Aqueous composition and its cured product, a water-stopping agent raw material set, a water-stopping agent, and a method for stopping water leakage from a leaking part.

Abstract

To provide an aqueous composition for giving a cut-off agent, a cured product of which has low hardness.SOLUTION: An aqueous composition contains a bifunctional allyl ether represented by the formula (1), and a di(meth)acrylic acid salt. Relative to the total amount of polymerizable components in the aqueous composition, the content of the bifunctional allyl ether is 40 mass% or less and the content of the di(meth)acrylic acid salt is 45 mass% or more. [In the formula, R1 is an alkylene group, and w is an integer of 2 or greater.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an aqueous composition and a cured product, a water-stopping agent raw material set, a water-stopping agent, and a method for stopping water leakage from a leaking part. [Background technology]

[0002] As a method to stop water leakage from cracks in concrete structures or water ingress from the conduit openings of pipes containing cables, various polymer-based water-stopping agents are known to be injected into the leak and allowed to harden.

[0003] Generally, to stop water leakage or seepage from concrete structures, liquid or slurry-type cement-based waterproofing agents are injected. When the crack width of the leak is large and the amount of leakage is large, a method of injecting sodium silicate (water glass) or a mixture of sodium silicate and cement into the leak is used to stop the water leakage. In addition, for leaks with small crack widths or small amounts of leakage, it is common to inject fine-particle cement. However, with the method of injecting sodium silicate or a mixture of sodium silicate and cement, the gelled sodium silicate is brittle and has a high shrinkage rate, making it prone to leakage again after stopping the water leakage. On the other hand, the method of injecting fine-particle cement has problems such as difficulty in quick solidification, inability to penetrate deeply into minute cracks, and frequent crack formation due to self-shrinkage, and solutions have been desired.

[0004] In addition to the cement-based waterproofing agents mentioned above, polyurethane-based waterproofing agents are also used. Polyurethane-based waterproofing agents have strong adhesion to the leaking material, such as concrete, wood, or metal, after hardening. However, they may not be able to keep up with changes in external environmental conditions such as the material temperature and vibration of the leaking area, and new cracks may develop from the adhesive joint.

[0005] On the other hand, instead of the above-mentioned waterstop agent, a (meth)acrylate-based waterstop agent has been developed and used. All of the following patent documents disclose a waterstop agent mainly containing polyalkylene glycol di(meth)acrylate in order to polymerize while maintaining the hydrophilicity of the waterstop agent.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Summary of the Invention

Problems to be Solved by the Invention

[0007] When the (meth)acrylate-based waterstop agent is filled in the leakage part, the leakage is suppressed and the waterstop effect is exerted. When performing a waterstop construction using the (meth)acrylate-based waterstop agent at the leakage site, in order to inject the (meth)acrylate-based waterstop agent into the leakage part, after excavating the vicinity of the leakage part with an excavator, an injection nozzle is attached, and after connecting an air-driven high-pressure injector to the injection nozzle, the (meth)acrylate-based waterstop agent is injected into the leakage location at high pressure through the injection nozzle.

[0008] According to the inventors' studies, the hardness required for a waterproofing agent is preferably 50 or less. If the hardness of the waterproofing agent is too high, the hardened (meth)acrylic acid ester waterproofing agent clogs the tip of the injection nozzle during waterproofing work, often requiring the work to be temporarily suspended and the injection nozzle replaced. The (meth)acrylic acid ester waterproofing agents described in Patent Documents 1 to 6 have a hardness of 60 or more, which presents problems with workability at construction sites, and there is still room for improvement.

[0009] The present invention aims to provide an aqueous composition for obtaining a low-hardness acrylic ester-based water-stopping agent in which the hardness of the cured (meth)acrylic acid ester-based water-stopping agent is 50 or less. [Means for solving the problem]

[0010] The present invention encompasses the following aspects.

[0011] [1] An aqueous composition containing a bifunctional allyl ether and a di(meth)acrylate, An aqueous composition characterized in that the aforementioned bifunctional allyl ether is represented by the following formula (1).

[0012] TIFF0007846498000001.tif16130[where, R 1 [where represents an alkylene group, and w represents an integer greater than or equal to 2.]

[0013] [2] The aqueous composition according to [1], characterized in that the content of the bifunctional allyl ether is 40% by mass or less, based on the total amount of polymerization components in the aqueous composition.

[0014] [3] The aqueous composition according to [1] and [2], characterized in that, based on the total amount of polymerization components in the aqueous composition, the content of the difunctional allyl ether is 40% by mass or less, and the content of the di(meth)acrylate is 45% by mass or more.

[0015] [4] The aqueous composition according to [1] to [3], further containing a monofunctional monomer.

[0016] [5] The aqueous composition according to [4], wherein the content of monofunctional monomers is 50% by mass or less based on the total amount of polymer components in the aqueous composition.

[0017] A water-stopping agent raw material set comprising a first raw material which is an aqueous composition described in any of [6][1] to [5], and a second raw material which is a composition containing ascorbic acid or a derivative thereof.

[0018] [7] The water-stopping agent raw material set according to [6], further comprising a third raw material which is a composition containing a persulfate.

[0019] [8] The water-stopping agent raw material set according to [6] and [7], further comprising, separately from the first raw material, a fourth raw material which is an aqueous composition according to any of [1] to [5].

[0020] A cured product of a mixture containing the aqueous composition described in any of [9][1] to [5], ascorbic acid or a derivative thereof, and a persulfate.

[0021]

[10] A method for stopping water leakage from a leaking part, A mixing step to obtain a mixture containing an aqueous composition described in any of [1] to [5], a composition containing ascorbic acid or a derivative thereof, and a composition containing a persulfate, A method comprising an injection step of injecting the aforementioned mixture into the leaking portion.

[0022]

[11] The process further comprises placing a porous body in the leaking area before the injection step, The method according to

[10] , wherein the injection step involves injecting the mixture into the porous body. [Effects of the Invention]

[0023] According to the present invention, because the hardened product of the (meth)acrylic acid ester-based waterproofing agent has low hardness, the injection nozzle does not become clogged when the waterproofing agent is injected at the site of a water leak, thereby improving work efficiency. [Modes for carrying out the invention]

[0024] Embodiments of the present invention will be described in detail below.

[0025] In this specification, a difunctional allyl ether means a compound having two allyl groups in its molecule, and a monofunctional allyl ether means a compound having one allyl group in its molecule. A polyfunctional (meth)acrylate means a compound having two or more (meth)acryloyl groups in its molecule, and a monofunctional (meth)acrylate means a compound having one (meth)acryloyl group in its molecule. "(meth)acrylate" means acrylate and its corresponding methacrylate, and "(meth)acrylic acid" means acrylic acid and its corresponding methacrylic acid. In this specification, an aqueous composition means a composition containing water. Polymerization components mean acrylic monomer components necessary for forming the acrylic resin, which is a water-stopping agent. Polymerization-involved components mean catalytic components necessary when forming the acrylic resin.

[0026] The waterproofing agent in one embodiment of the present invention is prepared from a waterproofing agent raw material set comprising a first raw material, a second raw material, a third raw material, and a fourth raw material, each separately, and is a cured product of a mixture containing these raw materials.

[0027] In one embodiment, the first raw material is an aqueous composition containing a bifunctional allyl ether represented by the following formula (1) and a di(meth)acrylate salt.

[0028] [ka]

[0029] In equation (1), R 1 The alkylene group represented by may be linear or branched. The number of carbon atoms in the alkylene group may be 2-30, 2-20, or 2-10. 1 The alkylene group represented by may be a methylene group or a propylene group.

[0030] In formula (1), W is an integer of 2 or more, preferably 3 or more, more preferably 4 or more, and also preferably an integer of 50 or less, 40 or less, 30 or less, 20 or less, or 10 or less.

[0031] Commercially available difunctional allyl ethers may be used. Examples of commercially available polyalkylene glycol diallyl ethers include Unisafe PKA-5018, Uniox AA-480R, and Uniox AA-800 (all manufactured by NOF Corporation).

[0032] From the viewpoint of adjusting the hardness of the cured product, the content of the bifunctional allyl ether is preferably 40% by mass or less, 38% by mass or less, or 36% by mass or less, based on the total amount of polymerization components in the aqueous composition. From the viewpoint of adjusting the hardness of the cured product, the content of the bifunctional allyl ether is preferably 2% by mass or more, 4% by mass or more, or 6% by mass or more, based on the total amount of polymerization components in the aqueous composition.

[0033] The first raw material, an aqueous composition, may further contain a polyfunctional (meth)acrylate in addition to the above. The polyfunctional (meth)acrylate may be, for example, a di(meth)acrylate (two-functional (meth)acrylate) or a tri(meth)acrylate (three-functional (meth)acrylate). The polyfunctional (meth)acrylate may be used alone or in combination of two or more types.

[0034] The above-mentioned di(meth)acrylate is preferably a di(meth)acrylate represented by the following formula (2).

[0035] [ka] In the formula, R 2 and R 3 Each of these independently represents a hydrogen atom or a methyl group, and R 4 This represents a divalent organic group.

[0036] R 4Examples of the divalent organic group represented by [formula] include groups represented by the following formulas (3) and (4).

[0037] [Chemical formula] In the formulas, p represents an integer from 2 to 30, and q represents an integer from 2 to 50.

[0038] [Chemical formula]

[0039] In formula (3), p is an integer of 2 or more, and preferably an integer of 30 or less, 25 or less, 20 or less, 10 or less, 5 or less, or 3 or less. p is particularly preferably 2.

[0040] In formula (3), q is 2 or more, preferably an integer of 3 or more, more preferably 4 or more, and preferably an integer of 50 or less, 40 or less, 30 or less, 20 or less, or 10 or less.

[0041] The bifunctional (meth)acrylate represented by formula (2) is preferably polyethylene glycol di(meth)acrylate (where R in formula (2) 4 is a group represented by formula (3) and p in formula (3) is 2).

[0042] The tri(meth)acrylate may be, for example, tri(meth)acrylate represented by the following formula (5) (alkoxylated glycerin tri(meth)acrylate).

[0043] [Chemical formula] In the formula, R 5 , R 6 , and R 7 each independently represent an alkylene group, and x, y, and z each independently represent a positive integer.

[0044] In formula (5), R5 , R 6 , and R 7 The alkylene group represented by may be linear or branched. The number of carbon atoms in the alkylene group may be 2-30, 2-20, or 2-10. 5 , R 6 , and R 7 The alkylene group represented by may be a methylene group or a propylene group.

[0045] In equation (5), the sum of x, y, and z is preferably 3 to 30, more preferably 5 to 28, and even more preferably 8 to 25.

[0046] The difunctional (meth)acrylates mentioned above can also be commercially available. Examples of commercially available di(meth)acrylates include: Brembo PDE-100, Brembo PDE-150, Brembo PDE-200, Brembo PDE-400, Brembo PDE-600, Brembo PDP-400N, Brembo PDT-650, Brembo ADE-200, Brembo ADE-300, Brembo ADE-400A, Brembo ADP-400, Brembo ADT-250, Brembo GMR-R, Brembo GMR-M, and Brembo GA. Examples include M, Bremmer GAM-R, Bremmer PDBE-200A, Bremmer PDBE-250, Bremmer PDBE-450A, Bremmer PDBE-1300 (all manufactured by NOF Corporation), NK Ester 4G, NK Ester 9G, NK Ester 14G, NK Ester 23G, NK Ester A-200, NK Ester A-400, NK Ester A-600, NK Ester A-BPE-30, and NK Ester BPE-1300N (all manufactured by Shin Nakamura Chemical Co., Ltd.).

[0047] Examples of commercially available tri(meth)acrylates include NK Ester A-GLY-9E and NK Ester A-GLY-20E (both manufactured by Shin Nakamura Chemical Co., Ltd.).

[0048] In one embodiment, the first raw material is required to be a diacrylate and a dimethacrylate. The diacrylate and dimethacrylate provide elasticity and moisture retention to the cured product of the aqueous composition. Diacrylates are often used when it is desired to speed up the reaction, while dimethacrylates are often used when it is desired to slow down the reaction. Examples of diacrylates and dimethacrylates include alkaline earth metal salts such as magnesium and calcium, and metal salts such as zinc and aluminum. From the viewpoint of enhancing the elasticity and moisture retention of the cured product, the diacrylates and dimethacrylates are preferably magnesium salts, calcium salts, and zinc salts.

[0049] The content of di(meth)acrylate is 45% by mass or more, based on the total amount of polymerization components in the aqueous composition, from the viewpoint of improving the elasticity and moisture retention of the cured product. Preferably, the content of di(meth)acrylate is 45% by mass or more, 47% by mass or more, or 49% by mass or more, based on the total amount of polymerization components in the aqueous composition. Preferably, the content of di(meth)acrylate is 99% by mass or less, 98% by mass or less, or 97% by mass or less, based on the total amount of polymerization components in the aqueous composition.

[0050] The content of di(meth)acrylate may be 60% by mass or more, 62% by mass or more, or 64% by mass or more, based on the total amount of the aqueous composition. The content of di(meth)acrylate may be 99% by mass or less, 98% by mass or less, or 97% by mass or less, based on the total amount of the aqueous composition.

[0051] The first raw material may further contain at least one monofunctional monomer selected from the group consisting of monofunctional (meth)acrylates represented by formula (6) and monofunctional allyl ethers represented by formula (7). (Hereinafter, these will also be collectively referred to as "monofunctional monomer X.")

[0052] [ka] In the formula, R 8 R represents a hydrogen atom or a methyl group. 9This represents a monovalent group having an oxyalkylene group, a glyceryl group, or a glycidyl group.

[0053] [ka] In the formula, R 10 This represents a monovalent group having an oxyalkylene group, a glyceryl group, or a glycidyl group.

[0054] R 9 and R 10 The monovalent group having an oxyalkylene group represented by is preferably the group represented by the following formula (8).

[0055] [ka] In the formula, R 11 represents a hydrogen atom or alkyl group, m represents an integer from 2 to 30, and n represents an integer from 1 to 50.

[0056] R 11 If R is an alkyl group, 11 The alkyl group represented by R may be linear or branched. 11 The number of carbon atoms in the alkyl group represented by is preferably 1 or more, and more preferably an integer of 50 or less, 30 or less, 25 or less, 20 or less, 10 or less, 5 or less, or 3 or less. 11 The alkyl group represented by may be a methyl group or an ethyl group.

[0057] m is preferably an integer of 2 or more, and more preferably an integer of 30 or less, 25 or less, 20 or less, 10 or less, 5 or less, or 3 or less. m is particularly preferably 2. Multiple -(C) contained within the same molecule m H 2m In -O)-, each m may be a different number.

[0058] The number n represents the degree of polymerization of the oxyalkylene portion in the monofunctional (meth)acrylate represented by formula (6) or the allyl ether represented by formula (7), and is an integer from 1 to 50. Preferably, n is an integer of 2 or more, more preferably 3 or more, and even more preferably 4 or more, and also preferably 50 or less, 40 or less, 30 or less, 20 or less, or 10 or less. When n is an integer of 1 or more, the water solubility of the aqueous composition is further improved, making it easier to prepare the water-stopping agent, and furthermore, the strength of the cured product can be improved by increasing the crosslinking density of the resulting cured product. On the other hand, when n is an integer of 50 or less, the distance between polymerizable double bonds does not become too long when the cured product is prepared, so a decrease in the strength of the cured product can be suppressed.

[0059] R 9 and R 10 This may be a glyceryl group, that is, a group represented by the following formula (9).

[0060] [ka]

[0061] If the monofunctional monomer X is a monofunctional (meth)acrylate represented by formula (6), then the monofunctional (meth)acrylate is a polyalkylene glycol (meth)acrylate (in formula (6), R 9 is the base represented by equation (8), and in equation (8), R 11 (A compound in which is a hydrogen atom and n is 2 or more), alkoxy polyalkylene glycol (meth)acrylate (in formula (6), R 9 is the base represented by equation (8), and in equation (8), R 11 Compounds in which R is an alkyl group and n is 2 or more), hydroxyalkyl (meth)acrylate (in formula (6), R 9 is the base represented by equation (8), and in equation (8), R 11 (A compound in which n is a hydrogen atom), alkoxyalkyl (meth)acrylate (in formula (6), R 9is the base represented by equation (8), and in equation (8), R 11 A compound in which is an alkyl group and n is 1, glycidyl (meth)acrylate (in formula (6), R 9 (A compound in which R is a glycidyl group), glycerin (meth)acrylate (in formula (6), 9 It may be a compound in which the group is a glyceryl group.

[0062] Examples of polyalkylene glycol (meth)acrylates include polyethylene glycol (meth)acrylate (a compound in formula (8) where m is 2), polypropylene glycol (meth)acrylate (a compound in formula (8) where m is 3), polyethylene glycol-polypropylene glycol (meth)acrylate (a compound having a group where m is 2 and a group where m is 3 in formula (8)), polyethylene glycol-polytetramethylene glycol (meth)acrylate (a compound in formula (8) having a group where m is 2 and a group where m is 4), and propylene glycol-polybutylene glycol (meth)acrylate (a compound having a group where m is 3 and a group where m is 4 in formula (8)).

[0063] As for alkoxypolyalkylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate (in formula (8), R 11 (A compound in which is a methyl group and m is 2), methoxypolypropylene glycol (meth)acrylate (in formula (8), R 11 Examples include compounds in which the group is a methyl group and m is 3.

[0064] Examples of hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate. Examples of alkoxyalkyl (meth)acrylates include 2-methoxyethyl (meth)acrylate.

[0065] The monofunctional (meth)acrylate may be at least one selected from the group consisting of polyethylene glycol (meth)acrylate and alkoxy polyethylene glycol (meth)acrylate. In the case of polyethylene glycol (meth)acrylate or alkoxy polyethylene glycol (meth)acrylate, the ester portion of the cured product obtained by polymerization is less susceptible to hydrolysis, and for example, the ester portion is less likely to break down even under alkaline conditions. Therefore, the resulting cured product can maintain sufficient strength.

[0066] The alkoxypolyalkylene glycol (meth)acrylate may be at least one selected from the group consisting of methoxypolyethylene glycol (meth)acrylate and methoxypolypropylene glycol (meth)acrylate. Preferably, the alkoxypolyalkylene glycol (meth)acrylate is methoxypolyethylene glycol (meth)acrylate.

[0067] The monofunctional (meth)acrylates mentioned above can be commercially available. Examples of commercially available polyalkylene glycol (meth)acrylates include Bremmer (registered trademark, hereinafter the same) PE-90, Bremmer PE-200, Bremmer PE-350, Bremmer PE-350G, Bremmer PP-1000, Bremmer PP-500, Bremmer PP-800, Bremmer 50PEP-300, Bremmer 70PEP-350B, Bremmer 55PET-800, Bremmer 10PPB-500B, Bremmer AE-90U, Bremmer AE-200, Bremmer AE-400, Bremmer AP-200, Bremmer AP-400, Bremmer AP-550, and Bremmer AP-800 (all manufactured by NOF Corporation).

[0068] Examples of commercially available alkoxy polyalkylene glycol (meth)acrylates include NK Ester M-20G, NK Ester M-40G, NK Ester M-90G, NK Ester M-130G, NK Ester M-230G, NK Ester AM-30G, NK Ester AM-90G, NK Ester AM-130G, and NK Ester AM-230G (all manufactured by Shin Nakamura Chemical Co., Ltd.).

[0069] Examples of commercially available hydroxyalkyl (meth)acrylates include Acrylics (registered trademark, hereinafter the same) HEA (manufactured by Toagosei Co., Ltd.). Examples of commercially available alkoxyalkyl (meth)acrylates include Acrylics C-1 (manufactured by Toagosei Co., Ltd.). Examples of commercially available glycidyl (meth)acrylates include Bremmer G, Bremmer GH, and Bremmer GS (all manufactured by NOF Corporation). Examples of commercially available glycerin (meth)acrylates include Bremmer GLM and Bremmer GLM-R (both manufactured by NOF Corporation).

[0070] When the monofunctional monomer X is an allyl ether (monoallyl ether) represented by formula (7), the allyl ether is, for example, a polyalkylene glycol allyl ether (in formula (7), R 10 is the base represented by equation (8), and in equation (8), R 11 Compounds in which R is a hydrogen atom), alkoxy polyalkylene glycol allyl ether (in formula (7), R 10 is the base represented by equation (8), and in equation (8), R 11 Compounds in which R is an alkyl group), allyl glycidyl ether (in formula (7), R 10 Compounds in which R is a glycidyl group), glycerin monoallyl ether (in formula (7), 10 It may be a compound in which the group is a glyceryl group.

[0071] Examples of polyalkylene glycol allyl ethers include polyethylene glycol allyl ether (a compound in formula (8) where m is 2), polypropylene glycol allyl ether (a compound in formula (8) where m is 3), and polyethylene glycol-polypropylene glycol allyl ether (a compound having a group where m is 2 and a group where m is 3 in formula (8)).

[0072] As an alkoxypolyalkylene glycol allyl ether, methoxypolyethylene glycol allyl ether (in formula (8), R 11 (A compound in which is a methyl group and m is 2), butoxy-polyethylene glycol-polypropylene glycol-allyl ether (in formula (8), R 11 Examples include compounds in which the group is a butyl group and which have a group with m = 2 and a group with m = 3.

[0073] The allyl ethers mentioned above can be commercially available. Examples of commercially available polyalkylene glycol allyl ethers include Uniox (registered trademark, hereinafter the same) PKA-5001, Uniox PKA-5002, Uniox PKA-5003, Uniox PKA-5004, Uniox PKA-5005, Unisafe PKA-5011, Unisafe PKA-5012, Unilube (registered trademark) PKA-5013, and Unisafe PKA-5014TF (all manufactured by NOF Corporation).

[0074] Examples of commercially available alkoxy polyalkylene glycol allyl ethers include Uniox PKA-5006, Uniox PKA-5007, Uniox PKA-5008, Uniox PKA-5009, Uniox PKA-5010, Unisafe PKA-5015, Unisafe PKA-5016, and Unisafe PKA-5017 (all manufactured by NOF Corporation).

[0075] The content of monofunctional monomer X is 50% by mass or less, based on the total amount of polymerization components in the aqueous composition, from the viewpoint of adjusting the swelling properties of the cured product in water. The content of monofunctional monomer X is preferably 50% by mass or less, 48% by mass or less, or 46% by mass or less, based on the total amount of polymerization components in the aqueous composition. The content of monofunctional monomer X is preferably 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more, based on the total amount of polymerization components in the aqueous composition.

[0076] The content of monofunctional monomer X may be 20% by mass or less, 19% by mass or less, or 18% by mass or less, based on the total amount of the aqueous composition. The content of monofunctional monomer X may be 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more, based on the total amount of the aqueous composition.

[0077] The first raw material, an aqueous composition, may further contain other additives as needed. Examples of other additives include glycols, such as ethylene glycol and propylene glycol. Additionally, to adjust the pH, examples include sodium hydroxide and potassium hydroxide. These other additives may be used individually or in combination of two or more.

[0078] The content of polymerization components in the aqueous composition is preferably 15% by mass or more, more preferably 16% by mass or more, even more preferably 17% by mass or more, preferably 50% by mass or less, more preferably 49% by mass or less, and even more preferably 48% by mass or less, based on the total amount of the aqueous composition.

[0079] The pH of the aqueous composition is preferably 7.0 or less, and as close to 7.0 as possible, from the viewpoint of accelerating the polymerization reaction to obtain the cured product. The pH of the aqueous composition is preferably 5.0 or more, more preferably 5.1 or more, even more preferably 5.2 or more, and also preferably 7.0 or less, more preferably 6.9 or less, and even more preferably 6.8 or less.

[0080] The second raw material is, in one embodiment, a composition containing ascorbic acid or a derivative thereof. Derivatives of ascorbic acid include salts such as sodium ascorbate, potassium ascorbate, and calcium ascorbate, inorganic acid esters of ascorbic acid such as ascorbic acid phosphate ester, and glycosides of ascorbic acid such as ascorbic acid-2-glucoside. Furthermore, examples include erythorbic acid, salts such as sodium erythorbate, potassium erythorbate, and calcium erythorbate, inorganic acid esters of erythorbic acid such as erythorbic acid phosphate ester, and glycosides of erythorbic acid such as erythorbic acid-2-glucoside.

[0081] The second raw material may be provided in the raw material set in solid form such as a powder, or in aqueous solution form. If the second raw material is in solid form such as a powder, the powder may be dissolved in the first raw material, or it may be made into an aqueous solution before use and then mixed with the first raw material. If the second raw material is an aqueous solution, the content of ascorbic acid or its derivative is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, and also preferably 25% by mass or less, more preferably 24% by mass or less, and even more preferably 23% by mass or less, based on the total amount of the aqueous solution.

[0082] The second raw material may further contain other additives as needed. Examples of other additives include sodium thiosulfate, rongalit, potassium sulfite, sodium sulfite, sodium bisulfite, pyrosulfite, ferrous sulfate, etc. These other additives may be used individually or in combination of two or more.

[0083] The water-stopping agent raw material set may further include a composition containing a persulfate as a third raw material, separate from the first and second raw materials. The salt in the persulfate may be an alkali metal salt such as ammonium, sodium, or potassium, and preferably a sodium salt or a potassium salt.

[0084] The third raw material may be provided in the raw material set in solid form such as a powder, or in the raw material set as an aqueous solution. When the third raw material is dissolved in water for use, or when it is provided in the raw material set as an aqueous solution, the persulfate content is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.4% by mass or more, and also preferably 40% by mass or less, more preferably 39% by mass or less, and even more preferably 38% by mass or less, based on the total amount of the aqueous solution.

[0085] The third raw material may further contain other additives as needed. Examples of other additives include sodium perchlorate and hydrogen peroxide. These other additives may be used individually or in combination of two or more.

[0086] The water-stopping agent raw material set may further include, as a fourth raw material, an aqueous composition containing the above-mentioned bifunctional allyl ether and the above-mentioned di(meth)acrylate, separately from the first, second, and third raw materials.

[0087] The fourth raw material may further contain other polyfunctional (meth)acrylates other than the difunctional allyl ether described above, and may further contain other additives as needed. The other additives may be the same as those used in the first raw material described above. The fourth raw material may have the same composition as the first raw material or a different composition.

[0088] The water-stopping agent raw material set according to this embodiment allows for long-term storage because the first raw material, the second raw material, and the third and fourth raw materials can each be stored separately.

[0089] In addition to the raw materials described above, the water-stopping agent raw material set may further include other raw materials such as corrosion inhibitors, cationic electrolyte monomers, cements, and incinerator ash. These raw materials may be included in the water-stopping agent raw material set as separate raw materials from the first to fourth raw materials, or they may be contained in any of the first to fourth raw materials.

[0090] The corrosion inhibitor may be one or more selected from the group consisting of carboxylic acids and their salts, phosphoric acid and its salts, phosphoric acid esters, nitrites and their salts, amines and their salts. By adding the corrosion inhibitor, the water-stopping agent exhibits a strong corrosion inhibitory effect on metals, especially commonly used iron-based materials such as steel.

[0091] The cationic electrolyte monomer may be dimethylaminoethyl (meth)acrylate and its salts and quaternaries, diethylaminoethyl (meth)acrylate and its salts and quaternaries, dimethylaminopropyl (meth)acrylamide and its salts and quaternaries, etc. As salts of these, salts with inorganic salts such as hydrochloric acid and sulfuric acid, or salts with di(meth)acrylic acid are used. As quaternaries, quaternaries of methyl chloride, dimethyl sulfuric acid, etc., or complex salts thereof are used. The cationic electrolyte monomer may be used individually or in combination of two or more.

[0092] The cements may include various types of portrant cement, blast furnace cement, silica cement, fly ash cement, jet cement, alumina cement, slag cement, etc. The incinerated ash may include fly ash, silica fume, blast furnace slag, gypsum, sewage treatment sludge, etc. The cements and incinerated ash may be used individually or in combination of two or more types.

[0093] Next, a water-stopping agent according to one embodiment will be described. The water-stopping agent according to one embodiment consists of a cured product of a mixture containing the above-mentioned difunctional allyl ether and di(meth)acrylate, ascorbic acid or a derivative thereof, and a persulfate. The cured product contains structural units derived from the difunctional allyl ether, structural units derived from di(meth)acrylate, and structural units derived from ascorbic acid or a derivative thereof. It may also further contain structural units derived from polyfunctional (meth)acrylate, monofunctional (meth)acrylate, and structural units derived from monofunctional allyl ether. The persulfate acts as a polymerization initiator to initiate the polymerization reaction of the difunctional allyl ether and di(meth)acrylate, and the ascorbic acid or a derivative thereof acts as a polymerization accelerator to promote the polymerization reaction of the difunctional allyl ether and di(meth)acrylate. This cured product is obtained by mixing each of the raw materials in the above-mentioned raw material set.

[0094] The aqueous composition, ascorbic acid or its derivative, and persulfate used as raw materials for the cured product may be the same as those used as the first and fourth raw materials, the second raw material, and the third raw material described above.

[0095] In the cured product, the content of structural units derived from the difunctional allyl ether is 40% by mass or less, 39% by mass or less, or 38% by mass or less, based on the total amount of polymerization-involved components in the cured product. The content of structural units derived from polymerizable monomer X is preferably 0.5% by mass or more, 0.6% by mass or more, or 0.7% by mass or more, based on the total amount of polymerization-involved components in the cured product.

[0096] In the cured product, the content of structural units derived from di(meth)acrylate is 40% by mass or more, 42% by mass or more, or 44% by mass or more, based on the total amount of polymerization-involved components in the cured product. The content of structural units derived from di(meth)acrylate is 99% by mass or less, 98% by mass or less, or 97% by mass or less, based on the total amount of polymerization-involved components in the cured product.

[0097] In the cured product, the content of structural units derived from ascorbic acid or its derivatives is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, even more preferably 0.03% by mass or more, and also preferably 20% by mass or less, more preferably 19% by mass or less, and even more preferably 18% by mass or less, based on the total amount of polymerization-involved components in the cured product.

[0098] If the cured product further contains the monofunctional (meth)acrylate and monofunctional allyl ether described above, the content of structural units derived from the monofunctional (meth)acrylate is preferably 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more, based on the total amount of polymerization-involved components of the cured product. The content of monofunctional allyl ether is preferably 50% by mass or less, 49% by mass or less, or 48% by mass or less, based on the total amount of polymerization-involved components of the cured product.

[0099] The cured product is a gel-like cured product containing water. From the viewpoint of increasing the strength of the cured product, the content of polymerization-involved components in the cured product is preferably 10% by mass or more, more preferably 11% by mass or more, and even more preferably 12% by mass or more, based on the total amount of the cured product. From the viewpoint of making it easier to dissolve the raw materials of the cured product and to easily prepare the cured product, the content of polymerization-involved components in the cured product is preferably 90% by mass or less, more preferably 89% by mass or less, and even more preferably 88% by mass or less, based on the total amount of the cured product.

[0100] The water content in the cured product may be 40% by mass or more, 41% by mass or more, or 42% by mass or more, and 95% by mass or less, 94% by mass or less, or 93% by mass or less, based on the total amount of the cured product.

[0101] According to the water-stopping agent of this embodiment, it is difficult to reduce the residual chlorine concentration in the water when stopping water leakage, so for example, it can be used not only in sewage facilities but also in water supply facilities. The water-stopping agent can adjust the reduction in residual chlorine in the water after leaching to less than 0.7 mg / L, even under conditions without conditioning treatment, in the leaching test items for water supply equipment and materials, which is a standard established by the Japan Water Works Association.

[0102] According to the water-stopping agent of this embodiment, the amount of amines leaching into the water during water-stopping can be reduced to a concentration that is suitable for use as a water-stopping material in water supply facilities, thus providing excellent safety. For example, the water-stopping agent can reduce the concentration of amines contained in the water after leaching to less than 0.01 mg / L, as measured by high-performance liquid chromatography (detection limit 0.002 ppm), without conditioning treatment (operation to stabilize leaching from hardened material), as measured in the leaching test for water supply equipment and materials, which is a standard set by the Japan Water Works Association.

[0103] Next, a method for stopping water leakage from a leaking area using a water-stopping agent consisting of the hardened material described above (hereinafter sometimes simply referred to as the "water-stopping method") will be described. One embodiment of the water-stopping method comprises a mixing step of obtaining a mixture containing the aqueous composition described above, a composition containing ascorbic acid or a derivative thereof, and a composition containing a persulfate, and an injection step of injecting the mixture into the leaking area.

[0104] In one embodiment, the mixing process is carried out by the following method. First, a mixture (Solution A) is obtained by mixing the above-mentioned aqueous composition (First Raw Material) and a composition containing ascorbic acid or a derivative thereof (Second Raw Material), and a mixture (Solution B) is obtained by mixing a composition containing persulfate (Third Raw Material) and an aqueous composition (Fourth Raw Material) separate from the First Raw Material. Then, Solution A and Solution B are mixed to obtain a mixture of the above-mentioned raw materials. As a method for mixing Solution A and Solution B, for example, Solution A and Solution B can be sent through a Y-shaped pipe or a double pipe and mixed at the junction of the Y-shaped pipe and the tip of the double pipe. Solution A and Solution B are preferably mixed in a ratio of Solution A:Solution B = 1:1 (by volume).

[0105] In the injection process, the mixture of liquids A and B obtained in the mixing process is injected under high pressure into the leak and its vicinity through an injection nozzle installed at the leak. Regarding the details of the injection, depending on the leak situation, after injecting the mixture under high pressure for several tens of seconds, the injection is temporarily stopped, and the reaction time required for the injected mixture to harden into a solid is waited for. After a sufficient reaction time has elapsed, the mixture is injected again under high pressure, and the hardened material is pushed into the void inside the leak using the subsequently injected mixture. This hardening process is performed approximately 1 to 20 times per injection nozzle, filling the void in the leak with the hardened material as much as possible.

[0106] The interval between high-pressure injection of the mixed solution depends on the reaction time of the hardened material, the leakage situation, the water-stopping status, and the operator, but it is repeated at intervals of 0.5 to 10 minutes. Even when the mixed solution is not being injected under high pressure, polymerization reactions proceed in the mixed solution at the confluence of the Y-pipe, the tip of the double pipe, and inside the injection nozzle, similar to the leakage void, and hardened material is formed. As the reaction time of the mixture of liquids A and B elapses, the polymerization reaction of the hardened material enters its later stages, and the hardness of the hardened material increases, approaching the same hardness as measured by the FP hardness tester. After 5 minutes or more, the polymerization reaction of the hardened material is almost complete, and the hardness of the hardened material is approximately the same as measured by the FP hardness tester. In such cases, if the hardened material has high hardness, even if the mixed solution is injected again under high pressure, the hardened material often clogs the junction of the Y-pipe, the tip of the double pipe, and the injection nozzle, making it impossible to inject the mixed solution under high pressure into the leak. As a result, the junction of the Y-pipe, the tip of the double pipe, and the injection nozzle must be replaced, and the water-stopping work is temporarily suspended.

[0107] Generally, when the hardness of the cured acrylic ester-based waterproofing agent is measured with an FP hardness tester and is between 60 and 90, the hardened material can be pushed out with the mixed solution within 3 minutes of high-pressure injection, allowing the waterproofing work to continue. However, if the situation remains unchanged for more than 3 minutes after high-pressure injection, the hardened material at the Y-pipe junction, the tip of the double pipe, and inside the injection nozzle will have completed its reaction, and its hardness will be the same as the hardness measured with the FP hardness tester (60-90). Therefore, even if the mixed solution is injected at high pressure, the hardened material cannot be pushed out, requiring the injection work to be interrupted, the injection nozzle to be replaced, and the high-pressure injection work to be resumed. If the hardened material hardness is 80 or higher, even after 1 minute of injection, the hardened material will not be pushed out from the injection nozzle even if the mixed solution is injected at high pressure. This would require interrupting the waterproofing work each time, making it unsuitable for use on site.

[0108] The hardness of cured acrylic ester-based waterproofing agents is generally 60-90 when measured with an FP-type hardness tester (manufactured by Polymer Instruments Co., Ltd.). For example, the hardness of the cured product of Vandeflexin (manufactured by Hodogaya Building Materials Co., Ltd.) is 60-70, the hardness of the cured product of Flexin Kyoku (manufactured by Hodogaya Building Materials Co., Ltd.) is 70-80, and the hardness of the cured products of Flexik (manufactured by Mitsubishi Chemical Corporation) and Chatani Sangyo Co., Ltd. is 80-90.

[0109] According to the waterproofing agent of this embodiment, the cured product using the aqueous composition of the present invention has a hardness of 50 or less as measured by an FP hardness meter. Therefore, during waterproofing work, the cured product does not clog the injection nozzle, eliminating the need to replace the injection nozzle, thus significantly improving work efficiency.

[0110] The injected mixture hardens, stopping the water leak at the point of leakage. When injecting the mixture, for example, if the leak is in a concrete wall, it is necessary to inject it at high pressure, so an air piston type plunger pump or the like is used. On the other hand, if the leak is in a cable conduit opening, for example, the mixture can be injected at low pressure, so this is done by using an air compressor or compressed gas cylinder that has been pressurized to low pressure to pump the liquid in a container.

[0111] In other embodiments, the water-stopping method may further include a step of placing a porous body at the water leak before the injection step. In this case, the mixture is injected into the porous body during the injection step to impregnate it. The water-stopping method according to this embodiment is suitable for water leaks at cable conduit openings. The porous body impregnated with the mixture can also be used as a water-stopping sealant such as a water-stopping plate.

[0112] The porous material preferably has excellent mechanical strength, elasticity, and weather resistance, as well as excellent permeability of the waterproofing agent (mixture), and may be a foam with an open-cell structure, or a fibrous mass formed by intertwined fibers. The porous material is preferably a urethane foam. The shape of the porous material is not particularly limited, but when placed in a leak at the opening of a cable conduit, it is preferably cylindrical, and when placed in a leak at a joint between concrete structures, it is preferably sheet-shaped.

[0113] In this embodiment, two or more porous bodies may be used. For example, in the case of a single cable at a leak in a cable conduit opening, the waterproofing method may be to place a cylindrical porous body, which has been processed by drilling holes to match the shape of the cable, at the leak and inject the mixture into the porous body. If the cable is a multi-cable, the waterproofing method may be to use two or more porous bodies and inject the mixture into the gaps between them, which makes the method simpler and provides a better waterproofing effect.

[0114] The water-stopping methods according to these embodiments make it possible to easily stop water leakage in concrete structures, water leakage at cable conduit openings, etc. The areas that have been stopped by the methods of these embodiments exhibit excellent chemical resistance, water pressure resistance, freeze-thaw resistance, drying shrinkage resistance, etc. [Examples]

[0115] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0116] <Preparation of the first raw material> [Examples 1-26, Comparative Examples 1-9] In the examples and comparative examples, aqueous compositions were prepared using the following ingredients based on the compositions shown in Tables 1 to 6. In Tables 1 to 6, the content of A-1 refers to the total content of A-1a and A-1b, the content of A-2 refers to the total content of A-2a, A-2b, and A-2c, and the content of A-3 refers to the total content of A-3a, A-3b, A-3c, A-3d, A-3e, and A-3f.

[0117] <A bifunctional allyl ether represented by formula (1)> (A-1a)(A-1b): A bifunctional allyl ether represented by the following formula (1) (R 1 =C2H4, W≈10, Product name: Uniox AA-480R, manufactured by NOF Corporation)(R 1 =C2H4, W≈16, Product name: Uniox AA-800, Manufactured by NOF Corporation)

[0118] [ka]

[0119] (A-2a): 35% by mass aqueous solution of magnesium diacrylate (product name: MA-35, manufactured by Asada Chemical Industries, Ltd.) (A-2b): 25% by mass aqueous solution of calcium diacrylate (product name: CA-25, manufactured by Asada Chemical Industries, Ltd.) (A-2c): 30% by mass aqueous solution of zinc diacrylate (product name: ZA-30, manufactured by Asada Chemical Industries, Ltd.)

[0120] <Polymerizable monomer represented by formula (6) or formula (7)> (A-3a): Methoxypolyethylene glycol methacrylate represented by the following formula (3A) (n ≈ 13, product name: NK Ester M-130G, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

[0121] [ka] (A-3b): Methoxypolyethylene glycol acrylate represented by the following formula (3B) (n ≈ 13, product name: NK Ester AM-130G, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

[0122] [ka] (A-3c): Hydroxypolyethylene glycol methacrylate represented by the following formula (3C) (n≒8, product name: Bremmer PE-350, manufactured by NOF Corporation)

[0123] [ka] (A-3d)(A-3e)(A-3f): Hydroxypolyalkylene glycol allyl ether represented by the following formula (3D) (n≒4, product name: Uniox PKA-5001, manufactured by NOF Corporation) (n≒9, product name: Uniox PKA-5003, manufactured by NOF Corporation) (n≒30, product name: Uniox PKA-5005, manufactured by NOF Corporation)

[0124] [ka]

[0125] <Polyfunctional (meth)acrylate> (A-4): Polyethylene glycol diacrylate represented by the following formula (4) (q ≈ 13, product name: NK Ester A-600, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

[0126] [ka] (A-5): 4% by mass aqueous solution of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) (A-6): Tap water

[0127] <Preparation of hardened material (water-stopping agent)> 106 g of the following first raw material and 10 g of an aqueous solution prepared to the aqueous solution mass % described in Tables 7 to 12 based on the total amount of the second raw material as the second raw material were mixed to obtain Solution A, and 10 g of water was used to prepare a third raw material, which is an aqueous solution adjusted to the aqueous solution mass % described in Tables 7 to 12, and 106 g of the fourth raw material were mixed to obtain Solution B. The mixture of Solution A and Solution B was immediately poured into a plastic container and stirred and mixed to obtain a cured product.

[0128] [Second Raw Material] (2-1): Aqueous solution of L-ascorbic acid (2-2): Aqueous solution of sodium L-ascorbate (2-3): Aqueous solution of erythorbic acid (2-4): Aqueous solution of sodium erythorbate [Third Raw Material] (3-1): Aqueous solution of ammonium persulfate (3-2): Aqueous solution of sodium persulfate (3-3): Aqueous solution of potassium persulfate

[0129] The combinations of the first raw material to the fourth raw material in the examples and comparative examples are shown in Tables 7 to 12. For the first raw material and the fourth raw material, their types are represented by the formulation numbers in Tables 1 to 6 described above. For the second raw material and the third raw material, the types of the raw materials are shown in the upper row, and their aqueous solution mass % are shown in Tables 7 to 12 in parentheses.

[0130] [Evaluation] The cured products of the examples and comparative examples were measured for their hardness, and the results are shown in Table 1. [Hardness Measurement] The hardness was measured using a cured product (volume 77 cm 3 ) prepared using the formulation described in Table 1, and the hardness of the cured product was measured using an FP type hardness meter (manufactured by Kobunshi Keiki Co., Ltd.).

[0131]

Table 1

[0132] Table 2

[0133] Table 3

[0134] Table 4

[0135] Table 5

[0136] Table 6

[0137] Table 7

[0138] Table 8

[0139] Table 9

[0140] Table 10

[0141] Table 11

[0142] Table 12

Claims

1. A water-stopping agent raw material set comprising: a first raw material which is an aqueous composition containing a bifunctional allyl ether and a di(meth)acrylate; a second raw material which is a composition containing ascorbic acid or erythorbic acid or their salts, inorganic acid esters or glycosides; and a third raw material which is a composition containing a persulfate. A water-stopping agent raw material set characterized in that the aforementioned bifunctional allyl ether is represented by the following formula (1). 【Chemistry 1】 [In the formula, R １ [where represents an alkylene group, and w represents an integer greater than or equal to 2.]

2. A water-stopping agent raw material set according to claim 1, comprising the first raw material according to claim 1, further containing a monofunctional monomer.

3. The water-stopping agent raw material set according to claim 1 or 2, further comprising a fourth raw material which is an aqueous composition according to claim 1 or 2, separately from the first raw material.

4. A cured product of a mixture containing the aqueous composition according to any one of claims 1 to 3, ascorbic acid or erythorbic acid or a salt thereof, an inorganic acid ester or glycoside, and a persulfate.

5. A method for stopping water leakage from a leaking area, A mixing step to obtain a mixture containing the aqueous composition according to any one of claims 1 to 3, a composition comprising ascorbic acid or erythorbic acid or salts thereof, inorganic acid esters or glycosides, and a composition comprising persulfates; A method comprising an injection step of injecting the aforementioned mixture into the leaking portion.

6. The process further includes placing a porous body in the leaking area before the injection step, The method according to claim 5, wherein the injection step involves injecting the mixture into the porous body.

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