JP5280646B2 - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition suitable as a building sealing material or the like continuously exhibiting excellent stain preventability and self-purification action after curing. <P>SOLUTION: The curable composition comprises: (A) a vinyl based polymer having a reactive silicon group; (B) a fluorine-containing nonionic surfactant; and (C) an amine compound. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a curable composition suitable as a sealing material for buildings having excellent antifouling properties and self-cleaning action.

  Curable compositions based on various polymer materials are known in the art, and these are used as a sealing material for a wide variety of applications such as civil engineering, construction or electrical machinery. For example, a curable composition based on a modified silicone polymer is widely used as a sealing material for buildings, such as an exposed joint of an outer wall.

  Modified silicone sealants are superior to other polymer-based sealants in terms of weather resistance, etc., but due to residual tack (stickiness) on the surface, dirt and other dirt can adhere, especially for long periods of time. There is a problem that the appearance is impaired in outdoor exposure. In particular, outer wall boards having excellent antifouling properties have been developed in recent years, and dirt on the sealing material portion as compared with the outer wall boards has become more conspicuous.

  A room temperature curable composition containing a modified silicone polymer and a fluorosurfactant is disclosed as a modified silicone sealant of the type that suppresses residual tack (stickiness) on the surface (Patent Document 1). However, this sealing material has an insufficient residual tack suppressing effect, and it cannot prevent the adhesion of dirt such as dust. Furthermore, the surface weather resistance is insufficient, and a large number of cracks are generated on the surface due to long-term outdoor exposure, and dust or the like accumulates in the cracks. Therefore, contamination cannot be prevented over time.

  Further, as a modified silicone sealing material that hardly causes contamination on the surface of the cured product over time, a modified silicone polymer, an amine compound having a melting point of 10 to 200 ° C., and a polyglycerol having a polymerization degree of 2 to 5 A room temperature curable composition containing a fatty acid ester or a nonionic surfactant having a melting point of 10 to 200 ° C. is disclosed (Patent Document 2). However, the surface contamination-preventing effect of the sealing material has not been sufficient as compared with recent outer wall boards having excellent antifouling properties. Further, the surface of the sealing material does not have a self-cleaning function in which attached dirt is washed away by rainwater.

In recent years, demand for high weather resistance, long life, high design, maintenance-free, etc. of buildings has increased, and antifouling exterior wall materials with antifouling functions have been proposed over a long period of time. In order to prevent deterioration of the appearance due to dirt over a long period of time, it is preferable that the attached dirt be easily washed away by rainfall.
JP 59-217757 A JP 11-193343 A

  The present invention continuously exhibits excellent antifouling property and self-cleaning action after curing, that is, it is difficult for dirt to adhere for a long period of time, and furthermore, it can be easily washed away by rain, for high weather resistant construction The object is to provide a curable composition suitable as a sealing material or the like.

The present inventors include (B) a fluorine-containing nonionic surfactant and (C) an amine compound in a curable composition containing (A) a vinyl polymer having a reactive silicon group as a main component. Thus, the present inventors have found that the above problems can be solved, and have completed the present invention.
That is, the present invention includes the following.
[1] A curable composition comprising (A) a vinyl polymer having a reactive silicon group, (B) a fluorine-containing nonionic surfactant, and (C) an amine compound.
[2] The curable composition according to the above [1], further comprising (D) an oxyalkylene polymer having a reactive silicon group.
[3] The curable composition according to [1] or [2], wherein the fluorine-containing nonionic surfactant (B) has an HLB value of 2 to 10.
[4] The fluorine-containing nonionic surfactant (B) is a fluorine-containing compound having a skeleton having a repeating unit of oxyalkylene and having a perfluoroalkyl group. The curable composition in any one.
[5] The content of the fluorine-containing nonionic surfactant (B) is 0.05% to 10% by weight of the entire curable composition, according to any one of [1] to [4] above. Curable composition.
[6] The curable composition according to any one of [1] to [5], wherein the amine compound (C) is a naturally occurring amine compound having a freezing point of 34 ° C. or lower and / or an amine compound having a melting point of 35 ° C. or higher. object.
[7] The curable composition according to [6] above, wherein the naturally derived amine compound having a freezing point of 34 ° C. or lower is a cocoalkylamine.
[8] The curable composition according to the above [6] or [7], wherein the amine compound having a melting point of 35 ° C. or higher is a fine powder coating amine in which fine powder is fixed on the surface of a solid amine.
[9] The curable composition according to any one of [1] to [8], wherein the content of the amine compound (C) is 0.05% by weight to 10% by weight of the entire curable composition.
[10] The curable polymer according to any one of [1] to [9], wherein the vinyl polymer (A) having a reactive silicon group is a (meth) acrylic polymer having a reactive silicon group. Composition.
[11] The curable composition according to any one of [2] to [10], wherein the oxyalkylene polymer (D) having a reactive silicon group is a polypropylene oxide having a reactive silicon group.
[12] The curable composition according to any one of [1] to [11], wherein a surface contact angle with water after curing is 15 ° or less.

  Since the curable composition of the present invention continuously exhibits excellent antifouling properties and self-cleaning action after curing, that is, it is difficult for dirt to adhere for a long period of time, and it can be easily washed away by rainfall. Therefore, it can be suitably used as a highly weather-resistant building sealing material or the like.

  The curable composition of the present invention contains a vinyl polymer (A) having a reactive silicon group as a main component. In the present invention, the “vinyl polymer having a reactive silicon group” is a vinyl polymer obtained by polymerizing one or more vinyl monomers having one or more polymerizable unsaturated groups in the molecule. It means a polymer having a polymer as a main chain skeleton and a reactive silicon group at the terminal or side chain. Such a vinyl polymer (A) having a reactive silicon group can be produced by a conventionally known method. Moreover, in the curable composition of this invention, the vinyl polymer (A) which has a reactive silicon group may be used independently, and may use 2 or more types together.

  Examples of the vinyl monomer constituting the main chain of the vinyl polymer (A) having a reactive silicon group include (meth) acrylic acid monomers, styrene monomers, silicon group-containing vinyl monomers, and maleic anhydride. Maleic acid, maleic acid ester, fumaric acid, fumaric acid ester, maleimide monomer, vinyl ester monomer, alkenes and the like. These may be used alone or two or more of them may be copolymerized.

  The “reactive silicon group” in the vinyl polymer (A) having a reactive silicon group has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and a siloxane bond is formed by a reaction catalyzed by a curing catalyst. It is a group that can be cross-linked by forming. It does not specifically limit as a hydrolysable group, What is necessary is just a conventionally well-known hydrolysable group. Specific examples 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. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable. Particularly preferred.

  The vinyl polymer (A) having a reactive silicon group in the present invention is preferably a reaction having a number average molecular weight of 3000 to 50000 (preferably 30000 to 50000) in terms of physical properties after curing and weather resistance. (Meth) acrylic polymers having a functional silicon group are preferred. Examples of such a (meth) acrylic polymer having a reactive silicon group include SA310S and SA110S manufactured by Kaneka Corporation.

  The content of the vinyl polymer (A) having a reactive silicon group in the curable composition of the present invention is usually 10 to 50% by weight, preferably 10 to 30% by weight, based on the entire curable composition. It is.

  In addition to the said component (A), the curable composition of this invention may contain the oxyalkylene type polymer (D) which has a reactive silicon group as a main component. In the present invention, the “oxyalkylene polymer having a reactive silicon group” means a polymer having polyoxyalkylene as the main chain skeleton and having a reactive silicon group at the terminal or side chain. Such an oxyalkylene polymer (D) having a reactive silicon group can be produced by a conventionally known method. Moreover, in the curable composition of this invention, the oxyalkylene type polymer (D) which has a reactive silicon group may be used independently, and may use 2 or more types together. The reactive silicon group in the oxyalkylene polymer (D) having a reactive silicon group is the same as the reactive silicon group in the component (A).

  Examples of the oxyalkylene polymer (D) having a reactive silicon group include polypropylene oxide having a reactive silicon group, polyethylene oxide having a reactive silicon group, and propylene oxide-ethylene oxide copolymer having a reactive silicon group. Examples include coalescence. Of these, polypropylene oxide is the main chain skeleton and has a reactive silicon group at the terminal or side chain, and preferably has a number average molecular weight of 8000 to 50,000 (preferably 20,000 to 50,000). Polypropylene oxide polymers are preferred. Examples of such a polypropylene oxide having a reactive silicon group include MS polymer series (“MS polymer S-203”, etc.) manufactured by Kaneka Co., Ltd., SAX-220, and “Exstar” manufactured by Asahi Glass Co., Ltd. (Trademark registration) series and the like.

  The content of the oxyalkylene polymer (D) having a reactive silicon group in the curable composition of the present invention is usually 10 to 50% by weight, preferably 10 to 30% by weight, based on the entire curable composition. %.

  Moreover, in the curable composition of this invention, in addition to the mixture of the said component (A) and component (D), the reaction material of the said component (A) and component (D) can also be used. As a mixture or a reaction product of the component (A) and the component (D), for example, a reaction with a polyoxyalkylene polymer having a reactive silicon group such as MA903, MSX908, MSX911, MSX943 manufactured by Kaneka Corporation And a mixture or a reaction product with a (meth) acrylic polymer having a functional silicon group. The content of such a mixture or reaction product in the curable composition of the present invention is usually 10 to 50% by weight, preferably 10 to 30% by weight, based on the entire curable composition.

The curable composition of this invention contains a fluorine-containing nonionic surfactant (B) in addition to the said component (A) (and component (D) as needed). By blending the fluorine-containing nonionic surfactant, the surface after curing of the curable composition of the present invention becomes superhydrophilic and has an excellent self-cleaning effect due to rain.
In the present invention, the “fluorine-containing nonionic surfactant” is a fluorine compound having a structure in which all (or part of) hydrogen atoms coordinated to a long-chain alkyl group which is a hydrophobic group are substituted with fluorine atoms. It means a compound that does not ionize when dissolved in water. Such a fluorine-containing nonionic surfactant (B) can be produced by a conventionally known method. Moreover, in the curable composition of this invention, a fluorine-containing nonionic surfactant (B) may be used independently, and may use 2 or more types together.

As the fluorine-containing nonionic surfactant (B) in the present invention, those having an HLB (Hydrophile-Lipophile Balance) value in the range of 2 to 10 (preferably in the range of 5 to 10) are preferable. When the HLB value is within the above range, the sustainability of the self-cleaning action is ensured satisfactorily.
In addition, the HLB value in this specification is a value calculated | required according to the following "Kawakami formula".
HLB = 7 + 11.7log (sum of formula weight of hydrophilic part / sum of formula weight of lipophilic part)

  Examples of the fluorine-containing nonionic surfactant (B) include a fluorine-containing compound having a skeleton having a repeating unit of oxyalkylene and having a perfluoroalkyl group. Specific examples of the compound and a mixture thereof include commercially available products such as Surflon S-381, S-383, and KH-40 (manufactured by Seimi Chemical Co., Ltd.).

  The content of the fluorine-containing nonionic surfactant (B) in the curable composition of the present invention is curable from the viewpoint of imparting a good self-cleaning action to the surface after curing without reducing its physical properties. It is preferable that it is 0.05 to 10 weight% of the whole composition, and it is more preferable that it is 0.2 to 4 weight%.

The curable composition of the present invention contains an amine compound (C) in addition to the components (A) and (B) (and component (D) if necessary). By compounding the amine compound, tackiness of the surface after curing of the curable composition of the present invention is suppressed, so that the surface is less likely to be soiled.
The amine compound (C) is not particularly limited as long as the surface tack after curing can be suppressed and the object of the present invention can be achieved. For example, a naturally occurring amine compound having a freezing point of 34 ° C. or lower. , Amine compounds having a melting point of 35 ° C. or higher, and mixtures thereof.

The naturally-occurring amine compound having a freezing point of 34 ° C. or lower is extracted from raw materials obtained from natural materials such as animals and plants (for example, natural fats and oils such as coconut oil (palm oil), palm kernel oil, palm oil), Alternatively, an amine compound having a freezing point of 34 ° C. or lower (preferably 20 ° C. or lower) obtained by synthesis may be used. Specific examples include Farmin (registered trademark) 08D, 20D, CS manufactured by Kao Corporation, and Armin CD, 08D, 12D manufactured by Lion Corporation. These amine compounds can be produced according to a conventionally known method.
Of these, amine compounds having an alkyl chain distribution with 8 to 18 carbon atoms are preferred, and in particular, about 7% octyl chains with 8 carbon atoms, about 7% decyl chains with 10 carbon atoms, 51% lauryl chains with 12 carbon atoms. About 14% tetradecyl chain having 14 carbon atoms, about 8% cetyl chain having 16 carbon atoms, about 2% stearyl chain having 18 carbon atoms, and about 6% oleyl chain having 18 carbon atoms, and freezing point Is preferably about 16 ° C. cocoalkylamine (amine made from coconut oil, also called coconut amine).
The content of the naturally-occurring amine compound having a freezing point of 34 ° C. or lower in the curable composition of the present invention is usually 0.05 to 10% by weight, preferably 0.15 to 5% by weight of the entire curable composition. is there. If it is less than 0.05% by weight, the tackiness of the surface after curing may not be sufficiently suppressed, and the antifouling property may not be sufficiently exhibited. If it exceeds 10% by weight, whitening will occur significantly on the surface of the cured product. , Tend to be a difficult point on the surface appearance.

Examples of the amine compound having a melting point of 35 ° C. or higher include aromatic or aliphatic amine compounds having a melting point of 35 ° C. or higher (preferably 50 ° C. or higher). For example, 4,4′-diaminodiphenylmethane, 2,4 '-Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminobiphenyl, 2,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,4-diamino Phenol, 2,5-diaminophenol, o-phenylenediamine, m-phenylenediamine, 2,3-toluenediamine, 2,4-toluenediamine, 2,5-toluenediamine, 2,6-toluenediamine, 3,4 -Aromatic amine compounds such as toluenediamine, 1,12-dodecanediamine, 1,10-decane Examples thereof include aliphatic amine compounds such as diamine, 1,8-octanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, and stearylamine. These amine compounds can be produced according to a conventionally known method.
Among them, it is preferable to use a fine powder coating amine in which a fine powder is fixed to a solid amine surface having a melting point of 35 ° C. or higher (preferably 50 ° C. or higher) without deteriorating its physical properties. It is particularly preferable from the viewpoint of imparting antifouling properties.

  The fine powder-coated amine is prepared by applying fine powder having a central particle size of 2 μm or less to the surface of a solid amine having a melting point of 35 ° C. or higher (preferably 50 ° C. or higher) and a central particle size of 20 μm or less. Is fixed so as to be 1 / 0.001 to 0.5, and the active amino group on the surface is coated. Such fine powder-coated amine is obtained by, for example, pulverizing a solid amine to a central particle size of 20 μm or less and simultaneously adding and pulverizing the fine powder to the central particle size of 2 μm or less; Using a high-speed impact mixing stirrer, compression shear mixing stirrer, or spray drying device, the fine powder is pulverized to a particle size of 20 μm or less with a fine powder having a center particle size of 2 μm or less. It can manufacture by making it adhere (refer Unexamined-Japanese-Patent No. 2000-1117090).

  Examples of the solid amine used as a raw material for the fine powder coating amine include aromatic or aliphatic amine compounds having a melting point of 35 ° C. or higher (preferably 50 ° C. or higher). One or a mixture of two or more of these may be used. The solid amine is adjusted to have a center particle size of 20 μm or less, preferably 3 to 15 μm.

  The fine powder used as the raw material of the fine powder coating amine can be arbitrarily used from inorganic or organic materials. For example, titanium oxide, calcium carbonate, clay, silica, zirconia, carbon, alumina as inorganic materials. In addition, polyvinyl chloride, polyacrylic resin, polystyrene, polyethylene and the like are exemplified as talc and the like, and one or a mixture of two or more thereof is used. The amount used is selected so that the weight ratio of solid amine to fine powder is 1 / 0.001 to 0.5, preferably 1 / 0.002 to 0.4.

  The amount of fine powder coating amine used in the curable composition of the present invention is usually selected in the range of 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight of the entire curable composition. . If it is less than 0.05 part by weight, the antifouling property of the surface of the cured product may not be sufficiently exhibited, and if it exceeds 10 parts by weight, a whitening phenomenon occurs remarkably on the surface of the cured product, resulting in a difficulty in surface appearance. There is a tendency.

  In the present invention, in order to give good antifouling property to the surface after curing, a naturally occurring amine compound having a freezing point of 34 ° C. or lower and an amine having a melting point of 35 ° C. or higher in the curable composition. It is also preferred to use a mixture of compounds. In this case, the content ratio (weight basis) of the naturally-derived amine compound having a freezing point of 34 ° C. or lower and the amine compound having a melting point of 35 ° C. or higher is 1: 9 to 9: 1. From the viewpoint of sex. A more preferable content ratio is 2: 8 to 8: 2, and 3: 7 to 7: 3 is particularly preferable.

  The total content of the amine compound (C) in the curable composition of the present invention is the entire curable composition from the viewpoint of imparting good antifouling properties to the cured product surface without reducing the physical properties of the cured product. It is preferable that it is 0.05 to 10 weight% of this, and it is more preferable that it is 0.1 to 5 weight%.

  The curable composition according to the present invention may further contain various additives used in ordinary curable compositions, for example, a curing catalyst, a colorant, an organic solvent, and the like, in addition to the above-described components. it can. These additives may be used alone or in combination of two or more, and the content in these curable compositions is usually 1.0 to 30.0% by weight, Preferably it is 1.0-10.0 weight%.

Examples of the curing catalyst include, for example, tin dioctylate, dibutyltin dilaurate, dibutyltin bisacetylacetonate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin oxide, dibutyltin bisethoxysilicate, dioctyl Examples thereof include tin catalysts such as tin oxide, titanium catalysts such as tetraisopropyl titanate, tetra n-butyl titanate and partial hydrolysis condensates thereof, titanium diisopropyl bisacetyl acetate, titanium diisopropyl bisethyl ethyl acetoacetate, and the like.
Examples of the colorant include bengara, titanium oxide, carbon black, other color pigments, and dyes.
Examples of the organic solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, butanol, acetone, methyl ethyl ketone, ligroin, ethyl acetate, tetrahydrofuran, n-hexane, heptane, isoparaffin-based high boiling point solvent, and the like.

The curable composition of the present invention is a particle having an average particle size of 30 to 500 μm (more preferably 70 to 400 μm) in order to impart designability to the cured product, particularly when used as a sealing material for construction. It is preferable to further contain. Such particles may be composed of inorganic and / or organic substances, and have any shape such as spherical (spherical, elliptical, flat, hollow), granular, chain, or fibrous. Things can be used. Specific examples thereof include alumina, silicon carbide, zirconia, silicon nitride, ceramic, synthetic ruby, sapphire, glass, phenolic resin, acrylic resin, polyacrylonitrile, silica, urethane resin, calcium carbonate, silica sand, cryolite, etc. Can be mentioned.
Among them, when organic particles composed of acrylic resin are used, the curing agent composition can be imparted with heat resistance, solvent resistance or weather resistance, and the matte finish or matte finish finish can be applied to the cured surface. Design properties suitable for an outer wall, a yuzu skin finish painted outer wall, or a sandstone-like painted outer wall can be imparted. Such acrylic resin particles preferably have a heat resistant temperature of 150 to 300 ° C., and such particles are preferably composed of polymers such as cross-linked polymethyl methacrylate and polyacrylonitrile. Examples of such commercially available crosslinked acrylic resin particles include Tufic (registered trademark) AR650LL manufactured by Toyobo Co., Ltd.
The inorganic particles and organic particles can be used alone or in combination of two or more, and the content in the curable composition is preferably 0.1 to 30% by weight, more preferably 2 to 20% by weight. .

  Further, if necessary, the curable composition of the present invention may be added to ordinary fillers (heavy calcium carbonate, fatty acid-treated calcium carbonate, fume silica, precipitated silica, carbon black, talc, titanium oxide, etc.), plasticizer ( Acrylic ester plasticizers, phthalic acid diesters, epoxidized hexahydrophthalic acid diesters, alkylene dicarboxylic acid diesters, alkylbenzenes, etc.), adhesives (epoxy compounds, silane coupling agents, etc.), anti-aging agents (hinders) Dophenols, mercaptans, sulfides, dithiocarboxylates, thioureas, thiophosphates, thioaldehydes, etc., thixotropic agents (colloidal silica, organic bentonite, fatty acid amide, polyamide wax, hydrogenated castor oil, etc.) ), Moisture retention agent (water, hydrates of inorganic salts, etc.) , Ultraviolet absorbers, light stabilizers (benzotriazoles, hindered amines, etc.), it may be blended with an appropriate amount range such as an antioxidant (hindered phenols).

  The curable composition of the present invention composed of the above components is a one-pack type in which the above-mentioned blending components are mixed together, or contains the above polymer, an amine compound having a saturated and / or unsaturated alkyl chain distribution, particles, and the like. And a two-part type composed of a toner liquid containing a curing catalyst, a colorant, a fine powder coating amine, or the like, or further separated as a separate component from the colorant. Alternatively, it may be used as a three-part type.

The curable composition of the present invention can be cured preferably in the range of 5 to 50 ° C. without being affected by the temperature during curing. In addition, when the curable composition of the present invention is cured under such temperature conditions, for example, the surface contact angle with respect to water of the surface of the cured product is preferably 15 ° or less, particularly preferably 10 ° or less. With such a surface contact angle, the antifouling property and the self-cleaning effect can be sufficiently exhibited.
In the present specification, the surface contact angle is a value determined by an image processing type three-point click method using a CA-X150 type manufactured by Kyowa Interface Science Co., Ltd.

  The curable composition of the present invention is particularly effective when applied to an architectural sealant, and is suitable for use as, for example, a sealant for a matte finish exterior wall, a yuzu skin finish exterior wall, or a sandstone finish exterior wall. Can be used. The curable composition of the present invention can be applied to sealing materials for automobiles, electrical appliances, civil engineering, and other adhesives, paints, coating materials, potting materials, molded products, etc. in addition to the above-mentioned architectural sealing materials. it can.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In Examples and the like, the units described are based on weight unless otherwise specified.
Moreover, the evaluation method of the performance test done about the curable composition obtained by each Example and the comparative example is shown below.
[Evaluation method of performance test]
Each curable composition was used as a sealing material and placed on a flexible board provided with a groove of about 3 mm (depth) × 30 mm (width) and immediately subjected to the following test.
A) Measurement of initial contact angle with water After standing for 7 days in an atmosphere of 23 ° C. and 50% relative humidity, 0.05 ml of pure water was dropped on the surface, and the contact angle after 1 minute was measured with a contact angle meter (Kyowa) It was measured using Interface Science Co., Ltd. CA-X150 type, image processing type 3 point click method).
B) Measurement of contact angle after immersion in warm water in water A) was left in warm water at 50 ° C. for 7 days, dried at a temperature of 23 ° C. and a relative humidity of 50% for 1 day, and then the surface was measured with a contact angle meter. Subsequently, 0.05 ml of pure water was dropped, and the contact angle after 1 minute was measured.
C) Volcanic ash test After standing for 7 days in an atmosphere at a temperature of 23 ° C and a relative humidity of 50%, sprinkle the volcanic ash, drop the test specimen vertically from the height of 20 cm to the floor three times, and shake off excess volcanic ash. The percentage of volcanic ash attached was determined.
D) Volcanic ash cleaning test After standing for 7 days at a temperature of 23 ° C and a relative humidity of 50%, sprinkle the volcanic ash and drop the test specimen vertically from the height of 20 cm to the floor three times to shake off the extra volcanic ash. Thereafter, 100CC of water was sprayed from a distance of 10 to 20 cm by spraying on a vertically standing test body, and the proportion of volcanic ash adhering to the specimen after standing drying was visually determined.
E) Red soil test After standing for 7 days in an atmosphere at a temperature of 23 ° C and a relative humidity of 50%, sprinkle the red soil, drop the test piece vertically from the height of 20 cm to the floor three times, and shake off the excess red soil. The percentage of red soil attached was determined.
F) Red soil washing test After standing for 7 days at a temperature of 23 ° C and a relative humidity of 50%, sprinkle the red soil, drop the test piece vertically from the height of 20 cm to the floor three times, and shake the excess red soil. Thereafter, 100 CC of water was sprayed from a distance of 10 to 20 cm by spraying on a vertically standing test body, and after standing to dry, the proportion of red soil adhered was visually determined.

[Reference Example: Production of fine powder coated amine]
A fine powder coated amine was produced in accordance with JP 2000-117090 as follows.
76.9 parts of 1,12-dodecanediamine (melting point 71 ° C.) having a center particle size of about 8 μm and 23.1 parts of ultrafine titanium oxide having a center particle size of about 0.02 μm were mixed together, and a high-speed impact mixing stirrer (day By combining with a Kiyo Engineering Co., Ltd. (Hi-X mixer), ultrafine titanium oxide having a center particle size of about 0.02 μm is formed on the surface of 1,12-dodecanediamine having a center particle size of about 8 μm. 100 parts of fine powder-coated amine fixed to be obtained.

[Examples 1-4 and Comparative Examples 1-3]
Each component shown in Table 1 was blended and mixed using a planetary stirrer to obtain a curable composition. About each obtained curable composition, performance evaluation was carried out using the said method. The results are shown in Table 1.

[Comparative Examples 4 to 6]
According to Examples 1 to 3 described in JP-A-59-217757, the components shown in Table 2 were blended and mixed using a planetary stirrer to obtain a curable composition. About each obtained curable composition, performance evaluation was carried out using the said method. The results are shown in Table 2.

[Comparative Examples 7-9]
According to Examples 14 to 16 described in JP-A-11-193343, the components shown in Table 3 were blended and mixed using a planetary stirrer to obtain a curable composition. About each obtained curable composition, performance evaluation was carried out using the said method. The results are shown in Table 3.

  As can be seen from the results of Tables 1 to 3, the curable compositions obtained in each Example corresponding to the curable composition of the present invention had a contact angle with water of 15 ° or less at the initial stage and after immersion in warm water. It is clear that it has a self-cleaning function even for red soil, which has excellent hydrophilicity and is more difficult to clean than volcanic ash.

Claims (12)

  A curable composition comprising (A) a vinyl polymer having a reactive silicon group, (B) a fluorine-containing nonionic surfactant, and (C) an amine compound.   The curable composition according to claim 1, further comprising (D) an oxyalkylene polymer having a reactive silicon group as a mixture with component (A) or a reaction product with component (A). The curable composition according to claim 2, wherein the oxyalkylene polymer (D) having a reactive silicon group is a polypropylene oxide having a reactive silicon group. The curable composition according to any one of claims 1 to 3, wherein the fluorine-containing nonionic surfactant (B) has an HLB value of 2 to 10. The curing according to any one of claims 1 to 4 , wherein the fluorine-containing nonionic surfactant (B) is a fluorine-containing compound having a skeleton having a repeating unit of oxyalkylene and having a perfluoroalkyl group. Sex composition. The curable composition according to any one of claims 1 to 5 , wherein the content of the fluorine-containing nonionic surfactant (B) is 0.05 wt% to 10 wt% of the entire curable composition. The curable composition according to any one of claims 1 to 6 , wherein the amine compound (C) is a naturally occurring amine compound having a freezing point of 34 ° C or lower and / or an amine compound having a melting point of 35 ° C or higher. The curable composition according to claim 7 , wherein the naturally-derived amine compound having a freezing point of 34 ° C or lower is cocoalkylamine. The curable composition according to claim 7 or 8 , wherein the amine compound having a melting point of 35 ° C or higher is a fine powder coating amine in which a fine powder is fixed on the surface of a solid amine. The curable composition according to any one of claims 1 to 9 , wherein the content of the amine compound (C) is 0.05 wt% to 10 wt% of the entire curable composition. The curable composition according to any one of claims 1 to 10 , wherein the vinyl polymer (A) having a reactive silicon group is a (meth) acrylic polymer having a reactive silicon group.   The curable composition according to any one of claims 1 to 11, wherein a surface contact angle with respect to water after curing is 15 ° or less.