JP2005306892A - Aqueous waterproofing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To use a water-based urethane that does not volatilize an organic solvent during work and is excellent in water resistance strength, water resistance appearance, water absorption rate, etc., and useful for outdoor waterproofing materials, wall waterproofing materials, flooring materials, sealing materials, etc. Provided is an aqueous waterproofing composition for construction.
[Solution]
An aqueous waterproofing material composition is prepared using an aqueous polyurethane resin. The polyol constituting the aqueous polyurethane resin contains an olefin polyol and / or vegetable oil-based polyol as an essential component, and the content of the olefin polyol and / or vegetable oil-based polyol is 10% by weight or more in the total polyol.
[Selection figure] None

Description

  The present invention relates to a water-based waterproof material composition and a waterproof construction method and a waterproof structure using the same, and more specifically, there is no adverse effect on the environment due to volatilization of an organic solvent, and durability and workability are excellent. The present invention relates to an aqueous waterproofing material composition for civil engineering construction, a waterproof structure, and a waterproof construction method.

  Polyurethane resin is excellent in various properties such as rubber elasticity, abrasion resistance, and durability, and has been widely used as a waterproof material that is conventionally applied to civil engineering structures. In consideration of the work environment, a waterproof material using an aqueous polyurethane resin not containing an organic solvent has been developed (for example, Patent Document 1).

However, the waterproof material using the above-mentioned water-based polyurethane resin may be inferior in terms of water resistance strength, water resistance appearance, water absorption rate, and the like depending on use conditions, and further improvement is desired.
JP 2002-129008 A

  The present invention has been made to solve the above problems, and the object of the present invention is to use an aqueous urethane that does not volatilize an organic solvent during work, and is excellent in terms of water resistance strength, water resistance appearance, water absorption rate, and the like. Another object of the present invention is to provide an aqueous waterproof material composition for civil engineering and construction that is useful for outdoor waterproof materials, wall waterproof materials, floor materials, sealing materials and the like. Another object of the present invention is to provide a waterproof construction method and a waterproof structure using the aqueous waterproof material composition.

  The aqueous waterproof material composition of the present invention is an aqueous waterproof material composition using an aqueous polyurethane resin, and the polyol constituting the aqueous polyurethane resin contains an olefin polyol and / or a vegetable oil-based polyol as an essential component, and the olefin The content of the polyol and / or the vegetable oil-based polyol is 10% by weight or more based on the total polyol.

  In addition, the waterproof construction method of the present invention is characterized in that a waterproof material containing any one of the above-described aqueous waterproof material compositions is applied to a base to prevent water from entering and dried to form a film. And

  Further, the waterproof structure of the present invention is characterized by comprising a base to prevent water from entering, and a film formed by applying and drying a waterproof material containing any of the above aqueous waterproof material compositions. And

  According to the water-based waterproof material composition of the present invention, it is excellent in water resistance strength, water-resistant appearance, water absorption rate, etc., and also has a fast drying property after application, and an extremely useful waterproof material can be obtained.

  As described above, the water-based waterproofing material composition of the present invention uses olefin polyol and / or vegetable oil-based polyol at 10% by weight or more of all polyols constituting the aqueous polyurethane resin. Thereby, the performance excellent in water resistance is exhibited and waterproof performance is exhibited over a long period of time.

  Here, by using the above-mentioned olefin polyol and / or vegetable oil-based polyol as 10% by weight or more, preferably 30% or more, and more preferably 50% or more, based on the total polyol used, performance excellent in water resistance can be obtained. Demonstrates waterproof performance over a long period of time.

  Examples of the olefin polyol include polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, and hydrogenated polyisoprene polyol. Examples of vegetable oil-based polyols include various hydroxyl group-containing vegetable oil derivatives such as modified soybean oil, castor oil, dehydrated castor oil, and hydrogenated castor oil.

  As the isocyanate to be reacted with the above polyol, naphthalene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, norbornane diisocyanate, polymethylene polyphenyl polyisocyanate, buretization Examples thereof include various aromatic, aliphatic, and alicyclic isocyanates such as hexamethylene diisocyanate and nurated hexamethylene diisocyanate, either alone or as a mixture.

  In addition to olefin polyols and vegetable oil-based polyols, active hydrogen group-containing compounds may be added. Specifically, polyethylenes such as diethylene glycol, butanediol, hexanediol, bisphenol A, trimethylolpropane, glycerin, and pentaerythritol. Alcohols, their alkylene derivatives or their esterified products such as poly (oxyethylene ether) polyol, poly (oxypropylene ether) polyol, poly (oxyethylene propylene ether) polyol, polyester polyol, polythioether polyol, polyacetal polyol, polytetra Examples include methylene glycol and mixtures thereof.

  In the above, it is preferable that the particle diameter of the aqueous polyurethane resin emulsion in the aqueous waterproof material composition is 5 μm or less.

  When the emulsion particle diameter exceeds 5 μm, it becomes impossible to form a uniform urethane coating layer at the time of construction particularly at a low temperature environment, and waterproof performance is not exhibited. Furthermore, cracks and the like are generated, causing a problem in practical use. Further, as a waterproofing material composition, particles are settled during long-term storage, which causes a practical problem.

  The aqueous polyurethane resin preferably contains 0.00003 to 0.0008 mol / g of ionic functional groups and / or salts thereof in terms of solid content. Further, the content of the on-functional group and / or salt thereof is more preferably 0.00007 to 0.0005 mol / g, and further preferably 0.0002 to 0.0003 mol / g. When the introduction amount of the ionic functional group and / or salt thereof exceeds 0.0008 mol / g, the hydrophilicity as the aqueous polyurethane resin becomes good and the particle diameter becomes large, but on the other hand, the water absorption of the waterproof layer is remarkably large. And water resistance decreases. On the other hand, if it is less than 0.00003, the stability of the aqueous polyurethane resin is poor when stored, and sedimentation or the like occurs.

  Examples of ionic functional groups and salts thereof introduced into the aqueous polyurethane resin include: (a) a compound having a salt-forming carboxylic acid or sulfonic acid group and a corresponding salt-forming agent, and (b) an acid. Compounds having groups capable of becoming quaternary or tertiary groups and corresponding salt forming agents, (c) compounds containing halogen atoms or corresponding strong acid esters that cause quaternization reactions and corresponding Salt-forming agents to be used.

  Examples of the compound (a) having a salt-forming carboxylic acid or sulfonic acid group include hydroxy acids such as glycolic acid, malic acid, glycine, aminobenzoic acid, alanine, dimethylolpropionic acid, and dimethylolbutanoic acid. Acid, aminocarboxylic acid, polyvalent hydroxy acids, aminosulfonic acids such as taurine and 2-hydroxyethanesulfonic acid, hydroxysulfonic acids and the like, and salt forming agents corresponding thereto include, for example, sodium hydroxide, calcium hydroxide And monovalent metal hydroxides such as ammonia, tertiary amine compounds such as ammonia, trimethylamine, and triethylamine.

  Examples of the compound (b) having a group capable of forming a quaternary or tertiary group that can be neutralized with an acid include alkoxylated amines such as N, N-dimethylethanolamine and N-methyldiethanolamine; Examples include amino alcohols such as N-methyl-N- (3-aminopropyl) -ethanolamine and N, N-dimethylhydrazine, amines, and the like. Examples of the corresponding salt forming agent include organic acids and inorganic acids such as hydrochloric acid, nitric acid, formic acid, acetic acid, dimethylsulfuric acid, methyl chloride, and benzyl chloride, and compounds having a reactive halogen atom.

  Examples of the compound (c) containing a halogen atom that causes a quaternization reaction or a corresponding strong acid ester include 2-chloroethanol, 2-bromomethanol, and the like. Moreover, as a salt formation agent corresponding to it, a tertiary amine, sulfides, phosphine etc. are mentioned, for example.

  The aqueous polyurethane resin is preferably emulsified with 5% by weight or less of a surfactant. When the surfactant is added in an amount exceeding 5% by weight, the hydrophilicity is improved, but the water-releasing rate of the waterproof material in the water resistance of the waterproof layer increases, and the water absorption of the waterproof layer increases remarkably. This is not preferable because the water resistance is lowered. Examples of surfactants that can be used include various conventionally known surfactants, which are appropriately selected according to the ionicity of the aqueous polyurethane resin.

  Moreover, in the above, it is preferable to further contain a hydrophobic organic compound having a boiling point of 250 ° C. or higher. Hydrophobic organic compounds exhibit the effect of improving water resistance as a waterproof material. Here, when the boiling point of this hydrophobic organic compound is lower than 250 ° C., the effect of improving water resistance is lowered, which is not preferable.

  In the above, it is preferable to further contain an inorganic filler. Examples of inorganic fillers include heavy calcium carbonate, talc, aluminum hydroxide, quartzite powder, various surface-treated calcium carbonates, and mixtures thereof. An inorganic filler is added in order to improve the resin strength of an aqueous waterproofing material composition, and to improve drying property in addition.

  In the above, the content ratio of the water-based polyurethane resin, the hydrophobic organic compound having a boiling point of 250 ° C. or higher, and the inorganic filler is 100/10 to 100/10 to 100 parts by weight in solid content ratio. Is preferred. When the blending amount of the hydrophobic organic compound is less than 10 parts by weight with respect to 100 parts by weight of the aqueous polyurethane resin, the water resistance as a waterproofing material becomes insufficient, and when it exceeds 100 parts by weight, the aqueous waterproofing material composition Problems with stability. Moreover, when the compounding quantity of an inorganic filler is less than 10 weight part, while contributing to the improvement of resin strength falls, the contribution to the drying property at the time of construction of an aqueous waterproofing material composition will decrease. Moreover, when the compounding quantity of an inorganic filler is 100 weight part or more, sedimentation etc. will arise and the storage stability as an aqueous waterproofing material composition will be a problem.

  The hydrophobic organic compound is preferably an organic resin that is liquid at a temperature of −20 ° C. or higher or has a glass transition temperature of −20 ° C. or lower.

  Examples of such hydrophobic organic compounds include plasticizers such as dioctyl phthalate and diisononyl phthalate, and organic resins such as urethane, acrylic, rubber, and ester.

  The above-mentioned hydrophobic organic compound and inorganic filler can be added to the aqueous polyurethane resin by any method when added and mixed before emulsification, which is in the process of manufacturing the aqueous polyurethane resin, or when added and mixed after manufacturing the aqueous polyurethane resin. It can be carried out. In view of emulsification stability and the like, it is preferable to add and mix before emulsification, which is in the middle of production of the aqueous polyurethane resin.

  The waterproof construction method of the present invention is to form the waterproof layer by applying the water-based waterproof material composition of the present invention to the base surface to prevent water from entering, and drying the surface of the coating film. If necessary, the aqueous waterproofing material composition of the present invention may be applied after forming a primer layer on the base surface in advance. In the construction method of the present invention, since an aqueous waterproof material composition is used, it is possible to prevent adverse effects on the health and environment of workers due to the volatilization of the organic solvent during the work.

  The waterproof structure of the present invention comprises: a base to prevent water from entering; and a film coated with a waterproof material containing the aqueous waterproof material composition according to any one of claims 1 to 9 and dried. I have. In the waterproof structure of the present invention, a primer layer may be formed as necessary.

  The aqueous waterproofing material composition of the present invention is used by coating on asphalt concrete, asbestos slate, ALC board, PC board, FRP, plastic, woody material, metal or the like as a base. The base waterproofing material of the present invention can be used in any shape as long as it is the surface of the base of the structure, for example, any of a spherical surface, a curved surface, an extended surface, a flat surface, a vertical surface, a slope, a ceiling surface, etc. A waterproof layer can be formed using the composition.

  The aqueous waterproofing material composition of the present invention is usually used alone as it is, but water dispersions of other resins, for example, vinyl acetate, ethylene vinyl acetate, acrylic, acrylic styrene emulsions, styrene It can be used by mixing and blending with butadiene-based, acrylonitrile-butadiene-based, acrylic-butadiene-based latex, polyethylene, polyolefin-based ionomer, polyester, polyamide, and epoxy-based water dispersions in an arbitrary ratio.

  In addition, the purpose of improving various durability such as heat resistance, water resistance, solvent resistance, etc. of the waterproof layer formed using the aqueous waterproof material composition of the present invention, adhesion, hardness, paint workability, and waterproofing Various stabilizers such as color pigments, antioxidants, UV absorbers, weathering agents, hydrolysis inhibitors, leveling agents, antifoaming agents, thickeners, protective colloids for the purpose of improving storage stability of material compositions An agent or the like can be added during or after the production process of the aqueous waterproofing material composition of the present invention. Furthermore, water-dispersed crosslinking agents such as isocyanate compounds, epoxy-based water-soluble or water-dispersible crosslinking agents, carbodiimide-based, oxazolidone-based and other water-soluble or water-dispersible crosslinking agents may be added and mixed. it can.

  Hereinafter, the present invention will be described by way of examples. However, the present invention is not limited to the examples. In addition, the part in an Example and a comparative example shows a weight part.

(Synthesis Example 1)
In a previously dried flask, as shown in Table 1, 50 parts of polybutadiene polyol (Poly bd R-45HT: manufactured by Idemitsu Petrochemical Co., Ltd.) and polyoxypropylene glycol (number average molecular weight = 3000: Daiichi Kogyo Seiyaku) 50 parts) was dissolved in 80 parts of methyl ethyl ketone. 14 parts of tolylene diisocyanate was added thereto and reacted at 75 ° C. for 2 hours. Then, 5 parts of dimethylolpropionic acid was added and reacted for further 2 hours to obtain a methyl ethyl ketone solution of a polyurethane resin.

  After adding 50 parts of diisononyl phthalate (DINP) to 100 parts of the solid content of the polyurethane resin solution and mixing the mixture uniformly, 3.4 parts of triethylamine and 3% of the surfactant with respect to the solid content of the polyurethane resin are mixed. (Neugen EA-157, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was dispersed in water previously dissolved, chain extension was performed with water, and then the solvent was removed to obtain an aqueous polyurethane resin composition.

(Synthesis Examples 2 to 6)
Using the raw materials shown in Table 1, aqueous polyurethane resin compositions of Synthesis Examples 2 to 6 were obtained in the same procedure as in Synthesis Example 1.

(Comparative Synthesis Example 1)
As shown in Table 1, 5 parts of polybutadiene polyol (Poly bd R-45HT: manufactured by Idemitsu Petrochemical Co., Ltd.) and polyoxypropylene glycol (number average molecular weight = 3000: Daiichi Kogyo Seiyaku) 95 parts) was dissolved in 80 parts of methyl ethyl ketone. This was charged with 14 parts of tolylene diisocyanate, reacted at 75 ° C. for 2 hours, then charged with 5 parts of dimethylolpropionic acid, and further reacted for 2 hours to obtain a methyl ethyl ketone solution of polyurethane resin.

  After adding 50 parts of diisononyl isophthalate (DINP) to 100 parts of the solid content of the polyurethane resin solution and mixing the mixture uniformly, 3.4 parts of triethylamine and 3% of the surface activity with respect to the solid content of the polyurethane resin are mixed. An agent (Neugen EA-157, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was dispersed in water previously dissolved and subjected to chain extension with water, followed by solvent removal to obtain an aqueous polyurethane resin composition.

(Comparative Synthesis Example 2)
Using the raw materials shown in Table 1, an aqueous polyurethane resin composition of Comparative Synthesis Example 2 was obtained in the same procedure as Comparative Synthesis Example 1.

(Examples 1-6)
Additives shown in Table 2 are added to 100 parts of the aqueous polyurethane resin composition obtained in Synthesis Examples 1 to 6, and uniform with Disper (TK Homo Disper: manufactured by Tokushu Kika Kogyo Co., Ltd.). After mixing as described above, defoaming was carried out to obtain aqueous waterproofing material compositions of Examples 1-6.

(Comparative Examples 1 and 2)
Fillers and additives shown in Table 2 were added to 100 parts of the aqueous polyurethane resin composition obtained in Comparative Synthesis Examples 1 and 2, and disperser (TK Homodisper: manufactured by Tokushu Kika Kogyo Co., Ltd.) After mixing so as to be uniform, defoaming was carried out to obtain aqueous waterproofing material compositions of Comparative Examples 1 and 2.

[performance test]
A test sample was prepared using the aqueous waterproofing material compositions of Examples 1 to 6 and Comparative Examples 1 and 2 obtained above, and the following tests were performed on this sample. The test results are shown in Table 2.

(Creation of test sample for strength test of isolated waterproof layer)
A ratio of the coating amount of 3000 g / m ² of the aqueous waterproofing material compositions of Examples 1 to 6 and Comparative Examples 1 and 2 on the surface of a polyethylene plate release plate (length 30 cm, width 30 cm, thickness 5 mm) using rubber spatula Each sample was coated uniformly, left for one week, and peeled off from the release plate to obtain a test sample.

(Test method for isolated waterproof layer strength test)
About the test sample for the isolated waterproof layer strength test before and after the above water resistance test, the tensile strength and elongation of the isolated waterproof layer were measured according to JIS A6021.

(Water resistance test)
About the test sample for said isolation waterproofing layer strength test, and the test sample for concrete adhesion tests, it immersed in 50 degreeC tap water for 30 days, and performed the water-proof test. In the evaluation after the water resistance test, the tensile strength and the elongation were measured in accordance with observing the appearance of the waterproof layer visually and in accordance with JIS A6021. The evaluation criteria are as follows.

○: Appearance is good. No abnormality △: Partially missing ×: Swelling occurred.

(Coating water absorption)
The water absorption is determined by immersing the above-mentioned coating film (4 cm × 4 cm) whose weight has been measured in advance in distilled water at 23 ° C. for 3 days, immediately removing the surface moisture with a dry cloth, measuring the weight, The rate of weight increase was determined.

(Dryness after application)
The aqueous waterproofing material composition of each example and each comparative example was applied on a polyethylene flat plate (25 cm × 25 cm, thickness 5 mm) so that the dry film thickness was 1 mm, and the standard state (temperature: 23 ± 2 ° C.). , Relative humidity: 50 ± 10%), and the dry state after 24 hours was evaluated.

  The evaluation criteria are as follows.

○: Dry state is good. Δ: Sticky, remaining tack ×: Undried part.

(Storage stability)
The aqueous waterproofing material composition of each Example and each Comparative Example was put in a glass sample bottle (100 ml) and evaluated for storage stability at 23 ° C. for 90 days.

  The evaluation criteria are as follows.

○: Stable, no abnormality Δ: Thickening ×: Partial gelation, filler sedimentation.

[Results of performance test]
As is clear from Table 2, the waterproof layer produced using the aqueous waterproof material compositions of Examples 1 to 6 was compared with the waterproof layers of Comparative Examples 1 and 2 in appearance before and after the water resistance test. The tensile strength was sufficiently large and the elongation value was also large. Moreover, it was excellent also about the film water absorption, the drying property after application | coating, and the stability of the composition.

If the composition of the present invention is used, it is excellent in water resistance strength, water resistance appearance, water absorption rate, etc., and also has a fast drying property after application, and an extremely useful waterproofing material can be obtained. Can do. Moreover, since the waterproof construction method and waterproof structure of the present invention use the water-based waterproof material composition, they can be used in the field of architecture and the like.

Claims (10)

  An aqueous waterproofing material composition using an aqueous polyurethane resin, wherein the polyol constituting the aqueous polyurethane resin contains an olefin polyol and / or a vegetable oil-based polyol as an essential component, and contains the olefin polyol and / or the vegetable oil-based polyol. An aqueous waterproofing material composition characterized in that the amount is 10% by weight or more in the total polyol.   The aqueous waterproof material composition according to claim 1, wherein the aqueous polyurethane resin emulsion in the aqueous waterproof material composition has a particle size of 5 µm or less.   The water-based waterproofing material composition according to claim 1 or 2, wherein the water-based polyurethane resin contains 0.00003 to 0.0008 mol / g of ionic functional groups and / or salts thereof in terms of solid content. Stuff.   The aqueous waterproofing material composition according to claim 3, wherein 5% by weight or less of a surfactant is blended and emulsified in the aqueous polyurethane resin.   The aqueous waterproofing material composition according to claim 4, further comprising a hydrophobic organic compound having a boiling point of 250 ° C. or higher.   The water-based waterproofing material composition according to claim 5, further comprising an inorganic filler.   The water-based waterproofing according to claim 6, wherein the content ratio of the water-based polyurethane resin, the hydrophobic organic compound having a boiling point of 250 ° C or higher, and the inorganic filler is 100/10 to 100/10 to 100 parts by weight in solid content ratio. Material composition.   The hydrophobic organic compound is liquid at a temperature of -20 ° C or higher, or an organic resin having a glass transition temperature of -20 ° C or lower, according to any one of claims 5 to 7. Aqueous waterproofing composition.   A waterproof construction characterized in that a waterproof material comprising the water-based waterproof material composition according to any one of claims 1 to 9 is applied to a base to prevent water from entering and dried to form a film. Method. A waterproofing system comprising: a base to prevent water from entering; and a film formed by applying and drying a waterproofing material containing the aqueous waterproofing material composition according to any one of claims 1 to 9. Structure.