Civil engineering injection solution composition

Abstract

To provide a civil engineering injection solution composition which, even in environments with significant water inflow or leakage occurring during tunnel excavation, and in small voids of water-containing ground and structures etc., ensures sufficient resin strength by suppressing foaming, while also exhibiting excellent permeability.SOLUTION: A civil engineering injection solution composition comprises: a first liquid containing a polyol component (A); a second liquid containing a polyisocyanate component (B); and a catalyst component (C), where the catalyst component (C) includes at least one selected from the group consisting of compounds represented by the formulas (1) to (4) in the figure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a civil engineering grouting composition that can be used even in environments with a lot of spring water and leaks. [Background technology]

[0002] One method for strengthening unstable rock mass or unstable ground is the rock bolting method, which stabilizes the surrounding ground after tunnel excavation. This method aims to protect the tunnel structure by fixing and securing bolts with a chemical solution. High-strength inorganic materials such as mortar have been used as the injection solution for consolidating rock mass. However, inorganic materials such as mortar require a long time to develop strength, which makes their work inefficient. Furthermore, there are problems with the material flowing into the water in the event of water leaks or springs.

[0003] Currently, tunnel excavation is being carried out in areas prone to water leaks and springs, and there are increasing cases of injecting chemicals to solidify rock under flowing water. However, water contamination by the chemicals and water leakage during injection are hindering the efficiency and safety of tunnel excavation work, and improvements are being called for.

[0004] To solve these problems, chemical solutions for soil stabilization are used, which include inorganic-organic composite systems of silicate aqueous solutions and polyisocyanate compositions, or polyurethane systems of polyol compositions and isocyanate compositions. These chemical solutions are used depending on factors such as the amount of water leakage and spring water, and in areas with a lot of spring water, polyurethane-based chemical solutions are used, as they have high strength to withstand water pressure.

[0005] For example, Patent Document 1 discloses a polyurethane-based liquid chemical composition that exhibits high strength when molded in the atmosphere. However, it is generally known that polyurethane-based liquid chemical compositions generate carbon dioxide and foam due to the reaction between water and isocyanate. Furthermore, commonly used catalysts such as triethylenediamine can promote the reaction between water and isocyanate as well as the reaction between polyol and isocyanate. Therefore, when molding in areas with frequent water leaks or springs, foaming can reduce the resin strength, resulting in an inherent problem of insufficient strength to support water pressure. In addition, because catalysts such as triethylenediamine have relatively high activity even at low temperatures, they react and thicken immediately after injection, resulting in poor penetration into small cracks and voids in the ground.

[0006] Furthermore, in recent years, with the aging of infrastructure facilities such as roads and buildings, paving work using asphalt, concrete, etc. has been carried out. However, these generally have problems such as insufficient work efficiency due to the long time required for them to develop strength, and their high viscosity makes them poorly permeable to small cracks and cavities. Therefore, there is a demand for polyurethane-based grouts and other grouts that develop strength quickly and have low viscosity. However, polyurethane-based grouts have inherent problems such as foaming when injected into ground or buildings that contain water due to rain, etc., making it impossible to achieve a sufficient reinforcing effect, and the amount injected cannot be controlled. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent Publication No. 2019-001838 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made in view of the above-mentioned background art, and aims to provide a civil engineering grouting composition that ensures sufficient resin strength by suppressing foaming, even in environments with many leaks and springs that occur during tunnel excavation, and in small voids in ground and buildings that contain water, and that has excellent permeability. [Means for solving the problem]

[0009] As a result of extensive research, the present inventors have discovered that the above-mentioned problems can be solved by a civil engineering grouting composition comprising a polyol component (A), a polyisocyanate component (B), and a specific catalyst component (C), and have thus completed the present invention.

[0010] That is, the present invention includes the following embodiments [1] to [6].

[0011] [1] A civil engineering grouting composition comprising a first liquid containing a polyol component (A), a second liquid containing a polyisocyanate component (B), and a catalyst component (C), wherein the catalyst component (C) contains at least one compound selected from the group consisting of compounds represented by the following formulas (1) to (4):

[0012] [ka]

[0013] (In the formula, X - represents an anion.) [2] The grout composition for civil engineering work according to [1], wherein the catalyst component (C) is 0.01 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the total of the polyol component (A) and the polyisocyanate component (B). [3] The civil engineering grout composition according to [1] or [2], wherein the viscosity of the first liquid containing the polyol component (A) is 1000 mPa·s or less. [4] The grouting composition for civil engineering work according to any one of [1] to [3], wherein the first liquid contains a polyamine component (D), and the polyamine component (D) is present in an amount of 0.01 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the total of the polyol component (A) and the polyisocyanate component (B). [5] The civil engineering liquid chemical composition according to any one of [1] to [4], wherein the first liquid is substantially free of a foaming agent (E). [6] A solidified body obtained from the civil engineering grout composition according to any one of [1] to [5]. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a civil engineering grouting composition that ensures sufficient resin strength by suppressing foaming and has excellent permeability, even in environments where there are many leaks and springs that occur during tunnel excavation, and in small voids in the ground and buildings that contain water. DETAILED DESCRIPTION OF THE INVENTION

[0015] Exemplary embodiments for carrying out each aspect of the present invention will be described in further detail below, although the present invention is not limited to the following embodiments.

[0016] A civil engineering grout composition according to one embodiment of the present invention comprises a first liquid containing a polyol component (A), a second liquid containing a polyisocyanate component (B), and a catalyst component (C), wherein the catalyst component (C) contains at least one compound selected from the group consisting of compounds represented by the following formulas (1) to (4):

[0017] [ka]

[0018] (In the formula, X - represents an anion.)

[0019] <First liquid> The first liquid contains a polyol component (A). The polyol component (A) undergoes polyaddition with a polyisocyanate component (B) to form a urethane. Examples of the polyol component (A) include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, animal and plant polyols, polymer polyols, short molecular weight polyols that function as chain extenders, halogen-containing polyols, phosphorus-containing polyols, and phenol-based polyols. One or more polyol components may be used alone or in combination.

[0020] Examples of polyether polyols include polypropylene ether polyol, polyethylene polypropylene ether polyol (polyoxyethylene polyoxypropylene polyol), polytetramethylene ether glycol, and the like.

[0021] Examples of polyester polyols include polycondensation polyester polyols and lactone polyester polyols. Examples of polycondensation polyester polyols include polyester polyols that are copolymers of adipic acid and diols. Examples of lactone polyester polyols include polycaprolactone polyols.

[0022] Examples of polycarbonate polyols include those obtained by a dealcoholization reaction or a dephenolization reaction between a short-chain diol, a short-chain triol, or the like and a low-molecular-weight carbonate such as ethylene carbonate, diethyl carbonate, or diphenyl carbonate.

[0023] Polyolefin polyol is a polyolefin having two hydroxyl groups. Examples of the polyolefin include polybutadiene, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene.

[0024] Examples of animal and plant polyols include castor oil polyols and silk fibroin.

[0025] Examples of polymer polyols include polymer polyols obtained by reacting polyether polyol with an ethylenically unsaturated monomer (such as butadiene, acrylonitrile, styrene, etc.) in the presence of a radical polymerization catalyst.

[0026] Examples of the chain extender include low molecular weight polyhydric alcohols such as ethylene glycol, 1,4-butanediol, glycerin, and trimethylolpropane.

[0027] Examples of halogen-containing polyols include those obtained by ring-opening polymerization of epichlorohydrin or trichlorobutylene oxide, and brominated polyhydric alcohols to which alkylene oxides are added.

[0028] Examples of phosphorus-containing polyols include those obtained by addition polymerization of alkylene oxide with phosphoric acid, phosphorous acid, organic phosphoric acid, etc., and those obtained by addition polymerization of alkylene oxide with polyhydroxypropylphosphine oxide.

[0029] Examples of phenol-based polyols include novolak resins obtained from phenol and formalin, polyols obtained by reacting alkylene oxides with resol resins, and Mannich-based polyols obtained by reacting phenols.

[0030] The polyol constituting the polyol component (A) preferably has an average number of functional groups of 2 to 4. This is more advantageous in terms of permeability.

[0031] The polyol constituting the polyol component (A) preferably has a number average molecular weight of 200 to 1200, more preferably 300 to 800. This improves the resin strength.

[0032] The viscosity of the first liquid is preferably 1000 mPa·s or less, and more preferably 500 mPa·s or less, which is more advantageous in terms of penetration.

[0033] The first liquid may contain a viscosity modifier.

[0034] <Second liquid> The second liquid contains a polyisocyanate component (B). Examples of the polyisocyanate component (B) include 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, polyphenylene polymethylene polyisocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, 1,3-phenylene diisocyanate, and the like, as well as modified products of these isocyanates (urethane-modified products, urea-modified products, allophanate-modified products, nurate-modified products, biuret-modified products, and the like). These isocyanate components may be used alone or in combination.

[0035] The polyisocyanate constituting the polyisocyanate component (B) preferably has a number average molecular weight of 100 to 1,000, more preferably 100 to 500, from the viewpoint of permeability.

[0036] The civil engineering grouting liquid composition according to one embodiment of the present invention is used by mixing the first liquid, the second liquid, and, in some cases, the third liquid. By mixing, the polyol component (A) contained in the first liquid and the polyisocyanate component (B) contained in the second liquid react to produce polyurethane. After mixing, the blending ratio of the polyol component (A) to the polyisocyanate component (B) is preferably 30 to 80 parts by mass, assuming that the total is 100 parts by mass.

[0037] The second liquid may contain a flame retardant.

[0038] <Catalyst component (C)> The catalyst component (C) has at least one compound represented by the following formulas (1) to (4).

[0039] [ka]

[0040] (In the formula, X - represents an anion.)

[0041] Formula (1) represents diazabicycloundecene, formula (2) represents diazabicyclononene, and formulas (3) and (4) represent salts thereof.

[0042] X in formula (3) or formula (4) - Examples of the anions include those derived from phenol, 2-ethylhexanoic acid, formic acid, and paratoluenesulfonic acid, and the temperature at which the catalytic activity is exhibited varies depending on the type of salt. Formulas (1) to (4) have very low activity below the catalytic activity temperature, but have high activity above the activity temperature.

[0043] In a high-temperature environment, from the viewpoint of permeability, X in formula (3) or formula (4) - In a low-temperature environment, from the viewpoint of workability, X in formula (1) or (2), or formula (3) or formula (4) is preferably used. - Preferably, the active material has a relatively low activation temperature and contains phenol, 2-ethylhexanoic acid, etc. From the viewpoint of permeability after mixing, it is preferable to use formulas (1) to (4) alone.

[0044] Other catalysts that are active even at low temperatures may also be used in combination. Examples of such other catalysts include triethylenediamine, tripropylamine, tributylamine, and dibutyltin dilaurate. These catalyst components may be used alone or in combination.

[0045] The catalyst component (C) may be contained in the first liquid, the second liquid, or neither of them but the third liquid. From the viewpoint of storage stability, the catalyst component (C) is preferably contained in the first liquid or the third liquid, and from the viewpoint of workability, it is more preferably contained in the first liquid.

[0046] The amount of catalyst component (C) blended is preferably 0.01 to 10 parts by mass per 100 parts by mass of the total of the polyol component (A) and the polyisocyanate component (B). In environments where flowing water such as spring water is present, from the viewpoint of resistance to spring water contamination, it is more preferably 0.5 to 7 parts by mass. In other environments, from the viewpoint of permeability, it is more preferably 0.1 to 5 parts by mass.

[0047] <Other ingredients> The civil engineering grout composition according to one embodiment of the present invention may also contain a polyamine component (D). Examples of the polyamine component (D) include low-molecular-weight amine polyols such as diethanolamine and triethanolamine, ethylenediamine, xylenediamine, and methylenebisorthochloroaniline. These components react with isocyanates relatively quickly compared to polyols.

[0048] From the viewpoint of the penetration property of the mixed solution, the amount of polyamine component (D) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the first liquid containing polyol component (A) and the second liquid containing polyisocyanate component (B). Furthermore, in an environment where the injection chemical composition may be washed away by spring water or the like, an amount of 0.5 to 5 parts by mass is even more preferable, and in other environments, an amount of 0.01 to 3 parts by mass is even more preferable from the viewpoint of the penetration property.

[0049] The polyamine component (D) is usually blended in the first liquid.

[0050] The civil engineering grout composition according to one embodiment of the present invention preferably contains substantially no blowing agent, and in particular, the first liquid preferably does not contain a blowing agent. This increases the resin strength. Here, "substantially no blowing agent" means that the amount of the blowing agent is 0.1 parts by mass or less per 100 parts by mass of the total of the polyol component (A) and the polyisocyanate component (B) at the time of mixing. Examples of the blowing agent (E) include urethane raw materials such as water, organic acids, inorganic acids (e.g., alkali carbonates), cyclic carbonates, and dialkyl carbonates (components that generate gases or the like upon reaction with or thermal decomposition of the polyol component (A) or the polyisocyanate component (B)), as well as hydrochlorofluoroolefins, hydrofluoroolefins, hydrofluorocarbons, halogenated hydrocarbons, hydrocarbons, chlorofluorocarbons, and perfluorocarbons.

[0051] The civil engineering grout composition may contain foam stabilizers, stabilizers, antioxidants, colorants, etc., as needed, and these auxiliary agents may be used alone or in combination.

[0052] One aspect of the present invention is a solidified body obtained from the above-mentioned grout composition for civil engineering. The solidified body can be suitably used for applications such as tunnel reinforcement and repair materials for roads and structures.

[0053] The grout composition for civil engineering of the present invention overcomes the drawbacks of conventionally known polyurethane-based grout compositions. That is, the grout composition for civil engineering of the present invention has high permeability even after mixing, has the ability to fill small cracks and voids, and is unaffected by moisture even in environments where water leaks and springs are common, thereby achieving stable reinforcement. [Example]

[0054] The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, "parts" and "%" are by mass.

[0055] In the following examples and comparative examples, the following raw materials were used. Polyol 1: Polyether polyol with an average functionality of 3 and a number average molecular weight of 500 (manufactured by Kaga Chemical Co., Ltd., product name: G-305) Polyol 2: 2,4-diethyl-1,5-pentanediol (manufactured by KH Neochem, trade name: Kyowadiol PD-9) Polyisocyanate 1: MDI / polymeric MDI = 40 / 60 (PA ratio), 2,4'-MDI and 2,2'-MDI / 4,4'-MDI ratio in MDI = 3 / 97, NCO content 31.0% (manufactured by Tosoh Corporation, product name: MR-200) Catalyst 1: Diazabicycloundecene (manufactured by San-Apro, trade name: DBU) Catalyst 2: Diazabicycloundecene phenol salt (manufactured by San-Apro, product name: U-CAT SA1) Catalyst 3: 2-ethylhexanoate of diazabicycloundecene (manufactured by San-Apro, trade name: U-CAT SA102) Catalyst 4: Diazabicyclononene (manufactured by San-Apro, product name: DBN) Catalyst 5: 33% dipropylene glycol solution of triethylenediamine (manufactured by Tosoh Corporation, product name: TEDA-L33) Catalyst 6: 70% dipropylene glycol solution of bis(2-dimethylaminoethyl) ether (manufactured by Tosoh Corporation, trade name: TOYOCAT-ET) Viscosity modifier 1: Diethylene glycol dibutyl ether (manufactured by Toho Chemical Industry, trade name: Hisolve BDB) Polyamine 1: 4,4'-methylenebis(cyclohexylamine) (Shenzhen Industrial Asahi, product name: PACM)

[0056] (Examples 1 to 6, Comparative Examples 1 to 4)

[0057] <Preparation of Polyol Composition (First Liquid)> Polyol composition P-1 was obtained by adding 91.5 g of polyol 1, 3.3 g of catalyst 1, 7.0 g of viscosity modifier 1, and 2.5 g of polyamine 1 and stirring for 30 minutes. The other polyol compositions (P-2 to P-10) were prepared in the same manner as polyol composition P-1, except that the raw materials were added according to the types and parts of the raw materials listed in Table 1.

[0058] <Preparation of polyisocyanate (second liquid)> 95.2 g of polyisocyanate 1 and 4.8 g of tri(chloropropyl)phosphate (hereinafter, TCPP) as flame retardant 1 were charged and stirred for 30 minutes to obtain polyisocyanate composition I-1.

[0059] <Method for evaluating reaction behavior> A foaming test was carried out using 52 g (50 mL) of the polyol composition P-1 and 62 g (50 mL) of the polyisocyanate component I-1 (liquid temperature: 20°C, stirring conditions: using a Three-One motor, 600 rpm x 3 seconds). The results are shown in Table 1.

[0060] The test methods and evaluation items for the "free foaming," "water-containing ground foaming," and "underwater foaming" in the reactivity tests are as follows:

[0061] Free foaming: The polyol composition and polyisocyanate composition are mixed and stirred in a 500 mL cup, and foamed in the cup. Water-containing ground foaming: After mixing and stirring the polyol composition and polyisocyanate composition in a 500 mL cup, 100 mL of the mixture was quickly poured into another 500 mL cup containing 40 g of quartz sand and 10 g of water, and foaming was performed. Foaming in water: After mixing and stirring the polyol composition and polyisocyanate composition in a 500 mL cup, 100 mL of the mixture is quickly poured into another cup containing 500 mL of water, and the water is vigorously stirred with a stirring rod to create foam.

[0062] Curing time: The time from the start of mixing and stirring the polyol composition and polyisocyanate composition until no marks remain when the resin surface is pressed with a stick. · Foaming ratio: The foaming ratio during foaming can be calculated using the following formula. Expansion ratio (times) = volume of molded product after expansion (cm 3 ) / Volume of molded body before foaming (cm 3 ) If the expansion ratio is 2.0 or less, it can be said to be good. Water turbidity after foaming: In the underwater foaming test, the turbidity of the water after the curing time was measured using a turbidity meter (TURBIDIMETER 2100N, manufactured by HACH) as an index of water contamination. A value of 20 or less is considered good.

[0063] Water foaming after foaming: In the underwater foaming test, water foaming is measured as an indicator of water contamination after the curing time has finished. 125 ml of water used in the underwater foaming test after the curing time has finished is placed in a 250 ml polyethylene bottle, sealed, shaken vigorously for 10 seconds, and then left to stand. The time (seconds) until the foam disappears from the water surface is measured. A value of 60 seconds or less is considered good. Resin strength: In the water-containing roadbed and underwater foaming tests, if the foaming ratio is 2.0 or less in both tests, it is considered very good (◎); if the foaming ratio is 2.0 or less under one condition, it is considered good (〇); and if the foaming ratio is not 2.0 or less under both conditions, it is considered unsuitable. · Ground permeability: If the mixture remains fluid until 20% of the hardening time, it is considered good (〇); if it does not remain fluid, it is considered unsuitable (×).

[0064] [Table 1]

Claims

1. A civil engineering grouting composition comprising a first liquid containing a polyol component (A), a second liquid containing a polyisocyanate component (B), and a catalyst component (C), wherein the catalyst component (C) contains at least one compound selected from the group consisting of compounds represented by the following formulas (1) to (4): 【Chemical 1】 (In the formula, X － represents an anion.)

2. 2. The civil engineering grouting composition according to claim 1, wherein the catalyst component (C) is 0.01 parts by mass or more and 10 parts by mass or less relative to a total of 100 parts by mass of the polyol component (A) and the polyisocyanate component (B).

3. 2. The civil engineering grout composition according to claim 1, wherein the viscosity of the first liquid containing the polyol component (A) is 1000 mPa·s or less.

4. 2. The civil engineering grouting liquid composition according to claim 1, wherein the first liquid contains a polyamine component (D), and the polyamine component (D) is contained in an amount of 0.01 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the polyol component (A) and the polyisocyanate component (B) combined.

5. 2. The civil engineering liquid chemical composition according to claim 1, wherein the first liquid containing the polyol component (A) is substantially free of a foaming agent (E).

6. A solidified body obtained from the civil engineering grout composition according to claim 1.

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