JP4527413B2 - Injection chemical composition for stabilization of soil and stable strengthened water stop method using the same - Google Patents

Description

  The present invention relates to an injectable liquid composition for stabilization of soil and the like and a stability strengthening method using the same. More specifically, the stability of unstable ground and bedrock is excellent, with excellent compatibility and workability, and with little possibility of causing drainage contamination even when the mixed and injected chemicals come into contact with groundwater before hardening. Infusion chemical composition, consolidation stabilization or sealing method of rocks and unstable soft ground with crush zone using the same, and water stoppage, groundwater stoppage or cavity filling method, etc. This is related to the method of strengthening stability.

  As a strengthening method for unstable ground and rock, inorganic-organic composite chemicals are used for soil stabilization. As this chemical solution, a combination of a silicate aqueous solution such as sodium silicate aqueous solution and a polyisocyanate is widely used. However, generally, an aqueous silicate solution and a polyisocyanate are a combination of an inorganic substance and an organic substance, respectively. In essence, there is a problem of poor compatibility. When the compatibility of the two components is poor, a uniform foam cannot be obtained, and there is a tendency that stable strength is hardly expressed.

  Patent Document 1 discloses a two-component type composition for consolidating natural soil, which is a combination of a component A mainly composed of a sodium silicate aqueous solution and a component B mainly composed of polymeric diphenylmethane diisocyanate (MDI), 45 to 65% by weight of the total amount of the isocyanate is dinuclear, particularly 5 to 35% by weight is 2,4′-diphenylmethane diisocyanate, and 10 or 45% by weight of polyphenylene polymethylene polyisocyanate having three or more nuclei. Is a chemical solution for consolidation of natural ground.

  Patent Document 2 discloses a two-component chemical composition for consolidation of natural ground, which is a combination of a component A mainly composed of an aqueous solution of sodium silicate and a component B mainly composed of polymeric MDI, the isocyanate There is described a natural ground consolidation chemical solution in which 43 to 70% by weight of the total amount is dinuclear, and polyphenylene polymethylene polyisocyanate having 3 or more nuclei is 8% by weight or more and less than 45% by weight.

  In these chemical solutions, the reactivity of the two components is improved by adjusting the composition ratio in the polyisocyanate component. However, there is a problem that sufficient compatibility between the A component mainly composed of an aqueous sodium silicate solution and the B component mainly composed of polyisocyanate cannot be secured.

Further, Patent Document 3 and Patent Document 4 have a description of an injectable liquid composition for soil consolidation comprising the following A liquid and B liquid.
Liquid A: Inorganic liquid B containing silicate aqueous solution B: Isocyanate group-terminated prepolymer obtained by reacting the following (a) to (c), the composition ratio of (a) and (b) Is an organic liquid (a) 2 containing an isocyanate group-terminated prepolymer obtained by reacting (c) with a polyisocyanate of (a) / (b) = 20/80 to 70/30 (weight ratio) , 2'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate in a total of 5 to 60% by weight, and 4,4'-diphenylmethane diisocyanate in a proportion of 95 to 40% by weight. The number average molecular weight of the methylene polyisocyanate (c) is 200 to 5000, and the ethylene oxide unit is 60 to 10 Hydroxyl-containing polyether containing wt% In these chemical solutions, for the purpose of improving the compatibility of the two components, an isocyanate group-terminated prepolymer obtained by addition reaction of a hydroxy group-containing polyether containing 60 to 100 wt% of ethylene oxide units is used. A polyisocyanate component containing a polymer is used. However, since this isocyanate group-terminated prepolymer is reacted using a polyether having a considerably high ethylene oxide unit content, the hydrophilicity is very strong. For this reason, when a chemical solution using this is in contact with water such as ground water before being cured, there is a risk of causing white turbidity and contaminating the waste water.

  Patent Documents 5, 6 and 7 contain an isocyanate group-terminated prepolymer obtained by addition reaction of an active hydrogen group-containing compound containing 5% by weight or more of a propylene oxide unit such as poly (oxypropylene) polyol. A chemical solution using a polyisocyanate component is described. Thereby, the waste water pollution property is suppressed. However, in reality, only the use of a polyol having a propylene oxide unit of 100% by weight is intended, so that there is a problem that the compatibility of the two components cannot be sufficiently ensured.

JP-A-9-71778 JP-A-8-157824 JP-A-11-116955 JP 11-116957 A JP 2000-345158 A JP 2000-345159 A Japanese Patent Laid-Open No. 2001-19959

  The present invention provides a material that achieves compatibility between ensuring compatibility of two components and suppresses wastewater contamination, and has excellent physical properties such as foaming curability and strength, safety, economy, and workability, and a construction method using the same. The purpose is to do.

That is, in the present invention, the polyisocyanate compound (B) is an isocyanate compound (B1) shown below, in the injectable liquid composition for stabilizing a soil composed of a silicate aqueous solution (A) and a polyisocyanate compound (B). The present invention relates to an injectable liquid composition for stabilizing a soil, comprising an isocyanate group-terminated prepolymer obtained by reacting a polyether (B4) with a polyisocyanate comprising an isocyanate compound (B2) and an isocyanate compound (B3).
(Isocyanate compound B1) 30 to 70% by weight of diphenylmethane diisocyanate consisting of 10 to 50% by weight of 2,2′-diphenylmethane diisocyanate and / or 2,4′-diphenylmethane diisocyanate and 90 to 50% by weight of 4,4′-diphenylmethane diisocyanate
(Isocyanate compound B2) 15 to 35% by weight of polyphenylene polymethylene polyisocyanate having three benzene rings and three isocyanate groups in one molecule
(Isocyanate compound B3) 15 to 35% by weight of polyphenylene polymethylene polyisocyanate having 4 or more benzene rings and 4 isocyanate groups in one molecule
(Polyether B4) A hydroxyl group-containing polyether having a number average molecular weight of 200 to 10,000 and containing 5 to 50% by weight of an ethylene oxide unit.

  The aqueous silicate solution (A) preferably contains an amine catalyst.

  It is preferable that the silicate aqueous solution (A) contains a polyol.

  The polyisocyanate compound (B) preferably contains a reactive diluent.

  The polyisocyanate compound (B) preferably contains a silicone foam stabilizer.

  Further, a step of drilling a plurality of holes in the rock or ground at predetermined intervals, a step of inserting a hollow bolt into the hole, and the injection medicinal solution composition according to any one of the above from the opening of the bolt In addition, it relates to a method for stable and strengthened water stoppage of rock or ground consisting of a process of pouring into the ground and consolidation.

  According to the present invention, since it contains an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate with a hydroxyl group-containing polyether having a number average molecular weight of 200 to 10,000 and containing 5 to 50% by weight of an ethylene oxide unit, It is possible to achieve compatibility between two components, ie, a component composed of an aqueous solution of sodium silicate and a component composed of polyisocyanate, and to suppress wastewater contamination.

  In addition, according to the stability-enhanced waterstop method of the present invention, the use of the stabilizing infusion chemical solution composition has a low viscosity of the chemical solution, good permeability to unstable areas, cracks, crush zones, etc., and wide Stabilization and water stoppage of unstable rock and ground can be achieved over a range. In addition, the formed hardened solid has high strength and durability, adheres to the bedrock, has excellent adhesion, and exhibits flame retardancy, and is economical, This is a practically advantageous method.

As the silicate aqueous solution (A) used in the present invention, a commercially available aqueous solution of sodium silicate can be used as a main component. This sodium silicate is represented by the general formula: Na ₂ O.xSiO ₂ .nH ₂ O. Here, x represents a molar ratio of SiO ₂ (silicon dioxide) and Na ₂ O (sodium oxide), preferably 0.5 to 4, more preferably 2 to 3.5. If x is less than 0.5, the proportion of the silicic acid gelation reaction in the foam curing reaction decreases, so the balance of reactivity tends to be poor. If it exceeds 4, the viscosity of the aqueous sodium silicate solution is high. Therefore, there exists a tendency for the mixability with a polyisocyanate compound (B) and workability | operativity at the time of use to fall.

  The solid content concentration of the silicate aqueous solution (A) is preferably adjusted to 20 to 60% by weight, more preferably 30 to 50% by weight. If the solid content concentration is lower than 20% by weight, the inorganic components in the consolidated product are reduced, so that the flame retardancy tends to be reduced. If the solid content concentration exceeds 60% by weight, the viscosity of the aqueous silicate solution (A) increases. Therefore, there is a tendency that the miscibility with the polyisocyanate compound (B) and the workability at the time of use are lowered.

  The polyisocyanate compound (B) used in the present invention is an isocyanate group-terminated prepolymer obtained by reacting a polyether (B4) with a polyisocyanate comprising an isocyanate compound (B1), an isocyanate compound (B2) and an isocyanate compound (B3). contains. This polyisocyanate compound (B) is extremely volatile under the handling environment temperature from the viewpoint of safety and hygiene and economy, and is liquid and economical.

  The isocyanate compounds (B1) to (B3) in the polyisocyanate compound (B) are as follows.

  Isocyanate compound (B1) is 2,2′-diphenylmethane diisocyanate (hereinafter abbreviated as 2,2′-MDI) and / or 2,4′-diphenylmethane diisocyanate (hereinafter abbreviated as 2,4′-MDI). Diphenylmethane diisocyanate consisting of 10 to 50% by weight and 90 to 50% by weight of 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as 4,4′-MDI).

  2,2'-MDI and / or 2,4'-MDI is contained in an amount of 10 to 50% by weight, preferably 10 to 40% by weight. 4,4'-MDI is contained in an amount of 90 to 50% by weight, preferably 90 to 60% by weight. When 2,2'-MDI and / or 2,4'-MDI is less than 10% by weight, MDI crystallizes at a low temperature, so that polyisocyanate compound (B) becomes non-uniform. If it exceeds 50% by weight, the reactivity with the aqueous silicate solution (A) decreases.

  The isocyanate compound (B1) is contained in the isocyanate compounds (B1) to (B3) in an amount of 30 to 70% by weight, preferably 35 to 65% by weight. If the content is less than 30% by weight, the viscosity of the polyisocyanate compound (B) becomes high and the workability decreases, and if it exceeds 70% by weight, MDI tends to crystallize at low temperatures. ) Tends to be uneven.

  The isocyanate compound (B2) is polyphenylene polymethylene polyisocyanate having three benzene rings and three isocyanate groups in one molecule.

  The isocyanate compound (B2) is contained in the isocyanate compounds (B1) to (B3) in an amount of 15 to 35% by weight, preferably 20 to 30% by weight. When the content is less than 15% by weight, the expansion ratio tends to decrease, and when it exceeds 35% by weight, the viscosity of the polyisocyanate compound (B) increases.

  The isocyanate compound (B3) is a polyphenylene polymethylene polyisocyanate having four or more benzene rings and four isocyanate groups in one molecule.

  The isocyanate compound (B3) is contained in the isocyanate compounds (B1) to (B3) in an amount of 15 to 35% by weight, preferably 20 to 30% by weight. When the content is less than 15% by weight, the expansion ratio tends to decrease, and when it exceeds 35% by weight, the viscosity of the polyisocyanate compound (B) increases.

  Moreover, the isocyanate compound (B3) has four or more benzene rings and isocyanate groups in one molecule.

  The polyether (B4) is a hydroxyl group-containing polyether having a number average molecular weight of 200 to 10,000 and containing 5 to 50% by weight of ethylene oxide units.

  The number average molecular weight of the polyether (B4) is 200 to 10,000, preferably 300 to 5,000. When the number average molecular weight is less than 200, the crosslinking density becomes high and the cured product becomes brittle. If it exceeds 10,000, the crosslink density becomes low and the strength of the cured product decreases.

  The ethylene oxide unit is contained in an amount of 5 to 50% by weight, preferably 5 to 40% by weight. When the ethylene oxide unit content is less than 5% by weight, the hydrophilicity of the polyisocyanate compound (B) is insufficient and the compatibility with the silicate aqueous solution (A) is deteriorated. If the polyisocyanate compound (B) becomes too hydrophilic and comes into contact with water such as groundwater before the two-component mixture is cured, it tends to become cloudy and contaminate wastewater.

  The hydroxyl group-containing polyether (B4) may be any as long as it satisfies these conditions as a whole, and examples thereof include the following polyether monools or polyether polyols, and mixtures thereof.

  The polyether monool and polyether polyol can be obtained by addition polymerization of an alkylene oxide to an active hydrogen compound by a known method. Examples of the active hydrogen compound include monools such as methanol, ethanol, propanol, butanol, octanol and lauryl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol and 1,3-butanediol. Diols such as 1,4-butanediol and 1,6-hexanediol, polyols such as glycerin, trimethylolpropane and pentaerythritol, other such as monoethanolamine, diethanolamine, triethanolamine, diglycerin, sorbitol and sucrose Examples include alcohols. These active hydrogen compounds may be used alone or in admixture of two or more. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. Of these, polyether polyols are preferred in view of versatility and economy.

  Furthermore, 1-5 are preferable and, as for the average number of hydroxyl groups of a hydroxyl-containing polyether (B4), 1-3 are more preferable. When the number of hydroxyl groups exceeds 5, the viscosity of the polyisocyanate compound (B) tends to increase.

  The isocyanate group-terminated prepolymer used in the present invention comprises a polyisocyanate compound (B) composed of an isocyanate compound (B1), an isocyanate compound (B2) and an isocyanate compound (B3) and a hydroxyl group-containing polyether (B4). For example, the reaction is carried out by a known method so that the equivalent ratio of NCO group to OH group (NCO group / OH group) is preferably in the range of 1.5 to 300, more preferably 2.0 to 100. It is obtained. When the equivalence ratio is less than 1.5, the viscosity of the polyisocyanate compound (B) tends to be high and workability tends to be lowered, and when it exceeds 300, the modification effect tends to be difficult to obtain.

  Furthermore, if it is a small amount, the following isocyanates can be used alone or in combination of two or more in the polyisocyanate.

  Examples of the isocyanates include polyisocyanates such as carbodiimide-modified diphenylmethane diisocyanate, tolylene diisocyanate, crude tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate and trimethylene xylylene diisocyanate. Can be given. Further, an adduct obtained by modifying the polyisocyanate with water, a lower monoalcohol or a polyhydric alcohol, a terminal isocyanate group-containing urethane prepolymer obtained by reacting a polyisocyanate and various polyols, or an adduct of these prepolymers Bodies, mixtures of prepolymers and various polyisocyanates, and dimers or trimers obtained by adding a catalyst to the polyisocyanate.

  The isocyanate group content of the isocyanate group-terminated prepolymer used in the present invention (hereinafter abbreviated as “NCO content”) is preferably 10 to 35% by weight, more preferably 15 to 30% by weight. If the NCO content is less than 10% by weight, the cross-linked structure due to the silicic anhydride-urethane composite reaction and urea bonds decreases, so the strength of the cured product tends to decrease. Since the number of cross-linking points increases extremely, the cured product tends to become brittle.

  The mixing ratio of the silicate aqueous solution (A) and the polyisocyanate compound (B) is such that the polyisocyanate compound (B) is 10 to 500 parts by weight, particularly 20 parts per 100 parts by weight of the silicate aqueous solution (A). It is preferable that it is -200 weight part. When the amount of the polyisocyanate compound (B) is less than 10 parts by weight, the isocyanate group content in the mixed solution is decreased, so that the strength of the cured product tends to decrease. If it exceeds 500 parts by weight, the inorganic components in the cured product will decrease, and sufficient flame retardancy will not be obtained.

  In this invention, it is preferable to mix | blend an amine catalyst with silicate aqueous solution (A). Thereby, reaction hardening of the silicate aqueous solution (A) and the polyisocyanate compound (B) can be promoted. Specific examples of the amine catalyst include 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, 1,2-dimethylimidazole, N, N-dimethylethanolamine, N, N-dimethylaminoethoxyethanol N, N-dimethylaminohexanol, N, N, N′-trimethylaminoethylethanolamine, N-methyl-N′-hydroxyethylpiperazine, and the like can be used alone or in combination. Of these, N, N-dimethylaminohexanol and N, N, N′-trimethylaminoethylethanolamine, which are weak in odor and skin irritation, are particularly preferred from the viewpoint of the working environment.

  The addition amount of the amine catalyst is preferably 0.01 to 20% by weight, particularly 0.1 to 5% by weight in the aqueous silicate solution (A). If the amount added is less than 0.01% by weight, it tends to be difficult to control the foam curing reaction, and if it exceeds 20% by weight, it tends to be expensive.

  Moreover, it is preferable to mix | blend a polyol with silicate aqueous solution (A). Thereby, the reaction curability of the mixture can be adjusted. As the polyol, polyester polyol, polycarbonate polyol and the like can be used in addition to the above-described polyether polyol. Among these, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, and 1,3-butanediol have good stability and relatively low molecular weight in the aqueous silicate solution (A). 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane and the like are particularly preferable.

  The amount of the polyol added is preferably from 0.1 to 50% by weight, and more preferably from 0.1 to 10% by weight in the silicate aqueous solution (A). If the addition amount is less than 0.1% by weight, the cross-linked structure due to the urethane bond is reduced, so that the cured product tends to be brittle, and if it exceeds 50% by weight, the inorganic components in the cured product are reduced. There exists a tendency for the flame retardance of hardened | cured material to fall.

Moreover, it is preferable to mix | blend a reactive diluent with a polyisocyanate compound (B) at the point from which the viscosity reduction effect is acquired, suppressing the environmental pollution by the elution from a solidified material. The reactive diluent means one that is alkali-hydrolyzed by an aqueous sodium silicate solution. The hydrolysis means that the hydrolysis rate after 2 hours is 5 to 100% when mixed with sodium silicate in the presence of an amine catalyst under boiling reflux conditions. In particular, No. 1 sodium silicate (solid content: 40%, SiO ₂ / Na ₂ O ratio: 2.%) added with 1% of N, N, N′-trimethylaminoethylethanolamine as an amine catalyst under boiling reflux. 2) When 15 parts by weight of the reactive diluent is mixed with 100 parts by weight, the hydrolysis rate after 2 hours is 5 to 100%. Specifically, low molecular weight dibasic acid diesters, mono- or polyhydric alcohol acetates, alkylene carbonates, ethers, cyclic esters which are listed as reactive diluents in Japanese Patent No. 2591540. Acid anhydrides, various acrylic esters and methacrylic esters can be used.

  Examples of the low molecular weight dibasic acid diesters include dimethyl esters such as glutaric acid, succinic acid, adipic acid, malonic acid, oxalic acid and pimelic acid, and dialkyl esters such as diethyl ester.

  Examples of alcohol acetates include acetates of glycol ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol methyl ether, ethyl carbitol and butyl carbitol; 3-methoxybutyl alcohol and 3-methyl-3- Examples include acetates of alkoxyalkyl alcohols such as methoxybutyl alcohol; diacetates of glycols such as ethylene glycol, diethylene glycol and triethylene glycol.

  Examples of the alkylene carbonates include propylene carbonate.

  Examples of ethers include cyclic ethers such as tetrahydrofuran, dioxane and dehydrated castor oil.

  Examples of the cyclic esters include lactones such as γ-butyllactone and lactams such as ε-caprolactam.

  As various acrylic acid esters or methacrylic acid esters, acrylic acid or methacrylic acid methyl ester such as methyl, ethyl and butyl, acrylic acid or methacrylic acid and ethylene glycol, diethylene glycol, polyethylene glycol having a molecular weight of 100 to 1000, propylene Examples thereof include glycol, dipropylene glycol, polypropylene glycol having a molecular weight of 100 to 1000, ethylene oxide having a molecular weight of 100 to 5000, an ester with an alcohol such as a propylene oxide copolymerized diol or triol, and the like.

  Examples of the acid anhydride include maleic anhydride.

  The addition amount of the reactive diluent is preferably 0.5 to 30% by weight, particularly 1 to 20% by weight in the polyisocyanate compound (B). When the addition amount is less than 0.5% by weight, the viscosity reducing effect tends to be difficult to obtain. When the addition amount exceeds 30% by weight, the content of isocyanate groups in the polyisocyanate compound (B) decreases, The strength tends to decrease.

  Moreover, it is preferable to mix | blend the silicone foam stabilizer which has a dimethylpolysiloxane as a main component to the polyisocyanate compound (B) at the point which homogenizes a foam and stabilizes a foaming ratio. In the polyisocyanate compound (B), those having good stability and not containing an active hydrogen group are preferred, and examples thereof include terminal alkoxy type polyether-modified dimethylpolysiloxane.

  The addition amount of the silicone foam stabilizer is preferably 0.01 to 5% by weight in the polyisocyanate compound (B). If the added amount is less than 0.01% by weight, the foam regulating effect of the foam is reduced, and therefore, the control of the foaming ratio tends to be difficult. Tend to be unsuitable.

  Furthermore, in the present invention, surfactants other than those described above, catalysts, pigments, dyes, fillers, anti-gelling agents, coupling agents, foaming agents, dispersants, thickeners, antioxidants as necessary. Various additives such as an ultraviolet absorber and a heat resistance imparting agent can also be added.

  The injection chemical composition of the present invention comprising the silicate aqueous solution (A) and the polyisocyanate compound (B) is a special injection chemical solution. For example, when tunnel excavation, collapse of the top of the face and prevention of expansion of loosening are prevented. In the urethane-based injection fore-polling method or the injection-type long tip receiving method (AGF method) performed for the purpose of injection, the material is injected and consolidated into soft or unstable ground, rock, or crush zone with many voids and cracks.

  The method for injecting and consolidating is not particularly limited, and a known method can be adopted. However, a step of drilling a plurality of holes at a predetermined interval in a rock or ground, and a hollow bolt is inserted into the hole. Preferably, the method comprises a step and a step of injecting the injectable liquid composition into the rock or ground from the opening of the bolt and solidifying.

  For example, there is a method using a comparative compounding pump that can control the injection amount, pressure, compounding ratio and the like of the silicate aqueous solution (A) and the polyisocyanate compound (B). In this method, the silicate aqueous solution (A) and the polyisocyanate compound (B) are put in separate tanks, and a plurality of holes drilled at predetermined locations (for example, at intervals of about 0.5 to 3 m) such as a bedrock. ) Is passed through a perforated rock bolt or injection rod with a static mixer or check valve fixed in advance, and the components in the tank are injected at an injection pressure of 0.05 to 5 MPa. Through a mixer, a predetermined amount of the component (A) and the component (B) are mixed uniformly, injected into a predetermined unstable rock or ground, and hardened to be consolidated and stabilized.

  For example, when injecting into the top of the tunnel, drilling is performed using, for example, a leg auger of 42 mmφ bit at a predetermined interval of, for example, about 2 m, and the depth is 2 m and the drilling angle is 10 to 10 mm. A 30-degree injection hole is provided, and a hollow carbon steel pipe lock bolt with a hole length of 3 m, which is equipped with a static mixer and a check valve, is inserted into the injection hole. In order to prevent the backflow of the liquid, it is preferable to seal with a waste cloth and a foamed hard urethane resin or the like, and to inject the chemical solution by the above-described method. The injection operation is terminated when the injection pressure suddenly increases or when the injection pressure is further increased by about 50% from the predetermined injection amount. Generally, it is preferable to inject 30 to 200 kg of the chemical solution per one injection hole.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to this Example.

<Preparation of liquid A>
As shown in Table 1, raw materials were added and mixed to prepare solution A. The raw materials used for preparing the liquid A will be described together below.

(Silicate aqueous solution)
Sodium silicate: SiO ₂ / Na ₂ O ratio 2.5 (molar ratio), solid content 40%

(Amine catalyst)
TMAEEA: N, N, N′-trimethylaminoethylethanolamine

(Polyol)
EG: Ethylene glycol

<Preparation of liquid B>
As shown in Table 2, the raw materials were added and mixed to prepare a liquid B. The raw materials used for the preparation of the B liquid will be described together below.

(Polyisocyanate)
P-MDI-1: (B1) / (B2) / (B3) = 54/23/23 (weight ratio), (total of 2,2′-MDI and 2,4′-MDI) / 4,4 ′ -MDI = 13/87 (weight ratio), NCO content 31.8%
P-MDI-2: (B1) / (B2) / (B3) = 49/25/26 (weight ratio), (total of 2,2′-MDI and 2,4′-MDI) / 4,4 ′ -MDI = 11/89 (weight ratio), NCO content 31.6%
P-MDI-3: (B1) / (B2) / (B3) = 58/21/21 (weight ratio), (total of 2,2′-MDI and 2,4′-MDI) / 4,4 ′ -MDI = 14/86 (weight ratio), NCO content 32.0%
P-MDI-4: (B1) / (B2) / (B3) = 42/28/30 (weight ratio), (total of 2,2′-MDI and 2,4′-MDI) / 4,4 ′ -MDI = 8/92 (weight ratio), NCO content 32.0%
P-MDI-5: (B1) / (B2) / (B3) = 83/9/8 (weight ratio), (total of 2,2′-MDI and 2,4′-MDI) / 4,4 ′ -MDI = 33/67 (weight ratio), NCO content 32.4%

(Polyether)
PE-1: number average molecular weight 1500, average number of hydroxyl groups 3, EO unit / PO unit = 30/70 (weight ratio)
PE-2: number average molecular weight 3000, average number of hydroxyl groups 3, EO unit / PO unit = 70/30 (weight ratio)

(Reactive diluent)
PC: Propylene carbonate

(Silicone foam stabilizer)
SZ-1642: Dimethylpolysiloxane derivative, manufactured by Nippon Unicar Co., Ltd.

  B liquid No. About B-I-B-IV, B-VI, and B-VII, polyisocyanate P-MDI-1 to 3 and polyether PE-1 to 2 are weight ratios shown in Table 2 at 3O 0 C. By reacting for a period of time, an isocyanate group-terminated prepolymer was synthesized, and a reactive diluent and a silicone foam stabilizer were further added and mixed as shown in Table 2 to prepare.

  In addition, Table 2 shows the NCO content (% by weight) of each liquid B prepared as described above.

Example 1 , Example 2, Reference Example 1, Reference Example 2, and Comparative Examples 1-4
100 g of A liquid and B liquid whose temperature was adjusted to 20 ° C. in the combination shown in Table 3 were weighed in a 1 liter capacity poly cup, and mixed and stirred with a mixer at a rotation speed of 500 RPM for 10 seconds. The following evaluation was performed about the property at this time. The results are shown in Table 3. In Comparative Examples 1 and 4, since the expansion ratio was low, it was not possible to mold a 3-fold foam specimen, and it was impossible to measure the compressive strength.

(1) Compatibility of the mixed liquid: The liquid obtained by mixing the A liquid and the B liquid by the above-mentioned method is visually checked, and the mixed liquid is uniformly mixed and the reaction cured product is uniform. The mixed liquid is non-uniform. The reaction-cured product was also marked with x.

(2) Water contamination: About 100 g of the mixed solution mixed by the above method is immediately put into a glass beaker containing 1 liter of distilled water, and the contents (mixed solution and distillation) in the glass beaker are immediately Water) The whole was stirred and mixed with a glass rod for about 15 seconds. At this time, the distilled water in the glass beaker was colorless and transparent, and ○ was white turbid.

(3) Curing time: The time when the liquid mixture was reacted and cured when mixed by the above method was measured with a stopwatch.

(4) Foaming ratio: The volume of the foam after reaction curing when mixed by the above method was read from the scale of the polycup and divided by the volume of the liquid mixture before reaction curing was taken as the foaming ratio.

(5) Compressive strength: About 90 g of the mixed solution mixed by the above method is immediately filled into a cylindrical mold having a diameter of 5 cm and a height of 10 cm, and then sealed to prevent the contents from leaking. About three times the foamed consolidated body was molded. The uniaxial compressive strength of the specimen obtained after standing at room temperature for 24 hours was measured according to JIS K 7220 (compression test method for rigid foamed plastic).

(6) Comprehensive evaluation: In the evaluations (1) to (5), the case where there was at least one x was indicated as x, and the case where it was not indicated as ◯.

Claims (5)

In an injectable liquid composition for stabilizing a soil comprising an aqueous silicate solution (A) and a polyisocyanate compound (B),
Polyisocyanate compound (B) is an isocyanate compound shown below (B1), isocyanate compound (B2) and isocyanate compound (B3) polyisocyanates polyether (B4) containing an isocyanate group-terminated prepolymer obtained by reacting consisting ,
An injectable liquid composition for stabilizing a soil, wherein the polyisocyanate compound (B) contains a reactive diluent .
(Isocyanate compound B1) 2,2'-diphenylmethane diisocyanate and / or 2,4'-diphenylmethane diisocyanate 10 to 50 wt%, and 4,4'-diphenylmethane diisocyanate 90 to 50 wt% diphenylmethane diisocyanate 35 to 65% by weight consisting of
Polyphenylene polymethylene polyisocyanates having three respective benzene ring and isocyanate groups (isocyanate compound B2) in one molecule 20-30 wt%
(Isocyanate compound B3) 15 to 35% by weight of polyphenylene polymethylene polyisocyanate having 4 or more benzene rings and 4 isocyanate groups in one molecule
(Polyether B4) A hydroxyl group-containing polyether having a number average molecular weight of 200 to 10,000 and containing 5 to 50% by weight of an ethylene oxide unit. The injectable liquid composition for stabilizing a soil according to claim 1, wherein the silicate aqueous solution (A) contains an amine catalyst. The injectable liquid composition for stabilizing a soil according to claim 1, wherein the aqueous silicate solution (A) contains a polyol. The injectable liquid composition for stabilizing a soil according to claim 1, wherein the polyisocyanate compound (B) contains a silicone foam stabilizer. 5. The injection chemical composition according to any one of claims 1 to 4 , wherein a plurality of holes are drilled in the rock or ground at predetermined intervals, a hollow bolt is inserted into the holes, and an opening of the bolt. A stable and strengthened waterproofing method for rock or ground, which consists of injecting objects into the rock or ground and solidifying.