JPH04283290A - Grouting composition for stabilizing soil, etc., and engineering method using same for stabilizing and reinforcing soil and preventing water from gushing - Google Patents

Abstract

PURPOSE:To provide a grouting composition useful for solidifying and stabilizing unstable portions of base rock, soil, artificial structures, etc., and preventing water from gushing, and an engineering method using same for stabilizing and reinforcing soil and preventing water from gushing. CONSTITUTION:A grouting composition comprising an aqueous sodium silicate solution (A) and a polyisocyanate composition (B) comprising a reactive diluent (b) which does not react with polyisocyanate (a) but is hydrolyzed by the solution (A) to react with it and/or the component (a), and an engineering method for stabilizing and reinforcing soil and preventing water from gushing wherein the composition is injected into and solidified in soil or artificial structures. The addition of the diluent (b) improves the permeability to base rock, etc., increases the strength of the solifdified composite, and enhances the stability in environmental and hygienic aspects.

Description

[Detailed description of the invention]

0001

[Industrial Application Fields] The present invention is useful for solidifying and stabilizing rock masses with fracture zones and unstable soft ground, for water-stopping rock masses or soils with water leaks and springs, and for cracks and voids in artificial structures such as concrete. The present invention relates to a stable reinforced water stop construction method such as, and an injection chemical composition used therein.

0002

[Prior Art and Problems to be Solved by the Invention] Conventionally, inorganic or organic grout has been injected as a method for stably strengthening unstable rock and ground, and filling cracks and voids in artificial structures. It is having some effect.

However, when these methods are examined in detail, they do not necessarily yield satisfactory results. For example, the cement milk system that is commonly used is in the form of a suspension, so it has poor permeability into cracks in rock and artificial structures, and into ground layers such as gravel, and the consolidation rate is slow, resulting in strength development. Because of the slowness of the process, it is impossible to achieve the goal of quickly stabilizing and strengthening unstable ground during tunnels and underground excavations, which require solidification and strength development in a short period of time. Furthermore, if there is spring water or water leakage, the injected cement milk will be diluted and washed away. In addition, water glass two-component system grout, which is a typical inorganic grout, has a solid strength of 3 to 10 kg/cm2.
To a lesser extent, when the solid body comes into contact with water, changes occur over time, and main components such as Na2O and SiO2 are leached out.
There are problems with alkali contamination and a significant decrease in strength.

On the other hand, organic grouts such as urea grouts also have problems such as insufficient consolidation strength and elution of curing components and auxiliary components such as sulfuric acid and formalin. Also,
JP 63-63687, JP 63-63688, JP 63-63688, JP 63-741
Publication No. 3, Publication No. 63-7490, Publication No. 63-74
Publication No. 91, Publication No. 63-8477, Publication No. 63-3
Publication No. 5913 and other documents describe a method of solidifying rock by injecting a fast-curing hard urethane foam system containing polyol and polyisocyanate as the main components, but although the consolidation effect can be expected, it is extremely expensive and is flammable. Therefore, there is a need for improvement in terms of economy and safety.

Further, JP-A-61-9482 discloses that polyisocyanate and water glass (sodium silicate aqueous solution) are used, and a specific tertiary amine or amino alcohol is added to the water glass side as a trimerization catalyst for the polyisocyanate. A liquid injection composition containing a Mannich base is described. Although this composition is flame retardant, it requires an expensive trimerization catalyst, and it also needs to be diluted with a large amount of organic solvent to improve the fluidity of the polyisocyanate.

[0006]

[Means for Solving the Problems] The present invention has been made in view of the problems of the prior art, and involves injecting an injectable drug composition consisting of specific components to form a non-foamed or foamed inorganic-organic composition. By forming a composite compact, it is possible to stably strengthen and watertight rock or ground and artificial structures with high consolidation strength, stable reinforcement effect, durability, injection workability, safety and economic efficiency. It is closed.

[0007] That is, the present invention is directed to (A) an aqueous sodium silicate solution, and (B) (a) polyisocyanate, which does not react with (b) component (a) but is alkaline hydrolyzed by component (A), and its An injection chemical composition for stabilizing soil or artificial structures, comprising a polyisocyanate composition whose decomposition product is a reactive diluent which is an oxygen-containing organic compound that reacts with component (A) and/or component (A). In the first invention, several holes are drilled at predetermined intervals in rock or ground, a hollow injection bolt is inserted into the holes, and the injection chemical composition is injected and solidified through the opening of the bolt. A second invention provides a water stop construction method for stabilizing rock or ground, which is characterized by: inserting an injection pipe into an artificial structure, and injecting and solidifying the injection chemical composition into the injection pipe. The third invention is a method for stably reinforcing water stoppage construction for artificial structures, which is characterized by the following.

[0008]

[Function and Examples] Although the solidification reaction in the present invention is extremely complicated and not clear, it is possible to
When mixed with polyisocyanate composition (B), the silanol groups formed in a part of component (A) and the isocyanate groups in component (A) react to form a silicic anhydride-urethane complex. In addition, component (A) reacts with water to generate carbon dioxide gas, and also bonds with urea to form a multimer or a silicic anhydride-urea crosslinked complex, and the carbon dioxide gas generated also reacts with the alkali in component (A). It is presumed that it is absorbed into the aqueous solution and gels the sodium silicate to form anhydrous silicic acid gel.

[0009] Component (b) blended in the present invention is:
It has the function of diluting the polyisocyanate, which is the component (A), and lowering its viscosity during injection, and also undergoes alkaline hydrolysis when it comes into contact with the aqueous solution of sodium silicate, which is the component (A), and the component (A) and/or It reacts with component (A) and actively participates in the curing reaction between component (A) and component (B), creating stronger silicic anhydride-urethane composites, silicic anhydride-urea crosslinked composites, and reticulated It is an ester or ether that forms an inorganic-organic composite solid mainly composed of anhydrous silicic acid gel.

The alkaline hydrolysis product of component (b) has at least one functional group that reacts with component (A) and/or component (b) as described above. Examples include alcoholic hydroxyl group, carboxyl group, primary or secondary amino group, and thiol group. For example, when ethylene glycol diacetate is used as component (B), ethylene glycol and acetic acid are produced as hydrolysis products, and this ethylene glycol reacts with the polyisocyanate of component (A) to form a three-dimensional polyurethane crosslinked product. On the other hand, it is presumed that acetic acid neutralizes or dehydrates the sodium silicate component (A) to form a network of siloxane bonds and promote gelation.

By blending component (b) in this manner, an inorganic-organic composite solid having even greater mechanical strength and hardness can be obtained.

The injectable drug composition of the present invention (hereinafter also referred to as injectable drug) will be described below.

First, as the sodium silicate aqueous solution of component (A), as mentioned above, a commercially available sodium silicate aqueous solution is used as the main component. This sodium silicate is represented by the formula: Na2O.xSiO2.nH2O, and the molar ratio of Na2O and SiO2 is 2:1 to 1:4.
It is. The solid content concentration of the aqueous solution is usually 10 to 70.
% (weight %, hereinafter the same), particularly preferably from 20 to 40%.

[0014] In the component (A), a curing accelerating catalyst may be blended to accelerate the reaction with the polyisocyanate of the component (B). From the viewpoint of catalytic activity and storage stability, such curing accelerating catalysts are particularly preferably tertiary alkylamines or cyclic amines, such as dimethyloctylamine, dimethyllaurylamine, morpholine, piperazine, and the like. Other examples include dibutyltin dilaurate, triethylenediamine, imidazole, monoethanolamine, diethanolamine,
Triethanolamine and other substances react with sodium silicate or are hydrolyzed and lose their catalytic ability, so they must be added immediately before injection. The amount of the curing accelerating catalyst is 0.1 to 20%, preferably 0.5 to 15% in component (A).

Further, if necessary, a surfactant may be used to emulsify and disperse the curing accelerating catalyst in the aqueous sodium silicate solution. For example, when using a tertiary alkylamine as a curing accelerating catalyst, any anionic, nonionic, cationic, or amphoteric surfactant can be used, and specific examples include alkyl sulfates, alkylbenzene sulfonates, and ethoxyalkyl sulfates. , sodium salts such as ethoxyalkylbenzene sulfates,
Examples include aqueous solutions of amine salts, ammonium salts, etc., alkyl phosphates, and nonionic surfactants prepared by addition-polymerizing several moles of ethylene oxide to alcohol or alkylphenol. The amount of these surfactants is 1 to 100%, preferably 10 to 20% of the curing accelerating catalyst.

In the present invention, the sodium silicate aqueous solution contains 3
Particularly excellent effects can be obtained when an alkylamine emulsified and dispersed with a surfactant is used as component (A).

Examples of the polyisocyanate (A) which is the main component in component (B) include polymethylene polyphenylisocyanate, liquid diphenylmethane diisocyanate, tolylene diisocyanate, crude tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, A polyisocyanate such as naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, trimethylene xylylene diisocyanate, etc. alone or in a mixture; further, an adduct or polyisocyanate obtained by modifying the polyisocyanate with water or a lower mono- to polyhydric alcohol is reacted with various polyols. urethane prepolymers containing terminal isocyanate groups alone or as a mixture; furthermore, adducts thereof; or mixtures of prepolymers and one or more of the above various polyisocyanates; furthermore, a catalyst is added to the above polyisocyanate; Examples include those in the form of mer or trimer.

Among these various polyisocyanates, liquid diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, urethane prepolymers containing terminal isocyanate groups and adducts are preferred from the viewpoint of consolidation strength, safety and hygiene, and economic efficiency, and they are suitable for the so-called handling environment. Preferably, the material has extremely low volatility under temperature, is liquid, and has a structure with good solidification strength and economical efficiency.

As the adduct, for example, 1 mole of trimethylolpropane to 3 tolylene diisocyanate is used.
Add moles and add ethyl acetate to reach a solid content of 75%.
Examples include those obtained by partially modifying polymethylene polyphenylisocyanate with a lower alcohol ethoxylate obtained by adding 1 to 10 moles of ethylene oxide to methyl alcohol, ethyl alcohol, or the like.

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

First, the polyol used in the prepolymer includes, for example, 1,3-butanediol, 1,
Dihydric alcohols such as 4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, glycerin, trimethylolpropane, mono-, di- or triethanolamine, Examples include polyols obtained by adding and polymerizing alkylene oxides such as propylene oxide or ethylene oxide to diglycerin, sorbitol, sucrose, etc. alone or in mixtures, and castor oil. Furthermore, various polyester polyols obtained by dehydration condensation reactions of dibasic acids such as adipic acid and phthalic anhydride with glycols and triols such as ethylene glycol, diethylene glycol, and trimethylolpropane, and lactones obtained by ring-opening polymerization of ε-caprolactam. Polyester polyols, polycarbonate diols synthesized by phosgenation of polyols, transesterification with diphenyl carbonate, other acrylic polyols,
Polybutadiene polyols, phenolic polyols obtained by addition polymerizing propylene oxide or ethylene oxide to Mannich polyols, novolac resins, resol resins, etc., and polyols obtained by radical polymerization of vinyl monomers such as acrylonitrile and styrene, Polymer polyols obtained by dispersing and dissolving these polymers in polyols, polytetramethylene glycols obtained by cationic polymerization of tetrahydrofuran, and modified polyols obtained by addition polymerizing alkylene oxides to these polymers may also be mentioned.

The molecular weight of these polyols is 40 to 20
,000 is preferred. In addition, when using the polymethylene polyphenylisocyanate as the polyisocyanate, it is preferable to use a slightly hydrophilic polyol because it has excellent compatibility. Specifically, when the average molecular weight exceeds 1000, ethylene oxide The unit is 5 to 99.5% in molecular weight, preferably 10 to 20%
It is preferable to add hydrophilicity by adding it so that it is contained therein.

Examples of the polyisocyanate to be reacted with these polyols include polymethylene polyphenylisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. alone or in mixtures. Preferably used.

Using these polyols and polyisocyanates, urethane prepolymers containing terminal isocyanate groups can be easily produced by known methods.

[0025] The polyisocyanate (A) component is (A)
It has excellent reactivity with components and solidifying properties. However, due to its relatively high viscosity, it does not have sufficient permeability into bedrock and ground.
Therefore, conventionally, organic solvents such as toluene, xylene, 1,1,1-trichloroethane, methylene chloride, and trichlorofluoromethane have been used as diluents to improve fluidity and permeability. However, since these organic solvents are volatile and may be released after solidification, damaging the environment, it is preferable not to use them as much as possible.

Therefore, in the present invention, as a diluent for component (A), it does not react with isocyanate groups even when mixed with component (A), and therefore has an excellent storage stabilizing effect and viscosity reducing effect for component (A). On the other hand, when mixed and contacted with component (A), a specific reactive diluent (b) is blended, which immediately reacts and hardens as described above, and therefore has little impact on the environment.

Compared to the case where the reactive diluent (b) is not added, (b) greatly improves the permeability into the rock and ground due to the lower viscosity of the component (b), and low volatility, which improves labor safety. Preferable from the viewpoint of environmental hygiene (1) (a) The storage stability of the component is improved. (2) A composite reaction solidified structure is obtained by the reaction, and the strength of the solidified body is greatly improved.

As mentioned above, the reactive diluent should be a liquid with low viscosity at the operating temperature (approximately -5 to 40°C) and have low volatility; (a) it should be inert to the components; )
that the hydrolysis product is (A
) component and/or (a) reacts with the component. Examples of reactive groups in the hydrolysis product include hydroxyl group, carboxyl group, primary or secondary amino group, and thiol group, and those having one or more of these groups are preferred.

Typical examples of reactive diluents include diesters of low molecular weight dibasic acids, acetate esters of mono- or polyhydric alcohols, alkylene carbonates, ethers, cyclic esters, acid anhydrides, Examples include various acrylic esters and methacrylic esters.

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;
Examples include dialkyl esters such as diethyl ester.

[0031] As the acetate esters of alcohols,
For example, acetates of glycol ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol methyl ether, ethyl carbitol, and butyl carbitol; alkoxyalkyl alcohols such as 3-methoxybutyl alcohol and 3-methyl-3-methoxybutyl alcohol. and diacetates of glycols such as ethylene glycol, diethylene glycol, and triethylene glycol.

Examples of alkylene carbonates include propylene carbonate.

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

Examples of the cyclic esters include lactones such as γ-butyllactone; lactams such as ε-caprolactam.

Various acrylic esters or methacrylic esters include alkyl esters of acrylic acid or methacrylic acid such as methyl, ethyl and butyl, as well as acrylic acid or methacrylic acid and ethylene glycol, diethylene glycol, with a molecular weight of 100 to 1000.
Examples include polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol with a molecular weight of 100 to 100, ethylene oxide with a molecular weight of 100 to 5,000, and esters of propylene oxide with alcohols such as copolymerized diols or triols.

[0036] Examples of the acid anhydride include maleic anhydride.

The blending amount of component (B) is 5 to 90%, preferably 10 to 50% in the polyisocyanate composition (B).
Within this range, (a) is appropriately selected depending on the type and viscosity of the component, purpose of use, etc. If the amount of component (b) is too small, the viscosity-reducing effect and the effect of improving solidification strength on component (a) will be reduced, and if it is too large, the strength of the solidified body will be reduced.

Furthermore, a conventional diluent may be used in combination for the purpose of supplementing the reactive diluent (b) or imparting foaming properties.

Furthermore, inorganic fillers such as cement, blast furnace slag, gypsum, calcium carbonate, clay, aluminum hydroxide, antimony trioxide, quicklime, slaked lime, and bentonite may be added to component (B). These inorganic fillers have the property of curing and forming a composite compact when mixed with component (A), and as a result, the compaction strength is improved and the crack and void filling sealing effect is also improved. The blending amount of these inorganic fillers is preferably 0 to 80%, preferably 0 to 50% in component (B), and is added and mixed into component (B) during the injection operation, and mixed together with component (A). Pump.

[0040] Furthermore, polyisocyanate composition (B)
If necessary, a catalyst for accelerating the reaction and curing with component (A), such as a metal catalyst such as dibutyltin dilaurate or stannous octylate, or an amine such as triethylenediamine or triethylamine, is usually added to the polyisocyanate (A). On the other hand, it may be added in an amount of about 0.1 to 5% at the time of use. When these catalysts are added in advance to component (A), (
Since component A) gels, it is added to component (a) at the time of use.

In addition, a silicone foam stabilizer such as organopolysiloxane is added to component (A) and/or (B).
It may be blended into the ingredients.

In order to improve the elasticity and mechanical strength of the solid body, various polymeric materials such as solvent-type vulcanized or unvulcanized rubbers such as butadiene rubber, chloroprene rubber, styrene-butadiene rubber, and ethylene can be used. −
When injecting propylene rubber, emulsions thereof, various polyacrylic resin emulsions, polyvinyl alcohol, ethylene-vinyl acid acid emulsions, polyurethane resin dispersions, polyethylene oxide, etc., the necessary amount is added to component (A) and/or component (B). You can also do that.

[0043] Furthermore, if necessary, stabilizers such as various anti-aging agents, heat resistance imparting agents, and antioxidants may be added to component (B). The amount of these stabilizers may be generally 0 to 2% in component (B).

[0044] Blending ratio of (A) component and (B) component (
(A) component/(B) component) cannot be determined unconditionally because it varies depending on the composition ratio of Na2O and Si2O contained in component (A), but it is usually 10/100 to 100 in weight ratio. /10, preferably 20/
It is desirable to adjust the ratio to 100 to 100/20. If the ratio is less than 10/100, the cost of the injected drug becomes expensive and uneconomical, and it becomes extremely difficult to control the mixing ratio with a proportional infusion pump, resulting in slow effects. Also 100/10
If it exceeds this range, the solidification will be insufficient and the product will be unhardened, and even if it hardens, it will be very weak and brittle and cannot be put to practical use.

The injection drug composition of the present invention comprises two components: a sodium silicate aqueous solution (A) and a polyisocyanate composition (B).
It basically consists of a liquid, and both components are mixed just before injection into rock. As for the mixing method, there are methods described below, and in cases where the gelation time is long or for small-scale injection, there are known methods such as mixing component (A) and component (B) in advance and injecting using the one-shot method. Can be adopted.

(A) When using the sodium silicate aqueous solution alone, the component (A) is prepared at a solid content concentration of about 10 to 10% as described above.
The amount may be 70%, but when other components such as a curing accelerating catalyst are added, a surfactant may be used if necessary to sufficiently disperse them while stirring.

Component (B) is prepared by adding a reactive diluent (b) to the polyisocyanate component (a), and if necessary, adding a conventional diluent and mixing thoroughly. When blending a curing accelerating catalyst such as dibutyltin dilaurate or an inorganic filler such as cement, if these are mixed in advance, component (B) may thicken or gel during storage, and may cause precipitation. Therefore, it is preferable to add it immediately before mixing with component (A).

[0048] This is a special injection drug solution in the present invention (A
) component and (B) component is injected into soft or unstable ground with many voids and cracks, bedrock, fractured zones, and even artificial structures with cracks and voids. However, there are no particular limitations on the method of injecting and solidifying, and any known method may be employed. For example, (A) component and (B
) Using a comparative mixing pump that can control the injection amount, pressure, mixing ratio, etc. of ingredients, (A) ingredient and (B)
The components are placed in separate tanks, and static mixers, check valves, etc. fixed in advance are installed in predetermined locations such as rock (for example, multiple holes drilled at intervals of about 0.5 to 3 m). Each component in the tank is injected into the tank through a perforated rock bolt or injection rod at a pressure of 0.
．． Inject at 5 to 50 kg/cm2・G, pass through a static mixer, uniformly mix predetermined amounts of component (A) and component (B), inject into a predetermined unstable rock or ground location, harden and solidify. There are methods to stabilize the bond.

For example, when pouring into the top of a tunnel, holes are drilled at predetermined intervals of, for example, about 2 m using a leg auger with a 42 mmφ bit to a depth of 2 m and a drilling angle. A length of 3 m is provided with an injection hole of 10 to 30 degrees, and a hole 4 in which a static mixer 2 and a check valve 3 as shown in FIG. 1 are inserted into the injection hole.
A lock bolt 1 made of a hollow carbon steel pipe is inserted, and the mouth of the lock bolt 1 is sealed using a rag, quick-setting cement, or a rag pre-impregnated with foamed hard urethane resin to prevent backflow of the injected chemical solution. , it is preferable to inject the drug solution 5 by the method described above. The injection operation ends when the injection pressure rises rapidly or when an amount increased by about 20% by volume over the predetermined injection amount is injected. Generally, each injection hole weighs 30 to 200 kg of chemical liquid.
Just inject it.

[0050] In addition, for stabilizing and reinforcing water stopping of cracks in artificial structures, for example, a distance of 20 to 50 cm from the surface of the crack is required.
Drill holes with a diameter of 10 mm and a depth of 5 to 10 cm at intervals of 10 mm, blow away the shavings and dust in the holes with compressed air, place absorbent cotton about 5 mm thick on the drilled holes, and place about 10 mm in diameter on top of the holes.
Inject an injection pipe with a length of 20 to 30 mm and set it in a state where there is no leakage of the injected chemical solution. Also, make U- or V-shaped cuts at a pitch of about 30 cm at locations where cracks or water leaks occur, and fix the injection pipe with quick-setting cement. Next, components (A) and (B) of the present invention are injected at a predetermined mixing ratio using a proportional mixing pump or hand pump through a Y-shaped tube or a T-shaped tube equipped with a static mixer or the like at a pressure of 0. 5~20kg/cm2・G,
Preferably, a predetermined amount of 0.5 to 2 kg/cm 2 ·G is injected. The injection volume is generally the estimated void volume plus α
That's fine.

[0051] The stable reinforced water stop method of the present invention has low viscosity of the chemical solution and has good permeability into unstable ground, cracks, fractured zones, etc., and can be used over a wide range of unstable rock and ground, as well as artificial structures, etc. It is possible to stabilize water and stop water. In addition, the formed hardened solids have high strength and durability, have excellent adhesion and adhesion to bedrock, are nonflammable or flame retardant, and are economical. This is a practically advantageous method.

The present invention will be explained in more detail below based on production examples and examples, but the present invention is not limited only to these examples. Note that parts in the production examples are parts by weight.

Production Examples 1 to 4 Components (A) and (B) shown in Table 1 were prepared separately, and component (B) was added to component (A) and mixed with stirring.

[0054] The time from the time of mixing to gelation, the bending and compression test of the obtained solid body (JIS R 520
1), density (JIS K 5400), and flammability test (burning time and burning distance. JIS A9514) results are shown in Table 1.
Shown below.

(A) Ingredients include sodium silicate No. 3 (Na
2O/SiO2 = 1/3, molar ratio) 40% aqueous solution was used.

(B) Component is polyisocyanate (A)
A reactive diluent (b) was added to the mixture, and a normal diluent was further mixed as appropriate. Note that the curing accelerating catalyst and inorganic filler were mixed with component (B) immediately before mixing with component (A). was used as the cement.

Production Examples 5 to 9 The compositions shown in Table 2 were prepared using, as component (A), a curing accelerating catalyst dispersed in an aqueous sodium silicate solution with a surfactant, and the compositions were prepared in the same manner as in Production Example 1. Te(A) ,(
B) The components were mixed and their properties were investigated. The results are shown in Table 2.

Comparative Examples 1 to 3 Comparative injection drug compositions were prepared in the same manner as Production Example 1, Production Example 3, and Production Example 8 except that a conventional diluent was used instead of the reactive diluent (b). were prepared and their properties were investigated. The results are shown in Table 3.

The abbreviations in Tables 1, 2 and 3 are as follows.

(Polyisocyanate) C-MDI Polymethylene polyphenyl polyisocyanate D-40
0MDI polyoxypropylene glycol (average molecular weight 400
) Polyoxypropylene triol (average molecular weight 350
) Terminated NCO group-containing urethane prepolymer TMP-TDI in which 941 parts of C-MDI was reacted with 100 parts.3 moles of tolylene diisocyanate was added to 1 mole of trimethylolpropane, and the solid content was 75% by diluting with methyl acetate.
% terminal NCO group-containing urethane prepolymer So-8
50MDI polyoxypropylene hexaol (average molecular weight 85
0) Terminal NCO group-containing urethane prepolymer LA-MDI in which 785 parts of C-MDI was reacted with 100 parts of ε-caprolactam polyester triol (average molecular weight 312) 10 parts of C-MDI was reacted with 100 parts of
53 parts reacted terminal NCO group-containing urethane prepolymer PET-MDI 100 parts of diethylene glycol phthalic anhydride polyester diol (average molecular weight 356) C-MI
Terminal NCO group-containing urethane prepolymer castor oil made by reacting 621 parts of D with terminal NCO group containing urethane prepolymer (reactive diluent) MMB-AC 3-methyl-3-methoxybutyl acetate PGM-
AC Acetate ester of propylene glycol methyl ether E
GDA Ethylene glycol diacetate POC Propylene carbonate GAME Glutaric acid methyl ester DHCO Dehydrated castor oil THF Tetrahydrofuran (catalyst) TVS Tin wax dibutyltin dilaurate (surfactant) NPE-11 Nonionic interface with 11 moles of ethylene oxide added to 1 mole of nonylphenol Activator NPS-4 Ammonium sulfate salt of 4 moles of ethylene oxide added to 1 mole of nonylphenol

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

Example 1 Holes were drilled at 2m intervals at an angle of 25 to 35° in the top of a tunnel having a crushing zone using a leg auger with a 42mmφ bit.
Five holes were drilled at an angle to the tunnel excavation direction, and a carbon steel (JIS G 3
445, STKM 17C) injection bolt (outline 27.
2 mm, internal diameter 15 mm, length 3 m, static mixer and check valve interior) was inserted, and approximately 30 cm of the mouth portion was sealed by pushing a knitted cloth impregnated with two-component hard urethane foam resin with an iron rod.

Next, the chemical solution of Production Example 1 in Table 1 was injected into each fixed injection hole at a pressure of about 5 to 10 kg/cm2.
・Approximately 80 to 120 kg was injected per hole at G.

Approximately 120 minutes after injecting the chemical solution, the state of improvement of the ground was investigated by excavation, and it was found that the consolidation area was hemispherical with a radius of 2 m, and the consolidation was stable.

[0067] The injection solidification part was 5cmφ×1 using a sampler.
When sampled in a cylindrical shape of 0 cm, the unconfined compressive strength was measured to be 135 kg/cm2. Note that sampling was not possible in the unimproved area due to the fractured zone. As a result, the effectiveness of the chemical solution of the present invention was fully demonstrated, and it was found that a solidified stabilizing layer was formed.

Example 2 In order to stabilize the top of a tunnel in a granite fracture zone having large voids, stabilization was carried out by injecting the chemical solution of Production Example 6 in Table 2. The construction method was the same as in Example 1.

That is, 10 injection holes 2 m deep were drilled at approximately 2 m intervals in the top plate using a leg auger with a 42 mmφ bit. The drilling angle was 20°. A carbon steel rock bolt (JI
SG 3455, STKM 17C) was inserted, and the mouth was sealed in the same manner as in Example 1.

[0070] 70 to 110 kg of the chemical solution of Production Example 6 in Table 2 was applied to each injection hole (injection pressure 2 to 10 kg/cm).
2.G) was injected. Approximately 150 minutes after injecting the drug solution
After several minutes, we excavated around the injection hole to check the stabilization status of the ground, and found that the area was solidified in a hemispherical shape with a radius of about 2 m, and the large voids were also dense and well-consolidated. It was sealed. For reference, the single solidified portion of the chemical solution of Production Example 6, which was sealed and solidified in a particularly large void, was core sampled into a 5 cm φ x 10 cm cylindrical shape using a sampler to measure the unconfined compressive strength and conduct a combustion test. was carried out. The results are shown in Table 4.

[0071]

[Table 4]

From the results of Example 2, it was found that by injecting the chemical solution of the present invention into a granite fracture zone having larger voids than the injection bolt, the voids were completely sealed and the chemical solution well penetrated into the fracture zone and solidified. It has been proven to be extremely useful in tunnel excavation work, as it can stabilize the rock mass.

Example 3 G. L. (A) of Manufacturing Example 3 in Table 1 for the purpose of water stoppage and stabilization of the surrounding ground during shield excavation work (groundwater level 5 m) in fine sand spring water ground (underground) 7 to 10 m mixed with sand and gravel. B) Pass the ingredients through a steel injection rod (outside diameter 40.5 mm) inside a static mixer, and use a proportional mixing pump to give 1.5 shots at a ratio such that (A)/(B) is approximately 2/1 in volume. Approximately 230 m3 of the soil was injected into the ground surrounding the planned excavation area in accordance with the method of improvement. Furthermore, (B)
The components were thoroughly premixed in the (B) component tank before injection. Compared to before injection, the ground stability was strengthened and water stopped as shown in Table 5, and shield excavation could be promoted.

[0074]

[Table 5]

Example 4 Cracks occurred at the corners of the roof slab of a three-story reinforced concrete building, and water leaked downstairs during rain. For this crack, use a drill with a diameter of 10 mm and drill approximately 20
After drilling 15 holes with a depth of approximately 5 cm at a cm pitch and blowing away the shavings and dust in the holes with compressed air, place absorbent cotton approximately 5 mm thick over the drilled holes, and then place a layer of absorbent cotton on top of the holes with an outer diameter of approximately 10 m.
I hammered in the m injection pipe with a wooden hammer. A Y-shaped tube with a static mixer inside was set in the injection pipe, and the components (A) and (B) of Production Example 4 in Table 1 were mixed with (A)/(
B) About 2 to 3 liters were injected per hole using a hand injection pump at a ratio such that the volume ratio was about 1/1.

After pouring, the pouring pipe was removed, a cork was inserted, and mortar was applied to finish. Approximately two weeks later, there was heavy rain, but the water leakage did not occur at all, proving that it was very effective in sealing cracks and stopping water.

[0077]

ADVANTAGEOUS EFFECTS OF THE INVENTION The injectable liquid composition of the present invention and the stably reinforced water stop construction method using the same exhibit the effects (1) to (4) described below.

■ A reliable urea-silicic anhydride complex, urethane-silicic anhydride complex, and A composite solid of silicic anhydride is formed, and the inorganic filler and the like also form a composite solid with sodium silicate or silicic anhydride and harden, resulting in a marked improvement in consolidation strength. Therefore, the solidification and hardening performance is very high, and it is possible to reliably stabilize and strengthen rock or the ground, and a reliable water-stopping effect can be achieved at leakage areas.

■ Both component (A) and component (B) have low viscosity and excellent permeability.

(A) Since an aqueous sodium silicate solution is used as a component, the cost is low and it is economical.

[0081] It has a high consolidated strength and is effective for stabilizing unstable rock or ground that requires strength.

■ It has excellent durability and is flame retardant or non-combustible, so there is little fear of fire. It is also excellent in terms of occupational safety and health.

[0083] As described above, the construction method of the present invention has excellent characteristics, and is more reliable and has higher strength, which is required not only for general mountain tunnels, but also for large-section tunnel excavation work, deep underground civil engineering work, etc. This method is economical, highly safe, and extremely effective for stabilizing unstable rock or ground and achieving water stoppage.

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view of an example of a rock bolt used in the construction method of the present invention.

[Explanation of symbols]

1 Lock bolt 5 Injection drug solution

Claims (5)

[Claims] Claim 1: (A) Sodium silicate aqueous solution and (B) (a) polyisocyanate do not react with (b) (a) component, but are alkaline hydrolyzed by (A) component and the decomposition products are An injection drug composition for stabilizing earth or artificial structures, comprising a polyisocyanate composition comprising a reactive diluent which is an ester or ether that reacts with component (A) and/or component (A). 2. The composition according to claim 1, wherein component (A) contains a tertiary alkylamine and a surfactant. 3. The composition according to claim 1, wherein the alkaline hydrolysis product of component (b) is a compound having a hydroxyl group and/or a carboxyl group as a reactive group. 4. A plurality of holes are drilled at predetermined intervals in rock or the ground, a hollow injection bolt is inserted into the hole, and the injection drug composition according to claim 1 is applied to the rock or the ground through the opening of the bolt. A water stop method for stabilizing and strengthening rock or ground, which is characterized by injecting water into the ground and solidifying it. 5. An artificial structure, characterized in that an injection pipe is inserted into the artificial structure, and the injection drug composition according to claim 1 is injected into the artificial structure through the injection pipe and solidified. Stable reinforced water stop method.