JP3125287B2 - Composition for soil-stabilized polyurethane foam resin, and soil stabilization method using the composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for a soil-stabilized polyurethane-based foamed resin, comprising an NCO-terminated prepolymer and an aqueous silicate solution and / or aqueous silica sol 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 used by mixing with a metal salt aqueous solution containing a curing accelerator. The invention has been 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 curing agent containing is disclosed. Also, JP-A-4-2832
No. 90 describes an injection 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 a similar invention,
JP-B-7-72271, JP-A-4-283290
In the invention of Japanese Patent Application Laid-Open Publication No. H10-157, a technique using an NCO group-containing hydrophilic urethane prepolymer obtained by reacting an organic polyisocyanate with a polyoxyalkylene mono or polyol, instead of the polyisocyanate and the reactive diluent, is disclosed. Furthermore, JP-A-5-78667 discloses that
There is disclosed a rock consolidation chemical solution containing an aqueous solution of an alkali metal silicate and an NCO group-containing 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. In order to improve such problems of the known art, the present inventors have proposed an NCO for obtaining a soil-stabilized polyurethane-based foamed resin.
As a result of intensive studies and investigations on the characteristics required as a soil stabilizing resin in a composite system consisting of an organic and inorganic aqueous liquid consisting of a base-terminated prepolymer, the coupling agent, amine catalyst and viscosity It has been found that by using a surfactant in combination with a modifier, not only the disadvantages of the prior art can be improved, but also the reaction rate is appropriate, the permeability into the soil and the filling property are excellent, and the soil can be stabilized. Thus, the present invention has been completed.

[0004]

That is, the present invention provides:
(A) a diphenylmethane diisocyanate dimer compound as a part of an organic polyisocyanate, an active hydrogen group-containing compound and a monoalcohol are used in combination, and an organic mixture comprising an NCO group-terminated prepolymer and a viscosity modifier obtained by reacting; (B) A soil stabilized polyurethane foamed resin composition comprising an aqueous silicate solution and / or aqueous silica sol, a coupling agent, an inorganic mixture comprising an amine catalyst and a foaming agent.

The present invention relates to (A) a diphenylmethane diisocyanate dimer compound as a part of an organic polyisocyanate, an active hydrogen group-containing compound and a monoalcohol in combination, and an NCO-terminated prepolymer obtained by reacting the compound and a viscosity modifier. And an organic mixture comprising a surfactant and (B) an aqueous silicate solution and / or an aqueous silica sol,
A soil-stabilized polyurethane-based foamed resin composition comprising a coupling agent, an amine-based catalyst, and an inorganic mixture including a foaming agent.

The present invention relates to (A) a diphenylmethane diisocyanate dimer compound as a part of an organic polyisocyanate, an NCO group-terminated prepolymer obtained by reacting an active hydrogen group-containing compound and a monoalcohol in combination, and a viscosity modifier. Soil-stabilized polyurethane foam resin comprising: an organic mixture consisting of: (B) an inorganic mixture consisting of (B) an aqueous silicate solution and / or aqueous silica sol, a coupling agent, an amine catalyst, a foaming agent and a surfactant. The composition for use.

The present invention relates to (A) a diphenylmethane diisocyanate dimer compound as a part of an organic polyisocyanate, an active hydrogen group-containing compound and a monoalcohol in combination, and an NCO group-terminated prepolymer obtained by reacting the compound and a viscosity modifier. And (B) an aqueous silicate solution and / or an aqueous silica sol,
A soil stabilized polyurethane foamed resin composition comprising a coupling agent, an amine catalyst, an inorganic mixture comprising a foaming agent and a surfactant.

The present invention relates to a polyphenylenepolymethylene polyisocyanate (hereinafter abbreviated as polymeric MDI) containing 0.1 to 30% by weight of a diphenylmethane diisocyanate dimer compound as an NCO group-terminated prepolymer. ~ 3
Diphenylmethane diisocyanate containing 0% by weight of diphenylmethane diisocyanate dimer compound,
Alternatively, a polyphenylenepolymethylene polyisocyanate containing 0.1 to 30% by weight of a diphenylmethane diisocyanate dimer compound is used in combination with diphenylmethane diisocyanate, and an ethylene oxide unit of 60% is used.
-95% by weight containing 2-8 functional groups, molecular weight 500-
A composition for a soil-stabilized polyurethane foam resin, which is obtained by reacting 5,000 polyether glycols and a monoalcohol having 4 to 50 carbon atoms in combination.

The present invention is a soil stabilizing method characterized by injecting the above-mentioned composition for soil-stabilizing polyurethane foam resin into soil and consolidating it.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION NCO which is the component (A) of the present invention
The organic polyisocyanate for obtaining the group-terminated prepolymer is a polyisocyanate containing 0.1 to 30% by weight of a diphenylmethane diisocyanate dimer compound (hereinafter abbreviated as MDI dimer compound). Examples of the polyisocyanate containing the MDI dimer compound include diphenylmethane diisocyanate (hereinafter referred to as M
DI), or MDI
What was purified as a dimer compound may be added to another polyisocyanate. Such other polyisocyanates include, for example, p-phenylene diisocyanate, m-phenylene diisocyanate,
1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, 4,
4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2 '
-Diphenylpropane-4,4'-diisocyanate,
Aromatic polyisocyanates such as 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, toluene diisocyanate (hereinafter abbreviated as TDI), MDI, and polymeric MDI; tetramethylene diisocyanate; Examples thereof include aliphatic diisocyanates such as hexamethylene diisocyanate, and alicyclic diisocyanates such as hydrogenated TDI, hydrogenated MDI, and 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. Of these, preferred organic polyisocyanates are MD
I, polymeric MDI, isomers thereof, MDI is 60-85% by weight of 4,4'-MDI,
5 to 30% by weight of 2,4'-MDI, 2,2'-MDI1
-5% by weight, and the 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 usage ratio of MDI and polymeric MDI is M
Polymeric MDI85 to 15 to 90 parts by weight of DI
To 10 parts by weight.

The active hydrogen group-containing compound having 2 to 8 functional groups for obtaining the NCO group-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 preferred use amount of such a monoalcohol is 0.5 to 10 parts by weight based on 100 parts by weight of an 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. The preferred amount of such a viscosity modifier is NCO
It is 1 to 15 parts by weight based on 100 parts by weight of the base terminal prepolymer.

Regarding the aqueous silicate solution of the component (B) used in the present invention, for example, the aqueous silicate solution is generally called water glass, and contains 20 to 40% by weight of silicon dioxide and 5 to 5% of sodium oxide. An aqueous solution containing 〜20% by weight is preferred. Most suitable for the present invention are 28 to 32% by weight of silicon dioxide and 11 to 13% by weight of sodium oxide.
It is a water glass contained. The aqueous silica sol is a transparent colloid liquid containing, for example, 15 to 20% by weight of silica as a solid content and using water as a dispersion medium. In the present invention, an aqueous silica sol can be used alone or in combination with an aqueous silicate solution. A method in which an aqueous silicate solution, particularly an aqueous sodium silicate solution, is used alone is preferable from the viewpoint 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 organic mixture and (B) the inorganic 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.

Examples of the silane coupling agent include vinyl silane compounds such as γ-methacryloxy propyl trimethoxy silane and vinyl triethoxy silane;
Epoxysilane compounds such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimex Examples include an aminosilane compound such as silane and a mercaptosilane compound such as γ-mercaptopropyltrimethoxysilane. Specifically, for example,
A-174 and A-187 manufactured by Nippon Unicar are preferred.

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 organic mixture and (B) the inorganic 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. 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. The surfactant can be added to one or both of (A) the organic mixture and (B) the inorganic mixture.

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 (B).

In the present invention, (A) the organic mixture and (B) the inorganic mixture are those in which the NCO content of the NCO group-terminated prepolymer in the organic mixture is not more than the equivalent to the 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 organic mixture and (B) an inorganic aqueous 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) organic mixture and the (B) inorganic aqueous mixture and to increase the contact area between the two layers as much as possible. An active hydrogen group-containing compound that 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, a double-ended polyether glycol is used, and preferably,
A branched monoalcohol is 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 low molecular weight isocyanates such as MDI, the NCO groups react with water, the carbon dioxide formed contributes to foaming in the material, and some of the carbon dioxide reacts with the surrounding aqueous silicate phase. Gel the interface. The foam thus obtained has the properties of a silicic acid foam containing a non-agglomerated zone of foamed polyurea, is easily crushed, and has low strength. 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 these combinations, a colloidal fiber structure is formed, so that the two phases can exist as an aggregate phase, and a homogeneous composite material is obtained, and the advantages of each of the organic and inorganic substances are sufficiently utilized. Will be demonstrated.

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 (A) organic mixture and the (B) inorganic aqueous mixture of the present invention is a soft or unstable ground, bedrock, shatter zone having many voids and cracks. Injection and consolidation into soil such as a layer are performed, but there is no particular limitation on the method of injection and consolidation, and any known method may be used. For example, using a proportional compounding pump capable of controlling the injection amount, pressure, compounding ratio, etc. of (A) the organic mixture and (B) the inorganic mixture, separate (A) the organic mixture and (B) the inorganic mixture. Into the tank
Through a perforated lock bolt or injection rod having a static mixer, a check valve, etc. fixed in advance, passing through a predetermined location (for example, a plurality of holes drilled at predetermined intervals) in a rock bed, and the like, Each component in the tank is injected under pressure, a predetermined amount of each component is evenly mixed through a static mixer, and injected into a predetermined soil such as unstable rock or ground, hardened, and consolidated to stabilize. Methods can be mentioned. 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 organic-inorganic composite system in soil, that is, heterogeneity as a foam,
Instability, friability, unnecessary internal heat generation, etc. can be easily solved. Furthermore, the viscosity and reaction rate are appropriate, the permeability and filling property to soil are excellent, and the flame retardant (organic , A foamable resin having both inorganic and inorganic properties). 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 28 and Comparative Examples 1 to 3 The organic polyisocyanates, active hydrogen group-containing compounds and monoalcohols shown in Tables 1 to 5 were heated to 80 ° C. and reacted for 3 hours to give NCO groups. A terminal prepolymer was obtained. To this was added a viscosity modifier to prepare (A) an organic mixture. On the other hand, a 50% aqueous solution of sodium silicate, water, an amine catalyst and a coupling agent shown in Tables 1 to 5 were mixed at a high speed for 15 minutes to obtain an aqueous solution of (B) an inorganic mixture.
This aqueous solution was left under an atmosphere of 5 ° C. or 25 ° C. for 24 hours, but no liquid separation was observed. Next, a predetermined amount of an aqueous solution of the (A) organic mixture and a predetermined amount of the aqueous solution of the (B) inorganic mixture are charged into a machine tank of an injection machine, and are discharged and solidified into a 500 ml beaker through a liquid feed pump and a static mixer to form a foam. I got Tables 1 to 5 show the reactivity and the physical property test results of the foam at that time. The amounts of the various components used in Tables 1 to 5 are parts by weight.

[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]

According to the present invention, the viscosity of the organic mixture (A) is low, so that the workability is good, the permeability and the filling property to the soil are good, and the range of solidifying and stabilizing 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] A-1: A mixture of 15% of MDI dimer compound and 85% of polymeric MDI A-2: A mixture of 5% of MDI dimer compound and 95% of polymeric MDI A-3: MDI dimer compound 7 % And 93% of a mixture consisting of 72% 4,4'-MDI, 25% 2,4'-MDI and 3% 2,2'-MDI MDI (1): 75% 4,4'-MDI, 2,4 ' -MDI PPG (1) consisting of 23% MDI and 2% 2,2'-MDI: 2 functional groups, molecular weight 3500, EO content 80% PPG (2): 2 functional groups, molecular weight 2000, EO content 95% PPG (3) : Functional group 2, molecular weight 400, EO content 80% Monoalcohol (1): Octyl alcohol Monoalcohol (2): Dimethyl-1-octanol Sodium silicate No .: tertiary amine catalyst (1): N, N-dimethyl-n-dodecylamine manufactured by Tosao Sangyo tertiary amine catalyst (2): N, N-dimethyl-n-tetradecylamine imidazole catalyst: 2-methyl Imidazole Coupling agent (1): manufactured by Nippon Unicar, A-174 Coupling agent (2): manufactured by Nippon Unicar, A-187 Surfactant: manufactured by Te Goldschmidt, B8451 The amount of raw materials used is parts by weight. It is.

Example 29 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, Example 1 was added to each of the fixed injection ports.
The aqueous solution of (A) the organic mixture and the aqueous solution of the (B) inorganic mixture adjusted in the step (1) were used at the ratio shown in Table 1 at an injection pressure of 20 to 50 kg / c.
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 4 A hole drilling angle of 25 to 35 ° was applied to the roof of a tunnel 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, Comparative Example 1 was added to each of the fixed injection ports.
The aqueous solution of (A) the organic mixture and the aqueous solution of the (B) inorganic mixture adjusted 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 .

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Claims (6)

(57) [Claims] (A) A diphenylmethane diisocyanate dimer compound is used as a part of an organic polyisocyanate, and an active hydrogen group-containing compound and a monoalcohol are used in combination and a NCO-terminated prepolymer and a viscosity modifier obtained by reacting the compounds. A composition for a soil-stabilized polyurethane-based foamed resin, comprising: an organic-based mixture; and (B) an inorganic-based mixture including a silicate aqueous solution and / or an aqueous silica sol, a coupling agent, an amine-based catalyst, and a foaming agent. 2. An (A) diphenylmethane diisocyanate dimer compound as a part of an organic polyisocyanate, an NCO group-terminated prepolymer, a viscosity modifier and an interface obtained by reacting an active hydrogen group-containing compound and a monoalcohol in combination. An organic mixture comprising an activator, and (B)
An inorganic mixture comprising a silicate aqueous solution and / or an aqueous silica sol, a coupling agent, an amine catalyst and a blowing agent;
A composition for a soil-stabilized polyurethane foam resin comprising: (A) A diphenylmethane diisocyanate dimer compound is used as a part of an organic polyisocyanate, and an active hydrogen group-containing compound is used in combination with a monoalcohol to comprise an NCO group-terminated prepolymer and a viscosity modifier. Composition for soil-stabilized polyurethane foam resin comprising an organic mixture and (B) an inorganic mixture comprising an aqueous silicate solution and / or aqueous silica sol, a coupling agent, an amine catalyst, a foaming agent and a surfactant. object. 4. An (A) diphenylmethane diisocyanate dimer compound as a part of an organic polyisocyanate, an active hydrogen group-containing compound and a monoalcohol are used in combination and reacted to obtain an NCO-terminated prepolymer, a viscosity modifier and an interface. An organic mixture comprising an activator;
(B) A composition for a soil-stabilized polyurethane-based foamed resin comprising an aqueous silicate solution and / or an aqueous silica sol, a coupling agent, an amine-based catalyst, an inorganic-based mixture including a foaming agent and a surfactant. 5. A polyphenylene polymethylene polyisocyanate in which the organic polyisocyanate used contains 0.1 to 30% by weight of a diphenylmethane diisocyanate dimer compound as an NCO-terminated prepolymer.
Alternatively, diphenylmethane diisocyanate containing 1 to 30% by weight of diphenylmethane diisocyanate dimer compound, or polyphenylene polymethylene polyisocyanate containing 0.1 to 30% by weight of diphenylmethane diisocyanate dimer compound and diphenylmethane diisocyanate are used in combination, and an ethylene oxide unit is used for 60 to 60% by weight. 95% by weight of a polyether glycol having 2 to 8 functional groups and a molecular weight of 500 to 5000, and 4 carbon atoms
The soil-stabilized polyurethane foam resin composition according to any one of claims 1 to 4, wherein the composition is obtained by reacting a monoalcohol with 50 to 50 monoalcohols in combination. 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.