JP3125286B2 - Composition for soil-stabilized polyurethane foam resin, and soil stabilization method using the composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a composition for a polyurethane foam-stabilized soil-based resin containing a silicate aqueous solution and / or an aqueous silica sol and an NCO-terminated prepolymer as main components, and using the composition. It relates to a soil stabilization method.

[0002]

2. Description of the Related Art It has been known that inorganic silica gel plastics can be produced from an aqueous solution of an alkali metal silicate by the action of an acid or a latent acid. Light glass foam is also produced from water glass. These products have high dimensional stability when heated and are completely non-flammable, but are friable, have low strength, and have poor water resistance until fully solidified. On the other hand, it is known that a polyurethane resin or a polyurea resin can be produced from an organic polyisocyanate and an active hydrogen group-containing compound. These are widely used as foaming soil stabilizing resins,
It is possible to widely change the curing speed, resin density, physical properties and the like. For example, JP-A-7-97566 discloses that an NCO group-containing prepolymer obtained by reacting diisocyanate and polyether glycol as a water-stopping agent is mixed with an aqueous metal salt solution containing a curing accelerator. Invention is disclosed. However, as compared with inorganic plastics, the cost is extremely high, the viscosity of the raw materials greatly changes due to the outside temperature, and the workability is poor. Therefore, various techniques have been proposed to remedy the disadvantages of these inorganic plastics and organic resins. For example, Japanese Patent Publication No. Sho 62-21039 discloses a main agent containing a urethane prepolymer having a terminal NCO group obtained by reacting a hydrophilic polyoxyalkylene polyol with an organic polyisocyanate, and a dilute aqueous solution of sodium silicate or Portland cement. A ground stabilization method using a contained curing agent is disclosed. Also, Japanese Patent Application Laid-Open No. 4-28329
No. 0 describes an injectable chemical composition for stabilizing soil and the like comprising a sodium silicate aqueous solution, a polyisocyanate, a reactive diluent, and the like, and a method for stopping the ground stability using the same. . As an invention similar to this, Japanese Patent Publication No. 7-72271 discloses Japanese Patent Application Laid-Open No. 4-28329.
In the invention of JP-A No. 0, an NCO obtained by reacting an organic polyisocyanate with a polyoxyalkylene mono- or polyol instead of the polyisocyanate and the reactive diluent
A technique using a group-containing hydrophilic urethane prepolymer is disclosed. Further, JP-A-5-78667 discloses a rock consolidation chemical solution containing an aqueous solution of an alkali metal silicate and an isocyanate prepolymer as main components.

[0003]

However, in these conventionally known inorganic-organic hybrid systems, large internal heat is generated during the consolidation, and the (exothermic) condensate produced is inhomogeneous and unstable. However, its physical properties are also insufficient. The present inventors, in order to improve such problems of the known art, when obtaining a soil-stabilized polyurethane foam resin, in a composite system of an inorganic aqueous liquid and an organic system comprising an NCO-terminated prepolymer, As a result of intensive studies on the properties required as a soil stabilizing resin, the use of a coupling agent, an amine-based catalyst, a viscosity modifier and a surfactant as the case may be in combination with an inorganic-organic composite system has led to the disadvantages of the prior art. It was found that not only can the soil be improved, but also that the reaction rate is appropriate, the permeability into the soil and the filling properties are excellent, and the soil can be stabilized, and the present invention has been completed.

[0004]

That is, the present invention provides:
(A) an inorganic mixture composed of an aqueous silicate solution and / or aqueous silica sol, a coupling agent, an amine catalyst and a blowing agent, (B) an organic polyisocyanate and two to two functional groups
8. An soil-stabilized polyurethane foam resin composition comprising: an active hydrogen group-containing compound of No. 8, an NCO group-terminated prepolymer obtained by reacting a monoalcohol in combination, and an organic mixture comprising a viscosity modifier.

The present invention relates to (A) an inorganic mixture comprising an aqueous silicate solution and / or an aqueous silica sol, a coupling agent, an amine catalyst, a blowing agent and a surfactant; (B) an organic polyisocyanate and a functional group. A soil-stabilized polyurethane foamed resin composition comprising: an active hydrogen group-containing compound of 2 to 8, an NCO group-terminated prepolymer obtained by reacting monoalcohol in combination, and an organic mixture comprising a viscosity modifier. is there.

The present invention relates to (A) an inorganic mixture comprising an aqueous silicate solution and / or an aqueous silica sol, a coupling agent, an amine catalyst and a foaming agent; (B) an organic polyisocyanate having 2 to 8 functional groups. An active hydrogen group-containing compound, an NCO group-terminated prepolymer obtained by reacting in combination with a monoalcohol, an organic mixture comprising a viscosity modifier and a surfactant, and a composition for a soil-stabilized polyurethane-based foamed resin. is there.

The present invention relates to (A) an inorganic mixture comprising an aqueous silicate solution and / or aqueous silica sol, a coupling agent, an amine catalyst, a blowing agent and a surfactant; (B) an organic polyisocyanate and a functional group. A soil-stabilized polyurethane foam resin comprising: an active hydrogen group-containing compound of 2 to 8; an NCO group-terminated prepolymer obtained by reacting monoalcohol in combination; an organic mixture of a viscosity modifier and a surfactant; It is a composition for use.

[0008] The present invention provides an NCO-terminated prepolymer comprising:
Diphenylmethane diisocyanate and / or polyphenylene polymethylene polyisocyanate, and a molecular weight of 50 to 60 to 95% by weight containing ethylene oxide units.
0 to 5000 polyether glycol and 4 to 5 carbon atoms
N obtained by reacting a monoalcohol
It is a composition for a soil-stabilized polyurethane foam resin that is a CO-based terminal prepolymer.

The present invention also provides a method for stabilizing a soil, which comprises injecting the above-mentioned composition for a soil-stabilized polyurethane foam resin into soil and consolidating it.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Regarding the silicate aqueous solution (A) used in the present invention, for example, the silicate aqueous solution is generally called water glass, and silicon dioxide is used in an amount of 20 to 40.
An aqueous solution containing 5% by weight and 5 to 20% by weight of sodium oxide is preferred. Most suitable for the present invention is water glass containing 28 to 32% by weight of silicon dioxide and 11 to 13% by weight of sodium oxide. As the aqueous silica sol,
It is a transparent colloid liquid containing 15 to 20% by weight of silica as a solid content and using water as a dispersion medium. In the present invention, it is more preferable to use an aqueous silicate solution, particularly an aqueous sodium silicate solution alone than the aqueous silica sol alone or a combination of the aqueous silica sol and the aqueous silicate solution in terms of the physical properties of the resulting foamed resin.

The coupling agent used in the present invention includes titanate-based coupling agents, silane-based coupling agents, and the like, whereby the compatibility between (A) the inorganic mixture and (B) the organic mixture is improved. And a homogeneous foaming resin excellent in soil permeability and filling property can be formed. Of these, silane coupling agents are particularly preferred.
These can be used alone or as a mixture of two or more. The amount of the coupling agent used is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5.0 parts by weight, based on 100 parts by weight of the NCO group-terminated prepolymer.

Examples of titanate-based coupling agents include tetra-n-butoxytitanium, tetraisopropoxytitanium, and bis [2-[(2-aminoethyl) amino].
Ethanolate] [2-[(2-aminoethyl) amino)
Ethanolate-0] (2-propanolate) titanium, tris (isooctadecanoate-0) (2-propanolate) titanium, bis (ditridecylphosphite-0 ″) tetrakis (2-propanolate) dihydrozentitanate, bis (Dioctyl phosphite-
0 ") tetrakis (2-propanolate) dihydrozentitanate, tris (dioctylphosphite-
0 ") (2-propanolate) titanium, bis (dioctylphosphite-0") [1,2-ethanediolate (2-)-0,0 '] titanium, tris (dodecylbenzenesulfonate-0) ( 2-propanolate)
Titanium and tetrakis [2,2-bis [(2-propenyloxy) methyl] -1-butanolate titanate. Specifically, for example, Ajinomoto's Prenact KR TTS, KR 46B, KR 55, KR
41B, KR 38S, KR 138S, KR 238
S, 338X, KR 12, KR 44, KR 9S
A, KR 34S and the like.

As the silane coupling agent, for example, vinyl silane compounds such as γ-methacryloxy propyl trimethoxy silane and vinyl triethoxy silane, and β-
Epoxysilane compounds such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimex Examples include aminosilane compounds such as silane and mercaptosilane compounds such as γ-mercaptopropyltrimethoxysilane. Specifically, for example, Nippon Unicar's A-174 and A-187 are preferable.

Suitable examples of the amine catalyst include long-chain amines and imidazoles. As long-chain amines, for example, n-butylamine, n-butylamine
Primary amines such as -octylamine, n-dodecylamine and n-hexamethylamine, and N, N-dimethyl-n-
Dodecylamine, N, N-dimethyl-n-tetradecylamine, N, N-dimethyl-n-hexadecylamine,
Tertiary amines such as N, N-dimethyl-n-octadecylamine are exemplified. Examples of imidazoles include, for example, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-
Methyl imidazole, 1-benzyl-2-methyl imidazole, 1-isobutyl-2-methyl imidazole and the like can be mentioned. These can be used alone or as a mixture of two or more. The amount of the amine catalyst used is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the aqueous silicate solution and / or the aqueous silica sol.

As the foaming agent, in addition to water, acetone,
Isoheptane, hexane, methylene chloride, urea,
Borax, boric acid, nitroethane and the like can be mentioned. Water is most preferred for environmental protection purposes. This amount is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the aqueous silicate solution and / or the aqueous silica sol.

The surfactant also has a performance as a foam stabilizer for dispersion and foaming in the mixing operation of (A) the inorganic mixture and (B) the organic mixture. Such surfactants include, for example, the condensation of a polyglycol ether containing the required number of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, and an organic compound containing at least one reactive hydrogen atom. It is obtained by doing. This at least one
Organic compounds containing one reactive hydrogen atom include alcohols, phenols, thiols, primary or secondary amines, carboxylic acids or sulfonic acids, amides thereof,
Examples include polyalkylene oxide derivatives of phenolic compounds having at least two alkyl substituents.
Preferred surfactants include pluronic surfactants. This generally involves the polymerization of a 1,2-alkylene oxide or substituted alkylene oxide, such as butylene oxide, amylene oxide, phenylethylene oxide, cyclohexene oxide, propylene oxide, or mixtures thereof, in the presence of an alkali catalyst, It is obtained by producing a water-insoluble polyalkylene glycol and then condensing it with the required number of moles of ethylene oxide or the like under the same conditions. Furthermore, alcohols obtained by reducing aldehydes generated by the catalytic reaction of polyolefins such as tripropylene, tetrapropylene, pentapropylene, ditributylene, triisobutylene, tetrabutylene, propylene isobutylene, and tribune with carbon monoxide and hydrogen are converted to alcohols. And a nonionic surfactant obtained by reacting a required number of moles of ethylene oxide. In addition, there can be mentioned a silicone-based surfactant, which includes one containing an active hydrogen group and one containing no active hydrogen group. Preferred are those containing no active hydrogen groups. For example, various siloxane polyalkylene oxide block copolymers can be mentioned. Specifically, L- made by Union Carbide
5340, B-145 made by Te Goldschmidt
1, B-8407 and the like. Such a surfactant can be added to (A) the inorganic mixture and / or (B) the organic mixture. The amount of the surfactant used is preferably 0.05 to 5 parts by weight based on 100 parts by weight of the NCO-terminated prepolymer.

In the present invention, a dispersant, a thickener, an antioxidant, a heat resistance imparting agent, an antioxidant and the like can be further added to the inorganic mixture (A).

The organic polyisocyanate for producing the NCO-terminated prepolymer in the present invention includes, for example, p-phenylene diisocyanate, m-phenylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 2,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, TDI, diphenylmethane diisocyanate (hereinafter abbreviated as MDI), polyphenylmethane polyiso Aneto (hereinafter referred to as polymeric MD
I); aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate; hydrogenated TD
I, hydrogenated MDI, and alicyclic diisocyanates such as isophorone diisocyanate. Further, as the organic polyisocyanate, those obtained by modifying a part of these NCO groups into biuret, allophanate, carbodiimide, oxazolidone, amide, imide and the like can also be used. These can be used alone or as a mixture of two or more. Among these, preferred organic polyisocyanates are MDI, polymeric MDI,
MDI-based polyisocyanates such as these isomers and crude mixtures thereof, and more preferably MDI and / or
Or polymeric MDI, polymeric MDI is MD
It is a mixture containing 30 to 55% by weight of I and 70 to 45% by weight of an MDI polynuclear condensate having three or more benzene rings.

The active hydrogen group-containing compound having 2 to 8 functional groups for obtaining the NCO-terminated prepolymer of the present invention includes, for example, ethylene glycol, propanediol, and the like.
Butanediol, diethylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, 3-methyl-
1,5-pentanediol, glycerin, trimethylolpropane, pentaerythritol, sucrose, glucose, fructose sorbitol, or a mixture of two or more thereof, and ethylenediamine, propylenediamine, diethylenetriamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine , Xylylenediamine or the like, or a mixture of two or more thereof, or using these as initiators such as ethylene oxide, propylene oxide, butylene oxide, amylene oxide, glycidyl ether, methyl glycidyl ether, t-butyl glycidyl ether, phenyl glycidyl ether, etc. And those obtained by addition polymerization of one or more of the above monomers by a known method. These can be used alone or as a mixture of two or more. These molecular weights are preferably from 250 to 5000. Among these, a preferred compound containing an active hydrogen group is polyether glycol having a molecular weight of 500 to 5000 and containing 60 to 95% by weight of an ethylene oxide unit. The active hydrogen group-containing compound is preferably used in an amount of 1 to 20 parts by weight, particularly preferably 2 to 18 parts by weight, based on 100 parts by weight of the organic polyisocyanate.

The monoalcohol for obtaining the NCO-terminated prepolymer of the present invention is a monoalcohol having 4 to 50 carbon atoms. The monoalcohol includes a linear monoalcohol and a branched monoalcohol. Examples of the linear monoalcohol having 4 to 50 carbon atoms include amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, lauryl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, and heptadecyl. Alcohol, octodecyl alcohol (stearyl alcohol), nonadecyl alcohol, eicosyl alcohol, seryl alcohol, melisyl alcohol and the like can be mentioned. Preferred linear monoalcohols have 5 to 40 carbon atoms.

Examples of the branched monoalcohol having 4 to 50 carbon atoms include 2-ethylhexanol, methyl-1-nonanol, dimethyl-1-octanol and tetramethyl-1.
-Hexanol, 3-ethyl 4,5,6-trimethyloctanol, 4,5,6,7-tetramethylnonanol, 4,5,8-trimethyldeenol, 4,7,8-
Trimethyl tridecanol, tridecanol, tetradecanol, 2-hexyl decanol, 2-hexadecyl octanol and the like can be mentioned. Preferred branched monoalcohols have 4 to 35 carbon atoms. Particularly preferred among such monoalcohols are branched monoalcohols. The amount of the monoalcohol used is preferably 0.5 to 10 parts by weight based on 100 parts by weight of the active hydrogen group-containing compound having 2 to 8 functional groups.

The NCO content of the NCO-terminated prepolymer in the present invention is preferably 20 to 30% by weight, and 24 to 2% by weight.
9 wt% is more preferred, and 25-28 wt% is most preferred.

Examples of the viscosity modifier of the present invention include carbonates such as ethylene carbonate, propylene carbonate and dimethyl carbonate, and aliphatic carboxylic acids, and carbonates are particularly preferred. These can be used alone or as a mixture of two or more. Such a viscosity modifier is preferably used in an amount of 1 to 15 parts by weight based on 100 parts by weight of the NCO-terminated prepolymer.

In the present invention, (A) the inorganic mixture and (B) the organic mixture are defined as those in which the NCO content of the NCO group-terminated prepolymer in the organic mixture is equal to or less than the equivalent of active hydrogen groups in the inorganic mixture. Although it is used at a certain ratio, it is specifically preferable to use it in a capacity ratio of (A) / (B) = 0.8 to 1.2.

The soil-stabilized polyurethane foamed resin according to the present invention can be obtained by forcibly mixing (A) an inorganic aqueous mixture and (B) an organic mixture using a known stirring / mixing device. For the purpose of adjusting the reactivity of these two correlations, an aqueous silicate solution and / or an aqueous silica sol include:
An amine catalyst having good stability in a water-soluble, slightly odorous and inorganic mixture is used in combination.

In the present invention, the organic polyisocyanate is converted to an active hydrogen group in order to improve the miscibility of the (A) inorganic aqueous mixture and (B) the organic mixture and to increase the contact area between the two layers as much as possible. As an active hydrogen group-containing compound, it is modified with an NCO-containing compound to form an NCO group-terminated water-dispersible prepolymer, and to adjust the viscosity of the organic phase, improve the miscibility with the inorganic phase, and improve the liquid stability after mixing. Preferably, double-ended polyether glycol is used, and a branched monoalcohol is preferably used in combination. In general, non-reactive additives are generally incorporated into the resin, and then slightly exude from the resin, which is not preferred in the present invention for the purpose of soil stabilization. However, in the present invention, exudation to the outside of the resin is scarcely observed by using both ends-blocked polyether glycol suitable as an active hydrogen group-containing compound and a suitable branched monoalcohol in combination. The compositions obtained according to the invention are foamable and have good properties both inorganic and organic.

For example, an aqueous solution of an alkali metal silicate is
When reacted with a low molecular weight isocyanate such as MDI, the isocyanate groups react with water, the carbon dioxide produced contributes to foaming in the material, and some of the carbon dioxide reacts with the surrounding silicate aqueous phase. Gel the interface. The foam thus obtained has the properties of a silicic acid foam containing a non-agglomerated zone of foamed polyurea, and is easily crushed,
The strength is small. Also, if a large excess of diisocyanate is used, the resulting product is a polyurea foam in which the non-agglomerated silicate layer is dispersed. The product therefore exhibits the properties of a silica-filled polyurea foam, is easily crushed, and has poor inorganic fire resistance.

A feature of the present invention lies in the colloidal distribution and interpenetration of the two phases, which allows for strong specific surface or interfacial interactions that are characteristic of xerosols. This colloidal form can only be obtained when the substance to be mixed with the aqueous silicate solution and / or the aqueous silica sol is a coupling agent and a water-dispersible prepolymer having terminal groups of NCO groups. By using such an NCO-terminated prepolymer in combination with a coupling agent or the like, the aqueous inorganic phase and the organic phase are homogeneously distributed, and as a result, the chemical interaction is increased and a new composite material is obtained. By the combination of these, a colloid fiber structure is formed, and as a result, the two types of phases can exist as an aggregated phase, and a homogeneous composite material is obtained, and the advantages of each of the inorganic and organic substances are fully exhibited. Will be done.

The viscosity modifier is selected and used so as to make the viscosity of the two liquids as close as possible for the purpose of improving the miscibility of the two liquids which are forcibly mixed. A water-soluble thickener such as carboxymethylcellulose is added to the aqueous inorganic phase as needed, and a viscosity modifier is added to the organic phase to reduce the viscosity and improve the permeability.

The composition for a soil-stabilized polyurethane foamed resin comprising the inorganic mixture (A) and the organic mixture (B) of the present invention can be used for soft or unstable ground, bedrock, and crushed strata having many voids and cracks. The method of injecting and consolidating the soil is not particularly limited, and any known method can be adopted. For example, using a proportional compounding pump capable of controlling the injection amount, pressure, compounding ratio, etc. of (A) the inorganic mixture and (B) the organic mixture, separate (A) the inorganic mixture and (B) the organic mixture. Through a perforated lock bolt or injection rod containing a static mixer, check valve, etc. fixed in advance in a predetermined location (for example, a plurality of holes drilled at a predetermined interval) such as rock. ,
Each component in the tank is injected under pressure into this, and a predetermined amount of each component is uniformly mixed through a static mixer.
A method of injecting and penetrating into predetermined soil such as unstable rock or ground and hardening it to stabilize the consolidation can be cited. Also, for example, when injecting into the roof of a tunnel, prior to the injection, holes are drilled at predetermined intervals using a leg auger or the like, and injection holes having a predetermined depth and a drilling angle are provided. Insert a static mixer and a lock bolt into the hole, and seal the mouth of the lock bolt with a quick-setting cement or a rag pre-impregnated with a foamed hard polyurethane resin in order to prevent backflow of the injected chemical solution, and The substance is injected in the same manner as described above. Generally, 30 to 200 kg of the composition is injected per injection hole.

[0031]

As described above, according to the present invention, disadvantages which are likely to occur in a conventionally known chemical solution for stabilizing an inorganic-organic composite system in soil, that is, heterogeneity as a foam,
Instability, friability, unnecessary internal heat generation, etc. can be easily resolved. Furthermore, the viscosity and reaction rate are appropriate, the permeability and filling property to soil are excellent, and the inorganic,
A foamable resin having both organic properties) can be obtained. In addition, the soil stabilization method of the present invention can reliably and stably stop the soil over a wide area in a mountain tunnel, a large section tunnel excavation work, a deep underground civil engineering work, and the like, and stop water.

[0032]

EXAMPLES Examples of the present invention will be described below in detail, but the present invention is not limited to these examples. Unless otherwise specified, “parts” and “%” in Examples and Comparative Examples are “parts by weight” and “% by weight”, respectively.
Is shown.

Examples 1 to 18 and Comparative Examples 1 to 4 A 50% aqueous solution of sodium silicate shown in Tables 1 to 4, water, an amine catalyst and a coupling agent If necessary, a surfactant is applied for 15 minutes. By mixing, (A) an inorganic mixture was obtained. This mixture was left under a 5 ° C. or 25 ° C. atmosphere for 24 hours, but no liquid separation was observed. On the other hand, the organic polyisocyanate, active hydrogen group-containing compound, and monoalcohol shown in Table 1 were heated to 80 ° C. and reacted for 3 hours to obtain an NCO-terminated prepolymer. A surfactant was added to the mixture as needed to prepare a (B) organic mixture. Next, a predetermined amount of each of (A) the inorganic mixture and (B) the organic mixture is charged into a machine tank of an injection machine, and a predetermined amount is passed through a liquid feed pump and a static mixer.
The mixture was discharged into a 0 ml beaker and solidified to obtain a foam.
Tables 1 to 4 show the reactivity and the physical property test results of the foam at that time.

[Method of Testing Physical Properties of Foam] (1) Expansion Ratio and Appearance of Foam The test was performed according to JIS A 9514. Evaluation criteria for foam appearance ○: good ×: soft and poor (2) Uniaxial compressive strength The test was performed in accordance with JSF T511 (conforms to the uniaxial compressive test method for soil of the Japan Society of Soil Engineering). (3) Combustibility The test was performed according to ASTM-D-1692.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

Since the viscosity of the organic mixture (B) of the present invention is low, the workability is good, the permeability into the soil and the filling property are good, and the range for stabilizing the solidification of the soil is wide. The foams obtained from the composition of the present invention are all homogeneous, have high uniaxial compressive strength, and have a large expansion ratio and are suitable, so that they have an excellent soil water stopping effect.

[Description of Raw Materials Used] Sodium silicate No. 2: Tertiary amine catalyst (1): N, N-dimethyl-n-dodecylamine manufactured by Tosao Sangyo Co., Ltd. Tertiary amine catalyst (2): N, N-dimethyl -N-tetradecylamine imidazole-based catalyst: 2-methylimidazole Coupling agent: Nippon Unicar, A-174 Coupling agent: Nippon Unicar, A-187 Surfactant: Te Goldschmidt, B 845
1 Polymeric MDI (1): manufactured by Nippon Polyurethane Industry, Millionate MR200 Polymeric MDI (2): manufactured by Nippon Polyurethane Industry, Coronate 1104 MDI (1): 4,4'-MDI 72%, 2,4'-
Mixture of 25.6% of MDI and 2.4% of 2,2'-MDI PPG (1): 2 functional groups, molecular weight 3500, EO content 80% PPG (2): 2 functional groups, molecular weight 2000, EO content 95% PPG (3): functional group number 2, molecular weight 400, EO content 8
0% Monoalcohol (1): Octyl alcohol Monoalcohol (2): Dimethyl-1-octanol EC: Ethylene carbonate PC: Propylene carbonate

Example 19 A hole drilling angle of 25 to 35 ° was formed on a tunnel roof having a crushing zone at intervals of 2 m using a 42 mmφ bit leg auger.
Five holes were drilled at an angle to the tunnel excavation direction, and carbon steel injection bolts (outer diameter 27.2 mm, inner diameter 15 mm, length 3 m, built-in static mixer and check valve) were bored in these holes. The knitted fabric was impregnated with a two-component rigid foamed polyurethane resin into the mouth portion 30 cm, and the mouth was sealed with an iron bar. Next, Example 1 was added to each of the fixed injection ports.
The aqueous solution of the (A) inorganic mixture and the (B) organic mixture prepared in the step (1) were mixed at an injection pressure of 20 to 50 kg / c as shown in Table 1.
80 to 120 kg per hole was injected at m ² . Fifty minutes after the injection, the state of the tunnel ground was examined by Hori Susumu. The state was a hemispherical shape with a radius of 5 m, and the consolidation was stabilized. No water leakage was observed from this range. The injection-consolidated part was sampled into a 5 cmφ × 10 cm cylindrical shape using a sampler, and the uniaxial compressive strength was measured.
The weight was 80 kg / cm ² . The unimproved part could not be sampled because of the crush zone.

COMPARATIVE EXAMPLE 5 A 42 mmφ bit leg auger was drilled at 2 m intervals on a tunnel roof having a crushing zone at an angle of 25 to 35 °.
Five holes were drilled at an angle to the tunnel excavation direction, and carbon steel injection bolts (outer diameter 27.2 mm, inner diameter 15 mm, length 3 m, built-in static mixer and check valve) were bored in these holes. The knitted fabric was impregnated with a two-component rigid foamed polyurethane resin into the mouth portion 30 cm, and the mouth was sealed with an iron bar. Next, Comparative Example 1 was added to each of the fixed injection ports.
The aqueous solution of the (A) inorganic mixture and the (B) organic mixture prepared in the above step were prepared at an injection pressure of 20 to 50 kg / c at a ratio shown in Table 5.
80 to 120 kg per hole was injected at m ² . Fifty minutes after the injection, the state of the tunnel ground was examined by Hori Susumu. As a result, a hemispherical shape with a radius of 1.5 m was obtained, and the consolidation was stabilized, but slight leakage was observed. The injection-consolidated part was sampled into a 5 cmφ × 10 cm cylindrical shape with a sampler, and the uniaxial compressive strength was measured.
^Two .

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ identification code FI // C09K 103: 00 (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 18/10 C08L 75/04-75 / 12 C09K 17 / 30,17 / 46,17 / 48

Claims (6)

(57) [Claims] 1. An inorganic mixture comprising (A) an aqueous silicate solution and / or an aqueous silica sol, a coupling agent, an amine catalyst and a blowing agent, (B) an organic polyisocyanate and active hydrogen having 2 to 8 functional groups. A soil-stabilized polyurethane foam resin composition comprising: a group-containing compound, an NCO group-terminated prepolymer obtained by reacting a monoalcohol in combination, and an organic mixture comprising a viscosity modifier. 2. An inorganic mixture comprising (A) an aqueous silicate solution and / or an aqueous silica sol, a coupling agent, an amine catalyst, a foaming agent and a surfactant, (B) an organic polyisocyanate and two to two functional groups. active hydrogen group-containing compound of 8, obtained by reacting a combination of mono-alcohol NC
An soil-stabilized polyurethane foamed resin composition comprising an O-terminal prepolymer, an organic mixture comprising a viscosity modifier and a surfactant. 3. An inorganic mixture comprising (A) an aqueous silicate solution and / or an aqueous silica sol, a coupling agent, an amine catalyst and a blowing agent; (B) an organic polyisocyanate and active hydrogen having 2 to 8 functional groups. group-containing compounds, NCO-terminated prepolymer obtained by reacting a combination of monoalcohols <br/> Lumpur, viscosity modifiers and organic surface-active agents ing mixture
For soil-stabilized polyurethane foam resin, comprising:
Adult. 4. An inorganic mixture comprising (A) an aqueous silicate solution and / or an aqueous silica sol, a coupling agent, an amine catalyst, a foaming agent and a surfactant, (B) an organic polyisocyanate and two to two functional groups. NCO obtained by reacting together an active hydrogen group-containing compound and monoalcohol 8
A composition for a soil-stabilized polyurethane-based foamed resin, comprising: a base-terminated prepolymer, an organic mixture including a viscosity modifier and a surfactant. 5. The isocyanate group-terminated prepolymer is a polyphenylenepolymethylene polyisocyanate and / or diphenylmethane diisocyanate, a polyether glycol having a molecular weight of 500 to 5000 containing ethylene oxide units in an amount of 60 to 95% by weight, and having 4 carbon atoms.
An isocyanate group-terminated prepolymer obtained by reacting a monoalcohol with a monoalcohol of from 50 to 50 in combination.
5. The composition for a soil-stabilized polyurethane-based foamed resin according to any one of items 4 to 4. 6. A method for stabilizing a soil, comprising injecting and solidifying the composition for a soil stabilized polyurethane foamed resin according to any one of claims 1 to 5 into soil.