JP2002226856A - Injection agent liquid composition for filling space, and space-filling construction method using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an injection agent liquid composition which is useful as a space-filling material, is used for filling spaces between concrete structures such as tunnels, underground structures or high building base structures and peripheral bedrocks or grounds or spaces formed in the bedrocks or the grounds, and scarcely gives a load to an environment on a filling work, can produce a foamed product capable of reducing the extent of soil contamination, and has excellent workability and good storage stability. SOLUTION: This injection agent liquid composition for filling spaces, comprising (A) an active hydrogen group-containing compound and (B) an isocyanate group-terminated urethane prepolymer, is characterized in that the component (B) is obtained by reacting (B1) a polymeric MDI containing bi-nuclear compounds in an amount of 20 to 70 wt.% with (B2) a hydroxyl group- containing polyether containing propylene oxide units in an amount of 5 wt.% and having a number-average mol.wt. of 100 to 10,000, and in that the bi-nuclear compounds in the component (B1) contains 2,2'-MDI and 2,4'-MDI in a total amount of 5 to 60 wt.%. And the construction method for filling spaces uses the injection agent liquid composition.

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 discloses ring-opening addition polymerization of propylene oxide to a polyfunctional alcohol in the component A when reacting an aqueous solution of sodium silicate (component A) with an isocyanate compound (component B) to foam and cure. A void filler characterized by containing a polyhydroxy compound and a silicone-based surfactant. 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, a hydrophilic isocyanate group-terminated urethane prepolymer obtained by modifying a polyisocyanate composition with a hydrophilic active hydrogen group-containing compound has an improved affinity for water contained in rock or ground, so that rainwater, etc. As a result, effluents are generated, which is likely to 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 intensive studies to provide a product, the isocyanate group-terminated urethane prepolymer obtained by urethane-modifying a diphenylmethane diisocyanate-based polynuclear condensate having a specific composition with a hydroxyl group-containing polyether having a specific composition has the above-mentioned problems. The inventors have found out that they can be solved, and have reached the present invention.

That is, the present invention provides the following (1) to (5)
It is shown in. (1) In an injectable chemical composition for filling voids, comprising an active hydrogen group-containing compound (A) and an isocyanate group-terminated urethane prepolymer (B), (B) has a binuclear body of 20 to 70.
5% by weight of a diphenylmethane diisocyanate-based polynuclear condensate (B1) and 5 parts of a propylene oxide unit
Number-average molecular weight of 100 to 10,000 contained by mass% or more
Obtained from the reaction with a hydroxyl group-containing polyether (B2), and wherein the binuclear compound in (B1) is 2,2'-
The said injection | pouring chemical-solution composition characterized by containing diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate in a total of 5-60 mass%.

(2) The injectable chemical composition for filling voids according to (1), further comprising a catalyst (C).

(3) The injectable liquid composition for filling voids according to the above (1) or (2), further comprising a surfactant (D).

(4) The injectable drug composition for filling voids according to any one of (1) to (3), further comprising a foaming agent (E).

[0014] The injection liquid composition for filling voids according to any one of the above (1) to (4), further comprising a flame retardant (F).

(6) A method of filling a gap, characterized by injecting the liquid chemical composition of any of the above (1) to (5) into a gap and consolidating it.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, an injectable drug solution composition for filling voids will be described. As the active hydrogen group-containing compound (A) used in the present invention, any compound having an active hydrogen group in one molecule can be used. Specifically, the hydroxyl group-containing polyether (B2) used for obtaining the isocyanate group-terminated urethane prepolymer (B) described below can be used as it is. Further, a polyether polyol other than (B2),
Hydroxyl-containing amine polyethers, amino alcohols,
Polyoxyethylene monoalkyl ethers, adipic acid, dibasic acids such as phthalic anhydride and ethylene glycol,
Diethylene glycol, various polyester polyols obtained by dehydration condensation reaction with glycols such as trimethylolpropane and triol, lactone-based polyols obtained by ring-opening polymerization of ε-caprolactam, polycarbonate polyols, acrylic polyols, polybutadiene-based polyols, novolak resins and the like. Examples include phenolic polyols such as resole resins, so-called polymer polyols obtained by radically polymerizing vinyl monomers such as acrylonitrile and styrene in polyols, and polytetramethylene-based polyols obtained by cationic polymerization of tetrahydrofuran. They are,
They can be used alone or as a mixture of two or more. The active hydrogen group-containing compound (A) preferred in the present invention is
It is a polyether polyol containing a propylene oxide unit in an amount of 50% by mass or more.

Considering the miscibility with the isocyanate group-terminated urethane prepolymer (B), the number average molecular weight of the active hydrogen group-containing compound (A) is 100 to 10,000, preferably 200 to 5,000. And more preferably 200 to 3,000. Number average molecular weight is 100
If it is smaller, the urethane group concentration becomes high, and the strength is developed, but there is a possibility of solidification at low temperatures. On the other hand, when the number average molecular weight is larger than 10,000, the urethane group concentration becomes low, and the strength is insufficient, so that it is not preferable as an injectable drug composition for filling voids. Further, the average number of functional groups is preferably from 1 to 10, particularly preferably from 2 to 6.

The isocyanate group-terminated urethane prepolymer (B) used in the present invention comprises a diphenylmethane diisocyanate polynuclear condensate (hereinafter abbreviated as polymeric MDI) (B1) and a hydroxyl group-containing polyether (B).
2).

The viscosity of (B) is preferably 300 mPa · s or less at 25 ° C. in order to improve not only the miscibility with the active hydrogen group-containing compound (A) but also the injectability into pores and the permeability. Preferably it is 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 content of the binuclear body 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 body 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 content of the binuclear compound of (B1) and the isomer composition ratio of the binuclear compound are determined from a calibration curve based on the area percentage of each peak obtained by gel permeation chromatography or gas chromatography. Can be.

If the amount is small, 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.

The hydroxyl group-containing polyether (B2) used in the present invention contains a propylene oxide unit in an amount of 5% by mass or more, has a number average molecular weight of 100 to 10,000, and preferably has a propylene oxide unit of 30%.
１００100% by mass, and the number average molecular weight is 150〜5.0.
00, particularly preferably 50 to 100% by mass of a propylene oxide unit and a number average molecular weight of 200 to
3,000. The average number of functional groups is preferably from 1 to 10, particularly preferably from 2 to 4.

When the number average molecular weight of (B2) is smaller 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.

If the content of the propylene oxide unit (B2) is lower than 5% by mass, the foam obtained by the reaction with the active hydrogen group-containing compound of the present invention has hydrophilicity, which may cause soil contamination. (B1) and (B
In the case of the isocyanate group-terminated urethane prepolymer (B) obtained by the reaction of 2), in the reaction with the active hydrogen group-containing compound (A), the isocyanate group-terminated urethane prepolymer or tertiary amino group imparted with hydrophilicity is provided. Unlike the case where the containing polyol is used, the viscosity rise due to the reaction is mild, so the filling is insufficient due to poor flow,
No void formation occurs.

When the average number of functional groups in (B2) is too large, viscosity reduction in (B) cannot be achieved.

(B2) is a single or two kinds of cyclic ether monomers such as ethylene oxide, propylene oxide, butylene oxide, glycidyl ether, methyl glycidyl ether and styrene oxide, using a low molecular weight compound having an active hydrogen group as an initiator. It can be obtained by addition polymerization of the above mixture by a known method.
In the present invention, the average number of functional groups of (A) and (B2) means the average number of functional groups of the initiator, and the content of the propylene oxide unit means the content of propylene oxide in the cyclic ether monomer to be added. Means content.

As the initiator, phenol and thiol are used in addition to low molecular monools, low molecular polyols, low molecular amino alcohols, low molecular monoamines, low molecular polyamines and the like.

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

Examples of low molecular polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,2-butanediol, and 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.

The low molecular weight amino alcohols include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N-ethylethanolamine,
n-butylethanolamine, Nn-butyldiethanolamine, N- (β-aminoethyl) ethanolamine, N- (β-aminoethyl) isopropanolamine and the like.

The low molecular weight monoamines include ethylamine, propylamine, butylamine, diethylamine,
Examples include dibutylamine, aniline, N-methylaniline and the like.

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

In the present invention, the preferred initiator (B2) is a compound having no amino group, and is specifically selected from the above-mentioned low molecular monools and low molecular polyols. When low molecular amino alcohols, low molecular monoamines, and low molecular polyamines are used as initiators, the resulting polyether becomes a tertiary amino group-containing polyol, and the reactivity with isocyanate groups becomes unnecessarily large. The viscosity of the mixed liquid of (A) and (B) in the above becomes too large, which is not preferable.

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

As described above, the isocyanate group-terminated urethane prepolymer (B) in the present invention has a propylene oxide unit and a urethane group. For this reason, the compatibility with the active hydrogen group-containing compound (A) is good, and 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 (A)
For the purpose of adjusting the reactivity between the isocyanate group-terminated urethane prepolymer (B) and the catalyst (C), it is preferable to use a catalyst (C). As the catalyst (C), 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), borane salt of these amine catalysts, DBU phenol salt, DBU octyl Amine catalysts which do not contain active hydrogen groups such as acid salts and DBU carbonates; amine catalysts having active hydrogen such as triethanolamine, N, N, N'-trimethylaminoethyl-ethanolamine; dibutyltin dilaurate; Tin catalysts such as octoate, carboxylates such as magnesium naphthenate, lead naphthenate, potassium acetate and potassium octylate; trialkylphosphines such as triethylphosphine and tribenzylphosphine; alkoxides such as sodium methoxide; zinc Organic metal catalysts and the like. The addition amount of the catalyst (C) is preferably from 0.01 to 5% by mass, particularly preferably from 0.05 to 3% by mass, based on the active hydrogen group-containing compound (A). It is preferable that (C) is previously blended with (A). If (C) is added to (B), the storage stability of (B) tends to decrease.

In the present invention, the active hydrogen group-containing compound (A)
It is preferable to add a surfactant (D) for the purpose of adjusting the mixing property and the reactivity of water used for a foaming agent (E) described later and the isocyanate group-terminated urethane prepolymer (B). 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 (E) can be added to (A) and / or (B). The amount of (E) added
0.05-5 mass% is preferable with respect to (A).

In the present invention, it is preferable to use a foaming agent (E) in order to sufficiently fill the voids with the mixed chemical solution after filling. The foaming agent (E) is selected from water, hydrocarbon, and hydrofluorocarbon, and water alone is particularly preferable. In addition, you may use together well-known foaming agents normally used for urethane foaming as needed.
In the case of water, the addition amount of the blowing agent (E) is 1 to 20% by mass based on the active hydrogen group-containing compound (A), and a blowing agent other than water, that is, a hydrocarbon such as pentane or hexane,
HFC-245fa, HFC-365mfc, HFC-
In the case of a hydrofluorocarbon such as 134a,
0 to 40% by mass based on (A).

In the present invention, a chemical is used in an enclosed space,
Further, since it is often used in a situation where a heat source is nearby, it is preferable to use a flame retardant (F). 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. As the nitrogen compound, trimethylolmelamine and N-
Methylol acrylamide and the like can be mentioned. 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, other than the above-mentioned catalyst (C), surfactant (D), blowing agent (E) and flame retardant (F), cement, blast furnace slag, gypsum, calcium carbonate, Inorganic fillers such as clay, quicklime, slaked lime and bentonite, diluents, coupling agents, and various additives such as dispersants, thickeners, antioxidants, heat resistance additives, antioxidants, leveling agents, etc. They can be added, but should be limited to those that do not cause soil contamination.

For example, the diluent is required to have excellent compatibility with the active hydrogen group-containing compound (A) and / or the isocyanate group-terminated urethane prepolymer (B), excellent viscosity reduction, and further excellent storage stability. Reactive diluents such as low molecular weight dibasic acid diesters, mono- or polyhydric alcohol acetates, alkylene carbonates, ethers, cyclic esters, acid anhydrides, various acrylates, methacrylates, etc. , And also ethyl acetate,
Toluene, xylene, tetrahydrofuran, 1,1,1
-Organic solvents such as trichloroethane, methylene chloride and trichlorofluoromethane. 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 catalyst (C), the surfactant (D), and the foaming agent (E) are used, it is preferable that a predetermined amount of each of them is added to the active hydrogen group-containing compound (A) and blended in advance. When the flame retardant (F) is used, it is preferable that the flame retardant (F) is previously added to and blended with the isocyanate group-terminated urethane prepolymer (B). Liquid A containing active hydrogen group-containing compound (A) and, if necessary, catalyst (C), surfactant (D) and foaming agent (E), isocyanate group-terminated urethane prepolymer (B), and if necessary And the liquid B comprising the flame retardant (F) in separate raw material tanks. The solution A and the solution B are sent using a proportional combination pump (liquid sending pump) that can control the flow rate, 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 mixture is injected using a gear pump, a screw pump, a plunger pump, an air pump, etc., with a perforated lock bolt, injection rod, injection pipe, injection nozzle, injection hose equipped with a check valve installed in the injection hole, etc. And so on. 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, solution A and B
A method is also possible in which the liquids are injected from different injection holes, respectively, and the liquid A and the liquid B are collision-mixed inside the gap to foam and harden. The injection pressure is preferably 0.05 to 5 MPa (gauge pressure). The foaming / curing of the chemical injected into the space starts immediately after the injection and is completely cured in about several hours. In addition, the equipment used in the method of the present invention is a mobile transportation of all raw materials and machines / equipment necessary for construction, such as a raw material tank, an injection pump, an injection nozzle, an injection hose, a pressure gauge, a flow meter, and an injection pump. Construction is possible with the vehicle loaded. Furthermore, the size of the loading vehicle is sufficient with a 4-ton flat body. Therefore, the construction method of the present invention makes it possible to perform a large amount of rapid construction with compact equipment so that it can exhibit mobility and respond at any time,
Since the work is unified, no special skill worker is required. For this reason, for example, when used for tunnel repair work,
Multiple locations can be constructed in a short period of time, and the effects of reducing the stress on the ground, preventing collapse, etc., and suppressing the occurrence and growth of cracks are exhibited in a short period of time after construction .

At this time, the compounding ratio of the active hydrogen group-containing compound (A) and the isocyanate group-terminated urethane prepolymer (B) ranges from (A) / (B) = 0.5 to 2.0 in terms of mass ratio. Is preferred.

[0048]

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 Liquid A] Preparation Examples 1 to 7 Table 1 shows the raw material charge amounts of Liquid A.

[0050]

[Table 1]

[Liquid A raw material] OH-1: polyether polyol Sanyox AP-470 manufactured by Sanyo Chemical Industry Co., Ltd. Number average molecular weight = 470 Average functional group number = 3 propylene oxide unit = 100% OH-2: polyether polyol Sanyo Chemical Industry Sannics HS-211 number average molecular weight = 590 average functional group number = 4 propylene oxide unit = 100% OH-3: polyether polyol CM-211 manufactured by Asahi Denka Kogyo number average molecular weight = 2,100 average functional group number = 2 propylene oxide Unit = 90% (Ethylene oxide unit = 10%) TMHDA: N, N, N ', N'-tetramethylhexamethylenediamine B-8404: Silicone surfactant manufactured by Te Goldschmidt

[Production of Liquid B] Synthesis Examples 1 to 9 A polyisocyanate and a polyol shown in Table 2 were reacted at 80 ° C. for 3 hours in a reactor equipped with a stirrer, thermometer, nitrogen seal tube and cooler. Thus, isocyanate group-terminated urethane prepolymers B-1 to B-9 were obtained. 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. In addition, B-9 is
Since the viscosity was high 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 also shows the results.

[Material for Polyisocyanate Synthesis] MDI-1: diphenylmethane diisocyanate (MDI) NCO content = 33.6% Total content of 2,2′-MDI and 2,4′-MDI = 50% 4,4 ′ MDI content = 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 = 0% PMDI-1: Polymeric MDI NCO content = 31.3% Total content of 2,2′-MDI and 2,4′-MDI = 5% 4,4 ′ −MDI content = 5% Total polynuclear content = 50% PMDI-2: Polymeric MDI NCO content = 31.3% 2,2′-MDI + 2,4′-MDI = 6% 4,4′-MDI = 30% Total content = 64% PMDI-3: Polymeric MDI NCO content = 31.1% 2,2′-MDI + 2,4′-MDI = 15% 4,4′-MDI = 15% Total content of polynuclears = 70 % PMDI-4: Polymeric MDI NCO content = 31.1% 2,2'-MDI + 2,4'MDI = 0% 4,4'-MDI = 42% Total content of polynuclears = 58% OH-4: Poly Ether polyol Sanyox G-250 manufactured by Sanyo Kasei Kogyo Co., Ltd. Number average molecular weight = 250 Average number of functional groups = 3 Propylene oxide unit = 100% OH-5: Polyether polyol Sanyo Kasei Kogyo PP-200 number average molecular weight = 200 average functional group = 2 propylene oxide unit = 100% OH-6: polyether polyol MF-16 manufactured by Takeda Pharmaceutical Co., Ltd. MF-16 number average molecular weight = 2,400 average functional group = 3 propylene oxide unit = 80% (Ethylene oxide unit = 20%) OH-7: Polyether polyol Sanyox FA-702 manufactured by Sanyo Chemical Industries Number average molecular weight = 6,000 Average functional group number = 4 Propylene oxide unit = 100% OH-8: Polyether Polyol Sanyo Chemical Industries PEG-200 Number average molecular weight = 200 Average functional group number = 2 Propylene oxide unit = 0% (Ethylene oxide unit = 100%) OH-9: Polyether polyol Sanyo Chemical Industries PEG-1540 number Average molecular weight = 1,500 Average functional group number = 2 Propylene oxide unit = 0% (Ethylene oxide unit = 100%) OH-10: Polyether polyol Nippon Yushi PEG-4000 Number average molecular weight = 4,000 Average functional group number = 2 Propylene oxide unit = 0% (Ethylene oxide unit = 100%)

[Low-temperature stability test] B-1 to B-9 were measured at -10 ° C.
After leaving it for one month under the conditions described above, its appearance was checked. When no crystal is generated, it is judged as “good”,
When crystals were generated, it was considered that heat retention and heat dissolution were necessary, and it was determined to be "defective".

[0055]

[Table 2]

[Expansion Test, Physical Property Test] Examples 1 to 5, Comparative Examples 1 to 4 Tables A-1 to 7 shown in Table 1 and B-1 to B-9 shown in Table 2 are shown in Table 3,
4 and blended in the ratio shown in Fig. 4, 600 rpm / 1
Mixing and stirring were performed for 0 second (20 ° C.). The appearance, expansion ratio, uniaxial compression strength and water resistance of the obtained foam were measured by the following methods. The results are shown in Tables 3 and 4.

[0057]

[Table 3]

[0058]

[Table 4]

[Test Method of 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.

[Water Contamination Test] Examples 6 to 10 and Comparative Examples 5 to 8 In each of the combinations shown in Table 5, 50 parts of solution A and
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 5 shows the results.

[0061]

[Table 5]

From Tables 3 to 5, there are some items which are not inferior to the examples depending on the types of the comparative examples. However, the comparative examples are generally inferior in the low-temperature stability of the polyisocyanate and the water contamination of the foam. We can judge that it is not desirable in terms of protection.

[Tunnel Void Filling Work] Example 11 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. In addition, pollution of underground water was not confirmed.

[Gap Filling Work in Ground] Example 12 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 8 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. Liquid feed pumps were installed in the raw material tanks A and B. The liquid sent from each tank is mixed by taking in the air hose at the tip, and finally the injection pipe 9
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, since the voids 3 are filled with the foam (urethane foam) 7, an effect of preventing depression and the like was obtained. In addition, pollution of underground water was not confirmed.

[0067]

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

Continued on front page F-term (reference) 2D055 JA00 LA02 4H026 CB08 CC06 4J002 CH022 CK031 CK041 CK051 CP182 DD047 DE047 DE127 DG047 DH007 DH057 DK007 EB047 EB097 ED077 EL147 EN116 EN136 EP017 EU187 EV127 EV256 EV267 EV 173 BA05 CA02 CA13 CB03 CB08 DA01 DB01 DB03 DB07 DF01 DF02 DF12 DF16 DF20 DF22 DG01 DG03 DG04 DG05 DG06 DG09 DG14 DG23 DH01 DH06 DJ01 DJ08 DP18 DQ16 DQ18 GA06 GA33 HA01 HA06 HA07 HA14 HB06 HC08 HC13 HC03 HC HC64 HC67 HC71 HC73 JA42 KB04 KC02 KC07 KC08 KC17 KC18 KD02 KD04 KD12 KD17 KE02 MA01 MA03 MA11 MA12 MA14 MA15 MA16 MA24 NA02 NA03 NA06 QA05 QB13 QC01 QC05 RA08 RA10

Claims (6)

[Claims] 1. An injectable chemical composition for filling voids, comprising an active hydrogen group-containing compound (A) and an isocyanate group-terminated urethane prepolymer (B), wherein (B) contains 20 nuclei.
A diphenylmethane diisocyanate-based polynuclear condensate (B1) containing propylene oxide unit of 5 to 70% by mass and a number average molecular weight of 100 to 10;
2,000 hydroxyl group-containing polyether (B2), and the binuclear compound in (B1) is 2,2.
2'-diphenylmethane diisocyanate and 2,4'-
The said injection | pouring chemical | medical solution composition characterized by containing diphenylmethane diisocyanate in a total of 5-60 mass%. 2. The injectable liquid chemical composition for filling voids according to claim 1, further comprising a catalyst (C). 3. The injectable drug solution composition for filling voids according to claim 1, further comprising a surfactant (D). 4. The injectable chemical composition for filling voids according to claim 1, further comprising a foaming agent (E). 5. The injectable chemical composition for filling voids according to claim 1, further comprising a flame retardant (F). 6. A method for filling a void, characterized by injecting the liquid medicine composition according to any one of claims 1 to 5 into a void and consolidating it.