JP2005087990A - Water impervious material injection type water impervious work, system, and polyvinyl alcohol-system injection type water impervious material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water impervious material injection type water impervious work causing little uneven solidification, and a polyvinyl alcohol-system injection type water impervious material. <P>SOLUTION: A plurality of layers of water impervious sheets 6a, 6b are laid with circumferential edges closely brought into contact with the ground face 1 where a load is set, a space d is secured between the adjacent water impervious sheets 6a, 6b against the load by using a porous spacer 7, and a polyvinyl alcohol-based impervious material aqueous solution 10 with adjustable gelation time t by pH is injected into the gap d. Preferably, the aqueous solution 10 has a pH value making the gelation time t equal to or longer than a solution charging time t<SB>0</SB>into the gap d, and the gap d is evacuated when the aqueous solution 10 is injected. One of examples of the water impervious material is an aqueous solution 10 in which a polyvinyl alcohol-based polymer of the degree of polymerization of 500 or more, a water soluble crosslinking agent having in its molecules two or more methylol groups, and a pH adjusting agent are dissolved. The degree of polymerization, polymer concentration and the mole ratio of the methylol groups to the vinyl alcohol unit in the polymer impart given water impervious properties to the water impervious gel. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-impervious material injection type water-impervious material and system and a polyvinyl alcohol-based injected water-impervious material, and in particular, a water-impervious material and system for impermeable to a ground surface supporting a load, and a polyvinyl alcohol-based injected water-impervious material used therefor About.

  A landfill-type waste disposal site that dumps industrial waste and general waste uses landforms of natural land or excavates the ground to bury the waste in a concave ground. In order to prevent seepage of leachate from landfill waste, which may cause environmental pollution, to the bottom of the disposal site will be impermeable. A water shielding work using a synthetic resin or rubber sheet has the advantages of easy construction and good water shielding, and is widely adopted. In addition to the waste disposal site, the same water-impervious sheet construction may be applied to the bottom ground surface for storing water such as water hazards, simple reservoirs, reservoirs, and pools of golf courses.

  Since the water shielding sheet works may be damaged by the waste to be placed, it is necessary to periodically check for damage. As a method for detecting breakage in the water-impervious sheet work, for example, Patent Document 1 divides the interval between the upper sheet and the lower sheet of the two-layer water-impervious sheet work into a plurality of sections by a sealing material, Disclosed is a double water-impervious sheet with a water leakage sensor installed at intervals. A system for electrically detecting water leakage from the water shielding sheet at the interval using phase detection of specific resistance, conductivity, current, etc., a system for detecting water leakage by pressure fluctuation within the interval, and collecting water leakage A system for detecting water leakage by piping or the like has also been proposed.

  Moreover, when the breakage of the water shielding sheet is found, it is necessary to repair the leaked portion quickly. In this case, it is not impossible to remove the objects placed on the water shielding sheet and replace the sheet. However, in waste disposal sites, wastes, earth and sand, etc. may be buried several tens of meters on the water shielding sheet. There is a great deal of labor and labor to remove the object. On the other hand, Patent Document 2 is provided with a wettable fiber layer (a composite material of a superabsorbent polymer and an acrylic fiber) and a core layer (a bentonite-impregnated non-woven fabric, etc.) in the space between the two-layer impermeable sheets. Disclosed is a water shielding sheet structure that absorbs water leached from a location into a wettable fiber layer and automatically blocks the damaged portion of the sheet by the expansion of the wettable fiber layer. Patent Document 3 discloses a water-blocking structure in which a repair layer made of a water-swellable water-blocking material (urethane resin or the like) is provided in advance between the two sheets.

  Further, Patent Documents 4 to 6 disclose, as a method for repairing the breakage of the water-impervious sheet, after detecting water leakage of the two-layer water-impervious sheet, a water-stopping material or a solidifying material ( Hereinafter, these are collectively referred to as a water shielding material). In Patent Document 4, a water shielding material having a gelation time (hereinafter, sometimes referred to as gel time) sufficient to fill the compartments between the water shielding sheets, for example, a hydrophilic urethane prepolymer as a main component and a gel time of 45 to 90. Proposal of water shielding material for minutes. Patent Documents 5 and 6 propose a urethane resin or a highly water-absorbent resin having strong elasticity after solidification, an epoxy resin or a polyester resin acting as an adhesive as a water shielding material. The use of an inorganic water shielding material such as cement-bentonite (CB) instead of an organic water shielding material such as resin has been proposed.

Japanese Patent Laid-Open No. 7-151631 JP-A-6-218345 Japanese Patent Laid-Open No. 2-176012 Japanese Patent No. 3076521 Japanese Patent No. 2981343 Japanese Patent No. 2960621 JP 2002-294014 A

  However, the conventional method of automatically repairing the damage by providing a water-swellable water shielding material or the like in the gap between the water shielding sheets in advance has a problem that uneven solidification is likely to occur at the repaired portion. If solidification unevenness occurs at the repair site, water is formed at the interface between the solidified water shielding material and the sheet, and if the water shield sheet near the repair site is damaged again for some reason, water leakage to the basement is surely prevented. It becomes difficult to do. Also, if the solidified water barrier material hardens and the flexibility decreases, it will not be able to follow the deformation of the ground, and cracks will occur in the hardened water barrier material due to ground deformation or other physical external factors. Thus, the water shielding function is impaired, and the crack surface may damage the water shielding sheet. Even in the conventional method of injecting a water shielding material into the gap between the water shielding sheets, when an inorganic water shielding material such as cement-bentonite is used, it is a suspension and the material is separated during injection. There is a risk that cracking or the like may occur because the concentration of the water becomes uneven and uneven solidification occurs, and the water shielding material hardens after solidification.

  On the other hand, the method of injecting an organic water shielding material such as urethane resin has an advantage that it can follow the deformation of the ground because it has some elasticity after solidification. However, conventional organic water barrier materials generally have a problem that uniform injection is difficult because the viscosity of the solution before solidification is high and several kinds of chemicals are mixed. In addition, the conventional organic water shielding material is difficult to adjust the solidification time, and the solidification time varies depending on weather conditions, etc., so when the site area of the water shielding sheet is vast and the injection time is long, There is a risk that solidification will begin on some of the water barrier material before sufficient filling is complete. If solidification of a part of the water shielding material starts before filling is completed, uniform filling becomes difficult, which may cause uneven solidification. In order to insulate the ground surface of a large area such as a waste disposal site by injecting a water shielding material, a water impermeable construction that has flexibility to follow the deformation of the ground etc. and has no solidification unevenness is required. is necessary.

  Therefore, an object of the present invention is to provide a water-impervious material injection type water-impervious construction and system that hardly causes uneven solidification, and a polyvinyl alcohol-based injected water-impervious material.

  This inventor paid attention to the composition for forming a polyvinyl alcohol gel disclosed in Patent Document 7. This composition mainly comprises (A) a polyvinyl alcohol-based polymer (hereinafter sometimes referred to as PVA polymer), (B) a water-soluble crosslinking agent having two or more methylol groups in the molecule, and (C) water. As a constituent component, the proportion of (A) in the total of (A) to (C) is 0.5 to 10% by weight, and vinyl alcohol units (hereinafter referred to as vinyl alcohol units) in (A) and (B). The molar ratio with the methylol group in the component is 1.0: 0.01 to 1.0: 0.5, and the polymerization degree of the PVA polymer (A) is 500 or more. When this composition is allowed to stand at room temperature for several hours to several days, it gels with time and becomes a water-insoluble gel having good strength and elasticity, so that it can be used as a flexible water shielding material. Moreover, it is a relatively low concentration and uniform aqueous solution before gelation, and there is no possibility of separation of the material when used as a water shielding material for injection, and it can be said that it is a water shielding material suitable for injection.

  Furthermore, the present inventors have the same effect even when a crosslinking agent comprising (B ′) a water-soluble transition metal compound is used in place of the (B) water-soluble crosslinking agent having two or more methylol groups in the molecule. It was found that it can be obtained. At that time, the molar ratio of the transition metal compound in the component (B ′) to the vinyl alcohol unit in (A) needs to be 0.01 to 1.0.

  Furthermore, the present inventors dissolved (A) a PVA polymer and (B) a water-soluble crosslinking agent having two or more methylol groups in the molecule or (B ′) a crosslinking agent comprising a water-soluble transition metal compound. It was experimentally found that the gel time of the aqueous solution can be adjusted by the pH. 3 to 6 are graphs showing experimental results showing the relationship between the gel time, pH and temperature of the aqueous solution having a PVA polymer concentration of 3 to 5% by weight. From these graphs, it can be seen that the gel time of the aqueous solution depends on the PVA polymer concentration, temperature and pH. Moreover, although it changes with PVA polymer concentration and temperature, it turns out that gel time can be adjusted in the range from about 10 hours to 100 hours or more by pH. When the ground surface of a large area is shielded by injecting a water shielding material, if the aqueous solution with the pH adjusted appropriately is used as the water shielding material, gelation during the injection is prevented and uniform and non-uniform shielding is achieved. Realization of waterworks can be expected. The present invention has been completed as a result of further research and development based on this finding.

Referring to the embodiment of FIG. 1 and FIG. 2 which is an enlarged view thereof, the water-impervious material injection type water-impervious work 5 of the present invention is a plurality of laid with a peripheral edge in close contact with a ground surface 1 on which a load is installed. A porous separation material 7 that maintains the distance d against the load between the adjacent water-impervious sheets 6a and 6b, and the adjacent water-impervious sheets 6a and 6b, and a gel time t injected into the gap d. It comprises a polyvinyl alcohol-based water shielding material aqueous solution 10 that can be adjusted by pH. Preferably, the aqueous solution 10 has a pH at which the gelation time t is equal to or longer than the filling time t ₀ for the interval d. More preferably, the interval d is degassed when the aqueous solution 10 is injected.

Further, referring to the embodiment of FIG. 1 and FIG. 2, the water-impervious material injection type water-impervious system of the present invention is a multi-layer water-impervious sheet laid on the ground surface 1 on which a load is placed with its peripheral edge closely attached. 6a, 6b, a porous separator 7 that holds the distance d against the load between the adjacent water-impervious sheets 6a, 6b, an injection path 8 and a deaeration path 9 that communicate with the distance d, and an injection path 8 is provided with an injection device 12 for injecting a polyvinyl alcohol-based water shielding material aqueous solution 10 whose gelation time t can be adjusted by pH. Preferably, pH adjusting means 14 is provided for adjusting the pH of the aqueous solution 10 to a pH at which the gelation time t becomes equal to or longer than the filling time t ₀ for the interval d according to the volume of the interval d and the flow rate of the injection device 12.

  In addition, the polyvinyl alcohol-based water-impermeable material of the present invention is an aqueous solution 10 in which a polyvinyl alcohol-based polymer having a polymerization degree of 500 or more, a water-soluble crosslinking agent having two or more methylol groups in the molecule, and a pH adjuster are dissolved in water. The polymer concentration in the aqueous solution 10 is 2.0 to 7.0% by weight, and the molar ratio of the methylol group in the crosslinking agent to the vinyl alcohol unit in the polymer is 0.01 to 0.5; or polyvinyl with a polymerization degree of 500 or more An aqueous solution 10 in which a crosslinking agent composed of an alcohol-based polymer and a water-soluble transition metal compound and a pH adjuster are dissolved, wherein the polymer concentration in the aqueous solution is 2.0 to 7.0% by weight, and in the crosslinking agent for the polyvinyl alcohol unit in the polymer The molar ratio of the metal atoms is set to 0.01 to 1.0. In any of the aqueous solutions 10, the pH can be adjusted within the range of the required gelation time.

  The water-impervious material injection type water-impervious construction and system according to the present invention lays a plurality of layers of water-impervious sheets with the peripheral edges closely adhered to the ground surface on which the load is to be installed, and resists the load between adjacent water-impervious sheets. Since the PVA water shielding material aqueous solution whose gelation time can be adjusted by the pH is injected within the interval, the following remarkable effects are exhibited.

(A) Since the gelation time of the PVA water shielding material aqueous solution can be adjusted by pH, solidification of the water shielding material during injection is prevented, and uniform filling without solidification is possible.
(B) Since the aqueous solution of PVA water shielding material has a relatively low viscosity and high uniformity, it is possible to perform uniform injection without unevenness in the interval between the water shielding sheets.
(C) Since the injected aqueous solution becomes a PVA water-insulating material gel rich in elasticity, a water-impervious work that has excellent adhesion to the water-impervious sheet and can follow deformation and distortion of the ground is obtained.
(D) PVA water-insulating material gel has a high water-impervious property equal to or higher than that of a clay liner and has a low biodegradability, so that it can be a long-term stable impermeable material.
(E) By applying it to the ground surface of waste disposal sites and reservoirs, it can be used as a repair system in the event of breakage of the water shielding sheet.
(F) In addition, when constructing a water shielding sheet, by injecting a PVA water shielding material aqueous solution, it can be used for construction of a water shielding work that is safer than conventional water shielding works.

  FIG. 1 shows a vertical sectional view of an embodiment in which a water barrier 5 of the present invention is applied to the bottom ground surface 1 of a waste disposal site 2, and FIG. 2A is a partially enlarged sectional view of the water barrier 5. Indicates. Hereinafter, the present invention will be described with reference to FIGS. 1 and 2, but the present invention is not limited to application to the bottom of the disposal site, but the ground surface on which loads such as the side of the disposal site and the bottom of the simple reservoir are placed. 1 is widely applicable. The water-impervious work 5 in the illustrated example includes a plurality of water-impervious sheets 6a and 6b laid in layers on the ground surface 1 on which a load is installed, and a porous hole that separates the water-impervious sheets 6a and 6b from each other against the load. And a material separating material 7.

  The water-impervious sheet 6 can be the same as the conventional water-impervious sheet work, and the material is not particularly limited. An example of the water shielding sheet 6 is a sheet made of thermoplastic resin such as high density polyethylene, low density polyethylene, polypropylene, chlorinated polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, polyvinyl chloride, or the like. Rubber-based sheets such as ethylene propylene rubber (EPDM), butyl rubber (IIR), chloroprene rubber (CR), chlorosulfonated polyethylene (CSM), and chlorinated polyethylene (CPE). The peripheral edges of the water-impervious sheets 6a and 6b are in close contact with each other or via an appropriate member, so that the water-impervious material aqueous solution 10 can be enclosed between the water-impervious sheets 6a and 6b. In order to facilitate construction and detection of water leakage, the water shielding sheets 6a and 6b can be divided into sections of appropriate sizes in the same manner as in Patent Documents 4 to 6, and in that case, a plurality of water shielding sheets in each section The peripheral edges are brought into close contact with each other or with an appropriate member using an appropriate sealing material or the like.

  The porous separating material 7 maintains a distance d for injecting a water shielding material aqueous solution 10 to be described later between the adjacent water shielding sheets 6a and 6b against the load on the water shielding sheet 6b. . An example of the separating material 7 is a non-woven fabric, woven fabric, or knitted sheet made of synthetic resin such as polyethylene, polypropylene, polyamide, polyester, and acrylic. There are no particular restrictions on the material and shape of the material. For example, the separating material 7 may have a mat shape with unevenness or a honeycomb structure, and a reinforcing material may be included as necessary. The nonwoven fabric sheet or the composite laminated material of the mat and the reinforcing material may be used. The illustrated example is an example in which the separating material 7 is provided between the two-layer impermeable sheets 6a and 6b, but when the impermeable sheet 6 has three or more layers, the separating material 7 is provided between the adjacent impermeable sheets 6 respectively. To secure the distance d.

  Preferably, the thickness of the water-impervious sheet 7 is small even when a large load is applied to prevent the gap d from being blocked due to the thickness change of the water-impervious sheet 7. For example, it is assumed that the load on the impervious work 1 such as a waste disposal site exceeds 50 kPa. If the rate of change of the thickness of the impermeable sheet 7 exceeds 50%, the interval d is clogged, and the interval d is increased. Uniform injection of the water shielding material aqueous solution 10 becomes difficult, and unevenness in thickness may occur in the water shielding material after gelation (hereinafter sometimes referred to as a water shielding material gel). In order to prevent clogging of the interval d in a waste disposal site, the thickness change rate of the water shielding sheet 7 is preferably 50% or less with respect to the upper load of 500 kPa, desirably 30% or less, which is reliably prevented. It is good to make it 20% or less.

A space d between the water shielding sheets 6a and 6b of the water shielding work 5 is filled with an aqueous solution 10 of a polyvinyl alcohol-based water shielding material (hereinafter also referred to as PVA water shielding material). In the illustrated example, a pressure pump type injection device 12 and an injection path 8 communicating with the interval d are provided, and the PVA water shielding material aqueous solution 10 is injected into the interval d through the injection device 12 and the injection path 8. For example, assuming that the two-layer impermeable sheets 6a and 6b are divided into about 500m ² sections at a waste disposal site, the distance d between the impermeable sheets 6a and 6b is about 10 to 100mm depending on the overload. Assuming that the amount of the water shielding material to be injected into each section is 5 to 50 m ³ . The flow rate that can be injected into the interval d of about 10 to 100 mm is limited. Assuming that the injection flow rate of the water shielding material is 2 to 20 liters / minute depending on the interval d, until each wall is filled with the water shielding material This time t ₀ (hereinafter referred to as filling time t ₀ ) is about 2500 minutes (≈42 hours). Depending on the weather conditions (temperature) and the like, the filling time t ₀ may be longer. The PVA water shielding material aqueous solution 10 maintains a relatively high fluidity until the filling time t ₀ (42 hours in the above example) to the interval d between the water shielding sheets 6a and 6b, and after the filling is completed, A gel having a high viscosity, a high strength, and a required water shielding property is preferable.

  An example of the PVA water shielding material aqueous solution 10 is an aqueous solution in which a PVA polymer, a water-soluble crosslinking agent having two or more methylol groups in the molecule, and a pH adjuster are dissolved. This aqueous solution 10 has a polymerization degree of the PVA polymer, a PVA polymer concentration in the aqueous solution, and a molar ratio of the methylol group in the crosslinking agent to the vinyl alcohol unit in the PVA polymer (hereinafter simply referred to as the molar ratio of the crosslinking agent). The strength and water shielding (water permeability coefficient) of the water shielding material gel can be adjusted. Further, the viscosity of the water shielding material aqueous solution 10 before gelation can be adjusted mainly by the concentration of the PVA polymer in the aqueous solution. Furthermore, as described above, the pH can be adjusted with the pH adjusting agent so that the required gelation time t can be obtained.

  Another example of the PVA water shielding material aqueous solution 10 is an aqueous solution in which a PVA polymer, a crosslinking agent composed of a water-soluble transition metal compound, and a pH adjuster are dissolved. This aqueous solution 10 is a water shielding material gel based on the degree of polymerization of the PVA polymer, the concentration of the PVA polymer in the aqueous solution, and the molar ratio of the metal atom in the crosslinking agent to the vinyl alcohol unit in the PVA polymer (molar ratio of the crosslinking agent). The strength and water impermeability can be adjusted. This PVA water shielding material aqueous solution 10 is also adjusted to a pH so that the required gelation time t can be obtained by adjusting the viscosity of the water shielding material aqueous solution 10 before gelation mainly by the PVA polymer concentration in the aqueous solution. it can.

  The viscosity of the PVA water shielding material aqueous solution 10 is desirably as low as possible within a range where the strength and water shielding necessary for the water shielding material gel can be secured. Assuming that the distance d between the water-impervious sheets 6 is 10 mm or less, for example, about 4 to 5 mm due to the overload, the water-impervious sheet 6 may be damaged at the time of injection if the viscosity of the aqueous solution 10 is too high. The load (see FIG. 1) increases. Considering the capacity of the general injection device 12 and the pressure resistance performance of the water-impervious sheet 6, the viscosity of the aqueous solution 10 is preferably in the range of 15 to 2000 mPa · s, and further considering the case where the distance d is small. A range of 15 to 500 mPa · s is desirable. Although depending on the degree of polymerization of the PVA polymer, etc., the viscosity of the aqueous solution 10 can be in the above range if the concentration of the PVA polymer in the aqueous solution 10 is in the range of 2.0 to 7.0% by weight. When the PVA polymer concentration is 2.0% by weight or less, the viscosity of the aqueous solution 10 is lowered, but the water shielding material gel is not completely gelled (see Comparative Example 1 of the experimental example described later).

Further, the water permeability of the PVA water shielding material gel is desirably a water permeability coefficient K = 10 ⁻⁵ or less, which is considered to be very low, when the water permeability coefficient K (cm / sec) is used as an index. The permeability coefficient K of fine sand, silt, sand-silt-clay mixed soil, which is generally considered to be very low in permeability, is 10 ^-7 to 10 ^-5. K is 10 ^-7 or less. The inventor sets the polymerization degree of the PVA polymer to 500 or more, sets the PVA polymer concentration in the aqueous solution to 2.0 to 7.0% by weight, sets the molar ratio of the methylol-based water-soluble crosslinking agent to 0.01 to 0.5, or the water-soluble transition metal compound crosslinking agent. It was experimentally confirmed that the water permeability coefficient K of the water shielding material gel can be made 10 ⁻⁵ or less, which is the same as that of sand-silt-clay mixed soil, etc. See experimental example). Preferably, the degree of polymerization and the concentration of the PVA polymer are cross-linked so that the water permeability coefficient K of the water shielding material gel is 10 ⁻⁶ or less, which is the same as that of a conventional water shielding material such as cement-bentonite system or water-swellable bentonite. The molar ratio of the agent is selected within the above range. More preferably, the water permeability coefficient K of the water shielding material gel is set to 10 ⁻⁷ or less which is practically impermeable.

  The type of PVA polymer dissolved in the PVA water shielding material aqueous solution 10 is not particularly limited, and may be modified or copolymerized with other components. For example, the hydroxyl group of PVA is modified with carboxylic acid or silica, or vinyl acetate -You may copolymerize with the component represented by ethylene. In order to ensure sufficient water shielding and strength for the water shielding material gel, the polymerization degree of the PVA polymer is preferably 500 or more, more preferably 1000 or more, and still more preferably 1500 or more. Further, if the hydroxyl group in the PVA molecule is too small, sufficient water shielding and strength cannot be obtained for the water shielding material gel. Therefore, the vinyl alcohol unit in the PVA polymer is preferably 85 mol% or more, more preferably 90%. The mol% or more, more preferably 95 mol% or more.

  Examples of methylol-based water-soluble crosslinking agents that dissolve in the PVA water shielding solution 10 are dimethylol urea, trimethylol melamine, dimethylol ethylene urea, dimethylol alkyltriazone, methylated dimethylol uron, hexamethylol melamine, dimethylol propylene. Urea, dimethylol hydroxyethylene urea, tetramethylol acetylenediurea, 4-methoxy-5-dimethylpropylene urea, dimethylol alkyl carbamate, or those methylol groups are etherified. Among these, trimethylol melamine and methoxylated trimethylol melamine having three methylol groups in the molecule are preferable from the viewpoint that high gel strength can be exhibited. In addition, since these compounds have self-condensation properties, the pH of the aqueous solution 10 is slightly acidic in a method of blocking the methylol group with an alkyl group typified by a methyl group or the use stage in order to ensure the long-term pot life of the aqueous solution 10. It is also practically preferable to change the reactivity of the methylol group by a method of adjusting to the side. These crosslinking agents may be used alone or in combination of two or more.

The ratio of the PVA polymer to the methylol-based water-soluble crosslinking agent in the PVA water shielding material aqueous solution 10 is preferably used within the range in which the above-described molar ratio of the crosslinking agent is 0.01 to 0.5. If the molar ratio of the cross-linking agent is less than 0.01, the chemical bond density mainly between PVA molecules becomes too low, and the strength and water shielding property of the water shielding material gel may be insufficient. Further, even if the molar ratio of the cross-linking agent is larger than 0.5, the improvement in strength and water-impervious performance is not recognized so much, but rather the uneconomical due to the increase of the amount of the cross-linking agent increases. The number of moles of methylol group (—CH ₂ —OH) in the crosslinking agent is calculated including the case where it is modified and blocked with an alkyl group such as —CH ₃ . Preferably, the molar ratio of the cross-linking agent is set in the range of 0.1 to 0.3 in order to improve the water shielding property and strength of the water shielding material gel.

  The water-soluble transition metal compound cross-linking agent that dissolves in the PVA water shielding material aqueous solution 10 may be any compound that reacts with PVA in water to cause PVA to have a cross-linked structure. Titanium compound, zirconium compound, vanadium compound, zinc compound, chromium Examples thereof include compounds, nickel compounds, palladium compounds, etc. Among them, titanium compounds and zirconium compounds are preferably used. These transition metal compounds preferably have a chelate-type ligand capable of coordinating with one or more bidentate by a covalent bond, hydrogen bond, or the like with respect to one metal atom. . Since the transition metal compound has a chelate-type ligand, the crosslinking reaction rate of PVA is moderately adjusted. Therefore, it is considered that a gelation rate of several hours to several days suitable for construction can be obtained. Examples of the chelate-type ligand include hydroxycarboxylic acid or a salt thereof, amino alcohol, and β-diketone, but are not limited thereto.

  Examples of titanium compounds that can be used as crosslinking agents include titanium lactate, titanium lactate ammonium salt, diisopropoxy titanium (triethanolaminate), di-n-butoxytitanium bis (triethanolaminate), diisopropoxytitanium bis (tri Ethanolaminate), titanium tetrakis (acetylacetonate) and the like, and examples of zirconium compounds are monohydroxytris (lactate) zirconium ammonium, tetrakis (lactate) zirconium ammonium, monihydroxytris (slate) zirconium ammonium, It is not limited to these. Among them, titanium compounds are preferable, and titanium lactate (titanium lactate) and titanium aminate are particularly preferable. These transition metal compounds are not necessarily used alone, and two or more kinds of them can be mixed and used as necessary.

  The molar ratio of the metal atom in the transition metal compound to the vinyl alcohol unit of PVA can be in the range of 0.01 to 1.0 for the metal atom with respect to the vinyl alcohol unit 1. When the amount of metal atoms is less than 0.01 mol per mol of vinyl alcohol unit, the crosslink density between PVA and metal atoms becomes too low, causing problems in compressive strength, water permeability, and water resistance. When the atomic weight exceeds 1.0 mol, the obtained gel loses its flexibility and causes defects such as cracking during deformation. More preferably, the molar ratio of metal atoms to 1 mol of vinyl alcohol units is in the range of 0.015 to 0.5.

The pH of the PVA water shielding material aqueous solution 10 is determined based on the polymerization degree and concentration of the PVA polymer and the molar ratio of the crosslinking agent so as to obtain the water shielding material gel strength and water shielding necessary for the water shielding work 5. The pH can be adjusted with a pH adjusting agent so that the required gelation time is obtained. For example, the injection flow rate is determined according to the viscosity of the PVA water shielding material aqueous solution 10 and the ability of the injection device 12 such as a pressure pump, and the filling time t ₀ is determined from the volume of the interval d between the water shielding sheets 6a and 6b and the injection flow rate. Is calculated, and the pH of the aqueous solution 10 is adjusted so that the gelation time t is equal to or greater than the filling time t ₀ based on the degree of polymerization, concentration, and cross-linking agent molar ratio of the aqueous solution 10. Preferably, the climatic conditions (air temperature) at the site of the impervious work and the ambient temperature of the ground surface 1 are measured with a thermometer, etc., and the degree of polymerization of the aqueous solution 10, the concentration, the cross-linking agent molar ratio and the ambient temperature of the ground surface 1 are determined. Adjust the pH based on this.

  The relationship between the pH of the PVA water shielding material aqueous solution 10 and the gelation time t can be experimentally determined in advance according to the polymerization degree and concentration of the PVA polymer and the crosslinker molar ratio. 3 and 4 show that a PVA polymer having a polymerization degree of 1700 is used, and the molar ratio of the methylol-based water-soluble crosslinking agent is vinyl alcohol unit / methylol group = 1 / 0.31 (crosslinking agent with respect to 1 kg of 5% PVA water shielding material aqueous solution). Is a graph showing the relationship between the gelation time t, pH and temperature of the aqueous solution 10 with a PVA polymer concentration of 3% by weight and 4% by weight.

  Fig. 5 shows the use of a PVA polymer with a polymerization degree of 1700, and the molar ratio of the water-soluble transition metal compound cross-linking agent is vinyl alcohol units / transition metal atoms = 1 / 0.13 (1 kg of 5% PVA water shielding material aqueous solution The graph shows the relationship between the gelation time t, pH and temperature of the aqueous solution 10 with an amount of 80 g) and a PVA polymer concentration of 5% by weight. Also, FIG. 6 shows that a PVA polymer having a polymerization degree of 1700 is used, and the molar ratio of the water-soluble transition metal compound crosslinking agent is vinyl alcohol unit / transition metal atom = 1 / 0.16 (crosslinking agent for 1 kg of 5% PVA water shielding material aqueous solution). Is a graph showing the relationship between the gelation time t and the temperature of the aqueous solution 10 in which the amount of PVA polymer is 100 g) and the concentration of the PVA polymer is 5% by weight.

  Similar relationship graphs can be obtained experimentally for other polymerization degrees / concentrations / crosslinking agent molar ratios of the aqueous solution 10, and the pH of the aqueous solution 10 that provides the required gelation time can be determined based on the graph. When a methylol-based water-soluble crosslinking agent is used, the type of pH adjuster is not particularly limited, and any acid that can adjust pH may be used. An example of a pH adjusting agent that gives the elasticity or strength of a preferred gel is acetic acid or lactic acid, and lactic acid when odor is a problem. If the pH is adjusted to about 4 to 6, the gelation time can be adjusted within the range of several hours to several hundred hours. However, the pH adjustment range is not limited to this example. In addition, gelation of the PVA water shielding material aqueous solution 10 is possible. When a transition metal compound-based crosslinking agent is used, an amine-based compound is preferably used as the pH adjuster, and ammonia water having a concentration of about 5% is preferably used. The pH is preferably adjusted in the range of 6 to 10. If the pH is 6 or less, the crosslinking reaction may not proceed. If the pH is 10 or more, the crosslinking / gelation may be too fast and the time required for liquid injection may be shortened. .

  Further, the PVA water shielding material aqueous solution 10 may have a methylol / PVA typified by aminomethylpropanol as long as the strength and water shielding properties of the water shielding material gel and the gelation time t of the aqueous solution 10 are not impaired. Representative of various polymers or pigments / glycols as liquid viscosity modifiers typified by organic and inorganic acids, acrylic esters / celluloses, etc. for the purpose of releasing the blocking of methylol groups by alkyl groups Various agents such as PVA plasticizers, stabilizers, inorganic fillers, starches, and celluloses can be blended.

  1 is provided with a deaeration path 9 communicating with the interval d between the water shielding sheets 6a and 6b so that the filling leakage of the PVA water shielding material aqueous solution 10 does not occur. When the aqueous solution 10 is injected into the interval d, the air in the interval d is discharged through the deaeration channel 9, thereby suppressing the occurrence of air accumulation or leachate accumulation in the interval d and filling without leakage is possible. And For example, by applying a negative pressure to the deaeration path 9 to promote the discharge of air or leachate, the aqueous solution 10 can be filled to every corner in the interval d.

[Experimental Example 1]
In order to confirm the performance of the water barrier 5 of the present invention, an experiment was conducted using a plurality of PVA water barrier material aqueous solutions 10 having different PVA polymer concentrations and crosslinker molar ratios. In this experiment, water was added to a PVA resin with 99.85 mol% vinyl alcohol units (Kuraray Co., Ltd., PVA-HC, polymerization degree 1700) to make a 10 wt% aqueous solution, and the mixture was heated to about 95 ° C and stirred. After completely dissolving the PVA resin, water was further added to prepare 2.5 wt%, 5.0 wt% and 1.5 wt% PVA aqueous solution 10 shown in Table 1. PVA polymerization degree was measured based on JISK6726.

  After cooling this PVA aqueous solution 10 to 20 ° C., etherified trimethylol melamine (Sumitomo Chemical Co., Ltd., sumitex resin M-3) as a crosslinking agent is added in a predetermined amount, and lactic acid is added as a pH adjuster to form an aqueous solution. Were adjusted to prepare four types of PVA water shielding material aqueous solutions 10 shown in Samples 1 to 3 of Table 1 and Comparative Example 1. Samples 1 to 3 are aqueous solutions having a PVA polymer concentration in the range of 2.0 to 7.0% by weight, and Comparative Example 1 is an aqueous solution having a PVA polymer concentration of 2.0% by weight or less.

  In addition, titanium lactate (manufactured by Matsumoto Pharmaceutical Co., Ltd., ORGATICS TC-315) as a cross-linking agent is added to a 5.0 wt% PVA aqueous solution 10 cooled to 20 ° C., and 5% ammonia as a pH adjuster. Water was added to adjust the pH of the aqueous solution, and four types of PVA water shielding material aqueous solutions 10 shown in Samples 4 to 7 in Table 1 were prepared. Samples 4 to 6 have a chemical pH in the range of 7.8 to 8.2, and Sample 7 has a crosslinker concentration of 10%.

  Furthermore, in order to compare the water-insulating performance of the present invention with the water-insulating performance of conventional cement-bentonite-based water-insulating works, 1.0 part of a dispersing material (Denka FT-500, manufactured by Denki Kagaku Kogyo Co., Ltd.) is added to 100 parts of water. After mixing and dispersing, 3 parts of bentonite (Kunimine Kogyo Co., Ltd., Kunigel V1) and 40 parts of ultrafine cement (Electrochemical Industry Co., Ltd., Denka Colloidal Super) are gradually added with stirring. A cement-bentonite mixed suspension shown in Comparative Example 2 was prepared.

For each of the aqueous solutions of Samples 1 to 7 and Comparative Example 1 and each of the suspensions of Comparative Example 2 (hereinafter referred to as “chemical solutions”), the chemical solution viscosity before gelation, gelation time, and water shielding by the following methods The water permeability of the material gel was measured.
(1) Measuring method of chemical viscosity It measured with the Brookfield rotational viscometer (B type viscometer).
(2) Method for measuring gelation time 100 cc of a chemical solution was placed in a glass container that could be sealed and sealed to prevent moisture from evaporating and placed in a constant temperature bath at a predetermined temperature. Thereafter, the viscosity of the liquid was measured every 30 minutes, and the time when the liquid viscosity reached 10,000 mPa · s was read from the graph plotting the temperature and the viscosity, and this was taken as the gel time of the chemical liquid.
(3) Measuring method of water permeability coefficient of water shielding material gel After solidifying each chemical solution by wet method according to JISA1210, water permeability coefficient was measured by JISA1218 water level method.

Moreover, about the water shielding material gel created with each chemical | medical solution, the water leak test was done with the following method.
(A) First, two high-density polyethylene (HDPE) water-impervious sheets (1 m × 1 m) 6a and 6b having a thickness of 2 mm are overlapped and 450 g / m as a porous separation material 7 having a thickness of 5 mm. ² polypropylene (PP) long fiber nonwoven fabric (water permeability 3.5 × 10 ^-1 ) is inserted and one end of each of the chemical injection pipe 8 with a cock and the deaeration pipe 9 with a cock is inserted, and the four sides of both water shielding sheets 6a and 6b are inserted. Was heat-sealed to prepare a water shielding sheet structure.
(B) Next, as shown in FIG. 7A, the cock of the injection tube 8 and the deaeration tube 9 is opened so that the water-impervious sheet structure is the downstream end and the deaeration tube 9 is the upstream end. The chemical solution is injected at a flow rate of 2 liters / minute from the injection tube 8 while being inclined, and after confirming the outflow of the chemical solution from the deaeration tube 9 at the upstream end, the cock of the injection tube 8 and the deaeration tube 9 is closed, and the chemical solution is spaced at intervals. The water shielding sheet structure filled with was left to stand in a 20 ° C. atmosphere for 10 days to prepare a water shielding material injecting sheet structure.
(C) Further, as shown in FIG. 4B, a hole 21 having a diameter of 10 cm is formed in the center of the upper and lower sheets of the water-impervious material injection sheet structure placed horizontally. The bottom edge of a cylindrical pipe 22 with a diameter of 50 cm was brought into close contact, 50 cm of water 23 was injected into the cylindrical pipe 22, and the change in the water level after one week (presence of water leakage) was measured.
(D) At the same time, by comparing the chemical solution injected from the injection tube 8 with the chemical solution flowing out from the deaeration tube 9, the quality of injection for each chemical solution was judged.
(E) Further, the inside of the water shielding material injecting sheet structure was visually observed from the hole 21 to determine whether the filling property for each chemical solution was good or bad.

Table 1 shows the experimental results for each of Samples 1 to 7 and Comparative Examples 1 and 2. From the comparison of Samples 1 and 2 in the same table, even when the PVA polymer concentration and the crosslinker molar ratio are the same, the gelation time of the PVA water shielding material aqueous solution 10 can be adjusted in the range of 13 to 210 hours depending on the pH. It could be confirmed. In addition, from the comparison of Samples 1 and 3 in the same table, the viscosity of the PVA water shielding material aqueous solution 10 was suppressed to about 17 to 23 mPa · s by adjusting the PVA polymer concentration and the cross-linking agent molar ratio. It was confirmed that the water impermeability (water permeability coefficient) could be adjusted in the range of 10 ⁻⁸ to 8 × 10 ⁻⁹ . Furthermore, according to the comparison between Sample 1 or 3 and Comparative Example 2 in the same table, the water barrier 5 of the present invention has a lower viscosity before gelation than the conventional cement-bentonite water barrier, and the barrier after the gelation. It was confirmed that the aqueous property was good, and the injectability and filling properties were excellent. Moreover, it was confirmed from the comparison of Samples 4 to 6 that the gelation time can be adjusted by adjusting the chemical solution pH even when titanium lactate is used as the crosslinking agent. Furthermore, from comparison between Sample 5 and Sample 7, it was confirmed that the gelation time could be adjusted by changing the crosslinker concentration even at the same PVA polymer concentration and the same chemical solution pH.

  In the present invention, since the PVA water shielding material aqueous solution 10 having relatively low viscosity and high uniformity is injected into the space between the water shielding sheets 6a and 6b, the material is separated as compared with the conventional cement-bentonite water shielding material and the like. There is no fear and uniform injection without unevenness is possible. In addition, since the gelation time t of the PVA water shielding material aqueous solution 10 can be adjusted by the pH, by selecting an appropriate pH so that the required gelation time t is obtained, the water shielding material can be prevented from solidifying during the injection. Uniform filling without unevenness is possible. Furthermore, since the PVA water shielding material gel is rich in elasticity and deforms together with the water shielding sheets 6a and 6b with respect to the uneven settlement of the ground, there is no possibility of damaging the water shielding sheets 6a and 6b. In addition, since the PVA water shielding material gel has a water shielding property equal to or higher than that of a general water shielding clay liner, the present invention can be used for water shielding work on the ground surface for various uses.

  Thus, it is possible to achieve the object of the present invention, “a water-insulating material injection type water-impervious structure and system that hardly causes solidification unevenness and a polyvinyl alcohol-based injected water-insulating material”.

  FIG. 1 shows a porous separation material provided between a plurality of layers of water shielding sheets 6a and 6b laid on the bottom ground surface 1 of a pre-graded waste disposal site 2 and adjacent water shielding sheets 6a and 6b. 7, an injection path 8 and a deaeration path 9 communicating with the distance d between the water shielding sheets 6 a and 6 b, an injection device 12 for injecting the PVA water shielding material aqueous solution 10 through the injection path 8, and the deaeration path 9 An embodiment of a water shielding material injection type water shielding system of the present invention having a deaeration device 15 in communication is shown. An example of the injection device 12 is a pressurizing pump, and an example of the deaeration device 15 is an intake pump. In the illustrated example, a pressure tube having a double-pipe structure is connected to the most downstream end of the interval d between the water shielding sheets 6a and 6b, the outer tube of the pressure tube is used as the injection path 8, and the inner tube of the pressure tube is used as the deaeration path 9 (See FIG. 2B). The tip of the injection tube 9 is fixed to the downstream end of the interval d, and the tip of the deaeration channel 8 is extended from the inside of the injection channel 9 to the inside of the interval d to be fixed to the most upstream end of the interval d. That is, in the illustrated system, the injection path 8 and the deaeration path 9 are communicated with the downstream end and the upstream end of the interval d, respectively. However, the structure of the injection path 8 and the deaeration path 9 is not limited to the double pipe structure, and the arrangement position thereof is not limited to the illustrated example.

  The system of the illustrated example includes a breakage detection means 16 that detects breakage of the water shielding sheets 6a and 6b, a control device 17 that drives the injection device 12 in response to the breakage detection, and an interval between the PVA water shielding material aqueous solution 10. and a filling detection means 18 for detecting the filling of d. The breakage detecting means 16 in the illustrated example is provided at the downstream end of the interval d, and the breakage of the water shielding sheets 6a and 6b is caused by the fact that leachate (leakage) from the broken portion of the water shielding sheets 6a and 6b flows into the injection pipe 8. And a damage detection signal is output to the control device 17. Further, the filling detection means 18 in the illustrated example is provided at the upstream end of the interval d, and detects that the PVA water shielding material aqueous solution 10 has flowed into the deaeration pipe 9 as filling in the interval d by the aqueous solution 10 and fills the control device 17. A detection signal is output. However, the breakage detection means 16 and the filling detection means 18 are not limited to the illustrated examples, and for example, a water leak detection sensor disclosed in Patent Document 1 can be used.

Further, the illustrated system includes a liquid storage tank 11 and a pH adjusting means 14 connected to the injection device 12. The liquid storage tank 11 stores a PVA water shielding material aqueous solution 10 that provides a water shielding material gel having strength and water shielding properties necessary for the water shielding work 5 of the waste disposal site 2. Such an aqueous solution 10 can be prepared by selecting the polymerization degree and concentration of the PVA polymer in the aqueous solution 10 and the molar ratio of the crosslinking agent as described above. The pH adjusting means 14 adjusts the pH of the aqueous solution 10 in the liquid storage tank 11 or the injection device 12 so that the gelation time t of the aqueous solution 10 is not less than the filling time t ₀ of the interval d by the aqueous solution 10. Such a filling time t ₀ can be calculated from the injection flow rate of the injection device 12 and the volume of the interval d as described above. Preferably, the pH adjusting means 14 includes a thermometer that measures the ambient temperature of the ground 1, and the pH of the aqueous solution 10 is adjusted according to the ambient temperature of the ground 1.

  When the water shielding sheets 6a and 6b are broken during use or maintenance of the waste disposal site 2, the breakage detection means 16 detects the breakage and outputs a breakage detection signal. And the deaerator 15 is driven. The injection device 12 injects the PVA water shielding material aqueous solution 10 stored in the liquid storage tank 11 to the downstream end of the interval d between the water shielding sheets 6a and 6b. If necessary, the pH of the aqueous solution 10 is adjusted by the pH adjusting means 14 before injection. Further, the deaeration device 15 sets the deaeration path 8 to a negative pressure with respect to the interval d, and sucks air and leachate in the interval d out of the interval d. The injection of the aqueous solution 10 by the injection device 12 and the deaeration by the deaeration device 15 are continued until the filling detection by the filling detection means 18. The filling detection means 18 detects the filling of the interval d by the aqueous solution 10 and outputs a filling detection signal, and the control device 17 stops the injection device 12 and the deaeration device 15.

  The PVA water shielding material aqueous solution 10 filled in the water shielding sheets 6a and 6b becomes a PVA water shielding material gel having the required strength and the required water shielding properties after the elapse of the gelation time t according to the pH, and the water shielding sheets 6a and 6b. Repair damaged parts. As described above, the PVA water shielding material gel has a high water shielding property equal to or higher than that of a clay liner, and has a low biodegradability, so it is very stable in the long term. In addition, since PVA water shielding material gel is a konjac-like elastic material, even if local subsidence of the ground occurs, it may follow the ground deformation and may break or damage the water shielding sheets 6a and 6b. Absent.

  In the illustrated example, the deaeration tube 8 is embedded as it is in the PVA water shielding material gel, but the deaeration tube 8 is not necessarily embedded in the PVA water shielding material gel. When embedding the degassing pipe 8 in the PVA water shielding material gel, in order to avoid problems with water shielding, for example, the degassing pipe 8 is also filled with the PVA water shielding material aqueous solution 10 to be gelled, and degassed as necessary. It is desirable to prevent generation of water at the interface between the outer peripheral edge of the trachea 8 and the PVA water shielding material gel.

  In the illustrated example, the present invention is used for repairing after the detection of breakage of the water shielding sheets 6a and 6b, but the present invention injects the PVA water shielding material aqueous solution 10 when constructing the water shielding sheets 6a and 6b. Therefore, it can also be used to construct a water barrier that is safer than conventional water barriers. That is, the present invention can be applied or used for both the pre-injection method and the post-injection method.

It is explanatory drawing of one Example in this invention. FIG. 2 is an enlarged explanatory view of (A) a water shielding work and (B) an injection path and a deaeration path in FIG. 1. It is a graph of the experimental result which shows the relationship between the gelation time, pH, and temperature of the PVA injection | pouring water-insulating material of 3% of PVA polymers using a methylol melamine type crosslinking agent. It is a graph of the experimental result which shows the relationship between the gelation time of a PVA injection | pouring water-insulating material with a PVA polymer concentration of 4% using a methylol melamine type crosslinking agent, pH, and temperature. It is a graph of the experimental result which shows the relationship between the gelation time, pH, and temperature of the PVA injection | pouring water shielding material of PVA polymer concentration 5% using a titanium lactate type crosslinking agent. It is a graph of the experimental result which shows the relationship between the gelation time and temperature of a PVA injection | pouring water-insulating material with a PVA polymer density | concentration of 5% using a titanium lactate type crosslinking agent. It is explanatory drawing of the experimental method which confirms the water shielding performance of the PVA injection | pouring water shielding material used by this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Ground surface 2 ... Waste disposal site 3 ... Waste layer 5 ... Water shielding work 6 ... Water shielding sheet 7 ... Porous separation material 8 ... Injection channel 9 ... Deaeration channel 10 ... Water shielding material aqueous solution
11 ... Storage tank 12 ... Injection device
14 ... pH adjustment means 15 ... Deaerator
16… Damage detection means 17… Control device
18 ... Filling detection means 21 ... Hole
22 ... Cylinder pipe 23 ... Water

Claims (27)

A plurality of layers of water shielding sheets laid on the ground surface on which the load is installed, with a peripheral edge closely adhered thereto, a porous separation material that keeps an interval between the adjacent water shielding sheets against the load, and within the interval A water-impervious material injection type water-impervious construction comprising a polyvinyl alcohol-based water-impervious material aqueous solution that is injected and whose gelation time can be adjusted by pH. The water-impervious construction according to claim 1, wherein the gap is deaerated at the time of the injection. 3. The water shielding work according to claim 1, wherein the aqueous solution has a pH at which the gelation time becomes equal to or longer than the filling time for the interval. 4. The water shielding work according to claim 3, wherein the pH of the aqueous solution is adjusted in accordance with the ground ambient temperature at the time of the filling. 5. The impermeable construction according to claim 1, wherein the aqueous solution is an aqueous solution in which a polyvinyl alcohol-based polymer, a water-soluble crosslinking agent having two or more methylol groups in the molecule, and a pH adjuster are dissolved. A water-impervious material injection type water-impervious construction which provides the required water-imperviousness to the gel by the degree of polymerization, the polymer concentration in the aqueous solution, and the molar ratio of methylol groups in the cross-linking agent to the vinyl alcohol units in the polymer. 5. The impermeable construction according to claim 1, wherein the aqueous solution is an aqueous solution in which a polyvinyl alcohol-based polymer, a crosslinking agent composed of a water-soluble transition metal compound and a pH adjuster are dissolved, and the degree of polymerization of the polymer and the aqueous solution A water-impervious material injection type water-impervious construction which provides the required water-impervious property to the gel by the polymer concentration of the polymer and the molar ratio of the transition metal compound in the cross-linking agent to the vinyl alcohol unit in the polymer. 7. The water-impervious structure according to claim 5 or 6, wherein the viscosity of the aqueous solution is in the range of 15 to 2000 mPa · s, and the water permeability of the gel is 1 × 10 ⁻⁵ cm / sec or less. . A plurality of layers of water-impervious sheets laid on the ground surface on which the load is installed, with a peripheral edge closely adhered thereto, a porous separating material that maintains an interval against the load between adjacent water-impervious sheets, and communicates with the interval A water-impervious material injection type water-impervious system comprising an injection channel, a deaeration channel, and an injection device for injecting a polyvinyl alcohol-based water-shielding material aqueous solution whose gelation time can be adjusted by pH through the injection channel. 9. The system according to claim 8, wherein a pH adjusting means is provided for adjusting the pH of the aqueous solution to a pH at which the gelation time is equal to or longer than the filling time of the interval according to the volume of the interval and the flow rate of the injection device. Water injection type water shielding system. The system according to claim 9, wherein the pH adjusting means includes a thermometer for measuring a ground ambient temperature, and the pH of the aqueous solution is adjusted according to the ground ambient temperature. 11. The system according to claim 8, wherein the injection path and the deaeration path are communicated with a downstream end and an upstream end of the interval, and a filling detection means for detecting the filling of the interval is provided in the deaeration path. Water shielding material injection type water shielding system. 12. The water shielding material injection type water shielding system according to any one of claims 8 to 11, wherein the porous separating material is a nonwoven fabric, a woven fabric or a knitted sheet, or a mat with a rugged or honeycomb structure. The system according to any one of claims 8 to 12, wherein the water shielding sheet has a small rate of change in thickness with respect to the load. 14. The system according to claim 8, further comprising: a breakage detecting means for detecting breakage of the water shielding sheet, and a water shielding material injection comprising a control device for driving the injection device in response to the breakage detection. Mold impermeable system. The system according to any one of claims 8 to 14, wherein the aqueous solution is an aqueous solution in which a polyvinyl alcohol polymer, a water-soluble crosslinking agent having two or more methylol groups in the molecule, and a pH adjuster are dissolved, and the degree of polymerization of the polymer. And a water-insulating material injection type water-insulating system in which a required water-insulating property is given to the gel by the polymer concentration in the aqueous solution and the molar ratio of the methylol group in the cross-linking agent to the vinyl alcohol unit in the polymer. 15. The system according to claim 8, wherein the aqueous solution is an aqueous solution in which a polyvinyl alcohol-based polymer, a crosslinking agent comprising a water-soluble transition metal compound and a pH adjuster are dissolved, and the degree of polymerization of the polymer and the polymer in the aqueous solution. A water-impervious material injection type water-impervious system which provides the required water-imperviousness to the gel by the concentration and the molar ratio of the transition metal compound in the cross-linking agent to the vinyl alcohol unit in the polymer. An aqueous solution in which a polyvinyl alcohol polymer having a polymerization degree of 500 or more, a water-soluble crosslinking agent having two or more methylol groups in the molecule, and a pH adjuster are dissolved, and the polymer concentration in the aqueous solution is 2.0 to 7.0% by weight, A polyvinyl alcohol-based injection impermeable material obtained by adjusting the molar ratio of the methylol group in the crosslinking agent to the vinyl alcohol unit in the polymer to 0.01 to 0.5 and adjusting the pH of the aqueous solution to the required gelation time. The water-insulating material according to claim 17, wherein the water-soluble crosslinking agent is a trimethylol melamine and / or a methoxylated trimethylol melamine. 19. The water shielding material according to claim 17 or 18, wherein the aqueous solution has a viscosity of 15 to 2000 mPa · s. 20. The water impermeable material according to any one of claims 17 to 19, wherein the water permeability coefficient after gelation of the aqueous solution is 1 × 10 ⁻⁵ cm / sec or less. 21. The water barrier material according to claim 17, wherein the pH adjusting agent is an acid and the aqueous solution is adjusted to a pH of 4 to 6. An aqueous solution in which a polyvinyl alcohol polymer having a polymerization degree of 500 or more, a crosslinking agent comprising a water-soluble transition metal compound, and a pH adjuster are dissolved, and the polymer concentration in the aqueous solution is 2.0 to 7.0% by weight, and the vinyl alcohol in the polymer A polyvinyl alcohol-based water-impermeable material obtained by adjusting the molar ratio of metal atoms in the cross-linking agent to the unit to 0.01 to 1.0 and adjusting the pH of the aqueous solution to the required gelation time. 23. The water-impermeable material according to claim 22, wherein the water-soluble transition metal compound-containing cross-linking agent is a titanium compound and / or a zirconium compound. 24. The water barrier material according to claim 23, wherein the water-soluble transition metal compound is titanium lactate. 25. The water shielding material according to claim 22, wherein the aqueous solution has a viscosity of 15 to 2000 mPa · s. 26. The water impermeable material according to claim 22, wherein the water permeability coefficient after gelation of the aqueous solution is 1 × 10 ⁻⁵ cm / sec or less. 27. The water-impermeable material according to claim 22, wherein the pH adjuster is ammonia water and the aqueous solution is adjusted to a pH of 6 to 10.

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