JP2024024353A - Impregnating agent composition for consolidation of rock bed - Google Patents

Abstract

PROBLEM TO BE SOLVED: 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

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to an injection drug composition that can be used even in environments with a lot of spring water and leakage.

As a method for strengthening unstable rock or unstable ground, there is, for example, a method called the rock bolt method, which stabilizes the surrounding ground during tunnel excavation. This construction method is carried out for the purpose of protecting the tunnel structure by fixing and fixing the bolts with a chemical solution. Conventionally, inorganic materials such as mortar having high strength have been used as injection chemicals for rock consolidation. However, these inorganic materials have a problem in that they have poor working efficiency because it takes a long time to develop their strength, and if water leaks or springs occur, the materials may flow into the water.

Recently, as tunnels are being excavated in areas prone to water leaks and springs, cases of injecting chemical solutions for rock solidification under spring water are increasing. Water leakage that cannot be stopped poses an obstacle to the efficiency and safety of excavation work, and improvements are needed.

To solve these problems, an inorganic-organic complex soil stabilizing chemical solution, ie, an injection chemical solution that combines a silicate aqueous solution called water glass and a polyisocyanate composition is used.

For example, in Patent Document 1, by using a silicate aqueous solution component containing an amine catalyst and a polyol and diphenylmethane diisocyanate modified with a polyether polyol as an injection chemical for rock consolidation, a long curing time, which is a disadvantage of inorganic systems, is achieved. It has been reported that the time and intensity onset time can be improved, as well as groundwater and spring water contamination. However, since the resin fluidity during foaming is low, the void filling property during injection is low, and there is also a concern that it may not be possible to secure the ground improvement range.

Furthermore, in Patent Document 2, by using an aqueous silicate solution containing a polyol with a solid content of 29 to 36% and polyisocyanate as an injection chemical for rock consolidation, resin fluidity is maintained while inorganic It has been reported that it is possible to improve the disadvantages of long curing time and strength development time. However, there is a concern that the obtained foam will become brittle, and furthermore, its hardening properties will deteriorate due to contact with groundwater or spring water, and there is also a concern that it may contaminate the groundwater with which it comes into contact.

Japanese Patent Application Publication No. 2005-225951 Japanese Patent Application Publication No. 2016-175982

The present invention was made in view of the above-mentioned background technology, and it ensures resin fluidity during foaming, hardenability under water, and excellent ground improvement properties due to sufficient void filling properties, and prevents water leakage and underground water from occurring. It is an object of the present invention to provide an injection chemical composition for rock consolidation that provides stable reactivity without contaminating water even in the environment.

As a result of extensive studies, the present inventors found that a polyisocyanate component (B) containing a reaction product of a polyol component (A) containing an aqueous sodium silicate solution, diphenylmethane diisocyanate, and a polyphenylpolymethylene polyisocyanate with a specific monool. The present inventors have discovered that the above-mentioned problems can be solved by an injection chemical composition for rock consolidation materials consisting of the following, and have completed the present invention.

That is, the present invention includes the following embodiments.

[1] An injection chemical composition for rock consolidation consisting of a polyol component (A) and a polyisocyanate component (B), wherein the polyol component (A) is a sodium silicate aqueous solution (A-1) and an ethylene oxide unit. A polyether polyol (A-2) with a number average molecular weight of 400 to 1000 containing 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 one active hydrogen. tertiary amine catalyst (A-4), the polyisocyanate component (B) contains a mixture (B-1) of diphenylmethane diisocyanate and polyphenylpolymethylene polyisocyanate having an isocyanate functional group number of 3 or more, and an ethylene oxide unit. Contains a reaction product of polyether polyol (B-2) with a number average molecular weight of 400 to 1000 in the range of 60 to 90% by mass and (B-1), and further contains diphenylmethane diisocyanate of (B-1) and an isocyanate functional The ratio of polyphenylpolymethylene polyisocyanate having a base number of 3 or more is 50/50 to 75/25 by mass, and 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, and 2,4 in diphenylmethane diisocyanate. An injection chemical composition for rock consolidation, characterized in that the mass ratio of '-diphenylmethane diisocyanate to the total is 70/30 to 55/45.

[2] The alcohol (A-3) having a primary hydroxyl group with a molecular weight of 150 or less contained in the polyol component (A) is made from diethylene glycol, glycerin, 1,3-butanediol, and 3-methyl-1,5-pentanediol. The injection chemical composition for rock consolidation according to the above [1], which is at least one selected type.

[3] The injection chemical composition for rock consolidation according to [1] or [2] above, wherein the polyol component (A) contains a dispersion stabilizer.

[4] The injection chemical composition for rock consolidation according to any one of [1] to [3] above, wherein the polyisocyanate component (B) contains a thinning agent.

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

According to the injection chemical composition for rock consolidation of the present invention, it is possible to ensure resin fluidity during foaming, hardenability under water, and excellent ground improvement properties due to sufficient void filling properties, and to prevent water leakage and groundwater. Stable reactivity can be obtained without contaminating water even in harsh environments.

The injection chemical composition for rock consolidation of the present invention comprises 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)"). ).

First, the polyol component (A) will be explained.

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

As (A-1) in the present invention, a commercially available sodium silicate aqueous solution can be used. This sodium silicate is represented by the general formula Na ₂ O.xSiO _{2.nH 2} O. Here, x represents the molar ratio of SiO ₂ (silicon dioxide) and Na ₂ O (sodium oxide), and in the present invention, it is preferably 2.0 to 3.0, more preferably 2.0 to 2.5. 2.0 to 2.4 is most preferred. When x is less than 2.0, foamability cannot be ensured when component (A) and component (B) are mixed and cured, and there is a possibility that curability may deteriorate. If it exceeds 3.0, the viscosity of the aqueous sodium silicate solution will increase, the miscibility with component (B) will deteriorate, and workability at low temperatures may decrease.

Further, the solid content of (A-1) excluding water is preferably 30 to 50% by mass, more preferably 33 to 42% by mass, even more preferably 34 to 41% by mass, and most preferably 35 to 40% by mass. If the solid content of the sodium silicate aqueous solution is too high, it can be adjusted by diluting it with water. If the solid content is lower than 30% by mass, foamability cannot be ensured when component (A) and component (B) are mixed and cured, and the mechanical strength of the foam after curing may decrease. If it exceeds 50% by mass, the viscosity of the sodium silicate aqueous solution will increase, the miscibility with component (B) will deteriorate, and workability at low temperatures may decrease.

Note that the solid content of (A-1) in the present invention refers to the ratio of components other than water in (A-1) to the total.

As (A-2) in the present invention, a polyol with a number average molecular weight of 400 to 1000 and an EO unit content 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, fluidity during foaming becomes poor and void filling properties deteriorate. When it exceeds 1000, the contamination of groundwater during foaming deteriorates, and the strength of the foam and the resin curing property upon contact with groundwater decrease.

The EO unit of (A-2) is 60 to 90% by mass, preferably 60 to 85% by mass. If it is less than 60% by mass, the miscibility of component (A) and component (B) will be poor, cells of the foam will collapse, and shrinkage will occur. If it exceeds 90% by mass, the viscosity of component (A) will increase and workability at low temperatures will decrease.

The components other than the EO unit in the polyether polyol are not particularly limited, but are preferably polypropylene oxide units (hereinafter also referred to as PO units or PO).

The content of (A-2) in component (A) is preferably 1 to 10% by mass. If it is less than 1% by mass, foaming properties during the reaction may not be ensured, and if it exceeds 10% by mass, the viscosity of component (A) will increase, resulting in poor workability and poor ground improvement properties during chemical injection. There is a risk that

(A-3) in the present invention includes, for example, 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, pentaerythritol and the like. From the viewpoint of curability in water and spring water stainability, 1,3-butanediol, diethylene glycol, 3-methyl-1,5-pentanediol, and glycerin are preferred. These alcohols may be used alone or in combination of two or more.

The content of (A-3) in component (A) is preferably 1 to 10% by mass. If it is less than 1% by mass, the foam may become brittle or harden in water, and if it exceeds 10% by mass, the viscosity of component (A) will increase, resulting in poor workability and chemical injection. There is a risk that the soil improvement properties during the construction period will be reduced.

(A-4) in the present invention 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-dimethylaminoethylamino)-2-propanol, N'-[2-(dimethylamino)ethyl]-N,N-dimethyl Ethylenediamine, 3,3-iminobis(N,N-dimethyl-1-propanamine), N'-[2-(dimethylamino)methyl]-N,N-dimethylmethylenediamine, N,N,N',N' -tetraethyldiethylenetriamine, 2-[2-(dimethylamino)ethoxy]-N-[2-[2-(dimethylamino)ethoxy]ethyl]-ethanamine, and the like.

In addition, 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, N,N',N'-tris(3-dimethylaminopropyl)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.

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

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

Examples of the anionic dispersion stabilizer include alkyl carboxylates, alkyl sulfates, alkyl sulfonates, and alkyl phosphates.

Examples of the cationic dispersion stabilizer include ammonium salts such as benzalkonium chloride.

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

These dispersion stabilizers can be used alone or in combination of two or more.

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

Note that MDI in the present invention includes various isomers of 4,4'-MDI, 2,4'-MDI, and 2,2'-MDI, and polymeric MDI is defined as phenyl which further has an isocyanate group in MDI. It means one or more groups added via a methylene group and the number of isocyanate functional groups is 3 or more.

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

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, more preferably 70/30 to 60/40. preferable. If the mass ratio of 2,4'-MDI and 2,2'-MDI is less than 30%, the low-temperature stability of the polyisocyanate may deteriorate and solidify, and if it exceeds 45%, the strength of the foamed resin will decrease. There is a fear.

As (B-2), a polyether polyol with a number average molecular weight of 400 to 1000 and an EO unit content of 60 to 90% by mass in the polyol is used. The number average molecular weight of (B-2) in the present invention is preferably 400 to 900, more preferably 400 to 800. When the number average molecular weight is less than 400, fluidity during foaming becomes poor and void filling properties deteriorate. When it exceeds 1000, the strength of the foam decreases.The EO unit (B-2) is 60 to 90% by mass, preferably 60 to 85% by mass. If it is less than 60% by mass, the miscibility of component (A) and component (B) will be poor, cells of the foam will collapse, and shrinkage will occur. When it exceeds 90% by mass, the viscosity of the polyol component (A) increases and workability at low temperatures decreases.

Note that components other than the EO unit in the polyether polyol are not particularly limited, but are preferably PO units.

In addition to polyether polyol, polyester polyol or glycol may be used in combination without departing from the spirit of the present invention.

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, triethylene glycol, and the like.

The modification rate of component (B) with (B-2) is preferably 0.5 to 10% by mass, more preferably 0.5 to 6.0% by mass. If it is less than 0.5% by mass, the compatibility with the polyol component (A) may deteriorate, and the strength of the cured product may decrease during chemical injection. If it exceeds 6.0% by mass, it becomes highly hydrophilic and when it comes into contact with groundwater, it dissolves into the water, causing cloudiness and foaming, which may contaminate spring water.

Note that (A-2) and (B-2) can be synthesized by a known method, or commercially available products can be used.

In the present invention, a foam stabilizer may be used in component (B) in order to stabilize the cell diameter during foaming, and examples of the foam stabilizer include silicone foam stabilizers. Examples of silicone foam stabilizers include polyoxyalkylene dimethyl polysiloxane copolymers, organopolysiloxanes, and the like.

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

Moreover, a thinner for the purpose of viscosity adjustment may be used in combination with component (B). Examples of the thinner include alkylene carbonates such as propylene carbonate, alkyl ethers such as propylene glycol monomethyl ether acetate, and diethylene glycol monomethyl ether acetate, as those having excellent compatibility with component (B), thinning properties, and mixing stability. and esters. From the viewpoint of working environment and safety, the amount added is preferably 1 to 5% by mass based on component (B).

By using the injection chemical composition for rock consolidation consisting of the component (A) and component (B) described above, a consolidated body having excellent void-filling properties can be obtained.

Examples of the present invention will be described in detail below, but the present invention is not limited to these Examples. Note that unless otherwise specified, "%" in the examples is based on mass.

<Preparation of polyisocyanate component>
<Preparation example 1>
494 g of polyisocyanate 1, 448 g of diisocyanate 1, and 50 g of polyol 1 were charged into a 1 L reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube, and the temperature was raised to 80°C. The urethane-forming reaction was carried out for 3 hours while maintaining the temperature and uniformly mixing with a stirring blade. Thereafter, the mixture was cooled to 60° C., 8 g of a foam stabilizer was added, and stirred for 30 minutes to obtain a polyisocyanate composition (B1) (NCO content 29.1%, viscosity at 25° C. 100 mPa·s).

<Preparation example 2>
494 g of polyisocyanate 1, 448 g of diisocyanate 1, and 50 g of polyol 1 were charged into a 1 L reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube, and the temperature was raised to 80°C. The urethane-forming reaction was carried out for 3 hours while maintaining the temperature and uniformly mixing with a stirring blade. Thereafter, it was cooled to 60°C, 30g of diluent 1 and 8g of foam stabilizer were added, and stirred for 30 minutes to obtain polyisocyanate composition (B2) (NCO content 28.5%, viscosity at 25°C 70mPa・s) I got it.

<Preparation example 3>
494 g of polyisocyanate 1, 448 g of diisocyanate 1, and 50 g of polyol 3 were charged into a 1 L reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube, and the temperature was raised to 80°C. The urethane-forming reaction was carried out for 3 hours while maintaining the temperature and uniformly mixing with a stirring blade. Thereafter, the mixture was cooled to 60° C., 8 g of a foam stabilizer was added, and stirred for 30 minutes to obtain a polyisocyanate composition (B3) (NCO content 30.1%, viscosity at 25° C. 63 mPa·s).

<Preparation example 4>
494 g of polyisocyanate 1, 448 g of diisocyanate 1, and 50 g of polyol 4 were charged into a 1 L reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube, and the temperature was raised to 80°C. The urethane-forming reaction was carried out for 3 hours while maintaining the temperature and uniformly mixing with a stirring blade. Thereafter, the mixture was cooled to 60°C, 8 g of a foam stabilizer was added, and stirred for 30 minutes to obtain a polyisocyanate composition (B4) (NCO content 29.8%, viscosity at 25°C 86 mPa·s).

<Preparation example 5>
494 g of polyisocyanate 1, 448 g of diisocyanate 1, and 50 g of polyol 5 were charged into a 1 L reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube, and the temperature was raised to 80°C. The urethane-forming reaction was carried out for 3 hours while maintaining the temperature and uniformly mixing with a stirring blade. Thereafter, the mixture was cooled to 60°C, 8 g of a foam stabilizer was added, and stirred for 30 minutes to obtain a polyisocyanate composition (B5) (NCO content 29.2%, viscosity at 25°C 111 mPa·s).

<Preparation example 6>
494 g of polyisocyanate 1, 448 g of diisocyanate 1, and 50 g of polyol 6 were charged into a 1 L reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube, and the temperature was raised to 80°C. The urethane-forming reaction was carried out for 3 hours while maintaining the temperature and uniformly mixing with a stirring blade. Thereafter, the mixture was cooled to 60°C, 8 g of a foam stabilizer was added, and stirred for 30 minutes to obtain a polyisocyanate composition (B6) (NCO content 29.7%, viscosity at 25°C 125 mPa·s).

<Preparation example 7>
914 g of polyisocyanate 1, 111 g of diisocyanate 1, and 18 g of polyol 1 were charged into a 1 L reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube, and the temperature was raised to 80°C. The urethane-forming reaction was carried out for 3 hours while maintaining the temperature and uniformly mixing with a stirring blade. Thereafter, the mixture was cooled to 60°C, 8 g of a foam stabilizer was added, and stirred for 30 minutes to obtain a polyisocyanate composition (B7) (NCO content 29.6%, viscosity at 25°C 175 mPa·s).

<Preparation example 8>
914 g of polyisocyanate 1, 111 g of diisocyanate 1, and 18 g of polyol 5 were charged into a 1 L reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube, and the temperature was raised to 80°C. The urethane-forming reaction was carried out for 3 hours while maintaining the temperature and uniformly mixing with a stirring blade. Thereafter, the mixture was cooled to 60°C, 8 g of a foam stabilizer was added, and stirred for 30 minutes to obtain a polyisocyanate composition (B8) (NCO content 28.6%, viscosity at 25°C 180 mPa·s).

<Preparation example 9>
494 g of polyisocyanate 1, 221 g of diisocyanate 1, and 227 g of diisocyanate 2 were charged into a 1 L reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube, and the temperature was raised to 50°C. Stirring was performed for 30 minutes while uniformly mixing with a stirring blade while maintaining the temperature. Thereafter, 100 g of diluent 2 and 8 g of foam stabilizer were added and stirred for 30 minutes to obtain a polyisocyanate composition (B9) (NCO content 28.5%, viscosity at 25° C. 28 mPa·s).

<Preparation example 10>
355 g of diisocyanate 1 and 645 g of diisocyanate 2 were charged into a 1 L reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube, and the temperature was raised to 50°C. Stirring was performed for 30 minutes while uniformly mixing with a stirring blade while maintaining the temperature. Thereafter, 100 g of diluent 2 and 8 g of foam stabilizer were added and stirred for 30 minutes to obtain a polyisocyanate composition (B10) (NCO content 30.1%, viscosity at 25° C. could not be measured due to solidification). .

Each raw material in Table 1 is as follows.
- Polyisocyanate 1: MDI/polymeric MDI = 40/60 (PA ratio), 2,4'-MDI and 2,2'-MDI to 4,4'-MDI ratio 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), 2,4'-MDI and 2,2'-MDI to 4,4'-MDI ratio in MDI = 55/45, NCO content 33.5 % (Product name: Millionate NM, manufactured by Tosoh Corporation)
〇Diisocyanate 2: MDI/polymeric MDI = 100/0 (PA ratio), 2,4'-MDI and 2,2'-MDI to 4,4'-MDI ratio 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 for preparation, it is heated to 60°C and melted.
・Polyol 1: PO/EO polyether polyol, number average molecular weight 400, EO content 75%
・Polyol 2: PO/EO polyether polyol, number average molecular weight 900, EO content 75%
・Polyol 3: PO/EO polyether polyol, number average molecular weight 1900, EO content 50%
・Polyol 4: PO/EO 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 ratio of MDI/polymeric MDI of polyisocyanate 1 and diisocyanate 1 is the ratio of peak areas obtained by GPC measurement (PA ratio), MDI monomer peak area)/(sum of peak areas of MDI oligomers other than MDI monomers).

The GPC measurement conditions are as follows.
(1) Measuring device: 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°C
(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.

<Preparation of polyol component>
Polyol components were prepared according to the formulations shown in Tables 2 and 3.

Each raw material in Tables 2 and 3 is as follows.
・Sodium silicate aqueous solution 1: Solid content 37.5%, molar ratio (SiO ₂ /Na ₂ O) = 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 (SiO ₂ /Na ₂ O) = 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 group)
・Alcohol 4: 2,4-diethyl-1,5-pentanediol (molecular weight 160, contains primary hydroxyl group)
・Alcohol 5: Polyethylene glycol (number average molecular weight 200, contains primary hydroxyl group)
・Alcohol 6: Glycerin (molecular weight 92, contains primary hydroxyl group)
・TMAEE: N-methyl-N-(N',N'-dimethylaminoethyl) aminoethanol (product name: TOYOCAT RX5, manufactured by Tosoh Corporation)
・TMHDA: N,N,N',N'-tetramethylhexamethylenediamine ・TEDA: Triethylenediamine (trade name: TEDA L33, manufactured by Tosoh Corporation).

<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 Tables 4 and 5 (stirring conditions: 300 rpm using a three-one motor when the liquid temperature was 15°C). x 10 seconds, when the liquid temperature was 25°C, stirring conditions: 400 rpm x 10 seconds using a three-one motor). The results are shown in Tables 4 and 5.

"Free foaming" in the reactivity test means that component (A) and component (B) are blended in a 1L cup under the above conditions, mixed and stirred, and then foamed in the cup as it is, and "foaming in water". What is Component (A) and Component (B) under the above conditions in a 1L cup? Immediately after mixing and stirring, quickly pour 100mL of the blended liquid into another 1L cup containing 500mL of water, and add water using a stirring rod. The mixture was stirred vigorously for 30 seconds to foam.

-Cream time: represents the time (in seconds) from when the polyol component (A) and the polyisocyanate component (B) begin to be mixed and stirred until the liquid mixture becomes cloudy and creamy and the liquid level rises.
- Rise time: represents the time (in seconds) from when the polyol component (A) and the polyisocyanate component (B) begin to be mixed and stirred until the blended liquid foams and reaches its maximum height.

・Foaming ratio: Calculate the foaming ratio during free foaming using the following formula.
Expansion ratio (times) = volume of molded body after foaming (cm ³ )/volume of compounded liquid before foaming (cm ³ ).

- Water turbidity after foaming: In the underwater foaming test, water turbidity was measured using a turbidity meter (TURBIDIMETER 2100N, manufactured by HACH) as an indicator of water pollution after the rise time. It can be said that a turbidity of 20 NTU or less is good.

- Foaming after foaming: In the underwater foaming test, water foaming is measured as an indicator of water pollution after the rise time. Pour 125 mL of the water after the rise time used in the underwater foaming test into a 250 mL polyethylene bottle, tightly stopper it, shake it vigorously for 10 seconds, then let it stand, and measure the time (seconds) it takes for the bubbles to disappear from the water surface. represent. If it is 60 seconds or less, it can be said to be good.

・Foaming speed: When foaming in a 1L cup, the time from after the cream time until the cup is filled is calculated using the following formula.

Foaming speed (/sec) = 100/(reaction time (sec) from start of stirring to filling 1L cup - cream time (sec))
If the foaming rate is 14.0 or less at a liquid temperature of 25°C, it can be said to be good.

-Surface hardness: The surface hardness is measured using a rubber hardness meter C type (manufactured by Asker) 5 minutes after free foaming. If it is 10 or more, it can be said that it is not brittle and is good.

- Underwater curability: The time required for the surface of the foam to become tacky after removing the water from the cup 2 minutes after foaming in water. If it is 180 seconds or less, it can be said to be good.

Claims (5)

An injection chemical composition for rock consolidation comprising a polyol component (A) and a polyisocyanate component (B), wherein the polyol component (A) contains an aqueous sodium silicate solution (A-1) and an ethylene oxide unit of 60 to A polyether polyol (A-2) with a number average molecular weight of 400 to 1000 contained in the range of 90% by mass, an alcohol (A-3) having a primary hydroxyl group with a molecular weight of 150 or less, and a tertiary amine having one active hydrogen. catalyst (A-4), the polyisocyanate component (B) is a mixture (B-1) of diphenylmethane diisocyanate and polyphenylpolymethylene polyisocyanate having an isocyanate functional group number of 3 or more, and 60 to 90 ethylene oxide units. Contains a reaction product of polyether polyol (B-2) with a number average molecular weight of 400 to 1000 in the range of mass % and (B-1), and further contains diphenylmethane diisocyanate of (B-1) and an isocyanate functional group number of 3 or more The ratio of polyphenylpolymethylene polyisocyanate is from 50/50 to 75/25 by mass, and 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, and 2,4'-diphenylmethane in diphenylmethane diisocyanate. An injection chemical composition for rock consolidation, characterized in that the mass ratio of diisocyanate to the total is 70/30 to 55/45. The alcohol (A-3) having a primary hydroxyl group with a molecular weight of 150 or less contained in the polyol component (A) is at least one selected from diethylene glycol, glycerin, 1,3-butanediol, and 3-methyl-1,5-pentanediol. The injection chemical composition for rock consolidation according to claim 1, which is one type. The injection chemical composition for rock consolidation according to claim 1 or 2, wherein the polyol component (A) contains a dispersion stabilizer. The injection chemical composition for rock consolidation according to claim 1 or 2, wherein the polyisocyanate component (B) contains a thinner. The injection chemical composition for rock consolidation according to claim 1 or 2, wherein the polyisocyanate component (B) contains a foam stabilizer.