JPH07179855A - Grout composition for stabilizing ground, artificial structure, etc., and method of stabilization, strengthening and water stopping therewith - Google Patents

Abstract

PURPOSE:To obtain a grout composition which is highly safe and useful for the solidification and stabilization, sealing and water stop of unstable parts of rock, ground, an artificial structure, etc. CONSTITUTION:This grout composition comprises an aqueous alkali silicate solution, an organic polyisocyanate compound and a tert. amine having one or two alcoholic hydroxyl group and a molecular weight of 120 or above. It can give a composite foam-like solid product excellent in penetrability, durability and economic profitability and free from any unreacted components, and is solvent-less and very safe.

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 discloses an injectable chemical liquid prepared by using polyisocyanate and water glass (sodium silicate aqueous solution) and mixing a water glass side with a specific aromatic tertiary amine Mannich base as a trimerization catalyst of polyisocyanate. The composition is described. However, this composition has a drawback that the Mannich base and the polyisocyanate and water glass have poor compatibility, so that when they are mixed, they are immediately separated. In order to increase the compatibility of the above, an expensive agent such as silicone polyol is required, which causes a problem of cost increase. Further, when Mannich base is used, formalin is generated due to heat of reaction, which is not desirable for the health of workers in the field, and it is not desirable that 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 Mannich bases which is water-insoluble and has a property of scratching the skin, it should be completely removed by washing with water. However, such an injectable liquid chemical composition has a serious problem in terms of safety, since it cannot be produced and remains easily.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made by paying attention to the above-mentioned conventional technique, and it has been difficult to form a highly safe injectable liquid chemical composition containing specific components by injection. By forming a foamed inorganic-organic composite solid body, the solidification strength is large, and the safety and stability enhancing effects,
The purpose of the present invention is to enable stable strengthening or water stoppage of rock or ground and artificial structures, which have excellent durability, workability for injection, and economy.

[0007]

That is, the present invention is
Stabilization of the ground or artificial structures, etc. consisting of (A) aqueous solution of alkali silicate, (B) organic polyisocyanate compound and (C) tertiary amine having one or two alcoholic hydroxyl groups having a molecular weight of 120 or more. The injectable liquid composition is the first invention, and in the injectable liquid composition for stabilization,
(D) The second aspect of the present invention is to contain a polyol component, and a plurality of holes are formed in rock or ground at predetermined intervals, hollow injection bolts are inserted into the holes, and an opening of the bolt is formed. The above-mentioned stabilizing injectable liquid composition is injected into rock or ground to consolidate or seal it, and a stable strengthening water stop construction method for rock or ground is defined as a third invention, and further injected into an artificial structure. Inserting a pipe, and injecting the stabilizing injectable chemical composition into the artificial structure and / or the back surface thereof through the injection pipe to solidify or seal the artificial structure, thereby stabilizing the stability of the artificial structure. A fourth aspect of the present invention is a water method.

[0008]

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) tertiary amine having one or two alcoholic hydroxyl groups having a molecular weight of 120 or more (hereinafter (C)). ) Ingredient)
It consists of

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 formed in the component (A) reacts with the isocyanate group in the component (B) to form a silicic acid anhydride-urethane composite, and at the same time. While the component (B) reacts with water to generate carbon dioxide, a multimer or silicic acid anhydride-urea cross-linked complex is formed by a urea bond, and part of the carbon dioxide produced as a by-product is dissolved in the component (A). However, it is presumed that it is based on the gelation of 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). The silicic acid anhydride-urethane composite forms a foamed solidified body by the steam evaporated by the heat of reaction generated during the reaction, thereby increasing the volume thereof. At this time, foaming occurs, but due to the foaming pressure at the time of foaming, the silicic acid anhydride-urethane composite easily enters the gaps of earth, sand, rocks, bricks, coal, artificial structures and the like.

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

As described above, the aqueous solution of the 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 a molar ratio of Na ₂ O and SiO ₂ of 2: 1 to 1: 4, for example.

The solid content concentration of the component (A) is usually adjusted to 10 to 70% by weight, preferably 20 to 40% by weight.

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 with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. The polyisocyanate and the monool or polyol obtained by addition polymerization by the method described in (1) above have an equivalent ratio of NCO groups to OH groups (NCO groups / OH groups) of 1.5 to 100, preferably 2.0 to 50. The terminal isocyanate group-containing urethane prepolymer obtained by reacting the above-mentioned compound by a known method can also be suitably used as the component (B).

Among these components (B), the consolidation strength,
From the viewpoints of safety and hygiene and economical efficiency, urethane isocyanate prepolymers containing terminal isocyanate groups are preferred, and those with a composition that has extremely low volatility at the so-called handling environment temperature, is liquid, and has consolidation strength and economic efficiency are preferred. .

The blending amount of the component (B) cannot be unconditionally determined because it varies depending on, for example, the molar ratio of Na ₂ O and SiO ₂ in the component (A). Mixing ratio with component (B) (component (A) /
It is preferable to adjust the component (B) to have a weight ratio of 10/100 to 100/10, especially 20/100 to 100/20. When the mixing ratio is less than the lower limit, the cost of the injectable liquid composition becomes expensive and uneconomical, and it tends to be extremely difficult to control the mixing ratio in the proportional injection pump. On the other hand, when the amount is larger than the upper limit, the injectable liquid composition is insufficiently solidified to be in an uncured state, and even if it is cured, the hardness is low, and it tends to be brittle and unusable for practical use.

The component (B) is excellent in reactivity and solidification with the component (A), but its permeability is relatively high, so that it does not have sufficient permeability to the rock or the ground, so that it has been conventionally flowed. To improve the water resistance and permeability, toluene, xylene, 1,
Organic solvents such as 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 them 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,
Excellent storage stability and viscosity reduction of component (B), while (A)
When mixed and contacted with the components, it is preferable to add a reactive diluent which immediately reacts and cures 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 the diesters of low molecular weight dibasic acids 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.

Acetic acid esters of monohydric or polyhydric alcohols include, for example, 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; 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.
100-1000 polyethylene glycol, propylene glycol, dipropylene glycol, weight average molecular weight 10
Examples thereof include polypropylene glycol of 0 to 1000, and (meth) acrylic acid ester with alcohols such as ethylene oxide and propylene oxide copolymerized diol or triol having a weight average molecular weight of 100 to 5000.

The amount of the reactive diluent used is 100 parts of the component (B).
It is preferably 5 to 100 parts, especially 10 to 50 parts with respect to parts (parts by weight, the same hereinafter), and it is preferable to appropriately select within this range depending on the type and viscosity of the component (B), the purpose of use, and the like. . If the amount of the reactive diluent is too small, the effect of reducing the viscosity and the improvement of the caking strength of the component (B) tend not to be sufficiently exhibited. In particular, the strength of the solidified body tends to decrease.

The tertiary amine having one or two alcoholic hydroxyl groups having a molecular weight of 120 or more, which is the component (C) used in the present invention, is used as the component (A), the component (B) and if necessary. It also acts as a catalyst for accelerating the reaction curing of the component (D) described later, and the component (C) has good compatibility with the component (A) and adheres to the skin or clothes. Since it is easily removed by washing with water and has a relatively high flash point, the injected chemical liquid composition containing the component (C) is highly safe against a fire source used during construction such as melting of a pipe. Further, the alcoholic hydroxyl group in the component (C) is different from the phenolic hydroxyl group which is a hydroxyl group directly bonded to the aromatic ring,
Since it easily reacts with the isocyanate group in the component and is not liberated in the solidified body, the component (C) does not elute due to the component in the soil or flow out due to drowning, and thus is extremely It is a safe reaction hardening accelerating catalyst.

Examples of the component (C) include N-dioxyethylene-N, N-dimethylamine, N-trioxyethylene-N, N-dimethylamine, N, N-dimethylaminohexanol, N, N, N'-trimethylaminoethylethanolamine, N, N, N ', N'-tetramethylhydroxypropylenediamine, N- (2-
Hydroxyethyl) morpholine, 1-methyl-4-hydroxyethylpiperazine, N, N-dimethyl-N ', N
′ -Di (hydroxyethyl) ethylenediamine, etc.,
Tertiary amines having one or two alcoholic hydroxyl groups such as addition compounds obtained by adding ethylene oxide to these amines and having a molecular weight of 120 or more can be mentioned.

When the molecular weight of the tertiary amine which is the component (C) is less than 120, such as triethylenediamine and N-dimethylethanolamine, the heat of reaction during reaction solidification causes the reaction to occur in the air. It tends to scatter, has a large odor, and is inferior in safety. The molecular weight of the tertiary amine as the component (C) is preferably 130 to 270 in consideration of safety.

Further, when the number of alcoholic hydroxyl groups in the tertiary amine as the component (C) is 3 or more, the reaction promoting effect becomes small.

The blending amount of the component (C) is preferably 0.1 to 20 parts, more preferably 0.5 to 15 parts, relative to 100 parts of the component (B). When the blending amount of the component (C) is less than the lower limit value described above, it tends to be hard to cure, the caking reaction is insufficient, and it tends to be difficult to obtain a clump having the intended performance. If it exceeds the upper limit, the curing reaction tends to be too fast, and it becomes difficult to uniformly mix the components (A) and (B) and the component (D), which will be described later and used as necessary.

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

Examples of the polyol component which is the component (D) used in the present invention include the polyol which is used in the urethane prepolymer having a terminal isocyanate group which is the component (B), and these are used alone or in two kinds. The above can be mixed and used. The weight average molecular weight of these polyols is preferably 40 to 20000.

The blending amount of the component (D) is the same as that of the component (B) used.
Although it cannot be unconditionally determined because it depends on the types of components, etc., the blending ratio of the (B) component and the (D) component is usually the NCO group in the (B) component and the OH in the (D) component.
It is preferable to adjust the equivalent ratio to the group (NCO group / OH group) to be 0.5 to 500, especially 1 to 120.
When the equivalent ratio is less than the lower limit, the solid obtained from the injectable liquid composition tends to be too soft for practical use, and when the upper limit is exceeded, The solids tend to be brittle.

Further, the injectable liquid composition of the present invention contains, if necessary, cement, blast furnace slag, gypsum, calcium carbonate, clay, aluminum hydroxide, antimony trioxide,
Inorganic fillers such as quick lime, slaked lime and bentonite, various surfactants, diluents, leveling agents, flame retardants, silicone-based foam stabilizers, antioxidants, heat resistance imparting agents, antioxidants,
The 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 thereof, for example, a proportional compound pump capable of controlling the injection amount, pressure, compounding ratio, etc. of the component (A), the component (B) and the component (C), and the component (D) is used. Component (C), 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 is injected at a pressure of 0.5 to 50 kg.
/ Cm ² · G, and mix a prescribed amount of the mixture and the component (B) uniformly through a static mixer, and then inject and infiltrate into a prescribed unstable rock or ground location to solidify or seal However, there is a method to stabilize it.

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

When pouring into the roof of the tip of a tunnel face, for example, about 1 m before pouring.
Using a jumbo machine, drill holes at a predetermined interval of, for example, 42 mmφ bits, provide injection holes with a depth of 2 m and a drilling angle of 10 to 25 °, and insert a static mixer into the injection holes to make a length of 3
It is preferable to insert a hollow carbon steel pipe injection bolt of m and inject the injection chemical composition by the method described above. The injection work ends when the injection pressure rises sharply. In general,
The amount of the liquid medicine per injection hole is preferably 30 to 200 kg.

Further, the stable strengthening waterproofing such as cracks of the artificial structure is drilled with a diameter of 10 mm and a depth of 5 to 10 cm at intervals of 20 to 50 cm with respect to the crack surface, and the shavings in the holes are cut. Blow away dust and dust with compressed air and put absorbent cotton on the drilled hole to a thickness of about 5 mm. From above, diameter of about 10 mm, length of 20-30
Drive an mm injection pipe and set it so that the injection liquid composition does not leak. 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 0.5 to 20 at a prescribed mixing ratio using a pump, etc.
kg / cm ² · G, preferably a predetermined amount injected at 0.5 ~2kg / cm ² · G. The injection volume can generally be the estimated void volume plus α.

In the stable strengthened water stop method of the present invention, an injectable liquid chemical composition having a low viscosity is used, so that it has good permeability to unstable ground, cracks and crush zones, and has a wide range of unstable rock and ground. Can 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 reinforced 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 the component A, gel time, odor during solidification, and foaming ratio and uniformity of the solidified product obtained were examined according to the following methods. The results are shown in Table 1. In the comprehensive evaluation, when the expansion ratio is 2 or more and all other physical properties are evaluated as ◯, the evaluation is ◯, and the other cases are evaluated as x. 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 component A and the component B at 20 ° C. until gelation was measured.

(C) Odor during solidification When the water vapor generated during solidification did not cause an amine odor, the case was evaluated as ◯, and the case where an amine odor occurred 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 break, it was evaluated as ◯, and if it was nonuniform and brittle, it 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 equivalent ratio in Table 1 is the NCO in the component (B).
It is the equivalent ratio of the group and the 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 liquid Nphenyl group-containing urethane prepolymer (reactive diluent) EGDA ethylene glycol diacetate EC / POC The mixing ratio of ethylene carbonate and propylene carbonate was 25/75. Mixture (weight ratio) MMB-AC 3-methyl-3-methoxybutylacetate ((C) component) (C) -1 N, N, N'-trimethylaminoethylethanolamine (molecular weight 146) (C) -2 N, N, N ', N'-Tetramethylhydroxypropylenediamine (Molecular weight 146) (C) -3 N, N-Dimethyl-N', N'-di (hydroxyethyl) ethylenediamine 1 mol with addition of ethylene oxide 2 mol Compound (Molecular weight 264) (C) -42,4,6-tris (dimethylamino) Chill) phenol (aromatic Mannich bases, molecular weight 265) (C) -5 N-methyldiethanolamine (molecular weight 119) ((D) component) (D) -1 ethylene glycol (D) -2 trimethylolpropane

[0060]

[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 the uniformity is excellent.

Example 1 At the top of the tunnel face with a fracture zone, 60 ° to the left and right from the center of the tunnel arch, a total of 120 ° in a fan-shaped range, a jumbo machine made a 42 mmφ bit and drilling angles of 15 ° at 1 m intervals. 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 injected 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, the tips of the discharge hoses of the component A and the component B were connected to a T-shaped unit and 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 consolidation was stabilized.

The injection-solidified portion is sampled with a sampler of 5 cmφ × 10 cm
It was 245 kg / cm ² when the uniaxial compressive strength was measured by sampling in the shape of a cylinder. 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 injection of a chemical solution in Production Example 1 in Table 1. It was The construction method was as follows.

That is, in a fan-shaped range of 60 ° to the left and right from the center of the tunnel arch, a total of 120 °, in the roof part at the tip of the tunnel face, 10 injection holes with a depth of 3 m were cut with a 42 mmφ bit at 80 cm intervals with a jumbo machine. 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 injectable liquid chemical composition of Production Example 1 in Table 1 was put in the chemical liquid tank A, and 40 kg of the component B was put in the chemical liquid 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 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.

When about 90 minutes have passed since the injection liquid composition was injected, the periphery of the injection hole was excavated and examined to confirm the stabilization status of the natural 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 larger void than the injecting bolt, the void was completely sealed and the crush zone was well infiltrated and consolidated. However, it was proved to be very useful for tunnel excavation work, because the rock mass can be stabilized.

Example 3 A crack occurred at the rising corner of the roof slab of a reinforced concrete three-story building, and water leaked 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 cracks using 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 placed in the chemical solution tank A with a hand pump, and 15 kg of the component B was placed in the chemical solution tank B with the hand pump.

The tips 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, and 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.

[0079]

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 foam-like composite solid body mainly composed of the urea-silicic anhydride complex, the urethane-silicic anhydride complex, and the 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 waterproofing effect is exhibited at the leakage portion.

Component (A), Component (B) and Component (C)
One component is an alcoholic hydroxyl group with a molecular weight of 120 or more.
Both of the tertiary amine having 2 or 2 and the component (D) have low viscosity, the compatibility of the (A) component and the (C) component is good, and the foaming and solidification is surely performed, so that the permeability is excellent. There is.

Since it reliably foams and hardens and has a high solidified body strength, it is effective for filling unstable rocks, grounds, structures, etc., which require large strength or have many cracks and strength, and for stable reinforcement.

Since the components (A) and (C) are easily dissolved in water, even if the injectable liquid chemical composition adheres to the skin or clothes of the operator, it can be easily washed with water to remove it. Very 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 and the component (C) does not react with the component (B) and does not elute, it is highly safe in terms of occupational safety and health, and has excellent durability of the solid.

As described above, the construction method of the present invention has excellent characteristics, and is more reliable and high-strength required not only for general mountain tunnels but also for large-section tunnel excavation work and deep underground construction work. It is a very effective method for achieving stable strengthening, sealing, and water stoppage of unstable rock or ground that is economical and has excellent safety.

Claims (4)

[Claims] 1. An (A) alkaline silicate aqueous solution, (B)
Organic polyisocyanate compound and (C) molecular weight 12
An injectable liquid composition for stabilization of a ground or artificial structure, which is composed of a tertiary amine having one or two alcoholic hydroxyl groups as described above. 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.