JP2002256054A - Grouting chemical liquid composition for filling gap and method of filling gap using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a grouting chemical liquid composition for a gap filler, giving a little environmental load in its filling work, enabling its foamed product to reduce the extent of contamination, excellent in workability and good in storage stability, in a grouting chemical composition for a gap filler which is applied to fill gaps between concrete structures such as a tunnel, an underground structure, a fundamental structure for a high-rise building, etc., and their surround base rocks or grounds, and is applied to fill a gap generated inside of a base rock or the ground. SOLUTION: In the grouting chemical liquid composition to fill a gap, consisting of an active hydrogen group-containing compound (A) and an organic polyisocyanate (B), this grouting chemical liquid composition is characterized by specifying the (B) as a polymeric MDI containing 20-70 mass% of a dinuclear compound and the dinuclear compound contains total 5-60 mass% of a 2,2'-MDI and 2,4'-MDI, and a method of filling a gap using the same solves conventional problems.

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 the viscosity of the liquid in winter. In the techniques disclosed in JP-A-52-78955 and JP-A-53-93623, the mixing property with water is improved, and the techniques disclosed in JP-A-55-39568 and JP-A-55-39568 are disclosed. According to the technique disclosed in Japanese Patent Application Laid-Open No. 55-122998, the reactivity between the polyisocyanate and the polyol is improved, so that the strength is rapidly increased. It is likely to cause defects, 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, and is eluted by rainwater or the like. Things are generated and easily cause pollution of groundwater, well water and river water. The technology disclosed in JP-A-8-302348 has an insufficient expansion ratio. JP 200
In the technique disclosed in Japanese Patent Application Laid-Open No. 0-281742, A
No consideration is given to the compatibility between the liquid and the liquid B and the water contamination of the resulting 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 studies to provide a product, they have found that a diphenylmethane diisocyanate-based polynuclear condensate having a specific composition can solve the above-mentioned problems, and have led to 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 organic polyisocyanate (B), (B) a diphenylmethane diisocyanate-based polynuclear condensate containing 20 to 70% by mass of a binuclear body And
The injectable drug composition, wherein the binuclear body contains 2,2'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate in a total amount of 5 to 60% by mass.

(2) The injectable liquid chemical composition for filling voids according to (1), further comprising a urethanization 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. The active hydrogen group-containing compound (A) used in the present invention is not particularly limited as long as it has at least two active hydrogen groups in one molecule. Specifically, polyether polyols, 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 and triols such as trimethylolpropane, lactone-based polyols obtained by ring-opening polymerization of ε-caprolactam, polycarbonate polyols, acrylic polyols, polybutadiene-based polyols, novolak resins and resol resins Phenolic polyols, such as so-called polymer polyols obtained by radical polymerization of vinyl monomers such as acrylonitrile and styrene, and polytetramethylene-based polyols obtained by cationic polymerization of tetrahydrofuran. It can be used as a mixture of more than one species. The active hydrogen group-containing compound (B) preferred in the present invention is a polyether-based polyol containing 50% by mass or more of a propylene oxide unit. In the present invention, the content of the propylene oxide unit means the content of propylene oxide in the cyclic ether monomer to be added.

In consideration of the miscibility with the organic polyisocyanate (B) described later, the number average molecular weight of the active hydrogen group-containing compound (A) is 100 to 10,000, preferably 200 to 5,000, More preferably 200 to
3,000. If 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 it will be solidified at a low temperature. On the other hand, when the number average molecular weight is 10,000
On the contrary, if it is larger than 0, the urethane group concentration becomes low, and the strength is insufficient, so that it is not preferable as an injection liquid composition for filling voids. Further, the average number of functional groups is preferably 1 to 10,
Particularly, 2 to 6 are preferable. In the present invention, the “average number of functional groups” of the polyol means the average number of functional groups of the initiator in the case of a polyether-based polyol. 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).

Hereinafter, preferred polyether polyols in the present invention will be described. Polyether-based polyol, ethylene oxide, propylene oxide, using a low molecular weight active hydrogen group-containing compound as an initiator,
It can be obtained by addition polymerization of a cyclic ether monomer such as butylene oxide, glycidyl ether, methyl glycidyl ether and styrene oxide, alone or in a mixture of two or more kinds, by a known method.

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.

Examples of 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, a preferred initiator is a compound having no amino group, and specifically, is selected from the above-mentioned low molecular monool and low molecular polyol. Low molecular weight amino alcohols, low molecular weight monoamines,
When low molecular weight polyamines are used as the initiator, the resulting polyether becomes a tertiary amino group-containing polyol, the reactivity with the isocyanate group becomes larger than necessary, and the mixing of (A) and (B) at the time of injection is performed. It is not preferable because the viscosity of the liquid becomes too large.

The organic polyisocyanate (B) used in the present invention comprises a polynuclear condensate of diphenylmethane diisocyanate (hereinafter abbreviated as polymeric MDI).

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 (B) 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
(B) 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 of aniline and formalin into an isocyanate group by phosgenation or the like. I do. Various compositions of (B) can be obtained by changing the raw material composition ratio, reaction conditions, the mixing ratio of various polymeric MDIs, and the like during the condensation of aniline and formalin. (B) used in the present invention is a reaction solution after the conversion to an isocyanate group or a bottoms solution obtained by removing a solvent from the reaction solution or distilling and separating partly diphenylmethane diisocyanate (hereinafter abbreviated as MDI). Mixtures of several different types such as conditions and separation conditions, as well as MDI
May be added. The composition of (B) used in the present invention has a so-called binuclear body having two isocyanate groups and two benzene rings in one molecule, that is, 20 to 70% by mass, and an isocyanate group and a benzene ring in one molecule. 80 to 3 so-called polynuclear mixture having three or more
0% by mass, preferably 30 to 100% binuclear.
A mixture containing 60% by mass and 70 to 40% by mass of a polynuclear mixture. 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 material in (B) is lower than 20% by mass, the viscosity cannot be reduced, and when it is higher than 70% by mass, the binuclear material itself is solidified (crystallized) at a low temperature. This is not preferable because the influence is strong and the storage stability in winter is particularly deteriorated.

The binuclear or 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 (B) is 2,2'-MDI and 2,4 '
-MDI in total of 5 to 60% by mass and 4,4'-MDI of 95 to 40% by mass.
The total content of 2'-MDI and 2,4'-MDI is 10 to 50% by mass, and 4,4'-MDI is 90 to 50% by mass.

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 (B) 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.

In the present invention, the active hydrogen group-containing compound (A)
It is preferable to use a urethanization catalyst (C) for the purpose of adjusting the reactivity between the compound and the organic polyisocyanate (B). As the catalyst (C), a known urethanization catalyst is used. Specifically, triethylamine, triethylenediamine, N-methylmorpholine, N-methylimidazole, pyridine, N, N, N ', N'-tetramethyl Hexamethylenediamine, bis (2-dimethylaminoethyl) ether, α-picoline, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-
Amine-based catalysts containing no active hydrogen group such as tetrakis (2-hydroxypropyl) ethylenediamine, N-methylmorpholine, 1,2-dimethylimidazole, triethanolamine, N, N, N'-trimethylaminoethyl-ethanolamine Examples thereof include an amine catalyst having active hydrogen, a tin catalyst such as dibutyltin dilaurate, dioctyltin dilaurate, and stannas octoate, and a zinc organic metal catalyst. The addition amount of the catalyst (C) is 0.01 to 5% by mass based on the active hydrogen group-containing compound (A).
Is preferred, and particularly preferably 0.05 to 3% by mass. 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 organic polyisocyanate (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 50% by mass or more of ethylene oxide. Polyethers obtained by ring-opening addition of alkylene oxides such as L-5340 manufactured by Nippon Unicar and B-Grade manufactured by T. Goldschmidt
Nonionic surfactants such as silicone-based surfactants such as various siloxane polyalkylene oxide block copolymers such as 8451 and B-8407. Surfactant (E) can be added to (A) and / or (B). (E) is added in an amount of 0.0
5 to 5% by mass is preferred.

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,
It is 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, in addition to 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 organic polyisocyanate (B), excellent viscosity reduction, and excellent 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 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 to add and blend it in the organic polyisocyanate (B) in advance. Liquid A containing an active hydrogen group-containing compound (A) and, if necessary, a catalyst (C), a surfactant (D) and a foaming agent (E), an organic polyisocyanate (B) and, if necessary, a flame retardant The solution B composed of (F) is put into 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. For mixing liquids, set up a mixing head,
Alternatively, it is possible by simply joining the liquid feeds. 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,
In some cases, it can be provided from outside the ground.
The mixed solution injected into the voids in this manner is
It will harden and fill the voids. Further, depending on the case, a method of injecting the A liquid and the B liquid from different injection holes respectively, collision-mixing the A liquid and the B liquid inside the gap, and foaming / curing is also possible. 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, 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.

At this time, the compounding ratio of the active hydrogen group-containing compound (B) to the organic polyisocyanate (B) is preferably in the range of (A) / (B) = 0.5 to 2.0 by mass ratio.

[0042]

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.

[0044]

[Table 1]

[A liquid raw material] OH-1: polyether polyol Sanyox AP-470 manufactured by Sanyo Chemical Industries, Ltd. Number average molecular weight = 470, average number of functional groups = 3 propylene oxide unit = 100% OH-2: polyether polyol Sanyo Chemical Industries 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

[Preparation of Solution B] Synthesis Examples 1 to 9 A polyisocyanate and a flame retardant shown in Table 2 were added to a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube, and a cooler.
The mixture was stirred at C for 1 hour to obtain B-1 to B-9. In addition, B-9
Was further diluted with propylene carbonate because of high viscosity without a diluent. The low-temperature stability of these liquids was measured under the following conditions. Table 2 also shows the results.

[Liquid B Material] MDI-1: Diphenylmethane diisocyanate (MDI) NCO content = 33.6% Total content of 2,2′-MDI and 2,4′-MDI = 50% 4,4′-MDI -2 = MDI-2: MDI NCO content = 33.6% 2,2'-MDI + 2,4'-MDI = 28% 4,4'-MDI = 72% MDI-3: MDI NCO content = 33 0.6% 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 = 45% Total polynuclear content Amount = 50% PMDI-2: Polymeric MDI NCO content = 31.3% 2,2′-MDI + 2,4′-MDI = 6% 4,4′-MDI = 30% Total polynuclear content = 64% PMDI -3: Polymeric MDI NCO content = 31.1% 2,2'-MDI + 2,4'-MDI = 15% 4,4'-MDI = 15% Total polynuclear content = 70% PMDI-4: Polymeric MDI NCO content = 31.1% 2,2'-MDI + 2,4'MDI = 0% 4,4'-MDI = 42% Total polynuclear content = 58% PMDI-5: Polymeric MDI NCO content = 21.5 % 2,2'-MDI + 2,4'MDI = 0% 4,4'-MDI = 5% Total polynuclear content = 95%

[Low-temperature stability test]
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".

[0049]

[Table 2]

[Expansion Test, Physical Properties Test] Examples 1 to 5, Comparative Examples 1 to 4 Combinations of A-1 to 7 shown in Table 1 and B-1 to 9 shown in Table 2 as shown in Tables 3 and 4, Mix at ratio, 600rpm
The mixture was stirred for 10 seconds (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.

[0051]

[Table 3]

[0052]

[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 the combinations shown in Table 5, each of the solutions A and B
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.

[0055]

[Table 5]

From Tables 3 to 5, it can be judged that the comparative examples are not inferior to the examples in physical properties of the foam, but the comparative examples are generally inferior in low-temperature stability of the polyisocyanate. Further, the one to which the diluent was added had poor water contamination.

[Tunnel Gap Filling Work] Example 11 As shown in FIG. 1, a gap 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 suppression of 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 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. Liquid feed pumps were installed in the raw material tanks A and B. 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, since the voids 3 are filled with the foam (urethane foam) 7, the effect of preventing depression and the like was obtained. In addition, pollution of underground water was not confirmed.

[0061]

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 KB10 4H026 CB08 CC06 4J034 BA01 BA05 CA04 CA12 CB02 CC08 CC12 DA01 DB03 DF01 DF12 DF22 DG03 DG04 DJ01 DP13 DP18 DP19 HA01 HA07 HA13 HC12 HC63 HC71 KA01 KB03 KC08 MAC MA17 NA06 RA10 SA01 SB04

Claims (6)

[Claims] 1. A diphenylmethane diisocyanate-based polynuclear containing 20 to 70% by mass of a binuclear compound in a filling liquid composition for filling a void comprising an active hydrogen group-containing compound (A) and an organic polyisocyanate (B). The injectable drug solution, which is a condensate, and wherein the binuclear body contains 2,2'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate in a total amount of 5 to 60% by mass. Composition. 2. The injectable chemical composition for filling voids according to claim 1, further comprising a urethanization 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.