JP7315131B2 - Natural ground solidification agent and method for solidifying natural ground using the same - Google Patents

Description

The present invention relates to a rock solidification agent and a rock solidification method using the same.

Conventionally, inorganic or organic grout is injected to stabilize and strengthen unstable bedrock and ground. Inorganic cement milk, which is commonly used, has a slow setting speed and a slow development of strength. Therefore, it was not possible to attain the purpose of stabilizing and strengthening unstable ground at an early stage during excavation of a tunnel, which is required to solidify in a short period of time to develop strength.

On the other hand, rigid polyurethane foams, which are mainly composed of polyol and polyisocyanate, have been used effectively because of their fast solidification speed and the ability to solidify ground in a short period of time to develop strength. Patent Literature 1 discloses a rock solidification agent containing a polyoxyalkylenediol and an isocyanate. Diphenylmethane diisocyanate has usually been used as an isocyanate component in these rock solidification agents in order to develop good curability and sufficient strength. Even when the isocyanate component is modified with a prepolymer, a partially modified product is used from the viewpoint of suppressing the increase in viscosity, and unreacted diphenylmethane diisocyanate remains.

Japanese Patent No. 3944878

By the way, bis(4-isocyanatophenyl)methane (4,4'-diphenylmethane diisocyanate) was judged to be a toxic substance in "Pharmaceutical Evaluation Notification No. 1225 No. 1" issued by the Ministry of Health, Labor and Welfare on December 25, 2018, and there is a demand for a rock solidification agent that does not use diphenylmethane diisocyanate.

On the other hand, the modified aliphatic polyisocyanate has problems such as poor curability and insufficient strength.

An object of the present invention is to provide a rock solidification agent capable of exhibiting sufficient strength without using diphenylmethane diisocyanate.

A rock solidifying agent according to an embodiment of the present invention comprises a component (A) containing an active hydrogen compound, a catalyst and water, and a component (B) containing an isocyanate compound, wherein the active hydrogen compound comprises an aromatic amine compound and an amine compound comprising a chain aliphatic amine compound and/or an alicyclic amine compound, and the isocyanate compound comprises a modified aliphatic polyisocyanate.

A rock solidification method according to an embodiment of the present invention includes the steps of drilling a plurality of holes in a rock bed or ground at predetermined intervals, inserting hollow bolts into the holes, and injecting the ground rock solidifying agent into the bed rock or ground through the openings of the bolts to solidify the ground rock or ground.

According to the embodiment of the present invention, it is possible to provide a rock solidification agent and a rock solidification method using the same, which can solidify rocks in a short time without using diphenylmethane diisocyanate to develop strength and suppress white turbidity when it comes into contact with water.

The rock solidification agent according to the present embodiment comprises a component (A) containing an active hydrogen compound, a catalyst, and water, and a component (B) containing an isocyanate compound. In addition to the components (A) and (B), an optional third component may be provided.

[(A) component]
(Active hydrogen compound)
The (A) component contains an active hydrogen compound. An active hydrogen compound is a compound (excluding water) having one or more active hydrogen groups in its molecule. Active hydrogen compounds include hydroxyl group-containing compounds such as amine compounds having primary or secondary amino groups and polyols.

In this embodiment, the active hydrogen compound includes an amine compound having a primary or secondary amino group as described above. From the viewpoint of increasing the compressive strength of the cured product, the amount of the amine compound is preferably 15 parts by mass or more, more preferably 18 parts by mass or more, and still more preferably 20 parts by mass or more based on 100 parts by mass of the total amount of components (A) and (B). When the content of the amine compound is 15 parts by mass or more, the effect of increasing the compression strength of the cured product is excellent. The upper limit of the content of the amine compound is not particularly limited. For example, it may be 60 parts by mass or less, 50 parts by mass or less, or 30 parts by mass or less with respect to 100 parts by mass of the total amount of components (A) and (B).

The amount of the amine compound having a primary or secondary amino group is preferably 80 parts by mass or more, more preferably 85 parts by mass or more, still more preferably 90 parts by mass or more, still more preferably 95 parts by mass or more, and may be 100 parts by mass with respect to 100 parts by mass of the active hydrogen compound in component (A), from the viewpoint of increasing the compressive strength of the cured product.

In the present embodiment, the amine compound includes an aromatic amine compound (a1) and a chain aliphatic amine compound and/or an alicyclic amine compound (a2) (hereinafter referred to as "aliphatic amine compound (a2)"). By using the aromatic amine compound (a1) and the aliphatic amine compound (a2) in combination, it is possible to increase the strength of the cured product while suppressing white turbidity upon contact with water.

Examples of the aromatic amine compound (a1) include aromatic monoamines such as N-methylbenzylamine, dibenzylamine, benzylamine and p-methylbenzylamine; aromatic diamines such as diaminodiphenylmethane, diaminodiphenyl ether, xylylenediamine, phenylenediamine, diethyltoluenediamine and dimethylthiotoluenediamine; and aromatic triamines such as 1,3,5-tris(aminomethyl)benzene. These aromatic amine compounds (a1) can be used alone or in combination of two or more.

Among the above compounds, the aromatic amine compound (a1) is preferably a bifunctional or higher aromatic amine compound, more preferably at least one selected from the group consisting of diethyltoluenediamine and dimethylthiotoluenediamine, from the viewpoint of further improving the compressive strength of the cured product.

From the viewpoint of increasing the compressive strength of the cured product, the amount of the aromatic amine compound (a1) is preferably 13 parts by mass or more, more preferably 15 parts by mass or more, and still more preferably 18 parts by mass or more based on 100 parts by mass of the total amount of components (A) and (B). When the amount of the aromatic amine compound (a1) is 13 parts by mass or more, the effect of increasing the compressive strength of the cured product is excellent. The upper limit of the content of the aromatic amine compound (a1) is not particularly limited. For example, it may be 50 parts by mass or less, 40 parts by mass or less, or 25 parts by mass or less with respect to 100 parts by mass of the total amount of components (A) and (B).

Further, the amount of the aromatic amine compound (a1) is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, and still more preferably 80 parts by mass or more with respect to 100 parts by mass of the active hydrogen compound in the component (A), from the viewpoint of increasing the compressive strength of the cured product. The upper limit of the content of the aromatic amine compound (a1) may be, for example, 95 parts by mass or less or 90 parts by mass or less with respect to 100 parts by mass of the active hydrogen compound in the component (A).

Examples of the aliphatic amine compound (a2) include chain aliphatic amine compounds such as monomethylamine, monoethylamine, monobutylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, methylethylamine, methylpropylamine, methylisopropylamine, ethylpropylamine, ethylisopropylamine, N-methyldodecylamine, bis(2-ethylhexyl)amine, and other alkyl monoamines; Alkanol monoamines such as isopropanolamine; Hydrazine; Chain aliphatic diamines such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, and neopentanediamine; Chain aliphatic triamines such as diethylenetriamine; polyether diamines (i.e., polyoxyalkylene diamines) obtained by converting groups to amino groups;

In addition, as the alicyclic amine compound, for example, cyclopentylamine, cyclohexylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, dicyclohexylamine and the like cycloaliphatic monoamines; morpholine, pyrrolidine, piperidine and other heterocyclic monoamines; alicyclic diamines such as tane, diaminocyclohexane and norbornanediamine; alicyclic triamines such as 1,3,5-tris(aminomethyl)cyclohexane;

These aliphatic amine compounds (a2) can be used alone or in combination of two or more.

Among the above-mentioned compounds, the aliphatic amine compound (a2) is preferably a chain aliphatic amine compound having a functionality of two or more and/or an alicyclic amine compound having a functionality of two or more, more preferably at least one selected from the group consisting of norbornanediamine, polyetherdiamine and polyethertriamine, from the viewpoint of further improving the effect of suppressing cloudiness.

The weight average molecular weight (Mw) of the above polyetherdiamine and polyethertriamine is not particularly limited, but is preferably 100 to 5,000, more preferably 150 to 2,000, and still more preferably 200 to 1,000.

As used herein, the weight average molecular weight is a value measured by the GPC method. As the GPC method, for example, HLC-8020 manufactured by Tosoh Corporation is used as the GPC main body, a column temperature of 40 ° C., a pump flow rate of 1.0 ml / min, and a method of using RI (built into the GPC main body) as a detector [Column: TSKgel G6000H HR + G4000H HR + G3000H HR + G2000H HR (4 tubes used in series); mobile phase: THF; injection volume: 80 μl; sample concentration: 0.2% (w/v)]. In this method, for example, the molecular weight can be determined as the PPG-equivalent molecular weight using a standard PPG calibration curve (calibration at a molecular weight of 250 or more) whose molecular weight is known in advance.

From the viewpoint of suppressing cloudiness, the amount of the aliphatic amine compound (a2) is preferably 0.1 to 9 parts by mass, more preferably 0.5 to 7 parts by mass, and still more preferably 1 to 5 parts by mass, based on 100 parts by mass of the total amount of components (A) and (B). When the amount of the aliphatic amine compound (a2) is 0.1 parts by mass or more, the effect of suppressing cloudiness can be enhanced, and when the amount is 9 parts by mass or less, workability can be improved.

In addition, the amount of the aliphatic amine compound (a2) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more with respect to 100 parts by mass of the active hydrogen compound in the component (A), from the viewpoint of further improving the cloudiness suppressing effect. The upper limit of the content of the aliphatic amine compound (a2) may be, for example, 40 parts by mass or less, 30 parts by mass or less, or 20 parts by mass or less with respect to 100 parts by mass of the active hydrogen compound in the component (A).

The mass ratio (a1)/(a2) of the aromatic amine compound (a1) and the aliphatic amine compound (a2) is not particularly limited, but from the viewpoint of enhancing the effect of improving strength and suppressing white turbidity, it is preferably 15/1 to 2/1, more preferably 12/1 to 3/1, and still more preferably 10/1 to 5/1.

The active hydrogen compound of component (A) may be only the amine compound having a primary or secondary amino group, and in addition to the amine compound, if necessary, for example, a polyol such as polyether polyol or polyester polyol may be used in combination.

(catalyst)
(A) The component contains a catalyst. Examples of catalysts include tertiary amine compounds, fatty acid alkali metal salts, and quaternary ammonium salts. These may be used singly or in combination of two or more.

Tertiary amine compounds include, for example, triethylenediamine, 2-methyltriethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-pentamethyldiethylenetriamine, trimethylaminoethylpiperazine, bis-(dimethylaminoethyl) ether, N,N',N''-tris(dialkylaminoalkyl )-s-hexahydrotriazine, N,N-dimethylaminoethylmorpholine, dimethylaminopropylimidazole, hexamethyltriethylenetetramine, hexamethyltripropylenetetramine, N,N,N-tris(3-dimethylaminopropyl)amine, etc. These may be used alone or in combination of two or more. Among these, it is preferable to use a triazine-based tertiary amine compound, and examples thereof include N,N',N''-tris(dialkylaminoalkyl)-s-hexahydrotriazine such as N,N',N''-tris(dimethylaminopropyl)-s-hexahydrotriazine.

Fatty acid alkali metal salts include, for example, alkali metal salts of acetic acid or octylic acid as trimerization catalysts. Here, the number of carbon atoms in the fatty acid constituting the fatty acid alkali metal salt may be 1 to 10. Specific examples of fatty acid alkali metal salts include potassium acetate and potassium octylate, and either one or both may be used in combination. Since potassium acetate and potassium octylate are solids, potassium acetate may be dissolved in water or the like, and potassium octylate may be dissolved in a polyol such as triethylene glycol or diethylene glycol. Here, when the fatty acid alkali metal salt is used by dissolving it in water, the amount of the water is included in the amount of water as the foaming agent, which will be described later. Moreover, when dissolved in a polyol and used, the amount of the polyol is included in the amount of the active hydrogen compound.

The quaternary ammonium salt is not particularly limited, and one commercially available as a trimerization catalyst can be used. 410, Kaolizer No. 420 (manufactured by Kao Corporation), TOYOCAT-TR20, TOYOCAT-TRX (manufactured by Tosoh Corporation) and the like.

Although the amount of the catalyst is not particularly limited, it is preferably 0.1 to 5.0 parts by mass, more preferably 1.0 to 4.0 parts by mass, per 100 parts by mass of component (A).

(water)
(A) A component contains water. Water acts as a blowing agent because it reacts with the isocyanate compound (B) to generate carbon dioxide gas. The amount of water is 0.2 to 5.0 parts by weight per 100 parts by weight of component (A). It is preferably 0.3 to 3.0 parts by mass, more preferably 0.5 to 2.0 parts by mass. Within these ranges, it is possible to obtain sufficient foam curability, as well as sufficient compressive strength, long-term durability, and strength development of the cured product.

(other ingredients)
In addition to the components described above, component (A) may optionally contain known additives such as silicone foam stabilizers, diluents, flame retardants, pigments, inorganic fillers, cross-linking agents, and coupling agents, as long as they do not impair the purpose of the present embodiment.

Examples of silicone-based foam stabilizers include polyoxyalkylenedimethylpolysiloxane copolymers commonly used in rigid urethane foam resins.

Examples of diluents include phthalates such as dibutyl phthalate, dioctyl phthalate and diisononyl phthalate, adipates such as dibutyl adipate, dioctyl adipate, diisononyl adipate, bis(2-(2-butoxyethoxy)ethyl) adipate, and trimellitates such as tri(2-ethylhexyl) trimellitate.

Both additive-type and reactive-type flame retardants can be used. Specific examples of additive-type compounds include phosphorus-containing compounds such as triethyl phosphate and tricresyl phosphate, phosphorus-containing halogen compounds such as trismonochloroisopropyl phosphate, and halogen-containing compounds such as chlorinated paraffin, pentabromoethylbenzene, and decabromodiphenyl ether.

(viscosity)
In the present embodiment, the viscosity of component (A) at 25° C. is preferably 650 mPa·s or less, more preferably 600 mPa·s or less, still more preferably 500 mPa·s or less, from the viewpoint of workability.

[(B) component]
(B) component contains an isocyanate compound. In this embodiment, the isocyanate compound includes a modified aliphatic polyisocyanate.

(Modified Aliphatic Polyisocyanate)
The aliphatic polyisocyanate is a non-aromatic polyisocyanate, and may be a chain aliphatic polyisocyanate or an alicyclic polyisocyanate. Examples of aliphatic polyisocyanates include hexamethylene diisocyanate, pentamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and norbornane diisocyanate. These may be used alone or in combination of two or more.

Modified aliphatic polyisocyanates include adducts, isocyanurates, allophanates, biurets, and the like of these aliphatic polyisocyanates. That is, the modified aliphatic polyisocyanate preferably contains at least one selected from the group consisting of an adduct of an aliphatic polyisocyanate, an isocyanurate of an aliphatic polyisocyanate, an allophanate of an aliphatic polyisocyanate, and a biuret of an aliphatic polyisocyanate.

Here, an adduct is obtained by adding a diisocyanate to a polyhydric alcohol. The isocyanurate is a trimer of diisocyanate. An allophanate compound is obtained by adding a diisocyanate to a urethane group formed by the reaction of a diisocyanate and an alcohol. A buret form is obtained by adding a diisocyanate to a urea group formed by a reaction of a diisocyanate with water or an amine.

As the modified aliphatic polyisocyanate, a modified hexamethylene diisocyanate or pentamethylene diisocyanate is preferable from the viewpoint of further improving the reduction of the load on the apparatus due to the compressive strength and low viscosity. More preferably, it is at least one selected from the group consisting of isocyanurate-modified pentamethylene diisocyanate, isocyanurate-modified hexamethylene diisocyanate, and adduct-modified hexamethylene diisocyanate.

The amount of the modified aliphatic polyisocyanate is not particularly limited, and may be, for example, 30 to 80 parts by mass or 40 to 65 parts by mass with respect to 100 parts by mass of the total amount of components (A) and (B). Further, the amount of the modified aliphatic polyisocyanate is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and may be 100 parts by mass with respect to 100 parts by mass of the isocyanate compound in the component (B).

The isocyanate compound (B) may be a modified aliphatic polyisocyanate alone, or may contain another isocyanate compound together with the modified aliphatic polyisocyanate. Other isocyanate compounds include non-toxic isocyanate compounds. Examples of non-toxic isocyanate compounds include xylylene diisocyanate (XDI), which is an araliphatic isocyanate. The amount of the araliphatic isocyanate is not particularly limited, and may be 30 parts by mass or less, 20 parts by mass or less, or 5 to 15 parts by mass with respect to 100 parts by mass of the isocyanate compound in the component (B).

(other ingredients)
To the component (B), as other components, conventionally known additives described in the section of the component (A) can be added, if necessary, as long as the object of the present embodiment is not impaired.

(viscosity)
In the present embodiment, the viscosity of component (B) at 25° C. is preferably 650 mPa·s or less, more preferably 600 mPa·s or less, still more preferably 500 mPa·s or less, from the viewpoint of workability.

[Mixing of (A) component and (B) component]
The components (A) and (B) are mixed at the time of use to form a cured product.

(mixing ratio)
The mixing ratio of component (A) and component (B) is such that the reaction equivalent ratio between the active hydrogen groups (NH ₂ , OH) of the active hydrogen compound in component (A) and the isocyanate group (NCO) in component (B), that is, active hydrogen group/NCO, is preferably in the range of 1/5 to 5/1, more preferably 1/3 to 2/1. When the reaction equivalent ratio is 5/1 or less, the hardness of the cured product can be increased.

[Mass consolidation method]
The rock solidification agent according to the present embodiment is used, for example, to stabilize and strengthen rocks having fractured zones or unstable soft ground during tunnel excavation, and the rocks or ground can be consolidated by mixing the components (A) and (B) and injecting the mixture into the rock or ground.

The injection and consolidation method is not particularly limited, and a known method can be employed. For example, it preferably includes a step of drilling a plurality of holes in the rock or ground at predetermined intervals, a step of inserting hollow bolts into the holes, and a step of injecting the above rock or ground consolidation agent into the rock or ground from the opening of the bolt and solidifying.

For example, using a pump capable of controlling the injection amount, pressure and compounding ratio of the components (A) and (B), the components (A) and (B) are placed in separate tanks, and a pre-fixed static mixer or a perforated rock bolt or injection rod equipped with a check valve is passed through the tunnel face or top plate of sandy soil that is difficult to penetrate, and the components (A) and (B) in the tank are injected at an injection pressure of 0.05 to 5 MPa into the static mixer. The (A) component and (B) component uniformly mixed through are permeated into the natural ground and hardened. As a result, the ground can be solidified and stabilized.

The present invention will be described in more detail below based on examples and comparative examples. The invention is not limited thereby.

<Raw materials used>
[Aromatic amine compound (a1)]
- Aromatic amine compound 1: diethyltoluenediamine (trade name: DETDA80, manufactured by Lonza Japan Co., Ltd.)
- Aromatic amine compound 2: dimethylthiotoluenediamine (trade name: Etacure 300, manufactured by Mitsui Chemicals Fine Co., Ltd.)

[Aliphatic amine compound (a2)]
・ Aliphatic amine compound 1: Norbornanediamine (trade name: NBDA, manufactured by Mitsui Chemicals Fine Co., Ltd.)
- Aliphatic amine compound 2: Polyoxypropylenediamine (trade name: Polyetheramine D-230, manufactured by Mitsui Chemicals Fine Co., Ltd., Mw: 230)
- Aliphatic amine compound 3: Polyoxypropylene triamine (trade name: Polyetheramine T-403, manufactured by Mitsui Chemicals Fine Co., Ltd., Mw: 440)

[Polyether polyol]
- Polyether polyol: Polyether polyol having an average hydroxyl value of 450 mgKOH/g obtained by addition polymerization of ethylene oxide and propylene oxide to ethylenediamine (trade name: EXENOL 450ED, manufactured by AGC Co., Ltd.)

[Isocyanate compound]
- Isocyanate compound 1: isocyanurate modified form of pentamethylene diisocyanate (PDI) (trade name: Stabio 376N, manufactured by Mitsui Chemicals, Inc.)
Isocyanate compound 2: isocyanurate modified form of hexamethylene diisocyanate (HDI) (trade name: Duranate TLA-100, manufactured by Asahi Kasei Corporation)
Isocyanate compound 3: Adduct modified form of hexamethylene diisocyanate (HDI) (trade name: Duranate D-101, manufactured by Asahi Kasei Corporation)
- Isocyanate compound 4: xylylene diisocyanate (XDI) (trade name: Takenate 500, manufactured by Mitsui Chemicals, Inc.)

[Flame retardants]
・Flame retardant 1: tris (chloropropyl) phosphate (trade name: TMCPP, Daihachi Chemical Industry Co., Ltd.)
・ Flame retardant 2: triethyl phosphate (trade name: TEP, Daihachi Chemical Industry Co., Ltd.)

[catalyst]
- Catalyst 1: potassium octylate (trade name: Pucat 15G, Nippon Kagaku Sangyo Co., Ltd.; solvent: diethylene glycol; potassium content: 15% by mass)
- Catalyst 2: quaternary ammonium salt (trade name: Kaolizer No. 420, Kao Corporation)
・ Catalyst 3: N,N',N''-tris(dimethylaminopropyl)-s-hexahydrotriazine (trade name: TOYOCAT-TRC, Tosoh Corporation)

[Preparation of liquid A and liquid B]
A liquid consisting of component (A) was defined as liquid A, and a liquid consisting of component (B) was defined as liquid B. Liquids A and B were prepared by appropriately mixing raw materials according to the formulations (parts by mass) shown in Table 1.

[viscosity]
The viscosities (mPa·s) at 25° C. of liquids A and B were measured according to JIS K-7117-1 using a Brookfield BM viscometer (manufactured by Eiko Seiki Co., Ltd.).

[Evaluation of cured product]
(Rise time, foaming ratio)
Liquids A and B prepared according to the formulations shown in Table 1 were mixed at the mixing ratio shown in Table 1 (the mass ratio of A and B was A/B = 1/x, and the value of x is shown in Table 1. The same applies hereinafter.). After the temperatures of both the A liquid and the B liquid were adjusted to 20° C., the A liquid and the B liquid were mixed by hand mixing, and the rise time (the time from the start of stirring to the completion of foaming) was measured. After completion of the curing reaction, the expansion ratio was calculated by dividing the volume of the cured product by the initial volumes of the liquids A and B as raw materials.

(compressive strength)
Liquids A and B prepared according to the formulations shown in Table 1 were separately prepared at the mixing ratios shown in Table 1. Using a container having a diameter of 50 mm and a height of 100 mm, a 4-fold foam was obtained by mixing and curing the A liquid and the B liquid under conditions constrained to form a 4-fold foam. The compressive strength of the resulting 4-fold foamed body with a diameter of 50 mm and a height of 100 mm was measured using a Shimadzu universal testing machine in accordance with JIS A1216.

[Water cloudiness test]
Liquids A and B prepared according to the formulations shown in Table 1 were separately prepared at the mixing ratios shown in Table 1. After both the A liquid and the B liquid were heated to 20° C., the A liquid and the B liquid were mixed by hand mixing for 10 seconds, and then the mixture was quickly put into a container containing 300 g of water. The container was covered, and 30 seconds after the start of mixing of the A and B solutions, the entire container was violently shaken up and down for 10 seconds. After the completion of foaming, water was collected from the container, and the turbidity of the water was measured visually and with a spectrophotometer (light transmittance (%) at 500 nm measured with a Hitachi spectrophotometer U-3900H (manufactured by Hitachi High-Technologies Corporation)). Those with visible cloudiness were evaluated as "x", and those without cloudiness were evaluated as "good". Moreover, the transmittance by a spectrophotometer is preferably 80% or more.

The results are shown in Table 1. In Table 1, the amine compound content is the ratio of the amount (parts by mass) of the amine compound to the total amount of 100 parts by mass of the A and B liquids.

As shown in Table 1, in Comparative Example 1 in which a modified aliphatic polyisocyanate was used as liquid B and an amine compound was used as liquid A, only an aromatic amine compound was used and no aliphatic amine compound was used, white turbidity was large when in contact with water. Further, in Comparative Example 2 in which an aliphatic amine compound was used in the A liquid but no aromatic amine compound was used, even if the A liquid and the B liquid were mixed, they did not cure. On the other hand, in Examples 1 to 10 in which an aromatic amine compound and an aliphatic amine compound were used in combination in the A liquid, a modified aliphatic polyisocyanate was used as the isocyanate compound in the B liquid.

Although several embodiments of the invention have been described above, these embodiments are presented by way of example and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and modifications can be made without departing from the scope of the invention. These embodiments, their omissions, replacements, modifications, etc., are included in the invention described in the scope of claims and equivalents thereof, as well as being included in the scope and gist of the invention.

According to the present embodiment, it is possible to provide a ground consolidation agent and a ground consolidation method using the same, which can exhibit sufficient strength to stably strengthen unstable rock, ground, etc. without using diphenylmethane diisocyanate, and does not become cloudy when it comes into contact with water.

Claims (9)

A component (A) containing an active hydrogen compound, a catalyst and water, and a component (B) containing an isocyanate compound,
The active hydrogen compound includes an amine compound having a primary or secondary amino group, including an aromatic amine compound and a chain aliphatic amine compound and/or an alicyclic amine compound ,
The isocyanate compound includes a modified aliphatic polyisocyanate,
Rock solidification agent. The rock solidification agent according to claim 1, wherein the modified aliphatic polyisocyanate is selected from the group consisting of an adduct of an aliphatic polyisocyanate, an isocyanurate of an aliphatic polyisocyanate, an allophanate of an aliphatic polyisocyanate, and a biuret of an aliphatic polyisocyanate. The rock solidification agent according to claim 1, wherein the modified aliphatic polyisocyanate contains at least one selected from the group consisting of isocyanurate-modified pentamethylene diisocyanate, isocyanurate-modified hexamethylene diisocyanate, and adduct-modified hexamethylene diisocyanate. The rock solidification agent according to any one of claims 1 to 3, wherein the amount of the amine compound is 15 parts by mass or more with respect to 100 parts by mass of the total amount of the components (A) and (B). The rock solidification agent according to any one of claims 1 to 4, wherein the amount of said amine compound is 80 parts by mass or more with respect to 100 parts by mass of said active hydrogen compound. The rock solidification agent according to any one of claims 1 to 5, wherein the catalyst is at least one selected from tertiary amine compounds, fatty acid alkali metal salts and quaternary ammonium salts. The rock solidification agent according to any one of claims 1 to 6, wherein the amount of water is 0.2 parts by mass to 5.0 parts by mass with respect to 100 parts by mass of component (A). The rock solidification agent according to any one of claims 1 to 7, wherein each of said component (A) and said component (B) has a viscosity of 650 mPa·s or less at 25°C. A step of drilling a plurality of holes in the bedrock or ground at predetermined intervals;
inserting a hollow bolt into the hole; and
A rock solidification method, comprising the step of injecting the rock solidification agent according to any one of claims 1 to 8 into the bedrock or ground through the opening of the bolt and solidifying it.