JP2021161429A - Curable composition, sealing material and adhesive - Google Patents

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

The present invention relates to a curable composition which is cured by moisture in an atmosphere to give a cured product capable of exhibiting an excellent antifouling effect for a long period of time, and a sealant and an adhesive made by using the curable composition. ..

Conventionally, a curable composition containing an oxyalkylene polymer having a crosslinkable hydrolyzable silyl group has been known (Patent Document 1). In the curable composition, a hydrolyzable silyl group that can be crosslinked by moisture contained in the atmosphere is hydrolyzed and then dehydrated and condensed to produce a cured product having excellent adhesiveness.

Such a curable composition is used in, for example, in the outer wall of a building structure, a joint (so-called "joint portion") 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.

On the outer wall of a building structure, the width of the joint part changes slightly because the outer wall member expands or contracts due to temperature changes, and the outer wall member moves due to vibration or external force caused by an earthquake or strong wind. Occurs. 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 the width of the joint portion.

In recent years, antifouling treatment may be applied to the surface of the outer wall member constituting the outer wall of the building structure. In such a case, the outer wall member is less likely to get dirty, and the appearance of the outer wall can be maintained for 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 be able to follow changes in the width of the joint portion. In such a case, tack remains on the surface of the cured product of the curable composition, so that dirt adheres to the surface of the cured product of the curable composition due to dust and contaminants. Therefore, there is a problem that the appearance is impaired when the entire outer wall is viewed. Therefore, it is required that the cured product of the curable composition can exert an antifouling effect for a long period of time.

Patent Document 2 discloses that by using a diamine compound, the surface of a cured product of a curable composition is made hydrophilic, and an antifouling effect due to a self-cleaning action can be obtained. However, the diamine compound cannot exhibit an excellent antifouling effect for a long period of time.

Therefore, Patent Document 3 discloses 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 due to the self-cleaning action can be improved. Has been done. However, the use of a fluorine-containing surfactant causes a significant price increase and is not practical in terms of cost.

Japanese Unexamined Patent Publication No. 2008-1833 Japanese Unexamined Patent Publication No. 2004-059870 Japanese Unexamined Patent Publication No. 2008-291159

Therefore, the present invention provides a curable composition that exhibits an excellent antifouling effect for a long period of time after curing.

The curable composition of the present invention contains 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. ..

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

(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.

The hydrolyzable silyl group is a group formed by bonding 1 to 3 hydrolyzable groups to a silicon atom. The hydrolyzable group of the hydrolyzable silyl group is not particularly limited, and 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 and a mercapto. Groups, alkenyloxy groups and the like can be mentioned.

As the hydrolyzable silyl group of the polyalkylene oxide (A), an alkoxysilyl group is preferable because the hydrolysis reaction is mild. The alkoxysilyl group includes a trialkoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, and a triphenoxysilyl group; a dialkoxysilyl group such as a methyldimethoxysilyl group and a methyldiethoxysilyl group. Groups; 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 preferable, and a methyldimethoxysilyl group is particularly preferable.

The polyalkylene oxide (A) has an average of 1 to 3 hydrolyzable silyl groups, more preferably 1 to 2 hydrolyzable silyl groups in one molecule. When the main chain of the polyalkylene oxide (A) is linear, the polyalkylene oxide (A) may have one or two hydrolyzable silyl groups in one molecule on average. preferable. When the main chain of the polyalkylene oxide (A) is branched, the polyalkylene oxide (A) has 1 to 3 hydrolyzable silyl groups in one molecule on average. Is preferable. When the number of hydrolyzable silyl groups in the polyalkylene oxide (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 (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, the polyalkylene oxide (A) preferably 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 (A) is the concentration of the hydrolyzable silyl groups in the polyalkylene oxide (A) determined by ^{1 H-NMR, and GPC.} It can be calculated based on the number average molecular weight of the polyalkylene oxide (A) obtained by the method.

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

Examples of the main chain skeleton of polyalkylene oxide (A) include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer, and polypropylene oxide-polybutylene oxide copolymer. Be done. 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 (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 extensibility 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 coatability of the curable composition is improved.

In the present invention, the number average molecular weight of the polyalkylene oxide (A) 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.

As the polyalkylene oxide (A) containing a hydrolyzable silyl group, a commercially available one can be used. For example, as the polyalkylene oxide (A) 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" , "Exester S2420" and the like.

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, and more preferably 40 to 70% by mass. 55 to 70% by mass is particularly preferable. 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.

(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 for a long period of time.

As the hydrolyzable silyl group of the acrylic polymer (B), 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 trialkoxysilyl 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. In addition, a monoalkoxysilyl group such as a dimethylmethoxysilyl group and a dimethylethoxysilyl group can be mentioned. Of these, a dialkoxysilyl group and a trialkoxyryl group are more preferable, a trialkoxysilyl group is more preferable, and a trimethoxysilyl group is particularly preferable.

Examples of the main chain skeleton of the acrylic polymer (B) include an acrylic polymer obtained by radical polymerization of a (meth) acrylate-based monomer 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, trimethylpropantri (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 other monomers 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-cyclohexyl maleimide, N-phenyl maleimide, N-lauryl maleimide, N-benzyl maleimide, 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, butyl benzoate (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) in which the 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.

The method for introducing the hydrolyzable silyl group into the acrylic polymer (B) is not particularly limited. 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 hydrosilylating by causing the above.

The number average molecular weight of the acrylic polymer (B) is preferably 1,000 to 50,000, more preferably 2,000 to 30,000. When the number average molecular weight of the acrylic polymer (B) is 50,000 or less, the coatability 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.

In the present invention, the number average molecular weight of the acrylic polymer (B) 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 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. preferable. 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 for a long period of time. When the content of the acrylic polymer (B) is 70% by mass or less, the coatability of the curable composition is improved.

[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 curable composition after curing can exhibit high water repellency for a long period of time. Since the surface of the cured product of the curable composition has high water repellency, it becomes difficult for stains to adhere to the surface of the cured product. Therefore, the curable composition of the present invention can exhibit an excellent antifouling effect for a long period of time after curing.

In the present invention, the monoamine compound (C) means a compound having _{one amino group (-NH 2) in one molecule.} The hydrogen atom of the amino group in the monoamine compound (C) may be substituted with an organic group such as an alkyl group or an aryl group. Further, the monoamine compound (C) preferably does not contain a silicon atom.

The melting point of the monoamine compound (C) is preferably 60 ° C. or lower, more preferably 20 to 60 ° C., 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) can easily move to the surface of the cured product of the curable composition. As a result, 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 occurrence of tack on the surface of the cured product can be reduced.

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, a differential scanning calorimetry device (for example, a device name “DSC-60” manufactured by Shimadzu Corporation) is used to heat the monoamine compound (C), and the melting peak temperature of the DSC curve in this heating process is determined. Let it be the melting point of the monoamine compound (C). As for the condition adjustment of the test piece, JIS K7121 (1987) 3. Adjust the state according to (1). When there are a plurality of melting peaks, the temperature at the apex of the melting peak having the highest endothermic value is taken as the melting point.

When the curable composition contains a plurality of types of monoamine compounds (C), the melting point of the monoamine compound (C) is the melting point of each monoamine compound (C).

As the monoamine compound (C), a monoamine compound represented by the following formula (1) is preferably mentioned.
R ^2- NH ₂ (1)
(In the formula (1), R ² is a linear or branched alkyl group or a monovalent saturated alicyclic hydrocarbon group.)

In the monoamine compound (C) represented by the 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 carbon number 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. As a result, the curable composition can exhibit an excellent antifouling effect for a long period of time immediately after curing.

Specific examples of the monoamine compound (C) include laurylamine (C ₁₂ H _25- NH ₂ , melting point 28 ° C.), stearylamine (C ₁₈ H _37- NH ₂ , melting point 50 ° C.), and myristylamine (C ₁₄ H). _29- NH ₂ , melting point 38 ° C.), and cetylamine (C ₁₆ H _33- NH ₂ , melting point 47 ° C.). The monoamine compound (C) may be used alone or in combination of two or more.

The content of the monoamine compound (C) in the curable composition is preferably 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the polymer (I) having a hydrolyzable silyl group. By mass is more preferable, and 1 to 5 parts by mass is particularly preferable. When the content of the monoamine compound (C) is 0.1 parts by mass or more, the surface of the cured product of the curable composition can exhibit an excellent antifouling effect for a long period of time. Further, when the content of the monoamine compound (C) is 20 parts by mass or less, it is possible to reduce the occurrence of tack on the surface of the cured product of the curable composition at a high temperature.

[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 (-NH 2) in one molecule.} The hydrogen atom of the amino group in the diamine compound may be substituted with an organic group such as an alkyl group or an aryl group. Further, the diamine compound preferably does not contain a silicon atom. The diamine compound may be used alone or in combination of two or more.

The diamine compound preferably contains a diamine compound (D) having a melting point higher than that of the monoamine compound (C) by 5 ° C. or more. The melting point of the diamine compound (D) is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, more preferably 10 to 55 ° C. higher, and 10 to 35 ° C. higher than the melting point of the monoamine compound (C). Higher is more preferable, and higher by 10 to 25 ° C. is particularly preferable. By using the diamine compound (D) having such a melting point, the surface of the cured product of the curable composition can exhibit higher water repellency. The mechanism by which such an effect is obtained is not clear, but the following mechanism can be considered.

By using the diamine compound (D) having the above melting point, the monoamine compound (C) easily moves to the surface of the cured product of the curable composition. After the monoamine compound (C) has moved to the surface of the cured product of the curable composition in this way, between the amino group of the diamine compound (D) existing inside the cured product and the amino group of the monoamine compound (C). An intermolecular force acts, whereby on the surface of the cured product, the monoamine compound (C) is oriented so that its amino group faces the inner side of the cured product and other parts face the surface side of the cured product. By directing the hydrophilic amino group toward the inside of the cured product, the surface of the cured product can exhibit higher water repellency. Since this mechanism is speculated by the present inventor, the present invention is not limited to the above mechanism.

The melting point of the diamine compound (D) is preferably 30 ° C. or higher, more preferably 30 ° C. to 80 ° C., more preferably 35 to 80 ° C., more preferably 40 to 80 ° C., more preferably 55 to 80 ° C., and 55 to 80 ° C. 75 ° C. is more preferable, and 60 to 70 ° C. is particularly preferable. Further, by setting the melting point of the diamine compound (D) in the above range, the monoamine compound (C) can easily move to the surface of the cured product of the curable composition. Moreover, in summer, the building structure is 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 generation of tack promotes the adhesion of stains such as dust and contaminants to the surface of the cured product of the curable composition, and reduces the antifouling effect. However, according to the diamine compound (D) having a melting point of 30 ° C. or higher, it is possible to highly reduce the occurrence of tack on the surface of the cured product of the curable composition at high temperatures, and it is possible to maintain an excellent antifouling effect. can.

When the curable composition contains a plurality of types of diamine compounds, the melting point of the diamine compound is the melting point of each diamine compound.

Further, in relation to the above-mentioned "the diamine compound contains a diamine compound (D) having a melting point higher than the melting point of the monoamine compound (C) by 5 ° C. or more", a plurality of types of monoamine compounds (C) are used. is the case is the highest melting point (P _high) monoamine compound having a melting point diamine compound having a melting point 5 ° C. or higher than (P _high) of (C _high) among a plurality of types of monoamine compound (C) Is referred to as "diamine compound (D)".

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, a differential scanning calorimetry device (for example, a device name “DSC-60” manufactured by Shimadzu Corporation) is used to heat the diamine compound, and the melting peak temperature of the DSC curve in this heating process is set to that of the diamine compound. Let it be the melting point. As for the condition adjustment of the test piece, JIS K7121 (1987) 3. Adjust the state according to (1). When there are a plurality of melting peaks, the temperature at the apex of the melting peak having the highest endothermic value is taken as the melting point.

In the cured composition, 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 Is preferable, 0.5 to 3 is more preferable, and 1.7 to 2.5 is more preferable. When the mass ratio of the monoamine compound (C) to the diamine compound (D) is in the above range, the surface of the cured product of the curable composition exhibits higher water repellency, thereby providing an excellent antifouling effect over a long period of time. Can be demonstrated.

Examples of the diamine compound include a diamine compound represented by the following formula (2).
R ^3- NH-R ^4- NH ₂ (2)
(In the 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.)

In the formula (2), as R ³ , a linear or branched alkyl group is preferable. Examples of the linear or branched alkyl group in R ³ include a decyl group, an isodecyl group, an undecyl group, a lauryl group, an isododecyl group, a tridecylic group, a myristyl group, a pentadecyl group, a palmityl group, a heptadecyl group and an isohexa. Examples thereof include a decyl group, a stearyl group, an isooctadecyl group, a nonadecyl group, an eicosyl group, and a behenyl group. The ^{unsaturated aliphatic hydrocarbon group in R 3} includes an undecenyl group, a cis-4-tetradecenyl group, a cis-5-tetradecenyl group, a cis-9-tetradecenyl group, a cis-6-hexadecenyl group, a palmitrail group, and a cis-. Examples thereof include 6-octadecenyl group, oleyl group, trans-9-octadecenyl group, cis-11-octadecenyl group, trans-11-octadecenyl group, myristolail group, palmitrail group, linoleyl group and the like.

In formula (2), R ⁴ is an alkylene group. Examples ^{of the alkylene group of R 4} include a methylene group, an ethylene group, an ethylidene group, a trimethylene group, a propylene group, an isopropylene group, a tetramethylene group, a butylene group, an isobutylene group, a pentylene group, a hexamethylene group, and a hexylene group. Be done.

As the diamine compound (D), a diamine compound represented by the formula (2) [in the formula (2), R ³ is a linear alkyl group and R ⁴ is an alkylene group] is preferably mentioned. In the diamine compound (D) represented by the 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 carbon number of R ³ and R ⁴ within the above range, the surface of the cured product of the curable composition can exhibit an excellent antifouling effect for a long period of time, and the curable composition at a high temperature can be exhibited. It is possible to highly reduce the occurrence of tack on the surface of the cured product.

As the diamine compound (D), behenyl propylene diamine (C ₂₂ H _45- NH-C ₃ H _6- NH ₂ , melting point 63 ° C.) is preferably mentioned.

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.

The diamine compound may further contain the diamine compound (E) having a melting point equal to or lower than the melting point of the monoamine compound (C) as long as the properties such as the antifouling effect of the curable composition are not adversely affected. However, the diamine compound preferably 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. The lower the content of the diamine compound (E), the higher the antifouling curing of the curable composition.

In the case where plural kinds of monoamine compound (C) is used, the melting point (P _Low of a plurality of types of monoamine compound lowest melting point (P _Low) monoamine compound having one of (C) (C _Low) ) A diamine compound having a melting point of the following is referred to as "diamine compound (E)".

The content of the diamine compound in the curable composition is preferably 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the polymer (I) having a hydrolyzable silyl group. More preferably, 1 to 5 parts by mass is particularly preferable. When the content of the diamine compound is 0.1 part by mass or more, the surface of the cured product of the curable composition can exhibit an excellent antifouling effect for a long period of time. Further, 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 surface of the cured product of the curable composition at a high temperature.

[Plasticizer]
The curable composition preferably further contains a plasticizer. Specific examples of the plasticizer include phthalates such as dioctyl phthalate, dibutyl phthalate and butyl benzyl phthalate, polyalkylene oxides such as polypropylene glycol, and acrylic polymers, and acrylic polymers are preferable. ..

The acrylic polymer used as a plasticizer preferably does not have a hydrolyzable silyl group.

Examples of the main chain skeleton of the acrylic polymer used as a plasticizer include an acrylic polymer obtained by radical polymerization of a (meth) acrylate-based monomer.

Specific examples of the (meth) acrylate-based monomer constituting the main chain of the acrylic polymer used as a plasticizing agent include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl ( Meta) 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, trimethyl propantri (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 (Meta) 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.

The weight average molecular weight of the acrylic polymer used as the plasticizer is preferably 1,000 to 50,000, more preferably 2,000 to 30,000. When the weight average molecular weight of the acrylic polymer used as the 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 the plasticizer is 1,000 or more, the mechanical strength or extensibility of the cured product of the curable composition is improved.

In the present invention, the weight average molecular weight of the acrylic polymer used as a plasticizer 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 plasticizer in the curable composition is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, and 1 to 70 parts by mass with respect to 100 parts by mass of the polymer (I) having a hydrolyzable silyl group. Parts by mass are more preferable, and parts by mass of 20 to 50 are particularly preferable. If the content of the plasticizer is too high, the plasticizer may precipitate on the surface of the cured product of the curable composition.

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

Examples of the filler include calcium carbonate, magnesium carbonate, calcium oxide, hydrous silicic acid, silicic anhydride, 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. Of these, calcium carbonate is preferably used.

The average particle size of calcium carbonate is preferably 0.01 to 5 μm, more preferably 0.05 to 2.5 μm. According to the calsim carbonate having such an average particle size, a cured product having excellent mechanical strength and extensibility can be obtained, and a curable composition having excellent adhesiveness can be obtained. Can be provided.

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

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 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 orthostate, 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 preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 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. Further, when the content of the dehydrating agent is 20 parts by mass or less, the curable composition has excellent curability.

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

Examples of the silanol condensation catalyst include 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltinphthalate, and bis (dibutyltin lauric acid). ) Oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (monoestermalate), tin octylate, dibutyltin octate, dioctyltin oxide, dibutyltin bis (triethoxysilicate), bis (dibutyltin bistriethoxysilicate) ) Oxide and organic tin compounds such as dibutyltin oxybisethoxysilicate; organic tin 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 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.

[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.

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

The content of the thixotropy-imparting agent in the curable composition is preferably 0.1 to 200 parts by mass, preferably 1 to 150 parts by mass with respect to 100 parts by mass of the polymer (I) having a hydrolyzable silyl group. More preferred. When the content of the thixotropy-imparting agent is 0.1 parts 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.

[UV absorber]
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 preferably 0.1 to 20 parts by mass, preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the polymer (I) having a hydrolyzable silyl group. Is more preferable.

[Antioxidant]
Examples of the antioxidant include a hindered phenolic antioxidant, a monophenolic antioxidant, a bisphenolic antioxidant, a polyphenolic antioxidant and the like, and the hindered phenolic antioxidant is preferable. Be done. The content of the antioxidant in the curable composition is preferably 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass, based on 100 parts by mass of the polymer (I) having a hydrolyzable silyl group. 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) 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-triazin-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-tetramethyl-1-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 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).

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 an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. 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 a 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 a 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 preferably 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the polymer (I) having a hydrolyzable silyl group. Parts by mass are more preferred.

[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 in which an alkoxy group is bonded in one molecule and a functional group containing a nitrogen atom.

Specific examples of the aminosilane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, and N- (2-aminoethyl) -3-aminopropyltrimethoxy. Silane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N, N'-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, N, N'-bis- [3- (tri) Ethoxysilyl) 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 can be mentioned. These aminosilane coupling agents may be used alone or in combination of two or more.

Among them, the aminosilane coupling agents include 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and N- (2-aminoethyl) -3-aminopropyltri. Ethoxysilane is preferred, with N- (2-aminoethyl) -3-aminopropyltrimethoxysilane being more preferred.

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 with respect to 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.

The curable composition of the present invention preferably has a water contact angle (W) of 130 ° or more on the surface of the cured product after curing for 3 days in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%. That is, the contact angle (W) of water on the surface of the cured product obtained by curing the curable composition of the present invention in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% for 3 days is 130 ° or more. Is preferable.

The contact angle (W) of water on the surface of the cured product obtained by curing the curable composition of the present invention in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% for 3 days is simply referred to as "water. Also called "contact angle (W)". The contact angle (W) of the water is preferably 130 ° or more, more preferably 130 to 180 °, and particularly preferably 150 to 180 °. According to the curable composition in which the contact angle (W) of water 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 becomes water droplets. It becomes easy to flow off the surface immediately. Therefore, dirt such as dust and contaminants is less likely to adhere to the surface of the cured product of the curable composition, and as a result, the cured composition after curing can exhibit an excellent antifouling effect. Further, it is possible to reduce the occurrence of rain streak stains on the surface of the cured product of the curable composition. Rain streak stains are streak marks formed by the flow of stains such as dust and contaminants adhering to the surface of a cured product of a 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.

In the present invention, the contact angle of water on the surface of the cured product of the curable composition is a contact angle θ value obtained by a measuring method based on the static drip method of JIS R3257 (1999) “Wetting property test method for substrate glass surface”. Means.

In the present invention, the measurement of the contact angle (W) of water on the surface of a cured product obtained by curing the curable composition in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% for 3 days is specifically measured. Can be measured according to the following procedure. First, the curable composition is applied onto a stainless steel plate and cured in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% for 3 days to cure the curable composition on the stainless steel plate. A laminate is obtained in which a cured product of the curable composition is formed. The thickness of the cured product of the curable composition is 5 mm. Then, the contact angle of water on the surface of the cured product of the curable composition is measured by the static drip method of JIS R3257 (1999) "Wetting property test method for the surface of the substrate glass" using a solid-liquid interface analyzer. The dropping liquid is distilled water, the amount of the liquid is 4 μL, and the contact angle is measured 2 minutes after the dropping. The contact angle is calculated by the θ / 2 method. The contact angles of water are measured at arbitrary 10 points on the surface of the cured product of the curable composition, and the arithmetic mean value of the measured values of all the contact angles is calculated as the contact angle of water on the surface of the cured product of the curable composition ( W). The contact angle measurement atmosphere is a temperature of 23 ° C. and a relative humidity of 50%. Further, as the solid-liquid interface analysis apparatus, for example, an apparatus commercially available from Kyowa Interface Science Co., Ltd. under the trade name “DMs-401” can be used. The contact angle can be calculated using, for example, the software "FAMAS" attached to the solid-liquid interface analyzer marketed by Kyowa Interface Science Co., Ltd. under the trade name "DMs-401".

Since the curable composition of the present invention can form a cured product which is excellent in adhesiveness and can maintain excellent rubber elasticity for a long period of time, it is a sealing material, a coating material, and an adhesive. , And can be used for various purposes such as paints. Among them, it is preferably used as a sealing material or an adhesive, and more preferably used as a sealing material for joint structure.

Further, since the cured product of the curable composition of the present invention has an excellent antifouling effect, it suppresses the adhesion of stains such as dust and contaminants, and even when used outdoors, for a long period of time. A beautiful appearance can be maintained throughout.

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, a ceiling portion, and the like, and the outer wall is particularly preferable. Examples of the wall member include an outer wall member, an inner wall member, a ceiling member, and the like, and an outer wall member is preferable.

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. The curable composition of the present invention can maintain an excellent antifouling effect for a long period of time after curing. Therefore, it is suitably used for sealing joints that are easily contaminated by dust and contaminants, which are also called "working joints", such as joints on the outer wall of a 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. ..

Since the curable composition of the present invention has the above-mentioned structure, the cured product of the curable composition has an excellent antifouling effect and reduces the adhesion of dust and contaminants to the cured product. It can maintain a beautiful appearance for a long period of time.

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.
[Polymer (I) having a hydrolyzable silyl group]
(Polyalkylene oxide (A) having a hydrolyzable silyl group)
-Polyalkylene oxide (A1) (polyalkylene oxide having a methyldimethoxysilyl group and a polypropylene oxide main chain skeleton, trade name "Exester S2420" manufactured by Asahi Glass Co., Ltd., average number of methyldimethoxysilyl groups per molecule 1.7 pieces, molecular weight distribution: 1.49, number average molecular weight: 18,990)

(Acrylic polymer having a hydrolyzable silyl group (B))
-Acrylic polymer (B1) (main chain skeleton consists of methyl methacrylate-n-butyl acrylate copolymer (content of methyl methacrylate component: 25% by mass, content of n-butyl acrylate component: 75% by mass)) , Acrylic polymer having a trimethoxysilyl group at the end or side chain of the main chain skeleton, manufactured by Toa Synthetic Co., Ltd. Product name "US-6150" Number average molecular weight: 2,400)

[Amine compound (C)]
-Stearylamine (melting point 50 ° C, product name "Farmin 80S" manufactured by Kao Corporation)
・ Laurylamine (melting point 28 ° C, product name "Nissanamine BB" manufactured by NOF CORPORATION)

[Diamine compound]
・ Behenyl propylene diamine (melting point 63 ° C, product name "Nissan Amine DV" manufactured by NOF CORPORATION)
・ Hardened beef tallow propylene diamine (trade name "Nissan Amine DT-H" manufactured by NOF CORPORATION)

The cured beef propylene diamine (trade name "Nissanamine DT-H" manufactured by Nichiyu Co., Ltd.) is a ^{linear alkyl having R 3} having 13 to 18 carbon atoms in the above formulas (2) and (2). The diamine compound (D) 47 to 55% by mass, which is a group and has a melting point of 55 to 80 ° C. and is represented by ( ^{R 4 is a propylene group), and R 3 in the above formulas (2) (formula (2)).} Is 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 the diamine compound (E) having a melting point of 28 ° C. or lower. board.

[Plasticizer]
-Plasticizer (1) (Acrylic polymer having no hydrolyzable silyl group, weight average molecular weight: 3,500, manufactured by Toa Synthetic Co., Ltd. Product name "UP-1110")

[filler]
・ Colloidal calcium carbonate (average particle size: 80 nm, surface treatment with fatty acid, Maruo Calcium product name "Calfine 200M")
-Heavy calcium carbonate (average particle size: 1.0 μm, surface treatment with fatty acids, product name "NCC2310" manufactured by Nitto Flour Chemical Co., Ltd.)

[Dehydrating agent]
-Vinyl trimetoshisilane (trade 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, manufactured by Nitto Kasei Co., Ltd., trade name "Neostan U-130")

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

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

[Light stabilizer]
・ NH-type hindered amine-based light stabilizer (BASF Japan, Inc. product name "Chinubin 770")

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

[others]
・ Shaking agent (fatty acid amide wax, manufactured by Kusumoto Kasei Co., Ltd. Product name "Disparon # 6500"
)

[solvent]
-Ethylene glycol tertiary butyl ether (ETB)

(Examples 1 to 5, Comparative Examples 1 to 7)
Polyalkylene oxide (A1), acrylic polymer (B1), stearylamine, laurylamine, behenylpropylenediamine, cured beef propylenediamine, plasticizer (1), colloidal calcium carbonate, heavy calcium carbonate, vinyl, respectively, as described above. Trimethosisilane, silanol condensation catalyst, benzotriazole-based ultraviolet absorber, hindered phenol-based antioxidant, NH-type hindered amine-based photostabilizer, aminosilane coupling agent, rocking agent, and ethylene glycol tertiary butyl ether (ETB) A curable composition was obtained by mixing the mixture in a sealed stirrer while reducing the pressure until the mixture was uniform.

[evaluation]
The contact angle (W) [°] of water on the surface of the cured product obtained by curing the obtained curable composition in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% for 3 days was set as described above. The results obtained were shown in Table 1.

In addition, the antifouling effect of the obtained curable composition immediately after curing and after the long-term exposure test was evaluated according to the following procedure.

[Anti-fouling effect (immediately after curing)]
The curable composition was applied onto a stainless steel plate in an atmosphere of 23 ° C. and 50% relative humidity so as to have a thickness of 5 mm, and cured for 1 day. No. 7 silica sand was sprinkled on the surface of the cured product of the curable composition, and the presence or absence of adhesion of silica sand was visually observed and evaluated based on the following criteria. The results are shown in the column of "Anti-fouling effect (immediately after curing)" in Table 1.
◎ ・ ・ There was no adhesion of silica sand.
◯ ・ ・ The number of silica sands attached per 5 cm square was 1 or more and less than 50.
Δ: The number of silica sands attached per 5 cm square was 50 or more and less than 200.
X ... The number of silica sands attached per 5 cm square was 200 or more.

[Anti-fouling effect (after long-term exposure test)]
A curable composition was applied to a release-treated polyethylene terephthalate (PET) substrate in an atmosphere of 23 ° C. and 50% relative humidity to a thickness of 5 mm and cured for 1 day. A sheet-like test piece made of a cured product of the curable composition was prepared on the PET substrate. Next, after peeling the PET base material from the sheet-shaped test piece, only the sheet-shaped test piece was attached to an aluminum plate to obtain a laminated body. Then, the laminated body was exposed to the outdoors (Koka City, Shiga Prefecture) for 3 months with the surface of the sheet-shaped test piece facing northward with an inclination angle of 45 degrees with respect to the horizontal direction. After exposure, the degree of adhesion of dirt such as dust and sand to the surface of the sheet-shaped test piece was visually observed and evaluated according to the following criteria. The results are shown in the column of "Anti-fouling effect (after long-term exposure test)" in Table 1.
⊚: No dirt was attached.
◯: Although a small amount of dirt adhered, it was in a good condition.
Δ: A lot of dirt was attached and the state was dirty.
X: Dirt covered the entire surface and was in a state of being considerably dirty.

[Table 1]

Since the curable composition of the present invention maintains an excellent antifouling effect for a long period of time after curing, for example, to a joint formed between outer wall members constituting the outer wall of a building structure. It can be suitably used as a filler.

Claims (8)

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), and a diamine compound. .. 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. The curable composition according to claim 1 or 2, wherein the monoamine compound (C) has a melting point of 60 ° C. or lower. 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 higher than that of the monoamine compound (C) by 5 ° C. or more. According to claim 4, 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. The curable composition according to description. The invention according to any one of claims 1 to 5, wherein the water contact angle of the surface of the cured product after curing for 3 days in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% is 130 ° C. or higher. Curable composition. A sealing material containing the curable composition according to any one of claims 1 to 6. An adhesive comprising the curable composition according to any one of claims 1 to 6.