JPH06207174A - Grouting liquid composition for stabilizing subsoil and artificial construction and stabilizing and reinforcing water-stopping process using the composition - Google Patents

Abstract

PURPOSE:To provide a grouting liquid composition useful for the consolidation, stabilization, sealing and water-stopping of unstable part of rock stratum, subsoil and artificial construction and to provide a stabilizing and reinforcing water- stopping process using the composition. CONSTITUTION:The grouting liquid composition for the stabilization of subsoil and artificial construction is composed of (A) an aqueous solution of an alkali metal silicate, (B) a polyisocyanate component and (C) a polyol component. The present invention also relates to a stabilizing and reinforcing water-stopping process using the composition. Since the obtained consolidated material has a foamed composite solid state, the composition has excellent impregnation property and durability and is economical. Since it is free from solvent, the composition has excellent safety and is extremely effective for the stabilization of subsoil required to have high subsoil-supporting power such as a tunnel having large cross section, an underground construction work at a deep part and the reinforcement of existing tunnel because of high strength of the consolidated product.

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 of rocks and grounds with spring water, cracks, voids, and existing tunnels in artificial structures such as concrete. The present invention relates to a method for strengthening stability, sealing, and sealing water, and a stabilizing injectable liquid chemical 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, in JP-A-61-9482, polyisocyanate and water glass (sodium silicate aqueous solution) are used, and a specific tertiary amine is blended on the water glass side as a polyisocyanate trimerization catalyst. An injectable liquid composition is described. This composition is flame-retardant, but since it is a non-foamed solidified body, it is an expensive injection material even though the strength of the solidified body is relatively large, and its generalization is hindered. In addition, in order to reduce costs, it has been considered to add an organic solvent to these systems to form a foamed solid, but when using an organic solvent like this, there is a safety and health problem. However, there are drawbacks such as low expansion ratio, insufficient economic effect, and insufficient strength due to brittleness of the foamed solidified body.

Further, JP-A-55-160079 discloses a composition containing a mixture of water glass and a product (C-MDI) obtained by treating an aniline-formaldehyde condensation product with phosgene as a main component. However, such a composition also has drawbacks such as low expansion ratio of the solidified body and insufficient strength because the foamed solidified body is brittle.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made by paying attention to the above-mentioned prior art, and it has been conventionally difficult to form by injecting an injectable liquid chemical composition comprising a solventless specific component. By forming a foamed inorganic-organic composite consolidate, it has a large consolidation strength, stable strengthening effect, durability, pouring workability, safety, and economical stability of rock or ground and artificial structures. The purpose is to strengthen or stop water.

[0008]

That is, the present invention is
A stabilizing injectable liquid composition, which comprises (A) an aqueous solution of an alkali silicate, (B) a polyisocyanate component, and (C) a polyol component, for stabilizing a ground or an artificial structure is defined as a first invention, and the stabilizing injectable liquid is In the composition, the second invention is that the (B) polyisocyanate component is polymethylene polyphenyl isocyanate having a polyol modification rate of 2% by weight or more, and the (B) polyisocyanate component is (a) polyisocyanate. And (b) it does not react with (a) polyisocyanate, but is alkali-hydrolyzed by (A) alkali silicate aqueous solution, and the decomposition product is (A) alkali silicate aqueous solution and / or (a) polyisocyanate. A third aspect of the present invention is that it comprises a reactive diluent that is a reacting ester or ether. In formula for injecting chemical composition,
(D) A fourth invention comprising a tertiary amine, wherein a plurality of holes are formed at predetermined intervals in the rock or 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 to solidify or seal the rock or the ground, thereby enhancing the stability of the rock or the ground. The water-stopping method is the fifth invention, and further, an injection pipe is inserted into the artificial structure, and the stabilizing injectable chemical liquid composition is injected into the artificial structure and / or the back surface thereof through the injection pipe to solidify. According to a sixth aspect of the present invention, there is provided a stable strengthening and waterproofing method for an artificial structure, which is characterized by being sealed.

[0009]

ACTION AND EXAMPLES The reaction solidification mechanism during curing in the present invention is not clear because it is complicated, but it is presumed that it is probably based on the gasification reaction and gelation reaction described below.

First, urea is reacted by reacting water in (A) an aqueous solution of an alkali silicate (hereinafter referred to as (A) component) with an isocyanate group in (B) polyisocyanate component (hereinafter referred to as (B) component). Bonds are formed and polymerize. Further, the isocyanate group in the component (B) and (C)
By the reaction with the hydroxyl group in the polyol component (hereinafter referred to as the component (C)), a urethane bond is formed and polymerized. At this time, carbon dioxide gas is generated (gasification reaction). Due to the action of the carbon dioxide gas, a part of the silicic acid anhydride colloid in the component (A) is dehydrated to form a silicic acid anhydride gel (gelation reaction). Next, a urethane bond is formed by the reaction between the silanol group in the component (A) and the isocyanate group in the component (B), and a silicic acid anhydride-urethane complex is formed. Further, if a reactive diluent is present in the component (B), it is decomposed by the alkali of the component (A), and its product is brought into contact with the silicic acid anhydride colloid in the component (A), so that the silicic acid gel is formed. It is formed (gelation reaction), and the decomposition product and the isocyanate group in the component (B) form a urethane bond and a urea bond to polymerize.

By the balance between the gasification reaction and the gelation reaction, a foamed or non-foamed solidified body is formed.
That is, when the gelation reaction is prioritized over the gasification reaction or the gasification reaction is extremely fast, the generated gas cannot be trapped and a non-foamed solid body is formed. on the other hand,
When the balance between the gasification reaction and the gelation reaction is appropriate, that is, when the gelation reaction is in progress when the gasification reaction is in progress, the generated gas is appropriately silicic acid. Entrapped in the skeleton of the soda-urethane composite, a foam-like solid is formed. In addition, (B) component and (C)
The urethane resin obtained by the reaction with the component imparts flexibility to the solidified body, and the strength of the solidified body is further improved as compared with a system in which the component (C) is not present.

The injectable liquid chemical composition for stabilization of the present invention easily foams without adding a conventional foaming agent such as CFC, methylene chloride, and acetone, and the strength of the foamed solid product obtained is high. It's a big one.

The stabilizing injectable chemical liquid composition of the present invention (hereinafter referred to as the injectable chemical liquid composition) will be described below.

The aqueous alkali silicate solution which is the component (A) used in the present invention has, for example, the formula: Na ₂ O.
An aqueous solution of sodium silicate represented by xSiO ₂ (wherein x represents a number of 1 to 4) can be given.

It is preferable to adjust the solid content concentration of the aqueous solution of alkali silicate to be usually 10 to 70% by weight, especially 40 to 50% by weight.

The polyisocyanate component which is the component (B) used in the present invention does not react with, for example, polyisocyanate (hereinafter referred to as the component (a)), the component (i) and the component (b) (i). What is comprised of a reactive diluent (hereinafter referred to as (b) component) which is an ester or an ether which is hydrolyzed by the component (a) and is hydrolyzed with the component (a) and / or (a). And so on.

Examples of the component (a) include diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate (polymeric MDI), liquid diphenylmethane diisocyanate, tolylene diisocyanate, crude tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, water. A polyisocyanate such as added diphenylmethane diisocyanate or trimethylene xylylene diisocyanate, or a mixture of two or more kinds thereof; and further, reacting an adduct or polyisocyanate obtained by modifying the above polyisocyanate with water or a lower monohydric or polyhydric alcohol, and various polyols The above-mentioned urethane prepolymer containing a terminal isocyanate group, or a mixture of two or more thereof Further, these adducts; or a mixture of prepolymers and one or more of the above polyisocyanates; and a dimer or trimer obtained by adding a catalyst to the polyisocyanate. .

Among these various polyisocyanates, polymethylene polyphenyl polyisocyanate and urethane prepolymer containing terminal isocyanate group are preferable from the viewpoints of consolidation strength, safety and hygiene, and economical efficiency, and their volatility under so-called handling environmental temperature. Is very small, and it is preferable that it is liquid and has a solidifying strength and economy.

The polyol modification ratio of the polymethylene polyphenyl polyisocyanate is preferably 2% by weight or more in order to improve the compressive strength of the formed solid, but if it is too large. Has
The modified polymethylene polyphenyl polyisocyanate has a high viscosity, which makes pumping difficult and also tends to reduce the compressive strength. Further, if the modification ratio is less than 2% by weight, the modification effect is extremely small, the solid is fragile, and the compressive strength cannot be improved. As a result of the test, it is desirable that the polyol modification ratio of the polymethylene polyphenyl polyisocyanate is 2 to 80% by weight, especially 5 to 50% by weight.

As the adduct, for example, 1 mol of trimethylolpropane to 3 parts of tolylene diisocyanate is used.
Add moles, add diluent to add 75% solids by weight
And a partially modified polymethylene polyphenyl polyisocyanate with a lower alcohol ethoxylate obtained by adding 1 to 10 mol of ethylene oxide to methyl alcohol, ethyl alcohol and the like.

Next, the urethane prepolymer containing a terminal isocyanate group will be described.

First, examples of the polyol used in the prepolymer include dihydric alcohols such as 1,3-butanediol, 1,4-butanediol and 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol, dipropylene glycol, butylene glycol, glycerin, trimethylolpropane, monoethanolamine, diethanolamine, triethanolamine, diglycerin,
Examples thereof include sorbitol, saccharose, and the like, or a polyol obtained by addition-polymerizing an alkylene oxide such as propylene oxide or ethylene oxide to a mixture of two or more kinds, castor oil, and the like. Furthermore, various polyester polyols obtained by dehydration condensation reaction of dibasic acids such as adipic acid and phthalic anhydride with glycols and triols such as ethylene glycol, diethylene glycol and trimethylolpropane, and lactone-based polymers obtained by ring-opening polymerization of ε-caprolactam. Polyester polyol, phosgenation of polyol, polycarbonate diol synthesized by transesterification method with diphenyl carbonate, other acrylic polyol, polybutadiene polyol,
Furthermore, Mannich polyols, novolac resins, phenolic polyols obtained by addition-polymerizing propylene oxide or ethylene oxide to resol resins, etc., radical-polymerized vinyl monomers such as acrylonitrile and styrene in polyols, and these polymers Other examples include polymer polyols dispersed and dissolved in a polyol, polytetramethylene glycol obtained by cationic polymerization of tetrahydrofuran, and modified polyols obtained by addition-polymerizing alkylene oxides with these.

The average molecular weight of these polyols is 40-20.
It is preferably 000. Further, when the polymethylene polyphenyl polyisocyanate is used as the polyisocyanate, it is preferable that the polyol having a slight hydrophilicity is excellent in compatibility, and specifically, when the average molecular weight exceeds 1,000. Contains 5 to 99.5% by weight of ethylene oxide units in the molecule, preferably
It is preferable to add 10 to 50% by weight so as to impart hydrophilicity.

Examples of the polyisocyanate to be reacted with these polyols include polymethylene polyphenyl polyisocyanate (polymeric MDI), diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate. A single type or a mixture of two or more types is preferably used.

The rate of modification of polyisocyanate with these various polyols is effectively 2% by weight or more in terms of the amount of polyol in terms of the effect of improving the compression strength of the solidified body.

Urethane prepolymers containing terminal isocyanate groups consisting of these polyols and polyisocyanates can be easily produced by known methods.

The component (a) is excellent in reactivity and solidification property with the component (A), but has a relatively high viscosity, so that it does not sufficiently penetrate into the rock or the ground, so that it is conventionally flowable. Toluene and xylene, 1,1,
Organic solvents such as 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.

Therefore, as a diluent for the component (a), (a)
Even if mixed with the ingredients, it does not react with the isocyanate group,
(A) It has excellent storage stability and viscosity reduction, while (A)
When mixed and contacted with the components, it is preferable to incorporate the component (b), which is a reactive diluent that reacts and cures immediately as described above and has little influence on the environment.

The component (b) has a function of diluting the component (a) to reduce the viscosity at the time of injection, and
When it is brought into contact with the component (A), it undergoes alkaline hydrolysis and reacts with the component (A) and / or the component (a) to actively participate in the curing reaction between the component (A) and the component (a). , 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 an improving ester or ether.

The alkaline hydrolysis product of the component (b) is
As described above, it has at least one functional group that reacts with the component (A) and / or the component (a). Examples of such reactive functional groups include alcoholic hydroxyl groups,
Examples thereof include a carboxyl group, a primary or secondary amino group and a thiol group. For example, when ethylene glycol diacetate is used as the component (b), ethylene glycol and acetic acid are produced as hydrolysis products, and the ethylene glycol reacts with the polyisocyanate as the component (b) to give a three-dimensional polyurethane. It is presumed that, while forming a crosslinked product, acetic acid neutralizes or dehydrates sodium silicate as the component (A) to form a reticulated siloxane bond to promote gelation.

As described above, by blending the component (b), it is possible to obtain an inorganic-organic composite solidified body having much higher mechanical strength and hardness without using an organic solvent.

Here, compared with the case where the component (b) is not blended, the permeability of the component (a) to the rock or the ground is greatly improved due to the low viscosity, and the volatility is small, which is preferable in terms of occupational safety and environmental hygiene. , (A) The storage stability of the component is improved,
The foaming property at the time of reaction consolidation is improved, a complex reaction-consolidated structure is obtained by the reaction, and the strength of the consolidated body is significantly improved.

As described above, the component (b) is a low-viscosity liquid at the use environment temperature (about -5 to 40 ° C) and has low volatility (boiling point at room temperature and 1 atm is 100 ° C or more). ), That it is inert to component (a), that it is hydrolyzed by component (A), and that the hydrolysis product reacts with component (A) and / or component (a). To do. Examples of the reactive group of the hydrolysis product include a hydroxyl group, a carboxyl group, a primary or secondary amino group, and a thiol group, and those having one or two or more of these reactive groups are preferable.

Typical examples of the component (b) include diesters of low molecular weight dibasic acids, acetic acid esters of monohydric or polyhydric alcohols, alkylene carbonates,
Examples thereof include ethers, cyclic esters, acid anhydrides and (meth) acrylic acid esters.

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.

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 an average molecular weight of 100.
~ 1000 polyethylene glycol, propylene glycol, dipropylene glycol, average molecular weight 100-1000
Polypropylene glycol, average molecular weight 100-5000
Examples thereof include (meth) acrylic acid esters with alcohols such as ethylene oxide and propylene oxide copolymerized diols or triols.

The blending amount of the component (b) is 5 to 5 in the component (B).
It is desirable to be 90% by weight, preferably 10 to 50% by weight, and it is preferable to appropriately select within this range depending on the kind and viscosity of the component (a), the purpose of use and the like. If the blending amount of the component (b) is too small, the effect of reducing the viscosity of the component (a) and the effect of improving the caking strength tend not to be sufficiently exhibited, and if it is too large, the reverse In particular, the strength of the solidified body tends to decrease.

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

The mixing ratio of the component (A) and the component (B) (component (A) / component (B)) is usually 10/100 by weight.
It is desirable to adjust so that it is up to 100/10, preferably 20/100 to 100/20. Such compounding ratio is 10/100
If it is smaller than 100 μm, the injection liquid composition cost becomes uneconomical and uneconomical, it becomes extremely difficult to control the compounding ratio with a proportional injection pump, and curing tends to be slow. If it exceeds / 10,
The foamability is impaired, the solidification is insufficient and uncured, and even if it is cured, it tends to be very weak, brittle and unusable for practical use.

The mixing ratio of the component (B) and the component (C) is
The equivalent ratio (NCO / OH) of the NCO group in the component (B) and the OH group in the component (C) is 0.5 to 500, preferably 1 to 12
It is desirable to adjust so that it becomes zero. When the equivalent ratio is less than 0.5, the solidified body obtained from the injectable liquid composition tends to be too soft and difficult to put into practical use, and when it exceeds 500, the solidified body becomes large. Tends to be brittle.

The injectable liquid composition of the present invention contains (D) a tertiary amine (hereinafter referred to as (D) component) in addition to the (A) component, (B) component and (C) component. can do.

The component (D) acts as a catalyst for promoting the reaction curing of the components (A), (B) and (C). As the component (D), a tertiary alkylamine or a cyclic tertiary amine is preferable from the viewpoint of catalytic activity and storage stability, and for example, dimethyloctylamine, dimethyllaurylamine, dimethylpalmitylamine, N-methylmorpholine, triethylenediamine. , Bisdimethylaminoethyl ether, triethanolamine and the like.

The content of the component (D) is 0.1 to 20% by weight, preferably 0.5 to 10% by weight in the component (A). When the content of the component (D) is less than 0.1% by weight, the solidification reaction is slow and the desired foamed solidified body tends to be difficult to obtain.
If the content exceeds 10% by weight, the component (A) tends to gel, or the solidification reaction tends to be too fast to make the solidified product practically useful.

In order to emulsify and disperse the component (D) in the component (A), a surfactant can be used if necessary. For example, when a tertiary alkylamine is used as the component (D), any of anionic, nonionic, cationic and amphoteric surfactants can be used, and specific examples thereof include alkyl sulphate. , Alkyl benzene sulfonate, ethoxy alkyl sulphate, ethoxy alkyl benzene sulphate, etc., sodium salt, amine salt, ammonium salt etc. in addition to alkyl phosphate, non-ionic surface active by adding several moles of ethylene oxide to alcohol or alkyl phenol Examples include agents. The amount of these surfactants used is 1 to 100% by weight, preferably 10 to 20% by weight of the component (D).

Further, in the present invention, an inorganic filler such as cement, blast furnace slag, gypsum, calcium carbonate, clay, aluminum hydroxide, antimony trioxide, quick lime, slaked lime, bentonite, etc. can be added to the liquid chemical composition for injection. . When these inorganic fillers are mixed with the component (A), they have the property of hardening to form a composite solidified body, and as a result, the consolidation strength is improved and the effect of filling and sealing cracks and voids is improved. To do. The blending amount of such an inorganic filler is (B)
It is desirable that the content of the component is 0 to 80% by weight, preferably 5 to 50% by weight, and it may be added and mixed into the component (B) at the time of injection work, and pumped with the component (A).

Further, a silicone type foam stabilizer such as organopolysiloxane, for example, solvent type vulcanized or unvulcanized rubber, that is, butadiene rubber, chloroprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, emulsions thereof, various poly types, and the like. Acrylic resin emulsion, polyvinyl alcohol, ethylene-vinyl acrylate resin emulsion, polyurethane dispersion, polyethylene oxide, etc. various polymer materials to improve the elasticity and mechanical strength of the solidified body, etc. are blended in the required amount at the time of injection. can do.

If desired, various stabilizers such as antiaging agents, heat resistance imparting agents and antioxidants may be added. The amount of these stabilizers is generally 0 in the component (B).
~ 2 wt% may be sufficient.

The injectable liquid composition of the present invention comprises the component (A),
It basically consists of three components, component (B) and component (C), and both components are mixed immediately before injection into rock or the like. Regarding the mixing method, if the gelling time is long or small-scale injection is performed, the components (A), (B) and (C) are pre-mixed and injected by a one-shot method. The publicly known method of can be adopted.

When the component (A) is used alone, the solid content concentration is about 10 to 70 when the component (A) is used alone.
It may be adjusted so as to be a weight%, but when other components such as the component (D) are blended, a surfactant may be used, if necessary, to sufficiently disperse under stirring.

When the component (B) is prepared from the component (a) and the component (b), the component (b) is prepared.
Add (b) component to the components and mix thoroughly. In addition,
When compounding inorganic fillers such as cement, if these are mixed in advance, thickening or gelation of component (B) may occur during storage, and precipitates may occur, so (A ) It is preferable to add just before mixing with the component.

Further, since the component (C) reacts with the component (B) in advance, it is preferable to mix it with the component (A) in advance.

The injectable liquid composition comprising the component (A), the component (B) and the component (C), which is a special injectable liquid in the present invention, is a soft or unstable ground, rock or crushed zone with many voids and cracks. It is injected into a layer, further into an artificial structure having cracks or voids, and solidified or sealed, but the method of injection and solidification or sealing is not particularly limited, and a known method can be used. Can be adopted. As an example thereof, a comparative blending pump capable of controlling the injection amount, pressure, blending ratio, etc. of the components (A), (B) and (C) is used, and the components (A) and (C) are used. Put the mixture and the component (B) in separate tanks, and fix them in advance at a predetermined location (eg, a plurality of holes drilled at intervals of 0.5 to 3 m) such as bedrock in a static mixer or check valve. Pass through a perforated rock bolt or injection rod with a valve etc. inside, and inject each component in the tank at an injection pressure of 0.5 to 70 kg / cm ² · G, and through a static mixer to a predetermined amount (A) There is a method of uniformly mixing the components, the component (B) and the component (C), injecting and permeating into a predetermined unstable rock or ground portion, hardening and consolidating or sealing, and stabilizing.

For example, when pouring into the roof part at the tip of the 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 chemical solution per injection hole is 30 to 200 kg.

Further, the stable strengthening waterproofing such as cracks of the artificial structure can be obtained by drilling a hole 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. 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 the components (A) and (C) and the component (B) are blended in a predetermined manner using a proportional blending pump or a hand pump. Injection pressure is 0.5 to 20 kg / cm ² · G, preferably
Inject a prescribed amount of 0.5 to ² kg / cm ² · G. The injection volume can generally be the estimated void volume plus α.

In the stable water-stop construction method of the present invention, a chemical composition having a low viscosity of the chemical solution used is used, and a foamed solidified body having a foaming ratio of 2 times or more is formed.
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 to and adhesion to bedrock, exhibits flame retardancy, and is economical.

Next, the injectable liquid chemical composition for stabilizing the ground or artificial structure of the present invention and the stable strengthening water stopping 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. The parts in the production examples are parts by weight.

Production Examples 1 to 6 and Comparative Production Example 1 Component A and component B were separately prepared at the blending ratios shown in Table 1, and component B was added to component A with stirring and mixed.

The time from the mixing to the gelation (gel time, 20 ° C.), the expansion ratio and the strength of the obtained solidified body were examined. The results are shown in Table 1.

The expansion ratio of the solidified body is a value obtained by dividing the volume of the solidified body by the total volume of the component A and the component B.

The strength of the solidified body was evaluated as ○ when the solidified body was easily broken by pouring it with a steel spatula and when it was easily broken. In the comprehensive evaluation, when the expansion ratio is 2 times or more and the strength evaluation is ◯, the evaluation is ◯, and the other cases are evaluated as x.

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

As the component (B), a mixture of the component (a) with the component (b) added and used.

[0068]

[Table 1]

The equivalent ratios in Table 1 are equivalent ratios of NCO groups in the component (B) and OH groups in the component (C).

The abbreviations in Table 1 mean the following.

(Component (a)) C-MDI Polymethylene polyphenyl polyisocyanate (Polymeric MDI) PEG-5000MDI Polyoxyethylene glycol (average molecular weight 5000) 150
850 parts of C-MDI with respect to 10 parts of urethane prepolymer containing terminal NCO group PEG-2000MDI Polyoxyethylene glycol (average molecular weight 2000) 100
900 parts of C-MDI was reacted with 100 parts of urethane prepolymer containing terminal NCO group So-850MDI Polyoxypropylene hexaol (average molecular weight 850)
25 parts of C-MDI was reacted with 975 parts of C-MDI urethane prepolymer containing terminal NCO group GPE-3000MDI-L Propylene oxide and ethylene oxide were mixed at a mixing ratio of 50.
Triol (average molecular weight 3000) obtained by addition-polymerizing mixed alkylene oxide of 50/50 (weight ratio) to glycerin
Urethane prepolymer containing terminal NCO group containing 900 parts of liquid diphenylmethane diisocyanate per 100 parts ((b) component) EGDA ethylene glycol diacetate EC / POC mixing ratio of ethylene carbonate and propylene carbonate is 25/75 (weight Ratio) PAH Propionic anhydride MMB-AC 3-Methyl-3-methoxybutylacetate POC Propylene carbonate ((C) component) GPE-3000 Mixing ratio of propylene oxide and ethylene oxide is 50
Triol (average molecular weight 3000) obtained by addition-polymerizing mixed alkylene oxide of 50/50 (weight ratio) to glycerin (average component weight of 3000) ((D) component) DPA dimethylpalmitylamine (surfactant) NPS-4 Nonylphenol with 1 mole of ethylene oxide Ammonium sulfate salt of 4 mol added NPE-11 Nonionic surfactant in which 11 mol of ethylene oxide is added to 1 mol of nonylphenol 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 , Within a total of 120 ° fan-shaped range, 10 holes were drilled with a 42mmφ bit at 1m intervals with a jumbo machine at an angle of 15 ° (angle to the tunnel excavation direction), and carbon steel ( 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 about 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
180kg could be injected smoothly.

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

The injection-solidified portion is sampled with a sampler of 5 cmφ × 10 cm
It was 220 kg / cm ² when the uniaxial compressive strength was measured by sampling into a columnar shape. 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 performed by injecting a chemical solution in Production Example 4 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 ° in the roof part at the tip 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.
From No. 1 to No. 10 toward the position of No.

20.5 kg of the component A of the injectable liquid chemical composition of Production Example 4 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, the tips of the discharge hoses of the component A and the component B were connected to a T-shaped unit and then fixed to the ground.
Connect to the bolts (No. 1-5) of each injection hole, and
Injection pressure 1 to 10 kg / cm ² · G in the order of 1, ³ , 5, ² , 4
Approximately 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, for the bolts Nos. 6 to 10 of the injection holes, the injection liquid chemical composition of Comparative Production Example 1 was used, and 600 kg in total was injected in the same manner in the order of Nos. 6, 8, 10, 7, and 9. did.

About 90 minutes after injecting the injectable liquid composition, the vicinity of the injection hole was excavated and examined in order to confirm the stabilization situation of the ground, and the left roof portion of Nos. 1 to 5 showed that 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, with respect to the right side roof parts of Nos. 6 to 10, the consolidation range was about 11 cm in radius and they were consolidated in a hemispherical shape.
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 a granite crush zone having a void larger than that of the injection bolt, the void was completely sealed and the crush zone was well solidified. 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 rooftop slab of a reinforced concrete three-story building, and water leaked downstairs during rainfall. The injectable chemical liquid composition of Production Example 3 was injected into this water leaking portion, and water stop work was performed.

First, 35 holes with a pitch of about 30 cm and a depth of about 5 cm were drilled along a crack 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 10 kg of the component B was placed in the chemical solution 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 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.

[0088]

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.

A reliable urea-containing compound is obtained by the aqueous solution of alkali silicate which is the component (A), the polyisocyanate component which is the component (B) and the polyol component which is the component (C).
A foamed composite conglomerate having a foaming ratio of at least 2 times is formed, which is mainly composed of a silicic acid anhydride composite, a urethane-silicic acid composite and a reticulated silicic acid anhydride gel, and further contains an inorganic filler and the like. When it is used, it forms a foamed composite solid body with sodium silicate or anhydrous silicic acid and hardens to increase the solidification strength. 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.

The components (A), (B), and (C) all have low viscosities, and have excellent permeability because they reliably foam and solidify.

Since a foamed solidified body having a foaming ratio of 2 times or more is obtained without using a conventional foaming agent such as chlorofluorocarbon or methylene chloride, the injection amount can be small, which is economical.

[0092] It is surely foamed and cured at a foaming ratio of 2 times or more, and the solidified body has a large strength, so that there are large voids or many cracks, and filling and stability of unstable rock, ground, or structure that requires strength is required. Effective for strengthening.

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 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 (6)

[Claims] 1. An (A) alkaline silicate aqueous solution, (B)
An injectable liquid composition for stabilizing the ground or artificial structure, which comprises a polyisocyanate component and a (C) polyol component. 2. The stabilizing injectable liquid chemical composition according to claim 1, wherein the polyisocyanate component (B) is polymethylene polyphenyl polyisocyanate having a polyol modification rate of 2% by weight or more. 3. The polyisocyanate component (B) is (a).
Although it does not react with polyisocyanate and (b) (a) polyisocyanate, it is hydrolyzed with an alkali aqueous solution of (A) alkali silicate and the decomposition product is (A).
The stabilizing injectable liquid composition according to claim 1, which comprises an alkaline silicate aqueous solution and / or (a) a reactive diluent which is an ester or an ether that reacts with a polyisocyanate. 4. The stabilizing injectable drug solution composition according to claim 1, 2 or 3, which comprises (D) a tertiary amine. 5. The stabilizing injection chemical liquid composition according to claim 1, wherein a plurality of holes are formed in the rock or ground at predetermined intervals, hollow injection bolts are inserted into the holes, and the openings of the bolts are used for stabilization. A method for stabilizing and waterproofing rock or ground by injecting water into the rock or ground to solidify or seal it. 6. An injection pipe is inserted into the artificial structure, and the stabilizing injectable chemical composition according to claim 1 is injected into the artificial structure and / or its back surface through the injection pipe to consolidate or seal. A stable and reinforced water stop method for artificial structures, which is characterized by stopping.