KR100216686B1 - Injection-type chemical composition for stabilization and reinforcement process using the same - Google Patents

Abstract

The present invention relates to an injectable chemical composition comprising (A) an aqueous alkali salt solution of silicate and (B) an organic polyisocyanate compound useful for solidifying and stabilizing an unstable portion on a rock mass, a mother rock or an artificial structure, and a reinforcing method using the composition. It is about.

Aqueous silicate aqueous salt solution (A) is compatible with the organic polyisocyanate compound (B), and the composition is suitable for rock mass, mother rock or artificial structure. Therefore, the permeability to rock mass and the like and the strength of the solidified complex are excellent and the work can be proceeded safely.

Description

Injection liquid composition for stabilization of soil and stabilization method

1 is a cross-sectional view showing rock bolts used in one embodiment of the present invention, where 1 represents rock bolts and 5 represents implantable chemical compositions of the present invention.

The present invention is suitable for use in reinforcement methods such as solidification and stabilization of cracked zones or rock masses with unstable and poor ground, and prevents water from leaking or outflowing rock mass or ground water, or cracks. Or stabilizing implantable chemical compositions for filling gaps in artificial structures, such as cracked concrete, and also reinforcement methods using the chemical compositions as mentioned above.

To date, inorganic or organic grouts have been injected as one of the stabilization and reinforcement processes or methods for filling cracks or gaps in artificial structures and some good results have been obtained.

However, a careful examination of the above-mentioned injection processes reveals that not necessarily satisfactory results are obtained. For example, the widely used cement-emulsion grout is used in suspension, so that the rock mass or artificial structure is poorly penetrated into the ground layer such as cracks or sand and gravel, and the solidification rate is slow to achieve satisfactory strength. It takes a long time to obtain. Therefore, grout cannot be used to achieve the purpose of stabilizing and strengthening unstable ground in a short time in tunneling work or underground excavation to quickly solidify and to exhibit the strength in a short time. In addition, when water leaks or spills, the injected cement-emulsion is diluted or released with water. On the other hand, typical inorganic grouted water glass two-liquid system grouts have a low strength of the solidified material. For example about 3 to 10 Of ² _{2 2}

Organic grouts, such as urea grouts, have poor solidification strength and have defects in which hardening components or auxiliary substances, such as sulfuric acid and formalin, elute. In addition, Japanese Patent Publication No. 636987/1988 or 63636/1988, Japanese Patent Publication No. 7263/1988, 7490/1988, 7471/1988, 8477/1988 or 35913/1988 A solidification method is disclosed in which a rapidly cured, hard, expandable urethane system, including polyols and polyisocyanates as the main component, is injected to solidify rock mass. Good solidification results can be expected with this method, but since the system is very expensive and flammable, there is a need to improve the system in terms of economics and safety.

In addition, Japanese Patent Laid-Open Publication No. 9482/1986 and Japanese Patent Publication No. 160079/1980 disclose polyisocyanates and water glass (in aqueous solution of sodium silicate, as a trimer catalyst of the polyisocyanate, such as specific tertiary amines or aminoalcohols). Injectable chemical compositions) are disclosed. Although the composition is fire resistant, it is necessary to use the expensive trimer catalyst. In addition, in order to improve the fluidity of the polyisocyanate, it is necessary to dilute the polyisocyanate with a large amount of an organic solvent. In addition, due to insufficient compatibility of the tertiary amine or aminoalcohol with the polyisocyanate or waterglass, when the two components are mixed, they are immediately separated from each other. In order to improve this compatibility, it is necessary to use expensive chemicals such as silicone polyols, which is disadvantageous in terms of cost.

It is an object of the present invention to provide excellent effects such as excellent solidification strength, stability and reinforcement effects, durability, injection workability, safety and economics in the stabilization and reinforcement methods of rock masses or ground and artificial structures and in the interception of water. It is to provide an injectable chemical composition that can be.

It is a further object of the present invention to provide a method for reinforcing rock masses or ground and artificial structures using the above-mentioned compositions.

These and other objects of the present invention will become apparent from the following description.

The present invention has been attempted with the aim of the above problems of the conventional techniques mentioned above. According to the present invention, when an injectable chemical composition comprising specific components is injected to form an expanded inorganic-organic mixed solid material, it has excellent solidification strength in stabilizing and reinforcing rock mass or ground and artificial structures and blocking water. It has been found that excellent effects such as stability and reinforcement effects, durability, injection operability, safety and economy can be obtained.

According to the present invention, there is provided a stabilizing implantable chemical composition comprising (A) an aqueous alkali salt solution of silicate and (B) an organic polyisocyanate compound.

According to the present invention, there is also provided a reinforcing method comprising injecting the above-mentioned composition into a rock mass, ground or artificial structure and solidifying the composition or filling gaps.

As used herein, the term fill means to fill a hole or crack with, for example, a composition.

The injection chemical composition of the present invention consists of (A) an aqueous alkali salt solution of silicate and (B) an organic polyisocyanate compound as mentioned above.

Alkali silicate aqueous solution (A) is a component which mainly forms the anhydrous silicic acid-urethane mixture by the reaction of the silanol group of component (A) and the isocyanate group of component (B). As component (A), commercially available aqueous potassium silicate or sodium silicate solution is usually used as the main component. Of these, sodium silicate is preferred. Sodium silicate of the general formula _{Na 2 O · xSiO 2 · nH} 2 O is a compound represented by (wherein the molar ratio of Na ₂ O SiO ₂ is about 2: 4: 1 to 1). The aqueous solution preferably has a solids concentration of 10 to 70% by weight, more preferably 20 to 40% by weight.

The organic polyisocyanate compound (B) may homogeneously disperse or emulsify component (A) and the tertiary amines (D) or the components (A), (B) and (D) mentioned below so that the reaction is carried out uniformly. It is a component having a property. Preference is given to using organic polyisocyanates as component (B). Examples of organic polyisocyanates include polymethylene polyphenyl polyisocyanate, liquid diphenylmethane diisocyanate, tolylene diisocyanate, crude tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, hydrogenated diphenyl Methane diisocyanate and the like. Polyisocyanates may be used alone or in mixtures thereof.

It is also preferable to use urethane prepolymers as component (B). Urethane prepolymers are obtained by reacting the above-mentioned organic polyisocyanates with polyoxyalkylene monools or polyols in a conventional manner in an NCO / OH equivalent ratio range of 1.5 to 100, preferably 2.0 to 50. Polyoxyalkylene monools or polyols are monools such as methanol, ethanol, propanol, butanol, octanol or lauryl alcohol, ethylene glycol, propylene glycol, 1, 3-butanediol, 1, 4-butanediol or 1, 6 Diols such as hexanediol, glycerol, trimethylolpropane, pentaerythritol, di- or triethanol amines, polyols such as diglycerol, sorbitol or sucrose or mixtures thereof, such as ethylene oxide, propylene oxide, butylene oxide or styrene oxide or Obtained by carrying out a mixture thereof and known addition polymerization. Preference is given to using polyoxyalkylene monools or polyols having at least 5%, preferably 10 to 100%, by weight of the oxyethylene chain in the oxyalkylene chain. The urethane prepolymers obtained usually have substantially unreacted isocyanate groups at the polymer end.

By introducing an oxyethylene chain into the main chain of the urethane prepolymer, hydrophilic properties can be imparted to the prepolymer, whereby the compatibility of the prepolymer with the aqueous alkali salt solution of silicic acid can be significantly improved. Thus, the phenomenon of insufficient blending of the used components in the injection device, which is often caused in operation, does not occur, and a uniform solid material can be formed. It is also excellent for wet rock masses, ground or artificial structures where water often leaks during operation and excellent adhesion of solidified materials to the rock masses, ground or artificial structures.

The amount of component (B) varies depending on the ratio of Na ₂ O to SiO ₂ in component (A), and the like, and generally cannot be determined. The weight ratio of component (A) to component (B) is preferably from 10/100 to 100/10, more preferably from 20/100 to 100/20. When the weight ratio is less than 10/100, the obtained composition tends to be expensive, which is uneconomical and tends to be difficult to control the weight ratio when constructed using proportional infusion pumps. On the other hand, when the weight ratio is 100/10 or more, the obtained injection chemical composition may be insufficiently solidified. That is, the composition tends not to cure, and although the composition can cure, the hardness of the solidified material is low and brittle and therefore poor in practicality.

In the present invention, the injectable chemical composition for stabilization may contain an expandable diluent (C) in addition to components (A) and (B).

The expandable diluent (C) is volatilized by the heat of reaction of components (A) and (B) and the formed inorganic-organic complex expands several times to several tens of its original volume, whereby the complex sufficiently penetrates into rock mass or ground. do. As a result, the strength of the rock mass is increased by the fixing effect of the solidified material. Furthermore, prior to expansion, the diluent (C) acts as a diluent of components (A) and (B) to lower the viscosity of the composition, thereby allowing the chemical composition to easily penetrate into the rock mass.

Examples of component (C) include acetone, methyl ethyl ketone, methylene chloride, trichloroethane, monofluorotrichloroethane, dichlorodifluoromethane, dichlorofluoromethane, dichlorotrifluoroethane, butane, pentane, hexane and the like. There is this. The amount of component (C) is preferably 50 parts by weight or less based on 100 parts by weight of the total amount of components (A) and (B). Component (C) is generally inert and soluble in component (B), so that it may be dissolved in advance in component (B).

Injectable chemical compositions in the present invention may contain tertiary amines (D) and surfactants (F) in addition to components (A) and (B).

Tertiary amine (D) is a component that can accelerate the reaction of component (B) with water or silanol groups to reduce the gelation time. Examples of component (D) include tertiary alkyl amines, cyclic amines, and the like. Among them, for example, dimethyl octylamine, dimethyl lauryl amine, morpholine, N-methyl morpholine, piperazine, dimethyl pyreazine, triethylenediamine, imidazole, N-methyldiethanolamine, N, N'-dimethyl Ethanolamine, polyethyleneimine, etc. are preferable.

The amount of component (D) is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight based on 100 parts by weight of component (B). When the amount of component (D) is less than 0.1 part by weight, the obtained composition tends not to cure, and thus cannot exhibit desirable performance. On the other hand, when the said amount is 20 weight part or more, hardening advances too fast and components (A), (B), (D), and (E) are unevenly blended.

Surfactant (E) is a component which disperse | distributes or emulsifies components (A), (B) and (D) uniformly, especially components (A) and (D) so that reaction may be unified. Examples of component (E) include cationic surfactants such as quaternary ammonium salts or fatty acid esters of isopropanol amines; Anionic surfactants such as sulfate esters of alkyl or fatty acids, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkyl allyl sulfonates, naphthalenesulfonate salts, sulfated or sulfonated aromatic compounds, fatty carboxylic acids or salts thereof, Sulfonated petroleum products, dialkylsulfocarboxylic acids or salts thereof, alkyl phosphate esters, oleoyl methyl tolide sulfonates or sulfated or sulfonated amides; Carboxylic acid or sulfonic acid amphoteric surfactants; Nonionic surfactants having a hydrophilic-lipophilic balance (HLB) of 4 to 10, for example polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyhydric alcohol ethers, another ether type nonionics Surfactants, polyhydric alcohol esters, other ester type nonionic surfactants or nitrogen-containing nonionic surfactants. Surfactants may be used alone or in mixtures thereof.

The amount of component (E) is preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight based on 100 parts by weight of component (D). When the amount of component (E) is less than 1 part by weight, it is difficult to uniformly mix components (A), (B) and (D), in particular components (A) and (D).

Thus, a non-uniform solidified material is obtained. On the other hand, when the amount exceeds 200 parts by weight, the solidified material cannot be obtained, or even if the solidified material can be obtained, the physical properties are very poor.

An organic polyisocyanate compound (B) is excellent in reactivity or solidification property with component (A). However, component (B) has insufficient permeability to rock mass or ground due to its relatively high viscosity. Thus, up to now, organic solvents such as toluene, xylene, 1, 1, 1-trichloroethane, methylene chloride or trifluoromethane have been used as diluents to increase flowability or permeability. However, the organic solvent is volatilized and its environment is damaged by its release after solidification. Therefore, it is desirable not to use as much of the organic solvent as possible.

In the present invention, a component (B) is a diluent reactive with an alkali metal silicate salt which does not react with an isocyanate group when mixed with component (B) but reacts immediately with component (A) upon mixing and contacting with component (A). Can be mixed. Since the reactive diluent does not react with the isocyanate group, the diluent exerts a good influence on the storage stability of component (B) or the decrease in its viscosity. In addition, the reactive diluent reacts immediately with component (A) and therefore has little effect on the surrounding environment.

In the present invention, the reactive diluent added is an ester or an ether. The reactive diluent serves to reduce the viscosity during injection by diluting the organic polyisocyanate compound (B). The reactive diluents also act as anhydrous silicic acid complexes crosslinked with urea or anhydrous silicate gels in a networked state to form a harder solidifying material of inorganic-organic complexes, mainly including anhydrous silicic acid-urethane complexes. Specifically, the reactive diluent is alkali-hydrolyzed by contact with an aqueous alkali silicate solution (A), and the hydrolyzed ester or ether reacts with component (A) and / or component (B), thus the reactive diluent Actively added to the curing reactions of (A) and (B), thereby forming a harder solidified material as mentioned above.

As mentioned above, the alkali hydrolyzate of the reactive diluent has one or more functional groups reactive with component (A) and / or component (B). Examples of functional groups include alcoholic hydroxyl groups, carboxyl groups, amino groups or secondary amino groups, thiol groups, and the like. For example, when ethylene glycol diacetate is used as the reactive diluent, ethylene glycol and acetic acid are produced as hydrolysates, and the resulting ethylene glycol reacts with the polyisocyanate (B) to form three-dimensionally crosslinked polyurethanes and The resulting acetic acid neutralizes or dehydrates the silicic acid alkali salt in component (A) to form a siloxane bond network, thereby accelerating gelation.

As mentioned above, when the reactive diluent is mixed with the compositions of the present invention, solidified masses of inorganic-organic complexes with superior mechanical strength and greater hardness are produced.

When comparing a composition containing a reactive diluent with a composition containing no reactive diluent, a composition containing the diluent has the following advantages.

(1) The permeability to rock mass or ground is markedly increased due to the decrease in component (B) viscosity.

(2) The diluent is slightly volatilized, so the working environment is excellent in terms of safety and hygiene.

(3) The storage stability of component (B) is improved.

(4) The solidified complex material can be obtained by the reaction, so that the strength of the solidified material is remarkably improved.

Preference is given to using reactive diluents which satisfy the following items. That is, the diluent is the temperature at which the composition is used (about -5 To about 40 Is a liquid state with low viscosity, low volatility, inert in component (B), hydrolyzed by component (A) and its hydrolyzate is component (A) and / or component (B) React with

Examples of reaction diluents include diesters of dibasic acids having low molecular weights, acetic acid esters of mono- or polyhydric alcohols, alkylene carbonates, ethers, cyclic esters, acid anhydrides, various acrylic esters, various methacrylic acid esters, and the like.

Examples of diesters of dibasic acids having low molecular weight include dialkyl esters of dibasic acids such as glutaric acid, succinic acid, adipic acid, malonic acid, oxalic acid or dimethyl esters or diekyl esters of pimelic acid.

Examples of acetic acid esters of alcohols include acetates of glycol ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol methyl ether, ethyl carbitol or butyl carbitol; Acetates of alkoxyalkyl alcohols of 3-methoxybutyl alcohol or 3-methyl-3-methoxybutyl alcohol; Diacetates of glycols such as ethylene glycol, diethylene glycol or triethylene glycol, and the like.

Examples of alkylene carbonates include propylene carbonate, dilute solutions prepared by dissolving ethylene carbonate in propylene carbonate, and the like.

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

Examples of cyclic esters are, for example, lactones such as γ-butyllactone, lactams such as ε-caprolactam, and the like.

Examples of various acrylates or methacrylates include, for example, alkyl esters of acrylic or methacrylic acid such as methyl acrylate or methacrylate, ethyl acrylate or methacrylate, or butyl acrylate or methacrylate; Ethylene glycol, diethylene glycol copolymerization with polyethylene glycol, propylene glycol, dipropylene glycol, molecular weight of 100 to 1000, polypropylene glycol with molecular weight of 100 to 1000, or ethylene oxide or propylene oxide with molecular weight of 100 to 5000 Alcohols such as diol or triol, and esters of acrylic acid or methacrylic acid.

Examples of acid anhydrides are, for example, pyrionic acid anhydride, butyric anhydride, maleic anhydride and the like.

The amount of the reaction diluent is preferably 5 to 90 parts by weight, more preferably 10 to 50 parts by weight based on 100 parts by weight of the organic polyisocyanate compound (B). The actual amount used is appropriately determined within the above-mentioned range depending on the kind or viscosity of the component (B), the intended use of the component (B), and the like. If the amount of the reaction diluent is too small, the effect of decreasing the viscosity of component (B) or increasing the strength of the solidified material is reduced. On the other hand, when the amount of the reaction diluent is too large, the strength of the solidified material is low.

Known diluents may be used in addition to the reaction diluents to supply or dilute the reaction diluents.

The composition of the present invention may also include plasticizers or process oils used in widely used resins such as dioctyl phthalate, dibutyl phthalate, dioctyl adipate, chlorinated paraffin.

The amount of the reaction diluent or plasticizer is preferably 0 to 100 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B).

In addition, the composition of the present invention may contain an inorganic filler. Examples of inorganic fillers are cement, blast furnace slag, gypsum, calcium carbonate, clay, aluminum hydroxide, antimony trioxide, calcium oxide, sodium hydroxide, bentonite and the like. These inorganic fillers are cured by mixing with component (A) to form a composite solidified material. As a result, the solidified material improves the strength and the effect for sealing cracks or cracks. The amount of the inorganic filler is 0 to 80 parts by weight, preferably 0 to 50 parts by weight, based on 100 parts by weight of component (B).

As mentioned above, injectable chemical compositions of the present invention include tertiary amines (D) which serve as curing catalysts to accelerate the reaction with component (B). In addition to the tertiary amine (D) as the curing accelerator, for example, dibutyl tin dilaurate, triethylene diamine, imidazole, monoethanol amine, diethanol amine, triethanol amine and the like are used. The amount of the curing accelerator is 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight based on 100 parts by weight of component (B).

As mentioned above, in order to uniformly emulsify or disperse components (A), (B) and (D) in the injectable chemical composition, the surfactant (E) is mixed with the above components. When tertiary alkyl amines (D) are used as cure accelerators, any surfactant may be used, such as cationic, anionic, amphoteric or nonionic surfactants. Examples of surfactants include, as exemplified above, aqueous solutions of sodium, amine or ammonium salts of alkyl sulfates, alkylzenzensulfonates, ethoxyalkylsulfates or ethoxyalkylbenzene sulfates; Alkyl phosphate salts; A nonionic surfactant prepared by addition polymerization of several moles of ethylene oxide with an alcohol or alkyl phenol. The amount of the surfactant is 1 to 100 parts by weight, preferably 10 to 20 parts by weight based on 100 parts by weight of the curing accelerator.

In addition, silicone foam modifiers such as organic polysiloxanes may be mixed with component (A) and / or component (B).

In order to improve the elasticity or mechanical strength of the solidifying material, various polymeric materials can be mixed with component (A) and / or component (B) in the required amount upon injection. Examples of various polymeric materials include, for example, solvent-type vulcanized or unvulcanized rubbers such as butadiene rubber, chloroprene rubber, styrene-butadiene rubber or ethylene-propylene rubber, emulsifiers thereof, various acrylic resin emulsifiers, polyvinyl alcohol, ethylene vinyl Acetate emulsifiers, urethane resin dispersants, polyethylene oxides, asphalt emulsifiers and the like.

If desired, various stabilizers such as anti-aging agents, heat-resisting substances or antioxidants may be mixed with component (B). The amount of stabilizer is generally from 0 to 2% by weight of component (B).

The composition of the present invention may also contain phosphorus or halogen flame retardants or the like as ester or lactone water glass curing agent.

The solidification reaction of the injectable chemical composition of the present invention is very complicated and indistinguishable. When the silicate aqueous alkali salt solution (A) is mixed with the organic polyisocyanate compound (B), the silanol group present in the alkali silicate aqueous solution reacts with the isocyanate group of the organic polyisocyanate compound to form an anhydrous silicic acid-urethane complex, At the same time, the organic polyisocyanate compound reacts with water to generate carbon dioxide gas, forming a polymer combined with a urea bond or a crosslinked anhydrous silicic acid-urea complex, and a portion of the carbon dioxide gas produced as a by-product is dissolved in an aqueous alkali silicate solution. It can then be assumed that the anhydrous silicate gel is formed from alkali silicate salts due to dissolved carbon dioxide gas.

In addition, the anhydrous silicic acid-urethane complex compound is formed of a solidified substance expanded by carbon dioxide gas generated during the reaction of component (B) with water and steam generated by the heat of reaction of components (A) and (B), whereby The volume of the expanded complex is increased. At this time expansion occurs. Anhydrous silicic acid-urethane complexes can easily enter gaps formed in soil, rock, brick, coal, or artificial structures by the expansion pressure created during expansion.

When using the composition of the present invention containing component (C), the complex formed by the above-mentioned reaction can be volatilized by the heat of reaction generated during the reaction of component (A) and (B). Because it expands and increases the volume of solidified material.

Preference is given to using the injectable chemical composition of the invention as a two-component (2-package) composition comprising component (A) and component (B). The two components (A) and (B) are mixed just before injection into a rock mass or the like.

When using a composition comprising components (A), (B) and (C), one package contains component (A) and the other package contains component (B) and component (C). It is preferable to use the composition in the state of the component (2-package) composition. Both packages are mixed together just before being injected into rock mass or the like. Known mixing methods mentioned hereinafter may be applied to mixing the compositions of the present invention. For example, if a long gelling time is required or if the injection is performed on a small scale, one-shot process in which component (A) and (B) or additionally component (C) is premixed and the mixture is injected. Do this.

When using a composition comprising components (A), (B), (D) and (E), the order of mixing the components (A), (B), (D) and (E) is not particularly limited. . For example, the composition is in a state of a two-component (two-package) composition in which one package comprises a mixture of components (A), (D) and (E) and the other package is component (B), That is, after mixing component (A), (D), and (E) beforehand, component (B) can be used in the state mixed with these.

Component (A) containing only aqueous silicate aqueous salt solution is prepared by adding alkali silicate salt to water at a solid content of about 10 to about 70 parts by weight based on 100 parts by weight of the above-mentioned aqueous solution. When preparing component (A) containing other components such as cure accelerators, it is often required to disperse completely in the aqueous solution, so it is stirred in the aqueous solution using a surfactant.

The reaction diluent is added to component (B). If necessary, the commonly used diluent is added to component (B) and the mixture is stirred thoroughly.

The unique implantation chemical compositions of the present invention are implanted and solidified in soft or unstable ground, rock masses, or artificial structures with sand or gravel layers, or many cracks or gaps. Without limitation, known methods may be applied to the methods of injecting and solidifying the compositions of the present invention. For example, two tanks may contain components (A) and (B) by using a proportional infusion pump that can adjust the amount, pressure or mixing ratio of components (A), (B), (C), (D) and (E). In the case of a composition comprising (B), components (A) and (B) are supplied, and in the case of compositions comprising components (A), (B), and (C), components (A) and (B) and ( Feeding a mixture of C), and for a composition comprising components (A), (B), (D) and (E), the mixture of components (A), (D) and (E) and component (B), respectively, Supply. Subsequently, each of the components in the tank is 0.5 to 50 Of ²

When injecting the composition into the ceiling of a tunnel, for example, prior to infusion, a depth of about 2 m and 10 To 30 Holes for injection with a drilling angle of 42 It is desirable to drill at intervals of about 2 m by using a leg auger with ø bits. As shown in FIG. 1, a hollow carbon steel rock bolt 1 (length: 3 m) with a hole 4, fitted with a static mixer 2 and a check valve 3, is fitted in each hole for injection. The inlet of the rock bolt 1 is sealed with alveoli, pulverized cement, alveoli containing expandable hard urethane resin, and then the injection-type chemical composition 5 is injected in the above-mentioned manner. The infusion operation ends when the infusion pressure suddenly increases or when the composition is infused in an amount greater than a predetermined amount, ie in an amount of about 20% by weight more than the predetermined amount. Generally, the composition is 30 to 200 per hole It can be injected in the amount of.

When stabilizing and reinforcing artificial structures with cracks or blocking water, for example, 10 Diameter and 5 to 10 Use a drill to drill a hole having a depth of about 20 to 50 on the surface with cracks Drilled at intervals of, cutting debris or dust is blown by the compressed air from the resulting holes, about 5 Place a cotton wool with a thickness of over a hole, then about 10 Diameter and 20 to 30 An injection pipe having a length of is put on the cotton wool, whereby the site to be stabilized is set in such a state that the injection chemical composition does not leak out. Also, about 30 cracks or leaks U-cut or V-cut at height, and the injection pipe is fastened with fastened cement. Then, the composition of the present invention is 0.5 to 20 Of ² Of ²

According to the reinforcing process of the present invention, since the composition has a low viscosity, it has excellent permeability to unstable ground, cracks or crack zones, and thus, stabilization of unstable rock masses, ground or man-made structures, or the blocking of water is carried out over the entire area. can do. In addition, the solidified materials formed are high in strength, excellent in durability and adhesion to rock mass, non-combustible and fire resistant, and are economically advantageous. Thus, the process of the present invention is actually useful.

The invention is described and described in more detail in the following examples, in which all percentages and parts are by weight unless otherwise indicated. It is to be understood that the invention is not limited to the examples, and that various changes and modifications may be made within the invention without departing from the spirit and scope of the invention.

[Reference Examples 1 to 4]

The component (B) shown in Table 1 is premixed with the additives and catalyst shown in Table 1 in the amounts shown in Table 1, and the component (B) obtained is then mixed with a static mixer (length: 15 , Diameter: 1 In a pump equipped with a) and mix with component (A) having the amounts shown in Table 1 5 to 10 in an amount of / m ² Of ^It is released by the pressure of ² · G.

With regard to the composition, the time required for gelling the released composition (gelling time) and the uniformity of the composition are investigated, and in connection with the solidified material, the bending test and the compression test are performed according to Japanese Industrial Standards (JIS) R 5201. And the expansion ratio is calculated from the density measured according to JIS K 5400, and the combustion test (burning time and combustion length) is performed according to JIS A 9514.

The uniformity of the composition is measured by whether it is separated into layers or not until the composition gels.

With respect to component (A), sodium silicate No. A 40% aqueous solution of 3 (Na ₂ O / SiO ₂ = 1/3, molar ratio) is used.

The results are shown in Table 1.

[Reference Examples 5 and 6]

88.0 parts of polyol and table using 98.0 parts of polymethylene polyphenyl polyisocyanate (C-MDI) as component (B) and the catalyst shown in Table 2 (Reference Example 5) or having no oxyethylene chain as component (B) Except for using the additive and catalyst shown in 2 (Reference Example 6), the process of Reference Example 1 was repeated to produce a composition.

Regarding the composition, uniformity is measured in the same manner as in Reference Example 1.

The results are shown in Table 2.

[Reference Examples 7 to 10]

The components (B) and (C) and catalysts shown in Table 3 were premixed and the mixture was then mixed with a static mixer (length: 15 , Diameter: 1 In a pump equipped with), mix with the same component (A) as the component used in Reference Example 1, and finally 5 to 10 gg / in an amount of / m ^{2 It} is released by the pressure of ² · G.

In relation to the composition, in relation to the uniformity and gelation time and the solidifying material, the expansion ratio, the compressive strength, the bending strength and the combustion test are investigated or performed in the same manner as in Reference Example 1.

The results are shown in Table 3.

[Reference Examples 11 and 12]

88 parts polymethylene polyphenyl polyisocyanate and component (C) shown in Table 4 as component (B) (see Example 11), or polyols having no oxyethylene chain as component (B) and shown in Table 4 The process of Reference Example 7 was repeated except that component (C) and catalyst were used (Reference Example 12) to produce a composition.

Uniformity of the composition is measured in the same manner as in Reference Example 1.

The results are shown in Table 4.

[Reference Examples 13 to 16]

The components (A), (D) and (E) shown in Table 5 were premixed and the mixture was mixed with a static mixer (length: 15 , Diameter: 1 And mix with component (B) shown in Table 5 in a pump equipped with 5 to 10 in an amount of / m ² Of ^It is released by the pressure of ² · G.

The same component (A) as that used in Reference Example 1 is used as component (A).

With regard to the obtained composition, the expansion ratio, the compressive strength, the bending strength and the combustion test are investigated or performed in the same manner as in Reference Example 1 with respect to the uniformity and gelation time and the solidifying material.

The results are shown in Table 5.

Reference Example 17

The process of Reference Example 16 was repeated except that no surfactant (E) was used to produce the composition.

The composition is separated into layers. However, it can be used immediately after the composition is forcibly stirred.

Reference Example 18

The process of Reference Example 15 was repeated except that the addition product of octyl phenol and 10 moles of ethylene oxide (HLB: 14) was used in place of the nonionic surfactant having HLB 8 as component (E). do.

The composition is separated into layers. However, it can be used immediately after the composition is forcibly stirred.

Example 1

42 25 at intervals of about 2 m on a tunnel ceiling with crack bands using a leg auger with a bit of ø To 35 Drill five holes at the drilling angle of the tunnel (angle with respect to the drilling direction of the tunnel) and bolt (inside diameter: 27.2) for injection of carbon steel (JIS G 3445, STKM 17 C) as shown in FIG. Inner diameter: 15 , Length: 3 m, equipped with a static mixer and a check valve) into each hole, about 30 inlet parts The knitted cotton alveoli impregnated with the 2-liquid hard foam urethane resin was pushed into an iron rod, and the hole was sealed.

Injectable chemical composition obtained in Reference Example 1 and the composition obtained in Reference Example 13 were about 20 to 50, respectively. Of About 80 to 120 per hole by injection pressure of ² Was injected into the fixing hole for injection. In addition, the composition obtained in Reference Example 7, the injection pressure of 5 to 10 Of ^A hole was injected in the same manner as described above except that it was adjusted to ² G. 120 minutes after injecting the composition, the ceiling infused with the composition was excavated to investigate how the ceiling improved. As a result, the solidification area is 3 It was found that it was in the state of a hemisphere with a diameter of, and this region was solidified and stabilized.

Cylindrical sample (5 ø × 10 ) Was collected from the solidified portion using a sampler and the uniaxial compressive strength was measured. The compositions of Reference Examples 1 and 7 were each 12 Of ² Of ²

Example 2

In order to stabilize the granite crack zone with large gaps in the tunnel ceiling, it was stabilized by injecting each of the compositions of Reference Examples 2, 8 and 14. The process is carried out in the same manner as in Example 1.

Ie 42 Ten holes (depth: 2 m) were drilled in the ceiling at intervals of about 2 m using a leg auger with ø bits. Drilling angle is 20 to be. The same carbon steel rock bolts (JIS G 3455, STKM 17 C) as used in Example 1 were inserted into the holes, and the openings of the holes were sealed in the same manner as in Example 1.

Each of the above-mentioned compositions (Injection pressure: 10 to 20 with respect to the compositions of Reference Examples 2 and 14). Of ^{2 to} G or 2 to 10 with respect to the composition of Reference Example 8 Of ² · G). In order to confirm the stable state, 150 minutes after the composition was injected, the site around the hole where the composition was injected was excavated and irradiated. These sites solidified into a hemisphere with a diameter of 2.5 m and large gaps were satisfactorily sealed with high density. For reference, the cylinder (5 ø × 10 sample the center of a particularly large cracked part with ø), cyrilize with the solidified composition to measure uniaxial compressive strength, and perform a combustion test.

The results are shown in Table 6.

From the results of Example 2, when injecting each chemical composition into a granite crack zone having a gap larger than the diameter of the injection bolt, the gap was completely sealed, and the composition was sufficiently penetrated into the crack zone and solidified to form a rock. It was confirmed that the ingots were stabilized. In other words, the composition of the present invention is very efficient in the tunneling process.

Example 3

Cracks appeared in the corners of the roof slab in the three-story reinforced concrete building, and rain leaked on the lower floors of the building. Five holes (depth: approximately 5 10) About 20 using a drill of diameter Drill to the pitch of. After blowing the cutting chips or dust in the hole with compressed air, about 5 A cotton wool having a thickness of 9 was placed on each hole, and then about 10 The injection pipe having an outer diameter of was embedded using a wood hammer. A Y-tube equipped with a static mixer was placed in each pipe and the compositions of Reference Examples 1, 7 and 15 were injected in amounts of about 2 to about 3 liters per hole, respectively, using a hand infusion pump. The volume ratio of component (A) to component (B) is about 1 / 1.5 when using the composition of Reference Example 1, and the volume ratio of component (A) to component (B) when using the composition of Reference Example 7 / 1 and when using the composition of Reference Example 15 the volume ratio of components (A), (D) and (E) to component (B) is about 1 / 1.5.

After injecting, the injecting pipe was taken out, corked and coated with mortar for finishing. After two weeks, it rained a lot. The water never leaked out of the ceiling. That is, the composition of the present invention was found to be very effective in sealing cracks or blocking water.

Example 4

In the tunnel pedestal process on the outflow nevus of fine sand containing sand and gravel in the 7-10 m underground (5 m depth of groundwater) to block water and stabilize the ground around the outflow site, the composition of Reference Example 16 The injection was made to the nevus and its periphery to be excavated in an amount of about 230 m ³ using a proportional injection pump according to the 1.5-shot method via a mounted injection iron rod. The composition was injected to obtain about 1/2 the volume ratio of components (A), (D) and (E) to composition (B). The state of birthmarks before and after injection is shown in Table 7. As shown in Table 7, it is possible to stabilize and reinforce birthmarks and obtain a water blocking effect. Thus, the tunnel pedestal process can be accelerated by using the composition of the present invention.

Injectable chemical compositions and stabilization and reinforcement methods of the present invention have the following effects (1) to (5).

(1) The alkali silicate aqueous solution (A) is very compatible with the organic polyisocyanate compound (B), and urea-anhydrous silicic acid complexes, urethane-anhydrous silicic acid complexes and anhydrous silicic acid-complexed complex materials may be formed. Because of their good fit, adhesion to rock masses or ground and man-made structures is increased. In addition, for compositions containing an intumescent diluent (C) in addition to components (A) and (B), component (C) is compatible with components (A) and (B) and, therefore, is not compatible with the solidified complex material of the composition. Similar complex materials may be formed necessarily. In addition, permeability is increased by the expansion pressure, and the solidification strength is significantly increased. Furthermore, for compositions containing tertiary amines (D) and surfactants (E) in addition to components (A) and (B), they are markedly compatible with each other due to the use of component (E) and the solidification of the composition Similar complex materials can necessarily be formed for the complex compounds. Moreover, the composition is compatible with rock masses or ground and artificial structures, thus increasing adhesion and filling effects.

Therefore, the solidification and hardening properties are large, rock stabilization or stabilization and reinforcement of the ground can be surely improved and the leakage blocking effect is necessarily obtained.

(2) the mixture of components (A) and (B), the mixture of components (A), (B) and (C) and the mixture of components (A), (B), (D) and (E), respectively; Very low and excellent permeability.

(3) The composition is low in cost per unit volume due to the use of an aqueous alkali salt solution and the expansion effect of the organic polyisocyanate, and is economically advantageous. The cost per unit volume of the composition containing the expandable diluent (C) in addition to components (A) and (B) is further reduced due to the expansion effect of component (C), and therefore the composition is economical. Similarly the cost of a composition containing tertiary amine (D) is further reduced due to the use of component (D) and the composition is economical.

(4) The composition has a high solidification strength and is therefore effective in stabilizing and reinforcing unstable rock masses or grounds requiring strength.

(5) The solidified material is excellent in durability and incombustibility or fire resistance. Thus, there is only a slight fire concern. In addition, the composition is excellent in terms of stability and hygiene in operation.

As mentioned above, the method of the present invention has excellent characteristics and is clearly, economically and safely unstable with the strength required for tunneling operations that are generally performed as well as for large-scale tunnel drilling operations or underground civil engineering works performed at depths. It is a remarkably effective method for stabilizing and reinforcing ingots or grounds or for preventing leaks.

In addition to the components used in the examples, other components can be used in the examples listed in the specification to obtain substantially the same results.

Claims (14)

Free isocyanate groups obtained by reacting mono- or polyols having (A) an aqueous alkali salt solution of silicate and (B) (a) an oxyalkylene chain containing at least 5% by weight of an oxyethylene chain with (b) an organic polyisocyanate. An injectable chemical composition comprising an organic polyisocyanate compound, which is a hydrophilic urethane prepolymer having a polymer. The composition of claim 1 further comprising (C) an expandable diluent. The method of claim 1, wherein at least one selected from the group consisting of (D) tertiary amines and (E) cationic surfactants, anionic surfactants, amphoteric surfactants and nonionic surfactants having HLB of 4 to 10 A composition further containing a surfactant. A composition according to claim 1, wherein said component (A) is an aqueous sodium silicate solution. A reactive diluent according to claim 1, wherein said component B is an ester or ether, which reactive diluent can be alkali-hydrolyzed by said component (A) without reacting with component (B), and thus hydrolyzed. The hydrolyzate may react with at least one component selected from the group consisting of component (A) and component (B). Free isocyanate groups obtained by reacting mono- or polyols having (A) an aqueous alkali salt solution of silicate and (B) (a) an oxyalkylene chain containing at least 5% by weight of an oxyethylene chain with (b) an organic polyisocyanate. Injecting a chemical composition comprising an organic polyisocyanate compound, which is a hydrophilic urethane prepolymer having, into the rock mass, ground or artificial structure, and solidifying the composition. 7. The method of claim 6, wherein said composition also contains an expandable diluent (C). 7. The composition of claim 6, wherein the composition is from the group consisting of (D) tertiary amines and (E) cationic surfactants, anionic surfactants, amphoteric surfactants and nonionic surfactants having an HLB of 4 to 10. And also containing at least one surfactant selected. The rock mass according to claim 6, wherein the rock mass or the ground is drilled at predetermined intervals, a hollow bolt for injection is inserted into each hole, and the composition is injected into the hole through the opening of the bolt. Or solidifying by injecting into the ground. 10. The method of claim 9, wherein said composition also contains an expandable diluent (C). 10. The composition of claim 9, wherein the composition is from the group consisting of (D) tertiary amines and (E) cationic surfactants, anionic surfactants, amphoteric surfactants and nonionic surfactants having HLB of 4 to 10. And also containing at least one surfactant selected. The method of claim 6, wherein the composition is injected into the artificial structure and solidified by inserting an injection pipe into the artificial structure and injecting the composition through the pipe into the artificial structure. 13. The method of claim 12, wherein the composition also contains (C) an expandable diluent. 13. The composition of claim 12, wherein the composition is from the group consisting of (D) tertiary amines and (E) cationic surfactants, anionic surfactants, amphoteric surfactants and nonionic surfactants having HLB of 4 to 10. And also containing at least one surfactant selected.