Hardening composition

Abstract

To provide a (storage stable) curable composition which can generate a cured product having an excellent antifouling effect with the effect of moisture and can generate a cured product having an excellent antifouling effect even when used after having been stored for a long period of time after production.SOLUTION: There is provided a curable composition which comprises a polyoxyalkylene-based polymer (A) having a hydrolyzable silyl group, an acrylic polymer (B), an amine compound (C), and a surfactant having a polyoxyalkylene skeleton.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable composition that cures with moisture to give a cured product that can exhibit antifouling properties even when used after long-term storage. [Background technology]

[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 with excellent adhesiveness by hydrolyzing the crosslinkable hydrolyzable silyl group due to moisture in the atmosphere and then dehydrating and condensing.

[0003] Such curable compositions are used, for example, in the exterior walls of building structures, by filling the joints (so-called "joints") between exterior wall members such as mortar boards, concrete boards, ALC (Autoclaved Lightweight Concrete) boards, metal boards, etc., to join the exterior wall members together. By using the curable composition in this way, rainwater is prevented from penetrating into the interior of the building structure through the joints between the exterior wall members.

[0004] In recent years, the surfaces of exterior wall materials that make up the exterior walls of building structures have been treated with antifouling treatments, which make it difficult for dirt to adhere to the exterior wall materials, allowing the exterior wall to maintain its beautiful appearance for a long period of time.

[0005] However, the cured product of the curable composition filled in the joints has not been subjected to antifouling treatment. In such cases, tack remains on the surface of the cured product of the curable composition, which allows dirt to adhere to the surface of the cured product of the curable composition due to dust and contaminants. This causes a problem of impaired appearance when viewed as a whole exterior wall. Therefore, it is required that the cured product of the curable composition also be able to exhibit antifouling effects over a long period of time.

[0006] Furthermore, the curable composition may be stored for a long period of time from its production until its use.

[0007] Patent Document 2 discloses that the use of a diamine compound (C2) makes the surface of the cured product of the curable composition hydrophilic, thereby providing an antifouling effect due to a self-cleaning action.

[0008] Patent Document 3 discloses that the use of a fluorine-containing surfactant in addition to the diamine compound (C2) can make the surface of the cured product of the curable composition more hydrophilic, thereby improving the antifouling effect due to the self-cleaning action. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 2008-1833 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-059870 [Patent Document 3] Japanese Patent Application Publication No. 2008-291159 Summary of the Invention [Problem to be solved by the invention]

[0010] However, the curable resin composition of Patent Document 2 has a problem in that if the curable resin composition is stored for a long period of time after production, the antifouling effect of the cured product of the curable resin composition is lost.

[0011] Patent Document 3 discloses that the curable composition further contains a fluorine-containing surfactant in addition to the diamine compound (C2), which makes the surface of the cured product of the curable composition more hydrophilic and improves the antifouling effect due to the self-cleaning action. However, the use of a fluorine-containing surfactant leads to a significant increase in price, making it impractical from a cost perspective.

[0012] The present invention provides a storage-stable curable composition that is cured by moisture to produce a cured product with excellent antifouling effect, and that can produce a cured product that has excellent antifouling effect even when used after being stored for a long period of time after production. [Means for solving the problem]

[0013] The curable composition of the present invention contains a polyoxyalkylene polymer (A) having a hydrolyzable silyl group, an acrylic polymer (B), an amine compound (C), and a surfactant having a polyoxyalkylene skeleton and a structural formula represented by formula (3). R 5 -O-(R 6 -O) p -H (3) However, R 5 is an alkyl group having 13 or more carbon atoms, and R 6 represents an alkylene group, and p is the number of repeating units and is a positive integer.

[0014] [Polyoxyalkylene polymer (A) having hydrolyzable silyl groups] The curable composition contains a polyoxyalkylene polymer (A) having a hydrolyzable silyl group (hereinafter, sometimes simply referred to as "polyoxyalkylene polymer (A)"). The polyoxyalkylene polymer (A) having a hydrolyzable silyl group makes it possible to provide a curable composition that can be cured by moisture present in the atmosphere, joints, etc.

[0015] In the present invention, 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, and an alkenyloxy group.

[0016] As the hydrolyzable silyl group of the polyoxyalkylene polymer (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. Of these, as the hydrolyzable silyl group of the polyoxyalkylene polymer (A), a dialkoxysilyl group is more preferred, and a methyldimethoxysilyl group is particularly preferred.

[0017] The polyoxyalkylene polymer (A) preferably has 1 to 3, more preferably 1 to 2 hydrolyzable silyl groups on average per molecule. When the main chain of the polyoxyalkylene polymer (A) is linear, the polyoxyalkylene polymer (A) preferably has 1 to 2 hydrolyzable silyl groups on average per molecule. When the main chain of the polyoxyalkylene polymer (A) is branched, the polyoxyalkylene polymer (A) preferably has 1 to 3 hydrolyzable silyl groups on average per molecule. When the number of hydrolyzable silyl groups in the polyoxyalkylene polymer (A) is 1 or more, the curability of the curable composition is improved. When the number of hydrolyzable silyl groups in the polyoxyalkylene polymer (A) is the above-mentioned upper limit or less, the rubber elasticity of the cured product of the curable composition is improved. Furthermore, the polyoxyalkylene polymer (A) preferably has a hydrolyzable silyl group at at least one of both ends of the main chain.

[0018] The average number of hydrolyzable silyl groups per molecule in the polyoxyalkylene polymer (A) is 1 It can be calculated based on the concentration of hydrolyzable silyl groups in the polyoxyalkylene polymer (A) determined by H-NMR and the number average molecular weight of the polyoxyalkylene polymer (A) determined by GPC.

[0019] The polyoxyalkylene polymer (A) may be a polymer having a main chain represented by the general formula: -(R 1 -O) n -(In the formula, 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. Preferred examples include polymers containing repeating units represented by the following formula: The main chain skeleton of the polyoxyalkylene polymer (A) may consist of only one type of repeating unit, or may consist of two or more types of repeating units. In the present invention, the main chain refers to the longest molecular chain, and is determined based on the number of atoms constituting the molecular chain; the greater the number of atoms, the longer the molecular chain.

[0020] Examples of the main chain skeleton of the polyoxyalkylene polymer (A) include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer, and polypropylene oxide-polybutylene oxide copolymer. Among these, polypropylene oxide is preferred. Polypropylene oxide can provide a curable composition that exhibits excellent rubber elasticity or adhesiveness after curing.

[0021] The weight-average molecular weight of the polyoxyalkylene polymer (A) is preferably 25,000 to 60,000, more preferably 26,000 to 40,000. When the weight-average molecular weight of the polyoxyalkylene polymer (A) is 25,000 or more, the rubber elasticity of the cured product of the curable composition is improved. When the weight-average molecular weight of the polyoxyalkylene polymer (A) is 60,000 or less, the coatability of the curable composition is improved.

[0022] The number average molecular weight of the polyoxyalkylene polymer (A) is preferably 15,000 to 50,000, more preferably 16,000 to 30,000. When the number average molecular weight of the polyoxyalkylene polymer (A) is 15,000 or more, the rubber elasticity of the cured product of the curable composition is improved. When the number average molecular weight of the polyoxyalkylene polymer (A) is 50,000 or less, the coatability of the curable composition is improved.

[0023] In the present invention, the number-average molecular weight and weight-average molecular weight of the polyoxyalkylene polymer (A) are values ​​measured by GPC (gel permeation chromatography) and converted into polystyrene. Specifically, 6 to 7 mg of the polyoxyalkylene polymer is collected and placed in a test tube. An o-DCB (ortho-dichlorobenzene) solution containing 0.05% by mass of BHT (dibutylhydroxytoluene) is added to the test tube to dilute the polyoxyalkylene polymer to a concentration of 1 mg / mL, thereby preparing a diluted solution.

[0024] The diluted solution is shaken at 25 rpm at 145°C for 1 hour using a dissolution filter to dissolve the polyoxyalkylene polymer in the o-DCB solution containing BHT, thereby preparing a measurement sample. The number-average molecular weight and weight-average molecular weight of the polyoxyalkylene polymer can be measured by GPC using this measurement sample.

[0025] In the present invention, the number average molecular weight and weight average molecular weight of the polyoxyalkylene polymer can be measured, for example, using the following measuring device and under the following measuring conditions. Measuring device: TOSOH Corporation, product name "HLC-8121GPC / HT" Measurement conditions Column: TSKgelGMHHR-H(20)HT x 3 TSKguardcolumn-HHR(30)HT x 1 Mobile phase: o-DCB 1.0mL / min Sample concentration: 1 mg / mL Detector: Bryce type refractometer Standard material: Polystyrene (TOSOH Corporation, molecular weight: 500-8420000) Elution conditions: 145℃ SEC temperature: 145℃

[0026] The polyoxyalkylene polymer (A) containing a hydrolyzable silyl group can be commercially available. For example, examples of the polyoxyalkylene polymer (A) having a polypropylene oxide main chain skeleton and a methyldimethoxysilyl group at the end of the main chain skeleton include those available under the trade names "Excestar S4530," "Excestar S2730C," and "Excestar S2420," manufactured by AGC.

[0027] The content of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group in the total amount of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group and the acrylic polymer (B) is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 55% by mass or more. When the content of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group is 30% by mass or more, the coatability of the curable composition is improved.

[0028] The content of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) in the total amount of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) and the acrylic polymer (B) is preferably 80 mass % or less, more preferably 70 mass % or less, and still more preferably 70 mass % or less. When the content of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) is 80 mass % or less, the cured product of the curable composition maintains excellent rubber elasticity for a long period of time.

[0029] [Acrylic polymer (B)] The curable composition contains an acrylic polymer (B). Use of the acrylic polymer (B) facilitates surface migration of a surfactant having a polyoxyalkylene skeleton, which will be described later and has low compatibility with the acrylic resin (B), thereby enhancing the antifouling effect of a cured product of the curable composition.

[0030] The acrylic polymer (B) may have a hydrolyzable silyl group. When the acrylic polymer (B) or a part thereof has a hydrolyzable silyl group, the antifouling properties of the cured product of the curable composition are improved.

[0031] The acrylic polymer (B) preferably contains an acrylic polymer having hydrolyzable silyl groups at both ends of the main chain skeleton and an acrylic polymer having a hydrolyzable silyl group at only one end of the main chain skeleton, which is preferable because it improves the storage stability of the curable composition, allows a surfactant having a polyoxyalkylene skeleton (described later) to be smoothly transferred to the surface of a cured product of the curable composition, and allows the cured product to exhibit excellent antifouling properties.

[0032] The hydrolyzable silyl group contained in the acrylic polymer (B) is preferably an alkoxysilyl group, since the cured product of the curable composition can maintain excellent rubber elasticity for a long period of time. Examples of the alkoxysilyl group include trialkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, and triphenoxysilyl; dimethoxysilyl groups such as methyldimethoxysilyl and methyldiethoxysilyl; and monoalkoxysilyl groups such as dimethylmethoxysilyl and dimethylethoxysilyl. Among these, dialkoxysilyl and trialkoxysilyl groups are more preferred, dialkoxysilyl groups are more preferred, and dimethoxysilyl groups are particularly preferred.

[0033] The acrylic polymer (B) preferably has an average of 0.1 or more, more preferably 0.5 or more, more preferably 0.6 or more, and more preferably 1 or more hydrolyzable silyl groups per molecule. The acrylic polymer (B) preferably has an average of 4 or less, more preferably 3 or less, more preferably 2 or less, and more preferably 1.5 or less hydrolyzable silyl groups per molecule. When the average number of hydrolyzable silyl groups per molecule of the acrylic polymer (B) is 0.1 or more, the curability of the curable composition is improved. When the average number of hydrolyzable silyl groups per molecule of the acrylic polymer (B) is 4 or less, the rubber elasticity of the cured product of the curable composition is improved.

[0034] The average number of hydrolyzable silyl groups per molecule in the acrylic polymer (B) is 1 It can be calculated based on the concentration of hydrolyzable silyl groups in the acrylic polymer (B) determined by H-NMR and the number average molecular weight of the acrylic polymer (B) determined by GPC.

[0035] The main chain skeleton of the acrylic polymer (B) may be an acrylic polymer (B) obtained by radical polymerization of a (meth)acrylate monomer, where (meth)acrylate means methacrylate or acrylate.

[0036] Specific examples of the (meth)acrylate monomer constituting the main chain of the acrylic polymer (B) 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, and isomyristyl (meth)acrylate. 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, trime Examples of the acrylates include tyrolpropane 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. As the (meth)acrylate monomer, methyl (meth)acrylate and butyl (meth)acrylate are preferred. These (meth)acrylate monomers may be used alone or in combination of two or more.

[0037] In the acrylic polymer (B), other monomers can also be copolymerized. Examples of such monomers include styrene derivatives such as styrene, indene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, and divinylbenzene; compounds having a vinyl ester group such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, and 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, and triethylene glycol butyl vinyl ether. Examples of vinyloxy groups include 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, and polyester vinyl ether. These monomers may be used alone or in combination.

[0038] Among these, the main chain skeleton of the acrylic polymer (B) is preferably a copolymer of butyl (meth)acrylate and methyl (meth)acrylate, and more preferably a copolymer of butyl acrylate and methyl methacrylate. The acrylic polymer (B) having a main chain skeleton composed of the above copolymer can provide a curable composition that can form a cured product having excellent rubber elasticity after curing.

[0039] The acrylic polymer (B) preferably does not have a polyoxyalkylene chain in the molecule. When the acrylic polymer (B) does not have a polyoxyalkylene chain in the molecule, the storage stability of the curable composition is improved, and a surfactant having a polyoxyalkylene skeleton, which will be described later, can be smoothly transferred to the surface of a cured product of the curable composition, and the cured product exhibits excellent antifouling properties.

[0040] The polyoxyalkylene chain may be a chain having the general formula: -(R 7 -O)m-(wherein, R 7 represents an alkylene group having 1 to 14 carbon atoms, and m is the number of repeating units and is a positive integer. The polyoxyalkylene chain may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.

[0041] Examples of the polyoxyalkylene chain include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer, and polypropylene oxide-polybutylene oxide copolymer.

[0042] The polymerization method for the acrylic polymer (B) is not particularly limited, and any known method can be used, including various polymerization methods such as free radical polymerization, anionic polymerization, cationic polymerization, UV radical polymerization, living anionic polymerization, living cationic polymerization, and living radical polymerization.

[0043] The method for introducing a hydrolyzable silyl group into the acrylic polymer (B) is not particularly limited, and any known method can be used, such as a method of hydrosilylating an acrylic polymer (B) having an unsaturated group introduced into the molecule by allowing a hydrosilane having a hydrolyzable silyl group to act on the polymer.

[0044] The weight average molecular weight of the acrylic polymer (B) is preferably 1,000 or more, more preferably 2,000 or more, more preferably 5,000 or more, more preferably 8,000 or more, and more preferably 11,000 or more. The weight average molecular weight of the acrylic polymer (B) is preferably 50,000 or less, more preferably 30,000 or less, more preferably 29,000 or less, more preferably 28,500 or less, and more preferably 28,000 or less. When the weight average molecular weight of the acrylic polymer (B) is 50,000 or less, the coatability of the curable composition is improved. When the weight average molecular weight of the acrylic polymer (B) is 1,000 or more, the rubber elasticity of the cured product of the curable composition is improved.

[0045] 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 rubber elasticity of the cured product of the curable composition is improved.

[0046] In the present invention, the number-average molecular weight and weight-average molecular weight of the acrylic polymer (B) refer to values ​​measured by gel permeation chromatography (GPC) in terms of polystyrene. In the GPC measurement, for example, a Shodex KF800D manufactured by Tosoh Corporation can be used as a GPC column, and chloroform or the like can be used as a solvent.

[0047] In the present invention, the number average molecular weight and weight average molecular weight of the acrylic polymer can be measured, for example, using the following measuring device and under the following measuring conditions. Measuring device: TOSOH Corporation, product name "HLC-8121GPC / HT" Measurement conditions Column: TSKgelGMHHR-H(20)HT x 3 TSKguardcolumn-HHR(30)HT x 1 Mobile phase: o-DCB 1.0mL / min Sample concentration: 1 mg / mL Detector: Bryce type refractometer Standard material: Polystyrene (TOSOH Corporation, molecular weight: 500-8420000) Elution conditions: 145℃ SEC temperature: 145℃

[0048] The content of the acrylic polymer (B) in the total amount of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) and the acrylic polymer (B) is preferably 20% by mass or more, more preferably 30% by mass or more. 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.

[0049] The content of the acrylic polymer (B) in the total amount of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group and the acrylic polymer (B) is preferably 70 mass % or less, more preferably 60 mass % or less, and even more preferably 45 mass % or less. When the content of the acrylic polymer (B) is 70 mass % or less, the coatability of the curable composition is improved.

[0050] [Amine compound (C)] The curable composition contains an amine compound (C). The amine compound (C) preferably contains a monoamine compound (C1) having one amino group (-NH2) per molecule, or a diamine compound (C2) having two amino groups (-NH2) per molecule, and more preferably contains a diamine compound (C2) having two amino groups (-NH2) per molecule. In the amine compound (C), the hydrogen atoms of the amino groups may be substituted with organic groups such as alkyl groups or aryl groups. Furthermore, the monoamine compound (C1) and the diamine compound (C2) preferably do not contain silicon atoms.

[0051] By using the monoamine compound (C1) or the diamine compound (C2) in the curable composition, it is possible to suppress stickiness on the surface of a cured product of the curable composition, and to improve the antifouling properties.

[0052] Furthermore, the curable composition uses an amine compound (C) in combination with a surfactant having a polyoxyalkylene skeleton, which will be described later. If only the amine compound (C) is used, the cured product of the curable composition will have insufficient hydrophilicity and reduced antifouling properties, or the storage stability will be reduced, resulting in a problem that the antifouling properties of the cured product of the curable composition will be reduced when used after being stored for a long period of time after production. Furthermore, if only the surfactant having a polyoxyalkylene skeleton is used, the cured product of the curable composition will become sticky (tacky), resulting in a problem that the antifouling properties of the cured product will be reduced.

[0053] In the curable composition, by using the amine compound (C) in combination with a surfactant having a polyoxyalkylene skeleton, which will be described later, it is possible to suppress the occurrence of problems that occur when either of them is used alone, to impart excellent hydrophilicity to the cured product of the curable composition, to suppress the occurrence of stickiness, and to improve storage stability.

[0054] Therefore, the cured product of the curable composition has excellent storage stability, and can exhibit excellent antifouling properties even after the curable composition has been stored for a long period of time.

[0055] The monoamine compound (C1) is preferably a monoamine compound (C1) 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.

[0056] In formula (1), R 2 R is preferably a linear or branched alkyl group. 2 Examples of the linear or branched alkyl group in the formula (I) include a decyl group, an isodecyl group, an undecyl group, a lauryl group, an isododecyl group, a tridecyl group, a myristyl group, a pentadecyl group, a palmityl group, a heptadecyl group, an n-hexadecyl group, an isohexadecyl group, a stearyl group, an isooctadecyl group, a nonadecyl group, an eicosyl group, and a behenyl group, and preferably a lauryl group, an isododecyl group, a tridecyl group, a myristyl group, a pentadecyl group, a palmityl group, a heptadecyl group, an n-hexadecyl group, an isohexadecyl group, a stearyl group, an isooctadecyl group, a nonadecyl group, an eicosyl group, and a behenyl group.

[0057] In the monoamine compound (C1) represented by formula (1), R 2 The number of carbon atoms in R is preferably 12 to 40, more preferably 15 to 30, and particularly preferably 15 to 25. 2 By using the monoamine compound (C1) having the number of carbon atoms in the above range, the tackiness of the surface of the cured product of the curable composition can be reduced in a short period of time, and the cured product of the curable composition can exhibit excellent antifouling effect over a long period of time.

[0058] As the monoamine compound (C1), laurylamine (C 12 H 25-NH2, melting point 28℃), stearylamine (C 18 H 37 -NH2, melting point 50°C), myristylamine (melting point 38°C), and cetylamine (n-hexadecylamine, C 16 H 33 -NH2, melting point 47°C) is preferred. The monoamine compound (C1) may be used alone or in combination of two or more kinds.

[0059] The diamine compound (C2) is preferably a diamine compound (C2) 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, a monovalent unsaturated aliphatic hydrocarbon group, a monovalent saturated alicyclic hydrocarbon group, or an aryl group, and R 4 is an alkylene group.

[0060] In equation (2), R 3 R is preferably a linear or branched alkyl group or a monovalent unsaturated aliphatic hydrocarbon group. 3 Examples of the linear or branched alkyl group in R include a decyl group, an isodecyl group, an undecyl group, a lauryl group, an isododecyl group, a tridecyl group, a myristyl group, a pentadecyl group, a palmityl group, a heptadecyl group, an isohexadecyl group, a stearyl group, an isooctadecyl group, a nonadecyl group, an eicosyl group, and a behenyl group. 3 Examples of the monovalent unsaturated aliphatic hydrocarbon group in include an undecenyl group, a cis-4-tetradecenyl group, a cis-5-tetradecenyl group, a cis-9-tetradecenyl group, a cis-6-hexadecenyl group, a palmitoleyl group, a cis-6-octadecenyl group, an oleyl group, a trans-9-octadecenyl group, a cis-11-octadecenyl group, a trans-11-octadecenyl group, a myristoleyl group, a palmitoleyl group, and a linoleyl group.

[0061] In equation (2), R 4is an alkylene group. 4 Examples of the alkylene group 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.

[0062] In the diamine compound (C2) represented by formula (2), R 3 and R 4 The total number of carbon atoms in R is preferably 15 to 40, more preferably 15 to 30, and particularly preferably 15 to 25. 3 and R 4 By setting the total number of carbon atoms 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 occurrence of tack on the surface of the cured product of the curable composition at high temperatures can be reduced.

[0063] Specific examples of the diamine compound (C2) represented by formula (2) include behenyl propylene diamine (C 22 H 45 -NH-C3H6-NH2, melting point 63°C), hardened tallow propylene diamine with a melting point of 40-45°C, tallow propylene diamine with a melting point of 25-34°C, and oleyl propylene diamine (C 18 H 35 -NH-C3H6-NH 2、 A melting point of 20° C. is exemplified, and hardened beef tallow propylene diamine having a melting point of 40 to 45° C. is preferred. The diamine compound (C2) may be used alone or in combination of two or more kinds.

[0064] In the present invention, the melting point of the diamine compound (C2) refers to the temperature measured by differential scanning calorimetry (DSC) in accordance with JIS K7121 (1987). Specifically, using a differential scanning calorimeter (e.g., a "DSC-60" manufactured by Shimadzu Corporation), the diamine compound (C2) is heated from 10°C to 150°C at a heating rate of 5°C / min, and the melting peak temperature of the DSC curve during this heating process is taken as the melting point of the diamine compound (C2). When there are multiple melting peaks, the temperature at the apex of the melting peak with the greatest endothermic heat is taken as the melting point.

[0065] Beef tallow propylene diamine is a diamine compound (C2) produced by a known method using beef tallow as the fatty acid. The beef tallow preferably contains saturated fatty acids such as myristic acid, palmitic acid, and stearic acid, and unsaturated fatty acids such as oleic acid and linoleic acid. Furthermore, hardened beef tallow propylene diamine is produced by a known method using hardened beef tallow as the fatty acid. Hardened beef tallow is obtained by hydrogenating at least a portion of the unsaturated double bonds of the unsaturated fatty acids contained in beef tallow.

[0066] The beef tallow propylene diamine and the hardened beef tallow propylene diamine are preferably those represented by the above formula (2), R 3 is a fatty acid residue, and R 4 is a diamine compound (C2) in which each of the groups is a propylene group. Here, the fatty acid residue refers to a group formed by removing a carboxy group (-COOH) from a fatty acid. Examples of the fatty acid residue include a myristyl group, a palmityl group, a stearyl group, an oleyl group, and a linoleyl group.

[0067] The content of the amine 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, per 100 parts by mass of the total of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) and the acrylic polymer (B). When the content of the amine compound (C) is 0.1 part by mass or more, the cured product surface of the curable composition can exhibit excellent antifouling effect over a long period of time, and the storage stability of the curable composition is improved, so that the cured product exhibits excellent antifouling properties even after long-term storage. Furthermore, when the content of the amine compound (C) is 20 parts by mass or less, tack formation on the cured product surface of the curable composition at high temperatures can be reduced, resulting in excellent antifouling properties.

[0068] [Surfactant (D) having a polyoxyalkylene skeleton] The curable composition contains a surfactant (D) having a polyoxyalkylene skeleton. The surfactant (D) reduces the surface tension of the cured surface of the curable composition. When the curable composition contains the surfactant (D) having a polyoxyalkylene skeleton, in the cured product obtained by curing the curable composition after long-term storage, the surfactant (D) having a polyoxyalkylene skeleton easily migrates to the surface of the cured product, reducing the surface tension of the cured product surface and improving hydrophilicity, resulting in excellent antifouling properties of the cured product. It is preferable that the surfactant (D) having a polyoxyalkylene skeleton does not contain a hydrolyzable silyl group.

[0069] The polyoxyalkylene skeleton contained in the surfactant (D) having a polyoxyalkylene skeleton is represented by the general formula: -(R 6 -O)p-(wherein, R 6 represents an alkylene group, and p is the number of repeating units and is a positive integer. Preferred examples include polymers containing repeating units represented by the following formula: The polyoxyalkylene skeleton may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.

[0070] The surfactant (D) having a polyoxyalkylene skeleton is preferably a nonionic surfactant. When the surfactant (D) having a polyoxyalkylene skeleton is nonionic, the hydrophilicity of the surface of the cured product can be further improved, and the cured product has better antifouling properties.

[0071] The nonionic surfactant (D) having a polyoxyalkylene skeleton may be any surfactant as long as it has a polyoxyalkylene skeleton, and examples thereof include polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, etc. In the cured product obtained by curing the curable composition after long-term storage, the surfactant (D) having a polyoxyalkylene skeleton is more easily migrated to the surface of the cured product, which can further improve the hydrophilicity of the surface of the cured product, and the cured product has better antifouling properties, so polyoxyalkylene alkyl ethers are preferred, and polyoxyalkylene tridecyl ethers are preferred.

[0072] The surfactant (D) having a polyoxyalkylene skeleton has a structural formula represented by formula (3). R 5 -O-(R 6 -O) p -H (3) (In formula (3), R 5 is an alkyl group having 13 or more carbon atoms, and R 6 represents an alkylene group, and p is the number of repeating units and is a positive integer.

[0073] Polyoxyalkylene skeleton [-(R 6 -O) p -] R 6is an alkylene group, preferably an alkylene group having 1 to 14 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. When the number of carbon atoms is 14 or less, in a cured product obtained by curing the curable composition after long-term storage, the surfactant (D) having a polyoxyalkylene skeleton can be more easily migrated to the surface of the cured product, further improving the hydrophilicity of the surface of the cured product, and the cured product has better antifouling properties.

[0074] Polyoxyalkylene skeleton [-(R 6 -O) p Examples of the hydroxyl group include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer, and polypropylene oxide-polybutylene oxide copolymer, with polyethylene oxide and polypropylene oxide being preferred, and polyethylene oxide being more preferred. Polyethylene oxide and polypropylene oxide make it easier for the surfactant (D) having a polyoxyalkylene skeleton to migrate to the surface of the cured product obtained by curing the curable composition after long-term storage, further improving the hydrophilicity of the surface of the cured product, and the cured product has better antifouling properties.

[0075] R 5 is an alkyl group having 13 or more carbon atoms. 5 When the alkyl group (D) is an alkyl group having 13 or more carbon atoms, in the cured product obtained by curing the curable composition after long-term storage, the surfactant (D) having a polyoxyalkylene skeleton can be more easily migrated to the surface of the cured product, the hydrophilicity of the surface of the cured product can be further improved, and the cured product has better antifouling properties.

[0076] R 5 is preferably an alkyl group having 20 or less carbon atoms. When the number of carbon atoms is 20 or less, the hydrophilicity of the cured product of the curable composition is improved, and the antifouling properties of the cured product are improved, which is preferable.

[0077] R 5 The alkyl group is not particularly limited, and examples thereof include a tridecyl group (number of carbon atoms: 13), a myristyl group (number of carbon atoms: 14), a cetyl group (number of carbon atoms: 16), and a stearyl group (number of carbon atoms: 18), with a tridecyl group being more preferred.

[0078] Examples of the surfactant (D) having a polyoxyalkylene skeleton having the structural formula represented by formula (3) include polyoxyethylene tridecyl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene myristyl ether. Polyoxyethylene tridecyl ether is preferred because it facilitates migration of the surfactant (D) having a polyoxyalkylene skeleton to the surface of the cured product obtained by curing the curable composition after long-term storage, further improving the hydrophilicity of the surface of the cured product, and giving the cured product better antifouling properties.

[0079] The HLB of the surfactant (D) having a polyoxyalkylene skeleton is preferably 8 or more, more preferably 8.5 or more, more preferably 9 or more, and more preferably 10 or more. The HLB of the surfactant (D) having a polyoxyalkylene skeleton is preferably 18 or less, more preferably 16 or less, more preferably 15 or less, and more preferably 14 or less. When the HLB of the surfactant (D) having a polyoxyalkylene skeleton is within the above range, in a cured product obtained by curing the curable composition after long-term storage, the surfactant (D) having a polyoxyalkylene skeleton can be more easily migrated to the surface of the cured product, further improving the hydrophilicity of the surface of the cured product, and the cured product has better antifouling properties.

[0080] HLB is a value representing the balance between hydrophobic groups and hydrophilic groups, and is expressed as a value from 0 to 20. A higher HLB value indicates a higher proportion of hydrophilic groups. HLB refers to the HLB value at 25°C, and is defined in J. Soc. Cosm. Chem., 1954, 5:249-256, and can be calculated by the Griffin method described below. HLB = 20 x molecular weight of hydrophilic group / molecular weight of surfactant

[0081] In the curable composition, the content of the surfactant (D) having a polyoxyalkylene skeleton is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, more preferably 2 parts by mass or more, more preferably 4 parts by mass or more, more preferably 10 parts by mass or more, more preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and more preferably 23 parts by mass or more, based on 100 parts by mass of the total amount of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group and the acrylic polymer (B). When the content of the surfactant (D) having a polyoxyalkylene skeleton is 0.1 parts by mass or more, in a cured product obtained by curing the curable composition after long-term storage, the surfactant (D) having a polyoxyalkylene skeleton can be more easily migrated to the surface of the cured product, further improving the hydrophilicity of the cured product surface, and the cured product has better antifouling properties.

[0082] In the curable composition, the content of the surfactant (D) having a polyoxyalkylene skeleton is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, more preferably 40 parts by mass or less, more preferably 37 parts by mass or less, more preferably 34 parts by mass or less, and more preferably 30 parts by mass or less, relative to 100 parts by mass of the total amount of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group and the acrylic polymer (B). When the content of the surfactant (D) having a polyoxyalkylene skeleton is 50 parts by mass or less, the stain resistance of the cured product obtained by curing the curable composition is improved.

[0083] [Plasticizer (E)] The curable composition preferably contains a plasticizer (E). When the curable composition contains the plasticizer (E), the plastic flexibility of the cured product of the curable composition can be improved. The plasticizer does not have the effect of reducing the surface tension of the cured product of the curable composition. Specific examples of the plasticizer include phthalate esters such as dioctyl phthalate, dibutyl phthalate, and butyl benzyl phthalate, polyalkylene glycols such as polypropylene glycol and polyethylene glycol, and acrylic polymers. The plasticizer preferably contains an acrylic polymer or a polyalkylene glycol, and more preferably contains an acrylic polymer.

[0084] When the plasticizer (E) contains polyalkylene glycols, the content of the polyalkylene glycols in the plasticizer (E) is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, and more preferably 100% by mass.

[0085] When the plasticizer (E) contains an acrylic polymer, the content of the acrylic polymer in the plasticizer (E) is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, and more preferably 100% by mass.

[0086] When the plasticizer is a polymer, the weight-average molecular weight of the plasticizer is preferably at least 1,000, more preferably at least 2,000. When the weight-average molecular weight of the plasticizer is at least 1,000, the cured product of the curable composition exhibits excellent rubber elasticity.

[0087] When the plasticizer is a polymer, the weight-average molecular weight of the plasticizer is preferably not more than 10,000, more preferably not more than 8,000. When the weight-average molecular weight of the plasticizer is not more than 10,000, in a cured product obtained by curing the curable composition after long-term storage, the plasticizer (E) can be more easily migrated to the surface of the cured product, the hydrophilicity of the surface of the cured product can be further improved, and the cured product has better antifouling properties.

[0088] When the plasticizer (E) is a polymer, the weight-average molecular weight of the plasticizer (E) refers to a value measured by gel permeation chromatography (GPC) in terms of polystyrene. In the GPC measurement, for example, a Shodex KF800D manufactured by Tosoh Corporation can be used as a GPC column, and chloroform or the like can be used as a solvent.

[0089] The acrylic polymer preferably contains an acrylic polymer (E1) having a polyoxyalkylene chain in the side chain and / or an acrylic polymer (E2) having no polyoxyalkylene chain in the molecule, and more preferably contains an acrylic polymer (E1) having a polyoxyalkylene chain in the side chain and an acrylic polymer having no polyoxyalkylene chain in the molecule. The acrylic polymer (E1) having a polyoxyalkylene chain in the side chain may be simply referred to as "acrylic polymer (W1)".

[0090] When the plasticizer (E) contains an acrylic polymer (E1) having a polyoxyalkylene chain in its side chain, the cured product of the curable composition can exhibit an excellent antifouling effect for a longer period of time, and further, the cured product of the curable composition can maintain excellent rubber elasticity for a longer period of time.

[0091] In the acrylic polymer (E1), a polyoxyalkylene chain is bonded as a side chain to the acrylic polymer main chain, and the polyoxyalkylene chain can improve the hydrophilicity of the acrylic polymer (E1).

[0092] The main chain of the acrylic polymer (E1) is preferably a polymer of a monomer containing alkyl (meth)acrylate. Examples of alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, and lauryl (meth)methacrylate. These alkyl (meth)acrylates may be used alone or in combination of two or more.

[0093] The polyoxyalkylene chain that the acrylic polymer (E1) has in its side chain is a group represented by the general formula: -(R 8 -O)q-(wherein, R 8 represents an alkylene group having 1 to 14 carbon atoms, and q is the number of repeating units and is a positive integer.) The polyoxyalkylene chain may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.

[0094] Examples of the polyoxyalkylene chain include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer, and polypropylene oxide-polybutylene oxide copolymer, and examples thereof include a polymethylene oxide chain, a polyethylene oxide chain, a polypropylene oxide chain, and a polybutylene oxide chain, with a polyethylene oxide chain being preferred.

[0095] The weight-average molecular weight of the acrylic polymer (E1) is preferably at least 1,000, more preferably at least 2,000. When the weight-average molecular weight of the acrylic polymer (E1) is at least 1,000, the cured product of the curable composition will have excellent rubber elasticity.

[0096] The weight-average molecular weight of the acrylic polymer (E1) is preferably not more than 10,000, more preferably not more than 8,000. When the weight-average molecular weight of the acrylic polymer (E1) is not more than 10,000, in a cured product obtained by curing the curable composition after long-term storage, the acrylic polymer (E1) can be more easily migrated to the surface of the cured product, the hydrophilicity of the surface of the cured product can be further improved, and the cured product has better antifouling properties.

[0097] In the present invention, the weight average molecular weight of the acrylic polymer (E1) refers to a value measured by gel permeation chromatography (GPC) in terms of polystyrene. In the measurement by GPC, for example, a Shodex KF800D manufactured by Tosoh Corporation is used as a GPC column, and chloroform or the like can be used as a solvent.

[0098] The acrylic polymer (E1) may further have a hydrolyzable silyl group.

[0099] As the hydrolyzable silyl group, an alkoxysilyl group is preferred because the cured product of the curable composition can maintain excellent rubber elasticity for a long period of time. 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, dialkoxysilyl groups are preferred, dimethoxysilyl groups are more preferred, and methyldimethoxysilyl groups are more preferred.

[0100] Preferred examples of the acrylic polymer (E1) include an acrylic polymer (E11) that does not have a hydrolyzable silyl group and has a polyoxyalkylene chain in the side chain, and an acrylic polymer (E12) that has a hydrolyzable silyl group and has a polyoxyalkylene chain in the side chain.

[0101] As the acrylic polymer (E1), either the acrylic polymer (E11) or the acrylic polymer (E12) may be used alone, but both are preferably used. That is, the acrylic polymer (E1) preferably contains both the acrylic polymer (E11) and the acrylic polymer (E12). Such an acrylic polymer (E1) allows the cured product of the curable composition to exhibit excellent antifouling effects for a longer period of time. The mechanism by which this effect is achieved is unknown, but the present inventors speculate that the acrylic polymer (E1) can be gradually migrated to the surface of the cured product of the curable composition, thereby allowing the surface of the cured product of the curable composition to maintain high hydrophilicity for a longer period of time. Furthermore, the acrylic polymer (E1) also allows the cured product of the curable composition to exhibit excellent rubber elasticity for a longer period of time.

[0102] The acrylic polymer (E11) is an acrylic polymer that does not have a hydrolyzable silyl group and has a polyoxyalkylene chain in the side chain.

[0103] The acrylic polymer (E12) is an acrylic polymer having a hydrolyzable silyl group and a polyoxyalkylene chain in the side chain.

[0104] The hydrolyzable silyl group of the acrylic polymer (E12) is preferably an alkoxysilyl group, since the cured product of the curable composition can maintain excellent rubber elasticity for a long period of time. Examples of the alkoxysilyl group include trialkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, and triphenoxysilyl; dimethoxysilyl groups such as methyldimethoxysilyl and methyldiethoxysilyl; and monoalkoxysilyl groups such as dimethylmethoxysilyl and dimethylethoxysilyl. Of these, dialkoxysilyl groups are more preferred, and methyldimethoxysilyl groups are particularly preferred.

[0105] When the acrylic polymer (E1) contains both the acrylic polymer (E11) and the acrylic polymer (E12), the acrylic polymer (E1) preferably has an average of 0.1 to less than 1.0 hydrolyzable silyl groups per molecule, more preferably 0.12 to 0.7, and particularly preferably 0.13 to 0.4. When the average number of hydrolyzable silyl groups in the acrylic polymer (E1) is 0.1 or more, the cured product of the curable composition can have excellent rubber elasticity. When the number of hydrolyzable silyl groups in the acrylic polymer (E1) is less than 1.0, the surface of the cured product of the curable composition can maintain high hydrophilicity for a longer period of time.

[0106] The average number of hydrolyzable silyl groups per molecule in the acrylic polymer (E1) is 1 It can be calculated based on the concentration of hydrolyzable silyl groups in the acrylic polymer (E1) determined by H-NMR and the number average molecular weight of the acrylic polymer (E1) determined by GPC.

[0107] The polymerization method for the acrylic polymer (E1) is not particularly limited, and any known method can be used, including various polymerization methods such as free radical polymerization, anionic polymerization, cationic polymerization, UV radical polymerization, living anionic polymerization, living cationic polymerization, and living radical polymerization.

[0108] The method for introducing a polyoxyalkylene chain into the acrylic polymer (E1) as a side chain is not particularly limited, and can be carried out using a known method such as graft polymerization.

[0109] The method for introducing a hydrolyzable silyl group into the acrylic polymer (E1) is not particularly limited, and any known method can be used, such as a method in which a hydrosilane having a hydrolyzable silyl group is allowed to react with an acrylic polymer having an unsaturated group introduced into the molecule to hydrosilylate the polymer.

[0110] The content of the acrylic polymer (E1) in the curable composition is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, more preferably 12 parts by mass or more, and still more preferably 13 parts by mass or more, relative to 100 parts by mass of the total amount of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) and the acrylic polymer (B). When the content of the acrylic polymer (E1) is 5 parts by mass or more, the cured product of the curable composition can maintain an excellent antifouling effect for a long period of time.

[0111] The content of the acrylic polymer (E1) in the curable composition is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, more preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and still more preferably 20 parts by mass or less, relative to 100 parts by mass of the total amount of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) and the acrylic polymer (B). When the content of the acrylic polymer (E1) is 50 parts by mass or less, excellent rubber elasticity can be ensured in the cured product of the curable composition.

[0112] Next, the acrylic polymer (E2) having no polyoxyalkylene chain in the molecule will be described. The acrylic polymer (E2) having no polyoxyalkylene chain in the molecule may be simply referred to as "acrylic polymer (E2)".

[0113] The acrylic polymer (E2) preferably does not have a hydrolyzable silyl group in the molecule. Note that the hydrolyzable silyl group and the polyoxyalkylene chain are the same as those described for the acrylic polymer (B), and therefore further description is omitted.

[0114] The main chain skeleton of the acrylic polymer (E2) may be an acrylic polymer obtained by radical polymerization of a (meth)acrylate monomer.

[0115] Specific examples of the (meth)acrylate monomer constituting the main chain of the acrylic polymer (E2) 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, and isomyristyl (meth)acrylate. 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, trime Examples of the acrylates include tyrolpropane 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.

[0116] The weight-average molecular weight of the acrylic polymer (E2) is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, more preferably 2,500 to 10,000, more preferably 2,600 to 5,000, and more preferably 3,000 to 4,000. When the weight-average molecular weight of the acrylic polymer (E2) 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 (E2) is 1,000 or more, the rubber elasticity of the cured product of the curable composition is improved.

[0117] In the present invention, the weight average molecular weight of the acrylic polymer (E2) refers to a value measured by gel permeation chromatography (GPC) in terms of polystyrene. In the measurement by GPC, for example, a Tosoh Shodex KF800D GPC column and chloroform or the like can be used as a solvent.

[0118] The content of the acrylic polymer (E2) in the curable composition is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, more preferably 1 to 70 parts by mass, and particularly preferably 20 to 50 parts by mass, relative to 100 parts by mass of the total amount of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group and the acrylic polymer (B). When the content of the plasticizer is 100 parts by mass or less, the stain resistance of the cured product obtained by curing the curable composition is improved.

[0119] In the curable composition, the total content of the plasticizer (E) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, more preferably 12 parts by mass or more, and more preferably 15 parts by mass or more, per 100 parts by mass of the total amount of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) and the acrylic polymer (B). When the content of the plasticizer is 1 part by mass or more, the cured product of the curable composition can maintain an excellent antifouling effect for a long period of time.

[0120] In the curable composition, the total content of the plasticizer (E) is preferably 150 parts by mass or less, more preferably 130 parts by mass or less, more preferably 100 parts by mass or less, more preferably 70 parts by mass or less, and more preferably 50 parts by mass or less, relative to 100 parts by mass of the total amount of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) and the acrylic polymer (B). When the content of the plasticizer is 150 parts by mass or less, excellent rubber elasticity can be ensured in the cured product of the curable composition.

[0121] [Filler] The curable composition preferably further contains a filler. When the curable composition contains a filler in the resin blend of the polyoxyalkylene polymer (A) and the acrylic polymer (B), the hardness of the cured product of the curable composition is improved, making it less susceptible to stains, and the cured product of the curable composition can maintain excellent stain resistance for a long period of time.

[0122] Examples of fillers include calcium carbonate, magnesium carbonate, calcium oxide, hydrous silicic acid, anhydrous silicic acid, finely powdered 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 these, calcium carbonate is preferred, and colloidal calcium carbonate and heavy calcium carbonate are more preferred.

[0123] The average particle size of the primary particles of calcium carbonate is preferably 0.01 to 5 μm, more preferably 0.05 to 2.5 μm. Calcium carbonate having such an average particle size can provide a cured product with excellent rubber elasticity and a curable composition with excellent adhesive properties. The average particle size of the primary particles of calcium carbonate refers to the particle size D50 at which the cumulative frequency of particles with smaller particle sizes in a volume-based particle size distribution measured by laser diffraction is 50% by mass.

[0124] The calcium carbonate is preferably surface-treated with a fatty acid, a fatty acid ester, etc. Calcium carbonate surface-treated with a fatty acid, a fatty acid ester, etc. can impart thixotropy to the curable composition and inhibit aggregation of calcium carbonate, and by improving the hydrophobicity of calcium carbonate, the surfactant (D) having a polyoxyalkylene skeleton can be more smoothly transferred to the surface of a cured product of the curable composition, improving the hydrophilicity of the surface of the cured product and improving the antifouling properties of the cured product.

[0125] 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, per 100 parts by mass of the total of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) and the acrylic polymer (B). When the content of the filler is 1 part by mass or more, the effect of adding the filler is sufficiently obtained. Furthermore, when the content of the filler is 700 parts by mass or less, the cured product obtained by curing the curable composition has excellent rubber elasticity.

[0126] [Dehydrating agent] The curable composition preferably further contains a dehydrating agent, which can prevent the curable composition from being cured by moisture contained in the air or the like during storage.

[0127] Examples of dehydrating agents 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. Among them, vinyltrimethoxysilane is preferred.

[0128] 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 total amount of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) and the acrylic polymer (B). 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. On the other hand, when the content of the dehydrating agent is 20 parts by mass or less, the curable composition has excellent curability.

[0129] [Silanol condensation catalyst] The curable composition preferably contains a silanol condensation catalyst, which is a catalyst for promoting a dehydration condensation reaction between silanol groups formed by hydrolysis of a hydrolyzable silyl group contained in a polyoxyalkylene polymer having a hydrolyzable silyl group.

[0130] Examples of silanol condensation catalysts include organic tin compounds such as 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis(dibutyltin laurate) oxide, dibutyltin bis(acetylacetonate), dibutyltin bis(monoester maleate), tin octoate, dibutyltin octoate, dioctyltin oxide, dibutyltin bis(triethoxysilicate), bis(dibutyltin bistriethoxysilicate) oxide, and dibutyltin oxybisethoxysilicate; and organic titanium compounds such as tetra-n-butoxytitanate and tetraisopropoxytitanate. These silanol condensation catalysts may be used alone or in combination of two or more.

[0131] The silanol condensation catalyst is preferably 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, which makes it possible to easily adjust the curing rate of the curable composition.

[0132] 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, per 100 parts by mass of the total amount of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) and the acrylic polymer (B). 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, thereby shortening the time required for curing the curable composition. 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.

[0133] [Other additives] The curable composition may contain other additives such as a thixotropic agent, an antioxidant, an ultraviolet absorber, a pigment, a dye, an anti-settling agent, and a solvent. Among these, the thixotropic agent, the ultraviolet absorber, and the antioxidant are preferred.

[0134] [Thixotropic agent] The thixotropy-imparting agent may be any agent capable of imparting thixotropy to the curable composition, and preferred examples of the thixotropy-imparting agent include hydrogenated castor oil, fatty acid bisamide, and fumed silica.

[0135] 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, per 100 parts by mass of the total amount of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) and the acrylic polymer (B). 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. When the content of the thixotropy-imparting agent is 200 parts by mass or less, the curable composition has an appropriate viscosity, improving the handleability of the curable composition.

[0136] [UV absorber] Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber, and the benzotriazole-based ultraviolet absorber is 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, per 100 parts by mass of the total amount of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group and the acrylic polymer (B).

[0137] [Antioxidants] Examples of the antioxidant include hindered phenol antioxidants, monophenol antioxidants, bisphenol antioxidants, and polyphenol antioxidants, and the hindered phenol antioxidants are preferred. 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, per 100 parts by mass of the total amount of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group and the acrylic polymer (B).

[0138] [Light stabilizer] The curable composition preferably contains a hindered amine light stabilizer, which can provide a curable composition that can maintain excellent rubber elasticity for a longer period of time after curing.

[0139] Examples of hindered amine light stabilizers 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-piperidyl-1,6-hexamethylenediamine) and N-(2,2,6,6 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}], and a polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol.

[0140] Preferred examples of the hindered amine light stabilizer include NOR-type hindered amine light stabilizers, which can provide a curable composition that is inhibited from decreasing in rubber elasticity over time after curing.

[0141] The NOR hindered amine light stabilizer has a NOR structure in which an alkyl group (R) is bonded to a nitrogen atom (N) contained in a piperidine ring skeleton via an oxygen atom (O). The number of carbon atoms in 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 (a saturated alicyclic hydrocarbon group).

[0142] Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, and n-decyl groups. Examples of branched alkyl groups include isopropyl, isobutyl, sec-butyl, and tert-butyl groups. Examples of cyclic alkyl groups (saturated alicyclic hydrocarbon groups) include cyclopentyl, cyclohexyl, and cyclooctyl groups. In addition, the hydrogen atoms constituting the alkyl groups may be substituted with halogen atoms (e.g., fluorine, chlorine, and bromine atoms) or hydroxyl groups.

[0143] Examples of the NOR type hindered amine light stabilizer include hindered amine light stabilizers represented by the following formula (4).

[0144] [ka]

[0145] When a NOR type hindered amine light stabilizer is used, it is preferable to use the NOR type hindered amine light stabilizer in combination with a benzotriazole type ultraviolet absorber or a triazine type ultraviolet absorber, which can provide a curable composition in which the decrease in rubber elasticity over time after curing is more significantly suppressed.

[0146] 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, relative to 100 parts by mass of the total amount of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group and the acrylic polymer (B).

[0147] [Aminosilane coupling agent] The curable composition 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 to which an alkoxy group is bonded and a functional group containing a nitrogen atom in one molecule.

[0148] Specific examples of aminosilane coupling agents 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, and N,N'-bis-[3-(triethoxysilyl)propyl]hexamethylenediamine. These aminosilane coupling agents may be used alone or in combination of two or more.

[0149] Among these, preferred examples of the aminosilane coupling agent include 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltriethoxysilane, and more preferred example is N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

[0150] 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, per 100 parts by mass of the total of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A) and the acrylic polymer (B). 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.

[0151] The curable composition can be produced by uniformly mixing the polyoxyalkylene polymer (A) having a hydrolyzable silyl group, the acrylic polymer (B), the amine compound (C), the surfactant having a polyoxyalkylene skeleton, and additives added as needed, using a general-purpose means under a vacuum atmosphere.

[0152] The curable composition has excellent adhesive properties and can form a cured product that can maintain excellent rubber elasticity for a long period of time, and therefore can be used in a variety of applications such as sealants, coating materials, adhesives, and paints.

[0153] In particular, the cured product obtained by curing the curable composition with moisture has excellent stain resistance. Therefore, even when used outdoors, the curable composition can maintain a beautiful appearance for a long period of time. Therefore, the curable composition is preferably used as a sealant or adhesive, and more preferably as a sealant for joint structures.

[0154] Furthermore, the curable composition may be stored for a long period of time after production. Even when the curable composition is used after being stored for a long period of time, the cured product obtained by curing the curable composition exhibits excellent antifouling properties.

[0155] A method of applying a curable composition to a joint portion to obtain a joint structure involves filling the joint portion with the curable composition and then curing the composition to harden it. The resulting joint structure comprises wall members that constitute the walls of an architectural structure and a cured product of the curable composition that has been filled into the joint portion formed between adjacent wall members. Examples of the wall portion of an architectural structure include exterior walls, interior walls, and ceiling portions, with exterior walls being preferred. Examples of wall members include exterior wall members, interior wall members, and ceiling members, with exterior wall members being preferred.

[0156] The joints are not particularly limited, and examples thereof include joints in the exterior walls, interior walls, and ceilings of building structures. The curable composition of the present invention can maintain an excellent antifouling effect for a long period of time after curing. Therefore, it is suitable for sealing so-called "working joints," such as joints in the exterior walls of building structures, which are easily soiled by dust and pollutants.

[0157] Examples of joints in the exterior walls of building structures include joints that occur at the joints between exterior wall components such as mortar boards, concrete boards, ceramic siding boards, metal siding boards, ALC boards, and metal plates. [Effects of the Invention]

[0158] The curable composition of the present invention has the above-described structure and can therefore exhibit excellent antifouling effect for a long period of time, and the cured product of the curable composition can therefore maintain a beautiful appearance for a long period of time.

[0159] Furthermore, even when the curable composition of the present invention is used after being stored for a long period of time after production, the cured product obtained by curing the curable composition exhibits excellent antifouling properties. DETAILED DESCRIPTION OF THE INVENTION

[0160] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. [Example]

[0161] The following raw materials were used in producing the curable compositions of the Examples and Comparative Examples. [Polyoxyalkylene polymer (A) having hydrolyzable silyl groups] Polyoxyalkylene polymer (A) having a hydrolyzable silyl group (a polyoxyalkylene having a methyldimethoxysilyl group and a main chain skeleton of polypropylene oxide (linear), manufactured by AGC Inc., trade name "Excestar S2420", average number of methyldimethoxysilyl groups per molecule: 1.7, molecular weight distribution: 1.49, number average molecular weight: 18,990, weight average molecular weight: 28,295)

[0162] [Acrylic polymer (B) having hydrolyzable silyl groups] Acrylic polymer (B) (an acrylic polymer containing an acrylic polymer having dimethoxysilyl groups at both ends of the main chain skeleton (having no polyoxyalkylene chains in the molecule) and an acrylic polymer having a dimethoxysilyl group at only one end of the main chain skeleton (having no polyoxyalkylene chains in the molecule), manufactured by Kaneka Corporation, product name "SA310S", number average molecular weight: 28,000, weight average molecular weight: 24,000, average number of dimethoxymethylsilyl groups per molecule: 1.7)

[0163] [Amine compound (C)] Monoamine compound (C1) (stearylamine, melting point 50°C, Kao Corporation, trade name "Furmin 80S") Diamine compound (C2) (hardened beef tallow propylene diamine, melting point 43°C, NOF Corporation, product name "Nissanamine DT-H") Note that hydrogenated beef tallow propylene diamine (manufactured by NOF Corporation under the trade name "Nissanamine DT-H") is a compound represented by the above formula (2) (wherein R 3 is a linear alkyl group having 13 to 18 carbon atoms, and R 4 is a propylene group) and has a melting point of 55 to 80°C, and 3 is an unsaturated aliphatic hydrocarbon group having 15 to 18 carbon atoms, and R 4 The copolymer contained 45 to 53 mass % of a diamine compound having a melting point of 28°C or lower and a structure represented by the formula (wherein each represents a propylene group).

[0164] [Surfactant (D) having a polyoxyalkylene skeleton] Polyoxyethylene tridecyl ether 1(C 13 H 27 -O-(CH2CH2O) p -H, Nippon Nyukazai Co., Ltd., product name "New Coal 1305", HLB: 10.5) Polyoxyethylene tridecyl ether 2(C 13 H 27 -O-(CH2CH2O) p -H, Nippon Nyukazai Co., Ltd., product name "Newcoal 1310", HLB: 13.7) Polyoxyethylene octyl ether (C8H 17 -O-(CH2CH2O) p -H, Nippon Nyukazai Co., Ltd., product name "New Coal 1008", HLB: 14.6) Polyoxyethylene decyl ether (C 10 H 19 -O-(CH2CH2O) p -H, Daiichi Kogyo Seiyaku Co., Ltd., product name "Noigen XL-50", HLB: 11.6) Polyoxyethylene lauryl ether (C 12 H 19 -O-(CH2CH2O) p -H, Daiichi Kogyo Seiyaku Co., Ltd. product name "Noigen LP-70", HLB: 12.0)

[0165] [Plasticizer (E)] Acrylic polymer (E1) (an acrylic polymer comprising an acrylic polymer (E11) having no hydrolyzable silyl groups and having polyoxyethylene chains in the side chains, and an acrylic polymer (E12) having methyldimethoxysilyl groups as hydrolyzable silyl groups and having polyoxyethylene chains in the side chains; weight-average molecular weight of the acrylic polymer: 7,000; viscosity (25°C) of the acrylic polymer: 800 mPa s; average number of hydrolyzable silyl groups per acrylic polymer molecule: 0.3) Acrylic polymer (E2) (acrylic polymer that does not have a hydrolyzable silyl group or polyoxyalkylene chain in the molecule, weight-average molecular weight: 3,500, manufactured by Toagosei Co., Ltd., product name "UP-1110") Polypropylene glycol (E3) (AGC Corporation, trade name "Exenol 3020", weight average molecular weight: 3,000, number average molecular weight: 3,000, no surfactant effect)

[0166] [Filler] Colloidal calcium carbonate (average primary particle size: 80 nm, surface treatment with fatty acid, manufactured by Maruo Calcium Co., Ltd., product name "Calcine 200M") Heavy calcium carbonate 1 (average primary particle size: 1.0 μm, surface treatment with fatty acid, manufactured by Nitto Funka Co., Ltd., product name "NCC2310") Heavy calcium carbonate 2 (average primary particle size: 5 μm, Toyo Fine Chemical Co., Ltd., product name "Whiten P-30", no surface treatment)

[0167] [Dehydrating agent] Vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-1003")

[0168] [Silanol condensation catalyst] Silanol condensation catalyst (1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, manufactured by Nitto Kasei Co., Ltd., product name "Neostan U-130")

[0169] [UV absorber] Benzotriazole-based UV absorber (product name "Tinuvin 326" manufactured by BASF Japan Ltd.)

[0170] [Antioxidants] Hindered phenol antioxidant (BASF Japan, product name "Irganox 1010")

[0171] [Light stabilizer] NH-type hindered amine light stabilizer (product name "Tinuvin 770" manufactured by BASF Japan Ltd.)

[0172] Aminosilane coupling agent (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, product name "KBM-603" manufactured by Shin-Etsu Chemical Co., Ltd.) Thixotropic agent (fatty acid amide wax, manufactured by Kusumoto Chemicals Co., Ltd., product name "Disparlon #6500") )

[0173] [solvent] Ethylene glycol tertiary butyl ether (ETB)

[0174] (Examples 1 to 12, Comparative Examples 1 to 7) The above-mentioned polyoxyalkylene polymer (A) having hydrolyzable silyl groups, acrylic polymer (B), monoamine compound (C1), diamine compound (C2), surfactant (D) having a polyoxyalkylene skeleton, plasticizer (E), filler, dehydrating agent, silanol condensation catalyst, benzotriazole UV absorber, hindered phenol antioxidant, NH-type hindered amine light stabilizer, aminosilane coupling agent, thixotropic agent, and ethylene glycol tertiary butyl ether (ETB) were mixed in the amounts shown in Table 1 in a sealed mixer under reduced pressure until uniform, to obtain a curable composition. In Table 1, "polyoxyalkylene polymer (A) having hydrolyzable silyl groups" is simply referred to as "polyoxyalkylene polymer (A)."

[0175] Immediately after production, the curable compositions were measured for water contact angle, red clay adhesion, and volume change rate after immersion in water in the following manner. The results are shown in the "Immediately after production" column in Table 1.

[0176] For the curable compositions stored in an atmosphere at 23°C for 6 months from the date of production (long-term storage), the water contact angle and red clay adhesion were measured in the following manner, and the results are shown in the "After long-term storage" column in Table 1.

[0177] (Water contact angle) The curable composition was cured for 14 days at 23°C and 50% relative humidity to obtain a cured product. The contact angle θ of water on the cured product surface was measured using the sessile drop method in accordance with JIS R3257 (1999) "Test Methods for Wettability of Substrate Glass Surfaces." The drop volume was 4 μL of distilled water, and the contact angle was measured 2 minutes after drop. The contact angle was calculated using the θ / 2 method. The water contact angle was measured at 10 random locations on the cured curable composition surface, and the arithmetic mean of all the measured contact angles was used as the water contact angle (W) on the cured curable composition surface. The contact angle was measured in an atmosphere at 23°C and 50% relative humidity. A commercially available solid-liquid interface analyzer, "DMs-401," from Kyowa Interface Science Co., Ltd., was used. The contact angle was calculated using the software "FAMAS" that comes with a solid-liquid interface analyzer commercially available under the product name "DMs-401" from Kyowa Interface Science Co., Ltd. The water contact angle (W1) on the surface of the obtained cured product was evaluated based on the following criteria. ◎ The water contact angle (W1) was less than 30°. ○: The water contact angle (W1) was 30° or more and less than 40°. △: The water contact angle (W1) was 40° or more and less than 50°. × The water contact angle (W1) exceeded 50°.

[0178] (red soil adhesion) The curable composition was applied to a stainless steel plate to a thickness of 5 mm in an atmosphere of 23°C and 50% relative humidity, and cured for 14 days to obtain a cured product. Red clay was sprinkled on the surface of the cured curable composition. The color difference (ΔE) of the red clay surface was measured using a colorimeter and evaluated based on the following criteria. The smaller the color difference, the less red clay adhered. ○ ΔE was less than 10. △··ΔE was 10 or more and less than 13. × ΔE was 13 or more.

[0179] (Volume change rate after immersion in water) The curable composition was applied to a polypropylene film in a 5 cm square shape with a thickness of 5 mm under an atmosphere of 23°C and 50% relative humidity. The coating was cured for 28 days, and then cured at 70°C for 7 days to obtain a test specimen. The test specimen was then immersed in water at 23°C for 7 days. The volume change ΔV of the test specimen was calculated using the following formula. A volume change ΔV of less than 1% was evaluated as "Good," a volume change ΔV of 1% or more but less than 3% was evaluated as "Good," and a volume change ΔV of 3% or more was evaluated as "Poor." The smaller the volume change ΔV, the less moisture the test specimen absorbed and the better its water resistance. The cured product of the curable composition has excellent water-stopping properties and rubber elasticity, making it suitable for use as a sealant. ΔV={(m3-m4)-(m1-m2} / (m1-m2) m1: Mass of the test specimen measured in the air immediately after preparation (g) m2: Mass (g) of the specimen measured in pure water immediately after preparation m3: Mass (g) of the test specimen measured in air immediately after immersion in water for 7 days m4: Mass (g) of the test specimen measured in pure water immediately after immersion in water for 7 days

[0180] [Table 1]

Claims

1. A curable composition comprising: a polyoxyalkylene polymer (A) having a hydrolyzable silyl group; an acrylic polymer (B); an amine compound (C); and a surfactant having a polyoxyalkylene skeleton having a structural formula represented by formula (3): R 5 -O-(R 6 -O) ｐ -H (3) However, R 5 is an alkyl group having 13 or more carbon atoms, and R 6 represents an alkylene group, and p is the number of repeating units and is a positive integer.

2. 2. The curable composition according to claim 1, further comprising 0.1 to 50 parts by mass of a surfactant having a polyoxyalkylene skeleton per 100 parts by mass of the total amount of the polyoxyalkylene polymer (A) having a hydrolyzable silyl group and the acrylic polymer (B).

3. 2. The curable composition according to claim 1, wherein the amine compound (C) contains a monoamine compound (C1) or a diamine compound (C2).

4. The curable composition according to claim 3, wherein the monoamine compound (C1) has a structural formula represented by formula (1). R 2 -NH 2 (1) However, in formula (1), R 2 is a linear or branched alkyl group or a monovalent saturated alicyclic hydrocarbon group.

5. The curable composition according to claim 3, wherein the diamine compound (C2) has a structural formula represented by formula (2). R 3 -NH-R 4 -NH 2 (2) However, in formula (2), R 3 is a linear or branched alkyl group, a monovalent unsaturated aliphatic hydrocarbon group, a monovalent saturated alicyclic hydrocarbon group, or an aryl group, and R 4 is an alkylene group.

6. The curable composition according to any one of claims 1 to 5, further comprising a plasticizer.

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