JP2006006994A - Repair agent for water shielding sheet - Google Patents

Abstract

【Task】
An object of the present invention is to provide a repair agent for a water shielding sheet that has a short curing time and can shorten the work period of repairing the water shielding sheet.
[Solution]
The present invention provides the following (1) to (3).
(1) A repair agent for water shielding sheets containing a compound that is cured by light.
(2) The light shielding compound according to (1), wherein the compound that is cured by light is at least one compound selected from urethane acrylate, urethane methacrylate, ester acrylate, ester methacrylate, an epoxy group-containing compound, and a polybutadiene polymer. Water sheet repair agent.
(3) The repair agent for a water shielding sheet according to (1) or (2), which contains a photopolymerization initiator.
[Selection figure] None

Description

  The present invention relates to a repair agent for a water shielding sheet used for a water shielding structure such as a final waste disposal site, a reservoir, and a dam, and a method for repairing the water shielding sheet.

  Water shielding sheets are used in water shielding structures such as waste final disposal sites, reservoirs, and dams. For example, in a managed waste final disposal site, a synthetic resin or rubber impermeable sheet having a thickness of about 1.5 to 2.0 mm is used. These water-impervious sheets may be damaged due to contact with sharp objects mixed in the waste, deficiencies in the construction of the water-impervious sheet, and partial deterioration of the water-impervious sheet due to long-term use. There is. When the impervious sheet breaks, the leachate leaks out of the landfill from the damaged part, and harmful substances in the waste that are dissolved in the leachate enter the groundwater and pollute the environment around the waste disposal site. There is a fear. For this reason, it is very important to detect the breakage of the impermeable sheet at an early stage and repair the damaged impermeable sheet.

In recent years, an electrical detection system or the like has been developed as a system for specifying a breakage position of a water shielding sheet with high accuracy, and various methods for repairing the water shielding sheet have been proposed (see Patent Document 1).
In the repair method of the water-impervious sheet, a method of heat-sealing or adhering so that the damaged portion of the water-impervious sheet is covered with a sheet of the same quality as the water-impervious sheet is common. However, for example, when a water shielding sheet is used at the final disposal site, it is necessary to remove the waste above the damaged part, and it is difficult to remove the waste when the landfill is deep. This is an extremely large-scale work. In addition, in an environment where methane gas or the like may be generated, it is necessary for a worker to enter and perform repair work for a long time, which is dangerous. Furthermore, since the worker manually cleans the repaired part, the repair completion level varies depending on the skill level of the worker.

  In addition, a method of repairing by injecting an injection from the upper part of the cavity after excavating the vicinity of the damaged part of the shielding sheet with jet water to form a vertical cavity above the damaged part (see Patent Document 2), A method of injecting and solidifying a chemical solution (see Patent Document 3) has been proposed. These methods do not require an operator to enter the hole and work. However, in these methods, final completion of repair cannot be visually confirmed, and in order to confirm, it is necessary to rely on an indirect detection system or the like. In the former, there is a risk of collapse in the space formed using jet water, and it is necessary to use a large amount of a repair agent, such as an asphalt emulsion, for repairing the damaged portion of the water shielding sheet. Furthermore, this repair agent is inferior in adhesiveness with the water-impervious sheet, and it is difficult to guarantee the adhesive property between the water-impervious sheet and the repair agent for a long time. Even in the latter case, a material completely different from a water shielding sheet such as a silica-based chemical solution is used as an injecting agent, and this is solidified and repaired. As in the case of the former repairing method, the repairing agent and the water shielding material are used. Since it is inferior in adhesiveness with a sheet | seat, it is difficult to guarantee the adhesiveness of a long-term water-proof sheet | seat and a repair agent.

In addition, as a repair method for performing repair work safely and easily, an unmanned repair method (see Patent Document 4) in which urethane resin is poured as a repair agent has been proposed. This method is an excellent method for obtaining excellent adhesion and long-term durability particularly in a polyurethane sheet. However, when the amount of the repair agent injected is large, it takes a long time for the repaired portion to harden after the injection of the repair agent.
Japanese Examined Patent Publication No. 6-63910 JP-A-11-300308 JP 2002-273368 A JP-A-9-108645

  An object of the present invention is to provide a repair agent for a water shielding sheet that has a short curing time and can shorten the work period of repairing the water shielding sheet.

The present invention provides the following (1) to (10).
(1) A repair agent for water shielding sheets containing a compound that is cured by light.
(2) The light shielding compound according to (1), wherein the compound that is cured by light is at least one compound selected from urethane acrylate, urethane methacrylate, ester acrylate, ester methacrylate, an epoxy group-containing compound, and a polybutadiene polymer. Water sheet repair agent.
(3) The repair agent for a water shielding sheet according to (1) or (2), which contains a photopolymerization initiator.
(4) A repair method for a water shielding sheet, comprising injecting a repair agent for a water shielding sheet containing a compound that is cured by light into a damaged portion of the water shielding sheet.
(5) The light-shielding compound according to (4), wherein the compound that is cured by light is at least one compound selected from urethane acrylate, urethane methacrylate, ester acrylate, ester methacrylate, a compound having an epoxy group, and a polybutadiene polymer. Water sheet repair method.
(6) The method for repairing a water shielding sheet according to (4) or (5), wherein the water shielding sheet repair agent further contains a photopolymerization initiator.
(7) After excavating a vertical hole from the upper part of the damaged part of the water shielding sheet on which waste has accumulated and exposing the damaged part, the repair agent for the water shielding sheet is applied to the damaged part using piping. The repairing method for a water shielding sheet according to any one of (4) to (6), wherein the repairing agent for the water shielding sheet is cured by pouring and irradiating light.
(8) The method for repairing a water shielding sheet according to any one of (4) to (7), wherein the water shielding sheet is repaired by remote control.
(9) A water shielding sheet repaired with the repair agent for water shielding sheets according to any one of (1) to (3).
(10) A water shielding sheet repaired by the method for repairing a water shielding sheet according to any one of (4) to (8).

  Hereinafter, methacrylate and acrylate may be combined and expressed as (meth) acrylate.

  According to the present invention, there is provided a repair agent for a water shielding sheet that has a short curing time and can shorten the work period of repairing the water shielding sheet.

Examples of water shielding sheets include thermoplastic polyurethane sheets (TPU sheets), thermoplastic polyolefin elastomer sheets [TPO sheets, polyethylene (PE) and polypropylene (PP)], high density polyethylene sheets (HDPE sheets), and vinyl chloride. Sheet (PVC sheet), chlorinated polyethylene sheet, low density polyethylene sheet (LDPE sheet), linear low density polyethylene sheet (LLDPE sheet), ethylene vinyl acetate copolymer sheet (EVA sheet), asphalt impregnated sheet, synthetic rubber Sheet. Among these, a thermoplastic polyurethane sheet, a thermoplastic polyolefin elastomer sheet, and the like are preferable from the viewpoint of adhesiveness.
(1) Compound cured by light The compound cured by light is not particularly limited, but urethane (meth) acrylate, ester (meth) acrylate, epoxy (meth) acrylate, compound having an epoxy group, urethane alkenyl ether, Examples thereof include ester alkenyl ethers and polybutadiene polymers. Among these, urethane (meth) acrylate, ester (meth) acrylate, a compound having an epoxy group or a polybutadiene-based polymer is preferable from the viewpoint of adhesiveness to a water shielding sheet, flexibility, strength, and the like. ) Acrylate or ester (meth) acrylate is more preferred.

Hereinafter, some of the compounds that are cured by light will be described in detail.
(1-1) Urethane (meth) acrylate The urethane (meth) acrylate is a (meth) acrylate compound having a polyol compound and an isocyanate group, or a (meth) acrylate compound having a polyisocyanate compound and a hydroxyl group, as raw materials. For example, it can be produced by the following production method.
[Production Method 1] A method of reacting a (meth) acrylate compound having a hydroxyl group with polyurethane having isocyanate groups at both ends obtained by reacting a polyol compound and a polyisocyanate compound.
[Production Method 2] A method in which a polyol compound is reacted with an isocyanate group of an intermediate obtained by reacting a polyisocyanate compound with a (meth) acrylate compound having a hydroxyl group.
[Production Method 3] A method in which a polyisocyanate compound, a polyol compound and a (meth) acrylate compound having a hydroxyl group are simultaneously reacted.
[Production Method 4] A method in which a polyurethane having hydroxyl groups at both ends obtained by reacting a polyol compound and a polyisocyanate compound is reacted with a (meth) acrylate compound having an isocyanate group.
[Production Method 5] A method of reacting a polyisocyanate compound with a polyurethane having hydroxyl groups at both ends obtained by reacting a polyol compound with a (meth) acrylate compound having an isocyanate group.
[Production Method 6] A method in which a polyisocyanate compound, a polyol compound and a (meth) acrylate compound having an isocyanate group are simultaneously reacted.

  Examples of the polyol compound include ethylene glycol, propylene glycol, tetramethylene glycol, diethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 2,4-diethyl-1,5- Pentanediol, neopentyl glycol, 1,6-hexane glycol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,4-bis (β-hydroxyethoxy ) Low molecular polyols such as benzene, glycerin, addition products of glycerin and propylene oxide, dimers such as pentanetriol, butanetriol, pentaerythritol, pentaerythritol, polyethylene glycol, polypropylene glycol, polyte Glycol, polyheptamethylene glycol, polyhexamethylene glycol, polydecamethylene glycol, polymer polyol of the polyether polyols obtained by one or more ion-polymerizable cyclic compounds by ring-opening copolymerization and the like. Here, examples of the ion polymerizable cyclic compound include ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bis (chloromethyl) oxetane, tetrahydrofuran, dioxane, trioxane, tetraoxane, and 3-methyltetrahydrofuran. 2-methyltetrahydrofuran, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monooxide, isoprene monooxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl Examples thereof include glycidyl ether and butyl glycidyl ether.

  In addition, as the polymer polyol, for example, the polyol compound is reacted with a dibasic acid such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, and 2,4-diethylglutaric acid. Polyester polyols obtained by reaction, polycaprolactone polyols obtained by reacting the above low molecular polyols with cyclic lactone compounds such as ε-caprolactone, dialkyl carbonates such as the above low molecular polyols and diethyl carbonate, and diaryls such as diphenyl carbonate Examples thereof include polycarbonate polyols obtained by reacting carbonate compounds such as carbonates and alkylene carbonates such as ethylene carbonate. The dibasic acid, cyclic lactone compound and carbonate compound may be used alone or in combination of two or more.

Examples of the polymer polyol include telechelic polyol compounds having alkenyl ethers as structural units.
Furthermore, examples of the polymer polyol include a polybutadiene polymer having a hydroxyl group. Examples of the polybutadiene-based polymer having a hydroxyl group include those in which a hydroxyl group is introduced into a butadiene homopolymer, a butadiene copolymer or the like obtained by anionic polymerization, coordination anionic polymerization, radical polymerization, or the like. Examples of monomers other than butadiene used in the production of the copolymer include isoprene, styrene, α-methylstyrene, acrylonitrile, ethyl acrylate and the like, and these are preferably 0.1 to 30% by weight based on butadiene. used. These polybutadiene-based polymers having hydroxyl groups may be those subjected to hydrogenation. Furthermore, the bond form may be either 1,2-bond or 1,4-bond, and these may be mixed. The ratio in the case of being mixed is not particularly limited.

Among these polyol compounds, polymer polyols are particularly preferable.
The polyol compounds may be used alone or in combination of two or more.
Further, a part of the polyol compound may be replaced with a polyamine compound and used together. You may use a polyamine compound individually or in mixture of 2 or more types. In this case, the amount of the polyamine compound used is preferably 0.01 to 30% by weight of the total amount of the polyol compound and the polyamine compound. Examples of the polyamine compound include aliphatic diamines such as ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butanediamine, and hexamethylenediamine, isophorone diamine, dicyclohexylmethanediamine, methylcyclohexanediamine, And alicyclic diamines such as 1,4-cyclohexyldiamine.

These polyol compounds are, for example, Hodogaya Chemical Co., Ltd., Sanyo Kasei Co., Ltd., Kuraray Co., Ltd., Mitsubishi Chemical Co., Ltd., Nippon Soda Co., Ltd., Idemitsu Petrochemical Co., Ltd., Kyowa Hakko Kogyo Co., Ltd. It is also possible to obtain it as a commercial product from Co., Ltd.
Examples of the polyisocyanate compound include tolylene diisocyanates such as diphenylmethane-4,4′-diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate, m- and p-phenyl. Aromatic isocyanates such as diisocyanate, polymethylpolyphenyl isocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, cyclohexanedi Aliphatic isocyanates such as isocyanate and isophorone diisocyanate, aliphatic isocyanates such as hexamethylene diisocyanate and lysine ester diisocyanate, lysine ester triisocyanate, and tris (4-isocyanate phenol) ) Thiophosphate, triphenylmethane triisocyanate and the like, among others, diphenylmethane-4,4'-diisocyanate, tolylene diisocyanate, isophorone diisocyanate is preferred. These polyisocyanate compounds may be used alone or in combination of two or more.

  Examples of the (meth) acrylate compound having a hydroxyl group include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and polyethylene. Glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimellilol ethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate Neopentyl glycol mono (meth) acrylate, glycerin di (meth) acrylate, ethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, 1,4-butanediol (meth) acrylate, 1,6-hexanediol (meta ) Acrylate, neopentyl glycol (meth) acrylate, trimethylolpropane dioxyethyl (meth) acrylate, etc., among which 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate and the like are preferred. These (meth) acrylate compounds having a hydroxyl group may be used alone or in combination of two or more.

Examples of the (meth) acrylate compound having an isocyanate group include 2-isocyanatoethyl (meth) acrylate.
In the raw materials of the production methods 1 to 6, the ratio of the total number of moles of hydroxyl groups to the total number of moles of isocyanate groups is preferably 1: 0.2 to 5, more preferably 1: 0.5 to 2. The reaction temperature in the said manufacturing methods 1-6 becomes like this. Preferably it is 0-200 degreeC, More preferably, it is 10-150 degreeC.

In the reactions of the above production methods 1 to 6, a catalyst such as tin octylate, dibutyltin dilaurate, copper naphthenate, cobalt naphthenate, zinc naphthenate, or triethylamine may be used as necessary. The amount of these catalysts used is preferably 0.001 to 3 parts by weight with respect to 100 parts by weight of the total amount of reaction raw materials.
In reaction of the said manufacturing methods 1-6, you may use a thermal-polymerization inhibitor as needed. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, hydroquinone monobenzyl ether, hydroquinone monopentyl ether, 2,6-di (tert-butyl) -4-methylphenol, 4,4′-thiobis (6- tert-butyl-3-methylphenol), 2,2′-methylenebis (6-tert-butyl-4-methylphenol), 2,2′-butylidenebis (6-tert-butyl-4-methylphenol), para- Examples thereof include tert-butylcatechol and phenothiazine. The amount of these thermal polymerization inhibitors used is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the total amount of reaction raw materials.

In reaction of the said manufacturing methods 1-6, you may use a solvent as needed. Examples of the solvent include ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and diethylene glycol monoethyl ether acetate, and aromatic hydrocarbons such as benzene, toluene and xylene.
The number average molecular weight of the urethane (meth) acrylate used in the present invention is not particularly limited, but is preferably 500 to 100,000.
(1-2) Ester (meth) acrylate The ester (meth) acrylate can be produced by reacting a polyol compound with acrylic acid or its ester, acryloyl chloride, and the like.

Examples of the polyol compound are the same as those described in the description of (1-1).
Examples of acrylic acids include acrylic acid and methacrylic acid.
Examples of acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate. , Cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, isobornyl (meth) An acrylate etc. are mention | raise | lifted.

Examples of acryloyl chloride include acrylic acid chloride and methacrylic acid chloride.
The amount of acrylic acid or its ester, acryloyl chloride, etc. used in the raw material is preferably 0.7 to 10 equivalents (molar ratio) with respect to the amount of polyol compound used.
The reaction temperature is preferably 0 to 180 ° C.

In the above reaction, a thermal polymerization inhibitor may be used as necessary. Examples of the thermal polymerization inhibitor include the same ones as described in the description of (1-1). The amount of the thermal polymerization inhibitor used is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the total amount of reaction raw materials.
In the above reaction, a solvent and a catalyst may be used as necessary. Examples of the solvent and the catalyst are the same as those described in the description of (1-1).

Moreover, ester (meth) acrylate can be obtained by making acrylic acid and polyol react in a solvent in presence of a catalyst amount-excess amount of an acid catalyst (p-toluenesulfonic acid etc.). Here, examples of the solvent include the same solvents as those described above in (1-1).
The number average molecular weight of the ester (meth) acrylate used in the present invention is not particularly limited, but is preferably 500 to 100,000.
(1-3) Compound having an epoxy group Examples of the compound having an epoxy group include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-m-dioxane, bis (2,3-epoxycyclopentyl) ether, limonene dioxide, 4-vinylcyclohexene dioxide, phenylglycidyl Ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin and other bisphenol type epoxy resins, phenol novolac type epoxy resin, Examples thereof include sol / novolac type epoxy resins, novolak type epoxy resins such as brominated phenol / novolak type epoxy resins, polyglycidyl ethers of polyhydric alcohols, and the like.
(1-4) Polybutadiene polymer As the polybutadiene polymer, for example, a butadiene homopolymer or butadiene copolymer obtained by anion polymerization, coordination anion polymerization, radical polymerization, etc., a hydroxyl group, an acrylic group, a methacryl group, Examples thereof include those having 1 to 50 carboxyl groups introduced per molecule. Examples of monomers other than butadiene used in the production of the copolymer include isoprene, styrene, α-methylstyrene, acrylonitrile, ethyl acrylate and the like, and these are preferably 0.1 to 30% by weight based on butadiene. used. Among these polybutadiene polymers, compounds in which a polymerizable functional group such as an acryl group or a methacryl group is introduced into one molecule may be obtained by hydrogenating part or all of the butadiene skeleton. Good. Furthermore, regarding the bond at the time of polymerization, either 1,2-bond or 1,4-bond may be used, and these may be mixed. When they are mixed, the ratio is not particularly limited.

The number average molecular weight of the polybutadiene polymer used in the present invention is not particularly limited, but is preferably 300 to 500,000, more preferably 500 to 5000.
These polybutadiene-based polymers can also be obtained as commercial products from, for example, Shin Nippon Petrochemical Co., Ltd., Idemitsu Petrochemical Co., Ltd., Nippon Soda Co., Ltd. and the like.

(2) Repair agent for water shielding sheet containing a compound that is cured by light The repair agent of the present invention preferably contains 0.1 to 90% by weight of the compound that is cured by light in the repair agent, It is more preferable to contain 0.5 to 85% by weight.
(2-1) When the repair agent of the present invention is cured by ultraviolet rays or visible light When the repair agent of the present invention is cured by ultraviolet rays or visible light, the repair agent of the present invention contains a photopolymerization initiator. Is preferable, and a photosensitizer can be contained if necessary. These photopolymerization initiators and photosensitizers can be appropriately selected depending on the type of the compound that is cured by light as follows.

In the case where the compound that is cured by light is urethane (meth) acrylate, ester (meth) acrylate, (meth) acrylate such as epoxy (meth) acrylate, or polybutadiene polymer, a radical-generating photopolymerization initiator and light It is preferable to use a sensitizer.
When the compound curable with light is a compound having an epoxy group, urethane alkenyl ether, ester alkenyl ether or the like, it is preferable to use a cation-generating photopolymerization initiator and a photosensitizer.

  Examples of radical-generating photopolymerization initiators include benzoin, benzoin isobutyl ether, benzyl, benzophenone, p-chlorobenzophenone, p-methoxybenzophenone, tetramethylturanium monosulfide, tetramethyltyrium disulfide, and 1-hydroxycyclohexyl. Phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone , Benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2- Tylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- (4- (methylthio) Phenyl) -2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, camphorquinone and the like. Examples of the photosensitizer used in combination with the radical-generating polymerization initiator include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4 -Ethyl dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate and the like. These radical-generating photopolymerization initiators can be obtained as commercially available products, such as IRGACURE651, IRGACURE184, IRGACURE907, IRGACURE819, DAROCURE1173, IRGACURE369 [above Ciba Specialty Chemicals Co., Ltd.], KAYACURE DETX-S, KAYACURE BMS [manufactured by Nippon Kayaku Co., Ltd.] and the like. Photosensitizers can also be obtained as commercial products, such as KAYACURE DMBI, KAYACURE EPA [manufactured by Nippon Kayaku Co., Ltd.] and the like.

Examples of the cation generation type photopolymerization initiator include salts of phosphorus pentafluoride such as aryldiazonium, sulfonium and iodonium, and boron trifluoride and antimony fluoride.
Examples of the photosensitizer used in combination with the cation-generating photopolymerization initiator include thioxanthone and anthracene. These cation generation type photopolymerization initiators can be obtained as commercial products. For example, Uvacure 1591 [manufactured by Daicel UCB Co., Ltd.], CI-2624, CI-2639, CI-5102 [Nippon Soda (above) Co., Ltd.], Adekaoptomer SP-150, Adekaoptomer SP-170 [above Asahi Denka Kogyo Co., Ltd.], Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L [Sanshin Chemical Industry (above) Co., Ltd.], Rhodesyl Photo Initiator PI2074 [manufactured by Rhodia Japan Co., Ltd.] and the like. Moreover, a photosensitizer can also be obtained as a commercial item, for example.
These photopolymerization initiators are preferably contained in the repairing agent of the present invention in an amount of 0.1 to 15% by weight, more preferably 1 to 10% by weight. Moreover, it is preferable that 0-15 weight% is contained in the repair agent of this invention, and, as for a photosensitizer, it is more preferable that 0-10 weight% is contained.
(2-2) When the repair agent of the present invention is cured by an electron beam When the repair agent of the present invention is cured by an electron beam, the repair agent of the present invention is a photopolymerization initiator or a photosensitizer as necessary. Etc. are preferably contained. These photopolymerization initiators and photosensitizers are appropriately selected depending on the type of compound that is cured by light as follows.

When the compound that is cured by light is urethane (meth) acrylate, ester (meth) acrylate, (meth) acrylate such as epoxy (meth) acrylate, or polybutadiene polymer, a photopolymerization initiator may not be added. Good.
When the compound curable with light is a compound having an epoxy group, urethane alkenyl ether, ester alkenyl ether or the like, it is preferable to use a cation-generating photopolymerization initiator and a photosensitizer.

Examples of the cation-generating photopolymerization initiator and photosensitizer include the same as those described in the description of (2-1).
In the repair method of the present invention, the repair agent of the present invention may be used alone or in a blend of two or more as required.
In addition, the repair agent of the present invention may be a polyolefin resin, polyester resin, polyurethane resin, vinyl acetate resin, polyamide resin, epoxy resin, polyester elastomer, polystyrene elastomer, polyurethane elastomer, polyamide, if necessary. It may contain conventional repair agents such as elastomers such as rubber-based elastomers and polyolefin-based elastomers, rubber, and asphalt.

Furthermore, the repairing agent of the present invention includes an antioxidant, a colorant, a light stabilizer, an ultraviolet absorber, a silane coupling agent, a storage stabilizer, a plasticizer, a lubricant, a solvent, a filler, and an anti-aging agent as necessary. And additives such as surfactants may be contained.
Examples of the antioxidant include IRGANOX 1010, IRGANOX 1035, and IRGANOX 1076 [manufactured by Ciba Specialty Chemicals Co., Ltd.]. Manufactured by Co., Ltd.].

In repairing the water shielding sheet, it is preferable to prepare in advance the compound that is cured by light used in the repair agent of the present invention, and the repair agent includes a polymerizable monomer, a photopolymerization initiator, if necessary. It is preferable to add a photosensitizer, a conventional repair agent, an additive and the like in advance.
The repair agent of the present invention is preferably stored in a cool and dark place where no light is applied, such as a refrigerator.
The repair agent of the present invention has the following effects.
(A) The curing time of the repair agent is short, and the work period for repairing the water shielding sheet can be shortened.
(B) It can be bonded to a wide variety of water shielding sheet materials.
(C) The influence of adhesiveness due to the degree of cleaning of the repaired portion is small.
(D) The repair agent can be transported over a long distance with energy saving using a thin pipe.
(E) No heating is required for curing the repair agent.
(F) Since the water shielding sheet is used at the final disposal site of the waste, it can be repaired without digging up the waste even when the landfill is deep.
(G) Repair is possible without human beings entering the excavation hole.
(H) Large equipment such as a backhoe and a reactor is not necessarily required, and the safety of workers during repair is high.
(3) Repair method of water shielding sheet Repair of the water shielding sheet using the repair agent of the present invention, for example, after exposing the damaged portion of the waterproof sheet, injecting the repair agent into the damaged portion of the waterproof sheet, It can be performed by a method of curing by light irradiation.

  As a method for exposing the breakage portion of the water shielding sheet, for example, when the water shielding sheet is used in a waste disposal site, for example, a backhoe method or a deep foundation method for removing waste on the broken portion with a backhoe or the like Well-known methods such as an all casing method and a boring method can be used. Of these methods, when the depth of waste is deep, the backhoe method requires a lot of waste to be removed, and the deep foundation method requires people to enter and work. An all-casing method and a boring method for removing the slag are preferable for the safety of the operator.

  In addition, as a method of injecting the repair agent into the damaged portion of the water shielding sheet, for example, a method in which the repair agent is manually installed on the damaged portion of the waterproof sheet, the repair agent is pumped to the damaged portion of the waterproof sheet using a pump or the like. In accordance with the method, the method of pouring the repair agent to the damaged portion of the water shielding sheet only by gravity without using a pump, etc., the light irradiation device was attached to the unmanned repair device etc. according to the method described in JP-A-9-108645 For example, a method of injecting a repairing agent into the damaged portion of the water shielding sheet using the apparatus may be used. Among these injection methods, there are a small excavation hole that uses a pump or the like to pump the repair agent to the damaged portion of the water shielding sheet and a method that uses only gravity to flow the repair agent to the damaged portion of the water shielding sheet without using a pump. This is preferable because it can be performed unattended. In the repair agent of the present invention, the compound that is cured by light has a number average molecular weight of preferably 50000 or less, more preferably 500 to 10,000. Since these are low-viscosity, they are suitable for small pipes, pumping with a pump, transportation by gravity, and the like.

When injecting a repair agent into the water-shielding sheet breakage part and irradiating light to cure the repair agent, it is preferable to repeatedly perform the operation of pouring thinly to cover the repair agent in the water-shielding sheet breakage part and curing. .
Although the form of the repair method of the impermeable sheet concerning this invention is demonstrated below, referring drawings, this invention is not limited to these repair methods.

  FIG. 1 is a schematic sectional view showing an example of a waste disposal site. In the waste disposal site 1, a synthetic resin or rubber impermeable sheet 2 is laid on the bottom surface, and most of the upper part thereof is Usually, a protective soil 4 such as sand is laid at a depth of about 50 cm, and the waste 5 is accommodated on the entire protective soil 4. When the water shielding sheet breakage hole 3 occurs in the water shielding sheet 2, it is necessary to repair the water shielding sheet breakage hole 3 quickly.

  FIG. 2 is a schematic cross-sectional view showing an example of an embodiment of a repair method for a water shielding sheet according to the present invention. In the present embodiment, the repair is performed as follows. First, when the water shielding sheet breakage hole 3 is specified by various detection systems or the like, the waste 5 and the protective soil 4 located above the water shielding sheet breakage hole 3 are dug up by a device 8 such as a backhoe, and the water shielding sheet breakage hole 3. To expose. Next, the repair agent 6 is poured so as to block the water shielding sheet breakage hole 3, and the repair agent 6 is cured using the light irradiation device 7 from above. When the repair agent 6 is cured, the water shielding sheet breakage hole 3 is completely blocked, and the repair is completed.

FIG. 3 is a schematic cross-sectional view showing another example of the embodiment of the method for repairing a water shielding sheet according to the present invention. In the present embodiment, the repair is performed as follows. First, when the water shielding sheet breakage hole 3 is specified by various detection systems or the like, the waste 5 and the protective soil 4 positioned above the water shielding sheet breakage hole 3 are removed from the top by a deep foundation method, an all casing method, a boring method, etc. Excavation is gradually carried out to expose the water impervious sheet breakage hole 3. Next, the repair agent introduction port 13 connected to the control panel 10, the light irradiation device 7, and the CCD camera 12 connected to the monitor 11 were lowered to the upper part of the water shielding sheet breakage hole 3, and the repair agent 6 was connected to the pump 9. The water blocking sheet breakage hole 3 is poured from the repair agent inlet 13 so as to close it. Here, it is possible to force the repair agent to flow into the water shielding sheet breakage hole 3 from the repair agent inlet 13 using the pump 9, but repair the repair agent 6 only by gravity without using the pump 9. It is also possible to pour from the agent inlet 13. Furthermore, it is possible to heat the repairing agent 6 in order to increase the fluidity. It is confirmed on the monitor 11 on the ground through the CCD camera 12 that the water blocking sheet breakage hole 3 is completely covered with the repair agent 6. After confirming that the water-impervious sheet breakage hole 3 is completely blocked, the repair agent 6 is cured using the light irradiation device 7 from the control panel 10 on the ground. When the repair agent 6 is cured, the water shielding sheet breakage hole 3 is completely blocked, and the repair is completed.
FIG. 4 is a schematic cross-sectional view showing another example of the embodiment of the method for repairing a water shielding sheet according to the present invention. In the present embodiment, the repair is performed as follows. First, when the water shielding sheet breakage hole 3 is specified by various detection systems or the like, the waste 5 and the protective soil 4 positioned above the water shielding sheet breakage hole 3 are removed from the top by a deep foundation method, an all casing method, a boring method, etc. Excavation is gradually carried out to expose the water impervious sheet breakage hole 3. Next, the repair agent charging device 15 provided with the CCD camera 12 connected to the monitor 11 is lowered to the upper part of the water shielding sheet breakage hole 3 with a crane or the like 14. As shown in FIG. 5, a light irradiation device 7 is attached to the repair agent charging device. The tank 16 contains the repair agent 6, and the temperature of the tank 16 and the stirring motor 17 can be controlled by the control panel 10 on the ground. The inside of the tank 16 can be confirmed on the monitor 11 on the ground through the CCD camera 12 attached to the upper part of the tank. The control agent 10 on the ground controls the motor 18 for supplying the repair agent, and the repair agent 6 is poured from the repair agent inlet 13 so as to block the water shielding sheet breakage hole 3. In order to improve the fluidity of the repair agent 6, the inside of the tank 16 can be heated. It can be confirmed on the monitor 11 on the ground through the CCD camera 12 attached to the lower part of the repair agent charging device that the water shielding sheet breakage hole 3 is completely blocked by the repair agent 6. After confirming that the water-impervious sheet breakage hole 3 is completely blocked, the repair agent 6 is cured using the light irradiation device 7 from the control panel 10 on the ground. When the repair agent 6 is cured, the water shielding sheet breakage hole 3 is completely blocked, and the repair is completed.

In addition to the above, the method for repairing a water shielding sheet of the present invention also uses a method in which a person enters a repair agent after exposing the water shielding sheet breakage hole 3 by a deep foundation method, an all casing method, a boring method, or the like. be able to.
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited only to these Examples.

The viscosity of the repair agent was measured at 23 ° C. using the following equipment.
Equipment: Dynamic stress rheometer (Rheometrics)
Geometry type: 25mmφ parallel plate Frequency: 10Hz
The number average molecular weight of the polymer was measured by gel permeation chromatography (GPC) under the following conditions.
(GPC analysis conditions)
Equipment: HLC-8120GPC [manufactured by Tosoh Corporation]
Column: TSKgel Super HM-M, HM-N and HM-L [manufactured by Tosoh Corporation] were connected in series.
Mobile phase: tetrahydrofuran (flow rate 0.5 ml / min)
Column oven: 40 ° C
Detector: Differential refractometer (RI)
[Reference Example 1] Urethane acrylate In a reaction vessel equipped with a stirrer, 141 g of 2,4-tolylene diisocyanate, 0.1 g of tin octylate, polytetramethylene glycol [trade name PTGL- manufactured by Hodogaya Chemical Co., Ltd.] 1000, number average molecular weight 986] 561 g, and hydroquinone monomethyl ether 0.3 g were charged and reacted at about 85 ° C. for about 3 hours with stirring. Next, 67 g of 2-hydroxyethyl acrylate was added, and the mixture was allowed to react at about 80 ° C. for about 4 hours while continuing stirring to obtain urethane acrylate [A-1] having a number average molecular weight of about 5000.
[Reference Example 2] Urethane acrylate In a reaction vessel equipped with a stirrer, 95 g of 2,4-tolylene diisocyanate, 0.1 g of tin octylate, polytetramethylene glycol [made by Hodogaya Chemical Co., Ltd., trade name PTGL- 2000, number average molecular weight 2000] 606 g and hydroquinone monomethyl ether 0.3 g were charged and reacted at about 60 ° C. for about 3 hours with stirring. Next, 50 g of 2-hydroxyethyl acrylate was added, and the mixture was reacted at about 70 ° C. for about 5 hours while stirring was continued to obtain urethane acrylate [A-2] having a number average molecular weight of about 5600.
[Reference Example 3] Urethane acrylate In a reaction vessel equipped with a stirrer, 432 g of 2,4-tolylene diisocyanate, 2.2 g of tin octylate, polyethyl vinyl ether having hydroxyl groups at both ends [manufactured by Kyowa Hakko Kogyo Co., Ltd.] , TOE-H, number average molecular weight 2408] 3070 g, and hydroquinone monomethyl ether 1.5 g were reacted at about 80 ° C. for about 1 hour with stirring. Next, 266 g of 2-hydroxyethyl acrylate was added, and the mixture was reacted at about 85 ° C. for about 3 hours while continuing stirring, to obtain urethane acrylate [A-3] having a number average molecular weight of about 3900.
[Reference Example 4] In a 300 mL glass flask equipped with an ester acrylate Dean-Stark trap, polyethyl vinyl ether having hydroxyl groups at both ends [manufactured by Kyowa Hakko Kogyo Co., Ltd., TOE-H, number average molecular weight 2408] 99.5 g (0.05 mol), toluene 50 g, hydroquinone 0.6 g (0.005 mol) and p-toluenesulfonic acid monohydrate 0.6 g (0.003 mol) were charged and heated to 100 ° C. 24.1 g (0.3 mol) of acrylic acid was added dropwise over 20 minutes, and the mixture was reacted for 15 hours while distilling off the water produced under reflux. After cooling the reaction solution, the organic layer to which 210 g of toluene was added was washed three times with a 5 wt% aqueous sodium hydroxide solution and 165 g of water. To the organic layer, 0.6 g of p-methoxyphenol was added, and concentrated at 50 ° C. and 4.1 kPa for 30 minutes to obtain ester acrylate [B-1].

Repairing agent In a reaction vessel equipped with a stirrer, 72 g of urethane acrylate [A-1], Aronix M-113 (manufactured by Toagosei Co., Ltd.) 32 g, 16 g of isobornyl acrylate, 7 g of N-vinyl-2-pyrrolidone, IRGACURE184 2 0.5 g, 0.6 g of IRGACURE 819 and 0.6 g of IRGANOX 1035 were charged and stirred and mixed at about 50 ° C. to obtain a repair agent [R-1].

Repair Agent Repair Agent [R-2] was obtained in the same manner as in Example 1 except that urethane acrylate [A-1] was changed to urethane acrylate [A-2].

Repair Agent Repair Agent [R-3] was obtained using the same method as in Example 1 except that urethane acrylate [A-1] was changed to urethane acrylate [A-3].

Repair Agent Repair Agent [S-1] was obtained using the same method as in Example 1 except that urethane acrylate [A-1] was changed to ester acrylate [B-1].

Repairing vessel A reactor equipped with a stirrer was charged with 66 g of polybutadiene polymer [Nisseki Polybutadiene MM-1000-80, Shin Nippon Petrochemical Co., Ltd.] and 2.0 g of IRGACURE 369, and stirred and mixed at about 50 ° C. A repair agent [T-1] was obtained.

Repair of water shielding sheet Thermoplastic polyurethane sheet [manufactured by Kyowa Hakko Kogyo Co., Ltd., TPU sheet], thermoplastic polyolefin elastomer sheet (TPO sheet, PE system), high density polyethylene sheet (HDPE sheet) and vinyl chloride sheet (PVC) In each of the sheets), a circular hole having a diameter of about 10 mm was made as a simulated shape of the damaged hole, and about 20 g of the repair agent [R-1] was poured at room temperature so as to close the hole. Using an ultraviolet curing device manufactured by Eye Graphics Co., Ltd., a metal halide lamp (optical path length: 25 cm) and a high-pressure mercury lamp (optical path length: 25 cm) are passed three times at 160 W / cm, a conveyor speed of about 5 m / min, and an irradiation distance of 20 cm. As a result, the repair agent [R-1] was cured, and the respective water shielding sheets were repaired.

Repair of water shielding sheet Each of the water shielding sheets was repaired using the same method as in Example 6 except that the repair agent [R-1] was changed to the repair agent [R-2].

Repair of water shielding sheet Each of the water shielding sheets was repaired using the same method as in Example 6 except that the repair agent [R-1] was changed to the repair agent [R-3].

Repair of water shielding sheet Each of the water shielding sheets was repaired using the same method as in Example 6 except that the repair agent [R-1] was changed to the repair agent [S-1].

Repair of water shielding sheet Each of the water shielding sheets was repaired using the same method as in Example 6 except that the repair agent [R-1] was changed to the repair agent [T-1].
[Comparative Example 1]
In a reaction vessel equipped with a stirrer, polytetramethylene glycol [Hodogaya Chemical Co., Ltd., trade name PTG-1000, number average molecular weight 1000] 189 g and 1,4-butanediol [Mitsubishi Chemical Co., Ltd.] 17 g And heated to 120 ° C. with stirring. 94 g of 4,4′-diphenylmethane diisocyanate (manufactured by Sumitomo Bayer Urethane Co., Ltd.) separately heated to 120 ° C. was added and reacted for about 2 minutes to obtain a polyurethane resin. Thereafter, a thermoplastic polyurethane sheet [manufactured by Kyowa Hakko Kogyo Co., Ltd., TPU sheet], a thermoplastic polyolefin elastomer sheet (TPO sheet, PE system), a high-density polyethylene sheet (HDPE sheet), and a vinyl chloride sheet (PVC sheet). In each case, a circular hole having a diameter of about 10 mm was made as a simulated shape of the damaged hole, and about 20 g of the polyurethane resin obtained above was poured at room temperature so as to close the hole. The surface temperature of the repair agent was raised to about 200 ° C., the repair agent was cured by natural cooling, and each water shielding sheet was repaired.
[Test Example 1]
For Examples 6 to 10 and Comparative Example 1, evaluation of repairability (adhesion with the water shielding sheet) and curability (curing time) and measurement of the viscosity of the repair agent were performed, and the repair agent for the water shielding sheet and the water shielding sheet were used. The repair method was evaluated. The evaluation results are shown in Table-1.
<Evaluation of repairability>
The repairability was evaluated according to the following indicators.
○: After repair, the repair agent and the water shielding sheet are in close contact with each other and do not easily peel off.
(Triangle | delta): Although a repair agent and a water shielding sheet are closely_contact | adhered after repair, it peels easily.
X: The repair agent and the water shielding sheet are not in close contact after the repair and are not repaired.
<Evaluation of curability>
The time from when the repair agent is injected until the repair agent is cured after the injection of the repair agent (Examples 6 to 10) or the time until the surface temperature of the repair agent reaches 50 ° C. or less (Comparative Example 1) Was set as the curing time. The surface temperature of the repair agent was measured using a radiation thermometer (IT-540E, manufactured by Horiba, Ltd.).

  From the above results, it can be said that the repair agent of the present invention has a short curing time and is excellent in adhesion to various water shielding sheets. Moreover, it can be said that it can be transported by a thin pipe because of its low viscosity. Furthermore, the repair method of the water shielding sheet of the present invention does not require heating and can contribute to energy saving.

  According to the present invention, there is provided a repair agent for a water shielding sheet that has a short curing time and can shorten the work period of repairing the water shielding sheet.

Schematic cross section showing an example of a waste disposal site It is the schematic sectional drawing which showed an example of embodiment of the repair method of the impermeable sheet which concerns on this invention. It is the schematic sectional drawing which showed an example of embodiment of the repair method of the impermeable sheet which concerns on this invention. It is the schematic sectional drawing which showed an example of embodiment of the repair method of the impermeable sheet which concerns on this invention. It is the schematic sectional drawing which showed an example of the injection device of the repair agent of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Waste disposal site 2 Water shielding sheet 3 Water shielding sheet broken hole 4 Protective soil 5 Waste 6 Repair agent 7 Light irradiation device 8 Backhoe etc. 9 Pump 10 Control version 11 Monitor 12 CCD camera 13 Repair agent inlet 14 Crane etc. 15 Repair agent charging device 16 Tank 17 Stirring motor 18 Motor for charging repair agent

Claims (10)

  A repair agent for water shielding sheets containing a compound that is cured by light.   2. The water shielding sheet according to claim 1, wherein the compound that is cured by light is at least one compound selected from urethane acrylate, urethane methacrylate, ester acrylate, ester methacrylate, a compound having an epoxy group, and a polybutadiene polymer. Repair agent.   The repair agent for water shielding sheets according to claim 1 or 2, comprising a photopolymerization initiator.   A repair method for a water shielding sheet comprising injecting a repair agent for a water shielding sheet containing a compound that is cured by light into a damaged portion of the water shielding sheet.   The water shielding sheet according to claim 4, wherein the compound that is cured by light is at least one compound selected from urethane acrylate, urethane methacrylate, ester acrylate, ester methacrylate, a compound having an epoxy group, and a polybutadiene polymer. Repair method.   The method for repairing a water shielding sheet according to claim 4 or 5, wherein the repair agent for the water shielding sheet further contains a photopolymerization initiator.   After excavating a vertical hole from the upper part of the damaged part of the impermeable sheet on which waste has accumulated, the damaged part is exposed, and then the repair agent for the impermeable sheet is injected into the damaged part using a pipe, The method for repairing a water shielding sheet according to any one of claims 4 to 6, wherein the repair agent for the water shielding sheet is cured by irradiating light.   The method for repairing a water shielding sheet according to any one of claims 4 to 7, wherein the water shielding sheet is repaired by remote control.   The waterproof sheet repaired with the repair agent for waterproof sheets in any one of Claims 1-3.   The waterproof sheet repaired by the repair method of the waterproof sheet in any one of Claims 4-8.

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