100 or more, and when the amount of component (B) is too small, the injectable liquid composition is insufficiently solidified and becomes uncured. However, even if it is hardened, its hardness is low, and it tends to become brittle and unusable for practical use. Therefore, the mixing ratio of the component (A) and the component (B) is 100 / by weight.
It is preferable to adjust to 10 or less, especially 100/20 or less.

The component (B) is excellent in reactivity and solidification with the component (A), but its permeability is relatively high, so that it is not sufficiently permeated into the rock or the ground. Toluene and xylene to improve fluidity and permeability,
Organic solvents such as 1,1,1-trichloroethane, methylene chloride and trichlorofluoromethane are used as diluents. However, since these organic solvents are volatile and may be released after solidification and damage the environment,
It is preferable not to use it as much as possible.

Then, as a diluent for the component (B),
Even if mixed with the ingredients, it does not react with the isocyanate group,
The component (B) has excellent storage stability and viscosity reduction, while
When mixed and contacted with the component (A), it is preferable to add a reactive diluent which reacts and cures immediately as described above and has a small effect on the environment.

The reactive diluent has a function of diluting the component (B) to reduce the viscosity at the time of injection, and
When it comes into contact with the component (A), it undergoes alkaline hydrolysis, reacts with the component (A) and / or the component (B), and actively participates in the curing reaction between the component (A) and the component (B). , Stronger silicic anhydride-urethane complex or silicic acid anhydride-urea cross-linked complex, to form an inorganic-organic composite solid body mainly composed of reticulated silicic acid anhydride gel, and the foaming property at the time of reaction solidification It is preferably an ester or an ether that can be improved.

Typical examples of the reactive diluents include diesters of low molecular weight dibasic acids, acetic acid esters of monohydric or polyhydric alcohols, alkylene carbonates, ethers, cyclic esters and acid anhydrides. , (Meth) acrylic acid ester and the like.

Examples of low molecular weight dibasic acid diesters include dimethyl esters such as glutaric acid, succinic acid, adipic acid, malonic acid, oxalic acid and pimelic acid, and dialkyl esters such as diethyl ester.

Examples of acetic acid esters of monohydric or polyhydric alcohols include acetates of glycol ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol methyl ether, ethyl carbitol and butyl carbitol; 3-methoxybutyl. Alcohols, acetates of alkoxyalkyl alcohols such as 3-methyl-3-methoxybutyl alcohol; diacetates of glycols such as ethylene glycol, diethylene glycol and triethylene glycol.

Examples of the alkylene carbonates include propylene carbonate and liquid ethylene carbonate dissolved in various diluents.

Examples of ethers include cyclic ethers such as tetrahydrofuran, dioxane and dehydrated castor oil.

Examples of the cyclic esters include lactones such as γ-butyl lactone and lactams such as ε-caprolactam.

Examples of the acid anhydride include propionic anhydride, butyric anhydride, maleic anhydride and the like.

Examples of the (meth) acrylic acid ester include alkyl esters of (meth) acrylic acid such as methyl, ethyl, and butyl, (meth) acrylic acid and ethylene glycol, diethylene glycol, and weight average molecular weights.
Alcohols such as polyethylene glycol, propylene glycol, dipropylene glycol having a weight average molecular weight of about 100 to 1000, polypropylene glycol having a weight average molecular weight of about 100 to 1000, and ethylene oxide or propylene oxide copolymerized diol or triol having a weight average molecular weight of about 100 to 5000. (Meth) acrylic acid ester and the like.

If the amount of the reactive diluent to be added is too small, the effect of reducing the viscosity of component (B) and the effect of improving the caking strength tend to be difficult to sufficiently develop.
It is preferable that the content of component (B) is 5 parts or more, especially 10 parts or more, relative to 100 parts (parts by weight, the same applies below). 1 for every 100 parts of component (B)
00 parts or less, preferably 50 parts or less,
Within this range, it is preferable to appropriately select the component (B) depending on the type and viscosity of the component and the purpose of use.

The tertiary amine as the component (C) used in the present invention has the general formula (I):

[0037]

[Chemical 4]

(Wherein R represents a cycloalkyl group or an aralkyl group), and such a tertiary amine is used as the above-mentioned component (A), component (B) and if necessary, and will be described later. It also acts as a catalyst for accelerating the reaction curing of the component (D). The component (C) has good compatibility with the component (A), is easily removed by washing with water even if it adheres to the skin or clothes, and has a relatively high flash point. The injectable chemical liquid composition containing is highly safe against a fire source used when performing pipe melting or the like.

Examples of the component (C) include N, N
-Dimethylcyclohexylamine, N, N-dimethylbenzylamine, N, N-dimethylphenylethylamine, N, N-dimethylmethylbenzylamine, N, N-
Examples thereof include dimethylnaphthylamine, and these can be used alone or in admixture of two or more.

In the general formula (I) representing the tertiary amine which is the component (C), R is a cycloalkyl group or an aralkyl group, but if the carbon number of these is small, the volatility becomes high, and Considering that the catalytic effect decreases when the number of carbons is large, the number of carbons of such a cycloalkyl group is 3 or more, especially 5 or more, and 15 or less,
The number of carbon atoms of the aralkyl group is preferably 7 or more, 15 or less, and more preferably 12 or less.

If the amount of the component (C) is too small, it is difficult to cure and the caking reaction is insufficient, and it tends to be difficult to obtain a clump having the desired performance. It is preferable that the amount is 0.1 part or more, especially 0.5 part or more per 100 parts of the component (B), and if it is too much, the curing reaction is too fast and the components (A) and (B) are too fast. Also, since the component (D) used as needed, which will be described later, tends to be difficult to be uniformly mixed, 20 parts or less per 100 parts of the component (B), especially
It is preferably 15 parts or less.

The injectable liquid composition of the present invention may contain a polyol component as the component (D) in addition to the components (A), (B) and (C).

The polyol component which is the component (D) used in the present invention includes, for example, the polyol which is used in the urethane prepolymer having a terminal isocyanate group which is the component (B). These are used alone or in combination of two kinds. The above can be mixed and used. The weight average molecular weight of these polyols is preferably about 40 to 20,000.

The amount of the component (D) used is the same as that of the component (B) used.
It cannot be unconditionally determined because it depends on the type of the component, etc. However, if the amount of the component (D) is too large, the solidified body obtained from the injectable liquid composition becomes too soft for practical use. Since it tends to be difficult to use it, the mixing ratio of the component (B) and the component (D) is usually
It is preferable to adjust the equivalent ratio (NCO group / OH group) of the NCO group in the component (B) to the OH group in the component (D) to be 0.5 or more, and particularly 1 or more. If the blending amount of the component (a) is too small, the solidified body tends to become brittle.
The compounding ratio with the component is 500 or less in terms of the equivalent ratio value of the NCO group in the component (B) and the OH group in the component (D).
It is preferable to adjust it to 20 or less.

Further, if necessary, the injectable liquid composition of the present invention includes an inorganic filler such as cement, blast furnace slag, gypsum, calcium carbonate, clay, aluminum hydroxide, antimony trioxide, quick lime, slaked lime, bentonite. And various surfactants, diluents, leveling agents, flame retardants, silicone foam stabilizers, antiaging agents, heat resistance imparting agents,
An antioxidant, a catalyst and the like can be blended by appropriately adjusting the blending amount.

There are no particular restrictions on the mixing order of the above-mentioned components (A), (B) and (C) and, if necessary, component (D) when preparing the injectable liquid composition of the present invention. However, if, for example, the components (A), (C) and (D) are mixed in advance and then these are mixed with the component (B), the components (A), (C)
It can be used as a binary system of a mixture of the component and the component (D) and the component (B).

The injectable liquid composition comprising the components (A), (B) and (C), which is a special injectable liquid in the present invention, and, if necessary, the component (D) is soft with many voids and cracks. Or, it is injected into unstable ground, rock, crushed zone layer, artificial structure with cracks or voids, etc., and is solidified or sealed. Is not particularly limited, and a known method can be adopted. As an example, for example, (A) component, (B) component and (C)
(A) using a proportional compounding type pump that can control the injection amount, pressure, compounding ratio, etc. of component (D)
Component (C), and mixture of component (D) and component (B) are put in separate tanks, and at predetermined locations such as bedrock (for example, a plurality of holes drilled at intervals of about 0.5 to 3 m) Through a pre-fixed static mixer, check valve, etc., with a perforated lock bolt or injection rod, into which each component in the tank was injected at 0.5
Inject at about 50 kg / cm ² · G, mix a predetermined amount of the mixture and the component (B) evenly through a static mixer, inject into a predetermined unstable rock or ground site, harden by hardening. Alternatively, there is a method of stabilizing by sealing.

In the present invention, the term "sealing" means filling a cavity or void with an injectable liquid chemical composition to fill the gap.

In addition, for example, when pouring into the roof part at the tip of a tunnel face, for example, about 1 m before pouring.
The holes are drilled with a jumbo machine at a predetermined interval of, for example, about 42 mmφ bit, and an injection hole with a depth of about 2 m and a drilling angle of about 10 to 25 ° is provided, and the length where the static mixer is inserted into this injection hole. It is preferable to insert an injection bolt made of a hollow carbon steel pipe having a length of about 3 m and inject the injection chemical liquid composition by the method described above.
The injection work ends when the injection pressure rises sharply.
Generally, it is preferable that the amount of the chemical liquid per injection hole is about 30 to 200 kg.

Further, the stable strengthening water stop such as cracks of the artificial structure is drilled into a hole having a diameter of about 10 mm and a depth of about 5 to 10 cm at intervals of about 20 to 50 cm with respect to the crack surface. Blow away shavings and dust with compressed air, place absorbent cotton on the drilled hole to a thickness of about 5 mm, and then inject an injection pipe with a diameter of about 10 mm and a length of about 20 to 30 mm to prevent leakage of the liquid chemical composition. Set it to the non-existent state. In addition, U-shaped or V-shaped cuts will be made at a pitch of approximately 30 cm for cracks and water leaks, and the injection pipe will be fixed with quick-setting cement. Then, through a Y-shaped tube or a T-shaped tube equipped with a static mixer or the like, a mixture of (A) component and (C) component, and a mixture of (D) component and (B) component are proportioned compound pump or hand-operated type. Injection pressure using a pump, etc. at a prescribed mixing ratio of about 0.5 to 20 kg / cm ² · G, preferably 0.5 to 2 kg /
Inject a specified amount of cm ² · G. The injection volume can generally be the estimated void volume plus α.

In the stable reinforced water-stopping method of the present invention, an injectable chemical composition having a low viscosity is used.
It has good permeability to cracks and shatter zones, and can stabilize unstable rocks and grounds, and even stabilize artificial structures and stop water. Further, the formed cured solid has high strength and durability, is excellent in adhesion and adhesion to rocks, etc., and exhibits flame retardancy, and is economical, so it is extremely practical. It is advantageous.

Next, the injectable liquid chemical composition for stabilization of the ground and artificial structures of the present invention and the stable strengthening waterproofing method using the same will be described in more detail with reference to Production Examples and Examples. Is not limited to only these manufacturing examples and examples.

Production Examples 1 to 3 and Comparative Production Examples 1 and 2 Component A and Component B were prepared separately at the compounding ratios shown in Table 1, and then Component B was added to Component A with stirring and mixed. Then, the injectable liquid composition was obtained.

The stability of component A, gel time, odor during solidification, and foaming ratio, homogeneity and oxygen index of the solidified product were examined according to the following methods. Table 1 shows the results. The overall evaluation is that the expansion ratio is 2
When it was more than double and all the other physical properties were evaluated as ○, the other cases were evaluated as ×. The results are also shown in Table 1.

(A) Stability of component A When the components (A) and (C) and the component (D) are mixed and agitated and a uniform state is maintained for 5 minutes or more, it is possible to perform the test in 5 minutes or less. When separated or a gelled product was formed, it was evaluated as x.

(B) Gel time The time (seconds) from the mixing of the components A and B at 20 ° C. to the gelation was measured.

(C) Odor during solidification When the water vapor generated during solidification did not give an amine odor, it was evaluated as ◯, and when it had an amine odor, it was evaluated as x.

(D) Foaming ratio of the solidified body The volume of the solidified body was divided by the total volume of the component A and the component B.

(E) Uniformity of Cemented Body: If the solidified body was uniform and difficult to be broken, it was evaluated as ◯, and if it was nonuniform and brittle, it was evaluated as ×.

(F) Oxygen index of the solidified body The oxygen index (numerical value of the minimum oxygen concentration expressed by volume% in oxygen necessary for sustaining combustion) in accordance with the combustion test method described in JIS K7201 In the case of 26 or more, the case was evaluated as ◯, and the case of less than 26 was evaluated as x.

An aqueous solution of sodium silicate was used as the component (A), and the components (C) and (D) were added to and mixed with the component (A).

As the component (B), a mixture prepared by adding a reactive diluent was used.

The values of the equivalence ratios in Table 1 are the values of N in the component (B).
It is a value of an equivalent ratio of a CO group and an OH group in the component (D).

The abbreviations in Table 1 mean the following.

(Component (B)) C-MDI Polymethylene polyphenyl polyisocyanate (Polymeric MDI) PEG-5000MDI Polyoxyethylene glycol (weight average molecular weight 5000)
Terminal NC obtained by reacting 850 parts of C-MDI with 150 parts
O group-containing urethane prepolymer PEG-2000MDI polyoxyethylene glycol (weight average molecular weight 2000)
Terminal NC reacted with 900 parts of C-MDI for 100 parts
O group-containing urethane prepolymer GPE-3000MDI-L The mixing ratio of propylene oxide and ethylene oxide is 50.
Triol (weight average molecular weight 30) obtained by addition-polymerizing mixed alkylene oxides of 50/50 (weight ratio) to glycerin
00) 900 parts of liquid diphenylmethane diisocyanate was reacted with 100 parts of urethane prepolymer containing terminal NCO group (reactive diluent) EGDA ethylene glycol diacetate EC / POC The mixing ratio of ethylene carbonate and propylene carbonate was 25/75. (Weight ratio) Mixture MMB-AC 3-Methyl-3-methoxybutylacetate (Component (C)) (C) -1 N, N-dimethylcyclohexylamine (C) -2 N, N-dimethylbenzylamine (C) ) -3 N, N-Dimethylmethylbenzylamine (C) -4 2,4,6-Tris (dimethylaminomethyl) phenol (phenolic tertiary amine) (C) -5 triethylamine ((D) component) (D) ) -1 Ethylene glycol (D) -2 Dipropylene glycol

[0066]

[Table 1]

From the results shown in Table 1, the injected liquid chemical compositions obtained in Production Examples 1 to 3 did not generate odor at the time of solidification, and the solidified products obtained had a high expansion ratio. It can be seen that it is excellent in uniformity, has a large oxygen index, and exhibits flame retardancy.

Example 1 60 ° to the left and right from the center of the tunnel arch at the top of the tunnel face with a fracture zone, a total of 120 ° in a fan-shaped range, with a jumbo machine, a drilling angle of 15 ° at 1 m intervals with a 42 mmφ bit. 10 holes were drilled (angle to the tunnel excavation direction) and carbon steel was made in the holes (JIS G 3445, STKM 17C).
Insert the injection bolt (outer diameter 27.2 mm, inner system 15 mm, length 3 m, static mixer and check valve internal), and the mouth part is about 30 cm
Was knitted with a two-component hard urethane foam resin with a knitted cloth and was sealed by pressing it with an iron rod.

20.5 kg of the component A of the injectable liquid chemical composition of Production Example 3 in Table 1 was put in the liquid chemical tank A, and 20 kg of the component B was put in the liquid chemical tank B, and about 1 to 1 for each of the component A and the component B.
Pump circulation was performed for 2 minutes.

Next, after connecting the tips of the discharge hoses of the component A and the component B to the T-shaped unit, they were fixed to the ground.
Joint with the bolt of each injection hole, injection pressure 1-40kg / cm
² · G, about 50 per hole in the injection speed 5~12kg / minute
180 kg could be injected smoothly.

About 120 minutes after the chemical solution was injected, the state of improvement of the ground was examined by excavation. The consolidation range was a hemisphere with a radius of 50 cm, and the consolidation was stabilized.

The injection-solidified portion is sampled with a sampler of 5 cmφ × 10 cm
The sample was sampled in the shape of a cylinder and the uniaxial compressive strength was measured to be 250 kg / cm ² . Sampling was not possible in the unimproved area because of the shatter zone. As a result, the effectiveness of the injectable liquid composition of the present invention was sufficiently proved, and it was revealed that a solidification stabilizing layer was formed.

Example 2 In order to fill and stabilize the roof part (granite crush zone having large voids) at the tip of an unstable tunnel face, stabilization was carried out by injecting a chemical solution of Production Example 1 in Table 1. It was The construction method was as follows.

That is, in the fan-shaped range of 60 ° to the left and right from the center of the tunnel arch, a total of 120 ° at the top of the tunnel face, a jumbo machine cuts 10 injection holes with a depth of 3 m at intervals of 80 cm by 42 mmφ bits. Perforated. The drilling angle was 20 °. Made of carbon steel similar to that of Example 1 (JIS
G 3455, STKM 17C) injection bolt was inserted, and the mouth was sealed in the same manner as in Example 1. The bolts for each injection hole are located at 60 ° to the right of the excavation direction.
No. toward the position of No. It was set to 1-10.

40 kg of the component A of the injected liquid chemical composition of Production Example 1 in Table 1 was put in the liquid chemical tank A, and 40 kg of the component B was put in the liquid chemical tank B.

Next, after connecting the tips of the discharge hoses of the component A and the component B to the T-shaped unit, they were fixed to the natural ground,
Joint with bolts (No. 1-5) of each injection hole,
o. Injection pressure 1-10kg / cm ^{2 in} order of 1, ³ , 5, ² , 4
G, about 120 kg per hole at injection speed 5-12 kg / min,
No. A total of 600 kg was injected from 1 to 5. For comparison, the bolt No. of the injection hole is set. For Nos. 6 to 10, the injectable liquid composition of Comparative Production Example 1 was used, and No. 6 was used. 6, 8, 10, 7, 9
A total of 600 kg was injected in the same manner as above.

About 90 minutes after the injection of the injection liquid composition, the vicinity of the injection hole was excavated and examined to confirm the stabilization status of the ground. 1 to 5 left roof part,
The consolidation area was a radius of about 40 cm and was consolidated in a hemispherical shape, and the large voids were also densely and well sealed. In addition, there was no collapse from the roof during excavation, and it was well stabilized.

On the other hand, No. Regarding the right roof part of 6 to 10, the consolidation area was a hemispherical consolidation with a radius of about 11 cm,
There was an unconsolidated portion where the chemical solution did not penetrate into the gap between the solidified soils, and some of the sediments collapsed during the excavation, and the improvement was insufficient.

From the results of Example 2, by injecting the injectable liquid composition of the present invention into the granite crush zone having a void larger than that of the injection bolt, the void was completely sealed and the crush zone was well treated. It has been proved to be very useful in tunnel excavation work because it can infiltrate and solidify and stabilize the rock mass.

Example 3 A crack occurred at the rising corner of the rooftop slab of a reinforced concrete three-story building, and water was leaking downstairs during rainfall. The injectable chemical liquid composition of Production Example 2 was injected into this leaking portion, and water-stopping work was performed.

First, 35 holes with a pitch of about 30 cm and a depth of about 5 cm were drilled along the crack with a φ10 mm drill, and the shavings and dust in the holes were blown off with compressed air, and then the holes were drilled. The absorbent cotton was placed on a thickness of about 5 mm, and an injection pipe with an outer diameter of about 10 mm was hammered in from above with a wooden hammer.

Next, 10 kg of the component A was put in the chemical liquid tank A with a hand pump, and 15 kg of the component B was put in the chemical liquid tank B with the hand pump.

The ends of the discharge hoses of tank A and tank B were connected to a Y-shaped tube containing a static mixer, and each injection pipe was set in a one-touch joint form. The mixing ratio (weight ratio) of component A and component B was approximately The hand pump was operated up and down at 1 / 1.5 to inject about 1 kg per hole. The injection work of all 35 pieces was completed in about 1.5 hours.

After the injection, the injection pipe was removed, a cork stopper was driven in, and mortar was applied to finish. After about two weeks, there was heavy rainfall, but no water leakage as before, and it was proved to be very effective for crack sealing and water stopping.

[0085]

INDUSTRIAL APPLICABILITY The injectable liquid chemical composition for stabilization of the ground or artificial structure of the present invention and the stable reinforcing water stopping method using the same exhibit the following effects.

When an aqueous solution of an alkali silicate which is the component (A) and an organic polyisocyanate compound which is the component (B) are used, a polyol component which is the component (D) is optionally used. The component (D) forms a reliable flame-retardant composite solid body mainly composed of a urea-silicic anhydride complex, a urethane-silicic anhydride complex, and a reticulated silicic anhydride gel body. Therefore, the solidification hardening performance is high, the stable strengthening of the rock or the ground can be reliably achieved, and a reliable water stopping effect is exhibited at the leakage portion.

Component (A), component (B) and (C)
Both the tertiary amine, which is a component, and the component (D) have low viscosities, and the compatibility between the components (A) and (C) is good, and the solidified foam is surely solidified to provide excellent permeability.

Since it is surely foamed and hardened and has a high solidified body strength, it is effective for filling unstable rocks, grounds, structures, etc., which require large strength with large voids or cracks, and stable reinforcement.

The components (A) and (C) have good compatibility with each other, and even if the injectable liquid composition adheres to the skin or clothes of the operator, it can be easily washed with water to remove it. Can be performed and is extremely safe. Further, the component (C) has a small odor and does not vaporize due to reaction heat to pollute the air. Furthermore, since it is a solvent-free system, it is highly safe in terms of occupational safety and health, and has excellent durability of the solidified body.

As described above, the construction method of the present invention has excellent characteristics, and is more reliable and higher than required for general mountain tunnels, large-section tunnel excavation work, and deep underground civil work. Strong, flame retardant,
This is a very effective method for economically achieving stable strengthening, sealing, and waterproofing of unstable rock or ground with excellent safety.

Claims (4)

[Claims] 1. An (A) alkaline silicate aqueous solution, (B)
Organic polyisocyanate compound and (C) general formula (I): An injectable liquid composition for stabilization of a ground or an artificial structure, which is composed of a tertiary amine represented by the formula (wherein R represents a cycloalkyl group or an aralkyl group). 2. The stabilizing injectable liquid chemical composition according to claim 1, which comprises (D) a polyol component. 3. The stabilizing injection chemical liquid according to claim 1 or 2, wherein a plurality of holes are formed in the rock or ground at a predetermined interval, hollow injection bolts are inserted into the holes, and the openings of the bolts are used for stabilization. A stable strengthening and water-stopping method for rock or ground, comprising injecting the composition into rock or ground to solidify or seal the composition. 4. An injection pipe is inserted into the artificial structure, and the stabilizing injectable liquid chemical composition according to claim 1 or 2 is injected into the artificial structure and / or the back surface thereof through the injection pipe to solidify. Or a method for stabilizing and waterproofing artificial structures, which is characterized by sealing.