Hardening composition, sealing material, and adhesive

Abstract

To provide a curable composition exhibiting an excellent anti-fouling effect over a long period of time after curing.SOLUTION: A curable composition includes: a polymer (I) having a hydrolyzable silyl group, including a polyalkylene oxide (A) having a hydrolyzable silyl group; a monoamine compound (C); and a diamine compound. A cured product made of the curable composition has an excellent anti-fouling effect, can reduce adhesion of dust and contaminants to the cured product, and maintains a beautiful appearance over a long period of time.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a curable composition that cures by moisture in the atmosphere and provides a cured product capable of exhibiting an excellent antifouling effect over a long period of time, and a sealing material and an adhesive using the same.

Background Art

[0002] Conventionally, a curable composition containing an oxyalkylene polymer having a crosslinkable hydrolyzable silyl group has been known (Patent Document 1). The curable composition produces a cured product having excellent adhesiveness by hydrolysis of the crosslinkable hydrolyzable silyl group by moisture contained in the atmosphere and subsequent dehydration condensation.

[0003] Such a curable composition is used, for example, in the joints (so-called "joint parts") between outer wall members such as mortar plates, concrete plates, ALC (Autoclaved Light-weight Concrete) plates, and metal plates on the outer wall of a building structure, etc. By filling the joints between the outer wall members, rainwater is prevented from entering the building structure from the joints between the outer wall members.

[0004] On the outer wall of a building structure, the width of the joint part changes slightly because the outer wall members expand or contract with temperature changes, or the outer wall members move due to vibrations or external forces caused by earthquakes or strong winds. Therefore, it is necessary for the curable composition to have excellent rubber elasticity after curing and be stretchable so as to follow the change in the width of the joint part.

[0005] In recent years, the surface of an outer wall member constituting the outer wall of a building structure may be subjected to antifouling treatment. In such a case, the outer wall member is less likely to be soiled and can maintain the aesthetic appearance of the outer wall over a long period of time. However, the cured product of the curable composition filled in the joint portion is not subjected to antifouling treatment. Further, the cured product of the curable composition is designed to have high flexibility so as to follow changes in the width of the joint portion. In such a case, since tack remains on the surface of the cured product of the curable composition, the surface of the cured product of the curable composition is soiled by dust and contaminants. Therefore, there has been a problem that the appearance is impaired when the entire outer wall is viewed. Accordingly, it is required that the cured product of the curable composition can also exhibit an antifouling effect over a long period of time.

[0006] In Patent Document 2, it is disclosed that by using a diamine compound, the surface of the cured product of the curable composition can be hydrophilized, and an antifouling effect by a self-cleaning action can be obtained. However, the diamine compound cannot exhibit an excellent antifouling effect over a long period of time.

[0007] Therefore, in Patent Document 3, it is disclosed that by further using a fluorine-containing surfactant in addition to the diamine compound, the surface of the cured product of the curable composition can be made more hydrophilic, and the antifouling effect by a self-cleaning action can be improved. However, the use of the fluorine-containing surfactant causes a significant price increase and is not practical in terms of cost.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0009] Therefore, the present invention provides a curable composition that exhibits an excellent antifouling effect over a long period after curing.

Means for Solving the Problems

[0010] The curable composition of the present invention includes a polymer (I) having a hydrolyzable silyl group containing a polyalkylene oxide (A) having a hydrolyzable silyl group, a monoamine compound (C), and a diamine compound.

[0011] [Polymer (I)] The curable composition includes a polymer (I) having a hydrolyzable silyl group. According to the polymer (I) having a hydrolyzable silyl group, it becomes possible to provide a moisture-curable composition that can be cured by moisture in the atmosphere.

[0012] (Polyalkylene Oxide (A)) The polymer (I) having a hydrolyzable silyl group contains a polyalkylene oxide (A) having a hydrolyzable silyl group. The polyalkylene oxide (A) has a hydrolyzable silyl group.

[0013] 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 examples thereof include 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, a mercapto group, an alkenyloxy group, and the like.

[0014] As the hydrolyzable silyl group of the polyalkylene oxide (A), an alkoxysilyl group is preferred because the hydrolysis reaction is mild. Examples of the alkoxysilyl group include trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, and triphenoxysilyl group; dialkoxysilyl groups such as methyldimethoxysilyl group and methyldiethoxysilyl group; and monoalkoxysilyl groups such as dimethylmethoxysilyl group and dimethylethoxysilyl group. Among them, as the hydrolyzable silyl group of the polyalkylene oxide (A), a dialkoxysilyl group is more preferred, and a methyldimethoxysilyl group is particularly preferred.

[0015] The polyalkylene oxide (A) preferably has, on average, 1 to 3, more preferably 1 to 2 hydrolyzable silyl groups per molecule. When the main chain of the polyalkylene oxide (A) is linear, the polyalkylene oxide (A) preferably has, on average, 1 to 2 hydrolyzable silyl groups per molecule. When the main chain of the polyalkylene oxide (A) is branched, the polyalkylene oxide (A) preferably has, on average, 1 to 3 hydrolyzable silyl groups per molecule. When the number of hydrolyzable silyl groups in the polyalkylene oxide (A) is 1 or more, the curability of the curable composition is improved. When the number of hydrolyzable silyl groups in the polyalkylene oxide (A) is not more than the above upper limit, the mechanical strength or elongation of the cured product of the curable composition is improved. Further, the polyalkylene oxide (A) preferably has a hydrolyzable silyl group at at least one of both ends of its main chain.

[0016] The average number of hydrolyzable silyl groups per molecule in the polyalkylene oxide (A) is 1 calculable based on the concentration of the hydrolyzable silyl group in the polyalkylene oxide (A) determined by H-NMR and the number average molecular weight of the polyalkylene oxide (A) determined by the GPC method.

[0017] As the polyalkylene oxide (A), a polymer having a main chain containing a repeating unit represented by the general formula: -(R 1 -O) n -(wherein R 1 represents an alkylene group having 1 to 14 carbon atoms, and n is the number of repeating units and is a positive integer) is preferably exemplified. The main chain skeleton of the polyalkylene oxide (A) may consist of only one kind of repeating unit or may consist of two or more kinds of repeating units.

[0018] Examples of the main chain skeleton of the polyalkylene oxide (A) include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer, and polypropylene oxide-polybutylene oxide copolymer. Among them, polypropylene oxide is preferred. According to polypropylene oxide, a curable composition excellent in rubber elasticity and adhesiveness after curing can be provided.

[0019] The number average molecular weight of the polyalkylene oxide (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 (A) is 15,000 or more, the mechanical strength or elongation of the cured product of the curable composition is improved. When the number average molecular weight of the polyalkylene oxide (A) is 50,000 or less, the coating property of the curable composition is improved.

[0020] In the present invention, the number average molecular weight of the polyalkylene oxide (A) means a value in terms of polystyrene measured by the 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.

[0021] As the polyalkylene oxide (A) containing a hydrolyzable silyl group, commercially available products can be used. For example, as the polyalkylene oxide (A) whose main chain skeleton is polypropylene oxide and which has a methyldimethoxysilyl group at the end of the main chain skeleton, there can be mentioned those manufactured by Asahi Glass Co., Ltd. under the trade names "Exester S4530", "Exester S2730C", "Exester S2420", etc.

[0022] The content of the polyalkylene oxide (A) in the polymer (I) having a hydrolyzable silyl group is preferably 20 to 100% by mass, more preferably 30 to 80% by mass, still more preferably 40 to 70% by mass, and particularly preferably 55 to 70% by mass. By setting the content of the polyalkylene oxide (A) within the above range, the flexibility of the cured product of the curable composition is improved.

[0023] (Acrylic polymer (B)) The polymer (I) having a hydrolyzable silyl group preferably further contains an acrylic polymer (B) having a hydrolyzable silyl group. By using the acrylic polymer (B), the cured product of the curable composition can maintain excellent rubber elasticity over a long period of time.

[0024] As the hydrolyzable silyl group that the acrylic polymer (B) has, since the cured product of the curable composition can maintain excellent rubber elasticity over a long period of time, an alkoxysilyl group is preferable. Examples of the alkoxysilyl group include trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, and triphenoxysilyl group; dimethoxysilyl groups such as methyldimethoxysilyl group and methyldiethoxysilyl group; and monoalkoxysilyl groups such as dimethylmethoxysilyl group and dimethylethoxysilyl group. Among them, a dialkoxysilyl group and a trialkoxysilyl group are more preferable, a trialkoxysilyl group is more preferable, and a trimethoxysilyl group is particularly preferable.

[0025] As the main chain skeleton of the acrylic polymer (B), examples include acrylic polymers obtained by radical polymerization of (meth)acrylate monomers such as ethyl (meth)acrylate and butyl (meth)acrylate. Here, (meth)acrylate means methacrylate or acrylate.

[0026] As the (meth)acrylate monomer constituting the main chain of the acrylic polymer (B), specifically, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 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, hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(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-hydroxyethyl phthalate, and 2-[acryloyloxy]ethyl-2-hydroxypropyl phthalate, etc. may be mentioned. These (meth)acrylate monomers may be used alone or in combination of two or more.

[0027] In the acrylic polymer (B), it is also possible to copolymerize other monomers. Examples of such monomers include styrene derivatives such as styrene, indene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, divinylbenzene; compounds having a vinyl ester group such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnamate; maleic anhydride, N-vinylpyrrolidone, N-vinylmorpholine, (meth)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, (4-vinyloxy)butyl benzoate, 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, di(4-vinyloxy)butyl isophthalate, di(4-vinyloxy)butyl glutarate, di(4-vinyloxy)butyl succinate, trimethylolpropane trivinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, cyclohexane-1,4-dimethanol monovinyl ether, diethylene glycol monovinyl ether, 3-aminopropyl vinyl ether, 2-(N,N-diethylamino)ethyl vinyl ether, urethane vinyl ether, polyester vinyl ether and other compounds having a vinyloxy group. These monomers may be used alone or in combination of two or more.

[0028] 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) having the main chain skeleton composed of the above copolymer, a curable composition capable of forming a cured product having both extensibility and flexibility after curing can be obtained.

[0029] The polymerization method of the acrylic polymer (B) is not particularly limited, and known methods can be used. For example, various polymerization methods such as free radical polymerization method, anionic polymerization method, cationic polymerization method, UV radical polymerization method, living anionic polymerization method, living cationic polymerization method, and living radical polymerization method can be mentioned.

[0030] The method for introducing a hydrolyzable silyl group into the acrylic polymer (B) is not particularly limited, and for example, a known method such as a method of hydrosilylating a hydrosilane having a hydrolyzable silyl group with an acrylic polymer having an unsaturated group introduced into the molecule can be used.

[0031] The number average molecular weight of the acrylic polymer (B) is preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000. When the number average molecular weight of the acrylic polymer (B) is 50,000 or less, the coating property of the curable composition is improved. When the number average molecular weight of the acrylic polymer (B) is 1,000 or more, the mechanical strength or extensibility of the cured product of the curable composition is improved.

[0032] In the present invention, the number average molecular weight of the acrylic polymer (B) means a value in terms of polystyrene measured by the 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.

[0033] The content of the acrylic polymer (B) in the polymer (I) having a hydrolyzable silyl group is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, and particularly preferably 30 to 45% by mass. When the content of the acrylic polymer (B) is 20% by mass or more, the cured product of the curable composition maintains excellent rubber elasticity over a long period. When the content of the acrylic polymer (B) is 70% by mass or less, the coatability of the curable composition is improved.

[0034] [Monoamine compound (C)] The curable composition of the present invention contains a monoamine compound (C) and a diamine compound. By using the monoamine compound (C) and the diamine compound in combination, the surface of the cured curable composition can exhibit high water repellency over a long period. Since the surface of the cured product of the curable composition has high water repellency, it is difficult for dirt to adhere to the surface of the cured product. Therefore, the curable composition of the present invention can exhibit an excellent antifouling effect over a long period after curing.

[0035] In the present invention, the monoamine compound (C) means a compound having 1 amino group (-NH2) in one molecule. The hydrogen atom of the amino group in the monoamine compound (C) may be substituted by an organic group such as an alkyl group or an aryl group. Further, the monoamine compound (C) preferably does not contain a silicon atom.

[0036] The melting point of the monoamine compound (C) is preferably 60°C or lower, more preferably 20 to 60°C, still more preferably 25 to 55°C, and particularly preferably 30 to 55°C. By setting the melting point of the monoamine compound (C) to 60°C or lower, the monoamine compound (C) easily moves to the surface of the cured product of the curable composition. Thereby, the water repellency of the surface of the cured product of the curable composition can be improved, and an excellent antifouling effect can be obtained. Further, by setting the melting point of the monoamine compound (C) to 20°C or higher, the generation of tack on the surface of the cured product can be reduced.

[0037] In the present invention, the melting point of the monoamine compound (C) refers to the temperature measured by differential scanning calorimetry (DSC) in accordance with JIS K7121 (1987). For example, using a differential scanning calorimeter (e.g., the device named "DSC-60" manufactured by Shimadzu Corporation), the monoamine compound (C) is heated, and the melting peak temperature of the DSC curve in this heating process is taken as the melting point of the monoamine compound (C). As for the state adjustment of the test piece, state adjustment is performed in accordance with 3.(1) of JIS K7121 (1987). Also, when there are multiple melting peaks, the temperature at the apex of the melting peak with the largest endotherm is taken as the melting point.

[0038] When the curable composition contains a plurality of types of monoamine compounds (C), the melting point of the monoamine compound (C) refers to the melting points of the respective monoamine compounds (C).

[0039] Preferred examples of the monoamine compound (C) include monoamine compounds represented by the following formula (1). R 2 -NH2(1) (In formula (1), R 2 is a linear or branched alkyl group, or a monovalent saturated alicyclic hydrocarbon group.)

[0040] In the monoamine compound (C) represented by formula (1), the number of carbon atoms of R 2 is preferably 12 to 40, more preferably 15 to 30, and particularly preferably 15 to 25. By using the monoamine compound (C) having the number of carbon atoms of R 2 within the above range, the surface of the cured product of the curable composition can exhibit high water repellency and low tack in a short time. Thereby, the curable composition can exhibit an excellent antifouling effect from immediately after curing over a long period.

[0041] Specific examples of the monoamine compound (C) include laurylamine (C 12 H 25 -NH2, melting point 28°C), stearylamine (C 18 H 37-NH2, melting point 50 °C), myristylamine (C 14 H 29 -NH2, melting point 38 °C), and cetylamine (C 16 H 33 -NH2, melting point 47 °C), etc. are mentioned. The monoamine compound (C) may be used alone or in combination of two or more.

[0042] The content of the monoamine compound (C) in the curable composition is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polymer (I) having a hydrolyzable silyl group. When the content of the monoamine compound (C) is 0.1 part by mass or more, the cured surface of the curable composition can exhibit an excellent antifouling effect over a long period. Also, when the content of the monoamine compound (C) is 20 parts by mass or less, the generation of tack on the cured surface of the curable composition at high temperatures can be reduced.

[0043] [Diamine compound] The curable composition of the present invention contains a diamine compound. In the present invention, the diamine compound means a compound having two amino groups (-NH2) in one molecule. The hydrogen atom of the amino group in the diamine compound may be substituted by an organic group such as an alkyl group or an aryl group. Also, the diamine compound preferably does not contain a silicon atom. The diamine compound may be used alone or in combination of two or more.

[0044] The diamine compound preferably contains a diamine compound (D) having a melting point 5°C or higher than that of the monoamine compound (C). The melting point of the diamine compound (D) is preferably 5°C or higher, more preferably 10°C or higher, still more preferably 10 - 55°C higher, even more preferably 10 - 35°C higher, and particularly preferably 10 - 25°C higher than that of the monoamine compound (C). By using the diamine compound (D) having such a melting point, the cured surface of the curable composition can exhibit higher water repellency. Although the mechanism by which such an effect is obtained is not clear, the following mechanism is conceivable.

[0045] By using the diamine compound (D) having the above melting point, the monoamine compound (C) becomes more likely to move to the cured surface of the curable composition. After the monoamine compound (C) has moved to the cured surface of the curable composition in this way, an intermolecular force acts between the amino group of the diamine compound (D) present inside the cured product and the amino group of the monoamine compound (C). As a result, on the cured surface, the monoamine compound (C) is oriented such that its amino group faces the inside of the cured product while the other part faces the surface side of the cured product. By thus directing the hydrophilic amino group toward the inside of the cured product, the cured surface can exhibit higher water repellency. It should be noted that since this mechanism is only the speculation of the inventor, the present invention is not limited to the above mechanism.

[0046] The melting point of the diamine compound (D) is preferably 30°C or higher, more preferably 30°C to 80°C, still more preferably 35 to 80°C, still more preferably 40 to 80°C, still more preferably 55 to 80°C, still more preferably 55 to 75°C, and particularly preferably 60 to 70°C. Further, by setting the melting point of the diamine compound (D) within the above range, the monoamine compound (C) becomes more likely to move to the surface of the cured product of the curable composition. Also, in summer etc., building structures are exposed to a high-temperature environment for a long time. In such an environment, tack may occur on the surface of the cured product of the curable composition. The occurrence of tack promotes the adhesion of dirt such as dust and contaminants to the surface of the cured product of the curable composition, reducing the antifouling effect. However, according to the diamine compound (D) having a melting point of 30°C or higher, the occurrence of tack on the surface of the cured product of the curable composition at high temperatures can be highly reduced, and an excellent antifouling effect can be maintained.

[0047] In addition, when the curable composition contains a plurality of types of diamine compounds, the melting point of the diamine compound refers to the melting point of each diamine compound.

[0048] Furthermore, in the relationship described above that "the diamine compound contains a diamine compound (D) having a melting point 5°C or higher than the melting point of the monoamine compound (C)", when a plurality of types of monoamine compounds (C) are used, among the plurality of types of monoamine compounds (C), the highest melting point (P High ) of the monoamine compound (C High ) The diamine compound having a melting point 5°C or higher than the above melting point (P High ) is defined as the "diamine compound (D)".

[0049] In the present invention, the melting point of the diamine compound refers to the temperature measured by differential scanning calorimetry (DSC) in accordance with JIS K7121 (1987). For example, using a differential scanning calorimeter (e.g., the device named "DSC-60" manufactured by Shimadzu Corporation), the diamine compound is heated, and the melting peak temperature of the DSC curve in this heating process is defined as the melting point of the diamine compound. As for the state adjustment of the test piece, state adjustment is performed in accordance with 3.(1) of JIS K7121 (1987). Further, when there are multiple melting peaks, the temperature at the apex of the melting peak with the largest endotherm is defined as the melting point.

[0050] In the cured composition, the mass ratio of the diamine compound (D) to the monoamine compound (C) [(mass of the above diamine compound (D)) / (mass of the above monoamine compound (C))] is preferably 0.1 to 5, more preferably 0.5 to 3, and even more preferably 1.7 to 2.5. When the mass ratio of the monoamine compound (C) to the diamine compound (D) is within the above range, the surface of the cured product of the curable composition exhibits higher water repellency, and thus an excellent antifouling effect can be exerted over a long period.

[0051] Examples of the diamine compound include the diamine compound represented by the following formula (2). R 3 -NH-R 4 -NH2(2) (In formula (2), R 3 is a linear or branched alkyl group, an unsaturated aliphatic hydrocarbon group, a monovalent saturated alicyclic hydrocarbon group, or an aryl group, and R 4 is an alkylene group.)

[0052] In formula (2), R 3 is preferably a linear or branched alkyl group. R 3Examples of the linear or branched alkyl group include a decyl group, isodecyl group, undecyl group, lauryl group, isododecyl group, tridecyl group, myristyl group, pentadecyl group, palmityl group, heptadecyl group, isohexadecyl group, stearyl group, isooctadecyl group, nonadecyl group, eicosyl group, behenyl group, and the like. R 3 Examples of the unsaturated aliphatic hydrocarbon group include an undecenyl group, cis-4-tetradecenyl group, cis-5-tetradecenyl group, cis-9-tetradecenyl group, cis-6-hexadecenyl group, palmitoleyl group, cis-6-octadecenyl group, oleyl group, trans-9-octadecenyl group, cis-11-octadecenyl group, trans-11-octadecenyl group, myristoleyl group, palmitoleyl group, linoleyl group, and the like.

[0053] In formula (2), R 4 is an alkylene group. Examples of the alkylene group of R 4 include a methylene group, ethylene group, ethylidene group, trimethylene group, propylene group, isopropylene group, tetramethylene group, butylene group, isobutylene group, pentylene group, hexamethylene group, hexylene group, and the like.

[0054] Examples of the diamine compound (D) preferably include a diamine compound represented by formula (2) [in formula (2), R 3 is a linear alkyl group and R 4 is an alkylene group]. In the diamine compound (D) represented by this formula (2), the total number of carbon atoms of R 3 and R 4 is preferably 15 to 40, more preferably 15 to 30, and particularly preferably 15 to 25. By setting the total number of carbon atoms of R 3 and R 4 within the above range, the cured product surface of the curable composition can exhibit an excellent antifouling effect over a long period, and the generation of tack on the cured product surface of the curable composition at high temperatures can be highly reduced.

[0055] As the diamine compound (D), behenylpropylenediamine (C 22 H 45 -NH-C3H6-NH2, melting point 63°C) is preferably mentioned.

[0056] The content of the diamine compound (D) in the diamine compound is preferably 45% by mass or more, preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and particularly preferably 90 to 100% by mass. By setting the content of the diamine compound (D) within the above range, the surface of the cured product of the curable composition can exhibit higher water repellency.

[0057] The diamine compound may further contain a diamine compound (E) having a melting point below the melting point of the monoamine compound (C) as long as it does not adversely affect the properties such as the antifouling effect of the curable composition. However, it is preferable that the diamine compound does not contain the diamine compound (E). Therefore, the content of the diamine compound (E) in the diamine compound is preferably 55% by mass or less, preferably 0 to 50% by mass, more preferably 0 to 30% by mass, and particularly preferably 0 to 10% by mass. A lower content of the diamine compound (E) can make the antifouling curing of the curable composition higher.

[0058] When a plurality of types of monoamine compounds (C) are used, among the plurality of types of monoamine compounds (C), the diamine compound having a melting point below the above melting point (P Low ) of the monoamine compound (C Low ) having the lowest melting point is defined as the "diamine compound (E)". Low )

[0059] The content of the diamine compound in the curable composition is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polymer (I) having a hydrolyzable silyl group. When the content of the diamine compound is 0.1 part by mass or more, the cured surface of the curable composition can exhibit an excellent antifouling effect over a long period. Also, when the content of the diamine compound is 20 parts by mass or less, it is possible to reduce the occurrence of tack on the cured surface of the curable composition at high temperatures.

[0060] [Plasticizer] The curable composition preferably further contains a plasticizer. Specific examples of the plasticizer include phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, and butyl benzyl phthalate, polyalkylene oxides such as polypropylene glycol, and acrylic polymers, with acrylic polymers being preferred.

[0061] The acrylic polymer used as the plasticizer preferably does not have a hydrolyzable silyl group.

[0062] Examples of the main chain skeleton of the acrylic polymer used as the plasticizer include acrylic polymers obtained by radical polymerization of (meth)acrylate-based monomers.

[0063] Examples of (meth)acrylate monomers that constitute the main chain of the acrylic polymer used as a plasticizer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 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, hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(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-hydroxyethyl phthalate, and 2-[acryloyloxy]ethyl-2-hydroxypropyl phthalate. These (meth)acrylate monomers may be used alone or in combination of two or more.

[0064] The weight average molecular weight of the acrylic polymer used as a plasticizer is preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000. When the weight average molecular weight of the acrylic polymer used as a plasticizer is 50,000 or less, the coatability of the curable composition is improved. When the weight average molecular weight of the acrylic polymer used as a plasticizer is 1,000 or more, the mechanical strength or stretchability of the cured product of the curable composition is improved.

[0065] In the present invention, the weight average molecular weight of the acrylic polymer used as a plasticizer means a value in terms of polystyrene measured by the GPC (gel permeation chromatography) method. In the measurement by the GPC method, for example, Shodex KF800D manufactured by Tosoh Corporation can be used as the GPC column, and chloroform or the like can be used as the solvent.

[0066] The content of the plasticizer in the curable composition is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, still more preferably from 1 to 70 parts by mass, and particularly preferably from 20 to 50 parts by mass with respect to 100 parts by mass of the polymer (I) having a hydrolyzable silyl group. If the content of the plasticizer is too high, the plasticizer may precipitate on the surface of the cured product of the curable composition.

[0067] [Filler] The curable composition preferably further contains a filler. According to the filler, a curable composition capable of obtaining a cured product having excellent mechanical strength can be provided.

[0068] Examples of the filler 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. These fillers may be used alone or in combination of two or more. Among them, calcium carbonate is preferably used.

[0069] The average particle diameter of calcium carbonate is preferably 0.01 to 5 μm, more preferably 0.05 to 2.5 μm. With calcium carbonate having such an average particle diameter, a cured product excellent in mechanical strength and elongation can be obtained, and a curable composition having excellent adhesiveness can be provided.

[0070] Calcium carbonate is preferably surface-treated with a fatty acid, a fatty acid ester, or the like. According to calcium carbonate surface-treated with a fatty acid, a fatty acid ester, or the like, thixotropy can be imparted to the curable composition, and aggregation of calcium carbonate can be suppressed.

[0071] The content of the filler in the curable composition is preferably 1 to 700 parts by mass, more preferably 10 to 200 parts by mass with respect to 100 parts by mass of the polymer (I) having a hydrolyzable silyl group. When the content of the filler is 1 part by mass or more, the effect by the addition of 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 elongation.

[0072] [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 suppress the curable composition from curing due to moisture contained in the air or the like.

[0073] Examples of the dehydrating agent include silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane; and ester compounds such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate. These dehydrating agents may be used alone or in combination of two or more. Among them, vinyltrimethoxysilane is preferable.

[0074] The content of the dehydrating agent in the curable composition is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the polymer (I) having a hydrolyzable silyl group. When the content of the dehydrating agent is 0.5 parts by mass or more, the effect of the dehydrating agent can be sufficiently obtained. Also, when the content of the dehydrating agent is 20 parts by mass or less, the curable composition has excellent curability.

[0075] [Silanol condensation catalyst] The curable composition preferably contains a silanol condensation catalyst. The silanol condensation catalyst is a catalyst for promoting the dehydration condensation reaction between silanol groups formed by hydrolysis of hydrolyzable silyl groups contained in the polymer (I) and the like.

[0076] Examples of the silanol condensation catalyst include organotin compounds such as 1,1,3,3-tetrabutyl-1,3-dilauroxycarbonyl-distannoxane, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis(dibutyltin laurate) oxide, dibutyltin bis(acetylacetonate), dibutyltin bis(monoester maleate), tin octylate, dibutyltin octoate, dioctyltin oxide, dibutyltin bis(triethoxysilicate), bis(dibutyltin bistriethoxysilicate) oxide, and dibutyltin oxybisethoxysilicate; and organotitanium compounds such as tetra-n-butoxytitanate and tetraisopropoxytitanate. These silanol condensation catalysts may be used alone or in combination of two or more.

[0077] As the silanol condensation catalyst, 1,1,3,3-tetrabutyl-1,3-dilauroxycarbonyl-distannoxane is preferred. According to such a silanol condensation catalyst, the curing rate of the curable composition can be easily adjusted.

[0078] The content of the silanol condensation catalyst in the curable composition is preferably 1 to 10 parts by mass, more preferably 1 to 5 parts by mass, with respect to 100 parts by mass of the polymer (I) having a hydrolyzable silyl group. When the content of the silanol condensation catalyst 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 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 can be improved.

[0079] [Other additives] The curable composition may contain other additives such as a thixotropy-imparting agent, an antioxidant, an ultraviolet absorber, a pigment, a dye, an anti-settling agent, and a solvent. Among them, a thixotropy-imparting agent, an ultraviolet absorber, and an antioxidant are preferably mentioned.

[0080] [Thixotropy-imparting agent] The thixotropy-imparting agent may be any agent that can impart thixotropy to the curable composition. Preferred examples of the thixotropy-imparting agent include hydrogenated castor oil, fatty acid bisamide, fumed silica, and the like.

[0081] The content of the thixotropy-imparting agent in the curable composition is preferably 0.1 to 200 parts by mass, more preferably 1 to 150 parts by mass, with respect to 100 parts by mass of the polymer (I) having a hydrolyzable silyl group. When the content of the thixotropy-imparting agent is 0.1 part by mass or more, thixotropy can be effectively imparted to the curable composition. Further, when the content of the thixotropy-imparting agent is 200 parts by mass or less, the curable composition has an appropriate viscosity, and the handleability of the curable composition is improved.

[0082] [Ultraviolet absorber] Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, etc., and benzotriazole-based ultraviolet absorbers are preferred. The content of the ultraviolet absorber in the curable composition is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the polymer (I) having a hydrolyzable silyl group.

[0083] [Antioxidant] Examples of the antioxidant include, for example, hindered phenol-based antioxidants, monophenol-based antioxidants, bisphenol-based antioxidants, and polyphenol-based antioxidants, etc., and hindered phenol-based antioxidants are preferably mentioned. The content of the antioxidant in the curable composition is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, based on 100 parts by mass of the polymer (I) having a hydrolyzable silyl group.

[0084] [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 after curing.

[0085] Examples of hindered amine light stabilizers include, for example, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and a mixture of 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-piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine polycondensate, 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}], a polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, and the like.

[0086] As the hindered amine light stabilizer, a NOR type hindered amine light stabilizer is preferably mentioned. According to the NOR type hindered amine light stabilizer, a curable composition can be provided in which a decrease in rubber elasticity over time after curing is suppressed.

[0087] The NOR type hindered amine light stabilizer has a NOR structure in which an alkyl group (R) is bonded to a nitrogen atom (N) contained in the 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 alkyl group, and a cyclic alkyl group (saturated alicyclic hydrocarbon group).

[0088] Examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-nonyl group, an n-decyl group, and the like. Examples of the branched alkyl group include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and the like. Examples of the cyclic alkyl group (saturated alicyclic hydrocarbon group) include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like. Further, a hydrogen atom constituting the alkyl group may be substituted with a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.) or a hydroxyl group, or the like.

[0089] Examples of the NOR type hindered amine light stabilizer include the hindered amine light stabilizer represented by the following formula (I).

[0090] [Chemical formula]

[0091] When using the NOR type hindered amine light stabilizer, it is preferable to use it in combination with a benzotriazole type ultraviolet absorber or a triazine type ultraviolet absorber. Thereby, a curable composition in which a decrease in rubber elasticity over time after curing is more highly suppressed can be provided.

[0092] The content of the hindered amine light stabilizer in the curable composition is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the polymer (I) having a hydrolyzable silyl group.

[0093] [Aminosilane coupling agent] The curable composition of the present invention preferably contains an aminosilane coupling agent. By using the aminosilane coupling agent, the rubber elasticity and adhesiveness of the cured product of the curable composition can be improved. The aminosilane coupling agent means a compound containing a silicon atom bonded with an alkoxy group in one molecule and a functional group containing a nitrogen atom.

[0094] Specific examples of the aminosilane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N,N'-bis-[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(triethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(methyldimethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(trimethoxysilyl)propyl]hexamethylenediamine, N,N'-bis-[3-(triethoxysilyl)propyl]hexamethylenediamine, and the like. These aminosilane coupling agents may be used alone or in combination of two or more.

[0095] Among them, preferred aminosilane coupling agents include 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltriethoxysilane, and more preferably N-(2-aminoethyl)-3-aminopropyltrimethoxysilane .

[0096] The content of the aminosilane coupling agent in the curable composition is preferably 1 to 10 parts by mass, more preferably 1 to 5 parts by mass, based on 100 parts by mass of the polymer (I) having a hydrolyzable silyl group. When the content of the aminosilane coupling agent is within the above range, the rubber elasticity and adhesiveness of the cured product of the curable composition can be improved.

[0097] It is preferable that the water contact angle (W) on the surface of the cured product after curing for 3 days in an atmosphere of 23°C and 50% relative humidity of the curable composition of the present invention is 130° or more. That is, it is preferable that the water contact angle (W) on the surface of the cured product obtained by curing the curable composition of the present invention for 3 days in an atmosphere of 23°C and 50% relative humidity is 130° or more.

[0098] The water contact angle (W) on the surface of the cured product obtained by curing the curable composition of the present invention for 3 days in an atmosphere of 23°C and 50% relative humidity is also simply referred to as the "water contact angle (W)". The above water contact angle (W) is preferably 130° or more, more preferably 130 to 180°, and particularly preferably 150 to 180°. According to the curable composition in which the water contact angle (W) is within the above range, when water comes into contact with the surface of the cured product of the curable composition, the water is easily repelled on the surface of the cured product, or easily forms water droplets and immediately flows down from the surface. Therefore, it becomes difficult for dirt such as dust and contaminants to adhere to the surface of the cured product of the curable composition. As a result, the cured curable composition can exhibit an excellent antifouling effect. Furthermore, the occurrence of rain streak stains on the surface of the cured product of the curable composition can also be reduced. Rain streak stains are streak-like marks formed by the flow-down of dirt such as dust and contaminants adhering to the surface of the cured product of the curable composition together with rainwater. The occurrence of such rain streak stains causes a deterioration in the appearance of the cured product of the curable composition.

[0099] In the present invention, the water contact angle on the surface of the cured product of the curable composition means the contact angle θ value obtained by a measurement method conforming to the sessile drop method of JIS R3257 (1999) "Test Method for Wettability of Substrate Glass Surface".

[0100] In the present invention, the measurement of the contact angle (W) of water on the surface of the cured product obtained by curing the curable composition for 3 days in an atmosphere of 23°C and 50% relative humidity can be specifically carried out according to the following procedure. First, the curable composition is applied on a stainless steel plate and cured by curing in an atmosphere of 23°C and 50% relative humidity for 3 days to form a laminate in which a cured product of the curable composition is formed on the stainless steel plate. Note that the thickness of the cured product of the curable composition is 5 mm. Thereafter, the contact angle of water on the surface of the cured product of the curable composition is measured by the sessile drop method of JIS R3257 (1999) "Test method for wettability of substrate glass surface" using a solid-liquid interface analyzer. The dropping liquid is distilled water, the liquid volume is 4 μL, and it is obtained by measuring the contact angle 2 minutes after dropping. The calculation of the contact angle is performed by the θ / 2 method. The contact angle of water is measured at any 10 locations on the surface of the cured product of the curable composition, and the arithmetic mean value of all the measured contact angle values is taken as the contact angle (W) of water on the surface of the cured product of the curable composition. The measurement atmosphere of the contact angle is 23°C and 50% relative humidity. Further, as the solid-liquid interface analyzer, for example, a device commercially available under the trade name "DMs-401" from Kyowa Interface Science Co., Ltd. can be used. The calculation of the contact angle can be performed, for example, using the software "FAMAS" attached to a solid-liquid interface analyzer commercially available under the trade name "DMs-401" from Kyowa Interface Science Co., Ltd.

[0101] The curable composition of the present invention is excellent in adhesiveness and can form a cured product capable of maintaining excellent rubber elasticity over a long period of time, and thus can be used for various applications such as sealing materials, coating materials, adhesives, and paints. Among them, it is preferably used as a sealing material or an adhesive, and more preferably used as a sealing material for a joint structure.

[0102] Furthermore, since the cured product of the curable composition of the present invention is excellent in antifouling effect, it can suppress the adhesion of dirt such as dust and contaminants, and can maintain a beautiful appearance over a long period of time, especially when used outdoors.

[0103] As a method for constructing a joint structure by applying a curable composition to a joint portion, a method of filling the joint portion with the curable composition and then curing it by curing is used. The resulting joint structure has a wall member constituting a wall portion of a building structure and a cured product of the curable composition filled in a joint portion formed between adjacent wall members. Examples of the wall portion of the building structure include an outer wall, an inner wall, a ceiling portion, etc., and among them, an outer wall is preferable. Examples of the wall member include an outer wall member, an inner wall member, a ceiling member, etc., and an outer wall member is preferable.

[0104] The joint portion is not particularly limited, and examples include joint portions in the outer wall, inner wall, and ceiling of a building structure. The curable composition of the present invention can maintain an excellent antifouling effect over a long period after curing. Therefore, it is suitably used for sealing joint portions such as joint portions in the outer wall of a building structure, so-called "working joints", which are easily soiled by dust and contaminants.

[0105] Examples of the joint portion in the outer wall of a building structure include joint portions formed between outer wall members such as mortar boards, concrete boards, ceramic siding boards, metal siding boards, ALC boards, and metal plates.

Advantages of the Invention

[0106] Since the curable composition of the present invention has the above-described configuration, the cured product of the curable composition is excellent in antifouling effect, can reduce the adhesion of dust and contaminants to the cured product, and maintains a beautiful appearance over a long period.

Modes for Carrying Out the Invention

[0107] Hereinafter, the present invention will be described more specifically using examples, but the present invention is not limited thereto.

Examples

[0108] The following raw materials were used in the production of the curable compositions of the examples and comparative examples. [Polymer (I) having a hydrolyzable silyl group] (Polyalkylene oxide (A) having a hydrolyzable silyl group) · Polyalkylene oxide (A1) (a polyalkylene oxide having a methyldimethoxysilyl group and a polypropylene oxide as the main chain skeleton, manufactured by Asahi Glass Co., Ltd., trade name "Excester S2420", average number of methyldimethoxysilyl groups per molecule: 1.7, molecular weight distribution: 1.49, number average molecular weight: 18,990)

[0109] (Acrylic polymer (B) having a hydrolyzable silyl group) · Acrylic polymer (B1) (a copolymer of methyl methacrylate - n - butyl acrylate (content of methyl methacrylate component: 25% by mass, content of n - butyl acrylate component: 75% by mass) as the main chain skeleton, having a trimethoxysilyl group at the terminal or side chain of the main chain skeleton, manufactured by Toagosei Co., Ltd., trade name "US - 6150", number average molecular weight: 2,400)

[0110] [Amine compound (C)] · Stearylamine (melting point 50 °C, manufactured by Kao Corporation, trade name "Farmin 80S") · Laurylamine (melting point 28 °C, manufactured by NOF Corporation, trade name "Nissan Amine BB")

[0111] [Diamine compound] · Behenylpropylenediamine (melting point 63 °C, manufactured by NOF Corporation, trade name "Nissan Amine DV") · Hydrogenated tallow propylenediamine (manufactured by NOF Corporation, trade name "Nissan Amine DT - H")

[0112] Note that the above hydrogenated tallow propylenediamine (manufactured by NOF Corporation, trade name "Nissan Amine DT - H") is a diamine compound (D) represented by the above formula (2) (in formula (2), R 3 is a linear alkyl group having 13 to 18 carbon atoms, and R 4 is a propylene group) and having a melting point of 55 to 80 °C, 47 to 55% by mass, and the above formula (2) (in formula (2), R 3is an unsaturated aliphatic hydrocarbon group having 15 to 18 carbon atoms, and R 4 is a propylene group), and contains 45 to 53% by mass of a diamine compound (E) having a melting point of 28°C or lower.

[0113] [Plasticizer] · Plasticizer (1) (an acrylic polymer having no hydrolyzable silyl group, weight average molecular weight: 3,500, manufactured by Toagosei Co., Ltd., product name "UP-1110")

[0114] [Filler] · Colloidal calcium carbonate (average particle diameter: 80 nm, surface-treated with fatty acid, manufactured by Maruo Calcium Co., Ltd., product name "Calfine 200M") · Heavy calcium carbonate (average particle diameter: 1.0 μm, surface-treated with fatty acid, manufactured by Nitto Funka Co., Ltd., product name "NCC2310")

[0115] [Dehydrating agent] · Vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-1003")

[0116] [Silanol condensation catalyst] · Silanol condensation catalyst (1,1,3,3-tetrabutyl-1,3-dilauryl-oxycarbonyl-distannoxane, manufactured by Nitto Kasei Co., Ltd., product name "Neostan U-130")

[0117] [UV absorber] · Benzotriazole-based UV absorber (manufactured by BASF Japan Ltd., product name "Tinuvin 326")

[0118] [Antioxidant] · Hindered phenol-based antioxidant (manufactured by BASF Japan Ltd., product name "Irganox 1010")

[0119] [Light stabilizer] · NH-type hindered amine-based light stabilizer (manufactured by BASF Japan Ltd., product name "Tinuvin 770")

[0120] [Aminosilane coupling agent] · Aminosilane coupling agent (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, trade name "KBM-603" manufactured by Shin-Etsu Chemical Co., Ltd.)

[0121] [Others] · Thixotropic agent (fatty acid amide wax, trade name "Disparon #6500" manufactured by Kusumoto Chemicals, Ltd.) )

[0122] [Solvent] · Ethylene glycol tertiary butyl ether (ETB)

[0123] (Examples 1 to 5, Comparative Examples 1 to 7) The above-mentioned polyalkylene oxide (A1), acrylic polymer (B1), stearylamine, laurylamine, behenyl propylenediamine, hardened tallow propylenediamine, plasticizer (1), colloidal calcium carbonate, heavy calcium carbonate, vinyltrimethoxysilane, silanol condensation catalyst, benzotriazole-based ultraviolet absorber, hindered phenol-based antioxidant, NH-type hindered amine-based light stabilizer, aminosilane coupling agent, thixotropic agent, and ethylene glycol tertiary butyl ether (ETB) were each made to have the compounding amounts shown in Table 1, and mixed uniformly in a sealed stirrer while reducing the pressure until uniform to obtain a curable composition.

[0124] [Evaluation] The contact angle (W) [°] of water on the surface of the cured product obtained by curing the obtained curable composition in an atmosphere at a temperature of 23°C and a relative humidity of 50% for 3 days was measured in the above manner, and the obtained results are shown in Table 1.

[0125] Also, the antifouling effects of the obtained curable composition immediately after curing and after the long-term exposure test were evaluated according to the following procedures, respectively.

[0126] [Antifouling effect (immediately after curing)] The curable composition was applied onto a stainless steel plate to a thickness of 5 mm in an atmosphere of 23°C and 50% relative humidity and cured for 1 day. No. 7 silica sand was sprinkled onto the surface of the cured product of the curable composition, and the presence or absence of silica sand adhesion was visually observed and evaluated based on the following criteria. The results are shown in the column of "Antifouling effect (immediately after curing)" in Table 1. ◎ ·· No silica sand adhered. ○ ·· The number of silica sand particles adhered per 5 cm square was 1 or more and less than 50. △ ·· The number of silica sand particles adhered per 5 cm square was 50 or more and less than 200. × ·· The number of silica sand particles adhered per 5 cm square was 200 or more.

[0127] [Antifouling effect (after long-term exposure test)] On a polyethylene terephthalate (PET) substrate subjected to a release treatment, the curable composition was applied to a thickness of 5 mm in an atmosphere of 23°C and 50% relative humidity and cured for 1 day, thereby producing a sheet-like test piece made of the cured product of the curable composition on the above PET substrate. Next, after peeling the above PET substrate from the sheet-like test piece, only the sheet-like test piece was attached to an aluminum plate to obtain a laminate. Thereafter, the laminate was exposed outdoors (Koga City, Shiga Prefecture) for 3 months with the surface of the sheet-like test piece facing north at an inclination angle of 45 degrees with respect to the horizontal direction. After the exposure, the degree of adhesion of dirt such as dust and sand to the surface of the sheet-like test piece was visually observed and evaluated according to the following criteria. The results are shown in the column of "Antifouling effect (after long-term exposure test)" in Table 1. ◎: No dirt adhered. ○: A small amount of dirt adhered, but it was in a good state. △: A large amount of dirt adhered and it was in a dirty state. ×: The dirt covered the entire surface and it was in a rather dirty state.

[0128] [Table 1] TIFF0007706141000002.tif221153 [Industrial applicability]

[0129] Since the curable composition of the present invention maintains an excellent antifouling effect for a long period after curing, it can be suitably used, for example, as a filler for joints formed between outer wall members constituting the outer wall of a building structure.

Claims

1. A curable composition comprising a polymer (I) having a hydrolyzable silyl group containing a polyalkylene oxide (A) having a hydrolyzable silyl group, a monoamine compound (C) represented by R 2 -NH 2, and a diamine compound (D) represented by R 3 -NH-R 4 -NH 2. However, R 2 is a linear or branched alkyl group, or a monovalent saturated alicyclic hydrocarbon group, R 3 is a linear or branched alkyl group, an unsaturated aliphatic hydrocarbon group, a monovalent saturated alicyclic hydrocarbon group, or an aryl group, and R 4 is an alkylene group.

2. The curable composition according to claim 1, wherein the polymer (I) having a hydrolyzable silyl group contains an acrylic polymer (B) having a hydrolyzable silyl group.

3. The curable composition according to claim 1 or 2, wherein the melting point of the monoamine compound (C) is 60°C or lower.

4. The curable composition according to any one of claims 1 to 3, wherein the diamine compound contains a diamine compound (D) having a melting point 5°C or higher than the melting point of the monoamine compound (C).

5. The curable composition according to claim 4, wherein the mass ratio of the diamine compound (D) to the monoamine compound (C) [(mass of the diamine compound (D)) / (mass of the monoamine compound (C))] is 0.1 to 5.

6. The curable composition according to any one of claims 1 to 5, wherein the water contact angle of the cured product surface after curing for 3 days in an atmosphere at a temperature of 23°C and a relative humidity of 50% is 130°C or higher.

7. A sealing material comprising the curable composition according to any one of claims 1 to 6.

8. An adhesive comprising the curable composition according to any one of claims 1 to 6.

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