JP2017082114A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition excellent in pollution prevention property and cure sheet adherence prevention property.SOLUTION: There is provided a curable composition containing an isocyanate group-containing urethane prepolymer, a silane compound represented by the general formula (1) and/or a partial hydrolysis condensate of the silane compound and surface treated calcium carbonate with a thermal reduction of 50 to 150 mg/g. RSi-(OR)(1), where R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms and may be the same or different when there are a plurality of Rs, Ris a monovalent hydrocarbon group having 1 or more carbon atoms and at least one of (OR) is an alkoxy group having 2 to 6 carbon atoms and may be the same or different when there are a plurality of (OR)s and m is an integer of 1 to 4.SELECTED DRAWING: None

Description

  The present invention relates to a curable composition excellent in antifouling properties and curing sheet adhesion prevention properties.

  Curable compositions containing polyurethane resins are widely used as sealing materials for construction and civil engineering, waterproofing materials, adhesives, and coating materials because of their excellent workability and adhesiveness. The polyurethane resin can relatively freely adjust the rubber physical properties after curing from low modulus to high modulus (from high elongation to low elongation). However, when a curable composition containing a polyurethane resin is designed from a low modulus to a medium modulus range, stickiness may remain on the surface after curing. In this case, dust or dust easily adheres to the surface of the curable composition, and the surface is contaminated to cause a design defect. Especially when the curable composition is used outdoors, or when the curable composition is in the middle of curing, the surface of the curable composition has a large stickiness (tack), so a lot of dust and dirt adhere to the curable composition. The surface of the object is contaminated.

  On the other hand, when a curable composition is used, a curing tape or a curing sheet is often affixed to peripheral members so that the curable composition does not adhere to a location other than the usage location. In addition, after applying the curable composition, when applying a top coating to the surface or its peripheral members, the curing sheet is cured even if the curable composition is in the middle of curing in order to shorten the construction period. It may be affixed to the surface of objects. In this case, the curing sheet adheres to the surface of the curable composition mainly due to tackiness of the surface of the curable composition, and when the curing sheet is peeled off after applying the top coat, the surface layer portion of the curable composition May be pulled by the curing sheet and peeled off. When the surface layer part of a curable composition peels, the part must be repaired. For this reason, the improvement of the curing sheet adhesion prevention property of a curable composition is calculated | required.

  A curable composition containing an isocyanate group-containing urethane prepolymer and a silane compound is known as a method for preventing contamination due to stickiness of the surface of the curable composition (for example, Patent Document 1 and Patent Document 2). The curable compositions described in these patent documents are excellent in the anti-staining property of the surface of the curable composition by dust or dust due to the improvement of the stickiness of the surface of the curable composition. Curing sheet adhesion prevention was not studied.

JP 2008-201980 A JP 2009-073882 A

  An object of the present invention is to provide a curable composition having excellent anti-contamination properties and anti-curing sheet adhesion properties.

As a result of intensive studies to solve the above-mentioned demands, the present inventor has obtained an isocyanate group-containing urethane prepolymer, a specific silane compound and / or a partially hydrolyzed condensate of a silane compound, and a thermal loss of 50 to 150 mg / g. The present inventors have found that a curable composition containing surface-treated calcium carbonate is excellent in antifouling property and curing sheet adhesion prevention property of the curable composition, and completed the present invention. That is, this invention relates to the curable composition which has the aspect shown to following (1)-(7).
(1) Contains an isocyanate group-containing urethane prepolymer, a silane compound represented by the following general formula (1) and / or a partially hydrolyzed condensate of the silane compound, and a surface-treated calcium carbonate having a heat loss of 50 to 150 mg / g. A curable composition characterized by that.
R _4-m Si- (OR ¹ ) _m (1)
(In Formula (1), R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when R is plural, they may be the same or different. R ¹ is 1 having 1 or more carbon atoms. is a valence of the hydrocarbon group, at least one (OR ¹⁾ good be different even for the same when it. (OR ¹⁾ is plural alkoxy group having 2 to 6 carbon atoms .m Is an integer from 1 to 4.)
(2) The curable composition according to (1), wherein the branch density of the isocyanate group-containing urethane prepolymer is 0.03 mmol / g or more.
(3) The curable composition according to (1) or (2), wherein the isocyanate group-containing urethane prepolymer has a photoreactive unsaturated bond in the molecule.
(4) The curable composition according to any one of (1) to (3), further comprising an oxazolidine compound.
(5) Further, at least one selected from a curing accelerating catalyst, a plasticizer, a weathering stabilizer, a filler, a thixotropic agent, an adhesion improver, a storage stability improver (dehydrating agent), a colorant and an organic solvent. The curable composition according to any one of (1) to (4), wherein the composition contains at least one kind of additive.
(6) The curable composition according to any one of (1) to (5), wherein the curable composition is a curable composition for construction or civil engineering.
(7) The curing according to any one of (1) to (6), wherein the curable composition is a sealing material composition, a waterproofing material composition, an adhesive composition, or a coating material composition. Sex composition.

  The curable composition of this invention is excellent in the contamination | blocking prevention property and curing sheet adhesion prevention property of a curable composition in outdoor exposure. Moreover, since the curable composition of this invention can be used as a one-component curable composition or a two-component curable composition, its application range is wide.

  The curable composition of the present invention includes an isocyanate group-containing urethane prepolymer (hereinafter sometimes referred to simply as “urethane prepolymer”, including an isocyanate group-containing urethane prepolymer into which a photoreactive unsaturated bond described below is introduced). And a specific silane compound and / or a partially hydrolyzed condensate of the silane compound, and surface-treated calcium carbonate having a heat loss of 50 to 150 mg / g. Hereinafter, each component will be described in detail.

  The isocyanate group-containing urethane prepolymer serves as a curing component in the curable composition of the present invention and gives the cured composition good adhesion to the adherend surface.

  The isocyanate group-containing urethane prepolymer is a resin having one or more isocyanate groups, and the isocyanate group reacts with an active hydrogen (group) -containing compound to form a urethane bond, a urea bond, etc., and is crosslinked and cured.

  In the isocyanate group-containing urethane prepolymer, the organic isocyanate compound and the active hydrogen-containing compound have an isocyanate group / active hydrogen molar ratio of preferably 1.2 to 10/1, more preferably 1.2 to 5/1. The reaction can be performed collectively or sequentially within the range so that the isocyanate group remains in the urethane prepolymer. When the molar ratio is less than 1.2 / 1, the viscosity of the urethane prepolymer increases, and the workability of the curable composition deteriorates. On the other hand, if the molar ratio exceeds 10/1, the amount of carbon dioxide generated when the isocyanate group reacts with water increases, which causes foaming during curing.

  The isocyanate group content of the isocyanate group-containing urethane prepolymer is preferably 0.3 to 15% by mass, particularly preferably 0.5 to 5% by mass. When isocyanate group content is less than 0.3 mass%, the viscosity of a urethane prepolymer will become high and the workability | operativity of a curable composition will worsen. Moreover, when isocyanate group content exceeds 15 mass%, the quantity of the carbon dioxide gas generate | occur | produced when an isocyanate group reacts with water increases, and causes foaming at the time of hardening.

  The number average molecular weight of the isocyanate group-containing urethane prepolymer is preferably 1,500 or more, more preferably 1,500 to 20,000, still more preferably 1,500 to 15,000, particularly 1,500 to 10,000. Is preferred. In addition, the number average molecular weight in this invention is a numerical value of polystyrene conversion measured by gel permeation chromatography (GPC).

  The branch density of the isocyanate group-containing urethane prepolymer is preferably 0.03 mmol / g or more, more preferably 0.03 to 0.1 mmol / g, and particularly preferably 0.03 to 0.08 mmol / g. When the branch density of the urethane prepolymer is less than 0.03 mmol / g, when the curing sheet is attached to the surface of the curable composition, the curing sheet adheres to the surface of the curable composition and is difficult to peel off. In addition, the branch density of a urethane prepolymer can be theoretically calculated | required by calculation from the raw material (content of the raw material which has a branched structure) which manufactures a urethane prepolymer.

  As a method for producing an isocyanate group-containing urethane prepolymer, specifically, an organic isocyanate compound and an active hydrogen-containing compound are charged into a reaction vessel made of glass or stainless steel, and in the presence or absence of a reaction catalyst or an organic solvent. Below, the method of making it react at 50-120 degreeC stirring is mentioned. In this case, if the isocyanate group reacts with water such as moisture, the urethane prepolymer thickens. Therefore, it is preferable to replace the inside of the container with nitrogen gas in advance or to perform the reaction under a nitrogen gas stream.

  An organic polyisocyanate can be mentioned as an organic isocyanate compound. The organic polyisocyanate is a compound having two or more isocyanate groups in the compound. Specifically, toluene polyisocyanate such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, 4,4′- Diphenylmethane polyisocyanate such as diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4,6 -Phenylene polyisocyanate such as trimethylphenyl-1,3-diisocyanate, 2,4,6-triisopropylphenyl-1,3-diisocyanate, 1,4-naphthalene diisocyanate, , 5-naphthalene diisocyanate naphthalene polyisocyanate, chlorophenylene-2,4-diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenyl And aromatic polyisocyanates such as -4,4'-diisocyanate. 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, Aliphatic polyisocyanates such as decamethylene diisocyanate and lysine diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, aromatic aliphatic polyisocyanates such as p-xylylene diisocyanate, 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenation Examples thereof include alicyclic polyisocyanates such as toluene diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Furthermore, polymeric isocyanates, such as polymethylene polyphenyl polyisocyanate and crude toluene diisocyanate, are mentioned. Furthermore, modified isocyanates having one or more uretdione bonds, isocyanurate bonds, allophanate bonds, burette bonds, uretonimine bonds, carbodiimide bonds, urethane bonds or urea bonds, obtained by modifying these organic polyisocyanates. Any of these may be used alone or in combination of two or more.

  Of these, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, and modified isocyanates obtained by modifying these organic polyisocyanates are preferred because the curable composition is excellent in weather resistance.

  Moreover, organic monoisocyanate can be used with organic polyisocyanate. That is, a mixture of organic polyisocyanate and organic monoisocyanate can be used as the above-mentioned organic isocyanate compound. The organic monoisocyanate is a compound having one isocyanate group in the compound, specifically, n-butyl monoisocyanate, n-hexyl monoisocyanate, n-hexadecyl monoisocyanate, n-octadecyl monoisocyanate, Examples thereof include p-isopropylphenyl monoisocyanate and p-benzyloxyphenyl monoisocyanate.

  An active hydrogen-containing compound is a compound having one or more active hydrogens (groups) in the compound. Specific examples include high molecular polyols, high molecular polyamines, low molecular polyols, low molecular amino alcohols, low molecular polyamines, high molecular monools, and low molecular monools. These can be used alone or in combination of two or more.

  Examples of the polymer polyol include polyoxyalkylene polyols, polyester polyols, polycarbonate polyols, hydrocarbon polyols, poly (meth) acrylate polyols, and animal and plant polyols. Of these, polyoxyalkylene polyols and poly (meth) acrylate polyols are preferred. In the present invention, “(meth) acrylate” means “acrylate and / or methacrylate”.

  The number average molecular weight of the polymer polyol is preferably 1,000 to 20,000.

  Examples of the polyoxyalkylene polyol include polyoxyalkylene triols and polyoxyalkylene diols.

  In the present invention, the “system” of the polyoxyalkylene triol and polyoxyalkylene diol means 50% by mass or more, further 80% by mass or more, particularly 90% by mass or more of the portion excluding the hydroxyl group in the molecule. If it is composed of polyoxyalkylene, it means that the remaining part may be modified with ester, urethane, polycarbonate, polyamide, poly (meth) acrylate, polyolefin or the like. Most preferably, 95% by mass or more of the molecule excluding the hydroxyl group is composed of polyoxyalkylene.

  Polyoxyalkylene triols and polyoxyalkylene diols are obtained by ring-opening addition polymerization of alkylene oxide with an initiator in the presence of a polymerization catalyst. The total unsaturation degree of the polyoxyalkylene triol, polyoxyalkylene diol, and polyoxyalkylene monool is preferably 0.1 meq / g or less, more preferably 0.07 meq / g or less, particularly 0.04 meq / g. The following is preferred.

  Examples of the polymerization catalyst include sodium metal catalysts, alkali metal compound catalysts such as potassium catalysts, cationic polymerization catalysts, composite metal cyanide complex catalysts such as zinc hexacyanocobaltate glyme complex and diglyme complex, and phosphazene compound catalysts. Of these, alkali metal compound catalysts and double metal cyanide complex catalysts are preferred.

  As the initiator, a compound having 2 to 3 active hydrogens (groups) (hydroxyl groups or amino groups capable of reacting with alkylene oxide) in the molecule is used. A small amount of a compound having 4 active hydrogens (groups) in the molecule may be used in combination.

  As the initiator for producing the polyoxyalkylene triol, a compound having 3 active hydrogens (groups) is mainly used. Specific examples of the compound having 3 active hydrogens include trihydric alcohols such as glycerin and trimethylolpropane.

  As the initiator for producing the polyoxyalkylene-based diol, a compound having 2 active hydrogens (groups) is mainly used. Specific examples of the compound having 2 active hydrogens include dihydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, bisphenol A, and bisphenol F.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-epoxybutane, and 2,3-epoxybutane. Of these, propylene oxide, ethylene oxide, and a combination of propylene oxide and ethylene oxide are preferable, and propylene oxide, and a combination of propylene oxide and ethylene oxide is preferable.

  As the polyoxyalkylene triol, polyoxypropylene triol, polyoxyethylene triol, and polyoxyethylene propylene triol are preferable, and polyoxypropylene triol and polyoxyethylene propylene triol are more preferable. In addition, the number average molecular weight of the polyoxyalkylene triol is preferably 1,000 to 30,000, more preferably 1,000 to 20,000.

In the present invention, “oxyethylenepropylene” includes an oxyethylene group (—CH ₂ CH ₂ O—) and an oxypropylene group (—CH (CH ₃ ) CH ₂ O—) in the molecule.

  As the polyoxyalkylene diol, polyoxypropylene diol, polyoxyethylene diol, and polyoxyethylene propylene diol are preferable, and polyoxypropylene diol and polyoxyethylene propylene diol are more preferable. The number average molecular weight of the polyoxyalkylene diol is preferably 1,000 to 30,000, more preferably 1,000 to 20,000.

  Polyester polyols include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, etc. Polycarboxylic acids of these; anhydrides of these acids or one or more of alkyl esters such as methyl ester and ethyl ester; and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene Polyester obtained by reaction with one or more of low molecular polyols such as glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, trimethylolpropane, glycerin, pentaerythritol, etc. A polyol is mentioned. In addition to these polycarboxylic acids and acid anhydrides and low-molecular polyols, low-molecular polyamines such as butylene diamine, hexamethylene diamine, xylylene diamine, and isophorone diamine, and low molecular polyamines such as monoethanol amine and diethanol amine are also included. Also included are polyester amide polyols obtained by reaction with one or more molecular amino alcohols.

  Polyester polyols include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, etc. Polycarboxylic acids of these; anhydrides of these acids or one or more of alkyl esters such as methyl ester and ethyl ester; and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene Polyester obtained by reaction with one or more of low molecular polyols such as glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, trimethylolpropane, glycerin, pentaerythritol, etc. A polyol is mentioned. In addition to these polycarboxylic acids and acid anhydrides and low-molecular polyols, low-molecular polyamines such as butylene diamine, hexamethylene diamine, xylylene diamine, and isophorone diamine, and low molecular polyamines such as monoethanol amine and diethanol amine are also included. Also included are polyester amide polyols obtained by reaction with one or more molecular amino alcohols.

  As polycarbonate polyol, dehydrochlorination reaction of low molecular polyols and phosgene used in the synthesis of the above-mentioned polyester polyol, or transesterification reaction of low molecular polyols with diethylene carbonate, dimethyl carbonate, diethyl carbonate, and diphenyl carbonate. Can be obtained.

  As a poly (meth) acrylate-based polyol, a (meth) acrylate monomer containing a hydroxyl group such as hydroxyethyl (meth) acrylate and another (meth) acrylic acid alkyl ester monomer are used as radical polymerization initiators. Examples thereof include those copolymerized in the presence or absence.

  Examples of hydrocarbon polyols include polyolefin polyols such as polybutadiene polyol and polyisoprene polyol; polyalkylene polyols such as hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol; halogenated polyalkylene polyols such as chlorinated polypropylene polyol and chlorinated polyethylene polyol Is mentioned.

  Examples of animal and plant-based polyols include castor oil-based polyols and silk fibroin.

  Any of the above polymer polyols can be used alone or in combination of two or more.

  A polymer monool can be used in combination with the above-described polymer polyol. The number average molecular weight of the polymer monool is preferably 1,000 to 30,000, more preferably 1,000 to 20,000.

  When a polymer polyol and a polymer monool are used in combination, the combination is preferably a polymer triol and a polymer diol and a polymer monool, or a polymer triol and a polymer monool.

  The polymer monool is preferably a polyoxyalkylene monool.

  In the present invention, the “system” of the polyoxyalkylene monool means that 50% by mass or more, more than 80% by mass, particularly 90% by mass or more of the portion excluding the hydroxyl group in the molecule is composed of polyoxyalkylene. If it is, it means that the remaining part may be modified with ester, urethane, polycarbonate, polyamide, poly (meth) acrylate, polyolefin or the like. Most preferably, 95% by mass or more of the molecule excluding the hydroxyl group is composed of polyoxyalkylene.

  The polyoxyalkylene monool is obtained by ring-opening addition polymerization of alkylene oxide with an initiator in the presence of a polymerization catalyst. The total unsaturation degree of the polyoxyalkylene monool is preferably 0.1 meq / g or less, more preferably 0.07 meq / g or less, and particularly preferably 0.04 meq / g or less.

  Examples of the polymerization catalyst include sodium metal catalysts, alkali metal compound catalysts such as potassium catalysts, cationic polymerization catalysts, composite metal cyanide complex catalysts such as zinc hexacyanocobaltate glyme complex and diglyme complex, and phosphazene compound catalysts. Of these, alkali metal compound catalysts and double metal cyanide complex catalysts are preferred.

  As an initiator for producing a polyoxyalkylene monool, a compound having 1 active hydrogen (group) is mainly used. Specific examples of the compound having 1 active hydrogen (group) include monohydric alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol; phenol, Monohydric phenols such as nonylphenol; secondary amines such as dimethylamine and diethylamine.

  When the polymer monool is used in combination, the content of the polymer monool in the isocyanate group-containing urethane prepolymer is preferably 5 to 30% by mass and more preferably 5 to 20% by mass with respect to the total amount of the urethane prepolymer. When the content of the polymer monool in the urethane prepolymer is within the above range, the curable composition is excellent in durability (for example, durability of JIS A 5758). In particular, when the branch density of the urethane prepolymer is increased, the physical properties of the curable composition after curing tend to be high modulus and low elongation, and the durability tends to decrease. By setting the content of oar in the above range, even if the branch density of the urethane prepolymer is increased, the physical properties after curing of the curable composition are excellent in durability.

  The isocyanate group-containing urethane prepolymer can also introduce a photoreactive unsaturated bond into the urethane prepolymer for the purpose of imparting weather resistance. The urethane prepolymer introduced with a photoreactive unsaturated bond acts as a curing component in the curable composition of the present invention, and gives the cured composition good adhesion to the adherend surface and excellent weather resistance. Is. The photoreactive unsaturated bond described above is an unsaturated bond that undergoes a chemical change such as polymerization in a relatively short time when exposed to light. Specific examples include unsaturated bonds derived from vinyl groups, vinylene groups, and (meth) acryloyl groups. In the present invention, “(meth) acryloyl group” means “acryloyl group and / or methacryloyl group”.

  The isocyanate group of the isocyanate group-containing urethane prepolymer into which the photoreactive unsaturated bond is introduced reacts with the active hydrogen-containing compound to be crosslinked and cured. Moreover, the photoreactive unsaturated bond of the isocyanate group-containing urethane prepolymer into which the photoreactive unsaturated bond is introduced undergoes a polymerization reaction when exposed to light, and a cured film having excellent weather resistance on the surface of the curable composition. Form. This cured film is considered to impart excellent weather resistance to the curable composition. The photoreactive unsaturated bond is preferably an unsaturated bond derived from a (meth) acryloyl group in that the weather resistance imparting effect is high.

As a method of introducing a photoreactive unsaturated bond into an isocyanate group-containing urethane prepolymer,
(A) an organic isocyanate compound, a high molecular active hydrogen-containing compound (number average molecular weight of 1,000 or more), and a low molecular active hydrogen-containing compound having active hydrogen and a photoreactive unsaturated bond in the molecule (several An average molecular weight of less than 1,000) and a reaction with an excess of isocyanate groups with respect to the total amount of active hydrogen;
(B) an active hydrogen-containing compound (for example, polyoxyalkylenetriol mono (meta)) having an organic isocyanate compound and a polymer (number average molecular weight of 1,000 or more) having active hydrogen and a photoreactive unsaturated bond in the molecule; ) An acrylate, an alkylene oxide adduct of (meth) acrylic acid, a polybutadiene polyol) and a reaction in which an isocyanate group is excessive with respect to the total amount of active hydrogen; and (c) an organic isocyanate compound and an intramolecular A low molecular weight (number average molecular weight less than 1,000) active hydrogen-containing compound (for example, (meth) acryloyl isocyanate) having a photoreactive unsaturated bond and an isocyanate group, and a polymer (number average molecular weight of 1,000 or more) ) Active hydrogen-containing compound with an excess of isocyanate groups with respect to the total amount of active hydrogen How obtainable by;
Is mentioned. The method (a) is preferred from the viewpoints of availability of raw materials and ease of reaction. In the present invention, “(meth) acrylic acid” means “acrylic acid and / or methacrylic acid”.

  In the reaction for introducing the photoreactive unsaturated bond into the isocyanate group-containing urethane prepolymer, raw materials may be charged all at once, or the raw materials may be charged and reacted sequentially. The equivalent ratio (isocyanate group / active hydrogen) of the isocyanate group of the organic isocyanate compound to the active hydrogen of the active hydrogen-containing compound (including a compound having an active hydrogen and a photoreactive unsaturated bond) is 1.2 to 10 / 1 is preferable, and 1.2 to 5/1 is more preferable. The isocyanate group content in the isocyanate group-containing urethane prepolymer introduced with a photoreactive unsaturated bond is preferably 0.3 to 15% by mass, and more preferably 0.5 to 5% by mass. When the isocyanate group content is less than 0.3% by mass, the molecular weight becomes too large, the viscosity increases, and the workability decreases. Moreover, since the crosslinking point in a urethane prepolymer decreases, sufficient adhesiveness cannot be obtained. If the isocyanate group content exceeds 15% by mass, the amount of carbon dioxide generated when the isocyanate group reacts with water increases, which causes foaming during curing.

  The concentration of the photoreactive unsaturated bond in the isocyanate group-containing urethane prepolymer introduced with the photoreactive unsaturated bond is preferably 0.01 mmol / g or more, more preferably 0.03 to 1 mmol / g, particularly 0.05-0.5 mmol / g is preferable.

  The active hydrogen-containing compound (low molecular weight and high molecular weight) having the above active hydrogen and a photoreactive unsaturated bond includes an active hydrogen (group) such as a hydroxyl group, an amino group, a carboxyl group, and a vinyl group in the compound. , A vinylene group, a compound having both photoreactive unsaturated bonds such as a (meth) acryloyl group. A compound having a hydroxyl group and a (meth) acryloyl group in the compound is preferable from the viewpoint of easy reaction and high weather resistance imparting effect. The molecular weight of the compound having an active hydrogen (group) and a photoreactive unsaturated bond is preferably less than 1,000 in terms of easy reaction.

  As an active hydrogen-containing compound having a hydroxyl group and a (meth) acryloyl group, 2-hydroxyethyl (meth) acrylate, which is a monoester of alkylene glycol such as ethylene glycol, propylene glycol, butylene glycol, and (meth) acrylic acid , 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxypentyl (meth) acrylate, hydroxyneopentyl (meth) acrylate, 6-hydroxyhexyl ( Monohydroxy mono (meth) acrylates such as (meth) acrylate, hydroxyheptyl (meth) acrylate, hydroxyoctyl (meth) acrylate, glycerin, trimethylolpropane, pentae Monoesters or diesters of tri- or higher functional alkylene polyols such as sitolol and (meth) acrylic acid, polyesters such as triesters, glycerol di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) ) Monohydroxy poly (meth) acrylates such as acrylate, glycerol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, poly (hydroxy) mono (meth) acrylates such as pentaerythritol mono (meth) acrylate, pentaerythritol di Examples thereof include polyhydroxy poly (meth) acrylates such as (meth) acrylate. In addition to these, monohydroxy mono (meta) such as diethylene glycol, dipropylene glycol, polyoxyethylene polyol, polyoxypropylene polyol, polyol obtained by adding alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to bisphenol A or bisphenol F. ) Acrylates, polyhydroxy mono (meth) acrylates, polyhydroxy poly (meth) acrylates, hydroxyalkyl (meth) acrylates such as (meth) acrylic acid and hydroxyethyl (meth) acrylate, and the active hydrogen, ethylene oxide, propylene oxide , Compounds to which alkylene oxide such as butylene oxide is added and having a hydroxyl group, modified caprolactone of hydroxyethyl acrylate, etc. Compound having a hydroxyl group may also be mentioned. These can be used alone or in combination of two or more. Of these, monohydroxy poly (meth) acrylates and dihydroxy poly (meth) acrylates are preferred in that the viscosity of the urethane prepolymer can be kept low and the weather resistance imparting effect can be enhanced.

  The silane compound and / or the partial hydrolysis condensate of the silane compound will be described. A silane compound and / or a partially hydrolyzed condensate of a silane compound gives an effect of preventing contamination and preventing curing sheet adhesion to a curable composition by combining with a urethane prepolymer. This is because when the curable composition is cured with water such as moisture, the silane compound and / or the partially hydrolyzed condensate of the silane compound migrates (bleeds) from the middle of curing to the surface of the curable composition. It is considered that the stickiness of the surface of the curable composition is reduced by being hydrolyzed with water such as water, condensed while dealcoholizing, and forming a hydrophilic film on the surface of the curable composition. By reducing the stickiness of the surface of the curable composition, it becomes difficult for dust and dirt to adhere to the surface of the curable composition, and the anti-contamination property is improved. Moreover, even if dust or dirt adheres to the surface of the curable composition, it is possible to remove dust and dirt relatively easily by spraying running water or compressed air such as rain or shower.

The silane compound is a compound represented by the following general formula (1), and is a silane compound having at least one alkoxy group other than a methoxy group in the molecule.
R _4-m Si (OR ¹ ) _m (1)
(In Formula (1), R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when R is plural, they may be the same or different. R ¹ is 1 having 1 or more carbon atoms. is a valence of the hydrocarbon group, at least one (OR ¹⁾ good be different even for the same when it. (OR ¹⁾ is plural alkoxy group having 2 to 6 carbon atoms .m Is an integer from 1 to 4.)

  R is a monovalent monovalent carbon having 1 to 6 carbon atoms having no reactive functional group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, heptyl group, hexyl group, and phenyl group. A hydrocarbon group is mentioned.

The (OR ¹ ) is an alkoxy group, and when m is 1, (OR ¹ ) is an alkoxy group other than a methoxy group. When m is 2, 3 or 4, at least one of (OR ¹ ) is an alkoxy group other than a methoxy group.

  Examples of the alkoxy group other than the methoxy group include alkoxy groups having 2 or more carbon atoms such as ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, pentoxy group, hexoxy group, and phenoxy.

  Examples of the silane compound include tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, and dimethoxydiethoxysilane. It is done. Any of these may be used alone or in combination of two or more.

  The partially hydrolyzed condensate of the silane compound is a multimer obtained by partially hydrolyzing the alkoxy group of the silane compound in the presence or absence of a solvent and condensing the silane compound linearly or three-dimensionally. . The partial hydrolysis-condensation product of the silane compound is preferably a 2 to 20-mer from the viewpoints of transferability (bleed) to the surface of the curable composition and film formation after transfer to the surface of the curable composition.

  Specific examples of the partial hydrolysis condensate of the silane compound include, for example, ethyl silicate 40 (average pentamer), ethyl silicate 48 (average 10 mer), and Colcoat, including a partial hydrolysis condensate of tetraethoxysilane. EMS-485 (average 10-mer) containing a partially hydrolyzed condensate of diethoxydimethoxysilane, manufactured by Colcoat Co., Ltd .; MKC containing a condensate obtained by partially butoxylating a partially hydrolyzed condensate of tetramethoxysilane with butanol Silicate MS58B15, MS58B30, MS51, MS56, M57, MS56S, manufactured by Mitsubishi Chemical Corporation. Any of these may be used alone or in combination of two or more.

  The usage-amount of the said silane compound and / or the partial hydrolysis-condensation product of a silane compound is 0.01-20 mass parts with respect to 100 mass parts of isocyanate group containing urethane prepolymers, Furthermore, 0.1-10 mass parts is preferable. . When the amount used is less than 0.01 parts by mass, the effect of preventing the contamination of the surface of the curable composition and the effect of preventing the adhesion of the curing sheet are small. If the amount used exceeds 20 parts by mass, the amount of alcohol generated by hydrolysis of the silane compound and / or the partial hydrolysis condensate of the silane compound increases, and the generated alcohol reacts with the isocyanate group of the urethane prepolymer. May cause poor curing.

  The surface-treated calcium carbonate will be described. The surface-treated calcium carbonate imparts thixotropic properties to the curable composition, prevents the occurrence of sagging and slump when the curable composition is used on a vertical surface or inclined surface, and bead-applied the curable composition. It is used for the purpose of maintaining the shape of the coating when it is applied with a comb or the like. The surface-treated calcium carbonate in the present invention is obtained by changing the surface-treated calcium carbonate having a heat loss of 50 to 150 mg / g at a temperature rising rate of 15 ° C./min to the above-mentioned urethane prepolymer, silane compound and / or silane compound. By using together with the partial hydrolysis-condensation product, the curable composition has excellent curing sheet adhesion prevention properties.

  Examples of the surface-treated calcium carbonate include fatty acid surface-treated calcium carbonate. Fatty acid surface-treated calcium carbonate is obtained by treating the surfaces of heavy calcium carbonate, light calcium carbonate, and colloidal calcium carbonate with fatty acids such as fatty acids, fatty acid alkyl esters, fatty acid metal salts, and fatty acid organic salts.

  As fatty acids, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, beef tallow stearic acid, palm kernel fatty acid, partially cured palm fatty acid, extremely cured palm fatty acid, palm fatty acid, partially cured palm fatty acid, extremely cured palm fatty acid, Examples include palm fatty acid, palm stearic acid, beef tallow fatty acid, partially cured beef tallow fatty acid, extremely cured beef tallow fatty acid, soybean fatty acid, partially cured soybean fatty acid, extremely cured soybean fatty acid, naphthenic acid, abietic acid, and neoabietic acid. Examples of metal salts include sodium salts, potassium salts, calcium salts, aluminum salts, and organic salts include ammonium salts.

  As commercially available products of fatty acid surface-treated calcium carbonate, Maruo Calcium Co., Ltd., Sealet 200, Calfine 200, Calfine 200M, Calfine 500, Calfine N-40, Calfine N-350; White gloss flower CCR, white gloss flower CCR-S, white gloss flower CCR-B, VIGOT-10, VIGOT-15, Viscolite-SV, Viscolite-OS, Viscolite EL-20; NCC # 3010, NCC # 1010 of Nitto Flour Industry Co., Ltd. . Any of these may be used alone or in combination of two or more. Among these, calcium carbonate surface-treated with a fatty acid or a fatty acid metal salt is preferable in that it has a high thixotropic effect.

The average particle size of the fatty acid surface-treated calcium carbonate is preferably 0.01 to 1.0 μm, more preferably 0.01 to 0.3 μm. BET specific surface area of the fatty acid surface-treated calcium carbonate is preferably 5 to 200 m ² / g, further 10 to 60 m ² / g are preferred. If the average particle size is less than 0.01 μm, or the BET specific surface area exceeds 200 m ² / g, the viscosity of the resulting curable composition is increased and workability is deteriorated. If the average particle size exceeds 1.0 μm or the BET specific surface area is less than 5 m ² / g, the thixotropic effect is reduced, which is not preferable.

The heat loss of the fatty acid surface-treated calcium carbonate is preferably 50 to 150 mg / g, more preferably 50 to 120 mg / g, because the curing sheet adhesion preventing property of the curable composition becomes good. The heat loss of the fatty acid surface-treated calcium carbonate can be determined by thermogravimetry (TG). Specifically, for example, it can be determined by the following measurement method.
[Measuring method]
10 mg of fatty acid surface-treated calcium carbonate is weighed in a platinum sample pan having a diameter of 5 mm, and the temperature is raised from room temperature to 510 ° C. at a rate of 15 ° C./min using a thermogravimetric analyzer (TG8120, manufactured by Rigaku Corporation). At this time, the weight decreased in the range of 200 to 500 ° C. is measured to determine the heat loss (mg / g) per gram of the fatty acid surface-treated calcium carbonate.

  1-200 mass parts is preferable with respect to 100 mass parts of isocyanate group containing urethane prepolymers, and, as for the usage-amount of fatty-acid surface treatment calcium carbonate, 5-150 mass parts is more preferable.

  The curable composition of the present invention can contain an oxazolidine compound. The oxazolidine compound is a compound having 1 or more, preferably 1 to 6 oxazolidine rings in the molecule, which is a saturated 5-membered heterocyclic ring containing an oxygen atom and a nitrogen atom. The oxazolidine compound reacts with water such as moisture to hydrolyze, and the oxazolidine ring generates (regenerates) a secondary amino group and an alcoholic hydroxyl group, thereby functioning as a latent curing agent for the isocyanate group-containing urethane prepolymer. Is. When the isocyanate group of the urethane prepolymer reacts with water such as moisture, it forms a urea bond and cures. At this time, carbon dioxide gas is also generated, and bubbles due to carbon dioxide gas are generated in the cured product, resulting in deterioration of appearance and curing. Problems such as breakage of objects and deterioration of adhesiveness may occur. On the other hand, when a curable composition containing an isocyanate group-containing urethane prepolymer and an oxazolidine compound is reacted with water, first, water and the oxazolidine compound react preferentially, and the oxazolidine ring of the oxazolidine compound has a secondary amino group. An alcoholic hydroxyl group (active hydrogen group) is generated. Next, since the generated active hydrogen groups (especially secondary amino groups) react preferentially with isocyanate groups, the generation of carbon dioxide gas due to the reaction of water and isocyanate groups is suppressed, and foaming during curing of the curable composition is suppressed. Can be prevented.

  Moreover, when an aliphatic polyisocyanate or an alicyclic polyisocyanate is used as the organic polyisocyanate compound used for the isocyanate group-containing urethane prepolymer, the curing of the curable composition may be delayed. When an isocyanate group-containing urethane prepolymer and an oxazolidine compound are used in combination with the curable composition, curing of the curable composition can be accelerated, and the amount of the curing accelerating catalyst described later can be reduced.

  Furthermore, the oxazolidine compound is incorporated into a curable composition containing an isocyanate group-containing urethane prepolymer and a silane compound and / or a partially hydrolyzed condensate of the silane compound, thereby preventing the occurrence of cracks on the surface of the curable composition. Has the effect of preventing. When the curable composition is cured, cracks on the surface of the curable composition cause the silane compound and / or partially hydrolyzed condensate of the silane compound to migrate (bleed) to the surface of the curable composition and hydrolyze. Since the formed cured film is hard, if a displacement occurs in the cured film, it is assumed that the displacement cannot follow the displacement and a crack occurs. When the oxazolidine compound is blended, the cured film of the silane compound and / or the partially hydrolyzed condensate of the silane compound has flexibility by the action of the secondary amino group and alcoholic hydroxyl group generated by hydrolysis of the oxazolidine compound. It is presumed that cracks are prevented from occurring.

  Examples of the oxazolidine compound include a urethane bond-containing oxazolidine compound, an ester group-containing oxazolidine compound, an oxazolidine silyl ether compound, and a carbonate group-containing oxazolidine compound. These oxazolidine compounds are obtained by reacting a hydroxyl group of a compound having a hydroxyl group and an oxazolidine ring with an isocyanate group of an organic polyisocyanate compound or a carboxyl group of an organic carboxylic acid compound. Of these oxazolidine compounds, urethane bond-containing oxazolidine compounds are preferred because they are easy to produce and have low viscosity.

  Specific examples of the compound having a hydroxyl group and an oxazolidine ring include N-hydroxyalkyloxazolidine obtained by a dehydration condensation reaction between a secondary amino group of an alkanolamine and a carbonyl group of a ketone compound or an aldehyde compound. As a method for producing the compound having a hydroxyl group and an oxazolidine ring, 1 mol or more, preferably 1 to 1.5 mol, more preferably 1 to 1.5 mol of a carbonyl group of an aldehyde compound or a ketone compound with respect to 1 mol of a secondary amino group of alkanolamine. Can be used in an amount of 1 to 1.2 moles, heating and refluxing in a solvent such as toluene and xylene, and performing a dehydration condensation reaction while removing by-product water. Excess aldehyde compounds and ketone compounds may be removed by distillation.

  Examples of the alkanolamine include diethanolamine, dipropanolamine, and N- (2-hydroxyethyl) -N- (2-hydroxypropyl) amine. Examples of the ketone compound include acetone, diethyl ketone, isopropyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl tert-butyl ketone, diisobutyl ketone, cyclopentanone, and cyclohexanone. Examples of the aldehyde compound include acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, 2-methylbutyraldehyde, n-hexylaldehyde, 2-methylpentylaldehyde, n-octylaldehyde, 3, 5 Aliphatic aldehyde compounds such as 1,5-trimethylhexylaldehyde; aromatic aldehyde compounds such as benzaldehyde, methylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, isopropylbenzaldehyde, isobutylbenzaldehyde, methoxybenzaldehyde, dimethoxybenzaldehyde, and trimethoxybenzaldehyde. Any of these may be used alone or in combination of two or more.

  Of these, diethanolamine is preferred as the alkanolamine because it is easy to produce a compound having a hydroxyl group and an oxazolidine ring and has excellent antifoaming properties when the curable composition is cured. Of these, aldehyde compounds are preferable, and isobutyraldehyde, 2-methylpentylaldehyde, and benzaldehyde are more preferable.

  Examples of the compound having a hydroxyl group and an oxazolidine ring include 2-isopropyl-3- (2-hydroxyethyl) oxazolidine, 2- (1-methylbutyl) -3- (2-hydroxyethyl) oxazolidine, 2-phenyl-3- (2 -Hydroxyethyl) oxazolidine.

  As the urethane bond-containing oxazolidine compound, the molar ratio of isocyanate group / hydroxyl group between the isocyanate group of the organic polyisocyanate compound and the hydroxyl group of the compound having an oxazolidine ring is 0.9 / 1 to 1.2 / 1, preferably 0. Suitable examples include those obtained by reacting at a temperature of 50 to 120 ° C. in the presence or absence of an organic solvent.

  Examples of the organic polyisocyanate compound used for the production of the urethane bond-containing oxazolidine compound include the same as those used for the production of the urethane prepolymer. Among these, araliphatic polyisocyanate and aliphatic polyisocyanate are preferable, and xylylene diisocyanate and hexamethylene diisocyanate are particularly preferable.

  The ester group-containing oxazolidine compound can be obtained by reacting the above-mentioned compound having a hydroxyl group and an oxazolidine ring with a lower alkyl ester of dicarboxylic acid or polycarboxylic acid.

  The oxazolidine silyl ether compound includes a compound having a hydroxyl group and an oxazolidine ring described above, trimethoxysilane, tetramethoxysilane, triethoxysilane, dimethoxydimethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethyl. It can be obtained by dealcoholization reaction with alkoxysilane such as methoxysilane and 3-glycidoxypropyltriethoxysilane.

  The carbonate group-containing oxazolidine compound can be obtained by reacting the above-mentioned compound having a hydroxyl group and an oxazolidine ring with a carbonate such as diallyl carbonate using a polyhydric alcohol such as diethylene glycol or glycerin.

  Any of these oxazolidine compounds can be used alone or in combination of two or more.

  The oxazolidine compound preferably does not have an active hydrogen-containing functional group such as an amino group or a hydroxyl group that reacts with the isocyanate group of the urethane prepolymer, or an isocyanate group. This is to prevent a rise in viscosity of the urethane prepolymer and a reduction in foaming prevention performance of the oxazolidine compound. However, in the production of the above-mentioned urethane bond-containing oxazolidine compound, a small amount of active hydrogen-containing functional group or isocyanate group may remain in the molecule depending on the molar ratio selected. In this case, the purpose of the present invention is achieved. It can be regarded as not having. The “small amount” means that the amount of active hydrogen-containing functional groups or isocyanate groups remaining in the molecule is preferably 0.05 mmol or less, more preferably 0.02 mmol or less per 1 g of the oxazolidine compound.

  When the oxazolidine compound is used, the compounding amount is 0.1 to 1 mol of active hydrogen of the secondary amino group that is generated (regenerated) by hydrolysis of the oxazolidine compound with respect to 1 mol of the isocyanate group of the urethane prepolymer. It is preferable to use 0.3 to 1 mol, and more preferably 0.5 to 1 mol. If the active hydrogen of the secondary amino group produced (regenerated) by hydrolysis of the oxazolidine compound is less than 0.1 mol, foaming prevention is insufficient, which is not preferable.

  The curable composition of the present invention can contain various additives as necessary in addition to the above-described components within a range not impairing the object of the present invention. Additives are blended into the curable composition and used to improve various performances such as viscosity adjustment, curing acceleration, and adhesiveness of the curable composition. Specific examples include curing accelerators, plasticizers, weathering stabilizers, fillers, thixotropic agents, adhesion improvers, storage stability improvers (dehydrating agents), colorants, and organic solvents. Any of these may be used alone or in combination of two or more.

  The curing accelerating catalyst is used to promote the crosslinking and curing of the isocyanate group-containing urethane prepolymer by reacting with water such as moisture. Moreover, when an oxazolidine compound is mix | blended with a curable composition, it uses in order to accelerate | stimulate reaction with the secondary amino group produced | generated from the oxazolidine compound, the alcoholic hydroxyl group, and the isocyanate group of a urethane prepolymer. Furthermore, the curing accelerating catalyst can also be used as a reaction catalyst during the production of the urethane prepolymer. In addition, when it uses as a reaction catalyst at the time of manufacture of a urethane prepolymer, the reaction catalyst which remains in a urethane prepolymer may act as a hardening acceleration | stimulation catalyst of a curable composition.

  Specific examples of the curing accelerating catalyst include a metal catalyst and an amine catalyst.

  Examples of the metal catalyst include a salt of a metal and an organic acid, a salt of an organic metal and an organic acid, and a metal chelate compound. Examples of the salt of metal and organic acid include salts of various metals such as tin, bismuth, zirconium, zinc and manganese with organic acids such as octylic acid, neodecanoic acid, stearic acid and naphthenic acid. Specific examples include tin octylate, tin naphthenate, bismuth octylate, and zirconium octylate. As salts of organic metal and organic acid, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversate, reaction of dibutyltin oxide and phthalate Things. As the metal chelate compound, dibutyltin bis (acetylacetonate), EXCESTAR C-501 made by Asahi Glass Co., which is a tin-based chelate compound, zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate), aluminum tris (acetylacetate) Natto), aluminum tris (ethyl acetoacetate), acetylacetone cobalt, acetylacetone iron, acetylacetone copper, acetylacetone magnesium, acetylacetone bismuth, acetylacetone nickel, acetylacetone zinc and acetylacetone manganese.

  Examples of the amine catalyst include tertiary amines. Tertiary amines include triethylamine, tributylamine, triethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1,4-diazabicyclo [2,2,2]. Examples include octane (DABCO) and salts of these tertiary amines and organic carboxylic acids.

  Any of these curing accelerating catalysts can be used alone or in combination of two or more.

  Among these, since it is excellent in curability of the curable composition, a salt of a metal and an organic acid, a salt of an organic metal and an organic acid, and a metal chelate compound are preferable. Salts of organic acids, salts of organic tin and organic acids, salts of organic bismuth and organic acids, tin chelate compounds, and bismuth chelate compounds are preferred.

  The use amount of the curing accelerating catalyst is preferably 0.005 to 5 parts by mass, particularly preferably 0.005 to 2 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer.

  In addition to the above-mentioned metal catalyst and amine catalyst, organic carboxylic acid catalyst, phosphate ester catalyst, p-toluenesulfonyl monoisocyanate, and a reaction product of p-toluenesulfonyl monoisocyanate and water can be used. An organic carboxylic acid catalyst, a phosphoric acid ester catalyst, p-toluenesulfonyl monoisocyanate, and a reaction product of p-toluenesulfonyl monoisocyanate and water, when an oxazolidine compound is added to the curable composition, is an oxazolidine ring of the oxazolidine compound It promotes the hydrolysis of. Of these, organic carboxylic acid catalysts are preferred. By the promotion of hydrolysis of the oxazolidine ring, the generated secondary amino group and alcoholic hydroxyl group (active hydrogen group) react with the isocyanate group of the urethane prepolymer to accelerate the curing of the curable composition. Furthermore, stickiness is improved from the initial stage of curing of the curable composition, and the contamination prevention property and the curing sheet adhesion prevention property of the curable composition are improved.

  Examples of organic carboxylic acid catalysts include formic acid, acetic acid, propionic acid, caproic acid, oxalic acid, succinic acid, adipic acid, 2-ethylhexanoic acid (octylic acid), octenoic acid, lauric acid, oleic acid, stearic acid, etc. Examples include α, β-unsaturated carboxylic acids such as aliphatic carboxylic acid, maleic acid, and acrylic acid, and aromatic carboxylic acids such as phthalic acid, benzoic acid, and salicylic acid.

  Examples of the phosphoric acid ester catalyst include regular phosphoric acid ester compounds and phosphorous acid ester compounds. Examples of the orthophosphate compound include acidic phosphate compounds such as ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, oleyl acid phosphate, and the phosphite compound includes triethyl phosphite, Triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite and other oxalic acid triester compounds, dilauryl hydrogen phosphite, dioleyl Examples thereof include phosphorous acid diester compounds such as hydrogen phosphite and diphenyl hydrogen phosphite.

  The reaction product of p-toluenesulfonyl monoisocyanate and water may be obtained by reacting p-toluenesulfonyl monoisocyanate and water in advance before blending with the curable composition of the present invention, What was made to react by adding water while mix | blending p-toluenesulfonyl monoisocyanate with a curable composition, or what was made to react with the water which exists in a curable composition may be used.

  The plasticizer is used for the purpose of lowering the viscosity of the curable composition to improve workability and adjusting the rubber physical properties after curing of the curable composition. Specific examples include phthalates such as dioctyl phthalate, diisononyl phthalate, dibutyl phthalate, and butyl benzyl phthalate; aliphatic carboxylic acid esters such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate, and butyl oleate. Low molecular weight plasticizers such as polyoxyalkylene triols, polyoxyalkylene triols, polyoxyalkylene diols, polyoxyalkylene monools that can be used for the synthesis of the above-mentioned isocyanate group-containing urethane prepolymers, etherified Or esterified high molecular weight plasticizer having a number average molecular weight of 1,000 or more; high molecular weight plasticizer having a number average molecular weight of 1,000 or more that does not react with isocyanate groups such as polystyrenes such as poly-α-methylstyrene and polystyrene. Agents. Any of these may be used alone or in combination of two or more.

  The plasticizer is preferably used in an amount of 1 to 200 parts by weight, more preferably 2 to 50 parts by weight, based on 100 parts by weight of the isocyanate group-containing urethane prepolymer.

  The weather resistance stabilizer is used for the purpose of further improving the weather resistance and heat resistance by preventing oxidation, light deterioration and heat deterioration of the curable composition. Examples of the weathering stabilizer include a hindered amine light stabilizer, a hindered phenol antioxidant, and an ultraviolet absorber. Any of these weather stabilizers can be used alone or in combination of two or more.

  Examples of hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (2,2,6,6-tetramethyl-1 (octyloxy) -4 decanoate. -Piperidyl) ester, 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 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]- Low molecular weight compounds having a molecular weight of less than 1,000, such as 2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine; dimethyl succinate 1- (2- Hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine -2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N , N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1 , 3,5-triazine condensate Other, ADEKA Corp. STAB LA-63P, compounds having a molecular weight of 1,000 or more high molecular weight, such as LA-68LD and the like.

  As the hindered phenol-based antioxidant, pentaerythritol-tetrakis [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-hydroxyphenyl) propioamide], 3,5-bisbenzenepropanoate (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol.

  Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers such as 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole; 2- (4,6-diphenyl-1, 3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol and other triazine ultraviolet absorbers; benzophenone ultraviolet absorbers such as octabenzone; 2,4-di-tert-butylphenyl-3 Benzoate ultraviolet absorbers such as, 5-di-tert-butyl-4-hydroxybenzoate.

  Among these, a hindered amine light stabilizer, a hindered phenol antioxidant, and a mixture thereof are preferable in that the effect of improving weather resistance is high. The weathering stabilizer is preferably used in an amount of 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the isocyanate group-containing urethane prepolymer.

  The filler is used as an extender for the curable composition and for the purpose of reinforcing the physical properties of the cured product. Examples include inorganic fillers and organic fillers. Inorganic fillers include heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, mica, kaolin, zeolite, graphite, diatomaceous earth, white clay, clay, talc, silicic anhydride, quartz, aluminum powder, zinc powder, hydroxylation Inorganic powder fillers such as calcium, magnesium carbonate, and alumina; inorganic fiber fillers such as glass fiber and carbon fiber; inorganic balloon fillers such as glass balloon, shirasu balloon, silica balloon, and ceramic balloon . Organic fillers include organic powder fillers such as wood flour, walnut flour, rice husk flour, pulp powder, rubber powder, thermoplastic or thermosetting resin powder; Examples include balloon-like fillers. In addition, flame retardant imparting fillers such as magnesium hydroxide and aluminum hydroxide can be used. Any of these may be used alone or in combination of two or more.

  The amount of the filler used is preferably 1 to 500 parts by mass, more preferably 10 to 300 parts by mass, and particularly preferably 10 to 200 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer.

  The thixotropic agent imparts thixotropic properties to the curable composition in the same manner as the above-mentioned surface-treated calcium carbonate, and prevents the occurrence of sagging and slump when the curable composition is used on a vertical surface or an inclined surface. In addition, it is used for the purpose of maintaining the coating shape when the curable composition is applied by bead coating, comb eyes, or the like. Examples of the thixotropic agent include an inorganic thixotropic agent and an organic thixotropic agent. Examples of the inorganic thixotropic agent include fine powdered silica such as hydrophilic or hydrophobic colloidal silica in addition to the above-mentioned surface-treated calcium carbonate. Examples of the organic thixotropic agent include fatty acid amide. Any of these may be used alone or in combination of two or more.

  The adhesion improver is used for the purpose of improving the adhesion of the curable composition. Specific examples include various coupling agents such as silane, aluminum, and zircoaluminate, and partial hydrolysis condensates thereof. Of these, a silane coupling agent or a partially hydrolyzed condensate thereof is preferable because of its excellent adhesiveness.

  Examples of silane coupling agents include vinyltrimethoxysilane, vinylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) Examples include compounds having a molecular weight of 500 or less containing alkoxysilyl groups such as -3-aminopropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. Alternatively, one or two or more partial hydrolysis condensates of these silane coupling agents include compounds having a molecular weight of 200 to 3,000. Any of these may be used alone or in combination of two or more.

  A storage stability improver (dehydrating agent) is used for the purpose of improving the storage stability of the curable composition. Specific examples include vinyltrimethoxysilane, calcium oxide, and p-toluenesulfonyl isocyanate (PTSI) that react with water present in the curable composition to act as a dehydrating agent. Any of these may be used alone or in combination of two or more.

  The colorant is used for the purpose of coloring the curable composition and imparting design properties to the cured product. Specific examples include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black. Any of these may be used alone or in combination of two or more.

  The organic solvent is used for the purpose of lowering the viscosity of the curable composition and improving workability such as extrudability, casting and coating. As the organic solvent, any organic solvent that has good compatibility with other components in the curable composition and does not react with other components can be used without particular limitation. Specifically, carbonate solvents such as dimethyl carbonate, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate and butyl acetate, aliphatic solvents such as n-hexane, and alicyclic systems such as cyclohexane Examples thereof include organic solvents such as solvents, aromatic solvents such as toluene and xylene, and petroleum distillate solvents such as mineral spirits and industrial gasoline. Any of these may be used alone or in combination of two or more.

  Since the curable composition of the present invention is cured by reacting with water such as moisture in the air, it can be used as a one-pack type moisture curable composition. Further, it can also be used as a two-component reaction curable composition having the curable composition of the present invention as a main component and an active hydrogen-containing compound such as polyamine or polyol as a curing agent. It is preferable to use it as a one-component moisture curable composition because it eliminates the hassle of mixing the main agent and curing agent, and does not cause curing failure due to mixing errors or insufficient mixing, and is excellent in workability.

  When constructing using the curable composition of the present invention, materials (members) to be constructed include mortar, concrete, ALC (Autoclaved Lightweight Concrete), glass, marble, granite, siding, tile, tile, brick Inorganic materials such as iron, copper, stainless steel, galvanium steel plate, metal materials such as iron, aluminum, titanium, acrylic resin, polyester resin, vinyl chloride, ABS (Acrylonitrile-Butadiene-Styrene copolymer), FRP (Fiber Reinforced Plastic), etc. A material made of synthetic resin, such as wood or plywood.

  Although it does not specifically limit as a manufacturing method of the curable composition of this invention, Specifically, the isocyanate group containing urethane prepolymer, the partial hydrolysis-condensation product of a silane compound and / or a silane compound, surface treatment calcium carbonate, and If necessary, add the oxazolidine compound and additives to a mixing vessel with a stirrer that can block moisture such as glass, stainless steel, iron, etc., and stir and mix batchwise or continuously under a dry nitrogen stream Can be manufactured.

  Since the curable composition of the present invention is thickened and cured by water such as moisture, it is preferably packed and sealed in a container capable of blocking water such as moisture. The container is not particularly limited as long as it is a container that can block water such as moisture. Specific examples include metal or resin pail cans, aluminum bags, paper or resin cartridges.

  Examples of the present invention are shown below, but the present invention is not construed as being limited to the examples.

[Synthesis Example 1] (Synthesis of Isocyanate Group-Containing Urethane Prepolymer PU-1)
717.5 g of polyoxypropylene diol (number average molecular weight 3,300, Exenol 3021, manufactured by Asahi Glass Co., Ltd.) while flowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube and heating / cooling device, polyoxy 160.0 g of propylenetriol (number average molecular weight 4,000, Triol-MN-4000, manufactured by Mitsui Chemicals) was charged, and while stirring, 122.5 g of isophorone diisocyanate (molecular weight 222.3, manufactured by Evonik Japan), dibutyltin 0.2 g of dilaurate (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.) was charged, heated, and reacted at 75 to 85 ° C. for 4 hours. The reaction was terminated when the isocyanate group content became the theoretical value (2.3% by mass) or less, and an isocyanate group-containing urethane prepolymer PU-1 was synthesized. The obtained isocyanate group-containing urethane prepolymer PU-1 was a viscous liquid transparent at room temperature with an isocyanate group content of 2.1% by mass measured by titration. The branch density (theoretical value) of the urethane prepolymer PU-1 is 0.04 mmol / g.

[Synthesis Example 2] (Synthesis of Isocyanate Group-Containing Urethane Prepolymer PU-2)
620.4 g of polyoxypropylene diol (number average molecular weight 3,300, Exenol 3021, manufactured by Asahi Glass Co., Ltd.) is introduced into the reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, and heating / cooling device while flowing nitrogen gas. 160.0 g propylene triol (number average molecular weight 4,000, Triol-MN-4000, manufactured by Mitsui Chemicals), 100.0 g polyoxypropylene monool (number average molecular weight 3,080, preminol 1003, manufactured by Asahi Glass Co., Ltd.) While charging and stirring, 119.6 g of isophorone diisocyanate (molecular weight 222.3, manufactured by Evonik Japan) and 0.2 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd., Neostan U-100) are charged and heated to 75 to 85 ° C. For 4 hours. The reaction was terminated when the isocyanate group content became the theoretical value (2.3 mass%) or less, and an isocyanate group-containing urethane prepolymer PU-2 was synthesized. The obtained isocyanate group-containing urethane prepolymer PU-1 was a viscous liquid transparent at room temperature with an isocyanate group content of 2.1% by mass measured by titration. The branch density (theoretical value) of the urethane prepolymer PU-2 is 0.04 mmol / g.

[Synthesis Example 3] (Synthesis of Isocyanate Group-Containing Urethane Prepolymer PU-3)
Polyoxypropylene diol (number average molecular weight 3,300, Exenol 3021, manufactured by Asahi Glass Co., Ltd.) 581.8g, polyoxy while flowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube and heating / cooling device 160.0 g propylene triol (number average molecular weight 4,000, Triol-MN-4000, manufactured by Mitsui Chemicals), 100.0 g polyoxypropylene monool (number average molecular weight 3080, preminol 1003, manufactured by Asahi Glass), penta 30.0 g of erythritol triacrylate (molecular weight 298) was charged, and while stirring, isophorone diisocyanate (molecular weight 222.3, manufactured by Evonik Japan) 128.2 g, dibutyltin dilaurate (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.) Charge 2g and heat to 75-8 It was reacted for 4 hours at ° C.. The reaction was terminated when the isocyanate group content became the theoretical value (2.3% by mass) or less, and an isocyanate group-containing urethane prepolymer PU-3 was synthesized. The obtained isocyanate group-containing urethane prepolymer PU-3 was a viscous liquid transparent at room temperature with an isocyanate group content of 2.1% by mass measured by titration. The branch density (theoretical value) of the urethane prepolymer PU-2 is 0.04 mmol / g, and the acryloyl group content (theoretical value) is 0.3 mmol / g.

[Synthesis Example 4] (Synthesis of Isocyanate Group-Containing Urethane Prepolymer PU-4)
798.6 g of polyoxypropylene diol (number average molecular weight 3,300, Exenol 3021, manufactured by Asahi Glass Co., Ltd.), polyoxy, while flowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube and heating / cooling device. 80.0 g of propylene triol (number average molecular weight 4,000, Triol-MN-4000, manufactured by Mitsui Chemicals) was charged, and while stirring, isophorone diisocyanate (molecular weight 222.3, manufactured by Evonik Japan) 121.4 g, dibutyltin dilaurate (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.) was charged in an amount of 0.2 g, heated, and reacted at 75 to 85 ° C. for 4 hours. The reaction was terminated when the isocyanate group content became the theoretical value (2.3 mass%) or less, and an isocyanate group-containing urethane prepolymer PU-4 was synthesized. The isocyanate group-containing urethane prepolymer PU-3 was a viscous liquid transparent at room temperature with an isocyanate group content of 2.1% by mass measured by titration. In addition, the branch density (theoretical value) of the isocyanate group-containing urethane prepolymer PU-3 is 0.02 mmol / g.

[Synthesis Example 5] (Synthesis of urethane bond-containing oxazolidine compound O-1)
A reactor equipped with a stirrer, thermometer, nitrogen seal tube, ester tube and heating / cooling device was charged with 435.0 g of diethanolamine (molecular weight 105) and 183.0 g of toluene, and isobutyraldehyde (molecular weight 72.1) was stirred. 328.0 g was charged, heated while flowing nitrogen gas, and reflux dehydration reaction was continued at 110 to 150 ° C., and by-product water (74.5 g) was taken out of the system. After completion of the reaction, the mixture was further heated under reduced pressure (50 to 70 hPa) to remove toluene and unreacted isobutyraldehyde to obtain N-hydroxyethyl-2-isopropyloxazolidine as an intermediate reaction product.

  Next, 348.0 g of hexamethylene diisocyanate (molecular weight 168) was further added to 659.0 g of the obtained N-hydroxyethyl-2-isopropyloxazolidine, and the mixture was heated at 80 ° C. for 8 hours. When the amount reached 0% by mass, the reaction was terminated, and a urethane bond-containing oxazolidine compound O-1 having two oxazolidine rings in the molecule was obtained. Urethane bond-containing oxazolidine compound O-1 was liquid at room temperature.

[Example 1]
100 g of the isocyanate group-containing urethane prepolymer PU-1 obtained in Synthesis Example 1 was charged into a kneading vessel equipped with a stirrer, a heating device, a cooling device, and a nitrogen seal tube while flowing nitrogen gas, and dried in advance at 100 to 110 ° C. while stirring. 20 g of heavy calcium carbonate (Whiteon B, manufactured by Shiraishi Calcium Co., Ltd.) dried in the machine to a moisture content of 0.05% by mass or less, fatty acid surface-treated calcium carbonate A (Calfine N-40, heat loss) 95.0 mg / g, manufactured by Maruo Calcium Co., Ltd.), 10 g of titanium oxide, and 10 g of diisononyl phthalate (DINP) were charged and mixed until the contents were uniform. Next, 2 g of silane compound partially hydrolyzed condensate A (ethyl silicate 40, a mixture of tetraethoxysilane and tetraethoxysilane oligomer (average pentamer), manufactured by Colcoat Co., Ltd.), 2 g of dimethyl carbonate, and a hindered amine light stabilizer 1 g of ADEKA (adekastab LA-63P), hindered phenol antioxidant {pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]} (BASF Made of Irganox 1010), 12 g of urethane bond-containing oxazolidine compound O-1 obtained in Synthesis Example 5, and 0.03 g of dibutyltin dilaurate (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.) Further mixing until the product was uniform. Next, the mixture was degassed under reduced pressure at 50 to 100 hPa, filled in a container and sealed to prepare a curable composition.

[Example 2]
In Example 1, instead of using the partially hydrolyzed condensate A of the silane compound, 2 g of the partially hydrolyzed condensate B of the silane compound (polybutoxymethoxysiloxane, MKC silicate MS58B30, manufactured by Mitsubishi Chemical Corporation) was used. The same operation was performed to prepare a curable composition.

[Example 3]
In Example 1, instead of using the isocyanate group-containing urethane prepolymer PU-1, the same operation was performed except that 100 g of the isocyanate group-containing urethane prepolymer PU-2 obtained in Synthesis Example 2 was used, and a curable composition was obtained. A product was prepared.

[Example 4]
In Example 2, instead of using the isocyanate group-containing urethane prepolymer PU-1, the same operation was performed except that 100 g of the isocyanate group-containing urethane prepolymer PU-2 obtained in Synthesis Example 2 was used, and a curable composition was obtained. A product was prepared.

[Example 5]
In Example 1, instead of using the isocyanate group-containing urethane prepolymer PU-1, the same operation was performed except that 100 g of the isocyanate group-containing urethane prepolymer PU-3 obtained in Synthesis Example 3 was used, and a curable composition was obtained. A product was prepared.

[Example 6]
In Example 2, instead of using the isocyanate group-containing urethane prepolymer PU-1, the same operation was performed except that 100 g of the isocyanate group-containing urethane prepolymer PU-3 obtained in Synthesis Example 3 was used, and a curable composition was obtained. A product was prepared.

[Example 7]
A curable composition was prepared in the same manner as in Example 1 except that 0.5 g of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was further added.

[Example 8]
A curable composition was prepared in the same manner as in Example 2 except that 0.5 g of acrylic acid (Wako Pure Chemical Industries, Ltd.) was further added.

[Example 9]
A curable composition was prepared in the same manner as in Example 3 except that 0.5 g of acrylic acid (Wako Pure Chemical Industries, Ltd.) was further added.

[Example 10]
A curable composition was prepared in the same manner as in Example 4 except that 0.5 g of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was further added.

[Example 11]
A curable composition was prepared in the same manner as in Example 5 except that 0.5 g of acrylic acid (Wako Pure Chemical Industries, Ltd.) was further added.

[Example 12]
A curable composition was prepared in the same manner as in Example 6 except that 0.5 g of acrylic acid (Wako Pure Chemical Industries, Ltd.) was further added.

[Comparative Example 1]
In Example 1, instead of using fatty acid surface-treated calcium carbonate A, fatty acid surface-treated calcium carbonate B (Shiraka Hana CCR-S, heat loss 34.4 mg / g, manufactured by Shiroishi Kogyo Co., Ltd.) was used except that 100 g was used. Operation was performed and the curable composition was prepared.

[Comparative Example 2]
In Example 2, instead of using the fatty acid surface-treated calcium carbonate A, the same operation was performed except that 100 g of the fatty acid surface-treated calcium carbonate B was used to prepare a curable composition.

[Comparative Example 3]
A curable composition was prepared in the same manner as in Example 1 except that the partially hydrolyzed condensate A of the silane compound was not used.

[Comparative Example 4]
Instead of using the isocyanate group-containing urethane prepolymer PU-1 in Example 1, instead of using 100 g of the isocyanate group-containing urethane prepolymer PU-2 obtained in Synthesis Example 2 and using the fatty acid surface-treated calcium carbonate A A curable composition was prepared in the same manner as above except that 100 g of the fatty acid surface-treated calcium carbonate B was charged.

[Comparative Example 5]
Instead of using the isocyanate group-containing urethane prepolymer PU-1 in Example 2, 100 g of the isocyanate group-containing urethane prepolymer PU-2 obtained in Synthesis Example 2 is used, and instead of using the fatty acid surface-treated calcium carbonate A. A curable composition was prepared in the same manner as above except that 100 g of fatty acid surface-treated calcium carbonate B was used.

[Comparative Example 6]
In Example 1, instead of using the isocyanate group-containing urethane prepolymer PU-1, 100 g of the isocyanate group-containing urethane prepolymer PU-2 obtained in Synthesis Example 2 was used, and a partially hydrolyzed condensate A of the silane compound was used. A curable composition was prepared by performing the same operation except that it was not used.

[Comparative Example 7]
Instead of using the isocyanate group-containing urethane prepolymer PU-1 in Example 1, 100 g of the isocyanate group-containing urethane prepolymer PU-4 obtained in Synthesis Example 4 was used, and instead of using the fatty acid surface-treated calcium carbonate A. A curable composition was prepared in the same manner as above except that 100 g of the fatty acid surface-treated calcium carbonate B was charged.

[Comparative Example 8]
Instead of using the isocyanate group-containing urethane prepolymer PU-1 in Example 2, 100 g of the isocyanate group-containing urethane prepolymer PU-4 obtained in Synthesis Example 4 is used, and instead of using the fatty acid surface-treated calcium carbonate A. A curable composition was prepared in the same manner as above except that 100 g of the fatty acid surface-treated calcium carbonate B was charged.

[Comparative Example 9]
In Example 1, instead of using the isocyanate group-containing urethane prepolymer PU-1, 100 g of the isocyanate group-containing urethane prepolymer PU-4 obtained in Synthesis Example 4 was used, and a partially hydrolyzed condensate A of the silane compound was used. A curable composition was prepared by performing the same operation except that it was not used.

<Evaluation A of curable composition>
The following evaluation was performed using the curable compositions of Examples 1 to 6 and Comparative Examples 1 to 9. The evaluation results are shown in Table 1.

[Prevention of curing sheet adhesion]
a) Curing sheet adhesion prevention (5 ° C 40% RH)
A joint having a width of 30 mm, a depth of 10 mm and a length of 100 mm was prepared on a slate plate using a 10 mm square backer. The joint was filled with the curable composition, the excess was scraped off with a spatula, and the surface was flattened to obtain a test specimen.

  The test specimens were immediately cured for 3 days or 5 days in an environment (room) at 5 ° C. and 40% RH. A curing sheet (Polymasker (cloth tape + polyethylene sheet), manufactured by Otsuka Brush Manufacturing Co., Ltd.) was attached to the surface of the curable composition after curing so as to be orthogonal to the longitudinal direction of the joint. One day after application, the curing sheet was peeled off, and the peeling state was visually confirmed. In addition, when the surface of the curable composition was touched at this time, the surface was hardened, but the inside was not hardened.

b) Curing sheet adhesion prevention (23 ° C., 50% RH)
A joint having a width of 30 mm, a depth of 10 mm and a length of 100 mm was prepared on a slate plate using a 10 mm square backer. The joint was filled with the curable composition, the excess was scraped off with a spatula, and the surface was flattened to obtain a test specimen.

The test specimens were immediately cured for 1 day or 2 days in an environment (room) at 23 ° C. and 50% RH. A curing sheet (Polymasker (cloth tape + polyethylene sheet), manufactured by Otsuka Brush Manufacturing Co., Ltd.) was attached to the surface of the curable composition after curing so as to be orthogonal to the longitudinal direction of the joint. One day after application, the curing sheet was peeled off, and the peeling state was visually confirmed. In addition, when the surface of the curable composition was touched at this time, the surface was hardened, but the inside was not hardened.
Curing sheet adhesion prevention was evaluated as follows.
Rating:
A: The curing sheet does not adhere to the surface of the curable composition and peels cleanly.
○: The curing sheet slightly adheres to the surface of the curable composition, but peels cleanly.
Δ: The curing sheet partially adheres to the surface of the curable composition, and if peeled off, the surface layer of the curable composition is pulled and there is a problem in the design.
X: The curing sheet adheres to the surface of the curable composition and does not peel off unless pulled strongly. When the curing sheet is peeled off, most of the surface layer portion of the curable composition is pulled and there is a design defect.

[Pollution prevention]
a) Black silica sand contamination A joint having a width of 20 mm, a depth of 20 mm and a length of 100 mm was prepared on a slate plate using a 10 mm square backer. The joint was filled with the curable composition, the excess was scraped off with a spatula, and the surface was flattened to obtain a test specimen.

The specimen was immediately cured for 10 days in an environment (indoor) at 23 ° C. and 50% RH. The surface of the curable composition after curing was sprinkled with black silica sand (8 black, manufactured by Keimu Bussera Co., Ltd.), the test specimen was immediately turned over, and the bottom of the slate plate was struck by hand to remove excess black silica sand. The state of the black quartz sand (dirt) remaining on the surface of the curable composition was visually observed, and the anti-contamination property during curing was evaluated as follows.
Rating:
○: Adhesion of black silica sand is hardly observed on the surface of the curable composition, and the surface is clean.
X: A state in which a large amount of black silica sand adheres to the surface of the curable composition and is blackened.

b) Outdoor exposure contamination A 10 mm square backer was stacked on a slate plate to produce a joint having a width of 20 mm, a depth of 20 mm and a length of 100 mm. The joint was filled with the curable composition, the excess was scraped off with a spatula, and the surface was flattened to obtain a test specimen.

The specimen was immediately cured for 7 days in an environment of 23 ° C. and 50% RH (indoors), and then the specimen was placed in the vicinity of an intersection with a lot of outdoor traffic so as to be perpendicular to the ground and exposed for 30 days. In addition, the test body was about 1 m in height from the ground, and the surface of the curable composition was made to face the road side. After 30 days of outdoor exposure, the state of contamination on the surface of the curable composition was visually observed, and the contamination prevention property was evaluated as follows.
Rating:
○: Dust and dust are hardly observed on the surface of the curable composition, and the surface is clean.
Δ: Dust or dust is slightly adhered to the surface of the curable composition, but it is clean.
X: A state in which a large amount of dust or dirt adheres to the surface of the curable composition and is dirty.

<Evaluation B of curable composition>
In addition to evaluation A of the above-mentioned curable composition, the following evaluation was performed using the curable composition of Examples 7-12. The evaluation results are shown in Table 2.

[Prevention of curing sheet adhesion]
a) Curing sheet adhesion prevention (5 ° C 40% RH)
A joint having a width of 30 mm, a depth of 10 mm and a length of 100 mm was prepared on a slate plate using a 10 mm square backer. The joint was filled with the curable composition, the excess was scraped off with a spatula, and the surface was flattened to obtain a test specimen.

  The test specimens were immediately cured for 1 day in an environment (room) at 5 ° C. and 40% RH. A curing sheet (Polymasker (cloth tape + polyethylene sheet), manufactured by Otsuka Brush Manufacturing Co., Ltd.) was attached to the surface of the curable composition after curing so as to be orthogonal to the longitudinal direction of the joint. One day after application, the curing sheet was peeled off, and the peeling state was visually confirmed. In addition, when the surface of the curable composition was touched at this time, the surface was hardened, but the inside was not hardened.

  From the results of Examples 1 to 12 and Comparative Examples 1 to 9 described above, the curable composition of the present invention has excellent antifouling properties in outdoor exposure, and the curing sheet does not adhere to the surface of the curable composition and is clean. It turns out that it is excellent also in the curing sheet adhesion prevention property which peels. Moreover, even if it is an early stage of hardening of the composition in the 1st day of 5 degreeC40% RH from the result of Examples 7-12, ie, low temperature, it turns out that it is excellent in a curing sheet adhesion prevention property.

  As described above, the curable composition of the present invention is excellent as a sealing material composition, a waterproofing material composition, an adhesive composition, and a coating material composition because it is excellent in antifouling property and anti-curing sheet adhesion property in outdoor exposure. Can be used for Moreover, the curable composition of this invention can be used conveniently for construction use and civil engineering.

Claims (7)

Containing an isocyanate group-containing urethane prepolymer, a silane compound represented by the following general formula (1) and / or a partially hydrolyzed condensate of the silane compound, and a surface-treated calcium carbonate having a heat loss of 50 to 150 mg / g. A curable composition characterized.
R _4-m Si- (OR ¹ ) _m (1)
(In Formula (1), R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and when R is plural, they may be the same or different. R ¹ is 1 having 1 or more carbon atoms. is a valence of the hydrocarbon group, at least one (OR ¹⁾ good be different even for the same when it. (OR ¹⁾ is plural alkoxy group having 2 to 6 carbon atoms .m Is an integer from 1 to 4.)   The curable composition according to claim 1, wherein the isocyanate group-containing urethane prepolymer has a branch density of 0.03 mmol / g or more.   The curable composition according to claim 1 or 2, wherein the isocyanate group-containing urethane prepolymer has a photoreactive unsaturated bond in the molecule.   Furthermore, an oxazolidine compound is contained, The curable composition as described in any one of Claims 1-3 characterized by the above-mentioned.   Further, at least one or more selected from curing accelerators, plasticizers, weathering stabilizers, fillers, thixotropic agents, adhesion improvers, storage stability improvers (dehydrating agents), colorants and organic solvents. An additive is contained, The curable composition as described in any one of Claims 1-4 characterized by the above-mentioned.   The said curable composition is a curable composition for construction or civil engineering, The curable composition as described in any one of Claims 1-5 characterized by the above-mentioned.   The curable composition according to any one of claims 1 to 6, wherein the curable composition is a sealing material composition, a waterproof material composition, an adhesive composition, or a coating material composition. .