Composition of injection chemicals for rock solidification

Abstract

To provide an impregnating agent composition for consolidation of a rock bed which secures resin flowability in foaming, curability under the water, excellent ground improvement property due to sufficient void filling property, and can obtain stable reactivity without contamination of water even under an environment that water leakage and underground water are large.SOLUTION: An impregnating agent composition for consolidation of a rock bed is composed of a polyol component and a polyisocyanate component, wherein the polyol component contains an aqueous solution of sodium silicate, specific polyether polyol, specific alcohol, and a specific tertiary amine catalyst, the polyisocyanate component contains a mixture of MDI and polymeric MDI, and a reaction product with specific polyether polyol, the MDI and the polymeric MDI have a specific mass ratio, and an isomer of the MDI has a specific mass ratio.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to an injection chemical composition that can be used even in environments with frequent groundwater seepage and water leakage. [Background technology]

[0002] One method for reinforcing unstable rock masses and ground is the rock bolt method, which stabilizes the surrounding ground during tunnel excavation. This method aims to protect the tunnel structure by fixing and anchoring bolts with a chemical solution. Traditionally, inorganic materials such as mortar, which have high strength, have been used as the injection chemical solution for rock solidification. However, these inorganic materials have problems with work efficiency due to the long time required to develop strength, and also because the material can be washed away into water if leakage or seepage occurs.

[0003] In recent years, with tunnel excavation taking place in areas prone to water leakage and seepage, there has been an increase in cases where rock-solidifying chemicals are injected beneath seepage. However, contamination of seepage water by the chemicals and leakage that cannot be stopped even with chemical injection are hindering the efficiency and safety of excavation work, and improvements are needed.

[0004] To solve these problems, an inorganic-organic composite soil stabilizing agent is used, which is an injection agent combining an aqueous silicate solution called water glass and a polyisocyanate composition.

[0005] For example, Patent Document 1 reports that by using an aqueous silicate component containing an amine catalyst and a polyol, along with diphenylmethane diisocyanate modified with a polyether polyol, as an injection solution for rock solidification, it is possible to improve the long curing time, strength development time, and groundwater and spring water contamination, which are drawbacks of inorganic systems. However, due to the low fluidity of the resin during foaming, there are concerns that the void-filling ability during injection will be poor, making it difficult to secure the area of ​​ground improvement.

[0006] Furthermore, Patent Document 2 reports that by using a silicate aqueous solution containing polyol with a solid content of 29-36% and polyisocyanate as an injection solution for rock solidification, it is possible to improve the long curing time and strength development time, which are drawbacks of inorganic materials, while maintaining resin fluidity. However, there are concerns that the resulting foam will become brittle, and furthermore, contact with groundwater or spring water will worsen its curing properties and may contaminate the groundwater it comes into contact with. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2005-225951 [Patent Document 2] Japanese Patent Publication No. 2016-175982 [Overview of the project] [Problems that the invention aims to solve]

[0008] The present invention has been made in view of the above-mentioned background art, and aims to provide an injection chemical composition for rock solidification that ensures excellent ground improvement performance by ensuring resin fluidity during foaming, curability underwater, and sufficient void filling, and that can obtain stable reactivity without contaminating water even in environments with a lot of water leakage or groundwater. [Means for solving the problem]

[0009] As a result of diligent research, the inventors of the present invention have found that the above problems can be solved by an injection chemical composition for rock solidification materials comprising a polyol component (A) containing an aqueous sodium silicate solution and a polyisocyanate component (B) containing reaction products of diphenylmethane diisocyanate and polyphenylpolymethylene polyisocyanate with a specific monool, and have completed the present invention.

[0010] In other words, the present invention includes the following embodiments.

[0011] [1] A rock solidification injection solution composition comprising a polyol component (A) and a polyisocyanate component (B), wherein the polyol component (A) comprises an aqueous sodium silicate solution (A-1), a polyether polyol (A-2) with a number average molecular weight of 400 to 1000 containing ethylene oxide units in the range of 60 to 90% by mass, an alcohol (A-3) having a primary hydroxyl group with a molecular weight of 150 or less, and a tertiary amine catalyst (A-4) having one active hydrogen, and the polyisocyanate component (B) comprises a mixture of diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate with 3 or more isocyanate functional groups (B-1), and ethylene oxide A rock solidification injection solution composition characterized by containing a reaction product of a polyether polyol (B-2) with a number average molecular weight of 400 to 1000 containing 60 to 90% by mass of kinase units and (B-1), and further characterized in that the ratio of diphenylmethane diisocyanate of (B-1) to polyphenyl polymethylene polyisocyanate with 3 or more isocyanate functional groups is 50 / 50 to 75 / 25 by mass, and the mass ratio of 4,4'-diphenylmethane diisocyanate in the diphenylmethane diisocyanate to the total of 2,2'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate is 70 / 30 to 55 / 45.

[0012] [2] The rock solidification injection solution composition according to [1] above, wherein the polyol component (A) contains at least one alcohol (A-3) having a primary hydroxyl group with a molecular weight of 150 or less, selected from diethylene glycol, glycerin, 1,3-butanediol, and 3-methyl-1,5-pentanediol.

[0013] [3] The rock solidification injection solution composition according to [1] or [2] above, comprising a dispersion stabilizer in the polyol component (A).

[0014] [4] A rock solidification injection solution composition according to any one of [1] to [3] above, comprising a polyisocyanate component (B) and a viscosity reducer.

[0015] [5] The injection chemical solution composition for rock consolidation according to any one of the above [1] to [4], wherein the polyisocyanate component (B) contains a foam stabilizer.

Advantages of the Invention

[0016] According to the injection chemical solution composition for rock consolidation of the present invention, it is possible to ensure the resin fluidity during foaming, the curability underwater, and excellent ground improvement properties due to sufficient void filling properties, and to obtain stable reactivity without contaminating water even in an environment with a lot of water leakage or groundwater.

Embodiments for Carrying Out the Invention

[0017] The injection chemical solution composition for rock consolidation in the present invention is composed of a polyol component (A) (hereinafter also simply referred to as "component (A)") and a polyisocyanate component (B) (hereinafter also simply referred to as "component (B)").

[0018] First, the polyol component (A) will be described.

[0019] The polyol component (A) contains an aqueous sodium silicate solution (A-1) (hereinafter also simply referred to as (A-1)), a polyether polyol (A-2) (hereinafter also simply referred to as (A-2)) having a number average molecular weight of 400 to 1000 and containing ethylene oxide units (hereinafter, also referred to as EO units or EO) in the range of 60 to 90% by mass, an alcohol (A-3) (hereinafter also simply referred to as (A-3)) having a primary hydroxyl group with a molecular weight of 150 or less, and a tertiary amine catalyst (A-4) (hereinafter also simply referred to as (A-4)) having one active hydrogen.

[0020] As (A-1) in the present invention, an aqueous sodium silicate solution that is usually commercially available can be used. This sodium silicate is represented by the general formula Na2O·xSiO2·nH2O. Here, x represents the molar ratio of SiO2 (silicon dioxide) to Na2O (sodium oxide), and in the present invention, 2.0 to 3.0 is preferable, 2.0 to 2.5 is more preferable, and 2.0 to 2.4 is most preferable. When x is less than 2.0, foaming property cannot be ensured when component (A) and component (B) are mixed and cured, and the curability may deteriorate. When it exceeds 3.0, the viscosity of the aqueous sodium silicate solution becomes high, the miscibility with component (B) deteriorates, and the workability at low temperatures may decrease.

[0021] Further, the solid content excluding water from (A-1) is preferably 30 to 50% by mass, more preferably 33 to 42% by mass, still more preferably 34 to 41% by mass, and most preferably 35 to 40% by mass. When the solid content of the aqueous sodium silicate solution is too high, it can be adjusted by diluting with water. When the solid content is less than 30% by mass, when component (A) and component (B) are mixed and cured, foaming property cannot be ensured, and the mechanical strength of the foam after curing may decrease. When it exceeds 50% by mass, the viscosity of the aqueous sodium silicate solution becomes high, the miscibility with component (B) deteriorates, and the workability at low temperatures may decrease.

[0022] Note that the solid content of (A-1) in the present invention represents the ratio in the whole of the components of (A-1) other than water.

[0023] As (A-2) in the present invention, a polyol having a number average molecular weight of 400 to 1000 and an EO unit of 60 to 90% by mass in the polyether polyol is used. The number average molecular weight of (A-2) in the present invention is preferably 400 to 900, more preferably 400 to 800. When it is less than 400, the fluidity during foaming deteriorates, and the void filling property deteriorates. When it exceeds 1000, the pollution of groundwater during foaming deteriorates, and the strength of the foam and the resin curability when contacting groundwater decrease.

[0024] The EO unit of (A-2) is 60-90% by mass, preferably 60-85% by mass. If it is less than 60% by mass, the mixing properties of component (A) and component (B) will be poor, causing the foam cells to collapse and shrinkage to occur. If it exceeds 90% by mass, the viscosity of component (A) will be high, reducing workability at low temperatures.

[0025] While there are no particular restrictions on components other than the EO unit in the polyether polyol, it is preferable that they be polypropylene oxide units (hereinafter also referred to as PO units or PO).

[0026] The content of (A-2) is preferably 1 to 10% by mass in component (A). If it is less than 1% by mass, foaming during the reaction may not be ensured, and if it exceeds 10% by mass, the viscosity of component (A) will increase, which may lead to poor workability and reduced ground improvement performance when the chemical solution is injected.

[0027] Examples of (A-3) in the present invention 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, neopentyl glycol, aliphatic diols such as hydrogenated bisphenol A, diethylene glycol, triethylene glycol, glycerin, trimethylolpropane, and pentaerythritol. From the viewpoint of curability in water and potential for contaminating groundwater, 1,3-butanediol, diethylene glycol, 3-methyl-1,5-pentanediol, and glycerin are preferred. These alcohols may be used individually or in combination of two or more.

[0028] The content of (A-3) is preferably 1 to 10% by mass in component (A). If it is less than 1% by mass, the foam may become brittle or hardening properties in water may not be ensured, and if it exceeds 10% by mass, the viscosity of component (A) will increase, which may lead to poor workability or a decrease in the ground improvement effect when the chemical solution is injected.

[0029] In the present invention, (A-4) is N,N-dimethylethanolamine, N-methyl-N-(N',N'-dimethylaminoethyl)aminoethanol, N,N-dimethylethoxyethanol, 1,4-diazabicyclo[2.2.2]octane-2-methanol, 6-dimethylamino-1-hexanol, N',N-dimethylethoxy-N'-methyl-N'-ethylmethanol, N'',N''-dimethylamino-N'-methylethylamino-N-methyl-2-propanol, bis(2- Examples include dimethylaminoethylamino)-2-propanol, N'-[2-(dimethylamino)ethyl]-N,N-dimethylethylenediamine, 3,3-iminobis(N,N-dimethyl-1-propanamine), N'-[2-(dimethylamino)methyl]-N,N-dimethylmethylenediamine, N,N,N',N'-tetraethyldiethylenetriamine, and 2-[2-(dimethylamino)ethoxy]-N-[2-[2-(dimethylamino)ethoxy]ethyl]-ethaneamine.

[0030] Additionally, to assist the reaction, tertiary amines without active hydrogen groups, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N',N''-pentamethyldiethylenetriamine, N,N',N'-trimethylaminoethylpiperazine, N,N,N',N'-tetramethylethylenediamine, bis-(dimethylaminoethyl) ether, and N,N',N'-tris(3-dimethylaminopropyl) are used. Hexahydro-S-triazine, 2-methyltriethylenediamine, N,N-dimethylaminoethylmorpholine, dimethylaminopropylimidazole, hexamethyltriethylenetetramine, hexamethyltripropylenetetramine, N,N,N-tris(3-dimethylaminopropyl)amine, N-methyl-N,N-bis(3-dimethylaminopropyl)amine, triethylenediamine, N-methylmorpholine, N-methylimidazole, etc. may be used in combination.

[0031] The content of (A-4) is preferably 0.1 to 5% by mass in component (A). If it is less than 0.1% by mass, there is a risk of deterioration of curing properties and a decrease in foaming properties, and if it exceeds 5% by mass, it becomes difficult to control the reactivity, and there is a risk of injection failure due to clogging of the resin during chemical injection.

[0032] In the present invention, additives such as dispersion stabilizers can be used to ensure the uniformity of component (A) and to improve the compatibility between component (A) and component (B). Examples of dispersion stabilizers include anionic dispersion stabilizers, cationic dispersion stabilizers, and nonionic dispersion stabilizers.

[0033] Examples of anionic dispersion stabilizers include alkyl carboxylates, alkyl sulfates, alkyl sulfonates, and alkyl phosphates.

[0034] Examples of cationic dispersion stabilizers include ammonium salts such as benzalkonium chloride.

[0035] Examples of nonionic dispersion stabilizers include glycerin fatty acid esters, alkyl polyethylene glycols, polyoxyethylene alkylphenyl ethers, and alkyl glycosides.

[0036] These dispersion stabilizers can be used individually or in combination of two or more.

[0037] Component (B) in the present invention includes a mixture (B-1) (hereinafter also referred to as (B-1)) of diphenylmethane diisocyanate (hereinafter referred to as MDI) and polyphenyl polymethylene polyisocyanate (hereinafter referred to as polymeric MDI) having 3 or more isocyanate functional groups, and a reaction product of (B-1) and a polyether polyol (B-2) (hereinafter referred to as (B-2)) having a number average molecular weight of 400 to 1000 and containing EO units in the range of 60 to 90% by mass.

[0038] In this invention, MDI includes various isomers of 4,4'-MDI, 2,4'-MDI, and 2,2'-MDI, and polymeric MDI means that MDI is further modified by adding one or more phenyl groups having isocyanate groups via methylene groups, resulting in a total of three or more isocyanate functional groups.

[0039] For (B-1), the mass ratio of MDI to polymeric MDI is preferably MDI / polymeric MDI = 50 / 50 to 75 / 25, and more preferably 55 / 45 to 75 / 25. If the mass ratio of MDI is less than 50%, the viscosity of the polyisocyanate will increase, which may worsen handling, and if it exceeds 75%, the strength of the foamed resin may decrease.

[0040] Furthermore, the mass ratio of 4,4'-MDI to 2,4'-MDI and 2,2'-MDI in MDI is preferably 70 / 30 to 55 / 45, and more preferably 70 / 30 to 60 / 40. If the mass ratio of 2,4'-MDI and 2,2'-MDI falls below 30%, the low-temperature stability of the polyisocyanate may deteriorate and it may solidify, and if it exceeds 45%, the strength of the foamed resin may decrease.

[0041] For (B-2), a polyether polyol is used with a number-average molecular weight of 400 to 1000 and an EO unit content of 60 to 90% by mass in the polyol. In this invention, the number-average molecular weight of (B-2) is preferably 400 to 900, and more preferably 400 to 800. If the number-average molecular weight is less than 400, the fluidity during foaming deteriorates, and the void-filling ability worsens. If it exceeds 1000, the strength of the foam decreases. The EO unit of (B-2) is 60-90% by mass, preferably 60-85% by mass. If it is less than 60% by mass, the miscibility between component (A) and component (B) deteriorates, causing the foam cells to collapse and shrinkage to occur. If it exceeds 90% by mass, the viscosity of polyol component (A) increases, reducing workability at low temperatures.

[0042] While there are no particular restrictions on components other than the EO unit in the polyether polyol, PO units are preferred.

[0043] Furthermore, in addition to polyether polyols, polyester polyols and glycols may also be used in combination, without departing from the spirit of the present invention.

[0044] Examples of glycols 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, neopentyl glycol, aliphatic diols such as hydrogenated bisphenol A, diethylene glycol, and triethylene glycol.

[0045] The modification rate of component (B) by (B-2) is preferably 0.5 to 10% by mass, and more preferably 0.5 to 6.0% by mass. If it is less than 0.5% by mass, the compatibility with polyol component (A) deteriorates, and there is a risk that the strength of the cured product will decrease when the chemical solution is injected. If it exceeds 6.0% by mass, the hydrophilicity increases, and when it comes into contact with groundwater, it may dissolve in the water, causing turbidity and foaming, and there is a risk of contaminating the spring water.

[0046] Furthermore, (A-2) and (B-2) can be synthesized by known methods or commercially available products can be used.

[0047] In the present invention, a foam stabilizer may be used in component (B) to stabilize the cell diameter during foaming, and examples of foam stabilizers include silicone-based foam stabilizers. Examples of silicone-based foam stabilizers include polyoxyalkylene dimethylpolysiloxane copolymer and organopolysiloxane.

[0048] In the present invention, when a foam stabilizer is used, its content is preferably 3% by mass or less in component (B). If it exceeds 3% by mass, the resin strength may decrease.

[0049] Furthermore, a viscosity reducer may be used in combination with component (B) for viscosity adjustment. Examples of viscosity reducers that have excellent compatibility with component (B), viscosity reducing properties, and mixing stability include alkylene carbonates such as propylene carbonate, alkyl ethers and esters such as propylene glycol monomethyl ether acetate and diethylene glycol monomethyl ether acetate. From the viewpoint of the working environment and safety, the amount added is preferably 1 to 5% by mass relative to component (B).

[0050] A rock solidification injection solution composition comprising the components (A) and (B) described above can be used to obtain a solidified body with excellent void-filling properties. [Examples]

[0051] The following describes in detail some embodiments of the present invention, but the present invention is not limited to these embodiments. Unless otherwise specified, "%" in the embodiments refers to mass.

[0052] <Preparation of polyisocyanate components> <Preparation Example 1> In a 1 L reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 494 g of polyisocyanate 1, 448 g of diisocyanate 1, and 50 g of polyol 1 were charged, 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, the mixture was cooled to 60°C, 8 g of foam stabilizer was added, and the mixture was stirred for 30 minutes to obtain polyisocyanate composition (B1) (NCO content 29.1%, viscosity 100 mPa·s at 25°C).

[0053] <Preparation Example 2> In a 1 L reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 494 g of polyisocyanate 1, 448 g of diisocyanate 1, and 50 g of polyol 1 were charged, 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, the temperature was cooled to 60°C, 30 g of diluent 1 and 8 g of foam stabilizer were added, and the mixture was stirred for 30 minutes to obtain polyisocyanate composition (B2) (NCO content 28.5%, viscosity at 25°C 70 mPa·s).

[0054] <Preparation Example 3> In a 1 L reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 494 g of polyisocyanate 1, 448 g of diisocyanate 1, and 50 g of polyol 3 were charged, 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, the temperature was cooled to 60°C, 8 g of foam stabilizer was added, and the mixture was stirred for 30 minutes to obtain polyisocyanate composition (B3) (NCO content 30.1%, viscosity at 25°C 63 mPa·s).

[0055] <Preparation Example 4> In a 1 L reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 494 g of polyisocyanate 1, 448 g of diisocyanate 1, and 50 g of polyol 4 were charged, 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, the temperature was cooled to 60°C, 8 g of foam stabilizer was added, and the mixture was stirred for 30 minutes to obtain polyisocyanate composition (B4) (NCO content 29.8%, viscosity at 25°C 86 mPa·s).

[0056] <Preparation Example 5> In a 1 L reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 494 g of polyisocyanate 1, 448 g of diisocyanate 1, and 50 g of polyol 5 were charged, 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, the temperature was cooled to 60°C, 8 g of foam stabilizer was added, and the mixture was stirred for 30 minutes to obtain polyisocyanate composition (B5) (NCO content 29.2%, viscosity at 25°C 111 mPa·s).

[0057] <Preparation Example 6> In a 1 L reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 494 g of polyisocyanate 1, 448 g of diisocyanate 1, and 50 g of polyol 6 were charged, 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, the mixture was cooled to 60°C, 8 g of foam stabilizer was added, and the mixture was stirred for 30 minutes to obtain polyisocyanate composition (B6) (NCO content 29.7%, viscosity at 25°C 125 mPa·s).

[0058] <Preparation Example 7> In a 1 L reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 914 g of polyisocyanate 1, 111 g of diisocyanate 1, and 18 g of polyol 1 were charged, 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, the mixture was cooled to 60°C, 8 g of foam stabilizer was added, and the mixture was stirred for 30 minutes to obtain polyisocyanate composition (B7) (NCO content 29.6%, viscosity at 25°C 175 mPa·s).

[0059] <Preparation Example 8> In a 1 L reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 914 g of polyisocyanate 1, 111 g of diisocyanate 1, and 18 g of polyol 5 were charged, 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, the mixture was cooled to 60°C, 8 g of foam stabilizer was added, and the mixture was stirred for 30 minutes to obtain polyisocyanate composition (B8) (NCO content 28.6%, viscosity at 25°C 180 mPa·s).

[0060] <Preparation Example 9> In a 1 L reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 494 g of polyisocyanate 1, 221 g of diisocyanate 1, and 227 g of diisocyanate 2 were charged, and the temperature was raised to 50°C. The mixture was stirred for 30 minutes while maintaining the temperature and ensuring uniform mixing with a stirring blade. Then, 100 g of diluent 2 and 8 g of foam stabilizer were added, and the mixture was stirred for another 30 minutes to obtain polyisocyanate composition (B9) (NCO content 28.5%, viscosity 28 mPa·s at 25°C).

[0061] <Preparation Example 10> In a 1 L reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 355 g of diisocyanate 1 and 645 g of diisocyanate 2 were charged, and the temperature was raised to 50°C. The mixture was stirred for 30 minutes while maintaining the temperature and ensuring uniform mixing with a stirring blade. Then, 100 g of diluent 2 and 8 g of foam stabilizer were added, and the mixture was stirred for another 30 minutes to obtain polyisocyanate composition (B10) (NCO content 30.1%, viscosity at 25°C could not be measured due to solidification).

[0062] [Table 1]

[0063] The ingredients listed in Table 1 are as follows: • Polyisocyanate 1:MDI / polymeric MDI = 40 / 60 (PA ratio), ratio of 2,4'-MDI and 2,2'-MDI to 4,4'-MDI in MDI = 3 / 97, NCO content 31.0% (product name: MR-200, manufactured by Tosoh Corporation) • Diisocyanate 1:MDI / polymeric MDI = 100 / 0 (PA ratio), ratio of 2,4'-MDI and 2,2'-MDI to 4,4'-MDI in MDI = 55 / 45, NCO content 33.5% (product name: Myrionate NM, manufactured by Tosoh Corporation) ○ Diisocyanate 2:MDI / polymeric MDI = 100 / 0 (PA ratio), ratio of 2,4'-MDI and 2,2'-MDI to 4,4'-MDI in MDI = 1 / 99, NCO content 33.5% (product name: Millionate MT, manufactured by Tosoh Corporation). This raw material is solid at room temperature, so when using it in preparation, heat it to 60°C to melt it before use. • Polyol 1: PO / EO-based polyether polyol, number-average molecular weight 400, EO content 75% • Polyol 2: PO / EO-based polyether polyol, number-average molecular weight 900, EO content 75% • Polyol 3: PO / EO-based polyether polyol, number-average molecular weight 1900, EO content 50% • Polyol 4:PO / EO-based polyether polyol, number-average molecular weight 2000, EO content 80% • Polyol 5: PO-based polyether polyol, number-average molecular weight 400, EO content 0% • Polyol 6:PO-based polyether polyol, number-average molecular weight 2000, EO content 0% • Foam stabilizer: Siloxane-polyalkylene oxide copolymer (product name: NIAX SILICONE Y-16136, manufactured by MOMENTIVE) • Diluent 1: Propylene carbonate • Diluent 2: Trischloropropyl phosphate The MDI / polymeric MDI ratio for polyisocyanate 1 and diisocyanate 1 is the ratio of peak areas obtained by GPC measurement (PA ratio), and represents (MDI monomer peak area) / (sum of peak areas of MDI oligomers other than MDI monomers).

[0064] The GPC measurement conditions are as follows: (1) Measuring instrument: HLC-8220 (manufactured by Tosoh Corporation) (2) Column: TSKgel (manufactured by Tosoh Corporation) · G3000H-XL · G2500H-XL · G2000H-XL · G1000H-XL (3) Carrier: THF (tetrahydrofuran) (4) Detector: RI (refractive index) detector (5) Temperature: 40℃ (6)Flow rate: 1.000ml / min (7) Calibration curve: Standard polystyrene (manufactured by Tosoh Corporation) ·F-80 (molecular weight: 7.06×10 5 , molecular weight distribution: 1.05) ·F-20 (molecular weight: 1.90×10 5 , molecular weight distribution: 1.05) ·F-10 (molecular weight: 9.64×10 4 , molecular weight distribution: 1.01) ·F-2 (molecular weight: 1.81×10 4 , molecular weight distribution: 1.01) ·F-1 (molecular weight: 1.02×10 4 , molecular weight distribution: 1.02) ·A-5000 (molecular weight: 5.97×10 3 , molecular weight distribution: 1.02) ·A-2500 (molecular weight: 2.63×10 3 , molecular weight distribution: 1.05) ·A-500 (molecular weight: 5.0×10 2 , molecular weight distribution: 1.14) (8) Sample solution concentration: 0.5% THF solution.

[0065] <Preparation of polyol components> The polyol components were prepared according to the formulations shown in Tables 2 and 3.

[0066] [Table 2]

[0067] [Table 3]

[0068] The ingredients listed in Tables 2 and 3 are as follows: • Sodium silicate aqueous solution 1: Solid content 37.5%, molar ratio (SiO2 / Na2O) = 2.0 (Product name: No. 1 Sodium Silicate R0, manufactured by Toso Sangyo Co., Ltd.) • Sodium silicate aqueous solution 2: Solid content 39.5%, molar ratio (SiO2 / Na2O) = 2.0 (Product name: No. 1 Sodium Silicate P0, manufactured by Toso Sangyo Co., Ltd.) • Alcohol 1:1,3-butanediol (molecular weight 90, contains primary hydroxyl group) • Alcohol 2:3-methyl-1,5-pentanediol (molecular weight 118, contains primary hydroxyl group) • Alcohol 3: Diethylene glycol (molecular weight 106, contains primary hydroxyl groups) • Alcohol 4: 2,4-diethyl-1,5-pentanediol (molecular weight 160, contains primary hydroxyl group) • Alcohol 5: Polyethylene glycol (number average molecular weight 200, containing primary hydroxyl groups) • Alcohol 6: Glycerin (molecular weight 92, contains primary hydroxyl groups) • TMAEE: N-methyl-N-(N',N'-dimethylaminoethyl)aminoethanol (Product name: TOYOCAT RX5, manufactured by Tosoh Corporation) TMHDA: N,N,N',N'-Tetramethylhexamethylenediamine • TEDA: Triethylenediamine (product name: TEDA L33, manufactured by Tosoh Corporation).

[0069] <Reaction behavior and various evaluation methods> Using the above polyol component (A) and polyisocyanate component (B), a foaming test was conducted with the formulations shown in Table 4 and Table 5 (stirring conditions: when the liquid temperature is 15°C, using a three-one motor at 300 rpm for 10 seconds; when the liquid temperature is 25°C, stirring conditions: using a three-one motor at 400 rpm for 10 seconds). The results are shown in Table 4 and Table 5.

[0070]

Table 4

[0071]

Table 5

[0072] In the "free foaming" in the reactivity test, components (A) and (B) were formulated and mixed and stirred in a 1 L cup under the above conditions, and then foamed in the cup as it was. "Foaming in water" means that immediately after components (A) and (B) were formulated, mixed and stirred in a 1 L cup under the above conditions, 100 mL of the formulated liquid was quickly poured into another 1 L cup containing 500 mL of water, and the water was vigorously stirred with a stirring rod for 30 seconds to cause foaming.

[0073] · Cream time: It represents the time (seconds) from when the polyol component (A) and the polyisocyanate component (B) start to be mixed and stirred until the formulated liquid becomes cloudy like cream and the liquid surface rises. · Rise time: It represents the time (seconds) from when the polyol component (A) and the polyisocyanate component (B) start to be mixed and stirred until the formulated liquid foams and reaches the highest height.

[0074] · Foaming ratio: The foaming ratio during free foaming is calculated by the following formula. Foaming ratio (times) = Volume of the molded body after foaming (cm 3 ) / Volume of the formulated liquid before foaming (cm 3 ).

[0075] • Water turbidity after foaming: In the underwater foaming test, water turbidity was measured using a turbidimeter (TURBIDIMETER 2100N, HACH) as an indicator of water quality contamination after the rise time. A turbidity of 20 NTU or less is considered good.

[0076] • Post-foaming foaming: In the underwater foaming test, foaming of the water is measured as an indicator of water quality contamination after the rise time has ended. 125 mL of water used in the underwater foaming test after the rise time has ended 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 bubbles disappear from the water surface is expressed as the foaming time. 60 seconds or less is considered good.

[0077] • Foaming speed: This is the time it takes from the end of the creaming time until the cup is filled when foaming in a 1L cup, calculated using the following formula.

[0078] Foaming rate ( / sec) = 100 / (Reaction time from start of stirring until filling a 1L cup (seconds) - Cream time (seconds)) At a liquid temperature of 25°C, a foaming rate of 14.0 or less is considered good.

[0079] • Surface hardness: The surface hardness was measured using a Type C rubber hardness tester (Asker) 5 minutes after free foaming. A value of 10 or higher indicates good quality and is not brittle.

[0080] • Underwater curing properties: This indicates the time it takes for the tack on the surface of the foam to disappear after removing the water from the cup 2 minutes after foaming in water. A time of 180 seconds or less is considered good.

Claims

1. A rock solidification injection solution composition comprising a polyol component (A) and a polyisocyanate component (B), wherein the polyol component (A) comprises an aqueous sodium silicate solution (A-1), a polyether polyol (A-2) with a number average molecular weight of 400 to 1000 containing 60 to 90% by mass of ethylene oxide units, an alcohol (A-3) having a primary hydroxyl group with a molecular weight of 150 or less, and a tertiary amine catalyst (A-4) having one active hydrogen, and the polyisocyanate component (B) comprises a mixture of diphenylmethane diisocyanate and polyphenylpolymethylene polyisocyanate with 3 or more isocyanate functional groups (B-1), and ethylene oxide A rock solidification injection solution composition characterized by containing a reaction product of a polyether polyol (B-2) having a number average molecular weight of 400 to 1000 and containing 60 to 90% by mass of side units, and (B-1), wherein the ratio of diphenylmethane diisocyanate of (B-1) to polyphenyl polymethylene polyisocyanate with 3 or more isocyanate functional groups is 50 / 50 to 75 / 25 by mass, and the mass ratio of 4,4'-diphenylmethane diisocyanate in the diphenylmethane diisocyanate to the total of 2,2'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate is 70 / 30 to 55 / 45.

2. The rock solidification injection solution composition according to claim 1, wherein the polyol component (A) contains at least one alcohol (A-3) having a primary hydroxyl group with a molecular weight of 150 or less, selected from diethylene glycol, glycerin, 1,3-butanediol, and 3-methyl-1,5-pentanediol.

3. The rock solidification injection solution composition according to claim 1 or 2, comprising a dispersion stabilizer in the polyol component (A).

4. The rock solidification injection solution composition according to claim 1 or 2, comprising a polyisocyanate component (B) and a viscosity reducer.

5. The rock solidification injection solution composition according to claim 1 or 2, comprising a foam stabilizer in the polyisocyanate component (B).

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