JP2002194354A - Injection chemical solution composition for filling in hole, and method for filling space with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an injection chemical liquid composition which is used for filling spaces formed between a concrete structure and a peripheral bedrock or ground in a tunnel, an underground structure, a high building base structure or the like, or spaces formed in the bedrock or ground, is little in environmental loading on a filling work, can give a foamed product that reduces a soil-staining degree, is excellent in workability and is good in storage stability. SOLUTION: This injection chemical liquid composition which is used for filling spaces and comprises an alkali silicate aqueous solution (A) and an organic polyisocyanate (B) is characterized in that the component (B) is polymeric MDI (B1) containing binuclear compounds in an amount of 20 to 70 wt.%, or an isocyanate group-terminated urethane prepolymer obtained by reacting the polymeric MDI (B1) with a active hydrogen group-containing compound (B2) having a number-average mol.wt. of 32 to 10,000 and in that the binuclear compounds in the component (B1) contains 2,2'-MDI and 2,4'-MDI in a total amount of 5 to 60 wt.%, and a method for filling spaces with the same is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for filling a gap between a concrete structure in a tunnel, an underground structure, a foundation structure of a high-rise building, etc. and a surrounding rock or the ground, or a gap formed in the rock or the ground. TECHNICAL FIELD The present invention relates to an injectable liquid medicine composition for filling voids and a method for filling voids using the same. More specifically, it is used to fill voids in the back of lining concrete or inside rock or ground during tunnel construction or high-rise building construction, etc.
Vapour-injecting chemical composition with excellent mixing properties, stable reactivity and foaming properties without being affected by water in the rock or ground, and less likely to cause soil contamination, and void filling using the same It concerns the construction method.

[0002]

2. Description of the Related Art Conventionally, a mortar filling method has been used to fill a gap between a foundation structure of a tunnel, an underground structure, a high-rise building and a surrounding rock or ground, or to fill a void created in the rock or ground. Construction methods, mortar filling method with expanded material, bentonite mortar filling method, and the like are being implemented. However, such a construction method requires a large volume of the material itself, requires large-scale facilities, and takes time to carry in, install, and other various preparations of the working machine, and thus sometimes reduces workability in a narrow space. Furthermore, when water is present in the voids, the curing of the filler is slowed down, and not only takes a long time for the construction, but also the hardening of the cement paste does not proceed, so that there is a problem that the workability and the water stoppage are reduced. . Therefore, in recent years, as a method of solving the above problems,
The use of urethane-based void fillers has been proposed and is being implemented

[0003] As such urethane-based gap filler,
JP-B-52-33412, JP-A-52-7895
No. 5, JP-A-53-93623, JP-A-55-93623
JP-A-39568, JP-A-55-122998, JP-A-6-33697, JP-A-8-3023
No. 48, Japanese Patent Application Laid-Open No. 2000-281742, and the like have been proposed.

Japanese Patent Publication No. 52-33412 discloses a filler comprising crude TDI or crude MDI, a polyol, a foaming expander, a curing accelerator and a surfactant. JP-A-52-78955 discloses a fast-curing polyurethane resin composition comprising a hydrophilic urethane prepolymer containing isocyanate groups, an organic polyisocyanate, cement and water. JP-A-53-93623
In Japanese Patent Application Laid-Open Publication No. H11-157, a technique is disclosed in which hydrophilicity is imparted to an organic polyisocyanate or an isocyanate group-terminated urethane prepolymer to improve the miscibility with cement or water. JP-A-55-39568, JP-A-55-55568
JP-A-122998 discloses a technique for improving foaming curability by using a tertiary amino group-containing polyol. JP-A-6-33697, and T solution mainly composed of polyisocyanate, two liquids of R solution mainly composed of polyol, T solution at a volume ratio: mixed at a ratio of 1: R solution = 2 A method of filling a gap, such as a tunnel, has been proposed, which is characterized by injecting into the gap, foaming and hardening and filling the gap. JP-A-8-302348 describes that
Patent Document 1: Polyhydroxy compound obtained by reacting an aqueous solution of sodium silicate (Component A) with an isocyanate compound (Component B) to foam and harden it by ring-opening addition polymerization of propylene oxide to a polyfunctional alcohol in Component A; A void filler characterized by containing a surfactant has been proposed. Japanese Patent Application Laid-Open No. 2000-281742 discloses that a liquid A containing a polyol, a nullating catalyst and water, and a liquid B containing isocyanate as a main component are mixed at a weight ratio of the liquid A and the liquid B. , Solution A: solution B: set in the range of 1: 3 to 1: 7, and the amount of water is set in the range of 0.8 to 2.5% by weight of the total amount of solution A and solution B. The illustrated cavity filling composition is shown.

[0005]

However, the fillers described in JP-B-52-33412 and JP-A-6-33697 do not consider the storage stability and high viscosity of the liquid in winter. JP-A-52-78955,
According to the technique disclosed in JP-A-53-93623, the mixing property with water is improved.
In the techniques disclosed in JP-A-39568 and JP-A-55-122998, the reactivity between the polyisocyanate and the polyol is improved, so that the strength development becomes faster. Viscosity rises during the process, resulting in poor liquid transfer, resulting in insufficient filling and voids. Furthermore, the resulting hydrophilic isocyanate group-terminated urethane prepolymer obtained by modifying the polyisocyanate composition with a hydrophilic active hydrogen group-containing compound has an improved affinity for water contained in the rock or ground, and is thus exposed to rainwater or the like. Leachables are likely to be generated and cause contamination of groundwater, well water, and river water. The technology disclosed in JP-A-8-302348 has an insufficient expansion ratio. JP-A-2000-
In the technology disclosed in Japanese Patent No. 281742, no consideration is given to the compatibility between the liquid A and the liquid B and the water contamination of the obtained foam.

In the case of using an isocyanate group-terminated urethane prepolymer, a method using a diluent has a viscosity lowering effect by dilution, so that it is possible to suppress a rise in viscosity during liquid feeding, and furthermore, a method of preparing a liquid between a top of an arch and a ground. Filling of voids,
In some cases, the gap between the tunnel excavated by the shield method and the lining consisting of the ring connecting the lining of this tunnel can be filled, and the permeability to rock and ground can be improved. is there.

[0007] However, regarding the general urethane-based injectable chemicals, including the injectable chemical composition for filling voids for tunnel construction, refer to "Guidelines on Safety Management of Urethane Injection in Mountain Tunneling Method" (October 1992, Japan Highway Public Corporation Issuance), and injectable chemicals that meet the groundwater quality standards specified in these guidelines are required. That is, the diluent is generally taken out of the resin gradually with time after being taken into the cured resin, which is not preferable from the viewpoint of preventing soil contamination.

If these diluents are not used in terms of environmental protection, the viscosity of the system is inevitably increased and solidification occurs at a low temperature, making it difficult to put into practical use. It has been difficult to achieve both.

[0009]

SUMMARY OF THE INVENTION Accordingly, the present inventors have developed an air gap, which is used to fill a gap between a concrete structure in a tunnel, an underground structure, a foundation structure of a high-rise building, etc., and surrounding rock or ground. Injectable liquid chemical composition for filling material, which has a small environmental load during filling work, can reduce the degree of soil contamination, is excellent in workability, and has good storage stability. As a result of diligent research to provide a product, it has been found that an injectable chemical composition using an organic polyisocyanate using a diphenylmethane diisocyanate-based polynuclear condensate of a specific composition and an aqueous alkali silicate solution can solve the above problems. This has led to the present invention.

That is, the present invention provides the following (1) to (7)
It is shown in. (1) In an injectable chemical composition for filling voids comprising an aqueous solution of an alkali silicate (A) and an organic polyisocyanate (B), (B) a polynuclear condensate of diphenylmethane diisocyanate containing 20 to 70% by mass of a binuclear substance ( B1), wherein said binuclear body contains 2,2'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate in a total amount of 5 to 60% by mass, Composition.

(2) In the injectable chemical composition for filling voids, comprising an aqueous solution of an alkali silicate (A) and an organic polyisocyanate (B), (B) contains 20 to 70% by mass of a binuclear substance.
Is obtained from the reaction of the contained diphenylmethane diisocyanate-based polynuclear condensate (B1) with an active hydrogen group-containing compound (B2) having a number average molecular weight of 32 to 10,000, and wherein the binuclear in (B1) is The injectable drug composition according to any one of claims 1 to 3, wherein the composition contains 2,2'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate in a total amount of 5 to 60% by mass.

(3) Further active hydrogen group-containing compound (C)
The injectable liquid composition for filling a void according to the above (1) or (2), comprising:

(4) The injection liquid composition for filling a void according to any one of the above (1) to (3), further comprising a catalyst (D).

(5) The injectable drug composition for filling a void according to any one of (1) to (4), further comprising a surfactant (E).

[0015] (6) further characterized in that it consists of a flame retardant (F), wherein (1) to one of the gap-filling injection chemical composition (5).

(7) A method of filling a gap, characterized by injecting the liquid medicine composition of any of the above (1) to (6) into a gap and solidifying it.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, an injectable drug solution composition for filling voids will be described. The injectable chemical composition for filling voids of the present invention (hereinafter referred to as injectable chemical composition) is an injectable chemical composition for filling voids comprising an aqueous alkali silicate solution (A) and an organic polyisocyanate (B). Accordingly, an active hydrogen group-containing compound (C), a catalyst (D), a surfactant (E), and a flame retardant (F) can be used.

The consolidation reaction of the injectable chemical composition of the present invention is not clear because it is extremely complicated, but it is considered that the following reactions proceed in parallel and consolidate. (1) When an alkali silicate aqueous solution (A) and an organic polyisocyanate (B) are mixed, a silanol group formed in (A) reacts with an isocyanate group in (B) to form silicic anhydride. A urethane complex is formed. (2) Simultaneously, the isocyanate group in (B) reacts with the water in (A) to generate carbon dioxide gas, thereby forming a polymer by urea bond or a silicic acid-urea crosslinked complex. (3) Further, a part of the by-produced carbon dioxide gas is dissolved in (A), and the alkali silicate in (A) is gelated to form a silicic anhydride gel. (4) Further, when the active hydrogen group-containing compound (C) is present, the hydroxyl group in (C) reacts with the isocyanate group in (B) to form a urethane bond.

The carbon dioxide gas generated by the reaction between (B) and water and the water vapor generated by the reaction heat generated during the reaction between (A) and (B) and the reaction between (B) and (C) cause: The silica-urethane composite forms a foam and increases its volume. At this time, foaming occurs, and due to the foaming pressure at the time of the foaming, the silicic acid-urethane composite is used to form a gap between a concrete structure in a tunnel, an underground structure, a foundation structure of a high-rise building, and the surrounding rock or ground. It becomes easy to enter.

Hereinafter, the components of the injectable drug solution composition of the present invention will be described. As described above, the aqueous alkali silicate solution (A) in the present invention is a component that mainly forms a silicic anhydride-urethane complex by reacting its silanol group with an isocyanate group in (B) described below.

The above (A) has the general formula: Na ₂ O.
Sodium silicate represented by nSiO ₂ (sodium silicate)
And a molar ratio of SiO ₂ (silicon dioxide) / Na ₂ O (sodium oxide) in the sodium silicate is represented by n. This n is generally 1 to 5, but is preferably 2 to 5 and particularly preferably 2 to 4 in the present invention. When n is smaller than 2, the pH value of the aqueous solution of sodium silicate becomes high, so that it becomes difficult to control the reaction in the process of forming the above-mentioned anhydrous silicic acid-urethane complex. On the other hand, when n is greater than 5, the viscosity of (A) becomes high when compared at the same solid content, and the miscibility with the organic polyisocyanate (B) specified in the present invention becomes poor. In such a case, the workability at the time of deterioration is poor, and the strength as an injectable drug solution composition is hardly developed, which is not preferable.

The solid content of (A) is usually 1
It is preferably from 0 to 70% by mass, particularly from 20 to 50% by mass.
It is preferable to adjust so as to be mass%. Specifically, No. 2 sodium silicate N6, No. 2 sodium silicate Q3, No. 2 sodium silicate H3, No. 2 sodium silicate T8, No. 3 sodium silicate,
No. 4 sodium silicate (all manufactured by Tosao Sangyo Co., Ltd.) and the like.

The organic polyisocyanate (B) used in the present invention is a polynuclear condensate of diphenylmethane diisocyanate (hereinafter abbreviated as polymeric MDI) (B1).
Or polymeric MDI (B1) and a number average molecular weight of 32 to
It is an isocyanate group-terminated urethane prepolymer obtained from the reaction with 10,000 active hydrogen group-containing compounds (B2).

The viscosity of (B) is determined not only by the mixing property with the aqueous alkali silicate solution (A) and the active hydrogen group-containing compound (C) used as required, but also by the injection property into the voids and the permeability. For improvement, the pressure is preferably 300 mPa · s or less at 25 ° C., and more preferably 50 to 200 mPa · s. If the viscosity is too large, not only the workability tends to decrease, but also the pump pressure must be increased when injecting the chemical solution, which tends to damage the line. The isocyanate content of (B) is 20 to 32% by mass, preferably 2 to 32% by mass.
The content is 5 to 32% by mass, and more preferably 28 to 32% by mass.

Polymeric MDI used in the present invention
(B1) means a mixture of organic isocyanate compounds having different degrees of condensation obtained by, for example, converting a condensation mixture (polyamine) obtained by a condensation reaction between aniline and formalin into an isocyanate group by phosgenation or the like. I do. Various compositions of (B1) can be obtained by changing the raw material composition ratio, reaction conditions, the mixing ratio of various polymeric MDI, and the like during the condensation of aniline and formalin. (B1) used in the present invention
Is a reaction liquid after conversion to isocyanate groups, or a bottom liquid obtained by removing a solvent from the reaction liquid or distilling and separating a part of diphenylmethane diisocyanate (hereinafter abbreviated as MDI), reaction conditions and separation conditions. mixtures of several, may further supplemented with MDI. The composition of (B1) used in the present invention has a so-called binuclear structure having two isocyanate groups and two benzene rings in one molecule.
Of a so-called polynuclear mixture having at least three isocyanate groups and three or more benzene rings in one molecule.
A mixture comprising 30 wt%, preferably binuclear bodies 3
0-60% by weight and a polynuclear mixture is a mixture containing 70 to 40 wt%. Further, a part of the isocyanate group may be modified to biuret, allophanate, carbodiimide, oxazolidone, amide, imide, isocyanurate, uretdione, or the like.

When the binuclear content in (B1) is lower than 20% by mass, the viscosity reduction of (B) cannot be achieved, and when it is higher than 70% by mass, the binuclear itself solidifies at low temperature ( Crystallization)
This is not preferred because of the strong influence of water and especially the storage stability in winter.

Binuclear, ie, M, in polymeric MDI
DI is 2,2'-diphenylmethane diisocyanate (hereinafter abbreviated as 2,2'-MDI), 2,4'-diphenylmethane diisocyanate (hereinafter 2,4'-MDI
) And 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as 4,4'-MDI). Polymeric M used in the present invention
The binuclear in DI (B1) is 2,2'-MDI and 2,
4'-MDI in total of 5 to 60% by mass, 4,4'-MD
I is contained in an amount of 95 to 40% by mass, and the total of 2,2'-MDI and 2,4'-MDI is preferably 10 to 5%.
0% by mass and 90 to 50% by mass of 4,4'-MDI.

2,2'-MDI and 2,4 'in binucleate
If the total content of -MDI is lower than 5% by mass, it is not preferred because the effect of solidification (crystallization) at low temperatures is strongly exerted and the compatibility with the active hydrogen group-containing compound is reduced. When it is higher than 60% by mass, 4,4'-MDI
2,2'-MDI and 2,4'-MDI are more difficult to develop strength due to their flexible molecular structure, and are unsuitable as a void-filling injection liquid composition for tunnel construction, which requires strength. It is.

The binuclear content and the binuclear isomer composition ratio of (B1) are based on the area percentage of each peak obtained by gel permeation chromatography (GPC) or gas chromatography (GC). Can be determined from the calibration curve.

[0030] In addition, if a small amount, tetramethylene diisocyanate, hexamethylene diisocyanate,
Aliphatic diisocyanates such as 3-methyl-1,5-pentane diisocyanate and lysine diisocyanate, furthermore, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate,
Alicyclic diisocyanates such as hydrogenated diphenylmethane diisocyanate and tetramethylxylene diisocyanate can also be used. Further, those obtained by modifying a part of these isocyanate groups with biuret, allophanate, isocyanurate, uretdione, oxazolidone, amide, imide, and the like can also be used. These can be used alone or as a mixture of two or more.

Next, as the organic polyisocyanate (B), an isocyanate group-terminated urethane prepolymer obtained by reacting the above-mentioned polymeric MDI (B1) with an active hydrogen group-containing compound (B2) described below will be described.

(B1) is as described above.
(B2) has a number average molecular weight of 32 to 10,000,
Preferably it is 100-5,000. The average number of functional groups is preferably 1 or more, and particularly preferably 1 to 4. Specifically, low molecular monools having a molecular weight of less than 500, low molecular polyols, low-molecular monoamines, low molecular polyamine, low molecular amino alcohol, a number average molecular weight of 500 or more polymeric polyols. These can be used alone or as a mixture of two or more.

As the low molecular weight monol, methanol,
Examples include ethanol, propanol, butanol, octanol, lauryl alcohol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and the like.

Examples of the low molecular polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, cyclohexane-1,
4-diol, cyclohexane-1,4-dimethanol, hydrogenated bisphenol A, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, diglycerin and the like.

[0035] As the low molecular monoamines include ethylamine, propylamine, butylamine, diethylamine,
Examples include dibutylamine, aniline, N-methylaniline and the like.

Examples of the low molecular weight polyamine include tetramethylenediamine, hexamethylenediamine, tolylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-
Dimethyl-4,4'-diaminodicyclohexylmethane, diethyltriamine, dibutyltriamine, dipropylenetriamine and the like can be mentioned.

Examples of the low molecular weight amino alcohol include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, Nn
-Butylethanolamine, Nn-butyldiethanolamine, N- (β-aminoethyl) ethanolamine, N- (β-aminoethyl) isopropanolamine and the like.

Examples of the high molecular polyol include polyether polyols, hydroxyl-containing amine polyethers, amino alcohols, polyoxyethylene monoalkyl ethers, dibasic acids such as adipic acid and phthalic anhydride, and ethylene glycol, diethylene glycol, and trimethylolpropane. Various polyester polyols obtained by a dehydration condensation reaction with glycols and triols such as lactone polyols obtained by ring-opening polymerization of ε-caprolactam, polycarbonate polyols, acrylic polyols, polybutadiene polyols, phenols such as novolak resins and resol resins So-called polymer polyols obtained by radical polymerization of vinyl monomers such as acrylonitrile and styrene in polyols, and tetrahydrofura The cationic polymerization include polytetramethylene polyols and the like obtained.

The active hydrogen group-containing compound (B2) preferred in the present invention comprises 5% by mass of a propylene oxide unit.
Containing more than a number average molecular weight of polyether polyol is 100 to 10,000, preferably propylene oxide units contain 30 to 100 wt%, the polyether polyol number average molecular weight of 150～5,000 Yes, particularly preferably a polyether polyol containing 50 to 100% by mass of a propylene oxide unit and having a number average molecular weight of 200 to 3,000.

When the number average molecular weight of (B2) is less than 100, the urethane group concentration in the obtained foam becomes high, and the foam exhibits strength but may be solidified at a low temperature. On the other hand, if it is larger than 10,000, the urethane group concentration will be low, and the strength will be insufficient.

When the content of the propylene oxide unit (B2) is lower than 5% by mass, hydrophilicity is imparted to the foam obtained by the reaction with the active hydrogen group-containing compound of the present invention, which may cause soil contamination. (B1) and (B
When the isocyanate group-terminated urethane prepolymer obtained by the reaction 2) is used for the organic polyisocyanate (B), the hydrophilicity described above is imparted in the reaction with the active hydrogen group-containing compound (C) described below. Unlike the case of using an isocyanate group-terminated urethane prepolymer or a tertiary amino group-containing polyol, since the viscosity rise is gentle due to the reaction, insufficient filling due to poor flow and formation of voids do not occur.

The average number of functional groups in the above polyether polyol is preferably 1 to 10, particularly preferably 2 to 10.
To 6 are preferable. If the average number of functional groups is too large, viscosity reduction of (B) cannot be achieved.

In the present invention, (B2) and (C)
In the case of polyether polyol, the “average number of functional groups” in the above means the average number of functional groups of the initiator. In the case of other polyols, it is a value calculated from the total amount of terminal groups determined by the terminal group quantification method and the number average molecular weight determined by gel permeation chromatography (GPC). The content of the propylene oxide unit means the content of propylene oxide in the cyclic ether monomer to be added to the initiator.

The preferred active hydrogen group-containing compound (B2) is a polyether polyol of the present invention, known a cyclic ether monomers containing propylene oxide more than 5 wt% with an active hydrogen group-containing compound of low molecular as an initiator Obtained by the addition polymerization according to the above method. Examples of the cyclic ether monomer include ethylene oxide, propylene oxide, butylene oxide, glycidyl ether, methyl glycidyl ether, styrene oxide and the like.

Examples of the initiator used include phenol and thiol in addition to the above-mentioned low molecular monool, low molecular polyol, low molecular amino alcohol, low molecular monoamine, low molecular polyamine and the like.

In the present invention, the initiator of the polyether polyol which is a preferred active hydrogen group-containing compound (B2) is a compound having no amino group, and is specifically selected from the above-mentioned low molecular monools and low molecular polyols. Is what is done. When a low-molecular amino alcohol, a low-molecular monoamine, or a low-molecular polyamine is used as an initiator, the resulting polyether becomes a tertiary amino group-containing polyol, and the reactivity with the isocyanate group becomes unnecessarily large. The viscosity of the mixture of A) and (B) is too high, which is not preferred.

When reacting (B1) with (B2), the equivalent ratio of isocyanate group to hydroxyl group (isocyanate group / hydroxyl group) is preferably 1.5 to 500, more preferably 5 to 4
A range of 00 is preferred.

As described above, the isocyanate group-terminated urethane prepolymer used in the present invention has a propylene oxide unit and a urethane group. For this reason, since the obtained foam has strong hydrophobicity, the amount of contaminants that seeps into groundwater or the like is reduced. Furthermore, since a urethane group is introduced into the isocyanate, it can be expected that the adhesiveness to concrete and bedrock is improved.

In the present invention, the active hydrogen group-containing compound (C)
Is preferred because the strength of the foam is improved. The active hydrogen group-containing compound (C) is not particularly limited as long as it is a compound having at least two or more active hydrogen groups in one molecule, and examples thereof include an active hydrogen group-containing compound used for the isocyanate group-terminated prepolymer. . (C)
Can be used alone or in combination of two or more. The number average molecular weight of (C) is 32 to 20,000.
And particularly preferably 76 to 10,000. The average number of functional groups is preferably 1 or more, and particularly preferably 1 to 4. The active hydrogen group-containing compound (C) preferred in the present invention contains 50% by mass of a propylene oxide unit.
It is a polyether polyol containing the above and the initiator is selected from low molecular monools and low molecular polyols.

Considering the miscibility with the organic polyisocyanate (B), the compound (C) having an active hydrogen group has a number average molecular weight of 32 to 10,000, preferably 200 to 10,000.
5,000, more preferably 500 to 3,000
It is. When the number average molecular weight is less than 100, the urethane group concentration becomes high and the strength is developed, but there is a possibility that the solidification occurs at a low temperature. On the other hand, when the number average molecular weight is more than 10,000, the urethane group concentration becomes low, and the strength is insufficient, which is not preferable as an injectable drug solution composition for filling voids.

In the present invention, the catalyst (D) is used for the purpose of adjusting the reactivity of the aqueous alkali silicate solution (A), the active hydrogen group-containing compound (C) used as required, and the organic polyisocyanate (B). ) Is preferably used.
As the catalyst (D), specifically, triethylamine,
Triethylenediamine, N-methylmorpholine, N-methylimidazole, pyridine, N, N, N ', N'-tetramethylhexamethylenediamine, bis (2-dimethylaminoethyl) ether, α-picoline, N, N,
N ', N'-tetramethylpropylenediamine, N,
N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, N-methylmorpholine, 1,2
-Dimethylimidazole, 1,5-diaza-bicyclo (4,3,0) nonene-5,1,8-diazabicyclo (5,4,0) -undecene-7 (hereinafter abbreviated as DBU), and these amine catalysts An amine catalyst not containing an active hydrogen group, such as a borane salt, a DBU phenol salt, a DBU octylate, and a DBU carbonate; triethanolamine;
Amine catalysts having active hydrogen such as N, N, N'-trimethylaminoethyl-ethanolamine; tin catalysts such as dibutyltin dilaurate and stannas octoate; magnesium naphthenate, lead naphthenate, potassium acetate, potassium octylate And the like, trialkylphosphines such as triethylphosphine and tribenzylphosphine, alkoxides such as sodium methoxide, and zinc-based organometallic catalysts. The addition amount of the catalyst (D) is 0.1 in an alkali silicate aqueous solution (A)
To 20% by mass, and particularly preferably 0.5 to 15% by mass. Further, (D) is preferably blended in advance with (A). If (C) is blended with (B),
The storage stability of (B) tends to decrease.

In the present invention, the purpose is to adjust the mixability and reactivity of the aqueous alkali silicate solution (A) and the organic polyisocyanate (B) with the active hydrogen group-containing compound (C) and the flame retardant (E) described below. It is preferable to add a surfactant (D). The surfactant (D) contains a known ionic surfactant such as a fatty acid salt, an alkyl sulfonate, an alkylbenzene sulfonate, an alkylammonium salt, an alkylbenzeneammonium salt, or an alkylamino acid, and ethylene oxide in an amount of 50% by mass or more. Silicones such as polyethers obtained by ring-opening addition of alkylene oxides and various siloxane polyalkylene oxide block copolymers such as L-5340 manufactured by Nippon Unicar, B-8451 and B-8407 manufactured by T. Goldschmidt Nonionic surfactants such as a system surfactant are exemplified. Surfactant (D) can be added to (A) and / or (B). The addition amount of (D)
0.05-5 mass% is preferable with respect to (A).

In the present invention, the chemical is used in an enclosed space,
In addition, since it is often used in a situation where a heat source is nearby, a flame retardant (F) can be used. Examples of the flame retardant (F) include a halogen compound, a phosphate compound, a phosphorus compound, a nitrogen compound, a boron compound,
And sulfur-based compounds. These can be used alone or in combination. Examples of the halogen-based compound for a flame retardant include hexabromocyclododecane, 1,1,2,2.
-Tetrabromoethane, 1,2,3,4-tetrabromoethane, 1,4,5,6-tetrabromophthalic anhydride,
And tetrabromobisphenol A. Phosphate-based compounds include trimethyl phosphate,
Non-halogen phosphates such as triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, and 2-ethylhexyl diphenyl phosphate. , Tris (β-chloroethyl) phosphate,
Tris (β-chloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (1,3-diclosopropyl) phosphate, tris (2-chloroethyl) phosphate , Tris (2,4,
Halogen-containing condensed phosphates such as 6-tribromophenyl) phosphate, bis (β-chloroethyl) vinylphosphonate, triallyl phosphate and the like. Examples of the phosphorus compound include orthophosphoric acid, ammonium phosphate, ammonium polyphosphate, urea phosphate, guanylurea phosphate, polyphosphorylamide, melamine phosphate, polyphosphorylamide ammonium, phosphoryltrianilide, phosphonitrile, tris (2 -Carbamoylethyl) phosphine, tris (2-carbamoylethyl) phosphine oxide, phosphorylamide, phosphinamide, vinylphosphonic acid and the like. Trimethylolmelamine and N
-Methylol acrylamide and the like. Examples of the boron compound include boric acid, boron phosphate, ammonium borate and the like. Examples of the sulfur-based compound include thiourea, ammonium sulfate, and ammonium sulfamate. Other compounds for flame retardants include antimony trioxide, antimony tetroxide, antimony pentoxide,
Examples include inorganic compounds such as sodium antimonate, antimony trichloride, zinc chloride, tin chloride, tin dioxide, aluminum hydroxide, and magnesium hydroxide. When a bromine-based flame retardant is used, the use of an antimony compound, for example, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, etc. as a flame retardant aid improves the flame retardant effect. In the present invention, a phosphate ester-based flame retardant which is liquid at ordinary temperature and has a small specific gravity is preferable. The addition amount of the flame retardant (F) is preferably 1 to 30% by mass based on (B).

In the present invention, a foaming agent may be used in order to sufficiently fill the voids with the mixed chemical solution after filling. The foaming agent is selected from water, hydrocarbon, and hydrofluorocarbon. Since water is already present in the aqueous alkali silicate solution (A), it is not necessary to add water again. When a foaming agent is used, the amount of the foaming agent is not limited to water, ie, a hydrocarbon such as pentane or hexane, HFC-245fa, HFC-365mfc, or HFC-245mfc.
In the case of a hydrofluorocarbon such as FC-134a, it is 0 to 40% by mass based on (B).

In the present invention, in addition to the above-mentioned catalyst (C), surfactant (D), flame retardant (F) and blowing agent, cement, blast furnace slag, gypsum, calcium carbonate, clay, quicklime , Slaked lime, inorganic fillers such as bentonite, diluents, coupling agents, further dispersants, thickeners,
Various additives such as an antioxidant, a heat resistance imparting agent, an antioxidant, and a leveling agent can be added, but they should be limited to those that do not cause soil contamination.

For example, the diluent is required to be excellent in compatibility with organic polyisocyanate (B) and / or active hydrogen group-containing compound (C), excellent in viscosity, and further excellent in storage stability. Reactive diluents such as diesters of basic acids, acetates of mono- or polyhydric alcohols, alkylene carbonates, ethers, cyclic esters, acid anhydrides, various acrylates, methacrylates, and the like. Ethyl acetate, toluene, xylene,
Tetrahydrofuran, 1,1,1-trichloroethane,
Organic solvents such as methylene chloride and trichlorofluoromethane are exemplified. In the present invention, since these diluents have volatility, part or all of them are released during or after the reaction, it is preferable not to use them from the viewpoint of disaster prevention and environmental destruction.

Next, the void filling method of the present invention will be described. When the active hydrogen group-containing compound (C), the catalyst (D), and the surfactant (E) are used, it is preferable to add and mix predetermined amounts of each of them into the aqueous alkali silicate solution (A) in advance. When a flame retardant (F) or a foaming agent is used, it is preferable to add and blend it in the organic polyisocyanate (B) in advance. Aqueous alkali silicate solution (A),
A liquid containing an active hydrogen group-containing compound (C), a catalyst (D), and a surfactant (E), an organic polyisocyanate (B), and a flame retardant (F) and a foaming agent as required. And the solution B consisting of A
The liquid and the liquid B are sent using a proportional combination pump (liquid sending pump) that can control the flow rate, the pressure, and the like, respectively. The mixing ratio of the A liquid and the B liquid can be set to an arbitrary mixing ratio by changing the flow rate of each liquid sending pump. The mixing of the liquids is possible by providing a mixing head or simply joining the liquids. The injection of the mixture
Gear pump, screw pump, plunger pump,
Using an air pump, etc., a perforated lock bolt, injection rod, injection pipe with a check valve installed in the injection hole, etc.
It can be performed through an injection nozzle, an injection hose, or the like.
The injection hole may be provided on the concrete surface, or may be provided from outside the ground in some cases. The mixed liquid injected into the space in this manner foams and hardens to fill the space. In some cases, A
A method is also possible in which the liquid and the B liquid are injected from different injection holes, respectively, and the A liquid and the B liquid are collision-mixed inside the gap to foam and harden. Injection pressure is 0.05-5MPa (gauge pressure)
Is preferred. The foaming / curing of the chemical injected into the space starts immediately after the injection and is completely cured in about several hours. The apparatus used in the method of the present invention includes a raw material tank, an injection pump, an injection nozzle, an injection hose, a pressure gauge, a flow meter,
Construction is possible while loading all the raw materials and machines and equipment necessary for construction, such as an injection pump, on a mobile carrier. Furthermore, the size of the loading vehicle is sufficient with a 4-ton flat body. Therefore, according to the method of the present invention, a large amount of rapid construction can be performed with compact equipment so that mobility can be exhibited and any time can be dealt with, and since the work is unified, no special skill worker is required. Thus, for example, when used in tunnel repair work, are possible construction of a plurality of locations in a short time, also stress the natural ground can be relaxed, or to prevent collapse or the like, and the like can be suppressed the occurrence and growth of cracks The effect of is exhibited in a short time after construction.

The compounding ratio of (A) and (B) is, for example, n (molar ratio) of Na ₂ O and SiO ₂ in (A), or (B)
Since it depends on the isocyanate content and the like, it cannot be unconditionally determined, but usually the mixing ratio ((A) / (B)) of (A) and (B) is 10/100 to 10 by mass ratio.
0/10 are preferred, in particular 20 / 100-100 / 20
It is preferable to adjust so that If the compounding ratio is smaller than the lower limit, the cost of the infused drug composition becomes expensive and uneconomical, and the control of the compounding ratio with a proportional infusion pump tends to be extremely difficult, and When it is larger than the above upper limit, the solidification of the injectable drug solution composition is insufficient and becomes uncured, and even if it is solidified, the strength tends to be low, brittle and unusable.

[0059]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.
Unless otherwise specified, "%" in Examples and Comparative Examples
Indicates "% by mass".

[Preparation of Solution A] Preparation Examples 1 to 9 Using a mixer with a stirrer and having a capacity of 150 kg, the amounts shown in Table 1 were charged and uniformly prepared to prepare A-1 to A-9. . Table 1 shows the amount of each raw material charged.

[Raw material for solution A] (Aqueous alkali silicate solution) S-1: silicon dioxide / sodium oxide = 2.6 (molar ratio) solid content = 36% S-2: silicon dioxide / sodium oxide = 1. 5 (molar ratio) solid content = 36% (active hydrogen group-containing compound) H-1: polyether polyol (Sannickes GP-600 manufactured by Sanyo Chemical Industries) H-2: polyether polyol (CM-211 manufactured by Asahi Denka Kogyo) H-3: Polyether polyol (Sanix HS-211 manufactured by Sanyo Chemical Industries, Ltd.) (Catalyst) TMHDA: N, N, N ', N'-tetramethylhexamethylenediamine (Surfactant) B-8404: Silicone Surfactant TE Goldschmidt

[0062]

[Table 1]

[Synthesis of Solution B] Synthesis Examples 1 to 12 A stirrer, a thermometer, a cooler and a nitrogen gas inlet tube were attached.
Using a 150 kg capacity reactor, polyisocyanates B-1 to B-12 were synthesized. The raw material isocyanate and polyol raw material were charged amount shown in Tables 2 and 3, 80
The temperature was raised to ° C. and the reaction was carried out for 3 hours to obtain a polyisocyanate. When a flame retardant was used, it was added after the reaction was completed. Table 2 shows the types, amounts and analytical values of these raw materials. Since B-12 has a high viscosity without a diluent, it was further diluted with propylene carbonate. The low-temperature stability of these isocyanate group-terminated urethane prepolymers was measured under the following conditions. Table 2 shows the results.
3 is shown.

[Raw material for liquid B synthesis] (Organic polyisocyanate composition) (Polyisocyanate raw material) MDI-1: MDI NCO content = 33.6% 2,2′-MDI + 2,4′-MDI = 50% 4, 4′-MDI = 50% MDI-2: MDI NCO content = 33.6% 2,2′-MDI + 2,4′-MDI = 28% 4,4′-MDI = 72% MDI-3: MDI NCO content = 33.6% 2,2'-MDI + 2,4'-MDI = 0% 4,4'MDI = 100% MDI-4: MDI NCO content = 33.6% 2,2'-MDI + 2,4'-MDI = 100% 4,4'-MDI form = 0% PMDI-1: Polymeric MDI NCO content = 31.3% 2,2'-MDI + 2,4'MDI = 5% 4,4'-MDI = 45% Polynuclear mixture = 50% P DI-2: Polymeric MDI NCO content = 31.3% 2,2'-MDI + 2,4'-MDI = 6% 4,4'-MDI = 30% Polynuclear mixture = 64% PMDI-3: Polymeric MDI NCO content = 31.1% 2,2'-MDI + 2,4'-MDI = 15% 4,4'-MDI = 15% Polynuclear mixture = 70% PMDI-4: Polymeric MDI NCO content = 31.1% 2,2 '-MDI + 2,4'-MDI = 0% 4,4'-MDI = 42% Polynuclear mixture = 58% PMDI-5: Polymeric MDI NCO content = 28.7% 2,2'-MDI + 2,4'-MDI = 3% 4,4'-MDI form = 7% Polynuclear mixture = 90% OH-1: polyether polyol SANNIX G-250 manufactured by Sanyo Chemical Industries, Ltd. Number average molecular weight = 250 average functional group = 3 Propylene oxide unit = 100% OH-2: polyether polyol MF-16 manufactured by Takeda Pharmaceutical Co., Ltd. Number average molecular weight = 2,400 Average number of functional groups = 3 3: Polyether polyol Sanyo Chemical Co., Ltd. Sannics Diol PP-4000 Number average molecular weight = 4,000 Average functional group = 2 Propylene oxide unit = 100% OH-4: Polyether polyol Sanyo Chemical Co., Ltd. Sanix FA-702 number Average molecular weight = 6,000 Average number of functional groups = 4 Propylene oxide unit = 100% OH-5: Polyether polyol GR-2505 manufactured by Asahi Denka Kogyo Number average molecular weight = 2,500 Average number of functional groups = 3 Propylene oxide unit = 5 % (Ethylene oxide unit = 50%) OH-6: polyether polyol Newpole 80-4000 manufactured by Sanyo Chemical Industries, Ltd. Number average molecular weight = 4,000 Average functional group number = 2 Propylene oxide unit = 20% (ethylene oxide unit = 80% ) OH-7: Polyether polyol PEG-200 manufactured by Sanyo Chemical Industries, Ltd. Number average molecular weight = 200 Average number of functional groups = 2 Propylene oxide unit = 0% (Ethylene oxide unit = 100%)

[Low-temperature stability test]
After standing for one month under the condition of ° C., the appearance was checked. When no crystal was generated, it was determined to be “good”, and when crystal was generated, it was considered that heat retention and heat dissolution were necessary, and it was determined to be “poor”.

[0066]

[Table 2]

[0067]

[Table 3]

[Expansion Test] Examples 1 to 7, Comparative Examples 1 to 5 Combinations and compounding amounts shown in Tables 4 and 5 and a capacity of 300 m
Solution A and Solution B were mixed and stirred in 1 l of a polycup under the conditions of 600 times per minute / 10 seconds (20 ° C.). The foam appearance of the foam, the expansion ratio of the foam, a physical property test, and water resistance were measured by the following methods. Tables 4 and 5 show the results.

[Test Method for Foam] (1) Appearance of Foam The obtained foam was cut with a knife, and the condition of the cut surface was observed. A sample having a non-uniform cross section was determined as “poor”, and a sample having a uniform cross section was determined as “good”. (2) Expansion ratio The expansion ratio was calculated by the following equation. The liquid temperature is 25
± 1 ° C., room temperature was 25 ± 5 ° C. Expansion ratio = volume of foam after foaming (cm ³ ) / volume of blended liquid before foaming (cm ³ ) (3) Uniaxial compressive strength According to JSF T511 (Uniaxial compressive test method for soil based on the Japan Society of Soil Engineering). It was measured. Measurement temperature is 10 ℃, 20 ℃,
Performed at 40 ° C.

[0070]

[Table 4]

[0071]

[Table 5]

[0072] [Water stain resistance test] Examples 8-14, in the combination shown in Comparative Examples 6-10 Table 5, A solution, B solution and respectively 50
g each, and immediately put the liquid in the fluid state immediately into a polycup containing 300 cm ³ of water,
Observe the foaming state in water. At that time, those in which the water in the polycup was transparent were judged as "good", and those in which the water became cloudy were judged as "poor". Table 6 shows the results.

[0073]

[Table 6]

From Tables 4 to 6, the physical properties of the foam in the comparative example were not so inferior to those of the example, but the water contamination of the foam was poor. Also, the polyisocyanate in Comparative Examples generally had poor low-temperature stability. In addition, B-9 2,
Since the total content of 2'-MDI and 2,4'-MDI was too large, the low-temperature stability was good, but the physical properties of the foam were low.

[Tunnel Void Filling Work] Example 15 As shown in FIG. 1, a void was formed on the back of the lining concrete of the existing tunnel near the top end of the arch. This gap 3
Then, a work of injecting the injectable chemical composition used in Example 2 was performed. As shown in FIG. 2, an injection hole 5 communicating the surface of the lining concrete 2 with the cavity 3 was formed. FIG.
As shown in the figure, the injection nozzle 6 was inserted through the injection hole 5. Next, A-2 was placed in the 30 kg raw material tank A, and B-2 was placed in the raw material tank 3.
0 kg was placed in the raw material tank B. Liquid feed pumps were installed in the raw material tanks A and B. The liquid sent from each tank was mixed in the mixing head, and the mixed chemical was injected into the gap 3 through the injection nozzle 6 by a gear pump. The mass mixing ratio of the chemical solution is as follows: solution A / solution B = 100 /
110. The injection pressure was 0.2 MPa. As shown in FIG. 3, the injected chemical solution foams and hardens the composition for filling voids to form a foam (urethane foam) 7, and finally, as shown in FIG. 4, this foam (urethane foam) 7
Void part 3 is almost completely filled with.

Since the voids 3 are filled with the foam (urethane foam) 7 by this construction, effects such as prevention of collapse due to stress relaxation of the ground 2 and pushing-up force to prevent generation of cracks and the like can be seen. Was done. No groundwater contamination was found.

[Filling of Gap in Ground] Example 16 As shown in FIG.
Work to inject the injectable chemical composition used in Example 1 into the gap 3 was performed. As shown in FIG. 6, a long hole 5 communicating the surface of the ground 2 with the gap 3 was formed in the ground 2, and an injection pipe 9 was inserted into the long hole 8. Next, A-1 was placed in a 30 kg raw material tank A, and B-1 was placed in a 30 kg raw material tank B. The raw material tank A and the raw material tank B has established a liquid feed pump. For the liquid sent from each tank, take in the air hose at the tip and make one, and finally,
In, it was injected into the gap portion 3. The mass mixing ratio of the chemical solution is A solution /
Solution B = 100/110. The injection pressure was 3 MPa. After the injection, the injection pipe 9 was pulled out, and the long hole 8 was backfilled. As shown in FIG. 6, the injected chemical solution foams and hardens the above-described composition for filling voids to form a foam (urethane foam) 7, and finally, as shown in FIG. 7, this foam (urethane foam) 7, the gap 3 was almost completely filled.

As a result of this construction, the voids 3 are filled with the foam (urethane foam) 7, so that the effect of preventing depression and the like was obtained. In addition, pollution of underground water was not confirmed.

[0079]

As described above, the injectable chemical composition for filling voids of the present invention has a low environmental load during the filling operation, and the obtained foam can reduce the degree of soil contamination, is excellent in workability, and can be stored. The stability was good. In addition, the gap filling method of the present invention is used to fill a gap between a concrete structure and a surrounding rock or the ground in a tunnel, an underground structure, a foundation structure of a high-rise building, or the like, or between the rock or the ground. suitable a method, in particular optimal for repair of existing tunnels.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing an example of a void filling method using the void filling chemical solution composition of the present invention.

FIG. 2 is a cross-sectional view showing one example of a gap filling method using the gap filling chemical solution composition of the present invention.

FIG. 3 is a cross-sectional view showing an example of a gap filling method using the gap filling chemical solution composition of the present invention.

FIG. 4 is a cross-sectional view showing an example of a void filling method using the void filling chemical composition of the present invention.

FIG. 5 is a cross-sectional view illustrating an example of a gap filling method using the gap filling chemical solution composition of the present invention.

FIG. 6 is a cross-sectional view showing one example of a gap filling method using the gap filling chemical solution composition of the present invention.

FIG. 7 is a cross-sectional view showing an example of a gap filling method using the gap filling chemical solution composition of the present invention.

[Explanation of symbols]

 1: tunnel 2: ground 3: void 4: lining concrete 5: injection hole 6: injection nozzle 7: foam (urethane foam) 8: long hole 9: injection pipe

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) // C09K 103: 00 C09K 103: 00 F term (reference) 2D040 AA06 AB01 AC01 BB03 BB09 CA10 CB03 CD01 CD09 2D055 JA00 4H026 CA03 CA06 CC06 4J034 BA02 BA03 CA13 CA15 CA16 CB03 CB04 CB05 CB07 CB08 CC02 CC03 CC05 CD01 CD04 DA01 DA03 DB04 DB05 DB07 DC02 DC35 DC42 DC43 DC50 DF02 DF03 DG06 DG10 DG22 DH02 DJ08 HA02 HA14 HC12 HC46 HC64 HC71 JA01 JA42 MA04 MA11 MA16 QA03 RA10

Claims (7)

[Claims] 1. A diphenylmethane diisocyanate-based polynuclear condensation in which (B) contains 20 to 70% by mass of a binuclear substance in an injectable liquid chemical composition for filling voids, comprising an aqueous alkali silicate solution (A) and an organic polyisocyanate (B). Body (B
1) and wherein said binuclear substance contains 2,2'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate in a total of 5 to 60% by mass, Composition. 2. A diphenylmethane diisocyanate-based polynuclear condensation containing 20 to 70% by mass of a binuclear substance in a cavity filling injectable liquid composition comprising an aqueous alkali silicate solution (A) and an organic polyisocyanate (B). Body (B
1) is obtained from the reaction of an active hydrogen group-containing compound (B2) having a number average molecular weight of 32 to 10,000, and a binuclear compound in (B1) is 2,2'-diphenylmethane diisocyanate and 2 The injectable drug composition according to any one of claims 1 to 4, wherein the composition contains 5 to 60% by mass of 4,4'-diphenylmethane diisocyanate. 3. The injection liquid composition for filling a void according to claim 1, further comprising an active hydrogen group-containing compound (C). 4. The injectable chemical composition for filling voids according to claim 1, further comprising a catalyst (D). 5. The injectable drug solution composition for filling voids according to any one of claims 1 to 4, further comprising a surfactant (E). 6. The injectable liquid chemical composition for filling voids according to claim 1, further comprising a flame retardant (F). 7. A method of filling a void, comprising injecting the liquid medicine composition according to any one of claims 1 to 6 into a void and consolidating it.