JP5203284B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition which is cured by moisture (humidity) in the atmosphere and becomes a rubbery elastic body, and particularly excellent in antifouling performance for a long period after curing.

Conventionally, as a moisture-curing resin component used for waterproof sealants, adhesives, paints, etc. for buildings, civil engineering, automobiles, etc., the main chain generally called modified silicone is a polyether molecule. Resins and polyurethane resins containing a crosslinkable silyl group are widely used because they are excellent in workability and adhesiveness.
However, when the crosslinkable silyl group-containing resin is designed in a low to medium tensile stress region in order to use it as a sealing material or a waterproof coating material, the curable composition containing this is tacky on the surface after curing ( Therefore, there is a drawback that dust such as soot and dust in automobile exhaust gas floating in the air is likely to adhere, and the surface is contaminated in black. In particular, when exposed to the outdoors for a long period of time of 6 months or longer after curing, there is a problem that a significant defect in appearance occurs due to continued adhesion of dust to the surface of the cured product and surface contamination.
As a technique for reducing the tack (adhesion) of the surface after curing, an invention in which a fluorosurfactant is added to a crosslinkable silyl group-containing resin is disclosed (see Patent Document 1). However, the addition of a general fluorosurfactant is not enough to prevent surface contamination due to the adhesion of dust. Although the effect is also observed immediately after exposure, it may be affected by rain after long-term exposure. There is a problem that the added fluorosurfactant is lost and the effect is not seen. In order to solve this problem, an invention in which a fluorosurfactant and an amine compound are used in combination in order to continuously exhibit the effect of preventing surface contamination has been disclosed (see Patent Document 2). There exists a problem that the effect will fall after storage.

JP 59-217757 A JP 2008-291159 A

  The present invention has a long-term anti-contamination performance (even when immersed in warm water) against dust such as soot and dust in automobile exhaust gas floating in the atmosphere, and stably contaminates even after storage. It aims at providing the curable composition which can exhibit prevention performance.

As a result of diligent research, the present inventor has found that a crosslinkable silyl group-containing resin (A) is reacted with a fluorine-based surfactant (B) and water to produce a primary and / or secondary amine ( It has been found that the above-mentioned problems can be solved by blending C), and the present invention has been completed.
That is, this invention is shown by the following (1)-(5).

(1) A crosslinkable silyl group-containing resin (A), a fluorosurfactant (B), and a compound (C) that reacts with water to produce a primary and / or secondary amine. The fluorinated surfactant (B) is 0.1 to 20 parts by mass relative to 100 parts by mass of the crosslinkable silyl group-containing resin (A), and the water and The said curable composition characterized by the compound (C) which reacts and produces | generates a primary and / or a secondary amine is 0.1-20 mass parts.
(2) The crosslinkable silyl group-containing resin (A) is an acrylic and / or methacrylic-modified polyoxyalkylene resin containing a crosslinkable silyl group, and / or a crosslinkable silyl group-containing polyacryl. And / or the curable composition of (1), which is a methacrylic resin.
(3) Curing of said (1) whose compound (C) which reacts with the said water and produces | generates a primary and / or a secondary amine is a ketimine compound of a primary and / or a secondary amine. Sex composition.
(4) The curable composition according to any one of (1) to (3), further containing an additive (D).
(5) The curable composition according to (4), which is a mixture of a hindered amine antioxidant, a hindered phenol antioxidant, and a benzotriazole ultraviolet absorber.

  For the first time according to the present invention, it has long-term anti-contamination performance after being cured (even immersed in hot water) against dust such as smoke and sand in automobile exhaust gas floating in the atmosphere, and stable even after storage. It has become possible to provide a curable composition that can exhibit antifouling performance.

The present invention is described in detail below.
As the crosslinkable silyl group-containing resin (A) in the present invention, those generally referred to as a silicone resin and a modified silicone resin can be preferably mentioned, and react with moisture (water) to form a siloxane bond. It is a resin containing a crosslinkable silyl group in the molecule, which forms a rubber-like cured product by cross-linking. In the present invention, a modified silicone resin is preferred.

The silicone resin is a resin having a main chain of organopolysiloxane and a crosslinkable silyl group in the molecule.
Specifically, a one-part silicone resin containing an organopolysiloxane having a silanol group at the terminal as a main component and a low-molecular compound containing a crosslinkable silyl group as a crosslinking component, and an organopolysiloxane having a silanol group at the terminal as a main component A typical example is a two-part silicone resin containing siloxane and an aminoxyalkylsilane as a curing agent. Examples of the crosslinkable silyl group-containing low molecular weight compound include acyloxyalkylsilane, aminoxyalkylsilane, and alkoxyalkylsilane.

As the modified silicone resin, for example, JP-A-52-73998, JP-A-55-9669, JP-A-59-122541, JP-A-60-6747, JP-A-61-233043 JP, 63-6003, JP 63-112642, JP 3-79627, JP 4-283259, JP 5-287186, JP 11-80571. Disclosed in JP-A-11-116763 and JP-A-11-130931, specifically, containing a crosslinkable silyl group in the molecule, the main chain being a vinyl polymer, polyoxy Aliphatic hydrocarbon polymers such as alkylene polymers, polyisoprene, polyisobutylene, polybutanediene, polyester polymers, polysulfide polymerization These copolymers, including mixtures thereof.
The main chain of the modified silicone resin is a polyoxyalkylene polymer which may be modified with acrylic and / or methacrylic and / or acrylic and / or methacrylic from the viewpoint of physical properties such as tensile adhesion after curing and modulus. A copolymer is preferred. Here, “which may be modified with acrylic and / or methacrylic” means that the polyoxypropylene polymer is acrylic and / or methacrylic (hereinafter “acrylic and / or methacrylic” is referred to as (meth) acrylic). Block or pendant copolymer of a monomer, a polyoxyalkylene polymer mixed with a (meth) acrylic copolymer, or a (meth) acrylic in a polyoxyalkylene polymer having a crosslinkable silyl group introduced This refers to polymerized monomers. Furthermore, a polyoxyalkylene polymer and / or a (meth) acrylic copolymer are preferable, and a polyoxyalkylene polymer which may be modified with (meth) acrylic in terms of improving weather resistance and facilitating production. A mixed system of a coalescence and a (meth) acrylic copolymer is preferred.
The crosslinkable silyl group is preferably contained in the molecule in an amount of 1.0 or more, particularly 1.0 to 5.0, in view of the curability of the curable composition and the physical properties after curing.
Further, the crosslinkable silyl group is preferably one represented by the following general formula which is easily crosslinked and easy to produce.

（式中、Ｒは炭化水素基であり、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基が好ましく、メチル基が最も好ましい。Ｘで示される反応性基はハロゲン原子、水素原子、水酸基、アルコキシ基、アシルオキシ基、ケトキシメート基、アミド基、酸アミド基、メルカプト基、アルケニルオキシ基及びアミノオキシ基より選ばれる加水分解性の基であり、Ｘが複数の場合には、Ｘは同じ基であっても異なった基であってもよい。このうちＸはアルコキシ基が好ましく、メトキシ基又はエトキシ基が最も好ましい。ａは０、１又は２の整数であり、０又は１が最も好ましい。）

Wherein R is a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and most preferably a methyl group. The reactive group is a hydrolyzable group selected from a halogen atom, hydrogen atom, hydroxyl group, alkoxy group, acyloxy group, ketoximate group, amide group, acid amide group, mercapto group, alkenyloxy group and aminooxy group, When X is plural, X may be the same group or different groups, among which X is preferably an alkoxy group, most preferably a methoxy group or an ethoxy group, and a is 0, 1, or 2. And is most preferably 0 or 1.)

Introduction of the crosslinkable silyl group into the main chain can be performed, for example, by the following known method.
(1) An organic compound (for example, allyl isocyanate) having an active group and an unsaturated group which are reactive with this functional group in a polymer such as a polyoxyalkylene or vinyl polymer having a functional group such as a hydroxyl group at the terminal. Then, the resulting reaction product is hydrosilylated by allowing hydrosilane having a hydrolyzable group to act.
(2) Polyoxyalkylene and vinyl polymers having functional groups such as hydroxyl groups, epoxy groups and isocyanate groups at the ends have functional groups and crosslinkable silyl groups that are reactive with these functional groups. The compound is reacted.
Examples of the compound having a reactive functional group and a crosslinkable silyl group include amino group-containing silanes, mercapto group-containing silanes, epoxy group-containing silanes, vinyl type unsaturated group-containing silanes, chlorine atom-containing silanes, and isocyanates. Examples thereof include group-containing silanes and hydrosilanes.
(3) Compounds having a polymerizable unsaturated bond and a crosslinkable silyl group (for example, CH ₂ ═CHSi (OCH ₃ ) ₃ or CH ₂ ═CHCOO (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ) and (meth) acryl An acid alkyl ester monomer is copolymerized.
(4) A compound having a polymerizable unsaturated bond and a functional group (for example, hydroxyethyl (meth) acrylate or allyl (meth) acrylate) is added to the (meth) acrylic acid alkyl ester monomer and copolymerized. Then, the resulting copolymer is converted into a compound having a reactive functional group and a crosslinkable silyl group (for example, a compound having an isocyanate group and —Si (OCH ₃ ) ₃ group, trimethoxysilane, triethoxysilane, etc. And hydrosilane having a hydrolyzable group).

  In the present invention, the number average molecular weight of the silicone resin and the modified silicone resin is 1,000 or more, particularly those having a narrow molecular weight distribution of 6,000 to 30,000, which are easy to handle because the viscosity of the curable composition is low. It is preferable because of its excellent physical properties such as strength, elongation and modulus.

In the present invention, the crosslinkable silyl group-containing polyoxyalkylene resin and / or the crosslinkable silyl group-containing poly (meth) acrylic resin, which is preferable as the crosslinkable silyl group-containing resin (A), is specifically a polyoxyalkylene-based resin. It can be obtained by reacting a polyol and / or a poly (meth) acrylic polyol, a crosslinkable silyl group-containing isocyanate compound, and optionally an organic isocyanate, sequentially or simultaneously. When sequentially reacting, either a crosslinkable silyl group-containing isocyanate compound and an organic monoisocyanate may be reacted first with a polyoxyalkylene polyol and / or a poly (meth) acrylic polyol. It is preferable to react the silyl group-containing isocyanate compound and then react with the organic monoisocyanate. The desired rubber elasticity in the resin is obtained by reacting the isocyanate group of the crosslinkable silyl group-containing isocyanate compound with the hydroxyl group of the polyoxyalkylene polyol and / or poly (meth) acrylic polyol in an equivalent ratio that leaves some hydroxyl groups. Introduce as many crosslinkable silyl groups as necessary to obtain physical properties, and react the isocyanate groups of the organic monoisocyanate with some or all of the remaining hydroxyl groups to form hydrophobic organic groups that are not moisture curable. By adopting the introduced structure, the water resistance after curing is greatly improved, the modulus and elongation can be adjusted freely according to the application, and the crosslinkable silyl group-containing resin becomes a rubber elastic body with excellent durability. (A) can be obtained.
When the polyoxyalkylene polyol and / or the poly (meth) acrylic polyol is reacted with the crosslinkable silyl group-containing isocyanate compound, the equivalent ratio of isocyanate group / hydroxyl group is 0.1 or more / 1.0, The reaction is preferably carried out in the range of 0.5 to 1.5 / 1.0, particularly 0.9 to 1.0 / 1.0. In the case where a polyoxyalkylene polyol and / or a poly (meth) acrylic polyol, a crosslinkable silyl group-containing isocyanate compound, and an organic monoisocyanate are reacted sequentially or simultaneously, the polyoxyalkylene polyol and / or For the poly (meth) acrylic polyol and the crosslinkable silyl group-containing isocyanate compound, the equivalent ratio of isocyanate group / hydroxyl group is 0.05 to 0.9 / 1.0, more preferably 0.3 to 0.6 / 1. It is preferable to carry out the reaction within the range of 0.0, and the resulting crosslinkable silyl group and hydroxyl group-containing polyoxyalkylene resin and / or the crosslinkable silyl group and hydroxyl group-containing poly (meth) acrylic resin and the organic monoisocyanate The equivalent ratio of isocyanate group / hydroxyl group of the total raw material is 0.1 or more / 1.0, 0.5-1.5 / 1.0, preferably reacted in a range of particular 0.9 to 1.0 / 1.0. When the isocyanate group / hydroxyl group equivalent ratio is less than 0.1 / 1.0, the crosslinkable silyl group-containing resin (A) has few crosslinkable silyl groups and a large amount of hydroxyl groups, and the physical properties of the cured product do not appear. Water resistance is not improved.
In this reaction, a known urethanization catalyst such as organic metal compounds such as dibutyltin dilaurate and dioctyltin dilaurate, organic amines such as triethylenediamine, triethylamine and tri-n-butylamine and salts thereof can be used. Further, a known organic solvent can also be used.

Examples of the polyoxyalkylene polyol include those obtained by ring-opening addition polymerization of alkylene oxide and those obtained by ring-opening addition polymerization of alkylene oxide in an initiator.
Initiators include low molecular weight compounds such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, and shoelace Examples include alcohols, polyhydric phenols such as bisphenol A, low molecular polyamines such as ethylenediamine, and low molecular amino alcohols such as diethanolamine.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran.
That is, the polyoxyalkylene-based polyol specifically includes, for example, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, poly (oxyethylene) -poly (oxypropylene) -glycol, poly (oxyethylene) -Poly (oxybutylene) -glycol can be mentioned, among which polyoxypropylene glycol is particularly preferred. Moreover, these various polyols and known polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are reacted in an excess of hydroxyl groups with respect to the isocyanate groups so that the molecular ends are hydroxyl groups. .
These can be used alone or in admixture of two or more.
The polyoxyalkylene-based polyol has a number average molecular weight of 500 to 40,000, more preferably 2,000 to 30,000, particularly 10,000 to 10,000, from the viewpoint of lowering the viscosity of the curable composition and increasing the elongation of the cured product. The average number of hydroxyl groups per molecule is preferably 2 to 8, particularly preferably 2 to 4, and the total degree of unsaturation is 0.07 meq / g or less, particularly 0.04 meq / g. The following molecular weight distribution is preferable.

  The poly (meth) acrylic polyol is an ethylenically unsaturated compound containing at least a hydroxyl group-containing (meth) acrylic monomer in the presence or absence of a polymerization initiator and in the presence or absence of a solvent. Below, what is obtained by a high temperature continuous polymerization reaction at 150 to 350 ° C. by a known radical polymerization method such as batch type or continuous polymerization is preferable because the molecular weight distribution of the reaction product is narrow and low viscosity. It is. The poly (meth) acrylic polyol may be obtained by polymerizing a hydroxyl group-containing (meth) acrylic monomer alone, or may be obtained by copolymerizing two or more of these. Furthermore, it may be obtained by copolymerizing one or more of each of these and an ethylenically unsaturated monomer other than these. Among these, one or two of the hydroxyl group-containing (meth) acrylic monomers is easily selected from the viewpoint that the hydroxyl group content of the poly (meth) acrylic polyol can be easily adjusted and the physical properties of the cured resin can be easily selected. Those obtained by copolymerizing at least one species and one or more other ethylenically unsaturated monomers are preferred. In this copolymerization, one or two or more hydroxyl group-containing (meth) acrylic monomers each have an average hydroxyl functionality of 1.0 to 20 per molecule of poly (meth) acrylic polyol, and 1 more. It is preferable to use it so that it may become 0.0-10 pieces, especially 2.0-6.0 pieces. If the average hydroxyl functionality exceeds 20, the physical properties after curing become too hard and the rubbery elasticity is lost. Among these, the number average molecular weight is 500 to 50,000, further 1,000 to 30,000, especially 2,000 to 20,000, Tg is 0 ° C. or lower, further −20 ° C. or lower, and the viscosity at 25 ° C. is 100, Poly (meth) acrylic polyols having a viscosity of 000 mPa · s or less, particularly 50,000 mPa · s or less are preferred. When the number average molecular weight exceeds 50,000, the Tg of 0 ° C., and the viscosity at 25 ° C. of 100,000 mPa · s, the workability during construction deteriorates.

The hydroxyl group-containing (meth) acrylic monomer is an alcoholic hydroxyl group from the viewpoint of good reactivity with the isocyanate group of the crosslinkable silyl group-containing isocyanate compound described below and the viscosity of the resulting crosslinkable silyl group-containing resin. Containing (meth) acrylic monomers are preferred. Specifically, hydroxyalkyl acrylates such as hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxybutyl acrylate, and hydroxyalkyl such as hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate Methacrylates, pentaerythritol triacrylate, glycerin monoacrylate, pentaerythritol diacrylate monostearate, dipentaerythritol pentaacrylate Monoacrylates of polyhydric alcohols such as acrylate, ditrimethylolpropane triacrylate, polypropylene glycol monoacrylate, or residual hydroxyl group polyacrylates, pentaerythritol trimethacrylate, glycerol monomethacrylate, pentaerythritol dimethacrylate monostearate, dipentaerythritol pentamethacrylate Monomethacrylates of polyhydric alcohols such as ditrimethylolpropane trimethacrylate and polypropylene glycol monomethacrylate, or hydroxyl group-retained polymethacrylates, adducts of epoxide and acrylic acid such as adducts of cyclohexene oxide and acrylic acid, cyclohexene oxide and Addition of epoxides such as adducts with methacrylic acid and methacrylic acid And the like.
Examples of other ethylenically unsaturated monomers include ethylene, propylene, isobutylene, butadiene, chloroprene, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid, vinyl acetate, acrylonitrile, styrene, chlorostyrene, and 2-methylstyrene. , Divinylbenzene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, tridecyl acrylate, cetyl acrylate, behenyl acrylate, benzyl acrylate , Glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, propyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate Tridecyl methacrylate, cetyl methacrylate, behenyl methacrylate, benzyl methacrylate, glycidyl methacrylate, acrylamide, methacrylamide, ethoxylated phenol acrylate, ethoxylated paracumyl phenol acrylate, ethoxylated nonyl phenol acrylate, propoxylated nonyl phenol acrylate, methoxydiethylene glycol acrylate , Ethoxydiethylene glycol acrylate, N-vinyl-2-pyrrolidone, isobornyl acrylate, ethoxylated bisphenol F diacrylate, ethoxylated bisphenol A diacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylol The Pantriacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, polyurethane diacrylate, acrylic acid dimer, polyester polyacrylate, 1,6-hexanediol diacrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, cyclohexyl Acrylate, lauryl acrylate, 2-phenoxy acrylate, isodecyl acrylate, isooctyl acrylate, tridecyl acrylate, caprolactone diacrylate, zinc diacrylate, neopentyl glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butane Diol diacrylate, ethylene glycol diacrylate, diethylene glycol Recall diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, propoxylated glycerin triacrylate, ethoxylated pentaerythritol tetraacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, lauryl Methacrylate, stearyl methacrylate, methoxydiethylene glycol methacrylate, ethoxydiethylene glycol methacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate DOO, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, ethoxylated bisphenol A dimethacrylate, zinc methacrylate, and trimethylol propane trimethacrylate and the like. Among these, as the ethylenically unsaturated monomer, from the viewpoint of weather resistance and characteristics after curing, the monomer of acrylic ester compound, the monomer of methacrylate ester compound, acrylamide, methacrylamide, acrylonitrile, etc. (Meth) acrylic compounds are preferred, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid 2 -Ethylhexyl is more preferred.
These can be used alone or in admixture of two or more.

The crosslinkable silyl group-containing isocyanate compound may contain at least one or more isocyanate groups and one or more crosslinkable silyl groups in the molecule, but it is easy to control the reaction and has a rubber elasticity after curing. From a good point, a compound containing one isocyanate group and one crosslinkable silyl group represented by the general formula in the molecule is preferable.
Specific examples of the crosslinkable silyl group-containing isocyanate compound include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 3- Examples thereof include isocyanate propyl isopropoxy silane, isocyanate trimethoxy silane, diisocyanate dimethoxy silane and the like, and these can be used alone or in admixture of two or more. Of these, 3-isocyanatopropyltrimethoxysilane is preferred.

The organic monoisocyanate may contain one isocyanate group in the molecule, but does not contain a crosslinkable silyl group. The organic group other than the isocyanate group of the organic monoisocyanate is preferably a hydrophobic organic group that does not contain a moisture-curable functional group such as moisture. Specifically, aliphatic monoisocyanates such as n-butyl monoisocyanate, n-hexyl monoisocyanate, n-tetradecyl monoisocyanate, n-hexadecyl monoisocyanate, octadecyl monoisocyanate, n-chloroethyl monoisocyanate, chlorophenyl monoisocyanate Isocyanate, 3,5-dichlorophenyl monoisocyanate, p-fluorophenyl monoisocyanate, 2,4-difluorophenyl monoisocyanate, o-trifluoromethylphenyl monoisocyanate, p-nitrophenyl monoisocyanate, p-isopropylphenyl monoisocyanate, 2 , 6-Diisopropyl monoisocyanate, p-toluenesulfonyl monoisocyanate, p-benzyloxyphenyl monoisocyanate Aromatic monoisocyanate such as, and other 2-methacryloyloxyethyl isocyanate. Of these, aliphatic monoisocyanates are preferable from the viewpoint of improving water resistance, and octadecyl monoisocyanate is particularly preferable.
These can be used alone or in admixture of two or more.

  The crosslinkable silyl group-containing (meth) acryl-modified polyoxyalkylene resin is prepared by the usual radical polymerization method such as addition of a radical polymerization initiator or ultraviolet irradiation in the presence of the crosslinkable silyl group-containing polyoxyalkylene resin. It can be obtained by polymerizing one kind or two or more kinds of the (meth) acrylic compounds (for example, see JP-A-59-78223 and JP-B-2-42367).

As the fluorosurfactant (B) in the present invention, commercially available ones can be used, and specific examples include Unidyne DS-403, DSN-403N (manufactured by Daikin Industries).
A fluorine-type surfactant (B) is 0.1-20 mass parts with respect to 100 mass parts of crosslinkable silyl group containing resin (A) , and it is preferable to use it in the range of 1-10 mass parts.

The compound (C) which reacts with water in the present invention to produce a primary and / or secondary amine is the first from the viewpoint of easy availability of raw materials, storage stability, reactivity with water, and the like. Examples thereof include ketimine compounds, enamine compounds and / or aldimine compounds of primary and / or secondary amines. Of these, ketimine compounds of primary and / or secondary amines are preferred. These ketimine compounds, enamine compounds, and aldimine compounds can be obtained by dehydration reaction of ketones or aldehydes with primary and / or secondary amines, respectively.
Examples of the ketones include methyl ethyl ketone, methyl isopropyl ketone, methyl tert-butyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 4-methyl-2-pentanone, 2-heptanone, 4-heptanone, diisopropyl ketone. , Aliphatic ketones such as diisobutyl ketone, aromatic ketones such as propiophenone and benzophenone, cyclic ketones such as cyclopentanone, cyclohexanone and methylcyclohexanone, and β-dicarbonyl compounds such as ethyl acetoacetate. Examples of aldehydes include butyraldehyde, isobutyraldehyde, hexyl aldehyde, and the like. Of these, 4-methyl-2-pentanone is preferred from the same points as described above.
The primary and / or secondary amines have a melting point of 35 ° C. or higher, or contain one or more nitrogen atoms and two or more nitrogen atom-bonded active hydrogens in the molecule. Since the surface glossiness of the cured product is reduced and the surface matting ability is large, for example, when used for sealing outer wall materials with surface matting, the sealing joints are not noticeable and the characteristic aesthetics of the outer wall materials are not impaired. Therefore, it is preferable.
As primary amines, monoamines include butylamine, hexylamine, heptylamine, 2-ethylhexylamine, octylamine, 3-methoxypropylamine, tetradecylamine, pentadecylamine, cetylamine, stearylamine, trimethylcyclohexylamine, benzyl Examples of the diamine include ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 1,7-diaminoheptane, and trimethylhexa. Methylenediamine, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, , 14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane 1,2-diaminogenticosan, 1,2-diaminodocosane, 1,3-diaminotricosane, 1,24-diaminotetracosane, isophoronediamine, diaminodicyclohexylmethane, 3,9-bis (3 -Aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, xylenediamine, phenylenediamine, diaminodiphenylmethane, diaminodiethylphenylmethane, polyoxyethylenediamine, polyoxypropylenediamine and the like. Can As Riamin, such as hexane tri (methylamino) can be exemplified. Secondary amines include monoamines such as dilaurylamine, distearylamine, methyllaurylamine, N, N'-dilaurylpropylamine, N, N'-distearylbutylamine, N-butyl-N'-laurylethylamine And diamines such as N-butyl-N′-laurylpropylamine and N-lauryl-N′-stearylbutylamine. Examples of other amines include N-lauryl propylene diamine and N-stearyl propylene diamine. Examples of the primary and secondary mixed polyamines include diethylenetriamine, triethylenetetramine, and methylaminopropylamine. Of these, primary amines stearylamine and hexamethylenediamine are particularly preferred. Those having a melting point of less than 35 ° C. are heat-resistant, particularly softening at high temperatures in summer, and those having a melting point of more than 100 ° C. are hardened, brittle, and easily damaged by elasticity. The secondary amine preferably has a melting point of 35 ° C. or higher, particularly 40 to 100 ° C.
The compound (C) that reacts with water to produce a primary and / or secondary amine is a crosslinkable silyl group-containing resin in order to keep the gloss and gloss of the cured surface of the curable composition to be significantly low. (A) It is the quantity used as 0.1-20 mass parts with respect to 100 mass parts, and it is preferable to use the quantity used as 0.5-10 mass parts.

  Additives (D) that are preferably blended in the present invention include weather resistance stabilizers, crosslinking catalysts, plasticizers, fillers, thixotropic agents, adhesion improvers, storage stability improvers (dehydrating agents), and coloring. One type or a mixture of two or more types such as an agent can be suitably exemplified.

A weathering stabilizer is used to prevent oxidation, light degradation, and thermal degradation of a cured resin and further improve not only the weather resistance but also the heat resistance, and examples thereof include an antioxidant and an ultraviolet absorber. It is done.
Specifically, examples of the antioxidant include hindered amine-based and hindered phenol-based antioxidants. Among these, the hindered amine-based antioxidant has a molecular weight of 200 or more, and further a molecular weight of 1,000 or more. High molecular weight type is preferred. When this high molecular weight type hindered amine antioxidant and UV absorber are used in combination, surface tack after curing can be prevented and the effect of preventing surface contamination can be maintained for a long period of time. Further, when a hindered phenol antioxidant, a hindered amine antioxidant, and a benzotriazole ultraviolet absorber are mixed and used, the weather resistance can be remarkably improved.

  Examples of the hindered amine antioxidant include N, N ′, N ″, N ″ ′-tetrakis- (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine- 4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N, N'-bis- (2,2,6 , 6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine · N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6- (1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2 , 2,6,6-tetramethyl-4- Peridyl) imino}], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, [bis (2,2,6,6-tetramethyl-decanedioic acid) 1 (octyloxy) -4-piperidyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane (70%)]-polypropylene (30%), bis (1,2,2,6,6- Pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl seba Kate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate 1- [2- [3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9- Tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, N, N'-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-butyl-N- ( 1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, and following the Adeka Stub series manufactured by Asahi Denka Kogyo Co., Ltd. Chemical formula of The compound represented by these is mentioned.

  Examples of the hindered phenol antioxidant include pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene-bis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropioamide], benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxyC7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1- Methylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4, 6-triyl) tri-p-cresol, calcium diethylbis [[[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthiomethyl) ) -O-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-tri Gin-2,4,6- (1H, 3H, 5H) -trione, reaction product of N-phenylbenzenamine and 2,4,4-trimethylpentene, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol.

  Examples of the ultraviolet absorber include 2- [2-hydroxy-3,5-bis (α, αdimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-tert-butyl-2- Hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, methyl 3- (3- (2H-benzotriazol-2-yl) -5 tert-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di Benzotriazole ultraviolet absorbers such as -tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (4,6-diphenyl-1 , 3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol and the like, benzophenone ultraviolet absorbers such as octabenzone, 2,4-di-tert-butylphenyl- Examples thereof include benzoate ultraviolet absorbers such as 3,5-di-tert-butyl-4-hydroxybenzoate.

  Each of the antioxidant and the ultraviolet absorber is preferably blended in an amount of 0.1 to 10 parts by weight, particularly 0.5 to 5 parts by weight, based on 100 parts by weight of the crosslinkable silyl group-containing resin (A).

The cross-linking catalyst is a catalyst for cross-linking (curing) the cross-linkable silyl group-containing resin (A), and specific examples include organometallic compounds and amines. Tin compounds are preferred. Specifically, this organic tin compound is stannous octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin bis (acetylacetonate), dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate. Dioctyltin dilaurate, dioctyltin diversate, etc. Among them, dibutyltin bis (acetylacetonate) is most preferable because it is a liquid having a high crosslinking rate, toxicity, and relatively low brightness.
The crosslinking catalyst is blended in an amount of 0.1 to 10 parts by mass, particularly 0.5 to 5 parts by mass with respect to 100 parts by mass of the crosslinkable silyl group-containing resin (A) from the viewpoints of crosslinking speed and physical properties of the cured product. Is preferred.

  The curable composition of the present invention further includes a plasticizer for adjusting viscosity and rubber elastic properties, reinforcing and increasing physical properties, preventing sagging (slump), improving adhesion, improving storage stability, coloring, and the like. , Fillers, thixotropic agents, adhesion improvers, storage stability improvers (dehydrating agents), colorants and the like can be used.

Examples of the plasticizer include a low molecular weight plasticizer having a molecular weight of less than 1,000, a high molecular weight plasticizer having a number average molecular weight of 1,000, and the low molecular weight plasticizer includes dioctyl phthalate, phthalate Phthalic acid esters such as diisononyl acid, dibutyl phthalate, butyl benzyl phthalate; Aliphatic carboxylic acid esters such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate, butyl oleate; trioctyl phosphate, tricresyl phosphate, etc. Phosphoric acid esters of the above; chlorinated paraffins, etc., and high molecular weight plasticizers include polyester resins from dicarboxylic acids and glycols; polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol Alkyl etherified derivatives and Alkyl esterified derivative; liquid polyoxyalkylene urethane resin having no isocyanate group or active hydrogen in the molecule obtained by reacting the polyoxylalkylene glycol with organic isocyanate; low viscosity (meth) acrylic acid alkyl ester ( Co) polymer resin; polyolefin resins such as polybutadiene and polyisoprene, and polyalkylene resins such as hydrogenated polybutadiene and hydrogenated polyisoprene.
Among these, the viscosity is low, the compatibility with the crosslinkable silyl group-containing resin (A) is good, the workability of the resulting curable composition is good, and there is little migration to the surface after curing. Phthalate esters are preferable in terms of less contamination, and diisononyl phthalate is more preferable.

  Examples of the filler include calcium carbonate, clay, talc, slate powder, mica, kaolin, zeolite, diatomaceous earth, fatty acid (surface) -treated calcium carbonate and the like, and those having a particle size of 1 to 100 μm are preferable. ) Treated calcium carbonate is more preferred.

  Examples of the thixotropic agent include inorganic thixotropic agents such as colloidal silica and asbestos powder, and organic thixotropic agents such as organic bentonite, modified polyester polyol, and fatty acid amide.

Examples of the adhesion improver include a coupling agent, and examples of the coupling agent include silane-based, aluminum-based, zircoaluminate-based, etc. Among them, the silane-based coupling agent is adhesive. Since it is excellent, it is preferable.
Specific examples of the silane coupling agent include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- A low molecular weight compound containing an alkoxysilyl group such as (2-aminoethyl) -3-aminopropylmethyldimethoxysilane having a molecular weight of 500 or less, preferably 400 or less can be mentioned.

  Examples of the storage stability improver (dehydrating agent) include low-molecular crosslinkable silyl group-containing compounds such as vinyltrimethoxysilane, calcium oxide, and the like that react with moisture present in the curable composition.

  Examples of the colorant include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black.

  The total amount of the plasticizer, filler, thixotropic agent, adhesion improver, storage stability improver (dehydrating agent) and colorant is based on 100 parts by mass of the crosslinkable silyl group-containing resin (A). A range of 0 to 500 parts by mass, particularly 50 to 300 parts by mass is preferred.

  In the curable composition of the present invention, each of the components can be used alone or in combination of two or more.

  In the curable composition of the present invention, if necessary, an ester solvent such as ethyl acetate, a ketone solvent such as methyl ethyl ketone, an aliphatic solvent such as n-hexane, an alicyclic solvent such as cyclohexane, toluene, Any conventionally known organic solvent such as an aromatic solvent such as xylene that does not react with the crosslinkable silyl group can be used alone or in admixture of two or more. What is necessary is just to determine the kind and usage-amount suitably according to the use of a curable composition.

Although the manufacturing method of the curable composition of this invention is not specifically limited, For example, it reacts with crosslinkable silyl group containing resin (A) and water first using the reaction apparatus made from stainless steel or iron, and is primary. And / or the compound (C) which produces | generates a secondary amine is separately reaction-synthesized. These reactions may be performed in the presence of the additive (D) or in the absence. Next, a compound (C) in which a crosslinkable silyl group-containing resin (A) and a fluorosurfactant (B) are charged into a stirring and mixing apparatus and further reacted with water to produce primary and / or secondary amines. ) And, if necessary, the additive (D) is added and kneaded and then degassed under reduced pressure for production. The crosslinkable silyl group-containing resin (A) and the compound (C) that reacts with water to produce primary and / or secondary amines react when exposed to moisture to cause thickening and hydrolysis. The reaction synthesis, stirring, and mixing are preferably performed in a sealed state and in a state where moisture is shut off such as in a nitrogen gas atmosphere so as not to be exposed to moisture.
Examples of the stirring and mixing apparatus include various types such as a planetary mixer made of stainless steel or iron, a kneader, an agitator, a nauta mixer, and a line mixer.
Since the produced curable composition also reacts when exposed to moisture, it thickens and cures. Therefore, when stored, it is preferably packed in a container that can block moisture, and sealed and stored.
The container is not particularly limited. For example, a metal drum can made of stainless steel or iron, a pail can or bag container made of metal or synthetic resin, a laminated paper cartridge or container made of synthetic resin, etc. There are various types.

  The materials to which the curable composition of the present invention is applied include cement-based materials such as mortar and concrete, natural stone materials such as marble, ceramic materials such as siding and tiles, and various synthetic resins such as polypropylene and vinyl chloride. A sheet-like or plate-like material made of wood, a wood-based material such as wood or plywood, and the like are preferable because of their good adhesiveness.

  Hereinafter, the present invention will be described in more detail with reference to examples. Here, although a sealing material composition is shown as an example of a curable composition, it is not limited to this.

Synthesis example 1
In a warming reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube and cooler, poly (meth) acrylic polyol (UH-2000 manufactured by Toagosei Co., Ltd., number average molecular weight 4,900, weight average) under nitrogen gas flow Charged 800 g (OH equivalent: 0.29) of molecular weight 13,000, hydroxyl value 20.5 mgKOH / g, average number of hydroxyl groups 1.8), and stirring with 3-isocyanatopropyltrimethoxysilane (Y-Unicar Corporation Y-) 5187, molecular weight 205.4) 30 g (NCO equivalent: 0.146) (R value (NCO equivalent / OH equivalent) = 0.5) and 0.08 g of dibutyltin dilaurate were added and heated to 70-80. Stirring was carried out at 2 ° C. for 2 hours, and disappearance of the peak of the isocyanate group was confirmed by FTIR, followed by cooling to room temperature. Next, in this, octadecyl monoisocyanate (Mionate O manufactured by Hodogaya Chemical Co., Ltd., molecular weight 295) 43.1 g (NCO equivalent: 0.146) (R value (total NCO equivalent / OH equivalent of raw materials) = 1.0) Was added, and the mixture was heated and stirred at 70 to 80 ° C. for 3 hours. The disappearance of the peak of the isocyanate group was confirmed by FTIR, and the reaction was terminated by cooling to room temperature.
The obtained trimethoxysil group-containing poly (meth) acrylic resin was a transparent liquid at room temperature with a viscosity of 15,000 mPa · s / 25 ° C. This resin is referred to as A-1.

Synthesis example 2
In a heating apparatus and a stirring vessel with an ester tube, 500 g of stearylamine (Kao Co., Pharmin 80, amine value 207) dissolved by heating was added, and then 4-methyl-2-pentanone (molecular weight 100.2) was added while stirring. 203 g was added. To this was further added 130 g of toluene, followed by heating and stirring at 110 to 150 ° C. for 3 hours to dehydrate 29.9 g of water using an ester tube. Subsequently, the pressure was reduced to remove excess 4-methyl-2-pentanone and toluene to obtain a stearylamine ketimine compound. This ketimine compound was a translucent liquid at room temperature. This compound is referred to as C-1.

Example 1
In a kneading vessel equipped with a nitrogen seal tube, under a nitrogen gas stream, 50 g of the trimethoxysilyl group-containing poly (meth) acrylic resin A-1 obtained in Synthesis Example 1 and a crosslinkable silyl group-containing acrylic-modified polyoxypropylene resin ( 50 g of Kaneka Corporation MS polymer S943, viscosity 55,000 mP · s / 25 ° C.) was charged and stirred, and then hindered phenol antioxidant: pentaerythritol tetrakis [3- (3,5-di-tert-butyl). -4-hydroxyphenyl) propionate] (Ciba Specialty Chemicals, Irganox 1010) 4 g, hindered amine antioxidant (Asahi Denka Kogyo Co., Ltd., Adekastab LA-63P, molecular weight 2,000) 2.5 g, benzo Triazole ultraviolet absorber: 2- (3,5-di-tert-butyl-2-hydride Roxyphenyl) -5-chlorobenzotriazole (manufactured by Ciba Specialty Chemicals, TINUVIN 327) 2.5 g, fatty acid (surface) treated calcium carbonate (manufactured by Maruo Calcium Co., Calfine 200M), fatty acid amide (manufactured by Kao Corporation) , Fatty acid amide S) 4.5 g and vinyltrimethoxysilane 3 g were added and stirred and mixed until the contents were uniform. Thereafter, pressure-pressure dehydration was performed at 110 ° C. for 1 hour, and after cooling, 2.5 g of a fluorosurfactant B-1 (Daikin, Yudyne DS-403), a ketimine compound of stearylamine obtained in Synthesis Example 2 C— 16 g, 1 g of dibutyltin bis (acetylacetonate) (manufactured by Nitto Kasei Co., Ltd., Neostan U-220) and 1 g of N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (manufactured by Chisso Corporation, Silaace S310) The sealant composition was prepared by charging, stirring and mixing.

Example 2
In Example 1, it is the same except that fluorine-based surfactant B-2 (manufactured by Daikin, Yudyne DSN-403N) was used instead of fluorine-based surfactant B-1 (manufactured by Daikin, Yudyne DS-403). Thus, a sealant composition was prepared.

Comparative Example 1
A sealing material composition was prepared in the same manner as in Example 1 except that fluorinated surfactant B-1 (Daikin, Yudyne DS-403) was not used.

Comparative Example 2
A sealing material composition was prepared in the same manner as in Example 1 except that the ketimine compound C-1 of stearylamine was not used.

Comparative Example 3
A sealing material composition was prepared in the same manner as in Example 2, except that the ketimine compound C-1 of stearylamine was not used.

Comparative Example 4
In Example 1, instead of 50 g of the trimethoxysilyl group-containing poly (meth) acrylic resin A-1 obtained in Synthesis Example 1, 15 g of a crosslinkable silyl group-containing resin (SA310S, manufactured by Kaneka Corporation) 10 g of crosslinkable silyl group-containing polyoxyalkylene resin (manufactured by Kaneka Corporation, MS polymer S-203) instead of 50 g of fluorine-containing resin (manufactured by Kaneka Corporation, MS polymer S943, viscosity 55,000 mP · s / 25 ° C.) In place of 2.5 g of the surfactant based surfactant B-1 (Daikin, Yudyne DS-403), 0.2 g of a fluorosurfactant (produced by Seimi Chemical Co., Surflon KH-40, HLB value 9.8) Fatty acid (surface) treated calcium carbonate (manufactured by Maruo Calcium Co., Ltd., Calfine 200M) instead of 100 g of fatty acid (surface) treated calcium carbonate (God 43g of Shima Chemical Co., Ltd., Calsees PLS-505), 1g of vinylethoxysilane (manufactured by Chisso, Silaace S-220) instead of 3g of vinyltrimethoxysilane, dibutyltin bis (acetylacetonate) (Nitto Kasei) Instead of 1 g of Neostan U-220), 0.6 g of dibutyltin bis (acetylacetonate) (manufactured by Nitto Kasei Co., Ltd., Neostan U-220) and 0.2 g of dibutyltin bis (triethoxysilicate) In place of 6 g of the stearylamine ketimine compound C-1 obtained in the above, 1.6 g of coconut amine (manufactured by Kao Corporation, Farmin CS) is used, and further 5.5 g of alkylbenzene (manufactured by Nippon Oil & Chemical Co., Ltd., Alkene 200P). And 1.3g of acrylic plasticizer (ARUFON UP-1000, manufactured by Toagosei Co., Ltd.) , Except that no hindered phenolic antioxidant, hindered amine antioxidant, benzotriazole ultraviolet absorber, fatty acid amide and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane are used, A sealant composition was prepared.

[Contamination prevention test]
A slate plate cut into a strip shape of 5 mm thickness x 20 mm width is placed on the surface of a 5 mm thickness slate plate, and bonded using an adhesive, 5 mm depth x 20 mm width x 150 mm length The joint was filled with a sealant composition, the excess sealant composition was scraped off with a spatula, and the surface was flattened and cured in a room at a temperature of 23 ° C. and a relative humidity of 50% for 14 days. The body.
(1) Surface contamination After spraying 5% carbon water on the surface of the test specimen, immediately wash with tap water by spraying, etc. in a room with a temperature of 23 ° C and a relative humidity of 50% without wiping the surface. After drying for 1 day, the color difference (ΔE) from the state before the test was measured using a spectrocolorimeter CM-2500d manufactured by Konica Minolta.
(2) Measurement of contact angle with water In a room at a temperature of 23 ° C. and a relative humidity of 50%, 1 microliter of pure water was dropped onto the surface of the test specimen, and the contact angle after 1 minute was measured using a contact angle meter. .
(3) Hot water durability After immersing the test specimen in warm water at 50 ° C. for a predetermined time, the taken specimen was dried in a room at 23 ° C. and a relative humidity of 50% for 1 day, and surface contamination and The contact angle with water was measured.
[Storage stability test]
The sealing material composition in a state filled in the container was placed in a thermostat at 50 ° C. immediately after production and stored for a predetermined period, and then the surface contamination was measured.
The raw material compositions and test results of the sealing material compositions of Examples 1 and 2 and Comparative Examples 1 to 3 are collectively shown in Table 1, and only the test results of Example 1 and Comparative Example 4 are collectively shown in Table 2. .

  The curable composition of the present invention can adjust the rubber elastic properties after curing from low hardness and high elongation to high hardness and low elongation, and further to durability such as adhesion, water resistance and weather resistance. Since it is excellent, it can be used in various applications such as paints for construction and civil engineering, waterproofing coatings, adhesives, and sealing materials, but it can be suitably used as sealing materials for construction and civil engineering.

Claims (5)

A crosslinkable silyl group-containing resin (A), the fluorine-based surfactant (B), and you containing a primary and / or a compound which forms a secondary amine reacts with water (C), curing A sex composition ,
The fluorosurfactant (B) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the crosslinkable silyl group-containing resin (A), reacts with the water, and is primary and / or The said curable composition characterized by the compound (C) which produces | generates a secondary amine being 0.1-20 mass parts.   The crosslinkable silyl group-containing resin (A) is an acrylic and / or methacryl-modified polyoxyalkylene resin containing a crosslinkable silyl group, and / or a crosslinkable silyl group-containing polyacryl and / or The curable composition according to claim 1, which is a methacrylic resin.   The curable composition according to claim 1, wherein the compound (C) which reacts with water to produce a primary and / or secondary amine is a ketimine compound of a primary and / or secondary amine. object.   Furthermore, the curable composition as described in any one of Claims 1-3 containing an additive (D). The curable composition according to claim 4, wherein the additive (D) is a mixture of a hindered amine-based antioxidant, a hindered phenol-based antioxidant, and a benzotriazole-based ultraviolet absorber.