JP2021066774A - Natural ground consolidating agent and natural ground consolidating method using the same - Google Patents

Abstract

To provide a natural ground consolidating agent that can express sufficient strength without using diphenylmethane diisocyanate.SOLUTION: A natural ground consolidating agent contains a component (a) containing an active hydrogen compound, a catalyst and water, and a component (b) containing an isocyanate compound. The active hydrogen compound contains amine compounds including an aromatic amine compound and a chain aliphatic amine compound and/or an alicyclic amine compound, and the isocyanate compound contains a modified product of aliphatic polyisocyanate.SELECTED DRAWING: None

Description

The present invention relates to a ground consolidation agent and a method of ground consolidation using the same.

Conventionally, inorganic or organic grout has been injected to stabilize and strengthen unstable rocks and ground. Inorganic cement milk, which is commonly used, has a slow solidification rate and a slow onset of strength. Therefore, the purpose of quickly stabilizing and strengthening the unstable ground during excavation of a tunnel, which is required to consolidate in a short time and develop strength, could not be achieved.

On the other hand, rigid foamed polyurethane containing polyol and polyisocyanate as main components has been usefully used because it has a high consolidation rate and can consolidate the ground in a short time to develop strength. Patent Document 1 discloses a ground consolidation agent containing a polyoxyalkylene diol and an isocyanate. Diphenylmethane diisocyanate has usually been used as an isocyanate component in these ground-caking agents in order to exhibit good curability and sufficient strength. Even when the isocyanate component was prepolymerized, a partially modified product was used from the viewpoint of suppressing an increase in the viscosity, and unreacted diphenylmethane diisocyanate remained.

Japanese Patent No. 3944878

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

On the other hand, the modified aliphatic polyisocyanate has problems such as not having good curability and not exhibiting sufficient strength.

It is an object of the present invention to provide a ground consolidation agent capable of exhibiting sufficient strength without using diphenylmethane diisocyanate.

The ground binder according to the 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, and the active hydrogen compound. However, the isocyanate compound contains an amine compound containing an aromatic amine compound and a chain aliphatic amine compound and / or an alicyclic amine compound, and the isocyanate compound contains a modified product of an aliphatic polyisocyanate.

The method for solidifying the ground according to the embodiment of the present invention includes a step of drilling a plurality of holes in the bedrock or the ground at predetermined intervals, a step of inserting a hollow bolt into the hole, and an opening of the bolt. This includes a step of injecting the above-mentioned ground solidifying agent into the bedrock or the ground and consolidating it.

According to the embodiment of the present invention, a ground consolidation agent capable of consolidating the ground in a short time to develop strength and suppressing white turbidity when in contact with water without using diphenylmethane diisocyanate. And a method of consolidation of the ground using it can be provided.

The ground consolidation 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, and usually contains the component (A). Is a liquid A, and the component (B) is a liquid B, which is a two-component curing type ground consolidation agent. In addition to the component (A) and the component (B), a third component as an optional component may be provided.

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

In the present embodiment, the active hydrogen compound includes the above-mentioned amine compound having a primary or secondary amino group. The amount of the amine compound is preferably 15 parts by mass or more, more preferably 18 parts by mass, based on 100 parts by mass of the total amount of the components (A) and (B) from the viewpoint of increasing the compressive strength of the cured product. It is 20 parts by mass or more, more preferably 20 parts by mass or more. When the content of the amine compound is 15 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 amine compound is not particularly limited, and may be, for example, 60 parts by mass or less or 50 parts by mass or less with respect to 100 parts by mass of the total amount of the components (A) and (B). It may be 30 parts by mass or less.

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

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

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

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

The amount of the aromatic amine compound (a1) is preferably 13 parts by mass or more, more preferably 15 parts by mass or more, based on 100 parts by mass of the total amount of the components (A) and (B) from the viewpoint of increasing the compressive strength of the cured product. It is by mass or more, and more preferably 18 parts by mass or more. 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, and may be, for example, 50 parts by mass or less, or 40 parts by mass, based on 100 parts by mass of the total amount of the components (A) and (B). It may be less than or equal to 25 parts by mass or less.

Further, the amount of the aromatic amine compound (a1) is preferably 60 parts by mass or more with respect to 100 parts by mass of the amount of the active hydrogen compound in the component (A) from the viewpoint of increasing the compressive strength of the cured product. It is more preferably 70 parts by mass or more, and further preferably 80 parts by mass or more. 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 amount 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, din-propylamine, diisopropylamine, dibutylamine, diamilamine and dihexylamine. Alkyl monoamines such as methyl ethyl amine, methyl propyl amine, methyl isopropyl amine, ethyl propyl amine, ethyl isopropyl amine, N-methyldodecyl amine, bis (2-ethylhexyl) amine; alkanols such as monoethanolamine, diethanolamine, diisopropanolamine Monoamines; hydrazines; ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, neopentanediamine and other chain aliphatic diamines; diethylenetriamine and the like. Chain aliphatic triamine; polyetherdiamine obtained by converting the hydroxyl group of polyoxyalkylene glycols obtained by addition polymerization of propylene oxide and / or ethylene oxide to water, ethylene glycol, propylene glycol, etc. to an amino group (polyetherdiamine). That is, polyoxyalkylenediamine); polyethertriamine (polyethertriamine) obtained by converting the hydroxyl group of polyoxyalkylenetriols obtained by addition polymerization of propylene oxide and / or ethylene oxide to glycerin, trimethylolpropane, etc. to an amino group. That is, polyoxyalkylene triamine) and the like can be mentioned.

Further, examples of the alicyclic amine compound include alicyclic monoamines such as cyclopentylamine, cyclohexylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine and dicyclohexylamine; and heterocyclic monoamines such as morpholin, pyrrolidine and piperidine; Alicyclic diamines such as 4,4'-diaminocyclohexylmethane, isophoronediamine, bisaminomethylcyclohexane, 2,5- or 2,6-diaminomethylbicyclo [2,2,1] heptane, diaminocyclohexane, norbornenandiamine; Examples thereof include 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.

As the aliphatic amine compound (a2), among the above compounds, a bifunctional or higher functional chain aliphatic amine compound and / or a bifunctional or higher alicyclic amine compound is preferable from the viewpoint of further improving the white turbidity suppressing effect. More preferably, it is at least one selected from the group consisting of norbornan diamine, polyether diamine and polyether triamine.

The weight average molecular weight (Mw) of the above-mentioned polyether diamine and polyether triamine is not particularly limited, but is preferably 100 to 5000, more preferably 150 to 2000, and further preferably 200 to 1000. is there.

In the present specification, 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, the column temperature is 40 ° C., the pump flow rate is 1.0 ml / min, and RI (built in the GPC main body) is used as the detector. [Column: TSKgel G6000H HR + G4000H HR + G3000H HR + G2000H HR (used by connecting 4); Mobile phase: THF; Injection amount: 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 by using a calibration curve of a standard PPG whose molecular weight is known in advance (calibration at a molecular weight of 250 or more).

The amount of the aliphatic amine compound (a2) is preferably 0.1 to 9 parts by mass, more preferably 0, based on 100 parts by mass of the total amount of the components (A) and (B) from the viewpoint of suppressing white turbidity. .5 to 7 parts by mass, more preferably 1 to 5 parts by mass. When the amount of the aliphatic amine compound (a2) is 0.1 parts by mass or more, the effect of suppressing white turbidity can be enhanced, and when it is 9 parts by mass or less, workability can be improved. it can.

The amount of the aliphatic amine compound (a2) is preferably 5 parts by mass or more with respect to 100 parts by mass of the amount of the active hydrogen compound in the component (A) from the viewpoint of further improving the white turbidity suppressing effect. More preferably, it is 10 parts by mass or more. 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 with respect to 100 parts by mass of the amount of the active hydrogen compound in the component (A). It may be less than or equal to a part.

The mass ratio (a1) / (a2) of the aromatic amine compound (a1) and the aliphatic amine compound (a2) is not particularly limited, but is 15/1 from the viewpoint of enhancing both the strength improvement and the white turbidity suppression effect. It is preferably ~ 2/1, more preferably 12 / 1-3 / 1, and even more preferably 10 / 1-5 / 1.

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

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

Examples of the tertiary amine compound include triethylenediamine, 2-methyltriethylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N, N, N', N'-tetramethylpropylenediamine and 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-dimethyl) Aminopropyl) amines and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, it is preferable to use a triazine-based tertiary amine compound, for example, N, N', N'' such as N, N', N''-tris (dimethylaminopropyl) -s-hexahydrotriazine. -Tris (dialkylaminoalkyl) -s-hexahydrotriazine and the like can be mentioned.

Examples of the fatty acid alkali metal salt include an alkali metal salt of acetic acid or octyl acid as a trimerization catalyst. Here, the number of carbon atoms of the fatty acid constituting the fatty acid alkali metal salt may be 1 to 10. Specific examples of the fatty acid alkali metal salt include potassium acetate and potassium octylate, and one or both of them may be used in combination. Since potassium acetate and potassium octylate are solid, 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 for use. Here, when the fatty acid alkali metal salt is dissolved in water and used, the amount of water is included in the amount of water as a foaming agent described later. 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 commercially available quaternary ammonium salts can be used. For example, Kaorizer No. 410, Kaorizer No. Examples include 420 (manufactured by Kao Corporation), TOYOCAT-TR20, and TOYOCAT-TRX (manufactured by Tosoh Corporation).

The amount of the catalyst is not particularly limited, but is preferably 0.1 to 5.0 parts by mass, more preferably 1.0 to 4.0 parts by mass with respect to 100 parts by mass of the amount of the component (A). is there.

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

(Other ingredients)
In addition to the above-mentioned components, the component (A) includes known additives such as silicone-based foam stabilizers, diluents, flame retardants, pigments, inorganic fillers, cross-linking agents, and coupling agents, if necessary. Can be added as long as the object of the present embodiment is not impaired.

Examples of the silicone-based defoaming agent include polyoxyalkylene dimethyl polysiloxane copolymers usually used for rigid urethane foam resins.

Examples of the diluent include phthalates such as dibutyl phthalate, dioctyl phthalate and diisononyl phthalate, adipates such as dibutyl adipate, dioctyl adipate, diisononyl adipate and bis (2- (2-butoxyethoxy) ethyl) adipate, and tri. Examples thereof include trimellitic acid esters such as (2-ethylhexyl) trimellitate.

As the flame retardant, either an additive type or a reaction type can be used. Specific examples of the additive type include phosphorus-containing systems such as triethyl phosphate and tricresyl phosphate, and phosphorus-containing halogen-containing systems such as trismonochloroisopropyl phosphate; halogen-containing systems such as chlorinated paraffin, pentabromoethylbenzene, and decabromodiphenyl ether. Examples include those of the system.

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

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

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

Examples of the modified product of the aliphatic polyisocyanate include an adduct body, an isocyanurate body, an allophanate body, and a biuret body of these aliphatic polyisocyanates. That is, the modified aliphatic polyisocyanate is selected from the group consisting of an adduct form of an aliphatic polyisocyanate, an isocyanurate form of an aliphatic polyisocyanate, an allophanate form of an aliphatic polyisocyanate, and a biuret form of an aliphatic polyisocyanate. It is preferable to contain at least one of them.

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

As the modified aliphatic polyisocyanate, a modified hexamethylene diisocyanate or pentamethylene diisocyanate is preferable from the viewpoint of further improving the load reduction on the apparatus due to the compressive strength and low viscosity. More preferably, it is at least one selected from the group consisting of an isocyanurate modified product of pentamethylene diisocyanate, an isocyanurate modified product of hexamethylene diisocyanate, and an adduct modified product of 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 the components (A) and (B). Good. The amount of the modified aliphatic polyisocyanate is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and 100 parts by mass with respect to 100 parts by mass of the isocyanate compound in the component (B). It may be a department.

As the isocyanate compound of the component (B), only the modified product of the above-mentioned aliphatic polyisocyanate may be used, or another isocyanate compound may be contained together with the modified product of the aliphatic polyisocyanate. Other isocyanate compounds include non-poisonous and deleterious isocyanate compounds. Examples of the non-poisonous and deleterious isocyanate compound include xylylene diisocyanate (XDI), which is an aromatic aliphatic isocyanate. The amount of the aromatic aliphatic 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). Good.

(Other ingredients)
If necessary, the conventionally known additives described in the section of the component (A) can be added to the component (B) as other components within a range that does not impair the object of the present embodiment.

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

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

(mixing ratio)
The mixing ratio of the component (A) and the component _{(B) is the reaction equivalent of the active hydrogen group (NH 2} , OH) of the active hydrogen compound in the component (A) and the isocyanate group (NCO) in the component (B). The ratio, that is, the active hydrogen group / NCO is preferably in the range of 1/5 to 5/1, more preferably 1/3 to 2/1. When this reaction equivalent ratio is 5/1 or less, the hardness of the cured product can be increased, and when it is 1/5 or more, the curing time is shortened, and the strength of the consolidated body is increased to make it brittle. It becomes difficult to become.

[Consolidation method of the ground]
The ground consolidation agent according to the present embodiment is used to stabilize and strengthen rocks having a crush zone, unstable soft ground, etc. during tunnel excavation, and contains components (A) and (B). The ground can be consolidated by mixing and injecting into rock or ground.

The method of injection and consolidation is not particularly limited, and a known method can be adopted. For example, in a step of drilling a plurality of holes at predetermined intervals in a bedrock or the ground, a hollow bolt is provided in the holes. It is preferable to include a step of inserting and a step of injecting the above-mentioned ground consolidation agent into the bedrock or the ground through the opening of the bolt to consolidate the ground.

For example, using a pump that can control the injection amount, pressure, blending ratio, etc. of the components (A) and (B), the components (A) and (B) are placed in separate tanks and permeated. A perforated lock bolt or injection rod equipped with a static mixer or check valve fixed in advance is passed through the tunnel face or top plate of difficult sandy soil, and the component (A) in the tank is inserted into this. The component (B) is injected at an injection pressure of 0.05 to 5 MPa, and the component (A) and the component (B) uniformly mixed through a static mixer are permeated into the ground and cured. As a result, the ground can be consolidated and stabilized.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. The present invention is not limited thereto.

<Raw materials used>
[Aromatic amine compound (a1)]
-Aromatic amine compound 1: Diethyl toluenediamine (trade name: DETDA80, manufactured by Lonza Japan Co., Ltd.)
-Aromatic amine compound 2: Dimethylthiotoluenediamine (trade name: EtaCure 300, manufactured by Mitsui Kagaku Fine Co., Ltd.)

[Aliphatic amine compound (a2)]
-Alphatic amine compound 1: Norbornane diamine (trade name: NBDA, manufactured by Mitsui Kagaku Fine Co., Ltd.)
-Alphatic amine compound 2: Polyoxypropylene diamine (trade name: polyetheramine D-230, manufactured by Mitsui Kagaku Fine Co., Ltd., Mw: 230)
Aliphatic amine compound 3: Polyoxypropylene triamine (trade name: polyetheramine T-403, manufactured by Mitsui Kagaku Fine Co., Ltd., Mw: 440)

[Polyether polyol]
-Polyet polyol: A 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: Excelol 450ED, manufactured by AGC Inc.).

[Isocyanate compound]
-Isocyanate compound 1: Isocyanurate modified product of pentamethylene diisocyanate (PDI) (trade name: Stavio 376N, manufactured by Mitsui Chemicals, Inc.)
-Isocyanate compound 2: Isocyanurate modified product of hexamethylene diisocyanate (HDI) (trade name: Duranate TLA-100, manufactured by Asahi Kasei Corporation)
-Isocyanate compound 3: Adduct modified product 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, Nihon Kagaku Sangyo Co., Ltd. Solvent: diethylene glycol. Potassium content: 15% by mass)
-Catalyst 2: Quaternary ammonium salt (trade name: Kaorizer No. 420, Kao Corporation)
-Catalyst 3: N, N', N''-tris (dimethylaminopropyl) -s-hexahydrotriazine (trade name: TOYOCAT-TRC, Tosoh Corporation)

[Preparation of solution A and solution B]
Liquid A and liquid B were prepared by appropriately mixing the raw materials according to the formulation (parts by mass) shown in Table 1 with the liquid consisting of the component (A) as the liquid A and the liquid consisting of the component (B) as the liquid B. ..

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

[Evaluation of cured product]
(Rise time, foaming magnification)
Liquids A and B prepared according to the formulation shown in Table 1 have a mixing ratio shown in Table 1 (mass ratio of liquid A and liquid B = 1 / x, and Table 1 shows the value of x. The same applies hereinafter.) Prepared separately. After the temperatures of both solutions A and B were set to 20 ° C., the solutions A and B were mixed by hand mixing, and the rise time (time from the start of stirring to the completion of foaming) was measured. After completion of the curing reaction, the foaming ratio was calculated by dividing the volume of the cured product by the initial volumes of the raw materials A and B.

(Compressive strength)
Solutions 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 quadruple foam was obtained by mixing and curing the liquid A and the liquid B under the condition of restraining the foam to be a quadruple foam. The compressive strength of the obtained quadruple foam having a diameter of 50 mm and a height of 100 mm was measured with a Shimadzu universal testing machine in accordance with JIS A1216.

[Underwater cloudiness test]
Solutions 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 solutions A and B were brought to 20 ° C., the solutions A and B were mixed by hand mixing for 10 seconds, and then the mixture was immediately put into a container containing 300 g of water. The container was covered, and 30 seconds after the start of mixing the liquids A and B, the entire container was vigorously shaken up and down and continued for 10 seconds. After the foaming is completed, water is collected from the inside of the container, and the turbidity of the water is visually measured and measured with a spectrophotometer (Hitachi Spectrophotometer U-3900H (manufactured by Hitachi High-Technologies Corporation)). )). Those with white turbidity were evaluated as "x", and those without white turbidity were evaluated as "○". Further, the transmittance by the 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 100 parts by mass of the total amount of the liquid A and the liquid B.

As shown in Table 1, in Comparative Example 1 in which the modified product of the aliphatic polyisocyanate was used in the liquid B and the amine compound was used in the liquid A, but only the aromatic amine compound was used and the aliphatic amine compound was not used. , The white turbidity was large when it came into contact with water. Further, in Comparative Example 2 in which the aliphatic amine compound was used in the liquid A but the aromatic amine compound was not used, the liquid A and the liquid B were not cured even when mixed. On the other hand, in Examples 1 to 10 in which the aromatic amine compound and the aliphatic amine compound were used in combination with the liquid A, although the modified product of the aliphatic polyisocyanate was used as the isocyanate compound of the liquid B, it was short. It foamed and cured over time, the cured product had sufficient strength, and there was no white turbidity when touched with water.

Although some embodiments of the present invention have been described above, these embodiments are presented as examples 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 changes can be made without departing from the gist of the invention. These embodiments, omissions, replacements, changes, etc. thereof are included in the scope and gist of the invention, as well as in the scope of the invention described in the claims and the equivalent scope thereof.

In the present embodiment, it is possible to develop sufficient strength to stably strengthen unstable rocks, ground, etc. without using diphenylmethane diisocyanate, and there is no white turbidity when it comes into contact with water. It is possible to provide a mountain consolidation agent and a method for solidifying the ground using the mountain binder.

Claims (9)

It comprises a component (A) containing an active hydrogen compound, a catalyst and water, and a component (B) containing an isocyanate compound.
The active hydrogen compound contains an amine compound including an aromatic amine compound and a chain aliphatic amine compound and / or an alicyclic amine compound.
The isocyanate compound comprises a modified aliphatic polyisocyanate.
Ground consolidation agent. The modified aliphatic polyisocyanate is selected from the group consisting of an adduct form of an aliphatic polyisocyanate, an isocyanurate form of an aliphatic polyisocyanate, an allophanate form of an aliphatic polyisocyanate, and a biuret form of an aliphatic polyisocyanate. The ground caking agent according to claim 1, which comprises at least one type. The modified aliphatic polyisocyanate comprises at least one selected from the group consisting of an isocyanurate modified product of pentamethylene diisocyanate, an isocyanurate modified product of hexamethylene diisocyanate, and an adduct modified product of hexamethylene diisocyanate. The ground binder according to 1. The consolidation 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 component (A) and the component (B). Consolidation. The ground consolidation agent according to any one of claims 1 to 4, wherein the amount of the amine compound is 80 parts by mass or more with respect to 100 parts by mass of the amount of the active hydrogen compound. The ground consolidation agent according to any one of claims 1 to 5, wherein the catalyst is at least one selected from a tertiary amine compound, a fatty acid alkali metal salt and a quaternary ammonium salt. The consolidation 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 the amount of the component (A). Consolidation. The ground consolidation agent according to any one of claims 1 to 7, wherein the viscosities of the component (A) and the component (B) are 650 mPa · s or less at 25 ° C., respectively. The process of drilling multiple holes in rock or ground at predetermined intervals,
The process of inserting a hollow bolt into the hole, and
A method for solidifying a ground, which comprises a step of injecting the ground consolidation agent according to any one of claims 1 to 8 into a bedrock or the ground and consolidating it from the opening of the bolt.