JP3191680B2 - Soil-stabilized polyurethane foam resin composition 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 containing an aqueous solution of an alkali metal silicate and an NCO-terminated 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 solve the conventional problems, the present inventors have attempted to obtain a soil-stabilized polyurethane foamed resin composition by using an organic component composed of an NCO-terminated prepolymer and an inorganic component in combination to form a soil-stabilized resin. As a result of diligent research and investigation on a resin satisfying the characteristics required as a product, an NCO-terminated prepolymer obtained by using an organic polyisocyanate and an active hydrogen group-containing compound, a silicate aqueous solution, a coupling agent and an amine-based resin The present inventors have found that the use of a surfactant as required for a catalyst and a foaming agent provides excellent performance, and have completed the present invention.

[0004]

That is, the present invention provides (A) an organic mixture comprising an NCO group-terminated prepolymer obtained by reacting an organic polyisocyanate with an active hydrogen group-containing compound and a viscosity modifier; B) A soil-stabilized polyurethane foamed resin composition comprising an aqueous silicate solution and / or an aqueous silica sol, a coupling agent, an amine-based catalyst, and an inorganic mixture comprising a blowing agent, wherein the NCO-terminated prepolymer component is Soil-stabilized polyurethane foam characterized in that the organic polyisocyanate used is an isocyanurate cyclic trimer of hexamethylene diisocyanate or a uretdione dimer of hexamethylene diisocyanate and an isocyanurate cyclic trimer of hexamethylene diisocyanate It is a resin composition.

[0005] The present invention relates to an NCO obtained by reacting (A) an organic polyisocyanate with an active hydrogen group-containing compound.
From an organic mixture comprising a base-terminated prepolymer, a viscosity modifier and a surfactant, and (B) an inorganic mixture comprising a silicate aqueous solution and / or aqueous silica sol, a coupling agent, an amine catalyst, and a foaming agent. A soil stabilized polyurethane foamed resin composition, wherein the organic polyisocyanate used for the NCO-terminated prepolymer component is hexamethylene diisocyanate isocyanurate cyclic trimer,
Or a soil-stabilized polyurethane foam resin composition comprising a uretdione dimer of hexamethylene didiisocyanate and an isocyanurate cyclic trimer of hexamethylene diisocyanate.

The present invention relates to an NCO obtained by reacting (A) an organic polyisocyanate with an active hydrogen group-containing compound.
An organic mixture comprising a base terminal prepolymer and a viscosity modifier, and (B) an aqueous silicate solution and / or aqueous silica sol,
An soil-stabilized polyurethane foamed resin composition comprising a coupling agent, an amine catalyst, an inorganic mixture comprising a foaming agent and a surfactant, wherein the organic polyisocyanate used for the NCO-terminated prepolymer component is hexagonal. A soil-stabilized polyurethane foam resin composition, which is an isocyanurate cyclic trimer of methylene diisocyanate or a uretdione dimer of hexamethylene diisocyanate and an isocyanurate cyclic trimer of hexamethylene diisocyanate.

The present invention relates to an NCO obtained by reacting (A) an organic polyisocyanate with a compound having an active hydrogen group.
An organic mixture comprising a base-terminated prepolymer, a viscosity modifier and a surfactant, and (B) an inorganic solution comprising a silicate aqueous solution and / or aqueous silica sol, a coupling agent, an amine catalyst, a foaming agent and a surfactant. A soil stabilized polyurethane foamed resin composition comprising:
The organic polyisocyanate used for the group-terminated prepolymer component is a hexamethylene diisocyanate isocyanurate cyclic trimer, or a hexamethylene diisocyanate uretdione dimer and a hexamethylene diisocyanate isocyanurate cyclic trimer, Soil stabilized polyurethane foamed resin composition.

According to the present invention, an active hydrogen group-containing compound is a polyether glycol having 2 to 8 functional groups containing 60 to 95% by weight of ethylene oxide units and having a molecular weight of 500 to 5000 or an ethylene oxide unit having 60 to 95% by weight.
% By weight containing 2 to 8 functional groups and a molecular weight of 500 to 500
The soil-stabilized polyurethane foam resin composition according to any one of claims 1 to 4, wherein a polyether glycol having 0 and a monoalcohol having 4 to 50 carbon atoms are used in combination.

The present invention is a method for stabilizing a soil, comprising injecting the above-mentioned soil stabilized polyurethane foamed resin composition into soil and consolidating the same.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION NCO which is the component (A) of the present invention
Hexamethylene diisocyanate (hereinafter referred to as HD) is used as the organic polyisocyanate for the terminal-terminated prepolymer.
I)) isocyanurate cyclic trimer or HDI
Uretdione dimer and HDI isocyanurate cyclic trimer. The isocyanurate cyclic trimer of HDI used in the present invention is HDI or NDI of HDI.
It is obtained by converting a part of the CO group into a polyol adduct and then isocyanurating it. In this HDI polyol adduct, a part (15% by weight or less) of all NCO groups is converted into a polyol adduct and then isocyanurated. As the polyol for obtaining the polyol adduct, a 2- or 3-functional polyol having a molecular weight of 3000 or less is used. Examples of the bifunctional polyol include ethylene glycol, diethylene glycol, 1,3-butanediol (hereinafter, abbreviated as 1,3-BD), 1,4-butanediol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,6-hexanediol (hereinafter abbreviated as 1,6-HD), 3-methyl-1,5
-Pentanediol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-
Examples thereof include diols such as propanediol (hereinafter abbreviated as 2BEPD), divalent polyester polyols, and polyether polyols.

Examples of the trifunctional polyol include triols such as glycerin, trimethylolethane, and trimethylolpropane, and trivalent polyether polyols. Furthermore, a bifunctional or more polyester polyol is mentioned. These polyols can be used alone or as a mixture of two or more. The preferred molecular weight of such polyols is from 62 to 1,000.

This urethanization ratio is based on all NCO groups.
It is preferably at most 15% by weight. If the content is 15% by weight or more, the characteristics of the isocyanurate trimer produced thereafter cannot be sufficiently exhibited. More preferably, it is 1 to 11% by weight.

A potassium or sodium salt of an organic acid represented by the general formula C _n H _{2n + 1} COOH is used alone or in combination as a catalyst with the obtained polyol adduct of HDI or HDI. The reaction can be performed at 100 ° C. or lower. Examples of the catalyst include propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, and potassium or sodium salts of these fatty acids.

When a co-catalyst is used simultaneously with these catalysts, the reaction proceeds more easily. As the co-catalyst, for example,
Examples include phenolic hydroxy compounds, alcoholic hydroxy compounds, and tertiary amines. The HDI isocyanuration reaction can be performed at 40 to 80 ° C. for 3 to 5 hours. The NCO content of the HDI isocyanurate cyclic trimer is 16.5 to 23.5% by weight.
In addition, in the reaction, a polyol and a trimerization catalyst can be simultaneously added to HDI to simultaneously obtain a polyol adduct and a cyclic trimer.

The mixture of the uretdione dimer of HDI and the isocyanurate cyclic trimer of HDI used in the present invention is obtained by converting a part of the NCO group of HDI into a polyol adduct, if necessary, followed by isocyanuration. can get. The HDI polyol adduct has a portion (15%) of all NCO groups.
(% By weight or less)) as a polyol adduct and then isocyanurated. As this polyol, the polyol used for obtaining an HDI isocyanurate cyclic trimer can be used. Effective catalysts for obtaining uretdione dimer of HDI and isocyanurate cyclic trimer of HDI include phosphines such as triethylphosphine, dibutylethylphosphine, tri-n-propylphosphine, trioctylphosphine and triamylphosphine. And the like. The reaction can be performed in the same manner as when obtaining a trimer. The reaction mixture thus obtained can be used, for example, by undistilled HDI by thin-film distillation.
(Monomer) can be removed. Uretdione dimer and isocyanurate cyclic trimer are the dimers 20 to
The cyclic trimer is in a ratio of 11 to 40% by weight to 60% by weight. The NCO content is between 17 and 25% by weight.

As the active hydrogen group-containing compound for obtaining the NCO-terminated prepolymer which is the component (A) of the present invention, the compound having 2 to 8 functional groups containing 60 to 95% by weight of ethylene oxide units and having a molecular weight of 500 to 5000 is used. Examples thereof include polyether glycol and monoalcohol having 4 to 50 carbon atoms. Examples of the polyether glycol having a molecular weight of 500 to 5000 include ethylene glycol,
Propanediol, butanediol, diethylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, glycerin, trimethylolpropane, penta Erythritol,
A single or a mixture of two or more of such as sucrose, glucose, fructose sorbitol, and a single or two or more of amines such as ethylenediamine, propylenediamine, diethylenetriamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylylenediamine, etc. Or ethylene oxide, propylene oxide, butylene oxide, amylene oxide,
Examples include those obtained by subjecting one or more monomers such as glycidyl ether, methyl glycidyl ether, t-butyl glycidyl ether, and phenyl glycidyl ether to addition polymerization by a known method.
Preferred ethylene oxide unit content is from 80 to 95
In weight%, the molecular weight is between 1000 and 4000. In this case, the amount of the active hydrogen group-containing compound used is 0.1 to 15 parts by weight based on 100 parts by weight of the organic polyisocyanate. Preferably, it is 2 to 10 parts by weight.

The active hydrogen group-containing compound for obtaining the NCO-terminated prepolymer component of the present invention is preferably a compound having 4 to 4 carbon atoms.
There are 50 monoalcohols. The monoalcohol includes a linear monoalcohol and a branched monoalcohol. Examples of the linear monoalcohol having 5 to 50 carbon atoms include amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol,
Examples include decyl alcohol, lauryl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, heptadecyl alcohol, octadecyl alcohol (stearyl alcohol), nonadecyl alcohol, eicosyl alcohol, seryl alcohol, and melisyl alcohol. 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. The amount of the monoalcohol used is 0.5 to 10 parts by weight based on 100 parts by weight of the polyol.

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, with carbonates being 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.

With respect to 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, it is more preferable to use a silicate aqueous solution, particularly a sodium silicate aqueous solution alone, than the aqueous silica sol alone or the combined use of the aqueous silica sol and the silicate aqueous solution in terms of physical properties of the resulting foamed resin.

Examples of the coupling agent used in the present invention include titanate-based coupling agents and silane-based coupling agents, 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 to be used is preferably 0.05 to 10.0 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, isopropyltriisostearoyl titanate, isopropyl-n-dodecylbenzenesulfonyl titanate, isopropyltris (dioctyl pyrophosphate) titanate, tetraisopropyl Bis (dioctyl phosphite titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2
-Dialkyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate,
Isopropyl trioctinoyl titanate, isopropyl propyl dimethacryloyl isostearyl titanate, isopropyl isopropyl isosteroyl diacryl titanate, isopropyl propyl tri (dioctyl phosphate) titanate, isopropyl propyl tricumyl phenyl titanate, isopropyl propyl tri (N-aminoethyl-aminoethyl) titanate And the like. Specifically, for example, Ajinomoto Prenact KR TTS, KR 46B, KR 5
5, KR 41B, KR 38S, KR 138S, K
R 238S, 338X, KR 12, KR 44, KR
9SA, 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 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. By using the coupling agent, the compatibility of the component (B) is improved, and the mixing of the component (A) and the component (B) is improved. Good and stable polyurethane foam.

Suitable examples of the amine catalyst used in the present invention include long-chain amines and imidazoles. As long-chain amines, for example, n
-Butylamine, n-octylamine, n-dodecylamine, n-hexamethylamine, etc., and N, N-dimethyl-n-dodecylamine, N, N
-Dimethyl-n-tetradecylamine, N, N-dimethyl-n-hexadecylamine, N, N-dimethyl-n-
Octadecylamine and the like. Examples of imidazoles include, for example, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole,
-Ethyl-4-methylimidazole, 1-benzyl-2
-Methylimidazole, 1-isobutyl-2-methylimidazole and the like. 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 a 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 used in the present invention includes:
In the mixing operation of (A) the organic mixture and (B) the inorganic mixture, it also has performance as a foam stabilizer for dispersion and foaming. Such surfactants include, for example, polyglycol ethers containing the required number of alkylene oxides such as propylene oxide, butylene oxide, preferably ethylene oxide, and organic compounds containing at least one reactive hydrogen atom. By condensation. Non-ionic surfactants such as alcohols, phenols, thiols, primary or secondary amines, carboxylic acids or sulfonic acids, or amides thereof, are organic compounds containing at least one reactive hydrogen atom. And a surfactant which is a polyalkylene oxide derivative of a phenolic compound having one or more alkyl substituents.

Preferred surfactants include Pluronic surfactants, which are generally
1,2-alkylene oxides or substituted alkylene oxides, such as butylene oxide, amylene oxide, phenylethylene oxide, cyclohexene oxide, propylene oxide, or mixtures thereof, are polymerized in the presence of an alkali catalyst to render them insoluble in the corresponding water. And a non-ionic surfactant obtained by condensing the polyalkylene glycol with the required number of moles of ethylene oxide 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.

There are also silicone surfactants, some of which have active hydrogen groups and some of which do not. Preferred are those containing no active hydrogen groups.
For example, N-5340 manufactured by Nippon Unicar, B-8451, B-8407 manufactured by Te Goldschmidt, and the like can be given. 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 is (A) an organic mixture,
(B) It can be added to one or both of the inorganic mixtures. As the foam stabilizer, various siloxane polyalkylene oxide block copolymers can be mentioned, and those which can be dispersed or dissolved in water are selected, and the selection is determined by the formulation. By adding the compound, a good foam having a good expansion ratio can be obtained.

In the present invention, (B) a dispersant, a thickener, an antioxidant, a heat resistance imparting agent,
Antioxidants can be added.

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 aqueous solution of the alkali metal silicate is treated with HDI
Isocyanurate cyclic trimer (hereinafter abbreviated as HDI trimer) or HDI uretdione dimer (hereinafter H
When reacted with a mixture of a dimer of DI) and a trimer of HDI, the isocyanate phase reacts with water and the carbon dioxide produced contributes to foaming in the material, and some of the carbon dioxide Reacts with the surrounding silicate aqueous phase to gel the interface. The resulting foam has the properties of a silicic acid foam containing a non-agglomerated zone of foamed polyurea and is easily crushed,
The strength is small. 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 friable 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 be obtained if the substance to be mixed with the aqueous silicate solution is a water-dispersible prepolymer having NCO groups at the end groups. The use of a prepolymer results in a homogeneous distribution of the organic and aqueous inorganic phases,
As a result, chemical interactions increase and a new type of composite material is obtained. Water-dispersed prepolymers with NCO-terminated end groups have the special effect of forming a colloidal fibrous structure, so that the two phases can exist as aggregated phases. That is, a homogeneous composite material is obtained, which has both advantages of organic and inorganic substances.

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. 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, when an aqueous solution of an alkali metal silicate is reacted with a low molecular weight isocyanate such as MDI, the isocyanate group reacts with water, and the generated carbon dioxide contributes to foaming in the substance. Some react with the surrounding aqueous silicate phase to 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 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 viscosities 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 can be adopted. 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. 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 of the components in the tank is pressurized and injected therein, and a predetermined amount of each component is uniformly mixed through a static mixer, and injected into a predetermined soil such as unstable rock or ground,
A method of curing and consolidating and stabilizing can be exemplified.
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 the static mixer and lock bolt into the
The mouth of the lock bolt is sealed 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 composition is injected in the same manner as described above. Generally, 30 to 200 kg of the composition is injected per injection hole.

[0040]

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.

[0041]

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.

[Production of HDI trimer or HDI dimer and HDI trimer] Production of HDI trimer (A-1) A 500 ml separator equipped with a thermometer, a stirrer, and a nitrogen sealed tube. 300 parts of HDI was placed in a bull flask, then 0.06 parts of potassium caprate as a catalyst and 0.3 parts of phenol as a co-catalyst were added, and reacted at 60 ° C. for 4.5 hours to carry out an isocyanuration reaction. Phosphoric acid is added as a terminator to this reaction solution.
After adding 0.042 parts and stirring at 60 ° C. for 1 hour, free HDI was removed by a molecular distillation apparatus. The obtained liquid is a pale yellow transparent liquid having an NCO content of 22.0%, a viscosity of 2100 mPa · s / 25 ° C. and free H
The DI content was 0.4%. This trimer of HDI is represented by A-1.
And

Preparation of trimer of HDI (A-2) 300 parts of HDI was placed in a 500 ml separable flask equipped with a thermometer, a stirrer, and a nitrogen sealed tube, and 1,3-polyol as a polyol.
Put 2.4 parts of BD, replace the air in the flask with nitrogen,
The mixture was heated to a reaction temperature of 80 ° C. with stirring and reacted at the same temperature for 2 hours. The NCO content was measured to be 48.8%. Next, 0.06 part of potassium caprate as a catalyst and 0.3 part of phenol as a cocatalyst were added, and an isocyanurate-forming reaction was performed at 60 ° C. for 4.5 hours. To this reaction solution, 0.042 part of phosphoric acid was added as a terminator, and the mixture was stirred at 80 ° C. for 1 hour, and then free HDI was removed by a molecular distillation apparatus. The obtained liquid was a pale yellow transparent liquid having an NCO content of 21.0%, a viscosity of 2200 mPa · s / 25 ° C, and a free HDI content of 0.4%. This trimer of HDI is called A-
Let it be 2.

Preparation of Trimer of HDI (A-3) 300 parts of HDI, 1,3-B
The reaction was carried out in the same manner as in A-2, using 10.2 parts of D, 0.06 part of potassium propionate, 0.3 part of phenol and 0.072 part of phosphoric acid as a catalyst. After reacting the polyol with HDI, NCO
The content was 45.3%. After distillation, the NCO content is 19.2%,
The viscosity was 2,800 mPa · s / 25 ° C., and the free HDI content was 0.3%. This modified product is designated as A-3.

Preparation of trimer of HDI (A-4) 300 parts of HDI, 1,6-H
D 3.3 parts, sodium undecylate 0.03 parts, phosphoric acid 0.1
The reaction was carried out in the same manner as in A-2 using 98 parts. After reacting the polyol with HDI, the NCO content was 48.6%. After distillation, NCO content 20.5%, viscosity 3000 mPa · s / 25 ° C, free H
The DI content was 0.4%. This trimer of HDI is designated as A-4
And

The dimer of HDI and the trimer of HDI (A-
Production of 5) 300 parts of HDI and 6.4 NPG using the same apparatus as A-2.
And 0.4 parts of tributylphosphine and 0.6 parts of phosphoric acid were reacted in the same manner as in A-2. After the reaction, the NCO content is 3
7.1%. After distillation, the NCO content was 21.2% and the viscosity was 21.
The content was 5 mPa · s / 25 ° C. and the content of free HDI was 0.2%. The HDI dimer was 32% and the HDI trimer was 28%. This HDI dimer and HDI trimer is designated as A-5. The free HDI was determined by gas chromatography analysis. The content of the HDI dimer and HDI trimer was determined from a calibration curve based on the area percentage of each peak obtained by gel permeation chromatography using a differential refractometer.

The dimer of HDI and the trimer of HDI (A-
Production of 6) 300 parts of HDI, 2-BEP using the same device as A-5
The reaction was carried out in the same manner as in A-5 using 6.0 parts of D, 0.3 parts of tributylphosphine and 0.33 parts of methyl paratoluenesulfonate. After the reaction, the NCO content was 39.0%. After distillation, the NCO content was 21.9%, the viscosity was 170 mPa · s / 25 ° C, and the free HDI content was 0.2%. 43% of dimer of HDI, H
The trimer of DI was 31%. This HDI dimer and H
The trimer of DI is designated as A-6.

Examples 1 to 14 and Comparative Examples 1 to 3 Organic polyisocyanates (HDI trimer or HDI dimer and HDI trimer) and an active hydrogen group-containing compound shown in Tables 1 to 3 were used. After raising the temperature to 0 ° C., the mixture was reacted for 3 hours to obtain an NCO-terminated prepolymer. A viscosity modifier and, if necessary, a surfactant were added thereto to prepare (A) an organic mixture. On the other hand, sodium silicate 50 shown in Tables 1 to 3
%, Water, an amine-based catalyst, a coupling agent, and a surfactant, if necessary, and mixed at a high speed for 15 minutes to obtain an aqueous solution of (B) an inorganic mixture. 5 ℃ or 25 ℃
After standing for 24 hours in an atmosphere, 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) component inorganic mixture are charged into a machine tank of an injector, and discharged into a beaker of a fixed amount of 500 ml through a liquid sending pump and a static mixer to be solidified. I got Table 1 shows the reactivity and the physical property test results of the foam at this time.
3 are shown. The amounts of the various components used in Tables 1 to 3 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 of foam appearance: ：: good ×: soft and poor (2) Uniaxial compressive strength The test was performed according to JSF T511 (uniaxial compressive test method for soil based on the Japan Society of Soil Engineering). (3) Combustibility The test was performed according to ASTM-D-1692.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

According to the present invention, (A) the viscosity of the organic mixture is low, so that the workability is good, the permeability to the soil and the filling property 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] HDI (1): a product obtained by reacting HDI with 1,3-BD and having an NCO content of 45.3% PPG (1): having 2 functional groups, a molecular weight of 3500 and an EO content of 65% PPG ( 2): Functional group 2, molecular weight 3000, EO content 85% PPG (3): Functional group 2, molecular weight 2000, EO content 95% PPG (4): Functional group 2, molecular weight 400, EO content 80% Monoalcohol (1) ): Octyl alcohol Monoalcohol (2): 2-ethyl-1,3-hexanol silicate aqueous solution: Toso Sangyo Co., Ltd., a solution of 5 parts of water in 100 parts of No. 2 (N5) Tertiary amine catalyst (1): N, N-dimethyl-n-dodecylamine Tertiary amine catalyst (2): N, N-dimethyl-n-tetradecylamine imidazole-based catalyst: 2-methylimidazole Coupling agent: Nihon Uni Car-made, A-174 Coupling agent: Nippon Unicar, A-187 Surfactant: T-Gold Schmidt, B8541

Example 15 A 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, 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 drilling angle of 25 to 35 ° was formed at intervals of 2 m by a 42 mmφ bit leg auger on a tunnel roof having a crush zone.
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 the ratio shown in Table 3.
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 .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C09K 103: 00

Claims (6)

(57) [Claims] 1. An organic mixture comprising (A) an NCO group-terminated prepolymer obtained by reacting an organic polyisocyanate with an active hydrogen group-containing compound and a viscosity modifier,
(B) a soil-stabilized polyurethane foamed resin composition comprising an aqueous silicate solution and / or an aqueous silica sol, a coupling agent, an amine catalyst, and an inorganic mixture comprising a foaming agent, wherein the NCO-terminated prepolymer component is Wherein the organic polyisocyanate used for is a isocyanurate cyclic trimer of hexamethylene diisocyanate, or a uretdione dimer of hexamethylene diisocyanate and an isocyanurate cyclic trimer of hexamethylene diisocyanate. Foam resin composition. 2. An organic mixture comprising (A) an NCO group-terminated prepolymer obtained by reacting an organic polyisocyanate with an active hydrogen group-containing compound, a viscosity modifier and a surfactant, and (B) a silicate. An soil-stabilized polyurethane foamed resin composition comprising an aqueous solution and / or an aqueous silica sol, a coupling agent, an amine-based catalyst, and an inorganic mixture comprising a blowing agent, wherein the organic polyisocyanate is used for an NCO-terminated prepolymer component. Is an isocyanurate cyclic trimer of hexamethylene diisocyanate, or a uretdione dimer of hexamethylene didiisocyanate and an isocyanurate cyclic trimer of hexamethylene diisocyanate. 3. An organic mixture comprising (A) an NCO group-terminated prepolymer obtained by reacting an organic polyisocyanate with an active hydrogen group-containing compound, and a viscosity modifier;
(B) a soil-stabilized polyurethane foamed resin composition comprising an aqueous silicate solution and / or an aqueous silica sol, a coupling agent, an amine-based catalyst, a foaming agent and a surfactant; The organic polyisocyanate used for the group-terminated prepolymer component is a hexamethylene diisocyanate isocyanurate cyclic trimer, or a hexamethylene diisocyanate uretdione dimer and a hexamethylene diisocyanate isocyanurate cyclic trimer, Soil stabilized polyurethane foam resin composition. 4. An organic mixture comprising (A) an NCO group-terminated prepolymer obtained by reacting an organic polyisocyanate with an active hydrogen group-containing compound, a viscosity modifier and a surfactant, and (B) a silicate An soil-stabilized polyurethane foamed resin composition comprising an aqueous solution and / or an aqueous silica sol, a coupling agent, an amine catalyst, a foaming agent and a surfactant, comprising: an NCO-terminated prepolymer component; Soil-stabilized polyurethane foam characterized in that the organic polyisocyanate used is an isocyanurate cyclic trimer of hexamethylene diisocyanate or a uretdione dimer of hexamethylene diisocyanate and an isocyanurate cyclic trimer of hexamethylene diisocyanate Resin composition. 5. The active hydrogen group-containing compound according to claim 1, wherein the compound having an ethylene oxide unit content of 60 to 95% by weight has 2 to 2 functional groups.
8. Use of a polyether glycol having a molecular weight of 500 to 5000 or a polyether glycol having a functional group number of 2 to 8 and containing a ethylene oxide unit of 60 to 95% by weight and a molecular weight of 500 to 5000 and a monoalcohol having 4 to 50 carbon atoms. The soil-stabilized polyurethane foamed resin composition according to any one of claims 1 to 4, wherein 6. A method for stabilizing a soil, comprising injecting and consolidating the soil-stabilized polyurethane foamed resin composition according to any one of claims 1 to 5 into soil.