JPH0623380B2 - Waterstop - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a water blocking agent using a polymerizable substance that can be cured into a water-insoluble elastic gel in a short time. The present invention relates to a waterproofing agent which is suitably used for general civil engineering work such as prevention of spring water and leakage, and particularly for prevention of infiltration water or leakage of water in sewer pipe facilities.

[Prior Art] As a polymer-based water stopping agent conventionally used for stabilizing the ground, preventing spring water, leakage, etc., for example, JP-A-58-206680
In the official gazette: General formula: (Wherein R is a hydrogen atom or a methyl group, m is an integer of 2 or more) alone or as a mixture of polyethylene glycol acrylic acid esters: 100 parts by weight; In the formula, R ₂ and R ₃ are hydrogen atoms or methyl groups, and n is 2 to
Polyethylene glycol diacrylic acid ester represented by (50 integer): 20 to 150 parts by weight of a mixture is added with an acrylic acid salt, if necessary, and then a polymerization catalyst is added to propose an aqueous water-based waterproofing agent. Has been done.

Also, U.S. Pat.No. 4,295,762 discloses a soil stabilizer for stabilizing soft ground, which is a water-soluble diacrylate ester of polyoxyalkylene glycol having a molecular weight of 300 or more, and 2 to 50 weight% thereof. % Aqueous solution of a water-soluble vinyl monomer and a polymerization catalyst has been proposed.

[Problems to be solved by the invention]

However, the strength of the gel body obtained by injecting the water blocking agent described in JP-A-58-206680 into soil and curing it is not sufficient, and this water blocking agent is used in a sewer pipe facility. The performance of the gel body itself, especially its strength, is not sufficient for application to prevent infiltration of water or leakage of water from cracks in connecting parts or pipes.

In addition, the above-mentioned U.S. Pat.
Over 300 dioxymethacrylates of polyoxyethylene glycol, acrylamide, methoxyethyl acrylate, ethoxyethyl acrylate, dimethylaminoethyl methacrylate, tetraethylene glycol diacrylate, hydroxypropyl acrylate, dimethylsulfate quaternary salt of dimethylaminoethyl methacrylate, acrylic acid Alternatively, a chemical solution prepared by copolymerizing 2 to 50% by weight of a water-soluble vinyl monomer such as an alkaline earth metal salt or an alkali metal salt of methacrylic acid has been proposed. However, using acrylamide as a copolymerization component is toxic. However, methoxyethyl acrylate, ethoxyethyl acrylate, tetraethylene glycol diacrylate, hydroxypropyl acrylate, etc. are used as copolymerization components. The case, release of the resulting gel body 漿性 there is a disadvantage that severe.

When dimethylaminoethyl methacrylate, quaternary dimethylsulfate of dimethylaminoethyl methacrylate, or an alkaline earth or alkali metal salt of acrylic acid or methacrylic acid is used alone for co-synthesis,
The strength of the sediment solid obtained by hardening after the chemical solution penetrates into the sand is not sufficient, and as the amount of these copolymerization components is increased, when the obtained gel body is immersed in water. The gel body is likely to swell and is not suitable as a water blocking agent.

In general, water-stopping agents, especially water-stopping agents for preventing infiltration or leakage of water in sewer pipeline facilities, have high chemical stability, good permeability to the ground, and easy setting of curing time. The resulting gel body is impermeable,
And not only to satisfy the performance required in the case of general soil stabilization such as having the strength to withstand excavation after construction, further, the gel body obtained has no syneresis, in water It is required that the gel body does not easily swell when soaked, that the gel body itself has sufficiently high strength, and that it has durability without breaking for a long period of time.

This is usually the case in the water stoppage construction of sewer pipeline facilities.
This is because the inside of the sewer pipe is injected and filled with a chemical solution to the joints and cracks to cause gelation, and after the trial, the repaired portion (hardened gel body) inside the pipe is always exposed to running water, that is, sewage. .

Therefore, the water-stopping agent used in such a case has no syneresis property of the obtained gel body, is difficult to swell when immersed in water, has a large strength of the gel body itself, and can be used for a long period of time. In addition to having well-balanced performance that is not always strictly required in the case of general soil stabilization such as having durability that does not break, concrete sewage pipe (fume pipe) is now available. Due to its frequent use, the gel body is required to have good adhesiveness with the cement-based substance so that it does not peel off or fall off from the concrete sewer pipe and can withstand long-term use.

The inventors of the present invention have conducted various studies to provide a water blocking agent having well-balanced properties such as those that have not been proposed, and as a result, the following composition is suitable for the purpose. The inventors have found that and reached the present invention.

[Means for Solving the Problems] That is, the present invention provides the following three components A, B and C:
As the weight ratio per 100 parts by weight of the sum of the three components, the component A is
It is in the range of 20 or more and less than 80, the sum of the components B and C is in the range of more than 20 and 80 or less, and the component ratio B / C.
A water blocking agent obtained by adding a polymerization catalyst to a chemical liquid containing 20:80 to 80/20 in a molar ratio.

Component A: a single compound or a mixture of compounds represented by formula (1).

Component B: at least one anionic electrolyte monomer selected from the group consisting of compounds represented by formula (2) or formula (3) and salts thereof.

Component C: at least one cationic electrolyte monomer selected from the group consisting of compounds represented by formula (4), and salts and quaternary compounds thereof.

Equation _{(1): CH 2 = C} (R 1) CO-O - (- CH 2 CH 2 O-) n -COC (R 2) = CH 2 ( in the formula (1), R ¹ and R ² are hydrogen Atom or a methyl group, and n represents an integer of 2 to 50). Equation _{(2): CH 2 = C} (R 3) COOH ( in the formula (2), R ³ represents a hydrogen atom or a methyl group). Equation _{(3): CH 2 = CHCONH} -C (CH 3) 2 -CH 2 SO 3 H Formula ^{(4): (R 4)} (R 5) N- (CH 2) n -Y-CO-C (R ⁶ ) = CH ₂ (In the formula (4), R ⁴ and R ⁵ are both a methyl group or an ethyl group, R ⁶ is a hydrogen atom or a methyl group, n is 2 or 3, and Y is an oxygen atom. Or NH group). ] And the summary.

The present invention will be described below.

The component A used in the present invention is specifically a diacrylate or dimethacrylate of polyethylene glycol, and the degree of polymerization of the polyethylene glycol portion thereof.
(n) is a crosslinkable monomer having a range of 2 or more and 50 or less.

Polyacrylate glycol diacrylate or dimethacrylate having a degree of polymerization (n) of less than 2 is inconvenient for preparing a drug solution due to its low water solubility, and the strength of the obtained gel body is low. It is not preferable.

On the other hand, a polyethylene glycol diacrylate or dimethacrylate having a degree of polymerization (n) of more than 50 is obtained because the distance between two polymerizable double bonds becomes long and the crosslink density of the gel decreases. The gel body has low strength and is easily swelled when immersed in water, which is not preferable as a raw material used in the present invention.

Component A used in the present invention is a liquid or solid substance having low toxicity and excellent water solubility, and its aqueous solution has low viscosity and good permeability to the connection part of a sewer pipe, a crack part or the ground, and It has good polymerizability and the setting of curing time is easy.

In the gel body obtained by polymerizing the dimethacrylate of polyethylene glycol among the components A, the ester portion of the gel body is not easily hydrolyzed, and the gel body can sufficiently retain its strength without disintegrating even under alkaline conditions.

Therefore, when the waterproofing agent of the present invention is mainly applied to a fume tube made of an alkaline material such as cement or concrete, it is particularly preferable to use polyethylene glycol dimethacrylate as the component A.

When polyethylene glycol dimethacrylate is used as the component A, when the degree of polymerization (n) of the polyethylene glycol portion is 18 to 40, the distance between the two polymerizable double bonds in the molecule is appropriate. It is because of good polymerizability, because the crosslink density of the obtained gel body is high,
Compared to those having a degree of polymerization (n) of polyethylene glycol portion of less than 18 or more than 40, the strength of the obtained gel body is particularly high, and it is particularly suitable as a raw material for a water blocking agent used in sewerage pipeline facilities.

In the present invention, the component A usually used is PEG #
400 diacrylate, PEG # 600 diacrylate, PEG # 600
Diacrylate, PEG # 1000 Dimethacrylate, PEG # 1540
Examples thereof include dimethacrylate and PEG # 2000 dimetalylate.

Further, in the present invention, any known cross-linking component such as methylenebisacrylamide, 1,3-di (acrylamidomethyl) -2-imidazolidone, hexahydro-1,3 within a range that does not lose the characteristics of the present invention. -Triacryl-S-Triazine, etc. may be used as component A
It is also possible to use mixed with.

In the waterstop agent of the present invention, a compound selected from an anionic electrolyte monomer (hereinafter referred to as component B) and a compound selected from a cationic electrolytic monomer (hereinafter referred to as component C) are used together with the above component A. .

It is known in the art to use either component B or component C with component A.

However, in the system in which the two components A and B are used in combination,
In the AB mixture, the gel body obtained when the content of the component B is less than 20% by weight has low syneresis and the degree of swelling of the gel body when immersed in water is small. Since the strength of the solidified body is low, it is not sufficient as a waterproofing agent.

Further, the gel body obtained when the content of the component B in the AB mixture is 20% by weight or more has a small syneresis property, but the gel body has a low strength and the swelling of the gel body when immersed in water is extremely large. Moreover, when the solidified body of the AB mixture and the earth and sand is dipped in water, the strength of the solidified body is remarkably decreased with time, and the stable solidified body cannot be retained for a long period of time.

On the other hand, in the system in which two components A and C are used in combination, A-
The gel body obtained when the content of the component C in the C mixture is less than 20% by weight has a small degree of swelling when immersed in water, but has almost no adhesiveness between the gel body and concrete, and sewer pipes Not enough as a waterproofing agent for road facilities.

Further, the gel body obtained when the content of the component C in the AC mixture is 20% by weight or more has small syneresis, but the gel body has low strength and easily swells when immersed in water. A-
When the solidified body of the C mixture and the earth and sand is immersed in water, the strength of the solidified body is remarkably reduced with time, and the stable solidified body cannot be retained for a long period of time.

From the above, the present inventors have conducted various studies to overcome the above-mentioned drawbacks observed when gelling a mixture of either component B or component C and component A, and as a result, The gel body obtained when the component B, which is an anionic electrolyte monomer, is used together has adhesiveness to the cement-based substance due to the strong binding force between the anion group and the cement-based substance, while the component A and the cation are used. As a result of further study, it was found that the gel body obtained when the component C, which is a polyelectrolyte monomer, is used in combination, has a strong binding force between the cation group and the sediment particles and the strength of the sediment solid is large. , A gel body obtained by mixing appropriate amounts of each of the component B and the component C with the component A and copolymerizing them does not have syneresis, and the gel body does not easily swell when immersed in water. Degree is large, resistant to distortion,
It has adhesiveness to cement-based substances, and the strength of the solidified sediment is dramatically higher than that of the conventional waterproofing agent of this kind, and when the solidified body is immersed in water. It has been found that the strength is extremely suitable as a waterproofing agent, for example, it retains a stable solidified body for a long period of time without decreasing with time.

Thus, it is not clear for what reason a very suitable waterproofing agent can be obtained when both the components B and C are used in combination with the component A, but the copolymerizability of the three components A, B and C The anion group and the cation group existing in the polymer chain three-dimensionalized by covalent bond form a complex salt, and the interaction between the anion group and the cation group makes the crosslinked structure denser to form a gel. It is considered that the strength of the composite salt is increased and the generated complex salt is appropriately low in hydrophilicity, so that the swelling property when the gel body is immersed in water can be suppressed to be low.

In addition, when the gel body comes into contact with the cement-based material, the binding force between the anion group existing in the cross-linked structure of the gel body and the cement-based material works effectively, and the gel body has an adhesive property to the cement-based material. In addition, the soil-sand solidified body obtained by hardening after the chemical solution consisting of the three components A, B and C has penetrated into the sand-sand is a bond between the cation groups in the cross-linked structure of the gel body and the sand-sand particles. It is considered that the strength increases because the force works effectively.

The present invention has been completed based on such findings.
Conventionally, it has not been reported that a gel body having excellent performance as a water blocking agent as described above can be obtained by using both components B and C together with component A.

There are various kinds of components B and C used in the present invention, and a preferable example thereof is a compound represented by the formula:
It is possible to use one or more anionic electrolyte monomers selected from the group consisting of the compound represented by (2) or formula (3) and salts thereof.

Equation _{(2): CH 2 = C} (R 3) COOH ( in the formula (2), R ³ represents a hydrogen atom or a methyl group). Equation _{(3): CH 2 = CHCONH} -C (CH 3) The ₂ -CH ₂ SO ₃ H embodiment, acrylic acid and its salts, methacrylic acid and salts thereof, 2-acrylamido - 2-methylpropanesulfonic acid and Examples of the salt include individual salts and mixtures thereof. As the salt, an alkali metal salt such as sodium and potassium, an ammonium salt, a salt with a component C which is a cationic electrolyte monomer, or a complex salt thereof is used. it can.

As the component C, a compound represented by the formula (4), and one or more kinds of cationic electrolyte monomers selected from the group consisting of salts and quaternary compounds thereof can be used.

Formula (4): (R ⁴ ) (R ⁵ ) N- (CH ₂ ) _n -Y-CO-C (R ⁶ ) = CH ₂ (In formula (4), R ⁴ and R ⁵ are both methyl groups. Is an ethyl group, R ⁶ is a hydrogen atom or a methyl group, n is 2 or 3, and Y is an oxygen atom or an NH group). Specific examples thereof include dimethylaminoethyl methacrylate, a salt thereof and a quaternary compound thereof, diethylaminoethyl methacrylate, a salt and a quaternary compound thereof, dimethylaminoethyl acrylate, a salt thereof and a quaternary compound thereof.
Graded product, diethylaminoethyl acrylate, its salt and its quaternized product, dimethylaminopropylmethacrylamide, its salt and its quaternized product, diethylaminopropylmethacrylamide, its salt and its quaternized product, dimethylaminopropylacrylamide, Examples thereof include salts and quaternary compounds thereof, diethylaminopropyl acrylamide, salts and quaternary compounds, etc., each alone or as a mixture. Examples of the salt include salts of inorganic acids such as hydrochloric acid and sulfuric acid, or anionic electrolyte monomers. Can be used as a salt with the component B, and as the quaternary compound, a quaternary compound with methyl chloride, dimethylsulfate or the like, or a complex salt thereof can be used.

In the present invention, the amounts of components B and C used in component A are in the range of 20 to less than 80 for component A as a weight ratio per 100 parts by weight of the sum of the three components.
The sum of and is preferably more than 20 and 80 or less.

If the usage ratio of component A and component (B + C) is within this range, A,
The gel obtained by copolymerizing the mixture of B and C has high strength, good adhesiveness to the cement-based substance, and sufficiently high strength of the solidified sediment body.

When the content of the component (B + C) in the mixture of A, B and C is 20% by weight or less, the content of the anionic component is small, and the adhesiveness between the gel body and the cementitious substance decreases. Also, since the content of the cationic component is small, the strength of the solidified sediment obtained by the penetration and hardening of the chemical solution is reduced.

On the other hand, the content of the component (B + C) in the mixture of A, B and C is
If it exceeds 80% by weight, the content of the crosslinkable component is reduced, so that the crosslink density of the gel body is lowered, and the strength of the gel body tends to be lowered.

In the present invention, the ratio of component B and component C used is the ratio of both components.
B / C is preferably 20/80 to 80/20 in terms of molar ratio.

If the ratio of the components B and C used is within this range, the components
A gel obtained by copolymerizing a mixture of A, B and C can be suppressed to have low swelling property when immersed in water, and can also suppress reduction in strength when the solidified solid body is immersed in water. You can

In using the water blocking agent of the present invention, it is preferable that the mixture of the components A, B and C is usually used in the form of an aqueous solution having a concentration of 3 to 60% by weight from the viewpoint of effects.

At this time, the oxidizing agent component of the redox catalyst used is, for example, ammonium persulfate, potassium persulfate, etc., while the reducing agent component is, for example, sodium thiosulfate, rongalit, sodium sulfite, triethanolamine, hexamethylene. Tetramine, ferrous sulfate, tartaric acid, citric acid and the like are preferable.

The amount of the redox catalyst used is usually the amount of components A, B and C.
In the range of 0.1 to 100% by weight with respect to the mixture.

〔The invention's effect〕

 The water blocking agent of the present invention has the following excellent properties.

(1) The gel body obtained by the method of the present invention does not have syneresis, is impermeable to water, has high strength, is difficult to swell when immersed in water, and has adhesiveness with a cement-based substance, and The solidified soil and sand has a high strength and does not deteriorate in water over time.

(2) Components A, B and C used in the present invention are all low-toxic, water-soluble, and have good polymerizability, so that they have good penetrability as an aqueous solution and set curing time when construction for waterproofing work. It can be used as an easy and safe drug.

For this reason, the water blocking agent of the present invention is preferably used as a water blocking agent for preventing infiltration water and water leakage in, for example, a sewer pipeline facility.

〔Example〕

 Next, the present invention will be described using examples and comparative examples.

Examples 1 to 8 and Comparative Examples 1 to 7 The ternary mixture of A, B and C in the proportions shown in Table 1 was prepared by adding the polymerization catalyst (ammonium persulfate and triethanolamine) and water in predetermined amounts. The chemical solution in which the total concentration of the component mixture was adjusted to 10% by weight was gelated in a cylindrical container to obtain a sample with a diameter of 50 mm and a height of 50 mm.

Curing time of the drug solution at this time, syneresis of the obtained gel body,
Table 1 shows the breaking strain, breaking strength, swelling property, cement adhesiveness and standard sand solidified strength.

The measurement of each evaluation item was performed by the following method.

Curing time: The time required for the chemical solution to gel was measured at 20 ° C.

Syneresis: Some amount of syneresis water one day after gelation was visually observed.

Fracture strain, Fracture strength: Values obtained by uniaxially compressing a gel body.

L _O : Specimen height before compression, (mm) △ L: Compression amount just before fracture, (mm) P: Load applied to the specimen immediately before fracture, (Kg) A: Cross-sectional area of the specimen immediately before fracture, (cm ² ) A _O : Cross-sectional area of the specimen before compression, (cm ² ) Swellability: The degree of weight increase when the gel body was immersed in 100 to 200 times the amount of water for 10 days was shown by the degree of swelling. The degree of swelling here is defined as follows.

Cement Adhesion: A cylindrical mortar molded product with a diameter of 28 mm and a height of 50 mm (Toyoura standard sand / Portland cement / water weight ratio: 3/1 / 0.6) should be concentric in a cylindrical container with a diameter of 50 mm. Then, 50 ml of the chemical solution described in Table 1 was poured into a cylindrical container to cause gelation, and the adhesiveness was observed from the tensile strength of the gel body and the mortar molded product.

Standard sand solidified strength: The chemicals listed in Table 1 were infiltrated and solidified in Toyoura standard sand to obtain solids with a diameter of 50 mm and a height of 100 mm, one day after solidification and one month in water. It is a value obtained by measuring each uniaxial compressive strength after immersion according to JIS A 1216.

Claims (3)

[Claims] 1. A weight ratio of the following three components A, B and C per 100 parts by weight of the sum of the three components is such that the component A is in the range of 20 or more and less than 80 and the sum of the components B and C. In the range of more than 20 and not more than 80, and the component ratio B / C is 20/80 to 80/20 in molar ratio, and a water blocking agent obtained by adding a polymerization catalyst. Component A: a single compound or a mixture of compounds represented by formula (1). Component B: at least one anionic electrolyte monomer selected from the group consisting of compounds represented by formula (2) or formula (3) and salts thereof. Component C: at least one cationic electrolyte monomer selected from the group consisting of compounds represented by formula (4), and salts and quaternary compounds thereof. Equation _{(1): CH 2 = C} (R 1) CO-O - (- CH 2 CH 2 O-) n -COC (R 2) = CH 2 ( in the formula (1), R ¹ and R ² are hydrogen Atom or a methyl group, and n represents an integer of 2 to 50). Equation _{(2): CH 2 = C} (R 3) COOH ( in the formula (2), R ³ represents a hydrogen atom or a methyl group). Equation _{(3): CH 2 = CHCONH} -C (CH 3) 2 -CH 2 SO 3 H Formula ^{(4): (R 4)} (R 5) N- (CH 2) n -Y-CO-C (R ⁶ ) = CH ₂ (In the formula (4), R ⁴ and R ⁵ are both a methyl group or an ethyl group, R ⁶ is a hydrogen atom or a methyl group, n is 2 or 3, and Y is an oxygen atom. Or NH group). 2. The component A as described above, wherein R ¹ and R ² in the formula (1) are both methyl groups, and n is an integer of 18 to 40, singly or as a mixture. Waterstop. 3. The waterproofing agent according to claim 1, which is used for preventing infiltration of water or leakage of water in a sewer pipeline facility.