JP3498656B2 - Injectable chemical composition for stabilization of ground and artificial structures, etc. - Google Patents

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 it has poor permeability to the ground layer such as cracks and gravel in rocks and artificial structures, etc. 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. Furthermore, when only spring water or water leakage occurs, the injected cement milk is diluted and washed out. Also, the water-based two-liquid system grout, which is a typical inorganic grout, has a low solidified strength of about 0.29 to 0.98 MPa, and when the solidified material comes into contact with water, a change with time occurs and Na ₂ O or S
There is a problem that the main component such as iO ₂ is 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. Further, JP-B-63-63687, JP-B-63-63688, JP-A-63-7413, and JP-A-63-74.
90, JP-A-63-7491, JP-A-63
No. 8477, Japanese Patent Laid-Open No. 63-35913 and the like describe a method for consolidating rock mass by injecting a fast-curing hard urethane foam system containing polyol and polyisocyanate as main components.

Further, in JP-A-61-9482 and JP-A-55-160079, a polyisocyanate and water glass (sodium silicate aqueous solution) are used, and as a trimerization catalyst for polyisocyanate on the water glass side. An injectable liquid composition containing a Mannich base which is a specific aromatic tertiary amine is described.

In JP-A-7-179855, a polyisocyanate and water glass (sodium silicate solution) are used, and a tertiary amine catalyst having one or two hydroxyl groups with a molecular weight of 120 or more on the water glass side. An injectable drug solution composition is described. In addition, JP-A-7-207
Japanese Patent No. 654 discloses an injectable liquid composition using a polyisocyanate and water glass, and using a water-soluble aliphatic tertiary amine having a molecular weight of 120 or more and a nitrogen atom number of 2 or more on the water glass side. There is.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made by paying attention to the above-mentioned prior art, and it is a foamed inorganic material which has been difficult to form by injecting an injectable liquid chemical composition comprising specific components. -By forming an organic composite consolidate, if it is possible to strengthen the rock or the ground and the artificial structure with high consolidation strength, stability strengthening effect, durability, pouring workability and economical efficiency, or to stop water. The purpose is to tighten.

[0008]

Means for Solving the Problems That is, the present invention is shown in the following (1) to ( 4 ). (1) (A) aqueous solution of alkali silicate, (B) diphenyl
Methane diisocyanate (B1) and diphenylmethane
Polyisocyanate composed of diisocyanate polynuclear condensate (B2)
Socyanate and poly (oxypropylene) polyol
Isocyanate-terminated prepolymer obtained by reaction
- , (C) 1,2-dimethylimidazole and (D)
An injectable liquid composition for stabilizing a ground, an artificial structure or the like, which comprises N, N-diethylethanolamine .

(2) (E) poly (oxypropylene ) poly
The stabilizing injectable liquid medicine composition according to (1) above, which comprises riol .

[0010]

[0011]

[0012]

( 3 ) A plurality of holes are formed in the rock or ground at a predetermined interval, and hollow injection bolts are inserted into the holes,
Stabilization of rock or ground characterized by injecting the stabilizing chemical liquid composition of (1) or (2) into the rock or ground through the opening of the bolt to consolidate or seal the rock or ground. Reinforced waterproof construction method.

(7) Insert the injection pipe into the artificial structure,
The stabilizing injectable liquid chemical composition according to any one of (1) and (2) is injected into the artificial structure and / or the back surface thereof through the injection pipe to be solidified or sealed. , Stabilizing water-stopping method for artificial structures.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Injectable liquid composition for stabilizing the ground or artificial structure of the present invention (hereinafter referred to as injectable liquid composition)
As mentioned above, (A) aqueous solution of alkali silicate (hereinafter referred to as “component (A)”), (B) diphenylmethanediii
Socyanate (B1) and diphenylmethane diisocyanate
Polyisocyanate comprising nate-based polynuclear condensate (B2)
Of poly (oxypropylene) polyol
The isocyanate group-terminated prepolymer obtained (hereinafter,
(Referred to as component (B)), (C) 1,2-dimethylimidazo
Lumpur (hereinafter, (C) referred to as the component) and (D) N, N-di
Ethyl ethanolamine (hereinafter referred to as component (D)),
And (E) poly (oxypropylene ) described later as necessary.
And) polyol (hereinafter referred to as component (E)).

The solidification reaction of the injectable liquid composition of the present invention is not clear because it is extremely complicated, but it is probably formed in the component (A) when the components (A) and (B) are mixed. The silanol group and the isocyanate group in the component (B) react to form a silicic acid anhydride-urethane complex,
At the same time, the component (B) reacts with water to generate carbon dioxide, thereby forming a multimer or a silicic acid anhydride-urea cross-linked complex 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 an anhydrous silicic acid gel. Further, when the component (E) is present, it is presumed that it is based on the fact that the hydroxyl group in the component (E) reacts with the component (B) to form a urethane resin.

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 with the components (A), (B) and (E). 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 its volume. At this time, foaming occurs, but due to the foaming pressure at the time of foaming, the silicic anhydride-urethane composite easily enters the gaps of earth, sand, rocks, bricks, coal, artificial structures and the like.

The components of 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 forms a silicic acid anhydride-urethane composite mainly by the reaction of its silanol groups with the isocyanate groups of the component (B) described later. It is a component to be formed.

Examples of the component (A) include those containing an aqueous solution such as potassium silicate or a sodium silicate represented by the formula: Na ₂ O.xSiO ₂ as a main component. Such a sodium silicate is, for example, Na. The molar ratio of ₂ O to SiO ₂ is 2: 1 to 1: 4.

The solid content concentration of the component (A) is usually preferably 10 to 70% by mass, particularly 20 to 70% by mass.
It is preferable to adjust the content to be 50% by mass. Specifically, No. 1 sodium silicate S2, No. 2 sodium silicate N5, 2
Sodium silicate Q3, No. 2 sodium silicate T8 (all manufactured by Toso Sangyo Co., Ltd.) and the like can be mentioned.

Polyisocyanate used as the component (B)
The nate is diphenylmethane diisocyanate (hereinafter,
Mixtures of MDI hereinafter) and MDI-based polynuclear condensate (hereinafter, it is referred to polymeric MDI).

In addition to this , for example, methanol, ethanol,
Monools such as 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- Diols such as hexanediol, glycerin, trimethylolpropane, polyols such as pentaerythritol: Other monoethanolamine, diethanolamine, triethanolamine, diglycerin,
Soluble sorbitol, sucrose, etc. alone or in a mixture with propylene glycol
Monool or polyol obtained by addition polymerization of side by a known method, and the polyisocyanate, for example, equivalent ratio of NCO group and OH group (NCO group / OH group)
But from 1.5 to 500, preferably an isocyanate group-containing urethane prepolymer obtained by reacting in a known manner to be in the range of 2.0 to 400, is used as the component (B).

The component (B) is preferably an isocyanate group-containing urethane prepolymer or the like from the viewpoints of consolidation strength, safety and hygiene, and economy, and it has extremely low volatility under so-called handling environmental temperature, and is liquid and consolidated. Considering strength, economic efficiency, low temperature stability, environmental load, etc., those containing an isocyanate group-terminated prepolymer obtained by reacting a polymeric MDI with a poly (oxypropylene) polyol are preferable. This is poly (oxyethylene)
When a polyol is used, the component (B) becomes hydrophilic, and the chemical may ooze into the groundwater layer when the chemical is injected into the rock or ground. However, since the poly (oxypropylene) polyol is hydrophobic, the chemical Is unlikely to seep into the groundwater layer.

The composition of the polymeric MDI at this time is
Mass ratio of MDI / MDI-based polynuclear condensate = 30/70 to 7
0/30 is preferable. If the MDI content is too low, the viscosity of the drug solution tends to increase. Further, if the MDI is too much, precipitates are likely to appear due to crystallization of MDI during low temperature storage of the chemical solution.

Further, the MDI in the polymeric MDI includes 2,2'-MDI, 2,4'-MDI and 4,4'-.
There are three isomers of MDI. In the present invention, M
The mass composition ratio of the isomers of DI is (2,2′-MDI +
2,4'-MDI) / 4,4'-MDI = 10/90 ~
50/50 is preferred. If the amount of 4,4'-MDI is too much, the low temperature storage stability of the drug solution tends to decrease. Also,
The compatibility with (A) aqueous alkali silicate solution and (E) polyol is likely to decrease, and 4,4′-MDI is
Since the reactivity is higher than that of 2,2'-MDI and 2,4'-MDI, thickening after mixing becomes vigorous and compatibility is poor unless the pressure of the mixing device (pump) is increased, which is not preferable. On the other hand, if too little 4,4'-MDI
2,2'-MDI or 2,4 'rather than 4,4'-MDI
-MDI is more flexible in terms of its molecular structure, so that strength is less likely to develop.

The poly (oxypropylene) polyol preferably has a number average molecular weight of 76 to 10,000, particularly preferably 76 to 5,000. If the molecular weight is too large, the viscosity of the chemical liquid increases, and the workability tends to decrease. Also, poly (oxypropylene) polio
2 or more is preferable and the average number of functional groups of
4 is particularly preferred. The "substantially average number of functional groups" means
It is the average number of functional groups of the polyol used as the initiator.
is there.

The viscosity of the component (B) used in the present invention is
It is preferably 500 mPa · s or less at 25 ° C., more preferably 50 to 450 mPa · s. If the viscosity is too large, not only the workability is likely to be lowered, but also the pump pressure must be increased at the time of injecting the chemical liquid, and the line is likely to be damaged.

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). The blending ratio with the component (B) (component (A) / component (B)) is preferably 10/100 to 100/10, and particularly preferably adjusted to 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 infusion pump. When the amount is larger than the upper limit, the injectable liquid composition may be insufficiently solidified to be in an uncured state, and even if it is cured, the hardness is low, and the composition tends to be brittle and unusable for practical use.

The component (B) is excellent in reactivity and solidification with the component (A). Further, in order to improve the permeability to the rock or the ground, an organic solvent such as toluene, xylene, 1,1,1-trichloroethane, methylene chloride or trichlorofluoromethane may be used as a diluent, but these organic solvents are Since it is volatile and may be released after solidification and damages the environment, it is preferably not used as much as possible.

Further, as a diluent for the component (B), (B)
Even if mixed with the ingredients, it does not react with the isocyanate group,
The component (B) is excellent in storage stability and viscosity reduction, while a reactive diluent that reacts and cures immediately when mixed and contacted with the component (A) can be used, but again a small amount is released. Therefore, it is preferable not to use it as much as possible because it may damage 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 is brought 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, silicic anhydride-urea cross-linked complex, inorganic mainly composed of reticulated silicic anhydride gel-
An organic composite solid will be formed.

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. , (Meta)
Examples thereof include acrylic acid ester.

Examples of 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.

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. Examples include alcohols, acetates of alkoxyalkyl alcohols such as 3-methyl-3-methoxybutyl alcohol, and 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 a weight average molecular weight of 10
With alcohols such as polyethylene glycol of 0 to 1000, propylene glycol, dipropylene glycol, polypropylene glycol having a weight average molecular weight of 100 to 1000, ethylene oxide having a weight average molecular weight of 100 to 5000, propylene oxide copolymerized diol, or triol ( Examples thereof include (meth) acrylic acid ester.

When a reactive diluent is used, the blending amount is a mass ratio of (B) component / reactive diluent = 100/5 to 5
It is common to use in the range of 100/100.

The component (C) used in the present invention is 1,
2-Dimethylimidazole and N, N which is the component (D)
-Diethylethanolamine is the component (A),
It also acts as a catalyst for accelerating the reaction curing of the component (B) and the component (E) which is optionally used, and the component (C) and the component (D) are combined with the component (A). It has good compatibility, is easily removed by washing with water even if it adheres to the skin or clothes, and has high catalytic activity.

[0043]

[0044]

The catalysts of the above-mentioned components (C) and (D) have a molecular weight of N, N, N'-trimethylaminoethylethanolamine or N, N, N ', N'-tetramethylhydroxypropylenediamine. When it is 120 or more, the component (B) needs to be hydrophilic since the catalytic activity is insufficient. In the present invention, this is not the case, and sufficient performance can be obtained even if an isocyanate group-terminated prepolymer using a hydrophobic polyol is used as the component (B).

[0046]

The mixing ratio of the (C) component and the (D) component is a mass ratio, and the (C) component: (D) component = 1: 1 to 10: 1.
Is preferred.

Further, the component (A), the component (C) and the component (D)
The blending amount of the components is a mass ratio, and the (A) component / ((C) component + (D) component) = 100 / 0.1 to 100/20 is preferable, and particularly 100 / 0.5 to 100/15. Preferably there is. When the blending amount of the component (C) and the component (D) is less than the lower limit value described above, it tends to be hard to cure and the caking reaction is insufficient, so that a clump having desired performance tends to be hardly obtained. If the amount exceeds the upper limit, the curing reaction tends to be too fast and the components (A) and (B) and the component (E), which will be described later and used as necessary, tend to be difficult to mix uniformly. is there.

In addition to the components (A), (B), (C) and (D), the injectable liquid composition of the present invention contains a polyol component (E). be able to.

Poly (E) component used in the present invention
Examples of the (oxypropylene) polyol include polyols used in the isocyanate group-containing urethane prepolymer which is the component (B), and these can be used alone or in admixture of two or more. The number average molecular weight of these poly (oxypropylene) polyols is preferably 62 to 20,000, and particularly preferably 76 to 10,000. Hydrophobic poly (oxypropylene) polyol is preferable in consideration of environmental load of the chemical solution, economy, stability at low temperature, workability at the time of injecting the chemical solution, and the like. The poly (oxypropylene) polyol preferably has a substantial average number of functional groups of 2 or more, and particularly 2
-4 are especially preferable.

The amount of the component (E) used 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 mixing ratio of the (B) component and the (E) component is usually the NCO group in the (B) component and the OH group in the (E) component. The molar ratio (NCO group / OH group) is preferably 0.5 to 500, and particularly preferably adjusted to 1 to 450. When the molar ratio of the NCO group and the OH group is less than the lower limit value, the solidified body obtained from the injectable liquid composition tends to be too soft to be practically used, and exceeds the upper limit value. In some cases, the solidified body tends to become brittle.

In the same manner as described above, it is preferable to use a surfactant for the purpose of adjusting the two-correlation dispersion and reactivity of the (A) alkaline silicate aqueous solution and the (B) component . The surfactant can be obtained by condensing a polyglycol ether containing an alkylene oxide such as ethylene oxide or propylene oxide and an organic compound containing at least one active hydrogen. This at least 1
Examples of the organic compound containing one active hydrogen include alcohol, phenol, thiol, primary or secondary amine, and 1
Mention may be made of polyalkylene oxide derivatives of phenolic compounds having one or more alkyl substituents.
The surfactant can be added in advance to the (A) alkaline silicate aqueous solution and / or the (B) component ,
When (A) the aqueous solution of alkali silicate is mixed in advance, bubbles are generated when stirring and accurate measurement cannot be performed. Therefore, it is preferable to mix only the component (B) before use.

Further, there may be mentioned silicone type surfactants, which may or may not contain active hydrogen groups. Preferred is a type containing no active hydrogen group. Examples thereof include various siloxane polyalkylene oxide block copolymers. Specific examples include L-5340 manufactured by Union Carbide, B-8451 and B-8407 manufactured by T. Goldschmidt. The amount of surfactant added is
(A) 0.05 to 5 with respect to the polyisocyanate compound
Mass% is preferred.

Furthermore, in the injectable liquid composition of the present invention, if necessary, an inorganic filler such as cement, blast furnace slag, gypsum, calcium carbonate, clay, aluminum hydroxide, antimony trioxide, quick lime, slaked lime, bentonite, etc. A diluent, a leveling agent, a flame retardant, a silicone-based foam stabilizer, an antiaging agent, a heat resistance imparting agent, an antioxidant, a catalyst and the like can be appropriately mixed and mixed.

Mixing order of the component (A), the component (B), the component (C) and the component (D), and the component (E) which is used as necessary when preparing the injectable liquid composition of the present invention. Is not particularly limited, but usually, a mixture (A liquid) of the component (A), the component (C), the component (D) and the component (E),
It can be used as a two-component system with the component (B) (liquid B).

Component (A), component (B), component (C) and component (D), which are special injection liquids in the present invention,
And, if necessary, the injectable liquid composition comprising the component (E) is injected into the soft or unstable ground having many voids and cracks, rock, fracture zone layer, and artificial structure having cracks and voids, Although it is solidified or sealed, the method of injecting and solidifying or sealing in this way is not particularly limited, and a known method can be adopted. To give an example,
For example, (A) component, (B) component, (C) component and (D)
(A) component, (C) component, (D) component, and (E) if necessary, by using a proportional compounding type pump capable of controlling the injection amount, pressure, compounding ratio, etc. of the component and the (E) component.
The mixture (A liquid) of the components and the (B) component (B liquid) are put in separate tanks, and the predetermined location (for example, 0.5 to 3) such as bedrock.
Through a plurality of holes perforated at intervals of about m), insert a pre-fixed perforated lock bolt or injection rod containing a static mixer, check valve, etc. into each of the above tanks. The components are injected at an injection pressure of 0.05 to 5 MPa (gauge pressure), a predetermined amount of the solution A and the solution B are evenly mixed through a static mixer, and the solution is injected and infiltrated into a predetermined unstable rock or ground site and hardened. There is a method of stabilizing by solidifying or sealing by making it.

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, prior to the pouring, holes are drilled using a jumbo machine at a predetermined interval of, for example, about 1 m, with a bit having a diameter of 42 mm, and a depth of 2 m, An injection hole with a drilling angle of 10 to 25 ° is provided, and an injection bolt made of a hollow carbon steel pipe having a length of 3 m and having a static mixer inserted therein is inserted into the injection hole, and the injection chemical composition is injected by the method described above. Is preferred. 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 30 to 200 kg.

Further, the stable reinforcing water stop such as cracks of the artificial structure is drilled to 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 shavings in the holes are shavings. Blow away dust and dust with compressed air and put absorbent cotton on the drilled hole to a thickness of about 5 mm.
Drive an injection pipe of 0 mm and a length of 20 to 30 mm,
Set the injectable liquid composition so that it does not leak. In addition, a U-shaped or V-shaped cut is made at a pitch of about 30 cm to the location where cracks, water leakage, etc. occur, and the injection pipe is fixed with quick-setting cement. Next, a Y equipped with a static mixer, etc.
Through a character tube or T-shaped tube, (A) component, (C) component,
Component (D) and, if necessary, mixture of component (E) (A
Liquid) and the component (B) (liquid B) at a predetermined blending ratio using a proportional blending pump or a hand-pushing pump, etc.
5-2 MPa (gauge pressure), preferably 0.05-0.
A predetermined amount is injected at 2 MPa (gauge pressure).

In the stable reinforced water-stopping method of the present invention, an injectable liquid composition having a low viscosity is used, so that it has good permeability to unstable ground, cracks and shatter zones, etc. Can stabilize artificial structures and stop water. In addition, the formed cured solid is
It is highly advantageous in practical use because it has high strength and durability, is excellent in adhesion to and adhering to bedrock, exhibits flame retardancy, and is economical.

[0061]

EXAMPLES Next, the injectable liquid chemical composition for stabilizing the ground or artificial structure of the present invention and the stable water-stopping construction method using the same will be described in more detail with reference to Production Examples and Examples. The invention is not limited to such manufacturing examples and examples.

[Preparation of solution A] Volume with stirrer: 1
Using a 50 kg mixer, the amounts shown in Table 1 were charged and homogenized to prepare A1 to A4. The charged amount of each raw material is shown in Table 1.

[0063] [Raw material for A liquid synthesis] No. 1 sodium silicate S2: Aqueous silicate solution (manufactured by Toso Sangyo Co., Ltd.) DMIZ: 1,2-dimethylimidazole (molecular weight = 96) DEEA: N, N-diethylethanolamine (molecular weight = 117) TMHPDA: N, N, N ', N'-tetramethylhydroxypropylene                     Diamine (molecular weight = 146) PPG200: poly (oxypropylene) polyol                     Number average molecular weight = 200                     Average number of functional groups = 2                     Oxypropylene group content = 100% DPG: Dipropylene glycol

[0064]

[Table 1]

[Synthesis of solution B] Polyisocyanates B1 to B9 were synthesized using a reactor having a capacity of 150 kg, which was equipped with a stirrer, a thermometer, a cooler and a nitrogen gas introducing tube.
After charging the raw material isocyanate and the raw material polyol in the amounts shown in Table 2, the temperature was raised to 80 ° C. and the reaction was carried out for 3 hours to obtain a polyisocyanate. Table 2 shows the types of raw materials, the amounts used, and the analytical values. The low temperature stability of these isocyanates was measured under the following conditions. The results are also shown in Table 2.

[Material for Synthesis of Liquid B] MDI1: Diphenylmethane diisocyanate NCO content = 33.6% 2,2′-MDI + 2,4′-MDI = 27.0% MDI2: Diphenylmethane diisocyanate NCO content = 33.6% 2, 2'-MDI + 2,4'-MDI = 0.1% MDI3: diphenylmethane diisocyanate NCO content = 33.6% 2,2'-MDI + 2,4'-MDI = 50.0% MDI4: diphenylmethane diisocyanate NCO content = 33. 6% 2,2'-MDI + 2,4'-MDI = 19.0% PMDI1: Polymeric MDI NCO content = 30.3% 2,2'-MDI + 2,4'-MDI = 11.0% MDI content in MDI Amount = 37.0% PMDI2: Polymeric MDI NCO content = 31.0 % 2,2′-MDI + 2,4′-MDI in MDI = 1.0% MDI content = 40.0% PPG4000: poly (oxypropylene) polyol number average molecular weight = 4,000 average number of functional groups = 2 oxypropylene Group content = 100% PPG1000: Poly (oxypropylene) polyol number average molecular weight = 1,000 Average number of functional groups = 2 Oxypropylene group content = 100% PPG200: Poly (oxypropylene) polyol number Average molecular weight = 200 Average number of functional groups = 2 Oxypropylene group content = 100% PEG2000: Poly (oxyethylene) polyol number average molecular weight = 2,000 Functional group number = 2 Oxyethylene group content = 100% B-8407: TA Goldschmitt silicone-based surfactant Low temperature stability test 1 month and allowed to stand under the conditions of the cyanate -10 ℃, check its appearance, I thought that if the crystal has occurred is warm, there is a need for heating dissolved, "bad"
It was determined to be “good” when no crystal was generated.

[0067]

[Table 2]

[Examples 1 to 9 and Comparative Examples 1 to 3] Tables 3 and 4
With the combination shown in,
Liquid B and Liquid B are weighed 100 g each and 600 times per minute / 10
The mixture was stirred under the condition of second (20 ° C.). Then, the appearance of foaming of the foam, the foaming ratio of the foam, the physical property test, and the water resistance were measured by the following methods. The results are shown in Tables 3 and 4.

[0069]

[Table 3]

[0070]

[Table 4]

Comparing the various data in Tables 3 and 4, some data are comparable to those in Examples depending on the type of Comparative Example, but in general, the Comparative Examples have a poor balance of the reactivity of the compounded liquids. The physical properties and workability are poor.

[Test Method for Foam] (1) Appearance of Foam The foam obtained by blending the polyisocyanate composition and the aqueous silicate solution as described above was cut with a knife to check the internal condition. I observed. The one having a non-uniform cross section was judged as "poor", and the one having a uniform cross section was judged as "good". (2) Expansion ratio Expansion ratio = Volume of foam after foaming (ml) / Volume of compounded liquid before foaming (ml) (3) Uniaxial compressive strength JSF T511 (Soil engineering uniaxial compression test method) Was carried out at 20 ° C. (4) Water-resistant liquid A and liquid B were mixed in an amount of 50 g each, and immediately after that, the fluid in a fluid state was quickly put into a polycup containing 300 ml of water in advance, and the foaming state in water was observed. At that time, the one in which the water in the polycup became cloudy was determined to be “poor”, and the one in which the water was transparent was determined to be “good”.

Example 10 In a fan-shaped range of 60 ° to the left and right from the center of the tunnel arch, a total of 120 ° at the roof part at the tip of the tunnel face having a crush zone, a jumbo machine was used to drill holes with a diameter of 42 mm and a drilling angle of 15 at an interval of 1 m. ° (angle to tunnel excavation direction)
10 holes were drilled with, and the resulting holes were made of carbon steel (JIS G
3445, STKM 17C) injection bolt (outer shape 2)
7.2 mm, inner system 15 mm, length 3 m, static mixer and check valve interior) were inserted, and a knitted waste cloth impregnated with a two-liquid rigid urethane foam resin was pressed into a mouthpiece portion of about 30 cm with an iron rod to seal it.

As liquid A, 20 kg of A3 in Table 1 was added to chemical liquid tank A, and as liquid B, 20 kg of B1 in Table 2.
The solution was placed in the chemical solution tank B, and the solution A and the solution B were pump-circulated for about 1 to 2 minutes.

Next, the tips of the discharge hoses for the liquid A and the liquid B are connected to the T
After connecting to the character-shaped unit, it is jointed to the bolt of each injection hole fixed to the ground, injection pressure 0.1 to 4 MPa (gauge pressure), injection speed 5 to 12 kg / min, and about 50 to 180 kg per hole. Could be injected smoothly.

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

The injection-solidified portion was sampled with a sampler to have a diameter of 5 cm ×
It was 24 MPa when the uniaxial compressive strength was measured by sampling in a cylindrical shape of 10 cm. 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 11 In order to fill and stabilize the roof of the unstable tunnel face (granite crush zone having large voids),
Stabilization was performed by injecting the chemical liquid of Production Example 1 in Table 1. 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 roof part at the tip of the tunnel face, there were 10 injection holes with a diameter of 42 mm and an interval of 80 cm and a depth of 3 m. Drilled. The drilling angle was 20 °. In the obtained holes, the same carbon steel as in Example 1 (JIS G 3455, STKM 17
The injection bolt of C) was inserted and the mouth was sealed in the same manner as in Example 1. In addition, the bolts of the respective injection holes are No. from the position at the left 60 ° to the position at the right 60 ° with respect to the excavation direction. It was set to 1-5.

As liquid A, 40 kg of A2 in Table 1 was added to chemical liquid tank A, and as liquid B, 40 kg of B1 in Table 2.
The solution was placed in the chemical solution tank B, and the solution A and the solution B were pump-circulated for about 1 to 2 minutes.

Next, the tip of each discharge hose of liquid A and liquid B was
After connecting to the character-shaped unit, it is connected to the bolts (No. 1 to 5) of the respective injection holes, which are fixed to the natural ground, and the No. 1,
Injection pressure 0.1 to 1 MPa (gauge pressure) in the order of 3, 5, 2, 4 and injection speed 5 to 12 kg / min, approximately 1 per hole.
20 kg, no. A total of 600 kg was injected from 1 to 5.

About 90 minutes after the injection of the injectable chemical composition, the vicinity of the injection hole was dug and examined to confirm the stabilization status of the ground, and No. The left roof parts of Nos. 1 to 5 were solidified in a hemispherical shape with a radius of about 40 cm, and large voids were well sealed with high density. In addition, there was no collapse from the roof during excavation, and it was well stabilized.

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 is completely sealed and well infiltrates into the crush zone to stabilize the rock mass. It has been proved to be very useful in tunnel excavation work.

Example 12 A crack was generated in the rising corner portion of the roof slab of a reinforced concrete three-story building, and water was leaking downstairs during rainfall. A2 in Table 1 and B in Table 2
The injectable chemical solution composition No. 1 was injected, and the water stop work was performed.

First, a hole having a depth of about 5 cm was formed along the crack with a drill having a diameter of 10 mm at a pitch of about 30 cm.
After making individual holes and blowing out the shavings and dust in the holes with compressed air, absorbent cotton was placed on the holes to a thickness of about 5 mm, and an injection pipe with an outer diameter of about 10 mm was hammered in with a cotton hammer.

Next, A2 was put into the chemical liquid tank A with a hand pump of 10 kg, and B1 was put into the chemical liquid tank B with a hand pump of 15 kg.

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 (mass 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. About 1.
The injection work of all 35 pieces was completed in 5 hours.

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

[0089]

EFFECTS OF THE INVENTION The injectable liquid chemical composition for stabilizing the ground and artificial structures of the present invention and the stable reinforcing water stopping method using the same are
The following effects are achieved.

Alkali silicate aqueous solution as component (A) and diphenylmethane diisocyanate as component (B)
(B1) and diphenylmethane diisocyanate-based polynuclear
Polyisocyanate and poly (OH) consisting of the condensate (B2)
Isopropyl obtained by reacting (xypropylene) polyol
Depending on the cyanate group-terminated prepolymer , the component (E), poly (oxypropylene ), which is optionally used
When a polyol is used, a reliable composite of urea-silicic anhydride complex, urethane-silicic anhydride complex and reticulated silicic anhydride gel body is formed by the component (E). It is formed. 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), component (C) and component (D), and component (E) have low viscosities, and further component (A), component (C) and component (D) Has good compatibility, and since it surely foams and solidifies, it has excellent permeability.

Since it is surely foamed and hardened and has a high solidified body strength, it is effective for filling unstable rocks, ground, structures, etc., which require large strength and have many cracks, and for strengthening stability.

Since the components (C) and (D) 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 and removed. Extremely high Further, since the component (A) is hydrophobic, it is unlikely to seep into the groundwater layer.

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 construction method for achieving stable strengthening, sealing, and water stoppage of unstable rock or ground that is economical and excellent in safety.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C09K 107: 00 C09K 107: 00

Claims (4)

(57) [Claims] 1. (A) Alkaline silicate aqueous solution, (B) Di
Phenylmethane diisocyanate (B1) and dipheni
Made of methane diisocyanate polynuclear condensate (B2)
Polyisocyanate and poly (oxypropylene) poly
Isocyanate group-terminated prepolymer obtained by reacting all
An injectable liquid composition for stabilization of a ground, an artificial structure or the like, which comprises a polymer , (C) 1,2-dimethylimidazole and (D) N, N-diethylethanolamine . 2. (E) Poly (oxypropylene) polio
The injectable liquid chemical composition for stabilization according to claim 1, which contains a sol. 3. A bored a plurality of holes at predetermined intervals in the bedrock or ground, inserting a hollow injection bolt into said hole, according to any one of claims 1 or 2 from the opening of the bolt A stable strengthening water stop construction method for a rock or a ground, comprising injecting the stabilizing injectable liquid chemical composition into the rock or the ground to consolidate or seal the rock or the ground. 4. Insert the filler pipe to the man-made structures, a stabilizing injecting chemical composition according to any one of claims 1 or 2 through the infusion pipe, man-made structures and / or A method for stabilizing and waterproofing artificial structures, which is characterized by injecting into the back surface and solidifying or sealing.