JPH05320647A - Self-extinguishing injectable liquid chemical composition for stabilization of soil and etc. and stable water-stop construction method using the same - Google Patents

Abstract

(57) [Abstract] [Purpose] Injectable liquid chemical composition for consolidating or sealing earth, sand, rock, brick, coal, etc., and sealing the cavity of rock or artificial structure, and stable water-stopping using the same. Providing construction methods. [Structure] (A) Polyol and / or organic polyamine compound, (B) Organic polyisocyanate compound and organic phosphorus-containing compound, and (C) The total amount of (A) component and (B) component per 100 parts by weight. And a stable strengthening method for injecting the injected liquid chemical composition into rock, ground, artificial structure and the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to rock and concrete with crush zones and stabilization of solidification of unstable soft ground, water leakage, stopping of rock or ground with spring water, shield ground excavation work, etc. Filling voids between segments, sealing voids such as earth and sand, rocks, bricks, coal, cracking artificial structures such as concrete, stable strengthening waterproofing method for voids and self-extinguishing type for stabilization It relates to an injectable liquid composition.

[0002]

2. Description of the Related Art Conventionally, inorganic or organic grout has been injected as one of the methods for strengthening the stability of unstable rocks and ground and 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, the cement milk system, which is widely used, is in the form of a suspension, so it has poor permeability to the ground layers such as cracks and gravel in rocks and artificial structures, and also has a slow consolidation rate and strength development. Since it is slow, the purpose of early and stable strengthening of unstable rocks at the time of tunneling and underground ground excavation, which is required to consolidate and develop strength in a short time, cannot be achieved. In addition, the injected cement milk is diluted and washed away even if there is spring water or leakage. Also, the water-glass two-liquid system grout, which is a typical inorganic grout, has a low solidified strength of about 3 to 10 kg / cm ² , and when the solidified material comes into contact with water, a change with time occurs.
There is a problem that the main components such as Na ₂ O 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.

Further, Japanese Patent Publication No. 63-63687 and 63-63688.
JP, JP 63-7413 JP, 63-7490 JP, JP
63-7491, 63-8477, 63-35913, etc. describe a rock consolidation method by injecting a fast-curing hard urethane foam system containing polyol and polyisocyanate as main components. However, although it can be expected to have a solidifying effect, it has the following problems.

That is, the reaction temperature after the two liquids are mixed is extremely high, and the ground having large voids,
If you inject a large amount into a void such as the back of an existing tunnel,
Reaction heat is accumulated, and the temperature of the foamed and cured urethane resin, including the raw material polyol, additives, and polyisocyanate, reaches a temperature above the ignition point, which may cause a fire, the viscosity of the polyol component is high, and the polyisocyanate component In order to improve the dispersibility with
Since it needs to be diluted with an organic solvent, it is not preferable in terms of safety and hygiene, and since the above raw materials are used, it is very expensive and there are problems such as environmental pollution.

Generally, according to the method using a rigid urethane foam, as described in the above-mentioned literature, a foaming agent such as polyol and freon, a catalyst, a foam stabilizer, and 0 to 2 parts by weight per 100 parts by weight of the polyol. By mixing a small amount of a mixed solution of water or the like with polyisocyanate at a predetermined ratio, a solidified body having an expansion ratio of 2 to 30 times can be obtained. However, in this method, since a large amount of heat is generated during the reaction when forming a foamed solidified body, it is possible to foam-mold a large amount at a time, or even for molded articles with a wall thickness of 10 mm or more and civil engineering applications. When a large amount is injected into the void, there is a concern that internal scorch and further fire may be generated due to the accumulation of reaction heat. Therefore, it was recognized that it cannot be applied to voids in rock, ground, artificial structures, and backfilling materials for shield construction. In addition, when the bolts and supports are fused or cut, a gas burner or an electric arc is used, but ordinary urethane foam is ignited by sparks or flames and easily burns, which is a risk of fire.

[0008]

Therefore, as a result of intensive studies conducted by the present inventors in view of the above-mentioned prior art, (A)
When a large amount of water is added to a polyol and / or an organic polyamine compound, and (B) an organic polyisocyanate compound and an organic phosphorus-containing compound, it is unexpected when it is injected into rock or ground or an artificial structure. In particular, there is no fire or scorch, and it is possible to stably enhance the stability of these rocks, ground, and artificial structures, seal the voids, and stop the water. Moreover, even if they ignite, they have self-extinguishing properties. Therefore, they have found that there is no risk of fire, and have completed the present invention.

[0009]

[Means for Solving the Problems] That is, the present invention is (A)
Polyol and / or organic polyamine compound, (B)
An organic polyisocyanate compound and an organic phosphorus-containing compound, and (C) the total amount of the component (A) and the component (B) 10
A first invention is a self-extinguishing injectable liquid composition for stabilizing soil and the like, which comprises 5 parts by weight or more of water with respect to 0 parts by weight,
A plurality of holes are formed in the rock or the ground at a predetermined interval, a hollow injection bolt is inserted into the hole, and the stabilizing self-extinguishing injection chemical composition for stabilization is applied to the rock or the ground from the opening of the bolt. A second aspect of the present invention is a stable water-stopping construction method for rock or ground, which is characterized by injecting and solidifying, and further, an injection pipe is inserted into an artificial structure, and the self-extinguishing for stabilization is performed through the injection pipe. A third aspect of the present invention is a stable strengthening and water-stopping method for an artificial structure, which comprises injecting a mold injection chemical composition into an artificial structure and solidifying the composition.

[0010]

[Operations and Examples] When the self-extinguishing injectable chemical liquid composition for stabilizing soil and the like of the present invention is injected into rock, ground or artificial structure, a large amount of added water causes the reaction. The heat is taken as the heat of vaporization when water is evaporated,
As a result, even if the slaughter heat temperature is usually 150 ℃ or higher, it is possible to suppress heat generation to a temperature below 100 ℃ to 120 ℃, which is the boiling point of water, so that no fire or scorch is generated. It won't happen.

The composition of the present invention contains an organic phosphorus-containing compound, and as a result of containing water, as a result of containing a large amount of water in the cells of the foam produced by solidification, self-extinguishing even if ignited. ..

Further, when the stabilizing self-extinguishing type injection liquid composition of the present invention is used, since a hard foamed polyurethane solidified body mainly containing a urea bond is formed, the solidified strength is large. In addition, it has excellent effects such as void sealing effect and stability strengthening result, and it is possible to effectively perform stable strengthening of rock or ground or artificial structure, void sealing and water stoppage.

The injectable liquid composition of the present invention contains a polyol and / or an organic polyamine compound as the component (A).

The hydrogen group value of the polyol is preferably 10 to 2000 mgKOH / g in order to obtain a hard foamed solidified body. Further, in order to facilitate mixing of the polyol and water, it is preferable that the polyol is slightly hydrophilic as it has excellent compatibility with water, specifically, a hydroxyl value of 300 mgKOH / g or less. The ethylene oxide unit has a molecular weight of 0 to 99.5% by weight, preferably 10 to 9%.
It is preferable to add 9.5% by weight to impart hydrophilicity.

Specific examples of the polyol 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, acetylene glycol, glycerin,
Trimethylolpropane, diglycerin, castor oil, dehydrated castor oil, sorbitol, sucrose, etc., alone or in a mixture; and polyols obtained by addition-polymerizing alkylene oxides such as propylene oxide and ethylene oxide. In addition, ethylenediamine, aniline,
Amine polyols obtained by addition-polymerizing alkylene oxides such as propylene oxide and ethylene oxide to tolylenediamine, mono-, di- or triethanolamine are also effective. 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-based polyol,
Furthermore, Mannich polyols, novolac resins, phenolic polyols obtained by addition-polymerizing propylene oxide or ethylene oxide to resole resins, etc., radical-polymerized vinyl monomers such as acrylonitrile and styrene in polyols, and these polymers Examples thereof 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.

Like the above-mentioned polyol, the above-mentioned organic polyamine compound is a component for reacting with the organic polyisocyanate compound and the organic phosphorus-containing compound, which are the components (B) described later, to form a skeleton of a solidified body, It is particularly effective in improving the strength of the solidified body. The organic polyamine compound is not particularly limited, but a water-soluble or hydrophilic compound is preferable in order to obtain a composition containing excessive water.

Specific examples of the organic polyamine compound include diamines such as ethylenediamine, tri, tetra, penta, hexamethylenediamine and urea,
Monoalcoholamines such as monoethanolamine,
Aromatic primary and secondary amines such as toluenediamine, diethyltoluenediamine, diphenylmethanediamine, m-phenylenediamine, xylylenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, and the end of polypropylene glycol Examples include various amine compounds such as various aminated Jeffamine series (manufactured by Jefferson Chemical Company), diesters of polytetramethylene glycol and aminobenzoic acid (manufactured by Kodak). These organic polyamine compounds can be used alone as the component (A) in combination with the organic polyisocyanate compound and the organic phosphorus-containing compound as the component (B), but they are economical, control of reaction curing time, workability, etc. From the point of view, it is practical to use it in combination with a polyol.

If necessary, for example, trichloromonofluoromethane (F-11), dichlorodifluoromethane (F-12) or the like may be added to the component (A) as a foaming agent. It is not necessary to use the effervescent agent, and there is no problem even if it is used in an extremely small amount as compared with the usual prescription.

As the foam stabilizer, if necessary, a small amount of organopolysiloxane, oxyethylated higher alcohol, etc. may be added to the component (A). When the foam stabilizer is blended, it is effective for compatibility with polyisocyanate and foam regulation of foam cells. The compounding amount of the foam stabilizer is usually the polyol (A) and / or the organic polyamine compound.
It is 3 parts or less with respect to 100 parts (weight part, the same applies hereinafter).

Further, as a catalyst for accelerating reaction curing of the organic polyisocyanate composition or the organic phosphorus-containing compound as the component (B) and the polyol and / or organic polyamine compound as the component (A), for example, dibutyl Metal catalysts such as tin dilaurate and stannous octylate,
Tertiary amines such as alkylamine and triethylamine are usually added in a proportion of about 0.01 to 5 parts per 100 parts of the component (A).

Furthermore, when a large amount of water is added to the component (A), a change with time in pH due to water can be expected.
It is preferable to incorporate a pH buffer to keep the pH of the system in the neutral range. Examples of such buffering agents include potassium dihydrogen phosphate, disodium hydrogen phosphate, sodium tetraborate (borax) and the like. The blending amount of these pH buffers may be about 1% by weight with respect to the amount of water.

Further, if necessary, an antioxidant, a heat resistance imparting agent, an antioxidant, an antifungal agent and the like may be added to the component (A).

The organic polyisocyanate compound in the component (B) is a component which reacts with the component (A) to form polyurethane. The organic polyisocyanate compound is not particularly limited, but any one of isocyanate monomers, polymers thereof such as dimers and trimers, and compounds modified with alcohol or polyol are effective. As the organic polyisocyanate, those having an isocyanate group content of 5 to 48% by weight, particularly 10 to 33% by weight are preferable from the viewpoint of solidified physical properties. Specific examples of the organic polyisocyanate compound include, for example, polymethylene polyphenyl isocyanate, liquid diphenylmethane diisocyanate, tolylene diisocyanate,
Crude tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, trimethylene xylylene diisocyanate, etc., alone or in a mixture; and further modified with water or a lower mono-polyhydric alcohol. A single or a mixture of an end isocyanate group-containing urethane prepolymer obtained by reacting an adduct or a polyisocyanate with various polyols; further these adducts; or a mixture of prepolymers and one or more of the above polyisocyanates. And the like; and a dimer or trimer obtained by further adding a catalyst to the polyisocyanate.

Of these various organic polyisocyanate compounds, liquid diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, urethane isocyanate prepolymers containing terminal isocyanate groups and adducts are preferred from the viewpoints of consolidation strength, safety and health and economical efficiency. It is preferable that the composition has a very low volatility under a so-called handling environment temperature, is in a liquid state, and has a consolidation strength and an economical efficiency. Further, a water-dispersible type in which polymethylene or polyphenylisocyanate is partially modified with a lower alcohol ethoxylate obtained by adding 1 to 10 mol of ethylene oxide to 1 mol of methyl alcohol, ethyl alcohol, etc. is also useful.

As the organic phosphorus-containing compound in the component (B), an organic phosphorus-containing compound which is liquid and has good compatibility with the organic polyisocyanate compound and which does not contain an active hydrogen compound which reacts with isocyanate is desirable. Specific examples of such an organic phosphorus-containing compound include, for example, tricresyl phosphate, trixylenyl phosphate,
Cresyl diphenyl phosphate, xylenyl diphenyl phosphate, triphenyl phosphate, resylcinol bis (diphenyl phosphate), 2-ethylhexyl diphenyl phosphate, trixylenyl phosphate, tris (betachloroethyl) phosphate, tris (Chloropropyl) phosphate, Tris (betachloropropyl) phosphate,
Tris (dichloropropyl) phosphate, diethyl
N, N-bis (2-hydroxyethyl) aminomethylphosphonate, dimethylmethylphosphonate, tributylphosphate, tris (betabromoethyl) phosphate, tris (bromopropyl) phosphate, tris (dibromopropyl) phosphonate Examples include fate.

The mixing ratio of the organic polyisocyanate compound and the organic phosphorus-containing compound is such that the content of the organic phosphorus-containing compound in the component (B) is 2 to 50% by weight, preferably 5 to 20% by weight. When the content of the organic phosphorus-containing compound is less than 2% by weight, the solidified body tends to lose its self-extinguishing property.
When it is more than 10% by weight, the solidified body tends to be soft and its strength tends to be very small.

It is possible to mix the organic phosphorus-containing compound with the component (A), but when mixed with the component (A), a change with time tends to occur. Therefore, in the present invention, by mixing the component (B) with the organic phosphorus-containing compound, an injectable liquid composition having a small change with time is obtained.

If desired, the component (B) may be mixed with a high-boiling diluent, a plasticizer, or the like.

The blending ratio of the component (A) and the component (B) ((A) component / (B) component) (weight ratio) is generally 1/10 to
10/1 is preferable, and 1/3 to 2/1 is more preferable.
When the compounding ratio is smaller than the above range, the curing time becomes long and the obtained solidified body tends to be brittle, and when it exceeds the above range, the solidified body becomes soft, The strength tends to be very low.

The reaction equivalent ratio of the OH groups and NH ₂ groups of the polyol in the component (A) to the NCO groups in the component (B) is (OH + NH ₂ ) / NCO of 1/10 to 10/1. Is preferable, and 1/3 to 2/1 is more preferable. When the reaction equivalence ratio is larger than the above range, the solidified body becomes soft and its strength becomes very small, and when it is smaller than the above range, the curing time becomes long and the solidified body becomes solidified. Body strength tends to be weak and brittle.

Water is added as the component (C) to the injectable drug solution composition of the present invention.

Water reacts with the organic polyisocyanate compound in the component (B) to form a urea bond and at the same time generate carbon dioxide gas, which is foamed by the action of the carbon dioxide gas to form a foamed solid body, and Due to the large amount of water present,
Part of it reacts with the NCO group, but at this time (OH + N
H ₂ + water) / NCO (equivalent ratio) is approximately 1/1 to 10/1
Since it reacts so that, the excess water exists. This excess water evaporates and takes away the heat of reaction generated when the components (A) and (B) are mixed, suppresses excessive heat storage, and prevents the occurrence of scorch and fire. Have. Water also has the effect of lowering the viscosity of the component (A), improving the permeability of the injection work and the ground, and improving the miscibility with the component (B).

The amount of water to be added is 5 parts or more per 100 parts of the total amount of the components (A) and (B). The amount of water is (A)
When the total amount of the component and the component (B) is less than 5 parts with respect to 100 parts, a fire or a scorch is likely to be generated due to heat storage of the reaction heat during solidification of the reaction with the organic polyisocyanate compound of the component (B). The effect of lowering the viscosity of the component (A) becomes small, the injection work becomes difficult, and the strength of the reaction solid is delayed. If the amount of water is too large, the solidified body tends to be foamed excessively and become brittle. Therefore, in the present invention, the blending amount of water is preferably 5 to 50 parts.

The injectable liquid composition of the present invention contains various polymeric materials for improving the elasticity and mechanical strength of the solidified body.
For example, solvent type vulcanized or unvulcanized rubber, that is, butadiene rubber, chloroprene rubber, styrene-butadiene rubber, ethylene-propylene rubber and their emulsions, various acrylic resin emulsions, polyvinyl alcohol, ethylene-vinyl acetate resin emulsion, polyurethane disperser. A bitumen emulsion such as john, polyethylene oxide, or asphalt or rubber-containing asphalt can be appropriately blended with the component (A) and / or the component (B).

Further, in the present invention, various flame retardants, flame retardant auxiliaries, inorganic modified fillers and the like may be used in combination in order to improve the consolidation strength of the consolidated body and the flame retardant effect. it can.

As the flame retardant, either an addition type or a reaction type can be used. Specific examples of the addition-type flame retardant include halogen-containing compounds such as chlorinated paraffin, pentabromoethylbenzene, and decabromodiphenyl ether. Specific examples of the reactive flame retardant include hydroxyl groups and amino groups such as dibromoneopentyl glycol, tetrabromobisphenol A, O, O-diethyl N, N-dihydroxyethylaminomethylphosphonate, and various phosphorus-containing polyols. Examples thereof include halogen-containing phosphorus-containing compounds.

Specific examples of the flame retardant auxiliary include antimony trioxide, molybdenum oxide, barium metaborate, zinc borate, aluminum hydroxide, magnesium hydroxide, melamine, melamine isocyanurate, red phosphorus,
Examples thereof include titanium phosphate, ammonium polyphosphate, calcium carbonate, calcium silicate and the like. These are used together with the flame retardant or alone to enhance the flame retardant effect.

Specific examples of the inorganic modified filler include Portland cement, colloidal cement having a small particle size, alumina cement, silica, calcium carbonate, calcium sulfate, bentonite, blast furnace slag, quick lime, slaked lime, fly ash, gypsum, Examples include carbon and pigments. These inorganic modified fillers are integrally hardened with the urethane component to form a composite solid body, and as a result, they have the property of significantly improving solid body strength, durability, crack and void sealing effect, flame retardant effect and the like. ..

The blending amount of these flame retardant, flame retardant auxiliary and inorganic modifying filler is such that the total amount of the components (A) and (B) is 100
It is preferable that the amount is adjusted to 0 to 100 parts, especially 10 to 70 parts.

These are usually the components (A) or
It is mixed with any of the components (B) and injected into the pump.

The injectable liquid composition of the present invention comprises a polyol and / or an organic polyamine compound as the component (A),
It consists essentially of a mixture of an organic polyisocyanate compound and an organic phosphorus-containing compound as component (B), and three liquids of water as component (C). Usually, a mixture of components (A) and (C) is mixed in advance. , Immediately before injecting into rock, etc., mix with component (B). A known method can be adopted as a mixing method.

In the present invention, the curing time is 10 in terms of stabilization of unstable ground, water blocking effect and work efficiency.
Seconds to 10 minutes, preferably 10 seconds to 5 minutes are preferable. The curing time can be adjusted mainly by adjusting the type and blending amount of the catalyst.

When the chemical composition of the present invention is used,
No scorch or fire is generated, injection workability is improved, it is economical, and a urea bond with a foaming ratio of about 1.5 to 30 times that is excellent in strength, void sealing effect, stability strengthening effect, and durability. Since a rigid urethane foam solidified body is mainly formed, stable strengthening of rock, ground, and artificial structures, void sealing, and water stopping are extremely good.

A special injectable drug solution in the present invention (A)
Injectable chemical composition consisting of component, (B) component and (C) component is injected into soft or unstable ground with many voids and cracks, rock, fracture zone layer, and artificial structures with cracks and voids. Although it is solidified, the method of solidification by injection is not particularly limited, and a known method can be adopted. For example, (C) component was added.
Using a comparative blending pump that can control the injection amount, pressure, blending ratio, etc. of component (A) and component (B), separate (A) component with (C) component and (B) component separately. Placed in a tank, at a predetermined location (for example, a plurality of holes drilled at intervals of 0.5 to 3 m) such as bedrock, a perforated lock bolt with a static mixer or check valve installed in advance is installed. Through the injection rod, each component in the tank was injected at an injection pressure of 0.5 to 50 kg / cm ² · G, and a predetermined amount of component (C) was added through the static mixer (A).
There is a method in which the components and the component (B) are uniformly mixed, and the mixture is injected and infiltrated into a predetermined unstable rock or ground to be hardened to stabilize and solidify.

When pouring into the roof of a tunnel, for example, a 42 mmφ bit is drilled with a jumbo machine at a predetermined interval of, for example, about 2 m to a depth of 2 m and a drilling angle. An injection hole of 10 to 30 ° is provided, and a lock bolt with a static mixer inserted therein is inserted into the injection hole, and the mouth of the lock bolt is a waste cloth, a quick-setting cement, or a foam hard material to prevent the backflow of the injected chemical solution. It is preferable to seal with a waste cloth or the like that has been previously impregnated with a urethane resin, and inject the chemical liquid by the method described above. The injection work ends when the injection pressure rises sharply or when the amount of about 20% by volume more than the predetermined injection amount is injected. Generally, 30 to 20 chemicals per injection hole
You can inject 0 kg.

Further, when backfilling the clearance (average of about 5 cm) between the ground and the shield segment in the shield construction by backfilling, a single tube rod with a stationary mixer inside the injection holes set at regular intervals inside the shield segment. And added (C) ingredient in the same manner as above.
The components (A) and (B) are injected in a fixed amount at a predetermined mixing ratio.

Further, the stable strengthening water stop such as cracks in the artificial structure is, for example, 20 to 50 cm with respect to the crack surface.
Drill a hole with a diameter of 10 mm and a depth of 5 to 10 cm, blow off the shavings and dust in the hole with compressed air, put absorbent cotton on the drilled hole to a thickness of about 5 mm, and about 10 mm in diameter from above, Length 20
Drive an injection pipe of ~ 30mm and set it so that the injection chemical does not leak. For cracks and leaks, U-shaped or V-shaped cuts should be made at a pitch of about 30 cm, and the injection pipe should be fixed with quick-setting cement. Then, through a Y-shaped tube or a T-shaped tube equipped with a static mixer, etc., use a proportional compounding pump or a hand pump to mix the (A) component with the addition of the (C) component and the (B) component. Injection pressure 0.5 to 20 kg / cm ² · G, preferably 0.5 to ² kg
Inject a specified amount of / cm ² · G. The injection volume may generally be the estimated void volume plus α.

The stable water-stop construction method of the present invention does not cause scorch or fire due to heat generation during injection and solidification of a chemical solution, has low viscosity of the chemical solution, and has permeability to unstable ground, cracks and crush zones. It is possible to stabilize unstable rocks and ground, and to stabilize artificial water and stop water over a wide range. In addition, the formed cured solid has high strength and durability, is excellent in adhesion and adhesion to bedrock, and is economical, and is therefore practical.

Hereinafter, the present invention will be described in more detail based on production examples and examples, but the present invention is not limited to these examples.

Production Examples 1 to 5 and Comparative Production Examples 1 and 2 The components (A) and (B) shown in Table 1 were separately prepared, and water was mixed with the component (A). The component (B) was added to and mixed with the component under stirring.

Time from gelling to gelation (gel time), rise time, compression test of the obtained solid (J
As a result of IS R 5201), the density (JIS K 5400), the temperature due to the heat of reaction, the presence / absence of scorch, and the self-extinguishability pass / fail (JIS A 9514) are shown in Table 1.

[0052]

[Table 1]

The abbreviations in Table 1 are as follows.

(Polyol) GP-350: Triol having a weight average molecular weight of 350 obtained by addition-polymerizing propylene oxide to glycerin [hydroxyl value 480 mgK
OH / g] G-1000-30: After addition-polymerizing propylene oxide to glycerin, ethylene oxide is further addition-polymerized at the terminal, and triol having a weight average molecular weight of 1000 and a repeating unit ratio of 30% by weight derived from ethylene oxide [ Hydroxyl value 168 mgKOH / g] EDA-2P: 1 mol of ethylenediamine, 2 mol of propylene oxide and 2 mol of ethylene oxide, tetraol having a weight average molecular weight of 272 [hydroxyl value 825 mgKOH / g] TEG: triethylene glycol [hydroxyl value 753 mgKOH / g g] (Foam stabilizer) DKS Silicone D332: Dai-ichi Kogyo Seiyaku Co., Ltd., modified polysiloxane (catalyst) DABCO 33LV: Triethylenediamine dissolved in dipropylene glycol [concentration 33% by weight] DBTL: dibutyltin dilaurate (Polyisocyanate) C-MDI: Polymethylene polyphenyl polyisocyanate (NCO Content of 32% by weight) So-MDI: 5 parts of a polyol having a weight average molecular weight of 1000, which is obtained by addition polymerization of sorbitol with propyne oxide, was added to 95 parts of C-MDI under heating and stirring to produce a modified C-MDI. Then
Propylene carbonate 5 parts was added to 100 parts of the modified C-MDI and diluted [NCO group content 27% by weight] DP-MDI: 4 parts of dipropyne glycol was added to 96 parts of C-MDI, Diluted by adding 5 parts of ethylene glycol diacetate to modified C-MDI heated and reacted [N
CO group content 26% by weight] (Organic phosphorus-containing compound) TBEP: Tris (betachloroethyl) phosphate CDP: Cresyldiphenylphosphate TBPP: Tris (betachloropropyl) phosphate (additive) SBR: Styrene-butadiene Resin emulsion [nonvolatile content 40% by weight] EVA: Ethylene-vinyl acetate resin emulsion [nonvolatile content 45% by weight] Example 1 A jumbo machine was used in a tunnel roof having a crush zone. 15 holes are drilled at ~ 35 ° (angle to the tunnel excavation direction), and carbon steel (JIS G 3445, STKM 17C) injection bolts (outer shape) are inside the holes.
27.2 mm, internal system 15 mm, length 3 m, static mixer and check valve internal) were inserted, and a knitted waste cloth impregnated with a two-component hard urethane foam resin at the mouth portion of about 30 cm was pushed and sealed with an iron rod.

Then, into each of the fixed injection holes, the injection liquid obtained in Production Example 2 in Table 1 was injected at a pressure of about 5 to 10 kg / cm ^2.
-In G, about 80 to 120 kg was injected per hole.

About 120 minutes after the chemical solution was injected, the state of improvement of the ground was investigated by excavation. As a result, the consolidation range was a hemisphere with a radius of 2 m, and the consolidation was stabilized.

The solidified portion of injection is sampled with a sampler of 5 cmφ × 10 cm
It was 50 kg / cm ² when uniaxial compressive strength was measured by sampling in the shape of a cylinder. Sampling was not possible in the unimproved area because of the shatter zone. As a result, the effectiveness of the drug solution of the present invention was sufficiently proved, and it was revealed that a consolidation stabilizing layer was formed.

Example 2 In order to stabilize the tunnel roof part of the granite crush zone having large voids, stabilization was performed by injecting a chemical solution of Manufacturing Example 5 in Table 1. The construction method was the same as in Example 1.

That is, ten injection holes having a depth of 2 m were drilled at intervals of about 2 m by using a 42 mmφ bit on the roof with a jumbo machine. The drilling angle was 20 °. A carbon steel lock bolt similar to that used in Example 1 (JIS G 3455, STKM 1
7C) was inserted and the mouth was sealed in the same manner as in Example 1.

70 to 110 kg (injection pressure 30 to 50 kg / cm ² · G) of the chemical solution of Production Example 5 in Table 1 was injected into each injection hole. Approximately 150 minutes after injecting the chemical solution, we dug into and investigated the area around the injection hole to check the stabilization status of the ground,
The consolidation area is a hemisphere with a radius of about 2 m, and
The large voids were dense and well sealed. In addition,
For reference, the single solidified portion of the chemical solution of Production Example 5, which is sealed and solidified in a particularly large void, is 5 cmφ ×
When uniaxial compressive strength was measured by core sampling into a cylindrical shape of 10 cm, it was 115 kg / cm ² .

Example 3 A crack was generated in a flat floor and a rising corner portion of a rooftop brick floor of a two-story building made of reinforced bricks, and water was leaking downstairs during rainfall. For this crack, 50 holes with a depth of about 5 cm were drilled at a pitch of about 30 cm using a drill with a diameter of 10 mm, and the shavings and dust in the holes were blown off with compressed air. It was put on 5 mm thick, and an injection pipe with an outer diameter of about 10 mm was hammered in from above with a wooden hammer. A Y-tube equipped with a static mixer was set in an injection pipe, and the components (A) and (B) and water in Production Example 4 in Table 1 were added to component (B) / (A) +
About 1 to 3 liters were injected per hole by a manual injection pump at a ratio of water (weight ratio) of 2.1 / 1 to 2.3 / 1.

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.

[0063]

INDUSTRIAL APPLICABILITY The injectable liquid composition of the present invention and the stable water-stop construction method using the same have the following effects.

Even if a large amount of the injected chemical composition is injected, there is no risk of scorch fire due to heat storage.

Since a large amount of water is used, the viscosity of the injectable liquid chemical composition is low, the injecting operation is easy, and the permeability to soil is excellent.

Since water is added as an active ingredient, the cost is low and it is economical.

Since the strength of the solidified body is high, it is effective for the stable strengthening of unstable rock or ground.

The solid material exhibits self-extinguishing property and is safe against fire.

As described above, the stabilized water-stopping method using the injectable chemical composition of the present invention has excellent characteristics. Not only for general mountain tunnels, but also for repairing existing tunnels, urban civil engineering and shields. It is extremely effective for stabilizing and stopping water in construction work and repair work of artificial structures.

Claims (3)

[Claims] 1. A total of 100 parts by weight of (A) a polyol and / or an organic polyamine compound, (B) an organic polyisocyanate compound and an organic phosphorus-containing compound, and (C) the component (A) and the component (B). On the other hand, a self-extinguishing injectable liquid chemical composition for stabilizing soil and the like which comprises 5 parts by weight or more of water. 2. The self-extinguishing type for stabilization 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 inserted into the holes. A stable and water-stopping method for stabilizing rock or ground, which comprises injecting a liquid composition for injection into rock or ground to solidify. 3. An injection pipe is inserted into the artificial structure, and the stabilizing self-extinguishing injectable liquid chemical composition according to claim 1 is injected into the artificial structure through the injection pipe to be solidified. Stabilization and waterproofing method for artificial structures.