JP5215656B2 - One-part water-stop material - Google Patents

Description

  The present invention relates to a one-pack type water-stopping material, and in particular, it is injected into a damaged portion of a structure such as brittle ground or concrete to react with moisture inside to form a high-strength cured body and to form a good water-stopping material. The present invention relates to a one-component water-stopping material that exhibits a water effect or a reinforcing effect.

Polyurethane resin has been used in various sewer facilities and buildings as an injecting agent for water stopping (Patent Documents 1 to 5). However, many of them are so-called hydrophilic types that react with water to form hydrous gels, so that the water-stopping effect does not continue due to shrinkage due to evaporation of water inside the gel body or decomposition degradation of the gel-like resin. There is. Moreover, even if it is hydrophobic, the type that foams and cures has a problem in terms of the strength of the resin, and sufficient water-stopping performance is difficult to be exhibited for large water leaks.
JP-A-62-265383 Japanese Patent Laid-Open No. 01-299993 JP-A-62-265383 JP-A-7-109369 JP 2002-003821 A

  The problem to be solved by the present invention is a one-component type stopper that is low in viscosity, excellent in workability, exhibits good performance as a water-stopping agent, and has adhesion performance to concrete and can be used as a reinforcing agent. It is to provide water material.

  As a result of the study by the present inventors, a urethane prepolymer obtained by reacting a polyol component essentially containing a tetrahydrofuran-neopentyl glycol copolymer with an organic polyisocyanate component reacts with water to cause shrinkage or It was found that a high-strength hardened body that hardly decomposes and deteriorates and that it has excellent adhesion to concrete and the like. That is, the present invention is a one-part water-stop agent containing a urethane prepolymer containing a terminal isocyanate group obtained by reacting a polyol component and an organic polyisocyanate component, wherein the polyol component is tetrahydrofuran-neopentyl glycol. The present invention relates to a one-part water-stopping material characterized in that it essentially contains a copolymer.

  The one-component type water-stopping material of the present invention can exert an effect as a reinforcing agent particularly on a damaged part of ground or concrete with water leakage, and can also be used as a spraying agent on concrete and other brittle ground. can do.

  The polyol component used in the present invention contains one or two or more polyols, but it is essential to use a tetrahydrofuran-neopentylglycol copolymer in order to obtain sufficient resin strength and water-stopping property. Features. The use ratio is not particularly limited, but it is preferable to use 5 to 50% by mass with respect to the entire polyol component in order to obtain sufficient resin strength and water stoppage, and more preferably 10 to 30% by mass. preferable.

  Polyols other than the tetrahydrofuran-neopentyl glycol copolymer that can be used in the present invention are not particularly limited, and examples thereof include polyether polyols, polyester polyols, and polyacetal polyols.

  Specific examples of polyether polyols include water, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerthritol, sorbitol, butanediol, neopentylglycol, hexanediol, and pentanediol. And alkylene oxide adducts of polyhydric alcohols. Here, it is preferable to use water, dipropylene glycol, glycerin, pentaerythritol, or trimethylolpropane as the polyhydric alcohol from the viewpoint of improving the water stopping performance. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. One or two or more of these can be added. In adjusting the hydrophilicity of the urethane prepolymer, ethylene oxide and propylene are used. What added both oxides is preferable. When adding 2 or more types, it may be a block shape or a random shape. Of these, those having an average molecular weight of 50 to 50000 are particularly preferred, and those having an average molecular weight of 100 to 20000 are more preferred.

  In addition to polyethylene glycol, polypropylene glycol, and polyethylene polypropylene glycol, the polyether polyol includes a dimer composed of one or more of ethylene glycol, propylene glycol, and butylene glycol, and other low molecular weight substances. Of these, those having an average molecular weight of 50 to 50000 are particularly preferred, and those having an average molecular weight of 100 to 20000 are more preferred.

  Specific examples of polyester polyols include polyols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, glycerin or trimethylolpropane, and succinic acid, glutaric acid, adipic acid, maleic acid. Saturated or unsaturated polyvalent carboxylic acids such as fumaric acid and phthalic acid, condensation products with these acid anhydrides, polycaprolactone polyols, and the like. These can be mixed and used as necessary. Of these, those having an average molecular weight of 100 to 50000 are particularly preferred, and those having an average molecular weight of 200 to 20000 are more preferred.

  Further, by adding a low molecular weight polyether polyol, polyester polyol or the like having a molecular weight of 50 to 500, a stronger resin can be obtained, but from the viewpoint of workability, it is preferably up to 30% by mass of the entire polyether.

  Furthermore, other polyols can be used in combination as long as the object of the present invention is not impaired.

  Specific examples of the organic polyisocyanate include polymethylene polyphenyl polyisocyanate (PMDI), diphenylmethane diisocyanate (MDI), carbodiimide-modified diphenylmethane diisocyanate (CMDI), xylene diisocyanate (XDI), tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI). ) And hexamethylene diisocyanate (HDI), but are not particularly limited thereto. The organic polyisocyanate component is preferably one containing polymethylene polyphenyl polyisocyanate from the viewpoint of reaction rate and economy. It is more preferred to use a total of two or more mixed isocyanates with methylene polyphenyl polyisocyanate. When organic polyisocyanates other than these are used in combination, excellent performance can be obtained by making this mixed isocyanate 70% by mass or more of the total isocyanate component.

  The prepolymerization is usually carried out by charging a polyol component and an organic polyisocyanate component into a synthetic reaction apparatus, stirring them, and reacting at 60 to 160 ° C. In prepolymerization, a tin-based catalyst such as monobutyltin oxide, dibutyltin oxide, tetraoctyltin, dioctyltin oxide, dibutyltin laurate, and dioctyltin laurate can be used as necessary.

  As a compounding agent for the urethane prepolymer synthesized as described above to react with water to form a cured product, organic amines and metal catalysts can be mainly used. Examples of organic amines include polyamines such as triethylamine, trimethylamine, dimethylmyristylamine, stearylamine, dimethyldecylamine, N-ethylmorpholine, triethylenetetramine, tolylenediamine, and xylylenediamine. As the metal catalyst, butyl lithium, sodium methoxide, bis (2-ethylhexanoate) tin, dibutyltin laurate, dioctyltin laurate, bis (neodecate) tin and the like can be preferably exemplified.

  Furthermore, the one-component water-stopping material of the present invention can be blended with a diluent as necessary so as to sufficiently impregnate a few concrete cracks. Specific examples of the diluent include gamma-butyl lactone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2oxo-4methyl-1, 3 dioxolane, methyl acetyl ricinolate, butyl acetyl ricinolate, glutar Dimethyl acid, dimethyl succinate, dimethyl adipate or mixtures thereof. In addition, examples of the auxiliary method include a method of reducing the viscosity using a surfactant, a method of blocking, and the like, but are not limited thereto.

  Further, various silicon compounds such as polydimethylsiloxane and silica can be added as additives depending on the purpose.

  In order to modify the urethane prepolymer according to the present invention, 0 to 50% by mass of an epoxy monomer, an acrylic monomer (such as methyl methacrylate), and a styrene monomer are blended with respect to the urethane prepolymer. be able to.

  The one-pack type water-stopping material of the present invention has a higher water-stopping performance than a commonly used urethane-based water-stopping material, and also exhibits the water-stopping performance over a long period of time. Furthermore, it has excellent adhesion performance to concrete and the like, and can be expected to be used as a reinforcing agent by injecting into a cracked portion of concrete. Further, since it is a one-pack type, it is very good in terms of workability as compared with a two-pack type foam type injection.

  The following examples illustrate the invention. However, the present invention is not limited to these examples and comparative examples.

Intermediate raw material synthesis example:
A 5 L stainless steel pressure-resistant reaction vessel with a stirring blade equipped with two dripping pipes and a gas inlet / outlet was sufficiently replaced with dry nitrogen gas, and then 140 g of dipropylene glycol (reagent grade 1) was added to the reaction vessel. 1.6 g of flaky NaOH (reagent grade 1) was charged, and the temperature of the reaction vessel was raised to 125 ° C. while stirring. While maintaining 125 ° C., 1430 g of propylene oxide and 1570 g of ethylene oxide were continuously injected from the dropping introduction tube over 10 hours, respectively, and propylene oxide and ethylene oxide were simultaneously randomly added to dipropylene glycol. Stirring was continued for 4 hours while maintaining 125 ° C. to complete the reaction. After the temperature was lowered to 100 ° C., 21 g of Kyoward 700SL (adsorbent manufactured by Kyowa Chemical Industry Co., Ltd.) was added. Stirring was continued for 1 hour while maintaining 100 ° C. to adsorb NaOH to the adsorbent. Next, the unreacted propylene oxide and ethylene oxide remaining in the vacuum pump and moisture contained in the adsorbent were degassed and dehydrated for 2 hours while maintaining 100 ° C. After the temperature was lowered to 70 ° C., the contents were taken out from the reaction vessel, and Kyoward 700SL adsorbing NaOH was removed by a pressure filter to obtain a transparent viscous polyether (confirmed that the molecular weight was 3000 by GPC. Called "modified polyether polyol").

Production Example 1
Sanix FA-703 (Sanyo Kasei Kogyo Co., Ltd. polyethylene polypropylene trifunctional polyether polyol, average molecular weight 5000) as a polyol component in a 0.8 kg capacity synthesizer equipped with a stirrer, thermometer and temperature controller 10 g, 12 g of TR-9080 (polyethylene polypropylene trifunctional polyether polyol, average molecular weight 9000, manufactured by Sanyo Chemical Industries, Ltd.), 3.0 g of 1.4-butanediol, and PTXG-1000 (Asahi Kasei Corporation) Tetrahydrofuran-neopentyl glycol copolymer, average molecular weight 1000) 10 g was charged. Next, 270 g of Coronate 1130 (crude MDI manufactured by Nippon Polyurethane Co., Ltd., PMDI: MDI ratio is 56:44, NCO% is 32.0%) is added as an isocyanate component, and the temperature is raised to 120 to 125 ° C. and reacted for 3 hours. I let you. Finally, 200 g of gamma-butyl lactone as a diluent and 1.0 g of silicone SAG-471 (a silicone compound manufactured by Toray Dow Corning Co., Ltd.) as a foam stabilizer were added to obtain a urethane prepolymer U-1 (NCO%; 15 0.0%).

Production Example 2
TR-9080 (polypropylene polypropylene trifunctional polyether polyol, average molecular weight 9000, manufactured by Sanyosei Kogyo Co., Ltd.) 9.0 g as a polyol component in a 0.8 kg internal synthesizer equipped with a stirrer, thermometer and temperature controller , 12 g of modified polyether polyol, 10 g of ADEKA polyether P-1000 (Asahi Denka Kogyo Co., Ltd. propylene glycol-based polypropylene-based bifunctional polyether, average molecular weight 1000), ADEKA polyether P-400 (Asahi Denka Kogyo) 10 g of propylene glycol base / polypropylene bifunctional polyether manufactured by Co., Ltd., average molecular weight 400), and 15 g of PTXG-1000 (tetrahydrofuran-neopentyl glycol copolymer, average molecular weight 1000 manufactured by Asahi Kasei Fibers Co., Ltd.) were further charged. . Next, Takenate 500 (Mitsui Takeda Chemical Co., Ltd. XDI, molecular weight 188) 9.0 g as an isocyanate component, Lupranate MB-9S (BASF polyurethane Co., Ltd. Crude MDI, PMDI: MDI ratio 59:41, NCO% 32.0%) was added, and the temperature was raised to 130 to 135 ° C. and reacted for 2 hours. Finally, 200 g of gamma-butyl lactone and 1.0 g of silicon SAG-471 (silicone compound manufactured by Toray Dow Corning Co., Ltd.) were added as diluents to obtain urethane prepolymer U-2 (NCO%; 10.0%). .

Production Example 3
As a polyol component, Sanix FA-703 (Sanyo Chemical Industries, Ltd., polyethylene polypropylene trifunctional polyether polyol, average molecular weight 5000) was added as a polyol component to a synthesizer equipped with a stirrer, thermometer and temperature controller. 10 g, DI-4060 (Sanyo Kasei Kogyo Co., Ltd. Polyethylene Polypropylene Bifunctional Polyether Polyol, Average Molecular Weight 4000) 20 g, Adeka Polyether P-400 (Asahi Denka Kogyo Co., Ltd. Propylene Glycol Base Polypropylene 2) 8.0 g of functional polyether polyol, average molecular weight 400), 3.0 g of 1.3-propanediol, and 9 g of PTXG-1800 (tetrahydrofuran-neopentyl glycol copolymer, average molecular weight 1800, manufactured by Asahi Kasei Fibers Co., Ltd.) It is. Next, as an isocyanate component, 30 g of Takenate 500 (Mitsui Takeda Chemical Co., Ltd. XDI, molecular weight 188), Coronate 1130 (Nippon Polyurethane Co., Ltd. Crude MDI, PMDI: MDI ratio is 56:44, NCO% is 32.0%. %) Was added, and the temperature was raised to 80 to 85 ° C. and reacted for 5 hours. Finally, 200 g of methylacetylricinoleate was added as a diluent to obtain urethane prepolymer U-3 (NCO%; 18.0%).

Production Example 4
18 g of TR-4085 (Sanyo Chemical Industries, Ltd., polyethylene polypropylene trifunctional polyether polyol, average molecular weight 4000) as a polyol component in a synthesis apparatus having an internal capacity of 0.8 kg equipped with a stirrer, a thermometer and a temperature controller, 6.0 g of modified polyether polyol, 10 g of ADEKA polyether P-2000 (Asahi Denka Kogyo Co., Ltd. propylene glycol base / polypropylene bifunctional polyether polyol, average molecular weight 2000), ADEKA polyether G-300 (Asahi) 20 g of propylene glycol base / polypropylene bifunctional polyether polyol manufactured by Denka Kogyo Co., Ltd., average molecular weight 300), and 10 g of PTXG-1000 (tetrahydrofuran-neopentyl glycol copolymer, average molecular weight 1000 manufactured by Asahi Kasei Fibers Co., Ltd.) Was charged. Next, as an isocyanate component, Lupranate MB-9S (crude MDI manufactured by BASF Polyurethane Co., Ltd., PMDI: MDI ratio 59:41, NCO% is 32.0%) is 120 g and ISONATE 143L (Dow Chemical Japan Co., Ltd.) 30 g of carbodiimide-modified MDI, CMDI: MDI ratio of 20-40: 60-80) was added, and the temperature was raised to 100-105 ° C. and reacted for 4 hours. Finally, 200 g of 2oxo-4methyl-1,3dioxolane was added as a diluent to obtain a urethane prepolymer U-4 (NCO%; 8.1%).

Production Example 5
TR-9080 (Sanyo Kasei Kogyo Co., Ltd. Polyethylene Polypropylene Trifunctional Polyether Polyol, Average Molecular Weight 9000) 12 g, Adeka Polyether in a 0.8 kg capacity synthesizer equipped with a stirrer, thermometer and temperature controller 12 g of P-3000 (Asahi Denka Kogyo Co., Ltd., propylene glycol base, polypropylene bifunctional polyether polyol, average molecular weight 3000), Adeka Polyether P-1000 (Asahi Denka Kogyo Co., Ltd., propylene glycol base, polypropylene) 9.0 g of bifunctional polyether polyol, average molecular weight 1000) 10 g, Adeka polyether G-300 (Asahi Denka Kogyo Co., Ltd. propylene glycol-based polypropylene bifunctional polyether polyol, average molecular weight 300), and PTXG- 1800 Asahi Kasei Fibers Corp. tetrahydrofuran - neopentyl glycol copolymer, charged with average molecular weight 1800) 6 g. Next, 20 g of ISONATE 143L (Dow Chemical Japan Co., Ltd. carbodiimide-modified MDI, CMDI: MDI ratio 20 to 40:60 to 80) as an isocyanate component, lupranate MB-9S (crude MDI manufactured by BASF Polyurethane Co., Ltd.) PMDI: MDI ratio is 59:41, NCO% is 32.0%) 320g, Takenate 500 (XDI, Mitsui Takeda Chemical Co., Ltd., molecular weight 188) is added, and the temperature is raised to 90-95 ° C for 6 hours. I let you. Finally, 150 g of gamma-butyl lactone was added as a diluent to obtain urethane prepolymer U-5 (NCO%; 20.5%).

Production Example 6
Using a stirring vessel equipped with a stirrer, a thermometer, and a temperature controller and having a content of 0.8 kg, 50 g of styrene was added to the urethane resin 200 g of Production Example 3 at room temperature and stirred for 10 minutes at room temperature. This was designated as modified urethane prepolymer UA-1.

Production Example 7
Using a stirring vessel having an internal capacity of 0.8 kg equipped with a stirrer, a thermometer, and a temperature controller, 50 g of methyl methacrylate was added to 200 g of urethane resin of Production Example 5 at room temperature and stirred for 10 minutes at room temperature. It was. This was designated as modified urethane prepolymer UA-2.

Comparative Example 1
A synthesizing apparatus equipped with a stirrer, a thermometer, and a temperature controller with a content of 0.8 kg as a polyol component is TR-4085 (Sanyo Kasei Co., Ltd. polyether polyol, average molecular weight 4000) 12 g, modified polyether polyol 9.0 g, and 18.0 g of Adeka Polyether G-300 (Asahi Denka Kogyo Co., Ltd. glycol-based polypropylene trifunctional polyether polyol, average molecular weight 300) were charged. Next, 200 g of lupranate MB-9S (crude MDI manufactured by BASF Polyurethane Co., Ltd., PMDI: MDI ratio is 59:41, NCO% is 32.0%) is added as an isocyanate component, and the temperature is raised to 80 to 85 ° C. Reacted for hours. Finally, 170 g of gamma butyl lactone and 2.0 g of silicon SAG-471 (silicone compound manufactured by Toray Dow Corning Co., Ltd.) were added as diluents to obtain a comparative urethane prepolymer E-1 (NCO%; 14.0%) ).

Comparative Example 2
20 g of DI-4060 (Sanyo Kasei Kogyo Co., Ltd. polyethylene polypropylene bifunctional polyether polyol, average molecular weight 4000) as a polyol component in a 0.8 kg internal synthesizer equipped with a stirrer, thermometer and temperature controller, 12 g of Adeka Polyether G-300 (Asahi Denka Kogyo Co., Ltd. glycol-based polypropylene trifunctional polyether polyol, average molecular weight 300), 24 g of modified polyether polyol, Adeka Polyether BPX-11 (Asahi Denka Kogyo ( Co., Ltd. Bisphenol A-based / polypropylene-based bifunctional polyether polyol, average molecular weight 360) 7.2 g and PTMG-650 (Mitsubishi Chemical Co., Ltd. polytetramethylene glycol, average molecular weight 650) 6.5 g were charged. Next, 150 g of tolylene diisocyanate (TDI, molecular weight 174) was added as an isocyanate component, and the temperature was raised to 120 to 125 ° C. and reacted for 2 hours. Finally, 200 g of 2oxo-4methyl-1,3dioxolane was added as a diluent to obtain a comparative urethane prepolymer E-2 (NCO%; 14.5%).

Comparative Example 3
TR-9080 (Sanyo Kasei Co., Ltd. polyether polyol, average molecular weight 4000) as a polyol component was added to a 0.8 kg internal synthesizer equipped with a stirrer, thermometer and temperature controller, TR-4085 (Sanyo) 20 g of polyether polyol manufactured by Kasei Kogyo Co., Ltd., average molecular weight 4000), Adeka polyether P-3000 (propylene glycol base / polypropylene bifunctional polyether, polyether polyol manufactured by Asahi Denka Kogyo Co., Ltd., average molecular weight, average) 30 g of molecular weight 3000) and 30 g of PTMG-1500 (Mitsubishi Chemical Co., Ltd. polytetramethylene glycol, average molecular weight 1500) were charged. Next, 200 g of coronate 1130 (crude MDI manufactured by Nippon Polyurethane Co., Ltd., NCO% is 32.0%) was added as an isocyanate component, and the temperature was raised to 130 to 135 ° C. and reacted for 1.5 hours. Finally, 200 g of gamma-butyl lactone was added as a diluent to obtain a comparative urethane prepolymer E-3 (NCO%; 10.0%).

Various performance evaluation tests were conducted as follows. The results are shown in Table 1.
(1) Basic performance The appearance was visually observed, and a B-type viscometer (manufactured by Brookfield) was used. The viscosity was measured at 2 rotors, 60 rpm, 20 ° C.
(2) Performance during curing After adding 10 g of the synthesized urethane prepolymer to a 100 g death cup, 0.5 g of triethylamine diluted to 10% with dibutylphthaldibutyrate and 1.0 g of water were added as a compounding agent, and the curing time of the resin And the properties of the resin during curing were observed.
(3) Liquid storage performance at the time of compounding agent addition The mixture of the synthesized urethane prepolymer and triethylamine was allowed to stand for 2 days without adding water, and it was confirmed whether the liquid state was maintained.
(4) Adhesive strength Based on JISK-7220, a 1.5 cm x 5 cm x 5 cm mortar plate was coated with a resin solution containing triethylamine and water as a whole with a brush and left at room temperature for 3 days. Measured with (5) Workability test Further, a mixed solution of urethane prepolymer and triethylamine was poured into a concrete crack impregnated with water with a grease gun, and its pouring property, adhesiveness and water-stopping property were evaluated.

Claims (2)

A one-component water-stop material containing a urethane prepolymer containing a terminal isocyanate group obtained by reacting a polyol component with an organic polyisocyanate component, wherein the polyol component requires a tetrahydrofuran-neopentyl glycol copolymer A one-component water-stopping material characterized by comprising. The one-component water-stopping material according to claim 1, wherein the organic polyisocyanate component contains polymethylene polyphenyl polyisocyanate.