Injection chemical composition, and a solidified body and soil stabilization method using the same.

Abstract

To provide an injection chemical composition that can achieve both curability in water and foaming and curability in non-water environments, even after being exposed to high temperature and high humidity environments. [Solution] An injection solution composition comprising a first agent (A) and a second agent (B), wherein the first agent (A) comprises an aqueous solution of sodium silicate (A-1), an organic polyol (A-2), and a tertiary amine catalyst (A-3), and the second agent (B) comprises an organic polyisocyanate containing a mixture of diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate having 3 or more isocyanate functional groups (B-1), or a reaction product (B-1') of an active hydrogen group-containing compound and a mixture (B-1), at least one acid component (B-2) selected from the group consisting of phosphate monoesters and phosphate diesters, and at least one hydrolyzable component (B-3) selected from the group consisting of orthoester compounds and acetal compounds.

Description

[Technical Field]

[0001] This disclosure relates to an injection chemical composition, and to a solidified body and soil stabilization method using the same. [Background technology]

[0002] Injection chemical compositions are known as materials for stabilizing the soil properties of the ground (bedrock, etc.). Injection chemical compositions are used, for example, as void-filling materials to fill voids between structures such as tunnels, underground structures, and high-rise buildings and the surrounding ground, or to fill voids that occur within the ground, and as ground injection materials to reinforce and improve the ground by penetrating into weak ground.

[0003] One known method for stabilizing soil using injected chemical compositions is the rock bolt method, which stabilizes the surrounding ground during tunnel excavation. In this method, unstable ground is solidified and strengthened using injected chemical compositions, and the tunnel structure is protected by fixing and anchoring bolts.

[0004] Conventionally, inorganic materials such as mortar, which have high strength, have been used as injection chemical compositions to solidify the ground as described above. However, these inorganic materials have the problem of poor work efficiency because it takes a long time for them to develop strength. In recent years, there has been an increase in cases where tunnel excavation is carried out in areas where water leakage and groundwater seepage are likely to occur (hereinafter referred to as "water-containing areas"). When the above inorganic materials are used in such areas, the slow solidification rate can lead to problems such as water leakage occurring because the water cannot be stopped even by chemical injection.

[0005] To solve these problems, an injection solution composition has been proposed that combines a first agent containing an aqueous silicate solution called water glass and an organic polyol, and a second agent containing an organic polyisocyanate (for example, Patent Document 1). These first and second agents are usually stored separately and mixed together immediately before injection. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 6-287558 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] Injection chemical compositions are typically stored for long periods in their operating environment. However, due to the effects of recent global warming, temperatures and humidity in humid regions are increasing. As a result, injection chemical compositions used in such regions may be exposed to high temperatures (e.g., above 40°C) and high humidity.

[0008] Injection solutions used in aquatic regions need to not only harden quickly in water, but also foam and harden well in the absence of water (hereinafter referred to as "non-aquatic"). However, it has become clear that conventional injection solution compositions containing water glass, such as those described in Patent Document 1, become difficult to achieve simultaneously with water-hardening properties and foaming and hardening properties in non-aquatic environments when exposed to high-temperature and high-humidity environments for extended periods.

[0009] This disclosure is made in view of the above circumstances and aims to provide an injection chemical composition that can achieve both curing properties in water and foaming and curing properties in non-water environments, even after exposure to high temperature and high humidity environments, as well as a solidified body and a soil stabilization method using the same. [Means for solving the problem]

[0010] As a result of the inventors of the present disclosure investigating the cause of the above problems, in a high-humidity environment, although no visually observable changes were found in the storage tank of the injection chemical solution composition, foaming due to the generation of carbon dioxide gas was confirmed in the rubber hose used for injecting the composition. Therefore, when the injection chemical solution composition in the storage tank was analyzed, it was revealed that in the above high-humidity environment, during the storage of the composition, a trace amount of moisture had mixed into the composition, causing the organic polyisocyanate in the composition to react with the moisture and resulting in the alteration of the organic polyisocyanate (formation of urea groups).

[0011] The present disclosure is based on the above findings. Although not clear, it is presumed that the above-mentioned mixing of moisture is due to the permeation of water vapor through the rubber hose, and it is presumed that in the storage tank with an open system, the bubbles disappeared due to natural defoaming.

[0012] The present disclosure provides at least the following [1] to

[17] . [1] An injection chemical solution composition comprising a first agent (A) containing an organic polyol and a second agent (B) containing an organic polyisocyanate, wherein the first agent (A) contains an aqueous solution of sodium silicate (A-1), an organic polyol (A-2), and a tertiary amine catalyst (A-3), and the second agent (B) contains a mixture (B-1) of diphenylmethane diisocyanate and a polymethylene polyphenyl polyisocyanate having 3 or more isocyanate functional groups, or an organic polyisocyanate containing a reaction product (B-1') of an active hydrogen group-containing compound and the mixture (B-1), at least one acid component (B-2) selected from the group consisting of phosphoric acid monoesters and phosphoric acid diesters, and at least one hydrolyzable component (B-3) selected from the group consisting of orthoester compounds and acetal compounds. [2] The injection chemical solution composition according to [1] above, wherein the acid component (B-2) contains a compound represented by the following formula (1). [Chemical formula] [In formula (1), R 1represents an alkyl group having 2 to 18 carbon atoms, and n represents an integer of 1 or 2. R 1 When there are a plurality of R 1 they may be the same as or different from each other.] [3] The injection liquid composition according to [1] or [2] above, wherein the hydrolyzable component (B-3) contains a compound represented by the following formula (2). [Chemical formula] [In formula (2), R 2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R 3 ~R 5 each independently represents an alkyl group having 1 to 8 carbon atoms.] [4] The injection liquid composition according to any one of [1] to [3] above, wherein the hydrolyzable component (B-3) contains a compound represented by the following formula (3). [Chemical formula] [In formula (3), R 6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 7 represents an alkyl group having 1 to 8 carbon atoms, and R 8 ~R 9 each independently represents an alkyl group having 1 to 8 carbon atoms.] [5] The injection liquid composition according to any one of [1] to [4] above, wherein the content of the acid component (B-2) is 0.1% by mass or less based on the total solid content of the second agent (B). [6] The injection liquid composition according to any one of [1] to [5] above, wherein the content of the hydrolyzable component (B-3) is 5% by mass or less based on the total solid content of the second agent (B). [7] The injection liquid composition according to any one of [1] to [6] above, wherein the molar ratio SiO2 / Na2O of sodium silicate is 1.5 to 3.0. [8] The injection liquid composition according to any one of [1] to [7] above, wherein the content of sodium silicate is 70 to 96% by mass based on the total solid content of the first agent (A). [9] The injection drug composition according to any one of [1] to [8] above, wherein the organic polyol (A-2) comprises an organic polyol having a primary hydroxyl group.

[10] The injection solution composition according to any one of [1] to [9] above, wherein the organic polyol (A-2) comprises at least one organic polyol selected from the group consisting of polyether polyols and aliphatic polyols.

[11] The injection solution composition according to any one of [1] to

[10] above, wherein the tertiary amine catalyst (A-3) comprises a tertiary amine catalyst having one or more active hydrogen groups.

[12] The injection solution composition according to any one of [1] to

[11] above, wherein the mass ratio of diphenylmethane diisocyanate to polymethylene polyphenyl polyisocyanate in mixture (B-1) is 30 / 70 to 75 / 25.

[13] The injectable drug composition according to any one of [1] to

[12] above, wherein the diphenylmethane diisocyanate comprises 4,4'-diphenylmethane diisocyanate and at least one selected from the group consisting of 2,2'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate, and the mass ratio of the total content of 2,2'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate to the content of 4,4'-diphenylmethane diisocyanate is 20 / 80 to 45 / 55.

[14] An injection solution composition according to any of [1] to

[13] above, wherein the second agent (B) contains a foam stabilizer.

[15] An injectable drug composition according to any of [1] to

[14] above, wherein the second agent (B) contains a diluent.

[16] A solidified body comprising a foamed hardened product of an injection chemical composition described in any of [1] to

[15] above, and ground solidified with the foamed hardened product.

[17] A soil stabilization method using an injection chemical composition described in any of [1] to

[15] above, comprising the steps of injecting the injection chemical composition between a structure and the ground, or into the ground, and allowing it to foam and harden. [Effects of the Invention]

[0013] According to this disclosure, it is possible to provide an injection chemical composition that can achieve both curing properties in water and foaming and curing properties in non-water environments, even after exposure to high temperature and high humidity environments, as well as a solidified body and a soil stabilization method using the same. [Modes for carrying out the invention]

[0014] The following describes exemplary embodiments of this disclosure in detail. However, this disclosure is not limited to the embodiments described below. In this specification, numerical ranges indicated using "~" indicate a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. Unless otherwise explicitly stated, the units of the numbers before and after "~" are the same. Furthermore, the upper and lower limits described individually can be combined in any way.

[0015] <Injectable drug solution composition> One embodiment of the present disclosure is an injection solution composition (hereinafter also simply referred to as "the composition") comprising a first agent (A) containing an organic polyol and a second agent (B) containing an organic polyisocyanate, wherein the first agent (A) comprises an aqueous solution of sodium silicate (A-1), an organic polyol (A-2), and a tertiary amine catalyst (A-3), and the second agent (B) comprises an organic polyisocyanate containing a mixture (B-1) of diphenylmethane diisocyanate (hereinafter referred to as "MDI") and polymethylene polyphenyl polyisocyanate with 3 or more isocyanate functional groups (hereinafter referred to as "polymeric MDI"), or a reaction product (B-1') of an active hydrogen group-containing compound and a mixture (B-1), at least one acid component (B-2) selected from the group consisting of phosphate monoesters and phosphate diesters, and at least one hydrolyzable component (B-3) selected from the group consisting of orthoester compounds and acetal compounds.

[0016] The above composition is, for example, an injection chemical composition for ground consolidation, and can be used to consolidate the ground by injecting it between a structure such as a tunnel, underground structure, or high-rise building and the ground (e.g., bedrock), or into the ground (e.g., bedrock), and allowing it to foam and harden.

[0017] According to the above composition, by using the above-mentioned specific acid component (B-2) and the above-mentioned specific hydrolyzable component (B-3) in combination with the above-mentioned other essential components, it is possible to achieve both curability in water and foaming and curability in non-water environments, even after exposure to high temperature and high humidity environments. Specifically, for example, when 1 part by mass of water is added to 100 parts by mass of the composition and stored at 50°C for 14 days, and then foamed and cured in water, a sufficient curing rate is obtained. When foamed and cured in non-water, foaming and curing occur quickly, and a foamed cured product with sufficient foaming ratio and hardness is obtained. Therefore, the above composition is useful as a soil stabilizer (soil stabilization injection chemical composition) that can be used at all times even in places where water leakage or seepage is likely to occur, regardless of the storage environment.

[0018] Furthermore, the above composition tends to be less likely to contaminate water (leaks, spring water, groundwater, etc.) during foaming, even after being exposed to high temperature and high humidity environments, and also tends to exhibit good defoaming properties. In addition, although the foaming properties required in water are not as high as in non-water environments because the composition flows with the water, the above composition tends to yield good foaming properties (foaming ratio) even in water. Moreover, the above composition tends to have a sufficiently long gel time when foamed in non-water environments and exhibits good resin fluidity during foaming.

[0019] (Part 1 (A)) The first agent (A) comprises an aqueous solution (A-1), an organic polyol (A-2), and a tertiary amine catalyst (A-3).

[0020] [Aqueous solution (A-1)] Aqueous solution (A-1) is a liquid mixture of three components: silicon dioxide (SiO2), sodium oxide (Na2O), and water (H2O), and is represented by the general formula Na2O·xSiO2·nH2O. Here, x represents the molar ratio of SiO2 (silicon dioxide) to Na2O (sodium oxide) (hereinafter referred to as "molar ratio of sodium silicate SiO2 / Na2O").

[0021] The molar ratio of sodium silicate (SiO2 / Na2O) may be 1.5 or higher, and may be 1.8 or higher or 2.0 or higher, from the viewpoint of improving foaming and curing properties in water and in non-water. The molar ratio of sodium silicate (SiO2 / Na2O) may be 3.0 or lower, and may be 2.5 or lower, 2.4 or lower, or 2.3 or lower, from the viewpoint of keeping the viscosity of the aqueous solution of sodium silicate low to improve the mixability between the first agent (A) and the second agent (B), from the viewpoint of improving workability at low temperatures, from the viewpoint of further increasing the hardness of the foamed cured product, and from the viewpoint of further suppressing water contamination during foaming. From the above viewpoint, the molar ratio of sodium silicate (SiO2 / Na2O) may be 1.5 to 3.0, and may be 1.8 to 2.5, 2.0 to 2.4, or 2.0 to 2.3.

[0022] The sodium silicate content may be 30% by mass or more, based on the total mass of the aqueous solution (A-1), from the viewpoint of improving foaming and curing properties in water and non-water, and increasing the hardness of the foamed cured product, and may also be 33% by mass or more, 34% by mass or more, 35% by mass or more, 36% by mass or more, 37% by mass or more, 38% by mass or more, 39% by mass or more, or 40% by mass or more. The sodium silicate content may be 50% by mass or less, based on the total mass of the aqueous solution (A-1), from the viewpoint of keeping the viscosity of the aqueous solution of sodium silicate low to improve the mixability between the first agent (A) and the second agent (B), and to improve workability at low temperatures, and may also be 45% by mass or less, 42% by mass or less, or 41% by mass or less. From the above perspective, the sodium silicate content may be 30-50% by mass, based on the total mass of the aqueous solution (A-1), and may also be 33-45% by mass, 34-42% by mass, 35-41% by mass, 36-41% by mass, 37-41% by mass, 38-41% by mass, 39-41% by mass, or 40-41% by mass. Here, the sodium silicate content refers to the content of the component (Na2O·xSiO2) remaining after the water has evaporated from the aqueous solution (A-1), and is also called the solid content.

[0023] The sodium silicate content may be 70% by mass or more, 73% by mass or more, or 75% by mass, based on the total solid content of the first agent (A), from the viewpoint of improving foaming and curing properties in water and non-water, and increasing the hardness of the foamed cured product. The sodium silicate content may be 96% by mass or less, 95% by mass or less, or 94.5% by mass or less, based on the total solid content of the first agent (A), from the viewpoint of keeping the viscosity of the aqueous solution of sodium silicate low to improve the mixability between the first agent (A) and the second agent (B), and to improve workability at low temperatures. From the above viewpoint, the sodium silicate content may be 70 to 96% by mass, 73 to 96% by mass, 73 to 95% by mass, or 75 to 94.5% by mass, based on the total solid content of the first agent (A). Note that the solid content of the first agent (A) refers to the components remaining after removing water from the first agent (A).

[0024] As the aqueous solution (A-1), a commercially available sodium silicate aqueous solution can be used. Alternatively, a commercially available sodium silicate aqueous solution may be used in which the sodium silicate content has been adjusted by adjusting the amount of water (adding or removing water). Commercially available sodium silicate aqueous solutions may contain components other than silicon dioxide (SiO2), sodium oxide (Na2O), and water (H2O) (impurities such as iron), but it is preferable that the content of such components is 0.3 parts by mass or less per 100 parts by mass of aqueous solution (A-1) (100 parts by mass of Na2O·xSiO2·nH2O).

[0025] [Organic polyol (A-2)] Examples of organic polyols (A-2) include polyester polyols, polycarbonate polyols, polyether polyols, and aliphatic polyols. These organic polyols may be used individually or in combination of two or more types.

[0026] As the polyester polyol, a polyester polyol obtained by condensation polymerization of a carboxylic acid and a polyhydric alcohol can be used. The carboxylic acid is, for example, a dibasic acid. Examples of carboxylic acids include succinic acid, adipic acid, sebacic acid, azelaic acid, isophthalic acid, terephthalic acid, and dimer acid. Examples of polyhydric alcohols include ethylene glycol, 1,4-butylene glycol, propylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, diethylene glycol, 1,6-hexanediol, and 1,8-octanediol. One compound may be used alone as the carboxylic acid and polyhydric alcohol, or two or more compounds may be used in combination. In addition, as the polyester polyol, a polycaprolactone-based polyester obtained by ring-opening polymerization of ε-caprolactam with an alcohol may be used.

[0027] As the polycarbonate polyol, for example, a polycarbonate polyol obtained by condensation polymerization of a diester carbonate and a polyhydric alcohol can be used. Examples of diester carbonates include dimethyl carbonate, ethylene carbonate, and propylene carbonate, and examples of polyhydric alcohols are the same as those used for the polyester polyols mentioned above. One compound may be used alone as the diester carbonate and polyhydric alcohol, or two or more may be used in combination.

[0028] As polyether polyols, for example, polyether polyols obtained by adding alkylene oxides to polyhydric alcohols, polyhydric amines, etc., can be used. Examples of alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide. Examples of polyhydric alcohols are the same as those used for polyester polyols above. Examples of polyhydric amines include ethylenediamine and diethylenetriamine. One compound may be used alone as the alkylene oxide, polyhydric alcohol, and polyhydric amine, or two or more may be used in combination. Specific examples of polyether polyols include polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene glycol, polytetramethylene glycol, N,N'-bis(2-hydroxypolyethoxy)ethylenediamine, and polyether polyols obtained by adding alkylene oxides (e.g., ethylene oxide, propylene oxide, butylene oxide, etc.) to alkanolamines (e.g., monoethanolamine, diethanolamine, triethanolamine, etc.). From the viewpoint of improving the miscibility between the first agent (A) and the second agent (B), the polyether polyol preferably contains ethylene oxide units (hereinafter also referred to as "EO units" or "EO"), and more preferably contains both EO units and propylene oxide units. From the above viewpoint, it is preferable to use polyoxyethylene polyoxypropylene glycol as the polyether polyol.

[0029] The EO unit content in polyoxyethylene polyoxypropylene glycol may be 60% by mass or more, and may be 70% by mass or more, from the viewpoint of improving the miscibility between the first agent (A) and the second agent (B) and suppressing the collapse of cells in the foamed cured product and the occurrence of shrinkage. The EO unit content in polyoxyethylene polyoxypropylene glycol may be 90% by mass or less, and may be 85% by mass or less, from the viewpoint of keeping the viscosity of the first agent (A) low and improving workability at low temperatures. From the above viewpoint, the EO unit content in polyoxyethylene polyoxypropylene glycol may be 60 to 90% by mass, and may be 70 to 85% by mass.

[0030] The number-average molecular weight of the polyether polyol is preferably 300 to 1200, more preferably 400 to 1000, and even more preferably 400 to 800, from the viewpoint of the viscosity of the first agent (A). If the number-average molecular weight of the polyether polyol is 300 or more, it tends to have better fluidity during foaming, and if the number-average molecular weight of the polyether polyol is 1200 or less, it is possible to further reduce water contamination during foaming, obtain a foamed cured product with higher hardness, and improve curability in water.

[0031] Examples of aliphatic polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, octanediol, 2,4-diethyl-1,5-pentanediol, neopentyl glycol, hydrogenated bisphenol A, and other aliphatic diols, as well as diethylene glycol, triethylene glycol, glycerin, trimethylolpropane, and pentaerythritol. Among these, from the viewpoint of improving curability in water and suppressing water contamination during foaming, it is preferable to use at least one compound from the group consisting of ethylene glycol, 1,3-butanediol, diethylene glycol, 3-methyl-1,5-pentanediol, and glycerin.

[0032] As for the organic polyol (A-2), it is preferable to use at least one organic polyol selected from the group consisting of polyether polyols and aliphatic polyols, from the viewpoint of keeping the viscosity of the first agent (A) low, improving the compatibility of the aqueous solution of sodium silicate, and improving the miscibility with the second agent (B), and it is more preferable to use a combination of polyether polyol and aliphatic polyol.

[0033] As for the organic polyol (A-2), it is preferable to use an organic polyol having a primary hydroxyl group from the viewpoint of increasing reactivity and resin strength, more preferably to use at least one organic polyol selected from the group consisting of polyether polyols having a primary hydroxyl group and aliphatic polyols having a primary hydroxyl group, and even more preferably to use a combination of a polyether polyol having a primary hydroxyl group and an aliphatic polyol having a primary hydroxyl group.

[0034] The content of organic polyol (A-2) may be 2% by mass or more, 5% by mass or more, or 6% by mass or more, based on the total solid content of the first agent (A), from the viewpoint of superior foaming properties during the reaction. The content of organic polyol (A-2) may be 25% by mass or less, 20% by mass or less, or 18% by mass or less, based on the total solid content of the first agent (A), from the viewpoint of improving workability and further improving curability in water and foaming and curability in non-water. From the above viewpoint, the content of organic polyol (A-2) may be 2 to 25% by mass, 2 to 20% by mass, 5 to 20% by mass or 6 to 18% by mass, based on the total solid content of the first agent (A).

[0035] [Tertiary amine catalyst (A-3)] Tertiary amine catalysts (A-3) are tertiary amines that exhibit catalytic activity. Examples of tertiary amine catalysts (A-3) include N,N-dimethylethanolamine, 2-{N-[2-(dimethylamino)ethyl]-N-methylamino}ethanol, 2-dimethylaminoethoxyethanol, 1,4-diazabicyclo[2.2.2]octane-2-methanol, 6-dimethylamino-1-hexanol, 2-({2-[2-(dimethylamino)ethoxy]ethyl}methylamino)ethanol, 1-[N-(2-{N-[2-(dimethylamino)ethyl] -N-methylamino}ethyl)-N-methylamino]-2-propanol, 1-{bis[(2-dimethylamino)ethyl]amino}-2-propanol, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N'-tetramethylpropanediamine, N,N,N',N',N''-pentamethyldiethylenetriamine, N,N',N'-trimethylaminoethylpiperazine, N,N,N',N'-tetramethylethylenediamine, bis-(dimethylamino) N,N',N'-Tris(3-dimethylaminopropyl)hexahydro-S-triazine, 2-methyltriethylenediamine, N,N-dimethylaminoethylmorpholine, dimethylaminopropylimidazole, hexamethyltriethylenetetramine, N-methylmorpholine, N-methylimidazole, 1,2-dimethylimidazole, N'-[2-(dimethylamino)ethyl]-N,N-dimethylethylenediamine, 3,3-iminovis(N,N Examples include N'-(dimethylamino)methyl N,N-(dimethylamino)methyl N,N-dimethylmethylenediamine, N,N,N',N'-tetraethyldiethylenetriamine, 2-(dimethylamino)ethoxy N-(dimethylamino)ethoxy)-N-(2-(dimethylamino)ethoxy)ethyl ethaneamine, N,N,N-tris(3-dimethylaminopropyl)amine, N-methyl-N,N-bis(3-dimethylaminopropyl)amine, triethylenediamine, etc.

[0036] For the tertiary amine catalyst (A-3), it is preferable to use a tertiary amine catalyst having one or more active hydrogen groups. The presence of active hydrogen groups that can react with isocyanates tends to suppress the elution of the composition into water during foaming. Examples of active hydrogen groups include hydroxyl groups and amino groups.

[0037] As a tertiary amine catalyst having one or more active hydrogen groups, it is preferable to use at least one compound selected from the group consisting of 2-{N-[2-(dimethylamino)ethyl]-N-methylamino}ethanol, 2-dimethylaminoethoxyethanol, 6-dimethylamino-1-hexanol, and 2-({2-[2-(dimethylamino)ethoxy]ethyl}methylamino)ethanol, from the viewpoint of obtaining the above effects more significantly.

[0038] From the viewpoint of superior curability and foaming properties, the content of the tertiary amine catalyst (A-3) may be 0.1% by mass or more, 0.5% by mass or more, or 1% by mass or more, based on the total solid content of the first agent (A). From the viewpoint of making it easier to control reactivity and suppressing the occurrence of injection failures due to resin clogging during chemical injection, the content of the tertiary amine catalyst (A-3) may be 6% by mass or less, 5.5% by mass or less, or 5% by mass or less, based on the total solid content of the first agent (A). From the above viewpoint, the content of the tertiary amine catalyst (A-3) may be 0.1 to 6% by mass, 0.5 to 5.5% by mass or 1 to 5% by mass, based on the total solid content of the first agent (A).

[0039] [Other ingredients] The first agent (A) may further contain other components besides those described above. The first agent (A) may also contain additives such as dispersion stabilizers, for example, from the viewpoint of improving the uniformity of the first agent (A) and improving the compatibility between the first agent (A) and the second agent (B). Examples of dispersion stabilizers include anionic dispersion stabilizers, cationic dispersion stabilizers, and nonionic dispersion stabilizers. These dispersion stabilizers can be used individually or in combination of two or more.

[0040] Examples of anionic dispersion stabilizers include alkyl carboxylates, alkyl sulfates, alkyl sulfonates, and alkyl phosphates.

[0041] Examples of cationic dispersion stabilizers include ammonium salts such as benzalkonium chloride.

[0042] Examples of nonionic dispersion stabilizers include glycerin fatty acid esters, alkyl polyethylene glycols, polyoxyethylene alkylphenyl ethers, and alkyl glycosides.

[0043] The content of the dispersion stabilizer may be 0.01 to 5% by mass, 0.05 to 4% by mass, or 0.1 to 3.5% by mass, based on the total solid content of the first agent (A).

[0044] [viscosity] The viscosity of the first agent (A) at 25°C is preferably 500 mPa·s or less, and more preferably 250 mPa·s or less, from the viewpoint of improving injectability and permeability into voids. The viscosity of the first agent (A) at 25°C may be 50 mPa·s or more, from the viewpoint of the miscibility of the aqueous solution of sodium silicate with the organic polyol and amine catalyst, etc. From the above viewpoint, the viscosity of the first agent (A) at 25°C may be 50 to 500 mPa·s, or 50 to 250 mPa·s.

[0045] (Second agent (B)) The second agent (B) contains an organic polyisocyanate, an acidic component (B-2), and a hydrolyzable component (B-3).

[0046] [Organic polyisocyanates] The organic polyisocyanate contains a mixture (B-1) or a reaction product (B-1').

[0047] The mixture (B-1) comprises MDI and polymeric MDI. In this specification, "MDI" encompasses the various isomers of 4,4'-MDI, 2,4'-MDI, and 2,2'-MDI. "Polymeric MDI" means MDI to which one or more phenyl groups having isocyanate groups are added via methylene groups, resulting in a total of three or more isocyanate functional groups.

[0048] MDI may include 4,4'-MDI and at least one selected from the group consisting of 2,4'-MDI and 2,2'-MDI. The mass ratio of the total content of 2,4'-MDI and 2,2'-MDI to the content of 4,4'-MDI ([2,4'-MDI and 2,2'-MDI] / 4,4'-MDI) may be 20 / 80 or higher, 30 / 70 or higher, or 35 / 65 or higher, from the viewpoint of improving low-temperature stability and further improving the hardness of the foamed cured product. The mass ratio ([2,4'-MDI and 2,2'-MDI] / 4,4'-MDI) may be 45 / 55 or lower, or 40 / 60 or lower, from the viewpoint of further improving the hardness of the foamed cured product. From the above viewpoint, the mass ratio ([2,4'-MDI and 2,2'-MDI] / 4,4'-MDI) may be 20 / 80 to 45 / 55, or 30 / 70 to 45 / 55 or 35 / 65 to 40 / 60.

[0049] The mass ratio of MDI to polymeric MDI in mixture (B-1) (MDI / polymeric MDI) may be 30 / 70 or higher, 50 / 50 or higher, or 55 / 45 or higher, from the viewpoint of improving the handling properties of the second agent (B). The mass ratio (MDI / polymeric MDI) may be 75 / 25 or lower, or 70 / 30 or lower, from the viewpoint of further increasing the hardness of the foamed cured product. From the above viewpoint, the mass ratio (MDI / polymeric MDI) may be 30 / 70 to 75 / 25, 50 / 50 to 75 / 25, or 55 / 45 to 70 / 30.

[0050] The MDI content in mixture (B-1) may be 30% by mass or more, 50% by mass or more, or 55% by mass or more, based on the total mass of mixture (B-1), from the viewpoint of improving the handling properties of the second agent (B). The MDI content in mixture (B-1) may be 75% by mass or less, or 70% by mass or less, based on the total mass of mixture (B-1), from the viewpoint of further increasing the hardness of the foamed cured product. From the above viewpoint, the MDI content in mixture (B-1) may be 30-75% by mass, 50-75% by mass or 55-70% by mass, based on the total mass of mixture (B-1).

[0051] From the viewpoint of further increasing the hardness of the foamed cured product, the polymeric MDI content in mixture (B-1) may be 25% by mass or more, or 30% by mass or more, based on the total mass of mixture (B-1). From the viewpoint of improving the handling properties of the second agent (B), the polymeric MDI content in mixture (B-1) may be 70% by mass or less, 50% by mass or less, or 45% by mass or less, based on the total mass of mixture (B-1). From the above viewpoint, the polymeric MDI content in mixture (B-1) may be 25-70% by mass, 25-50% by mass or 30-45% by mass, based on the total mass of mixture (B-1).

[0052] The reaction product (B-1') is a reactive product obtained by the reaction of the active hydrogen group of the active hydrogen group-containing compound with some of the isocyanate groups of the MDI and polymeric MDI in mixture (B-1).

[0053] Active hydrogen group-containing compounds are compounds having active hydrogen groups such as hydroxyl groups and amino groups. From the viewpoint of controlling the reaction between the isocyanate group and the active hydrogen group and the viscosity after the reaction, it is preferable to use a hydroxyl group-containing compound. The hydroxyl group-containing compound may be a monool or a polyol.

[0054] Examples of hydroxyl group-containing compounds include organic polyols such as ethylene glycol, butanediol, glycerin, trimethylolpropane, sorbitol, and sucrose; alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; polyether polyols; and polyester polyols. Examples of polyether polyols include the polyether polyols listed as examples of organic polyols (A-2), and compounds obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to the above organic polyols.

[0055] From the viewpoint of improving compatibility with the first agent (A), the hydroxyl group-containing compound is preferably a polyol, more preferably a polyether polyol, and even more preferably a polyether polyol having an EO unit. Among polyether polyols having an EO unit, polyether polyols having a propylene oxide unit are preferred, and polyoxyethylene polyoxypropylene glycol is particularly preferred.

[0056] The EO unit content in polyoxyethylene polyoxypropylene glycol may be 60% by mass or more, and may be 70% by mass or more, from the viewpoint of improving the miscibility between the first agent (A) and the second agent (B) and suppressing the collapse of cells in the foamed cured product and the occurrence of shrinkage. The EO unit content in polyoxyethylene polyoxypropylene glycol may be 90% by mass or less, and may be 85% by mass or less, from the viewpoint of keeping the viscosity of the second agent (B) low and improving workability at low temperatures. From the above viewpoint, the EO unit content in polyoxyethylene polyoxypropylene glycol may be 60 to 90% by mass, and may be 70 to 85% by mass.

[0057] The number-average molecular weight of the hydroxyl group-containing compound is preferably 300 to 4500, more preferably 400 to 4000, and even more preferably 400 to 1000. If the number-average molecular weight of the hydroxyl group-containing compound is 300 or more, the increase in viscosity of the second agent (B) is suppressed, and the fluidity and void-filling properties during foaming tend to improve. If the number-average molecular weight of the hydroxyl group-containing compound is 4500 or less, water contamination during foaming can be further reduced, and effects such as easier acquisition of a harder foamed cured product and improved curability in water can be obtained.

[0058] The introduction rate of the active hydrogen group-containing compound is preferably 0.5% by mass or more, from the viewpoint of improving compatibility with the first agent (A) and further increasing the hardness of the foamed cured product. The introduction rate of the active hydrogen group-containing compound is preferably 10% by mass or less, and more preferably 6.0% by mass or less, from the viewpoint of suppressing the elution of polyisocyanate into water due to excessive hydrophilicity and the resulting water contamination (turbidity, foaming, etc.). From the above viewpoint, the introduction rate of the active hydrogen group-containing compound is preferably 0.5 to 10% by mass, and more preferably 0.5 to 6.0% by mass. The introduction rate of the active hydrogen group-containing compound represents the proportion of the active hydrogen group-containing compound introduced into the reaction product, based on the total amount of the reaction product.

[0059] The reaction product (B-1') may include urethane-modified, allophanate-modified, biuret-modified, carbodiimide-modified, isocyanurate-modified, uretdione-modified, and the like as modified forms of MDI and polymeric MDI.

[0060] When the reaction product (B-1') includes a urethane-modified material, that is, when the active hydrogen group-containing compound is a hydroxyl group-containing compound, the reaction product (B-1') is preferably an isocyanate-terminated prepolymer obtained by reacting the reaction mixture (B-1) with the hydroxyl group-containing compound in a known method such that the equivalent ratio (NCO group / OH group) of isocyanate groups (hereinafter referred to as "NCO groups") in the reaction mixture (B-1) to hydroxyl groups (hereinafter referred to as "OH groups") in the hydroxyl group-containing compound is preferably in the range of 2 to 300, and more preferably in the range of 5 to 100.

[0061] The organic polyisocyanate is preferably composed of a reaction product (B-1') from the viewpoint of improving foaming and curing properties in water and non-water, and increasing the hardness of the foamed cured product, and more preferably composed of a reaction product of MDI, polymeric MDI, and polyether polyol.

[0062] The isocyanate group content (hereinafter also referred to as "NCO content") of the organic polyisocyanate may be 20% by mass or more, and may be 21% by mass or more, or 22% by mass or more, from the viewpoint of viscosity and curability of the organic polyisocyanate. The NCO content of the organic polyisocyanate may be 33% by mass or less, 32% by mass or less, or 31.5% by mass or less, from the viewpoint of foaming and curability. From the above viewpoint, the NCO content of the organic polyisocyanate may be 20 to 33% by mass, and may be 21 to 32% by mass or 22 to 31.5% by mass.

[0063] The content of organic polyisocyanate may be 80% by mass or more, 85% by mass or more, or 90% by mass or more, based on the total solid content of the second agent (B), from the viewpoint of foaming properties, curability and foam strength. The content of organic polyisocyanate may be less than 100% by mass, 99% by mass or less, or 98% by mass or less, based on the total solid content of the second agent (B), from the viewpoint of viscosity and curability of organic polyisocyanate. From the above viewpoint, the content of organic polyisocyanate may be 80% by mass or more and less than 100% by mass, or 85-99% by mass or 90-98% by mass. Note that the solid content of the second agent (B) refers to the components remaining after removing the diluent from the second agent (B) if the second agent (B) contains a diluent, and refers to the second agent (B) itself if the second agent (B) does not contain a diluent.

[0064] [Acid component (B-2)] As the acid component (B-2), at least one selected from the group consisting of phosphate monoesters and phosphate diesters is used.

[0065] A monophosphate ester is a compound in which one of the three hydroxyl groups of phosphoric acid is esterified. Monoalkyl phosphates are preferably used as monophosphate esters. The number of carbon atoms in the alkyl group in a monoalkyl phosphate ester may be, for example, 2 to 18. The alkyl group may be linear or branched. Examples of alkyl groups include ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, n-dodecyl group, n-tridecyl group, iso-tridecyl group, and the like.

[0066] Examples of monoalkyl phosphates include monoethyl phosphate, mono-n-propyl phosphate, mono-n-butyl phosphate, mono(2-ethylhexyl) phosphate, mono-n-dodecyl phosphate, and monoisotridecyl phosphate. Among these, mono-nethyl phosphate, mono-n-butyl phosphate, and monoisotridecyl phosphate are preferred.

[0067] A phosphate diester is a compound in which two of the three hydroxyl groups of phosphoric acid are esterified. Dialkyl phosphates are preferably used as phosphate diesters. The number of carbon atoms in the alkyl group of a dialkyl phosphate may be, for example, 2 to 18. The alkyl group may be linear or branched. Examples of alkyl groups are the same as those in the above-mentioned monoalkyl phosphates. The two alkyl groups in a dialkyl phosphate may be identical to each other.

[0068] Examples of dialkyl phosphates include diethyl phosphate, di-n-propyl phosphate, di-n-butyl phosphate, di(2-ethylhexyl) phosphate, di-n-dodecyl phosphate, and diisotridecyl phosphate. Among these, di-n-ethyl phosphate, di-n-butyl phosphate, and diisotridecyl phosphate are preferred.

[0069] As the acid component (B-2), it is preferable to use a compound represented by the following formula (1) from the viewpoint of compatibility with organic polyisocyanates. [ka]

[0070] In the above equation (1), R 1 R represents an alkyl group with 2 to 18 carbon atoms, and n represents an integer of 1 or 2. 1 If multiple R 1 They may be the same or different from one another.

[0071] As the compound represented by formula (1) above, it is preferable to use at least one selected from the group consisting of mono-n-ethyl phosphate, mono-n-butyl phosphate, monoisotridecyl phosphate, di-n-ethyl phosphate, di-n-butyl phosphate, and diisotridecyl phosphate, from the viewpoint of further improving curability in water and foaming and curability in non-water.

[0072] From the viewpoint of further improving curability in water and foaming and curability in non-water, the content of acid component (B-2) may be 0.001% by mass or more, or 0.01% by mass or more, based on the total solid content of agent (B). From the viewpoint of improving curability in water and non-water, the content of acid component (B-2) may be 0.1% by mass or less, 0.05% by mass or less, or 0.02% by mass or less, based on the total solid content of agent (B). From the viewpoint of improving curability in water and non-water, the content of acid component (B-2) may be 0.001 to 0.1% by mass, 0.01 to 0.05% by mass or 0.01 to 0.02% by mass.

[0073] [Hydrolyzable component (B-3)] As the hydrolyzable component (B-3), at least one selected from the group consisting of orthoester compounds and acetal compounds is used.

[0074] Orthoester compounds are compounds having an orthoester structure (a structure in which three alkoxy groups are bonded to the same carbon atom). Using orthoester compounds as the hydrolyzable component (B-3) tends to result in higher hardness. Orthoester compounds may be used individually or in combination of two or more types.

[0075] As the orthoester compound, it is preferable to use a compound represented by the following formula (2) from the viewpoint of further improving hydrolysis efficiency, curability in water, and foaming and curability in non-water environments. [ka]

[0076] In equation (2) above, R 2 R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. 3 ~R 5 Each of these independently represents an alkyl group having 1 to 8 carbon atoms.

[0077] R 2 ~R 5Each alkyl group represented by may be linear or branched. 2 ~R 5 Examples of alkyl groups represented by include methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, hexyl group, and octyl group.

[0078] R 2 From the viewpoint of hydrolysis efficiency, it is preferable that it be a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 3 ~R 5 From the viewpoint of hydrolysis efficiency, each of these is preferably an alkyl group having 1 to 3 carbon atoms.

[0079] Examples of orthoester compounds represented by formula (2) above include orthoformate ester compounds such as trimethyl orthoformate, triethyl orthoformate, and tripropyl orthoformate; orthoacetate ester compounds such as trimethyl orthoacetate, triethyl orthoacetate, and tripropyl orthoacetate; and orthopropionate ester compounds such as trimethyl orthopropionate, triethyl orthopropionate, tripropyl orthopropionate, and tributyl orthopropionate. Among these, trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, and triethyl orthopropionate are preferably used.

[0080] Acetal compounds are compounds having an acetal structure (a structure in which two alkoxy groups are bonded to the same carbon atom) and are obtained by the condensation reaction of an aldehyde or ketone with an alcohol. Acetal compounds may be used individually or in combination of two or more.

[0081] As the acetal compound, it is preferable to use a compound represented by the following formula (3) from the viewpoint of further improving hydrolysis efficiency, curability in water, and foaming and curability in non-water environments. [ka]

[0082] In equation (3) above, R 6 R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. 7 R represents an alkyl group with 1 to 8 carbon atoms. 8 ~R 9 Each of these independently represents an alkyl group having 1 to 8 carbon atoms.

[0083] R 6 ~R 9 Each alkyl group represented by may be linear or branched. 6 ~R 9 Examples of alkyl groups represented by include methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, hexyl group, and octyl group.

[0084] R 6 From the viewpoint of hydrolysis efficiency, it is preferable that the alkyl group has 1 to 3 carbon atoms. 7 From the viewpoint of hydrolysis efficiency, it is preferable that the alkyl group has 1 to 3 carbon atoms. 8 ~R 9 Each of these is preferably an alkyl group having 1 to 3 carbon atoms.

[0085] Examples of acetal compounds represented by formula (3) above include 2,2-dimethoxypropane, 2,2-dimethoxybutane, 3,3-dimethoxyhexane, 2,2-dimethoxyoctane, and 2,2-diethoxypropane. Among these, 2,2-dimethoxypropane is preferred.

[0086] The hydrolyzable component (B-3) may contain one or more compounds represented by formula (2) above, and may contain one or more compounds represented by formula (3) above. Furthermore, the hydrolyzable component (B-3) may contain one or more compounds represented by formula (2) above and one or more compounds represented by formula (3) above. From the viewpoint of further improving curability in water and foaming and curability in non-water, the hydrolyzable component (B-3) preferably contains at least one selected from the group consisting of trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, triethyl orthopropionate, and 2,2-dimethoxypropane. From the viewpoint of further improving hydrolysis efficiency, curability in water, and foaming and curability in non-water, it is more preferable that it contains at least one selected from the group consisting of trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, and triethyl orthopropionate.

[0087] From the viewpoint of further improving curability in water and foaming and curability in non-water, the content of hydrolyzable component (B-3) may be 0.1% by mass or more, 0.5% by mass or more, or 0.75% by mass or more, based on the total solid content of the second agent (B). From the viewpoint of further improving curability in water and foaming and curability in non-water, the content of hydrolyzable component (B-3) may be 5% by mass or less, 4.5% by mass or less, 3.5% by mass or less, 2.5% by mass or less, or 1.5% by mass or less, based on the total solid content of the second agent (B). From the viewpoint of further improving curability in water and foaming and curability in non-water, the content of hydrolyzable component (B-3) may be 0.1 to 5% by mass, 0.5 to 4.5% by mass, 0.75 to 3.5% by mass, 0.75 to 2.5% by mass or 0.75 to 1.5% by mass.

[0088] In one embodiment, from the viewpoint of further improving hydrolysis efficiency, curability in water, foaming properties and curability in non-water, it is preferable to use a combination of at least one compound selected from the group consisting of the compound represented by formula (2) and the compound represented by formula (3) above, and the compound represented by formula (1), which is at least one compound selected from the group consisting of trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, triethyl orthopropionate and 2,2-dimethoxypropane, and mono-n-ethyl phosphate, mono-n-butyl phosphate, monoisotridecyl phosphate It is more preferable to use a combination of at least one selected from the group consisting of di-n-ethyl phosphate, di-n-butyl phosphate, and diisotridecyl phosphate, and it is even more preferable to use a combination of at least one selected from the group consisting of trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, and triethyl orthopropionate, and at least one selected from the group consisting of mono-n-ethyl phosphate, mono-n-butyl phosphate, monoisotridecyl phosphate, di-n-ethyl phosphate, di-n-butyl phosphate, and diisotridecyl phosphate.

[0089] In the second agent (B), the ratio of the content of hydrolyzable component (B-3) to the content of acid component (B-2) (content of hydrolyzable component (B-3) / content of acid component (B-2)) may be 10 or more, 50 or more, or 150 or more by mass ratio, from the viewpoint of further improving curability in water and foaming and curability in non-water, and may be 300 or less, 200 or less, or 100 or less, from the viewpoint of suppressing turbidity and foaming of water during foaming in water. From the above viewpoint, the ratio of the content of hydrolyzable component (B-3) to the content of acid component (B-2) may be 10 to 300, 50 to 300, 150 to 300, 10 to 200, or 10 to 100 by mass ratio.

[0090] [Other ingredients] The second agent (B) may further contain other components in addition to those described above.

[0091] The second component (B) may contain a foam stabilizer, for example, to stabilize the cell diameter during foaming. Examples of foam stabilizers include silicone-based foam stabilizers. Examples of silicone-based foam stabilizers include polyoxyalkylene dimethylpolysiloxane copolymer and organopolysiloxane. From the viewpoint of suppressing a decrease in the hardness of the foamed cured product, the foam stabilizer content is preferably 3% by mass or less based on the total solid content of the second component (B). For example, the foam stabilizer content may be 0.1 to 3% by mass based on the total solid content of the second component (B).

[0092] The second component (B) may contain a diluent, for example, to adjust its viscosity. Examples of diluents include alkylene carbonate diluents such as propylene carbonate, alkyl ether diluents such as propylene glycol monomethyl ether acetate and diethylene glycol monomethyl ether acetate, and ester diluents. These diluents have excellent compatibility with the components contained in the second component (B), as well as excellent viscosity reduction and mixing stability. The amount of diluent may be 1 to 5% by mass, based on the total solid content of the second component (B), from the viewpoint of the working environment and safety.

[0093] [viscosity] The viscosity of the second component (B) at 25°C is preferably 500 mPa·s or less, and more preferably 450 mPa·s or less, from the viewpoint of improving injectability and penetration into voids. The viscosity of the second component (B) at 25°C may be 50 mPa·s or more, from the viewpoint of foaming and curing properties. From the above viewpoint, the viscosity of the second component (B) at 25°C may be 50 to 500 mPa·s, or 50 to 450 mPa·s.

[0094] The first agent (A) and the second agent (B) described above may exist separately or may be mixed together.

[0095] From the viewpoint of further increasing the hardness of the foamed cured product, the mixing ratio of the first agent (A) to the second agent (B) is preferably 50 parts by mass or more, and more preferably 70 parts by mass or more, of the first agent (A) to the second agent (B). From the viewpoint of suppressing turbidity and foaming of the water during foaming in water, the mixing ratio of the first agent (A) to the second agent (B) is preferably 150 parts by mass or less, and more preferably 130 parts by mass or less, of the first agent (A) to the second agent (B). From the above viewpoint, the mixing ratio of the first agent (A) to the second agent (B) is preferably 50 to 150 parts by mass, and more preferably 70 to 130 parts by mass, of the first agent (A) to the second agent (B).

[0096] The composition may contain, in addition to the first agent (A) and the second agent (B), other agents (or other liquids).

[0097] <Solid solid> Another embodiment of the present disclosure is a solidified body comprising a foamed cured product of the injection chemical composition of the above embodiment and ground solidified with the foamed cured product. Since this solidified body is formed by the foamed cured product of the injection chemical composition of the above embodiment, it has excellent durability and strength.

[0098] The solidified body can be obtained, for example, by injecting the injection chemical composition of the above embodiment between a structure such as a tunnel, underground structure, or high-rise building and the ground (e.g., bedrock), or into the ground (e.g., bedrock), and allowing it to foam and harden, thereby solidifying the ground with the foamed hardened material formed from the injection chemical composition.

[0099] The method for injecting the grout composition into the ground is not particularly limited and can be carried out by conventionally known methods. For example, the first agent (A) and the second agent (B) of the grout composition may be mixed, and the resulting mixture may be injected into the ground to form a foamed hardened material by causing the first agent (A) and the second agent (B) to react (foam and harden) in the ground. In this case, the first agent (A) and the second agent (B) may be mixed in the above-mentioned mixing ratio. The mixing of the first agent (A) and the second agent (B) may be performed immediately before injecting the composition into the ground.

[0100] <Soil stabilization method> Another embodiment of the present disclosure is a soil stabilization method using the injection chemical composition of the above embodiment. This method includes the steps of injecting the injection chemical composition of the above embodiment between a structure and the ground, or into the ground, and allowing it to foam and harden.

[0101] According to the above method, voids between the structure and the ground, or within the ground, are filled with the foamed hardened material of the injection chemical composition, or unstable ground is solidified with the foamed hardened material of the injection chemical composition, thereby forming the solidified body of the above embodiment and stabilizing the soil properties of the ground.

[0102] The method for injecting the composition in the above method is as described above. The injection of the composition may be carried out after the composition has been exposed to a moist, high-temperature environment (for example, an environment of 40°C or higher). In the above method, since the injection chemical composition of the above embodiment is used, sufficient void filling and excellent ground stability can be ensured even after the composition has been exposed to a moist, high-temperature environment.

[0103] The ground into which the injection chemical composition is injected may contain water such as leaks, seepage, or groundwater. According to the above method, even if the ground contains water, contamination of the water is unlikely, and leakage due to delayed hardening is unlikely. Examples of structures include, but are not limited to, tunnels, underground structures, and high-rise buildings. [Examples]

[0104] The embodiments of this disclosure will be described in detail below, but this disclosure is not limited to these embodiments. Unless otherwise specified, "%" in the embodiments refers to mass.

[0105] <Preparation of Agent 1 (A)> (Preparation examples 1A to 8A) The first agent (A) was prepared using the raw materials listed in Table 1. Specifically, an aqueous solution of sodium silicate (A-1), an organic polyol of the type shown in Table 1 (A-2), and a tertiary amine catalyst of the type shown in Table 1 (A-3) were charged in the amounts (in g) shown in Table 1 into a 0.2 L plastic cup. The mixture was stirred with a stirring rod at room temperature for 3 minutes to obtain the first agents (1A) to (8A) shown in Table 1.

[0106] (Viscosity measurement) The viscosity of the first agent (A) prepared according to the above preparation examples 1A to 8A was measured. The viscosity was measured using a B-type viscometer (TVB-10, manufactured by Toki Sangyo Co., Ltd.) with the liquid temperature of the first agent (A) adjusted to 25°C. The value obtained 120 seconds after the start of measurement was taken as the measured value.

[0107] [Table 1]

[0108] The ingredients listed in Table 1 are as follows:

[0109] (A-1) • Aqueous solution of sodium silicate: Adjusted to have a solid content of 36.5-40.5% and a molar ratio (SiO2 / Na2O) of 2.0-2.2 (Sodium silicate No. 1 and Sodium silicate No. 2, manufactured by Toso Sangyo Co., Ltd.)

[0110] (A-2) • Organic polyol 1:PO / EO-based polyether polyol, number average molecular weight 400, EO content 75% (product name: Puranol D-204E, manufactured by Jiahua Chemicals, "Puranol" is a registered trademark) • Organic polyol 2: diethylene glycol • Organic polyol 3: Glycerin • Organic polyol 4:1,3-butanediol • Organic polyol 5:3-methyl-1,5-pentanediol • Organic polyol 6:PO-based polyether polyol, number average molecular weight 1000, EO content 0% (product name: Sannix PP-1000, manufactured by Sanyo Chemical Industries, Ltd.)

[0111] (A-3) • Tertiary amine 1:2-{N-[2-(dimethylamino)ethyl]-N-methylamino}ethanol (Product name: TOYOCAT RX5, manufactured by Tosoh Corporation) • Tertiary amine 2:2-dimethylaminoethoxyethanol (product name: TOYOCAT RX3, manufactured by Tosoh Corporation) • Tertiary amine 3:6-dimethylamino-1-hexanol (product name: Kaolizer No. 25, manufactured by Kao Corporation) • Tertiary amine 4:2-({2-[2-(dimethylamino)ethoxy]ethyl}methylamino)ethanol (product name: TOYOCAT RX10, manufactured by Tosoh Corporation) • Tertiary amine 5: Triethylenediamine (Product name: TEDA L33, manufactured by Tosoh Corporation) • Tertiary amine 6: N,N,N',N'-tetramethylhexamethylenediamine (product name: TOYOCAT MR, manufactured by Tosoh Corporation)

[0112] <Preparation of the second agent (B)> (Preparation Examples 1B-5B and 8B-13B) The second agent (B) was prepared using the raw materials shown in Table 2. Specifically, polyisocyanate 1, polyisocyanate 2, and polyol 1 were charged in the amounts (in g) shown in Table 2 into a 1 L reactor equipped with a stirrer, thermometer, cooler, and nitrogen gas inlet tube, and the temperature was raised to 80°C. The urethane reaction was carried out for 3 hours while uniformly mixing with a stirring blade while maintaining the temperature. After that, it was cooled to 60°C, and a foam stabilizer (siloxane-polyalkylene oxide copolymer), the acid component (B-2) shown in Table 2, and the hydrolyzable component (B-3) shown in Table 2 were added in the amounts (in g) shown in Table 2. Subsequently, stirring was continued for another 30 minutes to obtain the second agents (1B) to (5B) and (8B) to (13B), respectively, which contained an organic polyisocyanate (a reaction product of polyisocyanate 1, polyisocyanate 2, and polyol 1), a foam stabilizer, an acidic component (B-2), and a hydrolyzable component (B-3).

[0113] (Preparation Example 6B) The second agent (6B) was obtained in the same manner as in Preparation Example 8B, except that a diluent (propylene carbonate) was added in the amounts shown in Table 2, along with a foam stabilizer, an acid component (B-2), and a hydrolyzable component (B-3).

[0114] (Preparation Example 7B) Except for using polyol 2 instead of polyol 1, and adding polyisocyanate 3 along with polyisocyanate 1, polyisocyanate 2, and polyol 2 in the amounts shown in Table 2, a second agent (7B) containing an organic polyisocyanate (the reaction product of polyisocyanate 1, polyisocyanate 2, polyisocyanate 3, and polyol 2), a foam stabilizer, an acid component (B-2), and a hydrolyzable component (B-3) was obtained in the same manner as in Preparation Example 8B.

[0115] (Preparation Example 14B) The second preparation (14B) was obtained in the same manner as in Preparation Example 1B, except that the hydrolyzable component (B-3) was not added.

[0116] (Preparation Example 15B) The second agent (15B) was obtained in the same manner as in preparation example 8B, except that phthalate chloride was used instead of the acid component (B-2).

[0117] (Viscosity measurement) The viscosity of the second agent (B) prepared in the above preparation examples 1B to 15B was measured under the same conditions as the viscosity measurement of the first agent (A) described above.

[0118] [Table 2]

[0119] The raw materials in Table 2 are as follows. In Table 2, "NCO content" represents the isocyanate group content (unit: mass%) of the organic polyisocyanate contained in the second agent (B), "MDI amount" represents the mass ratio (unit: mass%) of MDI to the total amount of MDI and polymeric MDI in the total polyisocyanates used as raw materials, and "2,4'-MDI and 2,2'-MDI amount" represents the mass ratio (unit: mass%) of the total amount of 2,4'-MDI and 2,2'-MDI to the total amount of 2,4'-MDI, 2,2'-MDI and 4,4'-MDI in the total polyisocyanates used as raw materials.

[0120] (B-1) • Polyisocyanate 1:MDI / Polymeric MDI = 40 / 60 (peak area ratio (mass ratio)), mass ratio of 2,4'-MDI and 2,2'-MDI to 4,4'-MDI in MDI ([2,4'-MDI and 2,2'-MDI] / 4,4'-MDI) = 3 / 97, NCO content 31.0% (product name: MR-200, manufactured by Tosoh Corporation) • Polyisocyanate 2: MDI / polymeric MDI = 100 / 0 (peak area ratio (mass ratio)), mass ratio of 2,4'-MDI and 2,2'-MDI to 4,4'-MDI in MDI ([2,4'-MDI and 2,2'-MDI] / 4,4'-MDI) = 55 / 45, NCO content 33.5% (product name: Millionate NM, manufactured by Tosoh Corporation, "Millionate" is a registered trademark (the same applies hereinafter)). • Polyisocyanate 3: MDI / polymeric MDI = 100 / 0 (peak area ratio (mass ratio)), mass ratio of 2,4'-MDI and 2,2'-MDI to 4,4'-MDI in MDI ([2,4'-MDI and 2,2'-MDI] / 4,4'-MDI) = 1 / 99, NCO content 33.5% (product name: Millionate MT, manufactured by Tosoh Corporation). Since this raw material is solid at room temperature, it was heated to 60°C to melt before use in preparation. • Polyol 1:PO / EO-based polyether polyol, number average molecular weight 400, EO content 75% (Trade name: Puranol D-204E, manufactured by Jiahua Chemicals, "Puranol" is a registered trademark) • Polyol 2: PO-based polyether polyol, number average molecular weight 4000, EO content 0% (Product name: Sannix PP-1000, manufactured by Sanyo Chemical Industries, Ltd.)

[0121] (B-2) • Acid component 1: A mixture of monoethyl phosphate and diethyl phosphate (product name: JP-502, manufactured by Johoku Chemical Co., Ltd.) • Acid component 2: A mixture of monobutyl phosphate and dibutyl phosphate (product name: JP-504, manufactured by Johoku Chemical Co., Ltd.) • Acid component 3: A mixture of monoisotridecyl phosphate and diisotridecyl phosphate (product name: JP-513, manufactured by Johoku Chemical Co., Ltd.) • Acid component 4: Dibutyl phosphate (product name: DBP, manufactured by Johoku Chemical Co., Ltd.) • Acid component 5: Monobutyl phosphate (product name: JAMP-4P, manufactured by Johoku Chemical Co., Ltd.)

[0122] (B-3) • Hydrolyzable component 1: Triethyl orthoformate (product name: OFE, manufactured by Nippo Chemical Co., Ltd.) • Hydrolyzable component 2: Trimethyl orthoformate (product name: OFM, manufactured by Nippo Chemical Co., Ltd.) • Hydrolyzable component 3: Trimethyl orthoacetate (product name: MOA, manufactured by Nippo Chemical Co., Ltd.) • Hydrolyzable component 4: Triethyl orthoacetate (product name: EOA, manufactured by Nippo Chemical Co., Ltd.) • Hydrolyzable component 5: 2,2-dimethoxypropane • Hydrolyzable component 6: Triethyl orthopropionate (product name: EOP, manufactured by Nippo Chemical Co., Ltd.)

[0123] (others) • Phthalate chloride • Foam stabilizer: Siloxane-polyalkylene oxide copolymer (product name: NIAX SILICONE Y-16136, manufactured by MOMENTIVE) • Diluent: Propylene carbonate

[0124] <Examples 1-20 and Comparative Examples 1-2> Water was added to each of the first agent (A) and second agent (B) obtained in the above preparation example, and they were left to stand at 50°C for 14 days. The amount of water added was 1 part by mass per 100 parts by mass of the first agent (A) and second agent (B). When the state of the first agent (A) and second agent (B) was checked after standing, a volume increase of more than 200% was confirmed in the second agent (14B) compared to the volume before water addition. The volume increase in the second agents (1B) to (13B) and (15B) was less than 120% compared to the volume before water addition. The above volume increase is due to foaming, and it is presumed that carbon dioxide gas was generated by the reaction of water with the organic polyisocyanate. No particular changes were observed in the first agents (1A) to (8A).

[0125] After adding water and allowing the mixture to stand at 50°C for 14 days, the first agent (A) and the second agent (B) were prepared as the injection drug compositions for the examples and comparative examples in the combinations shown in Tables 3 and 4.

[0126] (Evaluation 1: Free foaming test) Free foaming tests were performed on the injection solution compositions of the examples and comparative examples, and the cream time, gel time, rise time, foaming ratio, foaming speed, and hardness of the foamed and cured product were measured. In the free foaming test, the first agent (A) and the second agent (B) were adjusted to a liquid temperature of 25°C, and then mixed in 1L cups in the proportions shown in Tables 3 and 4. The mixture was then stirred at 400 rpm for 10 seconds using a three-one motor, and foaming and curing were allowed to occur in the cup. Details of each measurement item are shown below, and the measurement results are shown in Tables 3 and 4.

[0127] • Cream time: This refers to the time (in seconds) from when the first agent (A) and the second agent (B) are mixed and stirred until the mixture becomes cloudy and creamy and the liquid surface rises.

[0128] • Gel Time: This represents the time (in seconds) from the start of mixing and stirring of the first agent (A) and the second agent (B) until the fluidity of the mixture disappears. The fluidity of the mixture was determined to have disappeared when the foamed resin stopped moving when the cup containing the mixture was shaken slightly.

[0129] • Rise time: This represents the time (in seconds) from when the first agent (A) and the second agent (B) are mixed and stirred until the mixture starts to foam and reaches its highest point.

[0130] • Expansion ratio: Calculated using the following formula. Foaming ratio (times) = Volume of molded body after foaming (cm³) 3 ) / Volume of the mixture before foaming (cm³) 3 ) If the expansion ratio calculated using the above formula is between 4 and 10 times, it can be said that the expansion ratio is good.

[0131] • Foaming speed: When foaming in a 1L cup, if the cup is filled before hardening, the foaming speed is calculated using the time from the end of the creaming time until the cup is filled, using the following formula. Foaming rate ( / sec) = 100 / (Reaction time from start of stirring until filling a 1L cup (seconds) - Cream time (seconds)) If the mixture hardens without filling the cup, the calculation is performed using the following formula. Foaming rate ( / second) = 100 / (Rise time (seconds) - Cream time (seconds)) At a liquid temperature of 25°C, if the foaming rate calculated using the above formula is 14.0 or less, the foaming rate can be considered good.

[0132] • Hardness: The surface hardness of the hardened foam was measured using a Type C rubber hardness tester (Asker) 5 minutes after free foaming was complete. A surface hardness of 10 or higher indicates good hardness.

[0133] (Evaluation 2: Underwater foaming test) Underwater foaming tests were conducted on the injection chemical compositions of the examples and comparative examples, and the cream time, rise time, foaming ratio, flow water turbidity, defoaming time, water pH, and curing time (underwater curability) were measured. In the underwater foaming test, the first agent (A) and the second agent (B) were mixed in 1L cups in the proportions shown in Tables 3 and 4 after adjusting the liquid temperature to 25°C. Immediately after mixing and stirring for 10 seconds at 400 rpm using a three-one motor, 100 mL of the mixture was quickly poured into another 1L cup containing 500 mL of water, and the mixture and water in the cups were vigorously stirred with a stirring rod for 30 seconds to induce foaming and curing. Details of the various measurement methods are shown below, and the measurement results are shown in Tables 3 and 4.

[0134] • Cream Time: This refers to the time (in seconds) from when the mixture in the cup and water are vigorously stirred for 30 seconds until the mixture becomes cloudy and creamy and the surface rises.

[0135] • Rise Time: This represents the time (in seconds) from when the mixture in the cup is vigorously stirred for 30 seconds until the mixture starts to foam and reaches its highest point.

[0136] • Expansion ratio: Calculated using the following formula. Foaming ratio (times) = Volume of molded body after foaming (cm³) 3 ) / Volume of the mixture before foaming (cm³) 3 )

[0137] • Turbidity of flowing water (water turbidity): This value is measured using a turbidimeter (TURBIDIMETER 2100N, HACH) after the rise time has ended. A turbidity of 30 NTU or less indicates good turbidity resistance. Turbidity resistance, along with defoaming properties and pH, is an indicator of how easily water can cause pollution.

[0138] • Defoaming time: After the rise time has ended, 125 mL of water is placed in a 250 mL polyethylene bottle, sealed tightly, shaken vigorously for 10 seconds, and then allowed to stand. The time (in seconds) until the foam disappears from the water surface is measured. A defoaming time of 60 seconds or less indicates good defoaming performance.

[0139] • Water pH: This shows the pH value measured after the rise time has ended. If the pH is 10 or lower, it can be said that the rise in pH has been suppressed.

[0140] • Curing time (water curing): This indicates the time from when water foaming begins (immediately after vigorously stirring the mixture and water in the cup for 30 seconds) until the tackiness on the surface of the cured foam disappears, after removing the water from the cup 2 minutes later. A time of 200 seconds or less is considered good.

[0141] [Table 3]

[0142] [Table 4]

Claims

1. The product comprises a first agent (A) containing an organic polyol and a second agent (B) containing an organic polyisocyanate. The first agent (A) is Aqueous solution of sodium silicate (A-1), Organic polyol (A-2) and, It contains a tertiary amine catalyst (A-3), The second agent (B) is An organic polyisocyanate comprising a mixture of diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate having 3 or more isocyanate functional groups (B-1), or a reaction product (B-1') of an active hydrogen group-containing compound and the mixture (B-1), At least one acid component (B-2) selected from the group consisting of phosphate monoesters and phosphate diesters, An injectable drug composition comprising at least one hydrolyzable component (B-3) selected from the group consisting of orthoester compounds and acetal compounds.

2. The injectable drug composition according to claim 1, wherein the acid component (B-2) contains a compound represented by the following formula (1). 【Chemistry 1】 [In formula (1), R １ R represents an alkyl group having 2 to 18 carbon atoms, and n represents an integer of 1 or 2. １ If multiple R １ These may be identical or different from one another.

3. The injectable drug composition according to claim 1, wherein the hydrolyzable component (B-3) comprises a compound represented by the following formula (2). 【Chemistry 2】 [In formula (2), R ２ R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ３ ~R ５ Each of these independently represents an alkyl group having 1 to 8 carbon atoms.

4. The injectable drug composition according to claim 1, wherein the hydrolyzable component (B-3) comprises a compound represented by the following formula (3). 【Transformation 3】 [In formula (3), R ６ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ７ represents an alkyl group having 1 to 8 carbon atoms, and R ８ to R ９ each independently represent an alkyl group having 1 to 8 carbon atoms.]

5. The injectable drug composition according to claim 1, wherein the content of the acid component (B-2) is 0.1% by mass or less, based on the total amount of solids in the second agent (B).

6. The injectable drug composition according to claim 1, wherein the content of the hydrolyzable component (B-3) is 5% by mass or less based on the total amount of solids in the second agent (B).

7. The molar ratio of sodium silicate SiO ２ / Na ２ The injectable drug composition according to claim 1, wherein O is 1.5 to 3.

0.

8. The injectable drug composition according to claim 1, wherein the sodium silicate content is 70 to 96% by mass, based on the total amount of solids in the first agent (A).

9. The injection drug composition according to claim 1, wherein the organic polyol (A-2) comprises an organic polyol having a primary hydroxyl group.

10. The injectable drug composition according to claim 1, wherein the organic polyol (A-2) comprises at least one organic polyol selected from the group consisting of polyether polyols and aliphatic polyols.

11. The injection solution composition according to claim 1, wherein the tertiary amine catalyst (A-3) comprises a tertiary amine catalyst having one or more active hydrogen groups.

12. The injection drug composition according to claim 1, wherein the mass ratio of the diphenylmethane diisocyanate to the polymethylene polyphenyl polyisocyanate in the mixture (B-1) is 30 / 70 to 75 / 25.

13. The diphenylmethane diisocyanate comprises 4,4'-diphenylmethane diisocyanate and at least one selected from the group consisting of 2,2'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate. The injection drug composition according to claim 1, wherein the mass ratio of the total content of the 2,2'-diphenylmethane diisocyanate and the 2,4'-diphenylmethane diisocyanate to the content of the 4,4'-diphenylmethane diisocyanate is 20 / 80 to 45 / 55.

14. The injection drug composition according to claim 1, wherein the second agent (B) contains a foam stabilizer.

15. The injectable drug composition according to claim 1, wherein the second agent (B) comprises a diluent.

16. A solidified body comprising a foamed hardened product of an injection chemical composition according to any one of claims 1 to 15, and ground solidified with the foamed hardened product.

17. A method for stabilizing soil using an injection chemical composition according to any one of claims 1 to 15, A soil stabilization method comprising the step of injecting the aforementioned injection chemical composition between a structure and the ground, or into the ground, and allowing it to foam and harden.

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