JP6990900B2 - Curable composition and joint structure and waterproof structure using it - Google Patents

Description

The present invention relates to a curable composition that is cured by moisture in the atmosphere, and a joint structure and a waterproof structure using the same.

Conventionally, a curable composition containing an oxyalkylene polymer having a crosslinkable hydrolyzable silyl group has been known (for example, Patent Document 1). The curable composition produces a cured product having excellent adhesiveness by dehydrating and condensing after the hydrolyzable silyl group that can be crosslinked by the moisture contained in the atmosphere is hydrolyzed.

Such a curable composition is, for example, in an outer wall of a building structure, a joint portion (so-called "joint") between outer wall members such as a mortar plate, a concrete plate, an ALC (Autoclaved Light-weight Concrete) plate, and a metal plate. ) Is used to join the outer wall members to each other. By using the curable composition in this way, it is possible to prevent rainwater from entering the inside of the building structure from the joint between the outer wall members.

In the outer wall of a building structure, the joint width changes slightly because the outer wall member expands or contracts with a temperature change, or the outer wall member moves due to vibration or external force caused by an earthquake or strong wind. Therefore, it is required that the curable composition has excellent rubber elasticity after curing and can be expanded and contracted so as to be able to follow changes in joint width.

In particular, in a high-rise building, the amount of change in the joint width is also large, so that the curable composition is required to have more excellent rubber elasticity after its curing.

In addition, outdoor exposed parts such as verandas and rooftops of building structures are exposed to rain, and there is a risk that rainwater will come into contact with or permeate and deteriorate. Therefore, a waterproof sheet is arranged on the waterproof surface of the outdoor exposed portion, and a waterproof construction is performed in which the edge portion of the waterproof sheet and the waterproof surface connected to the edge portion of the waterproof sheet are covered with a sealing material.

Japanese Patent No. 5636141

However, in the conventional curable composition, after curing, the rubber elasticity decreases with time and becomes hard, and when the joint width changes, it becomes difficult to expand and contract according to the change in the joint width, and the adhesive is adhered. There is a problem that rainwater infiltrates into the building structure and causes water leakage due to peeling at the interface, damage to the outer wall member, and cracks in the cured product of the curable composition.

Further, when the conventional curable composition is used as a sealing material, there arises a problem that the curable composition deteriorates the waterproof sheet, and the curing of the waterproof sheet causes cracks and impairs the waterproof property.

Furthermore, in recent years, synthetic resins have come to be used for structural members of building structures, and as in the case of waterproof sheets, the structural members are deteriorated by the curable composition, and the waterproof property is impaired. There is also the problem of reducing the strength of the structure.

The present invention provides a curable composition that cures due to moisture in the air, has excellent rubber elasticity over a long period of time, and produces a cured product in which deterioration of the synthetic resin is largely suppressed.

The curable composition of the present invention is a curable composition containing a polyalkylene oxide-based polymer (A) having a hydrolyzable silyl group, an acrylic-based polymer (B), and a monoamine compound (C). The content of the mercapto-based compound is 50 ppm or less with respect to the total mass of the curable composition.

[Polyalkylene oxide-based polymer (A)]
The polyalkylene oxide-based polymer (A) contained in the curable composition has a hydrolyzable silyl group. The hydrolyzable silyl group is a group in which 1 to 3 hydrolyzable groups are bonded to a silicon atom.

The hydrolyzable group of the hydrolyzable silyl group is not particularly limited, and is, for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, or a mercapto. Groups, alkenyloxy groups and the like can be mentioned.

Among them, as the hydrolyzable silyl group, an alkoxysilyl group is preferable because the hydrolysis reaction is mild. The alkoxysilyl group includes a triethoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, and a triphenoxysilyl group; a dimethoxysilyl group such as a methyldimethoxysilyl group and a methyldiethoxysilyl group. ; Also, monoalkoxysilyl groups such as a dimethylmethoxysilyl group and a dimethylethoxysilyl group can be mentioned. Of these, a dialkoxysilyl group is preferable, and a methyldimethoxysilyl group is more preferable.

The polyalkylene oxide-based polymer (A) has an average of 1 to 2 hydrolyzable silyl groups in one molecule and 1 to 3 hydrolyzable silyl groups in the case of branching. It is preferable to have. When the number of hydrolyzable silyl groups in the polyalkylene oxide-based polymer (A) is one or more, the curability of the curable composition is improved. Further, when the number of hydrolyzable silyl groups in the polyalkylene oxide-based polymer (A) is not more than the above upper limit value, the mechanical strength or extensibility of the cured product of the curable composition is improved. Further, it is preferable that the polyalkylene oxide-based polymer (A) has a hydrolyzable silyl group at at least one of both ends of its main chain.

The average number of hydrolyzable silyl groups per molecule in the polyalkylene oxide-based polymer (A) is ¹ H-NMR, which is the hydrolyzable silyl group in the polyalkylene oxide-based polymer (A). It can be calculated based on the concentration of the group and the number average molecular weight of the polyalkylene oxide-based polymer (A) obtained by the GPC method.

In the polyalkylene oxide-based polymer (A), the main chain has a general formula:-(RO) _n- (in the formula, R represents an alkylene group having 1 to 14 carbon atoms, and n is a repeating unit. A polymer containing a repeating unit represented by (1), which is a positive integer, is preferably mentioned. The main chain skeleton of the polyalkylene oxide-based polymer may consist of only one type of repeating unit, or may consist of two or more types of repeating units.

The main chain skeleton of the polyalkylene oxide-based polymer (A) includes polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer, and polypropylene oxide-polybutylene oxide copolymer. And so on. Of these, polypropylene oxide is preferable. According to polypropylene oxide, it is possible to provide a curable composition having excellent rubber elasticity and adhesiveness after curing.

The number average molecular weight of the polyalkylene oxide-based polymer (A) is preferably 15,000 to 50,000, more preferably 16,000 to 30,000. When the number average molecular weight of the polyalkylene oxide-based polymer (A) is 15,000 or more, the mechanical strength or extensibility of the cured product of the curable composition is improved. When the number average molecular weight of the polyalkylene oxide-based polymer (A) is 50,000 or less, the coatability of the curable composition is improved.

In the present invention, the number average molecular weight of the polyalkylene oxide-based polymer (A) means a polystyrene-converted value measured by a GPC (gel permeation chromatography) method. In the measurement by the GPC method, for example, Shodex KF800D manufactured by Tosoh can be used as the GPC column, and chloroform or the like can be used as the solvent.

As the polyalkylene oxide-based polymer (A) containing a hydrolyzable silyl group, a commercially available one can be used. For example, as polyalkylene oxide-based polymers having a main chain skeleton of polypropylene oxide and a methyldimethoxysilyl group at the end of the main chain skeleton, Asahi Glass Co., Ltd. trade names "Exester S4530" and "Exester S2730C" are available. , "Exester S2420", "ESSXT02" and the like.

The content of the polyalkylene oxide-based polymer (A) having a hydrolyzable silyl group in the curable composition is the polyalkylene oxide-based polymer (A) having a hydrolyzable silyl group and the acrylic polymer described later. Of the total amount of (B), 20 to 90% by mass is preferable, 30 to 80% by mass is more preferable, and 40 to 70% by mass is particularly preferable. When the content of the polyalkylene oxide-based polymer (A) having a hydrolyzable silyl group is 20% by mass or more, the extensibility of the curable composition is improved. When the content of the polyalkylene oxide-based polymer (A) having a hydrolyzable silyl group is 90% by mass or less, the weather resistance of the curable composition is improved.

[Acrylic polymer (B)]
The curable composition contains an acrylic polymer (B).

Examples of the main chain skeleton of the acrylic polymer (B) include acrylic polymers obtained by radical polymerization of (meth) acrylate-based monomers such as ethyl (meth) acrylate and butyl (meth) acrylate. In addition, (meth) acrylate means methacrylate or acrylate.

Specific examples of the (meth) acrylate-based monomer constituting the main chain of the acrylic polymer (B) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth). Acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate , Stearyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate , Hexadiol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylol propanetri (meth) acrylate, pentaerythritol di (meth) acrylate. , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, 2-hydroxyethyl (meth) ) Acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6- Hydroxyhexyl (meth) acrylate, 3-hydroxy-3-methylbutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- [acryloyloxy] ethyl-2-hydroxyethylphthalic acid, and 2- [Acryloyloxy] Ethyl-2-hydroxypropylphthalic acid and the like can be mentioned. These (meth) acrylate-based monomers may be used alone or in combination of two or more.

It is also possible to copolymerize another monomer in the acrylic polymer (B). Examples of such monomers include styrene, inden, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, divinylbenzene and the like. Compounds with vinyl ester groups such as styrene derivatives, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl silicate, maleic anhydride, N-vinylpyrrolidone, N-vinylmorpholine, ( Meta) Acrylonitrile, (meth) acrylamide, N-cyclohexylmaleimide, N-phenylmaleimide, N-laurylmaleimide, N-benzylmaleimide, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, tert-amyl Vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2-chloroethyl vinyl ether, ethylene glycol butyl vinyl ether, triethylene glycol methyl vinyl ether, benzoic acid (4-vinyloxy) butyl, ethylene glycol divinyl ether, diethylene glycol divinyl ether , Triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butane-1,4-diol-divinyl ether, hexane-1,6-diol-divinyl ether, cyclohexane-1,4-dimethanol-divinyl ether, diisophthalate (4-Vinyloxy) butyl, di (4-vinyloxy) butyl glutarate, di (4-vinyloxy) succinate butyl trimethyl propantrivinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, Examples include compounds having a vinyloxy group such as cyclohexane-1,4-dimethanol monovinyl ether, diethylene glycol monovinyl ether, 3-aminopropyl vinyl ether, 2- (N, N-diethylamino) ethyl vinyl ether, urethane vinyl ether, and polyester vinyl ether. can. These monomers may be used alone or in combination of two or more.

Among them, as the main chain skeleton of the acrylic polymer (B), a copolymer of butyl (meth) acrylate and methyl (meth) acrylate is preferable, and a copolymer of butyl acrylate and methyl methacrylate is more preferable. According to the acrylic polymer (B) whose main chain skeleton is the above-mentioned copolymer, a curable composition capable of forming a cured product having both extensibility and flexibility after curing can be obtained.

The polymerization method of the acrylic polymer (B) is not particularly limited, and a known method can be used. For example, a free radical polymerization method, an anion polymerization method, a cationic polymerization method, a UV radical polymerization method, and a living anion weight can be used. Various polymerization methods such as legal, living cationic polymerization method, and living radical polymerization method can be mentioned.

As will be described later, the curable composition has a mercapto-based compound content of 50 ppm or less based on the total mass of the curable composition. In order to reduce the mercapto-based compound in the curable composition, it is preferable that the mercapto-based compound contained in the acrylic polymer (B) is reduced. The mercapto-based compound is a compound having a functional group (-SH) to which a hydrogen atom is directly bonded. Examples of the mercapto-based compound include methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, thiophenol, and toluenethiol. , Naphthalenethiol, mercaptopropylmethyldimethoxysilane, mercaptopropylmethyldiethoxysilane and the like.

Examples of the method for producing the acrylic polymer (B) having a reduced content of the mercapto-based compound or containing no mercapto-based compound include the following methods. For example, (1) a method of supplying (meth) acrylate as a monomer and jittery butyl peroxide as a polymerization catalyst to a pressurized stirring tank reactor maintained at 150 to 200 ° C. to polymerize the monomer. (2) (Meta) acrylate is continuously supplied as a monomer to a continuous stirring tank type reactor maintained at 300 to 350 ° C., and jittery butyl peroxide is dropped as a polymerization initiator to carry out continuous bulk polymerization. A method of adjusting the molecular weight by causing β-cleavage of the polymer while performing the above.

The acrylic polymer (B) preferably contains an acrylic polymer having a hydrolyzable silyl group. Further, the acrylic polymer (B) preferably contains an acrylic polymer having no hydrolyzable silyl group and an acrylic polymer having a hydrolyzable silyl group.

As the hydrolyzable silyl group, an alkoxysilyl group is preferable because the cured product of the curable composition can maintain excellent rubber elasticity for a long period of time. The alkoxysilyl group includes a triethoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, and a triphenoxysilyl group; a dimethoxysilyl group such as a methyldimethoxysilyl group and a methyldiethoxysilyl group. ; Also, monoalkoxysilyl groups such as a dimethylmethoxysilyl group and a dimethylethoxysilyl group can be mentioned. Of these, a dialkoxysilyl group and a trialkoxysilyl group are preferable, and a methyldimethoxysilyl group and a trimethoxycysilyl group are more preferable.

The acrylic polymer (B) preferably has 0.1 to 3 hydrolyzable silyl groups in one molecule on average. When the number of hydrolyzable silyl groups in the acrylic polymer (B) is 0.1 or more, the curability of the curable composition is improved. When the number of hydrolyzable silyl groups in the acrylic polymer (B) is 3 or less, the mechanical strength or extensibility of the cured product of the curable composition is improved.

The average number of hydrolyzable silyl groups per molecule in the acrylic polymer (B) is the concentration of hydrolyzable silyl groups in the acrylic polymer (B) determined by ¹ H-NMR. And, it can be calculated based on the number average molecular weight of the acrylic polymer (B) obtained by the GPC method.

The method for introducing the hydrolyzable silyl group into the acrylic polymer (B) is not particularly limited, and for example, a hydrosilane having a hydrolyzable silyl group in the acrylic polymer having an unsaturated group introduced in the molecule. A known method can be used, such as a method of hydrolysylated by allowing the above to act.

The number average molecular weight of the acrylic polymer (B) is preferably 1000 to 50,000, preferably 1000 to 30,000, and more preferably 15,000 to 30,000. When the number average molecular weight of the acrylic polymer (B) having a hydrolyzable silyl group is 10,000 or less, the coatability of the curable composition is improved. When the number average molecular weight of the acrylic polymer (B) having a hydrolyzable silyl group is 1000 or more, deterioration of the synthetic resin, particularly the polyvinyl chloride resin can be suppressed.

In the present invention, the number average molecular weight of the acrylic polymer means a polystyrene-equivalent value measured by a GPC (gel permeation chromatography) method. In the measurement by the GPC method, for example, Shodex KF800D manufactured by Tosoh can be used as the GPC column, and chloroform or the like can be used as the solvent.

The content of the acrylic polymer (B) in the curable composition is 10 to 80 mass by mass in the total amount of the polyalkylene oxide polymer (A) having a hydrolyzable silyl group and the acrylic polymer (B). % Is preferable, 20 to 70% by mass is more preferable, and 30 to 60% by mass is preferable in the country. When the content of the acrylic polymer (B) is 10% by mass or more, the cured product of the curable composition maintains excellent rubber elasticity for a long period of time. When the content of the acrylic polymer (B) is 80% by mass or less, the coatability of the curable composition is improved.

[Monoamine compound (C)]
The curable composition contains a monoamine compound (C). The monoamine compound has only one amino group (-NH ₂ ) in one molecule.

The monoamine compound (C) is not particularly limited, and is, for example, butylamine, hexylamine, heptylamine, 2-ethylhexylamine, octylamine, 3-methoxypropylamine, tetradecylamine, pentadecylamine, stearylamine, and trimethylcyclohexyl. Examples thereof include primary aliphatic amines such as amines, primary aromatic amines such as benzylamine, and secondary aliphatic amines such as dilaurylamine, distearylamine and methyllaurylamine.

As the monoamine compound (C), an aliphatic amine is preferable because it precipitates on the surface of the cured product after curing of the curable composition to exhibit an anti-tack effect and suppress the adhesion of contaminants. Amine is more preferable, and stearylamine and laurylamine are particularly preferable.

The monoamine compound preferably has 6 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, and particularly preferably 12 to 18 carbon atoms. When the number of carbon atoms of the monoamine compound is within the above range, after the curable composition is cured, it is smoothly precipitated on the surface of the cured product to exhibit an anti-tack effect, and the adhesion of contaminants is further suppressed.

The content of the monoamine compound (C) in the curable composition is 0. 1 to 10 parts by mass is preferable, 0.5 to 8 parts by mass is more preferable, and 0.8 to 5 parts by mass is particularly preferable. When the monoamine compound is contained in an amount of 0.1 part by mass or more, after the curable composition is cured, it is smoothly precipitated on the surface of the cured product to exhibit an anti-tack effect, and the adhesion of contaminants is further suppressed. When the monoamine compound is contained in an amount of 10 parts by mass or less, the precipitation of the monoamine compound on the surface of the cured product of the curable composition can be suppressed and the appearance of the cured product is improved, which is preferable.

[Plasticizer]
The curable composition may further contain a plasticizer. Specific examples of the plasticizer include phthalates such as dioctylphthalate, dibutylphthalate and butylbenzylphthalate, and polyalkylene oxides such as polypropylene glycol. Polyalkylene oxides do not contain hydrolyzable silyl groups.

The content of the plasticizer in the curable composition is 100 parts by mass or less with respect to 100 parts by mass of the total amount of the polyalkylene oxide-based polymer (A) and the acrylic-based polymer (B) having a hydrolyzable silyl group. It is preferably 70 parts by mass or less, and particularly preferably 1 to 70 parts by mass. If the content of the plasticizer is too high, the plasticizer may cause bleeding.

[Filler (D)]
The curable composition preferably further contains the filler (D). According to the filler (D), it is possible to provide a curable composition capable of obtaining a cured product having excellent mechanical strength.

Examples of the filler (D) include calcium carbonate, magnesium carbonate, calcium oxide, hydrous silicic acid, anhydrous silicic acid, fine powder silica, calcium silicate, titanium dioxide, clay, talc, carbon black, and glass balloons. Can be done. These fillers may be used alone or in combination of two or more. Among them, calcium carbonate and silica are preferably used, colloidal calcium carbonate and silica are more preferably used, and silica is particularly preferably used.

The average particle size of the filler (D) is preferably 0.01 to 5 μm, more preferably 0.05 to 2.5 μm. According to the filler (D) having such an average particle size, a cured product having excellent mechanical strength and extensibility can be obtained, and curability having excellent adhesiveness can be obtained. The composition can be provided. The average particle size of the filler (D) is a value measured as follows. An SEM image magnified 1000 times that of the filler is taken. Ten fillers are arbitrarily extracted from the SEM image, a perfect circle having the smallest diameter that can surround the filler is drawn for each of the extracted fillers, and the diameter of the perfect circle is measured. The arithmetic mean value of the diameter of a perfect circle obtained for each filler is taken as the average particle diameter of the filler.

The content of the filler in the curable composition is 1 to 700 parts by mass with respect to 100 parts by mass of the total amount of the polyalkylene oxide-based polymer (A) and the acrylic-based polymer (B) having a hydrolyzable silyl group. Is preferable, and 10 to 200 parts by mass is more preferable. When the content of the filler is 1 part by mass or more, the effect of adding the filler can be sufficiently obtained. Further, when the content of the filler is 700 parts by mass or less, the cured product obtained by curing the curable composition has excellent extensibility.

[Dehydrating agent]
The curable composition preferably further contains a dehydrating agent. According to the dehydrating agent, when the curable composition is stored, it is possible to prevent the curable composition from being cured by the moisture contained in the air or the like.

Dehydrating agents include silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane; and methyl orthostate. , Ethyl compounds such as ethyl orthoate, methyl orthoacetate, and ethyl orthoacetate. These dehydrating agents may be used alone or in combination of two or more. Of these, vinyltrimethoxysilane is preferable.

The content of the dehydrating agent in the curable composition is 0.5 to 20 with respect to 100 parts by mass of the total amount of the polyalkylene oxide-based polymer (A) and the acrylic-based polymer (B) having a hydrolyzable silyl group. By mass is preferable, and 1 to 15 parts by mass is more preferable. When the content of the dehydrating agent in the curable composition is 0.5 parts by mass or more, the effect obtained by the dehydrating agent can be sufficiently obtained. Further, when the content of the dehydrating agent in the curable composition is 20 parts by mass or less, the curable composition has excellent curability.

[Silanol condensation catalyst]
The curable composition preferably further contains a silanol condensation catalyst. The silanol condensation catalyst is a hydrolyzable silyl group contained in the polyalkylene oxide-based polymer (A) having a hydrolyzable silyl group, and a hydrolyzable silyl contained in the acrylic polymer (B) as needed. It is a catalyst for promoting the dehydration condensation reaction between silanol groups formed by hydrolysis of groups and the like.

Examples of the silanol condensation catalyst include 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, and bis (dibutyltin lauric acid). ) Oxide, dibutyl tin bis (acetylacetonate), dibutyl tin bis (monoester malate), tin octylate, dibutyl tin octate, dioctyl tin oxide, dibutyl tin bis (triethoxysilicate), bis (dibutyltin bistriethoxysilicate) ) Oxides and organic tin compounds such as dibutyltin oxybisethoxysilicate; organic titanium compounds such as tetra-n-butoxytitanate and tetraisopropoxytitanate. These silanol condensation catalysts may be used alone or in combination of two or more.

As the silanol condensation catalyst, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane is preferable. With such a silanol condensation catalyst, the curing rate of the curable composition can be easily adjusted.

The content of the silanol condensation catalyst in the curable composition is 1 to 10% by mass with respect to 100 parts by mass of the total amount of the polyalkylene oxide-based polymer (A) and the acrylic-based polymer (B) having a hydrolyzable silyl group. Parts are preferable, and 1 to 5 parts by mass are more preferable. When the content of the silanol condensation catalyst in the curable composition is 1 part by mass or more, the curing rate of the curable composition can be increased and the time required for curing the curable composition can be shortened. .. Further, when the content of the silanol condensation catalyst in the curable composition is 10 parts by mass or less, the curable composition has an appropriate curing rate, and the storage stability and handleability of the curable composition are improved. be able to.

[Other additives]
The curable composition may contain other additives such as thixotropic agents, antioxidants, UV absorbers, pigments, dyes, antioxidants, and solvents. Among them, thixotropic agents, ultraviolet absorbers, and antioxidants are preferably mentioned.

The thixotropy-imparting agent may be any as long as it can exhibit thixotropy in the curable composition. Preferred examples of the thixotropic agent include hydrogenated castor oil, fatty acid bisamide, and fumed silica.

The content of the thixo property-imparting agent in the curable composition is 0.1 with respect to 100 parts by mass of the total amount of the polyalkylene oxide-based polymer (A) and the acrylic-based polymer (B) having a hydrolyzable silyl group. It is preferably up to 200 parts by mass, more preferably 1 to 150 parts by mass. When the content of the thixotropic agent in the curable composition is 0.1 part by mass or more, thixotropic property can be effectively imparted to the curable composition. Further, when the content of the thixotropic agent in the curable composition is 200 parts by mass or less, the curable composition has an appropriate viscosity and the handleability of the curable composition is improved.

Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and the like, and a benzotriazole-based ultraviolet absorber is preferable. The content of the ultraviolet absorber in the curable composition is 0.1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the polyalkylene oxide-based polymer (A) and the acrylic-based polymer (B) having a hydrolyzable silyl group. 20 parts by mass is preferable, and 0.1 to 10 parts by mass is more preferable.

Examples of the antioxidant include hindered phenolic antioxidants, monophenolic antioxidants, bisphenolic antioxidants, polyphenolic antioxidants and the like, and hindered phenolic antioxidants are preferable. Be done. The content of the antioxidant in the curable composition is 0.1 to 100 parts by mass based on 100 parts by mass of the total amount of the polyalkylene oxide-based polymer (A) and the acrylic-based polymer (B) having a hydrolyzable silyl group. 20 parts by mass is preferable, and 0.3 to 10 parts by mass is more preferable.

[Light stabilizer]
The curable composition preferably contains a hindered amine-based light stabilizer. According to the hindered amine-based light stabilizer, it is possible to provide a curable composition capable of maintaining excellent rubber elasticity for a longer period of time after curing.

Examples of the hindered amine-based light stabilizer include a mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate. , Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dibutylamine, 1,3,5-triazine, N, N'-bis (2,2,6,6-tetramethyl-4) -A polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{6- (1,1,3,3-) Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6) -Tetramethyl-4-piperidyl) imino}], polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-piperidinethanol.

As the hindered amine-based light stabilizer, a NOR-type hindered amine-based light stabilizer is preferably mentioned. According to the NOR-type hindered amine-based light stabilizer, it is possible to provide a curable composition in which a decrease in rubber elasticity with time is suppressed after curing.

The NOR-type hindered amine-based photostabilizer has a NOR structure in which an alkyl group (R) is bonded to a nitrogen atom (N) contained in a piperidine ring skeleton via an oxygen atom (O). The number of carbon atoms of the alkyl group in the NOR structure is preferably 1 to 20, more preferably 1 to 18, and particularly preferably 18. Examples of the alkyl group include a linear alkyl group, a branched chain alkyl group, and a cyclic alkyl group (saturated alicyclic hydrocarbon group).

Examples of the linear alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group and n-decyl. Group etc. can be mentioned. Examples of the branched-chain alkyl group include isopropyl, isobutyl, sec-butyl, tert-butyl and the like. Examples of the cyclic alkyl group (saturated alicyclic hydrocarbon group) include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Further, the hydrogen atom constituting the alkyl group may be substituted with a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or a hydroxyl group.

Examples of the NOR-type hindered amine-based light stabilizer include a hindered amine-based light stabilizer represented by the following formula (I).

When a NOR-type hindered amine-based light stabilizer is used, it is preferable to use the NOR-type hindered amine-based light stabilizer in combination with a benzotriazole-based ultraviolet absorber or a triazine-based ultraviolet absorber. Thereby, it is possible to provide a curable composition in which the decrease in rubber elasticity with time after curing is more suppressed.

The content of the hindered amine-based light stabilizer in the curable composition is 0 with respect to 100 parts by mass of the total amount of the polyalkylene oxide-based polymer (A) and the acrylic-based polymer (B) having a hydrolyzable silyl group. It is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass.

The curable composition has a mercapto-based compound content of 50 ppm or less, preferably 30 ppm or less, more preferably 15 ppm or less, particularly preferably 10 ppm or less, and most preferably 8 ppm or less, based on the total amount thereof. When the content of the mercapto-based compound is 50 ppm or less, deterioration of the synthetic resin due to the cured product of the curable composition can be effectively suppressed, and the waterproof property of the joint structure and the waterproof structure can be maintained for a long period of time. Can be maintained stably.

The content of the mercapto compound in the curable composition is measured as follows. The content of the mercapto compound in the curable composition is measured by GC-MS. For example, as the GC-MS column, a column sold by Shimadzu Corporation under the product name "DB-5" is used, and high-concentration helium is used as the carrier gas. The detector holds the flame photometric detector (FPD) column at 40 ° C., raises the temperature to 100 ° C. at 10 ° C./min, and then raises the temperature to 250 ° C. at 25 ° C./min for measurement. The injection temperature is 100 ° C. and the interface temperature is 250 ° C. Quantification is performed by the internal standard method.

The curable composition is excellent in adhesiveness and can form a cured product capable of maintaining excellent rubber elasticity for a long period of time. Therefore, a sealing material, a coating material, an adhesive, and a coating material can be formed. It can be used for various purposes. Among them, it is preferably used as a sealing material, and more preferably used as a joint structure sealing material and a waterproof structure sealing material.

As a method of applying the curable composition to the joint portion to obtain a joint structure, a method of filling the joint portion with the curable composition and then curing and curing the curable composition is used. The obtained joint structure has a wall member constituting the wall portion of the building structure and a cured product of the curable composition filled in the joint portion formed between the wall members adjacent to each other. There is. Examples of the wall portion of the building structure include an outer wall, an inner wall, and a ceiling portion. Examples of the wall member include an outer wall member, an inner wall member, and a ceiling member.

The joint portion is not particularly limited, and examples thereof include joint portions on the outer wall, inner wall, and ceiling of the building structure. Since the curable composition can maintain excellent rubber elasticity for a long period of time after curing, it is a joint due to expansion or contraction of a member due to a temperature change such as air temperature or sunshine, or due to an action such as vibration or wind pressure. It exhibits excellent followability to changes in the width of the part, and can prevent damage to members and water leakage into the building structure. Therefore, it is suitably used for sealing joints having a large change in width, which is also called a so-called "working joint", such as joints on the outer wall of a building structure.

Further, even when the wall member contains a synthetic resin, particularly when the polyvinyl chloride-based resin is contained, the cured product of the curable composition is largely prevented from deteriorating the synthetic resin. Therefore, even if the wall member is made of synthetic resin, there is no possibility that the wall member will deteriorate due to the cured product of the curable composition and cause cracks or the like, and water into the building structure will not occur. It is possible to almost prevent the entry of the building and the decrease in the mechanical strength of the building structure.

Examples of joints on the outer wall of a building structure include joints formed between outer wall members such as mortar plates, concrete plates, ceramic siding boards, metal siding boards, ALC plates, and metal plates. ..

Examples of the method for constructing a waterproof structure using the curable composition include the following construction methods. (1) A waterproof sheet 2 is laid on the waterproof surface 1 of the outdoor exposed part (outdoor exposed part) such as the veranda part, the roof part and the corridor part of the building structure A, and the edge portion 21 of the waterproof sheet 2 and this A construction method in which a curable composition is applied so as to cover a continuous prevention surface 11 on an edge portion 21, and then the curable composition is cured and cured to produce a cured product 3. (2) After laying a plurality of waterproof sheets 2 and 2 on the waterproof surface 1 of the outdoor exposed portion of the building structure A in a state where the facing ends 22 and 22 are overlapped with each other, the waterproof sheet 2 2. A construction method in which a curable composition is applied so as to cover the overlapped portions of the opposite end portions 22 and 22, and then the curable composition is cured and cured to produce a cured product 3.

As mentioned above, when the tarpaulin contains a synthetic resin (when the tarpaulin is made of a synthetic resin), especially when the tarpaulin contains a polyvinyl chloride resin, it is cured. The cured product of the sex composition is largely prevented from deteriorating the synthetic resin. Therefore, even if the waterproof sheet is made of synthetic resin, there is no possibility that the waterproof sheet will deteriorate and crack due to the cured product of the curable composition, and the waterproof structure will be provided for a long period of time. Excellent waterproofness can be maintained throughout.

Examples of the polyvinyl chloride-based resin include a vinyl chloride homopolymer, a copolymer containing a vinyl chloride as a main component (50% by weight or more), a vinyl chloride monomer and a copolymerizable monomer, and chlorinated products thereof. Be done.

Examples of the monomer copolymerizable with the vinyl chloride monomer include α-olefins such as ethylene, propylene and butylene; vinyl esters such as vinyl acetate and vinyl propionate; alkyl vinyl ethers such as ethyl vinyl ether and butyl vinyl ether; (Meta) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate; aromatic vinyls such as styrene and α-methylstyrene; vinyl fluoride, fluoride Vinyl halides such as vinylidene and vinylidene chloride; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide can be mentioned.

Since the curable composition of the present invention has the above-mentioned structure, it can be cured by moisture in the air, has excellent rubber elasticity, and is generally suppressed from deteriorating the synthetic resin. Can be generated.

It is sectional drawing which showed the waterproof structure of this invention. It is sectional drawing which showed another example of the waterproof structure of this invention.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

The following raw materials were used in the production of the curable compositions of Examples and Comparative Examples.
[Polyalkylene oxide-based polymer having a hydrolyzable silyl group (A)]
-Polyalkylene oxide-based polymer (A1) containing a methyldimethoxysilyl group and having a polypropylene oxide main chain skeleton (Product name "Exester S2420" manufactured by Asahi Glass Co., Ltd., molecular weight distribution: 1.49, number average molecular weight: 18990)
-Polyalkylene oxide-based polymer (A2) containing a methyldimethoxysilyl group and having a main chain skeleton made of polypropylene oxide (Product name "Exester S4530" manufactured by Asahi Glass Co., Ltd.) Molecular weight distribution: 1.16, number average molecular weight: 25294 )
Polyalkylene oxide-based polymer (A3) containing a methyldimethoxysilyl group and having a polypropylene oxide main chain skeleton (Product name "ESSXT02" manufactured by Asahi Glass Co., Ltd., molecular weight distribution: 1.10, number average molecular weight: 19500, )

[Acrylic polymer (B)]
Acrylic polymer (B1) having a dimethoxysilyl group (average number of methyldimethoxysilyl groups per molecule: 1.47, number average molecular weight: 20000, mercapto compound: about 0.6% by mass used for polymerization )
Acrylic polymer (B2) having a methyldimethoxysilyl group (average number of dimethoxysilyl groups per molecule: 1.9, number average molecular weight: 24000, mercapto compound for polymerization: unused)
Acrylic polymer (B3) having a trimethoxysilyl group (product name "US6170" manufactured by Toagosei Co., Ltd.), average number of trimethoxysilyl groups per molecule: 0.5, number average molecular weight: 2000, for polymerization Mercapto-based compound: unused)
Acrylic polymer (B4) having a trimethoxysilyl group (product name "US6110" manufactured by Toagosei Co., Ltd.), average number of trimethoxysilyl groups per molecule: 0.9, number average molecular weight: 2400, for polymerization Mercapto-based compound: unused)
Acrylic polymer (B5) having a methyldimethoxysilyl group (product name "SA310S" manufactured by Kaneka Corporation), average number of dimethoxymethylsilyl groups 2.0 per molecule: number average molecular weight: 28000, mercapto-based polymerization Compound: unused)

[Monoamine compound (C)]
-Monoamine compound (C1) (stearylamine, carbon number: 18)
-Monoamine compound (C2) (hexamethylenediamine)

[filler]
・ Colloidal calcium carbonate (D1) (Product name "Calfine 200M" manufactured by Maruo Calcium Co., Ltd., average particle size: 80 nm)
・ Colloidal calcium carbonate (D2) (Product name "EL-20" manufactured by Shiraishi Calcium Co., Ltd., average particle size: 100 nm)
-Silica (D3) (manufactured by Nippon Aerosil Co., Ltd., product name "Aerosil R972", average particle size: 16 nm)

[Aminosilane coupling agent]
-Aminosilane coupling agent (N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, product name "KBM-603" manufactured by Shin-Etsu Chemical Co., Ltd.)

[Dehydrating agent]
-Vinyl trimetoshisilane (Product name "KBM-1003" manufactured by Shin-Etsu Chemical Co., Ltd.)

[Silanol condensation catalyst]
-Silanol condensation catalyst (1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane, product name "Neostan U-130" manufactured by Nitto Kasei Co., Ltd.)

[UV absorber]
・ Benzotriazole-based UV absorber (BASF Japan product name "Tinubin 326")

[Antioxidant]
-Hindered phenolic antioxidant (BASF Japan product name "Irganox 1010")

[Light stabilizer]
・ NH-type hindered amine-based light stabilizer (Product name "Chinubin 770" manufactured by BASF Japan Ltd.)

[Synthesis of acrylic polymer (B1)]
In a 0.5 L separable flask equipped with a stirrer, cooler, thermometer and nitrogen gas inlet, 100 parts by mass of n-butyl acrylate (manufactured by Nippon Catalyst), 3-methacryloxypropylmethyldimethoxysilane (Shinetsu Chemical Co., Ltd.) Manufactured by, trade name "KBM-502") 0.6 parts by mass, 3-mercaptopropylmethyldimethoxysilane (chain transfer agent, manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-802") 0.9 parts by mass and ethyl acetate 100 A mass portion was supplied and mixed to prepare a monomer mixed solution.

Dissolved oxygen in the monomer mixture was removed by bubbling nitrogen gas into the monomer mixture for 20 minutes. Next, the air in the separable flask was replaced with nitrogen gas, and then the temperature was raised while stirring the monomer mixture solution until it reached recirculation.

0.024 parts by mass of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane was dissolved in 1 part by mass of ethyl acetate to prepare a first polymerization initiator solution. The first polymerization initiator solution was supplied to the monomer mixed solution.

A second polymerization initiator solution was prepared by dissolving 0.036 parts by mass of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane in 1 part by mass of ethyl acetate. After 1 hour had passed since the first polymerization initiator solution was supplied to the monomer mixed solution, the second polymerization initiator solution was further supplied to the monomer mixed solution.

0.048 parts by mass of di (3,5,5-trimethylhexanoyl) peroxide was dissolved in 1 part by mass of ethyl acetate to prepare a third polymerization initiator solution. After 2 hours have passed since the second polymerization initiator solution was supplied to the monomer mixed solution, the third polymerization initiator solution was further supplied to the monomer mixed solution.

0.12 parts by mass of di (3,5,5-trimethylhexanoyl) peroxide was dissolved in 1 part by mass of ethyl acetate to prepare a fourth polymerization initiator solution. After 3 hours had passed since the second polymerization initiator solution was supplied to the monomer mixed solution, the fourth polymerization initiator solution was further supplied to the monomer mixed solution.

A fifth polymerization initiator solution was prepared by dissolving 0.36 parts by mass of di (3,5,5-trimethylhexanoyl) peroxide in 1 part by mass of ethyl acetate. After 4 hours had passed since the second polymerization initiator solution was supplied to the monomer mixed solution, the fifth polymerization initiator solution was further supplied to the monomer mixed solution.

After 7 hours had passed since the first polymerization initiator solution was supplied to the monomer mixed solution, the reaction solution was cooled to room temperature to complete the polymerization. An ethyl acetate solution containing an acrylic polymer (B1) having a dimethoxymethylsilyl group was obtained.

Next, ethyl acetate was removed by an evaporator to obtain an acrylic polymer (B1). The obtained acrylic polymer (B1) had 1.47 methyldimethoxysilyl groups on average in one molecule, had a number average molecular weight of 20000, and had a molecular weight distribution of 1.90.

[Synthesis of acrylic polymer (B2)]
The inside of the stainless steel reaction vessel with a stirrer was deoxidized, 0.8 parts by mass of cuprous bromide and 60 parts by mass of butyl acrylate were charged to prepare a mixed solution, and then the mixed solution was stirred while heating.

After adding acetonitrile as a polymerization reaction solvent and diethyl 2,5-dibromoadipate as a polymerization initiator to the mixture, the temperature of the mixture was adjusted to 80 ° C., and triamine was added to the mixture to initiate the polymerization reaction. ..

The remaining 40 parts by mass of butyl acrylate was sequentially added to the mixed solution, and the polymerization reaction was carried out over several hours. After completion of the polymerization, acetonitrile was removed by devolatile under reduced pressure to obtain an acrylic acid ester polymer (terminal acetonitrile butyl acrylate polymer).

1,7-Octadiene and acetonitrile as a solvent were added to the terminal acetonitrile butyl acrylate polymer, and the diene reaction was started by adding triamine.

The mixture was stirred while heating the inside of the reaction vessel to 80 to 90 ° C. for several hours to react octadiene at the end of the polymer. Further, the temperature of the mixture was raised to about 200 ° C., the mixture was stirred while heating at a high temperature for several hours, and then devolatile was carried out under reduced pressure to obtain a polymer having alkenyl groups at both ends.

Methyl orthoformate, a platinum catalyst and methyldimethoxysilane are added to the obtained polymer in this order and mixed, and the mixed solution is stirred while heating at 115 ° C. for 1 hour under a nitrogen atmosphere to form a methyldimethoxysilyl group. An acrylic polymer containing the above was obtained. The obtained acrylic polymer had 1.9 methyldimethoxysilyl groups on average in one molecule, had a number average molecular weight of 24,000, and had a molecular weight distribution of 1.30.

(Examples 1 to 7, Comparative Examples 1 to 4)
Polyalkylene oxide-based polymer (A), acrylic-based polymer (B), monoamine compound (C), filler, aminosilane coupling agent, dehydrating agent, silanol condensation catalyst, ultraviolet absorber, having a hydrolyzable silyl group, A curable composition was obtained by mixing the antioxidant and the light stabilizer in the amounts shown in Table 1 under reduced pressure in a sealed stirrer until uniform.

The content of the mercapto-based compound was measured for the obtained curable composition, and the content of the mercapto-based compound with respect to the total mass of the curable composition is shown in Table 1.

With respect to the obtained curable composition, H-type 50% modulus, H-type elongation, weather resistance and deterioration resistance of polyvinyl chloride (PVC) sheet were measured in the following manner, and the results are shown in Table 1.

(H type test)
Using the curable composition, an H-type test piece was prepared according to JIS A1439 4.21.

Specifically, two alumite-treated aluminum plates (length 50 mm x width 50 mm x thickness 3 mm) are used, and a spacer is sandwiched between these aluminum plates to form a rectangular space (vertical) in the central part between the aluminum plates. 12 mm x 50 mm wide x 12 mm high) is formed, and this space is filled with a curable composition so that air does not enter, and after being left in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% for 14 days, the temperature is further increased. An H-type test piece in which two aluminum plates are bonded and integrated by the cured product of the curable composition by curing and curing the curable composition by leaving it in an atmosphere of 30 ° C. for 14 days. Was produced.

Then, a tensile test was performed on the H-type test piece immediately after production at a tensile speed of 50 mm / min in accordance with JIS A1439, and the 50% modulus [N / cm ² ] was performed in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%. ] And the maximum weighted elongation [%] were measured. The obtained results are shown in the columns of "H-type 50% modulus" and "H-type elongation rate" in Table 1, respectively.

(Weatherability)
The curable composition is coated on an aluminum plate to a thickness of 1 mm, and the curable composition is cured and cured in an atmosphere of 23 ° C. and a relative humidity of 50% for 14 days to obtain a cured product. Obtained.

After irradiating the cured product with ultraviolet rays using a sunshine weather meter under the conditions of a black panel temperature of 63 ° C. and a rainfall cycle of 12 minutes / 60 minutes based on JIS A1415, the cured product was irradiated with ultraviolet rays for 5000 hours. , The appearance of the cured product was visually observed. "◎" when the cured product did not whiten or crack, "○" when the cured product had fine cracks, and "×" when the cured product had whitening or cracks. And said.

(Polyvinyl chloride (PVC) sheet deterioration resistance)
The curable composition is coated on a polyvinyl chloride (PVC) sheet cut out in the shape of a No. 3 dumbbell to a thickness of 10 mm, and the curable composition is cured in an atmosphere of 23 ° C. and 50% relative humidity for 14 days. The curable composition was cured to obtain a test piece.

Further, after curing the test piece at 80 ° C. for 70 days, the cured product of the curable composition was removed from the polyvinyl chloride sheet, and a tensile test was performed at a speed of 200 mm / min. When the elongation retention rate of the dumbbell is 90% or more compared to the initial value of the polyvinyl chloride sheet alone, "◎",
The case of 80% or more and less than 90% was evaluated as “◯”, and the case of less than 80% was evaluated as “x”.

1 Waterproof surface
11 Preventive surface continuous to the edge of the waterproof sheet 2 Waterproof sheet
21 Edge of tarpaulin
22 Facing end of waterproof sheet 3 Hardened material A Building structure

Claims (5)

A polyalkylene oxide-based polymer (A) having a dialkoxysilyl group as a hydrolyzable silyl group, having a main chain skeleton containing polypropylene oxide, and having a number average molecular weight of 16,000 to 30,000, and as a hydrolyzable silyl group. An acrylic polymer (B) containing an acrylic polymer having a dialkoxysilyl group or a trialkoxysilyl group and having a number average molecular weight of 1000 to 30,000, the polyalkylene oxide polymer (A) and the acrylic. Curable composition containing 0.1 to 10 parts by mass of the monoamine compound (C) which is a primary aliphatic monoamine and has 12 to 24 carbon atoms with respect to 100 parts by mass of the total amount of the system polymer (B). It is a product, and the content of the mercapto-based compound is 50 ppm or less with respect to the total mass of the curable composition, and includes a structural member including a polyvinyl chloride-based resin of a building structure or a polyvinyl chloride-based resin. A curable composition characterized in that the curable composition and the polyvinyl chloride-based resin are used in contact with each other as a sealing material for a waterproof sheet. The curable composition according to claim 1, further containing silica. A wall member that constitutes the wall of a building structure and contains a polyvinyl chloride resin,
The cured product of the curable composition according to claim 1 or 2, which is filled in the joint portion formed between the wall members, and the cured product of the curable composition and the polyvinyl chloride resin. A joint structure characterized by being in contact with each other . Building structures and
A waterproof sheet disposed on the waterproof surface of the above building structure and containing a polyvinyl chloride resin,
The cured product of the curable composition according to claim 1 or 2, which covers the edge portion of the waterproof sheet and the waterproof surface of the building structure connected to the edge portion of the waterproof sheet. A waterproof structure characterized in that the cured product of the curable composition is in contact with the polyvinyl chloride resin . Building structures and
A plurality of waterproof sheets arranged on the waterproof surface of the above building structure, containing polyvinyl chloride resin, and having facing ends overlapped with each other.
The cured product of the curable composition according to claim 1 or 2, which covers the overlapped portion of the waterproof sheet, and the cured product of the curable composition and the polyvinyl chloride resin come into contact with each other. Waterproof structure characterized by being .

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