JP2017031399A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition excellent in workability, pollution resistance, weather resistance, and rubber physical properties and capable of being suitably used as a sealing material composition, a water resistant material composition or a coating material composition.SOLUTION: There is provided a curable composition which contains an ordinary temperature curable resin which is crosslink cured by reaction with an active hydrogen-containing compound, and a compound having a nitroxide free group with number average molecular weight of 2,000 or more and can be suitably used as a sealing material composition, a water resistant material composition or a coating material composition.SELECTED DRAWING: None

Description

  The present invention relates to a curable composition having excellent workability, antifouling properties, weather resistance, and rubber properties.

  Curable composition containing polyurethane resin, silicone resin, modified silicone resin, polysulfide resin as curing component is used as sealing material composition, waterproofing material composition, coating material composition for construction, civil engineering, automobile, etc. Has been. Among them, curable compositions containing polyurethane resins and modified silicone resins as curing components are widely used for construction and civil engineering because of their good workability and excellent rubber properties after curing and adhesion to various components. ing. When the curable composition is used for construction or civil engineering, it is often directly exposed to sunlight or rainwater, and a curable composition having excellent weather resistance is desired. As a technique for imparting weather resistance to a curable composition, conventionally, there has been known a technique in which a weathering stabilizer such as a hindered phenol antioxidant, an ultraviolet absorber, or a hindered amine light stabilizer is added to the curable composition. (Patent Document 1, Patent Document 2). However, curable compositions containing these weathering stabilizers do not always satisfy the long-term weather resistance (needs for longer life) that has recently been required, but other methods for improving long-term weatherability. Is required. In addition, when the cured product is used for a long period of time, the rubber property of the cured product tends to be gradually hardened, which causes cracking of the cured product and separation from the member, resulting in a low modulus and high elongation rubber property. What has is desired.

  Furthermore, a curable composition containing a polyurethane resin or a modified silicone resin as a curing component often contains a plasticizer such as dioctyl phthalate in order to improve workability and adjust rubber physical properties after curing. However, when a curable composition containing a plasticizer is cured, the plasticizer may ooze out from the cured product over time, causing problems. For example, when the plasticizer moves to the surface of the cured product, the surface of the cured product becomes sticky, and dust or dirt adheres to the surface and the surface is contaminated. Further, even when a top coating is applied to the surface of the cured product, the surface is transferred to the top coating (coating film), the surface of the top coating becomes sticky, and dust or dust adheres to the surface to contaminate the surface. Furthermore, the plasticizer may move to a member around the cured product (attached member), and the surface of the member is similarly contaminated. As described above, when the plasticizer is transferred from the cured product, the cured product gradually becomes hard and brittle, and there is a problem in that it is peeled off from members around the cured product.

JP 2002-348463 A JP 2001-342341 A

  An object of the present invention is to provide a curable composition having excellent workability, antifouling properties, weather resistance, and rubber properties.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a curable composition comprising a room temperature curable resin and a compound having a nitroxide free radical having a number average molecular weight of 2,000 or more. The present inventors have found that it is excellent in workability, antifouling property, weather resistance, and rubber physical properties, and completed the present invention. That is, this invention is shown to following (1)-(7).
(1) A curable composition comprising a room temperature curable resin and a compound having a nitroxide free radical having a number average molecular weight of 2,000 or more.
(2) The curable composition according to (1), wherein the room temperature curable resin is an isocyanate group-containing resin or a crosslinkable silyl group-containing resin.
(3) The compound having a nitroxide free group having a number average molecular weight of 2,000 or more is a compound having a nitroxide free group having a number average molecular weight of 2,000 or more and a piperidine ring (1) or (2) ).
(4) The compound having a nitroxide free group having a number average molecular weight of 2,000 or more is a polyoxyalkylene compound having a nitroxide free group having a number average molecular weight of 2,000 or more and / or a nitroxide having a number average molecular weight of 2,000 or more. The curable composition according to any one of (1) to (3), which is a poly (meth) acrylic compound having a free radical.
(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. One or more additives are contained, The curable composition in any one of (1)-(4) characterized by the above-mentioned.
(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 curable composition according to any one of (1) to (6), wherein the curable composition is a sealing material composition, a waterproof material composition, or a coating material composition.

  The curable composition of the present invention is excellent in workability, antifouling properties, weather resistance, and rubber properties, and can be suitably used as a sealing material composition, a waterproof material composition, and a coating material composition.

  Hereinafter, the present invention will be described in detail according to embodiments.

  The present invention is a curable composition comprising a room temperature curable resin and a compound having a nitroxide free radical having a number average molecular weight of 2,000 or more. Hereinafter, each component will be described in detail.

  The room temperature curable resin is one in which the curable resin reacts with an active hydrogen-containing compound or the like (for example, water such as moisture) at least at room temperature to be crosslinked and cured. In this invention, normal temperature means the normal temperature (5-35 degreeC) described in JISZ8703 (1983). Moreover, even if it is a curable resin that reacts with an active hydrogen-containing compound at a temperature lower than 5 ° C. or exceeds 35 ° C. and cures by crosslinking, the curability that reacts with an active hydrogen-containing compound at room temperature (5 to 35 ° C.) to cure by crosslinking. If it is resin, it is contained in room temperature curable resin.

  The room temperature curable resin is not particularly limited as long as it is crosslinked and cured by reacting with an active hydrogen-containing compound at room temperature. Specific examples include isocyanate group-containing resins and crosslinkable (hydrolyzable) silyl group-containing resins.

  The isocyanate group-containing resin is a resin having one or more isocyanate groups in the resin, and the isocyanate groups react with active hydrogen (groups) to form urethane bonds, urea bonds, and the like, and are cured by crosslinking. Isocyanate group-containing resins include isocyanate group-containing urethane prepolymers (hereinafter referred to as “urethane prepolymers” including isocyanate group-containing urethane prepolymers and isocyanate group-containing urethane prepolymers into which photoreactive unsaturated bonds described below have been introduced. In some cases).

  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 in 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, and particularly preferably 1,500 to 10,000. preferable. In addition, the number average molecular weight in this invention is a numerical value of polystyrene conversion measured by gel permeation chromatography (GPC).

  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 of the excellent weather resistance of the curable composition.

  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, etc. Aliphatic monoisocyanate, 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. Specifically, in addition to polymer polyols and polymer polyamines, low molecular polyols, low molecular amino alcohols, low molecular polyamines used as chain extenders in some cases, polymers and low molecular materials used for modification of urethane prepolymers Monool is mentioned.

  Examples of the polymer polyol include polyester polyol, polycarbonate polyol, polyoxyalkylene polyol, poly (meth) acryl polyol, hydrocarbon polyol, animal and plant polyol, and copolyols thereof. In the present invention, “(meth) acryl” means “acryl and / or methacryl”.

  The number average molecular weight of the polymer polyol is preferably 1,000 to 30,000, and 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, low-molecular polyols, low-molecular polyamines such as butylene diamine, hexamethylene diamine, xylylene diamine, and isophorone diamine, and low-molecular molecules such as monoethanol amine and diethanol amine Also included are polyester amide polyols obtained by reaction with one or more amino alcohols.

  Furthermore, lactone polyester polyols obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone and γ-valerolactone using low molecular polyols, low molecular polyamines, and low molecular amino alcohols as initiators Can be mentioned.

  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.

  Examples of the polyoxyalkylene polyol include low molecular polyols, low molecular polyamines, low molecular amino alcohols, polycarboxylic acids similar to those used for the synthesis of the above-described polyester polyols; sorbitol, mannitol, sucrose ( Sucrose), sugar-based low molecular weight polyhydric alcohols such as glucose; cyclic ethers such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using one or more low molecular weight polyphenols such as bisphenol A and bisphenol F as initiators Polyoxyethylene polyol, polyoxypropylene polyol, polyoxybutylene polyol obtained by ring-opening addition polymerization or copolymerization (hereinafter, “polymerization or copolymerization” is referred to as (co) polymerization) of one or more compounds. , Polyoxy Examples include tetramethylene polyols, poly- (oxyethylene)-(oxypropylene) -random or block copolymer polyols, and polyester ether polyols and polycarbonate ether polyols using the above-described polyester polyols and polycarbonate polyols as initiators. Moreover, the polyol which made these various polyols and an organic isocyanate compound react with hydroxyl group excess with respect to an isocyanate group, and made the molecular terminal a hydroxyl group is also mentioned.

  The number of alcoholic hydroxyl groups in the polyoxyalkylene polyol is preferably 2 or more, more preferably 2 to 4, particularly 2 to 3 on average per molecule.

  Catalysts for synthesizing polyoxyalkylene polyols are alkali metal compound catalysts such as sodium catalysts and potassium catalysts, cationic polymerization catalysts, composite metal cyanide complex catalysts such as zinc hexacyanocobaltate glyme complex and diglyme complex, A phosphazene compound catalyst is mentioned. Of these, alkali metal compound catalysts and double metal cyanide complex catalysts are preferred. Polyoxyalkylene polyols synthesized using a complex cyanide complex catalyst are preferred because the total unsaturation is low and the polyol viscosity is low.

  The total unsaturation degree of the polyoxyalkylene polyol is preferably 0.1 meq / g or less. Further, the molecular weight distribution of polyoxyalkylene polyol [ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography (GPC) = Mw / Mn] is 1.6 or less. Particularly preferred is 1 to 1.3. By setting the total unsaturation degree and molecular weight distribution of the polyoxyalkylene polyol to the above-described ranges, the viscosity of the obtained urethane prepolymer can be reduced, and the workability of the curable composition is improved. Further, the physical properties of the rubber after curing of the curable composition are low modulus and high elongation.

  For modification of urethane prepolymers, polyoxypropylene-based monopolymers obtained by ring-opening addition polymerization of cyclic ether compounds such as propylene oxide using low molecular monoalcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol as initiators. Polyoxyalkylene monools such as all can also be used. The number average molecular weight of the polyoxyalkylene monool is preferably 1,000 to 10,000.

  The “system” of the polyoxyalkylene-based polyol or polyoxyalkylene-based monool mentioned above is 50% by mass or more of the portion excluding the hydroxyl group in 1 mol of the molecule, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Is composed of polyoxyalkylene, it means that the remaining part may be modified with ester, urethane, polycarbonate, polyamide, poly (meth) acrylate, polyolefin, etc. Most preferably, 95% by mass or more is made of polyoxyalkylene. In the present invention, “(meth) acrylate” means “acrylate and / or methacrylate”.

  Poly (meth) acrylic polyol is a radical polymerization such as batch polymerization or continuous polymerization of hydroxyl group-containing (meth) acrylic monomer and other ethylenically unsaturated compounds in the presence or absence of solvent. It is obtained by copolymerization by the method. Furthermore, what is obtained by continuous bulk copolymerization reaction at a high temperature of 150 to 350 ° C., more preferably 210 to 250 ° C. in the absence of a solvent has a narrow molecular weight distribution of the reaction product and a low viscosity. Therefore, it is preferable. In the case of this copolymerization, it is preferable to use a hydroxyl group-containing (meth) acrylic monomer so that the average hydroxyl group functionality is 1.2 to 10 per molecule of poly (meth) acrylic polyol. .2 to 6 are preferably used. If the average hydroxyl group functionality is less than 1.2, the adhesiveness after curing of the resulting curable composition is lowered, and if it exceeds 10, the curable composition becomes brittle. The glass transition point (Tg) of the poly (meth) acryl polyol is preferably 50 ° C. or lower, more preferably 0 ° C. or lower, still more preferably −70 to −20 ° C., particularly preferably −70 to −30 ° C.

The hydroxyl group-containing (meth) acrylic monomer is a (meth) acrylic monomer having at least one hydroxyl group in the molecule, specifically, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) Hydroxyalkyl (meth) acrylates such as acrylate and hydroxybutyl (meth) acrylate; pentaerythritol tri (meth) acrylate, glycerol mono (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, dipentaerythritol penta (meth) ) Acrylates, ditrimethylolpropane tri (meth) acrylates, mono (meth) acrylates of polyhydric alcohols such as polypropylene glycol mono (meth) acrylate or hydroxyl group residual poly (meth) acrylates. That. These can be used alone or in combination of two or more. Of these, hydroxyalkyl (meth) acrylates are preferred from the viewpoint of low viscosity of (meth) acrylic polyol and good reactivity with isocyanate groups. Furthermore, hydroxyethyl (meth) acrylate is preferable.
Examples of the ethylenically unsaturated compound other than the hydroxyl group-containing (meth) acrylic monomer include (meth) acrylic monomers and other ethylenically unsaturated compounds. Examples of ethylenic compounds other than (meth) acrylic monomers include vinyl compounds such as ethylene, propylene, isobutylene, butadiene, chloroprene, styrene, chlorostyrene, 2-methylstyrene, and divinylbenzene. As (meth) acrylic monomers, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl, benzyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, tridecyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate , Tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Gurishijirutori (meth) acrylate, trimethylolpropane tri (meth) acrylate. These can be used alone or in combination of two or more. Among these, a monomer of a (meth) acrylic acid ester compound is preferable because the viscosity of the (meth) acrylic polyol is low, and further, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , (Butyl) (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferred. In the present invention, “(meth) acrylic acid” means “acrylic acid and / or methacrylic acid”.

  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. Of these, polyoxyalkylene polyols and poly (meth) acrylic polyols are preferred from the viewpoint of good rubber properties and adhesiveness of the resulting curable composition.

  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 introduced with a photoreactive unsaturated bond undergoes a polymerization reaction when exposed to light, and forms 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 And an average molecular weight of less than 1,000) are reacted under 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 obtained by reacting the total amount of active hydrogens with an excess of isocyanate groups.
(C) an organic isocyanate compound, a low molecular (number average molecular weight less than 1,000) active hydrogen-containing compound having a photoreactive unsaturated bond and an isocyanate group in the molecule (for example, (meth) acryloyl isocyanate), A method obtained by reacting a polymer (number average molecular weight of 1,000 or more) of an active hydrogen-containing compound with an excess of isocyanate groups with respect to the total amount of active hydrogen.
Is mentioned. The method (a) is preferred from the viewpoints of availability of raw materials and ease of reaction. Examples of the high molecular active hydrogen-containing compound include high molecular polyols (for example, polyoxyalkylene polyols and poly (meth) acrylic polyols) that can be used in producing a urethane prepolymer.

  Examples of the method for introducing the photoreactive unsaturated bond into the isocyanate group-containing urethane prepolymer include a method in which the above-mentioned raw materials are charged and reacted in a batch or sequentially. The molar 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 the active hydrogen-containing compound having 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.

  Compounds having active hydrogen and photoreactive unsaturated bonds (low molecular weight and high molecular weight) are composed of active hydrogen (group) such as hydroxyl group, amino group, carboxyl group and the like, vinyl group, vinylene group, (meta ) A compound having both a photoreactive unsaturated bond such as an acryloyl group, and a compound having a hydroxyl group and a (meth) acryloyl group in the compound 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.

  Examples of the compound having a hydroxyl group and a (meth) acryloyl group include 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 (meth) acrylate , Hydroxyheptyl (meth) acrylate, monohydroxy mono (meth) acrylates such as hydroxyoctyl (meth) acrylate, glycerin, trimethylolpropane, pentaerythritol A monoester or diester of a tri- or higher-functional alkylene polyol and a polyester such as a triester, glycerol di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate Monohydroxy poly (meth) acrylates such as, glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, polyhydroxymono (meth) acrylates such as pentaerythritol mono (meth) acrylate, pentaerythritol di (meta) And polyhydroxy poly (meth) acrylates such as 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.

  A crosslinkable silyl group-containing resin is a resin having at least one crosslinkable (hydrolyzable) silyl group in the resin, and the crosslinkable silyl group reacts with active hydrogen (group) to form a siloxane bond. It is then cross-linked and cured to form a cured product. Examples of the crosslinkable silyl group-containing resin include those generally called silicone resins or modified silicone resins. Particularly preferred are modified silicone resins.

  The silicone resin is a resin having a main chain of organopolysiloxane and a crosslinkable silyl group in the resin. Specifically, a one-part silicone resin containing an organopolysiloxane having a silanol group at the terminal as a main component and a low-molecular compound containing a crosslinkable silyl group as a crosslinking component, and an organopolysiloxane having a silanol group at the terminal as a main component A two-part silicone resin containing siloxane and aminoxyalkylsilane as a curing agent can be mentioned. Examples of the crosslinkable silyl group-containing low molecular weight compound include acyloxyalkylsilanes, aminoxyalkylsilanes, and alkoxyalkylsilanes.

  As the modified silicone resin, for example, JP-A-52-73998, JP-A-55-9669, JP-A-59-122541, JP-A-60-6747, JP-A-61-233043 JP, 63-6003, JP 63-112642, JP 3-79627, JP 4-283259, JP 5-287186, JP 11-80571. And those disclosed in JP-A-11-116763 and JP-A-11-130931. Specifically, the resin has a crosslinkable silyl group and the main chain is an aliphatic hydrocarbon hydrocarbon such as vinyl polymer, polyoxyalkylene polymer, polyisoprene, polyisobutylene or polybutanediene. Examples thereof include a polymer, a polyester polymer, a polysulfide polymer, a copolymer thereof, and a mixture thereof. Any of these may be used alone or in combination of two or more.

  The main chain of the modified silicone resin is composed of a polyoxyalkylene polymer, a (meth) acrylic-modified polyoxyalkylene polymer, (meth) from the viewpoint of rubber properties such as tensile adhesion after curing and modulus. ) Acrylic copolymers are preferred.

  In the present invention, “(meth) acryl-modified” may mean a polyoxypropylene polymer obtained by block or pendant copolymerization of a (meth) acrylic monomer, or a polyoxyalkylene polymer. It means a mixture of (meth) acrylic copolymers, or a polymer of (meth) acrylic monomers in a polyoxyalkylene polymer having a crosslinkable silyl group introduced.

From the viewpoint of curability of the curable composition and physical properties after curing, it is preferable that one or more crosslinkable silyl groups are contained in the molecule, and more preferably 1 to 5, more preferably 1 to 3. Preferably included.
Further, the crosslinkable silyl group is preferably one represented by the following general formula which is easily crosslinked and easy to produce.

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

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

The introduction of the crosslinkable silyl group into the main chain can be specifically performed by, for example, the following known methods.
(A) An organic compound (for example, allyl isocyanate) having an active group and an unsaturated group that are reactive with a polyoxyalkylene-based or vinyl-based polymer having a functional group such as a hydroxyl group at the terminal. And then hydrosilylating the resulting reaction product with a hydrosilane having a hydrolyzable group.
(B) A compound having a functional group and a crosslinkable silyl group which are reactive with a polyoxyalkylene-based or vinyl-based polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group at the terminal How to react.
Examples of the compound having a reactive functional group and a crosslinkable silyl group include amino group-containing silanes, mercapto group-containing silanes, epoxy group-containing silanes, vinyl type unsaturated group-containing silanes, chlorine atom-containing silanes, and isocyanates. Examples thereof include group-containing silanes and hydrosilanes.
(C) A compound having a polymerizable unsaturated bond and a crosslinkable silyl group (for example, CH ₂ ═CHSi (OCH ₃ ) ₃ or CH ₂ ═CHCOO (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ) and (meth) acrylic A method of copolymerizing an acid alkyl ester monomer.
(D) a compound having a polymerizable unsaturated bond and a functional group (for example, hydroxyethyl (meth) acrylate or allyl (meth) acrylate) is added to the (meth) acrylic acid alkyl ester monomer and copolymerized; Subsequently, the resulting copolymer is converted into a compound having a reactive functional group and a crosslinkable silyl group (for example, a compound having an isocyanate group and —Si (OCH ₃ ) ₃ group, trimethoxysilane, triethoxysilane or the like). A hydrosilane having a decomposable group).

  In the present invention, the number average molecular weight of the silicone resin and the modified silicone resin is preferably 1,000 or more, and particularly preferably 6,000 to 30,000. A narrow molecular weight distribution is preferred because the viscosity of the curable composition is low, and rubber properties such as strength, elongation and modulus after curing are excellent.

  A compound having a nitroxide free group having a number average molecular weight of 2,000 or more (hereinafter sometimes simply referred to as “compound having a nitroxide free group”) will be described. The compound having a nitroxide free group is a compound having a number average molecular weight of 2,000 or more having at least one nitroxide free group in the compound. By mix | blending this compound with the curable composition containing room temperature curable resin, the viscosity of a curable composition can be reduced and workability | operativity at the time of using a curable composition can be improved. Further, a curable composition containing a compound having a nitroxide free group is difficult to bleed from a cured product after curing, so that it is difficult to contaminate the surface, and the rubber physical properties are also difficult to harden. Furthermore, weather resistance is imparted over a long period of time without impairing thixotropy of the curable composition. The number average molecular weight of the compound having a nitroxide free group is preferably 2,000 or more, more preferably 2,000 to 30,000, and particularly preferably 2,000 to 20,000.

  The compound having a nitroxide free group is a group represented by the following general formula (1).

  Examples of the compound having a nitroxide free group include a polyoxyalkylene compound having a nitroxide free group having a number average molecular weight of 2,000 or more and a poly (meth) acrylic compound having a number average molecular weight of 2,000 or more. These compounds have good compatibility with a room temperature curable resin and tend to be difficult to bleed after the curable composition is cured. Any of these may be used alone or in combination of two or more.

  A polyoxyalkylene compound having a nitroxide free group having a number average molecular weight of 2,000 or more has one or more nitroxide free groups in the compound, and the main chain thereof is (poly) oxyethylene, (poly) oxypropylene. , (Poly) oxyethylenepropylene, (poly) oxybutylene, and other polyoxyalkylene compounds.

  A poly (meth) acrylic compound having a nitroxide free group having a number average molecular weight of 2,000 or more is a compound having one or more nitroxide free groups in the compound and the main chain of which is a (meth) acrylate ester It is.

  “System” of a polyoxyalkylene compound having a nitroxide free group is 50% by mass or more of the portion excluding the nitroxide free group in the compound, and further 80% by mass or more is composed of polyoxyalkylene. It means that the part may be modified with ester, urethane or the like. In addition, the “system” of the poly (meth) acrylic compound having a nitroxide free group is 50% by mass or more of the portion excluding the nitroxide free group in the compound, and more than 80% by mass is composed of (meth) acrylic acid ester. If it is, it means that the remaining part may be modified with urethane or the like.

  As a method for producing a polyoxyalkylene compound having a nitroxide free group, specifically, an organic isocyanate compound and a polyoxyalkylene alcohol (polyoxyalkylene polyol and / or a reaction vessel such as glass or stainless steel) are used. Polyoxyalkylene-based monool) and an active hydrogen-containing compound having a nitroxide free radical are charged all at once or sequentially and stirred at 50 to 120 ° C. in the presence or absence of a reaction catalyst or an organic solvent. The method of making it react is mentioned. At this time, if the isocyanate group reacts with water such as moisture, the polyoxyalkylene compound having a nitroxide free group thickens, so the inside of the container is replaced with nitrogen gas in advance or the reaction is performed under a nitrogen gas stream. Is preferred. Molar ratio of the isocyanate group of the organic isocyanate compound to the total active hydrogen (group) of the polyoxyalkylene alcohol (polyoxyalkylene polyol and / or polyoxyalkylene monool) and the active hydrogen-containing compound having a nitroxide free radical (Isocyanate group / active hydrogen) is preferably 0.9 to 1.1, more preferably 0.95 to 1.05, and particularly preferably 1.0.

  Specifically, as a method for producing a poly (meth) acrylic compound having a nitroxide free radical, an organic isocyanate compound and a hydroxyl group-containing poly (meth) acrylic polymer (poly (meth) ) Acrylic polyol and / or poly (meth) acrylic monool) and an active hydrogen-containing compound having a nitroxide free group are charged all at once or in the presence or absence of a reaction catalyst or an organic solvent. The method of making it react at -120 degreeC stirring is mentioned. At this time, when the isocyanate group reacts with water such as moisture, the poly (meth) acrylic compound having a nitroxide free group thickens. Therefore, the reaction can be carried out by substituting the inside of the container with nitrogen gas in advance or under a nitrogen gas stream. Preferably it is done. The total active hydrogen of the isocyanate group of the organic isocyanate compound and the active hydrogen-containing compound having a hydroxyl group-containing poly (meth) acrylic polymer (poly (meth) acrylic polyol and / or poly (meth) acrylic monool) and a nitroxide free radical ( Group) (isocyanate group / active hydrogen) is preferably 0.9 to 1.1, more preferably 0.95 to 1.05, and particularly preferably 1.0.

  In the production of the polyoxyalkylene compound having a nitroxide free group and the poly (meth) acrylic compound having a nitroxide free group, a small amount of active hydrogen-containing functional group (for example, hydroxyl group) or isocyanate group may be produced by selecting a molar ratio. Although it may remain in the molecule, in this case, it can be regarded as not having for achieving the object of the present invention. The “small amount” means that the amount of the active hydrogen-containing functional group or isocyanate group remaining in the molecule is 1 g of a polyoxyalkylene compound having a nitroxide free group or a poly (meth) acrylic compound having a nitroxide free group. It is preferably 0.05 mmol or less, more preferably 0.02 mmol or less.

  The organic isocyanate compound used when producing the above-mentioned urethane prepolymer, organic polyisocyanate compound when producing a polyoxyalkylene compound having a nitroxide free group and a poly (meth) acrylic compound having a nitroxide free group Monoisocyanates can be used. As the organic polyisocyanate, an aliphatic polyisocyanate, an araliphatic polyisocyanate, an alicyclic polyisocyanate, and a modified isocyanate obtained by modifying these organic polyisocyanates are preferable in that the weather resistance imparting effect is high. As the organic monoisocyanate, aliphatic monoisocyanate is preferable. Any of these may be used alone or in combination of two or more.

  Examples of the polyoxyalkylene alcohol used in the production of the polyoxyalkylene compound having a nitroxide free group include polyoxyalkylene polyols and polyoxyalkylene monomonos that can be used in the production of the urethane prepolymer. Oars. Any of these can be used alone or in combination.

  The total unsaturation degree of the polyoxyalkylene polyol and 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. Also, molecular weight distribution of polyoxyalkylene polyol and polyoxyalkylene monool [ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography (GPC) = Mw / Mn ] Is preferably 1.6 or less, particularly preferably a polyoxyalkylene polyol of 1 to 1.3. By setting the total unsaturation and molecular weight distribution of the polyoxyalkylene polyol and polyoxyalkylene monool within the above ranges, the viscosity of the polyoxyalkylene compound having a nitroxide free radical can be reduced, and the curable composition can be reduced. Increases viscosity reduction effect when blended. Moreover, the rubber physical property after hardening of a curable composition tends to become high elongation with a low modulus.

  Examples of the hydroxyl group-containing (meth) acrylic polymer in producing a poly (meth) acrylic compound having a nitroxide free group include poly (meth) acrylic polyols that can be used in producing the above urethane prepolymer. It is done.

  The active hydrogen-containing compound having a nitroxide free group is preferably an active hydrogen-containing compound having a piperidine ring in which the nitroxide free group is chemically stable at room temperature and in the presence of oxygen.

  Examples of the active hydrogen-containing compound having a nitroxide free group include an active hydrogen-containing compound having a 2,2,6,6-substituted piperidine 1-oxy free radical and a 2,2,5,5-substituted piperidine 1-oxy free radical. Active hydrogen-containing compounds having nitroxide free radicals derived from cyclic hydroxyamines, such as active hydrogen-containing compounds, are preferred. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable. Examples of the active hydrogen-containing compound having a nitroxide free group derived from a cyclic hydroxyamine include compounds represented by the following general formula (2).

（式中、Ｒ^１〜Ｒ^６はそれぞれ独立に水素原子または炭素数１〜４のアルキル基を表し、Ｘ^１およびＸ^２はヒドロキシ基（−ＯＨ）、アミノ基（ＮＨ_２）または水素原子を表す。ただし、Ｘ^１およびＸ^２のいずれかは、ヒドロキシ基またはアミノ基である。）

(Wherein R ^{1 to} R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X ¹ and X ² represent a hydroxy group (—OH), an amino group (NH ₂ ), or a hydrogen atom, respectively. However, any one of X ¹ and X ² is a hydroxy group or an amino group.)

  Specific examples of the active hydrogen-containing compound having a nitroxide free group include 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetraethylpiperidine. 1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-amino-2,2,6,6-tetraethylpiperidine 1-oxyl, 3-hydroxy-2,2,5 , 5-tetramethylpiperidine 1-oxyl, 3-hydroxy-2,2,5,5-tetraethylpiperidine 1-oxyl, 3-amino-2,2,5,5-tetramethylpyrrolidine 1-oxyl, 3-amino -2,2,5,5-tetraethylpyrrolidine 1-oxyl. Any of these may be used alone or in combination of two or more. Of these, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl is preferred because of its availability.

  The blending amount of the polyoxyalkylene compound having a nitroxide free group is preferably 5 to 150 parts by mass, and more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the room temperature curable resin.

  The curable composition of the present invention can further contain a block amine compound. The blocked amine compound is a compound obtained by blocking the active hydrogen bonded to the nitrogen atom of a compound having a primary and / or secondary amino group by dehydration reaction with a compound having a carbonyl group such as a ketone or aldehyde.

  Specific examples of the block amine compound include an oxazolidine compound that is a reaction product of an amino alcohol and a carbonyl 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. When an oxazolidine compound is blended with an isocyanate group-containing resin which is a room temperature curable resin, it functions as a latent curing agent. More specifically, when the isocyanate group of the isocyanate group-containing resin reacts with water, it forms a urea bond and cures. At this time, carbon dioxide gas is also generated, and bubbles are generated in the cured product due to carbon dioxide gas. Problems such as deterioration of appearance, breakage, and deterioration of adhesiveness may occur. The oxazolidine compound reacts with water to hydrolyze, and the oxazolidine ring generates (regenerates) a secondary amino group and an alcoholic hydroxyl group. On the other hand, when an oxazolidine compound blended with an isocyanate group-containing resin is reacted with water, water and the oxazolidine compound react first, and the oxazolidine ring of the oxazolidine compound reacts with a secondary amino group and an alcoholic hydroxyl group (active Hydrogen group). 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.

  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. Among these oxazolidine compounds, urethane bond-containing oxazolidine compounds are preferable because they are easy to produce.

  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.

  Specific 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 is mentioned.

  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. And 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 an isocyanate group of an isocyanate group-containing resin at room temperature, or an isocyanate group. This is to prevent an increase in viscosity of the isocyanate group-containing resin and a decrease 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 generated (regenerated) by hydrolysis of the oxazolidine compound with respect to 1 mol of isocyanate group of the isocyanate group-containing resin. It is preferable to mix | blend so that it may become, and it is more preferable to mix | blend so that it may become 0.3-1 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 as long as the object of the present invention is not impaired. 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 room temperature curable resin by reacting with an active hydrogen-containing compound (for example, water such as moisture). Further, the curing accelerating catalyst can also be used as a reaction catalyst during the production of the above-mentioned urethane prepolymer and a polyoxyalkylene compound having a nitroxide free group. In addition, when used as a reaction catalyst in the production of a urethane prepolymer and a polyoxyalkylene compound having a nitroxide free group, the reaction catalyst remaining in the urethane prepolymer and a polyoxyalkylene compound having a nitroxide free group is curable. It may act as a catalyst for accelerating the curing of the 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, and a salt of tin and an organic acid, bismuth and 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 amount of the curing accelerating catalyst used 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 room temperature curable resin.

  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. Kind.

  The plasticizer is preferably used in an amount of 1 to 200 parts by mass, and more preferably 2 to 50 parts by mass, with respect to 100 parts by mass of the room temperature curable resin.

  The weather resistance stabilizer is used for the purpose of further improving the weather resistance and heat resistance by preventing oxidation, photodegradation, and thermal degradation 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]- 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 ADEKA in addition to -2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate ADK STAB LA-6 P, include LA-68LD.

  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 and a hindered phenol antioxidant 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 mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the room temperature curable resin.

  The filler is used for the purpose of increasing the amount of the curable composition or reinforcing the physical properties of the cured product. Specifically, synthetic silica such as mica, kaolin, zeolite, graphite, diatomaceous earth, white clay, clay, talc, slate powder, anhydrous silicic acid, quartz fine powder, aluminum powder, zinc powder, precipitated silica, calcium carbonate, carbonic acid Inorganic powder fillers such as magnesium, alumina, calcium oxide, magnesium oxide; fibrous fillers such as glass fiber and carbon fiber; inorganic balloon fillers such as glass balloon, shirasu balloon, silica balloon, ceramic balloon; wood Powder, walnut shell powder, rice husk powder, pulp powder, cotton chips, rubber powder, fine powder of thermoplastic or thermosetting resin, powder such as polyethylene, hollow body, organic balloon-like filling such as Saran microballoon; In addition, flame retardant imparting fillers such as magnesium hydroxide and aluminum hydroxide are also included. The filler preferably has a particle size of 0.01 to 1,000 μm.

  The thixotropic agent is used for the purpose of preventing sagging (slump) of the curable composition. Specific examples include inorganic thixotropic agents such as fine powdered silica and fatty acid-treated calcium carbonate; organic thixotropic agents such as organic bentonite and fatty acid amide. Any of these may be used alone or in combination of two or more. A compound having a nitroxide free radical having a number average molecular weight of 2,000 or more is difficult to inhibit the effects of these thixotropic agents. In particular, it is difficult to inhibit the thixotropic effect of finely divided silica.

  Examples of the fine powder silica include hydrophilic silica and hydrophobic silica. Any of these may be used alone or in combination of two or more.

  Examples of hydrophilic silica include natural silica obtained by finely pulverizing quartz, silica sand, and the like, and synthetic silica such as dry silica and wet silica. Dry silica is obtained by burning a silane-based gas such as silicon tetrachloride in an oxyhydrogen flame, and is sometimes referred to as fumed silica. In addition, wet silica includes precipitated silica in which silica is precipitated in a solution by neutralizing sodium silicate with mineral acid, and is sometimes called white carbon.

  Examples of the hydrophobic silica include those made hydrophobic by subjecting hydrophilic silica to a surface treatment using an organosilicon compound having reactivity with hydrophilic silica.

  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. Examples of the fatty acid include fatty acids having 10 to 25 carbon atoms such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and hebenic acid. Examples of metal salts include sodium salts, potassium salts, calcium salts, aluminum salts, and organic salts include ammonium salts.

  The amount of the thixotropic agent used is preferably 1 to 200 parts by mass, more preferably 5 to 150 parts by mass with respect to 100 parts by mass of the room temperature curable resin.

  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 extrudability, workability during 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. These organic solvents may be used at the time of synthesizing the urethane prepolymer or at the time of synthesizing the compound having a nitroxide free group, or may be used at the time of preparing the curable composition.

  Since the curable composition of the present invention reacts with an active hydrogen-containing compound (for example, water such as moisture) and crosslinks and cures, it can be used as a one-pack type moisture curable composition. In addition, a two-component (multi-component) reaction curable composition comprising a normal temperature curable resin in the present invention as a main component and a compound having a nitroxide free radical having a number average molecular weight of 2,000 or more is blended therein. Can also be used.

When used as a two-component reaction curable composition, an active hydrogen-containing compound such as polyol or polyamine can be used as the curing agent when an isocyanate group-containing resin is used as the main-temperature curable resin. Examples of active hydrogen-containing compounds such as polyols and polyamines used in the curing agent include active hydrogen-containing compounds (for example, polymer polyols and polymer polyamines) that can be used when synthesizing an isocyanate group-containing urethane prepolymer.
In the two-component reaction curable composition, the reaction molar ratio (isocyanate group / active hydrogen) of the isocyanate group of the main component isocyanate group-containing resin and the active hydrogen (group) of the active hydrogen compound such as polyol or polyamine of the curing agent is 0.9 to 1.3, more preferably 1 to 1.2.

  Further, when a crosslinkable silyl group-containing resin is used as the main-temperature curable resin, a curing accelerating catalyst can be used as the curing agent. Examples of the curing accelerating catalyst used in the curing agent include the above-described metal catalysts and amine catalysts, and metal catalysts are particularly preferable.

  A compound having a number average of 2,000 or more nitroxide free radicals to be blended in the two-component reaction curable composition may be blended in advance with the main agent or may be blended with the curing agent. Moreover, when mixing a main ingredient and a hardening | curing agent, you may mix | blend a predetermined amount and may mix with a main ingredient and a hardening | curing agent.

  Even when used as a two-component reaction curable composition, in addition to the above-mentioned room temperature curable resin, a compound having a nitroxide free radical having a number average of 2,000 or more, and a curing agent, a block amine compound or an additive is blended be able to. Examples of the block amine compound and additives include the above-mentioned block amine compounds and additives. The block amine compound and additives may be blended in advance with the main agent or may be blended with the curing agent. Moreover, when mixing a main ingredient and a hardening | curing agent, you may mix | blend a predetermined amount and may mix with a main ingredient and a hardening | curing agent.

  As a mixing method of the two-component reaction curable composition, there is a method of uniformly mixing each component using a mixer such as a hand mixer, a vacuum defoaming mixer, or a drum rotary mixer.

  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.

  The method for producing the curable composition of the present invention is not particularly limited in the case of a one-part moisture curable composition, and specifically, a room temperature curable resin, a nitroxide free radical having a number average molecular weight of 2,000 or more. , And if necessary, block amine compounds and additives in glass (stainless steel) or iron (mixing or kneading) containers equipped with a stirrer, shut off moisture and other water, and batch under a dry nitrogen stream The method of stirring and mixing to a formula and a continuous type is mentioned. In the case of a two-component reactive curable composition, each component of the main agent and the curing agent is individually charged into a mixing (kneading) container with a stirrer, water such as moisture is shut off, and batch type or The method of manufacturing by stirring and mixing continuously is mentioned.

  When the curable composition of the present invention is used as a one-pack type moisture curable composition, the room temperature curable resin reacts with water such as moisture to thicken and cure, so that the container can block water such as moisture. It is preferable to store in a sealed state. 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. Even when used as a two-component reaction type curable composition, it is preferable to store each component such as the main agent and the curing agent in a container that can block water such as moisture and sealed.

  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)
595.8 g of polyoxypropylene diol (manufactured by Asahi Glass Co., Ltd., product name EL-3021, hydroxyl value 34.68 mgKOH / g) while flowing nitrogen gas through a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet tube and heating / cooling device. , 175.2 g of polyoxypropylene triol (manufactured by Asahi Glass Co., Ltd., product name EL-4030, hydroxyl value 41.47 mgKOH / g), 157 of organic solvent (manufactured by JX Nippon Mining & Energy Corporation, product name Cactus Solvent P-20) 71.2 g of xylylene diisocyanate (product name Takenate 500, manufactured by Mitsui Chemicals) was added while stirring and 0.1 g of dibutyltin dilaurate was added as a reaction catalyst, followed by heating and reaction at 70-80 ° C. for 2 hours. The reaction was completed when the isocyanate group content became less than the theoretical value (1.09% by mass). To obtain an isocyanate group-containing urethane prepolymer. The isocyanate group-containing urethane prepolymer has a viscosity at 25 ° C. of 3,800 mPa · s, and the measured isocyanate group content by titration is 1.06% by mass (the isocyanate group content of the isocyanate group-containing urethane prepolymer minus the solvent content is 1.26% by mass). The number average molecular weight of the isocyanate group-containing urethane prepolymer was 3,600 in terms of polystyrene as measured by gel permeation chromatography (GPC).

Synthesis Example 2 (Synthesis of isocyanate group-containing urethane prepolymer)
While flowing nitrogen gas into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube and a heating / cooling device, 409.0 g of polyoxypropylene diol (manufactured by Asahi Glass Co., Ltd., product name EL-3021, hydroxyl value 34.53 mgKOH / g) , 379.3 g of polyoxypropylene triol (product name EL-4030, manufactured by Asahi Glass Co., Ltd., hydroxyl value 41.3 mg KOH / g), 17.4 g of pentaerythritol triacrylate, organic solvent (manufactured by JX Nippon Mining & Energy Corporation, product 119.3 g of Cactus Solvent P-20) was added, 74.9 g of xylylene diisocyanate (product name Takenate 500, manufactured by Mitsui Chemicals, Inc.) and 0.1 g of dibutyltin dilaurate as a reaction catalyst were added and stirred. The reaction is carried out at 70-80 ° C for 2 hours, and the isocyanate group content is the theoretical value. The reaction was terminated at the time point when 0.87 wt%) or less, to obtain an isocyanate group-containing urethane prepolymer.

Synthesis Example 3 (Synthesis of polyoxyalkylene compound having a nitroxide free group)
While flowing nitrogen gas through a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet tube and heating / cooling device, polyoxypropylene diol (manufactured by Asahi Glass Co., Ltd., product name PML-4001, hydroxyl value 56.39 mg KOH / g, total unsaturation degree) 277.8 g of 0.008 meq / g) was charged, 62.0 g of isophorone diisocyanate (manufactured by Evonik Japan Co., Ltd.) was added while stirring, 0.1 g of dibutyltin dilaurate was added as a reaction catalyst, and the mixture was heated to 2 at 70-80 ° C. The reaction was continued for a period of time, and when the isocyanate group content was below the theoretical value, cooling was performed to 30 ° C. or below. Next, a solution in which 48.0 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 112.1 g of dimethyl carbonate was charged and heated. After reacting at 70 to 80 ° C. for 4 hours and confirming disappearance of the peak of the isocyanate group by FT-IR, the mixture was cooled to 30 ° C. or less to obtain a polyoxyalkylene compound having a nitroxide free group. The number average molecular weight of the polyoxyalkylene compound having a nitroxide free group was 2,830 in terms of polystyrene measured by gel permeation chromatography (GPC). The content (theoretical value) of the nitroxide free radical (NO.) In the polyoxyalkylene compound having a nitroxide free radical (excluding the solvent) is 2.16% by mass.

Example 1
While flowing nitrogen gas into a kneading vessel equipped with a stirrer, a decompressor, and a nitrogen introduction tube, 1000 g of the urethane group-containing urethane prepolymer of Synthesis Example 1 and 300 g of the polyoxyalkylene compound having a nitroxide free group of Synthesis Example 3 were charged. While stirring, 690 g of heavy calcium carbonate (product name: Whiten B, manufactured by Shiraishi Calcium Co., Ltd.) and 70 g of organic solvent (product name: Cactus Solvent P-20, manufactured by JX Nippon Mining & Energy Co., Ltd.) were added to make the contents uniform. It knead | mixed until it became. Next, 15 g of an antioxidant (manufactured by BASF, product name Irganox 245), 35 g of dimethyl carbonate as an organic solvent, 5 g of p-toluenesulfonyl isocyanate (PTSI), fine powder silica (manufactured by Tokuyama Co., Ltd., 64 g of a product name Leolosil QS-102S) was charged and kneaded until the contents were uniform. Furthermore, defoaming was performed under reduced pressure at 20 to 50 hPa to prepare a curable composition (sealing material composition).

Example 2
While flowing nitrogen gas into a kneading vessel equipped with a stirrer, a decompression device and a nitrogen introduction tube, 1000 g of the isocyanate group-containing urethane prepolymer of Synthesis Example 2 and 300 g of the polyoxyalkylene compound having a nitroxide free group of Synthesis Example 3 were charged. While stirring, 600 g of heavy calcium carbonate (product name: Whiten B, manufactured by Shiraishi Calcium Co., Ltd.) and 30 g of organic solvent (product name: Cactus Solvent P-20, manufactured by JX Nippon Oil & Energy Co., Ltd.) are added to make the contents uniform. It knead | mixed until it became. Next, 15 g of an antioxidant (manufactured by BASF, product name Irganox 245), 30 g of dimethyl carbonate as an organic solvent, 5 g of p-toluenesulfonyl isocyanate (PTSI), and fine powder silica (made by Tokuyama Co., Ltd.) as a thixotropic agent , 15 g of product name Leoroseal QS-102S) was added and kneaded until the contents were uniform. Furthermore, defoaming was performed under reduced pressure at 20 to 50 hPa to prepare a curable composition (sealing material composition).

Comparative Example 1
In the same manner as in Example 1, except that 11.8 g of a hindered amine light stabilizer (manufactured by BASF, product name TINUVIN292) was used instead of using a polyoxyalkylene compound having a nitroxide free group, a curable composition was used. A product (sealing material composition) was prepared.

Comparative Example 2
The same as Example 1 except that 6.5 g of 2,2,6,6-tetramethylpiperidine 1-oxyl (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of using a polyoxyalkylene compound having a nitroxide free group. Then, a curable composition (sealing material composition) was prepared.

Comparative Example 3
In Example 1, 11.8 g of a hindered amine light stabilizer (manufactured by BASF, product name TINUVIN292) was used instead of using a polyoxyalkylene compound having a nitroxide free group, and 350 g of dioctyl phthalate was used. Then, a curable composition (sealing material composition) was prepared.

Comparative Example 4
Instead of using a polyoxyalkylene compound having a nitroxide free group in Example 1, 6.5 g of 2,2,6,6-tetramethylpiperidine 1-oxyl (manufactured by Wako Pure Chemical Industries, Ltd.) was used, and dioctyl was further used. A curable composition (sealing material composition) was prepared in the same manner except that 350 g of phthalate was used.

Comparative Example 5
A curable composition (sealing material composition) was prepared in the same manner as in Example 1 except that 350 g of dioctyl phthalate was used instead of using a polyoxyalkylene compound having a nitroxide free group.

Comparative Example 6
A curable composition was prepared in the same manner as in Example 2 except that 11.8 g of a hindered amine light stabilizer (manufactured by BASF, product name TINUVIN292) was used instead of using a polyoxyalkylene compound having a nitroxide free group. A product (sealing material composition) was prepared.

<Evaluation of curable composition>
Extrudability, contamination, and weather resistance were evaluated using the curable compositions (sealing material compositions) of Example 1 and Comparative Examples 1 to 5. The evaluation results are shown in Table 1.

[Extrudability]
The paper tube cartridge was filled with a curable composition (sealing material composition) so that air would not enter, and the cartridge was sealed under an environment of 23 ° C. for 24 hours, and then the cartridge was extruded using a manual sealing gun. Extrudability was evaluated by the following judgment from the situation of extrusion.
○: The contents can be easily obtained by extruding.

[Contamination]
A joint having a width of 20 mm, a depth of 10 mm, and a length of 130 mm was produced on the slate plate using a strip-like slate piece. The joint was filled with a curable composition (sealing material composition), the excess was scraped off with a spatula, and the test body having a flat finished surface was cured for 7 days in an environment of 23 ° C. and 50% RH. Next, a water-based acrylic paint (made by Nippon Paint Co., Ltd., Nippe tile crack, water-based top glossy first) was applied to the surface of the test body, cured at 23 ° C. and 50% RH for 7 days, and then placed in a 50 ° C. incubator. Set a day. Sprinkle black silica sand (product name: 8 product black, manufactured by Keimu View Cella Co., Ltd.) on the painted surface of the test specimen taken out from the thermostat. . The state of the black silica sand (dirt) remaining on the painted surface was visually observed, and the contamination was evaluated according to the following judgment.
○: Black silica sand does not adhere to the painted surface or is slightly adhered ×: A large amount of black silica sand adheres to the painted surface, and dirt is conspicuous

[Weatherability]
On a 5 mm thick slate plate, a foamed polyethylene backup material of 5 mm thickness x 12 mm width was affixed to form a square shape (frame) of 5 mm thickness x 30 mm width x 100 mm length. A curable composition (sealing material composition) was placed in this frame, and the excess was scraped off with a spatula to flatten the surface. Subsequently, it was cured for 14 days in an environment of 23 ° C. and 50% RH to prepare a test body (cured product).
The test specimen is the WS-A method (Sunshine weatherometer, black panel) of the 6.3 open frame carbon arc lamp exposure test method of JIS A 1415 (1999) "Exposure test method of laboratory building light source for polymer building materials". The appearance change of the surface of each specimen after 1,000 hours, after irradiating at a temperature of 63 ° C. for 102 minutes, after 18 minutes irradiation and water jetting) after 1,000 hours, after 2,000 hours, and after 2,500 hours was visually observed and weathered. Sex was evaluated according to the following criteria.
Judgment criteria ○: There are no cracks on the surface of the specimen △: There are fine cracks on the specimen surface ×: There are many cracks on the specimen surface

<Evaluation of curable composition>
Tensile adhesiveness was evaluated using the curable compositions (sealing material compositions) of Example 2 and Comparative Example 6. The evaluation results are shown in Table 2.
[Tensile adhesion]
A tensile adhesiveness test (23 ° C.) was performed according to the 5.20 tensile adhesiveness test of JIS A 1439 (2010) “Testing methods for building sealants”. The adherend is mortar, and a one-component urethane primer (OP-2531, manufactured by Auto Chemical Industry Co., Ltd.) is applied to the adherend surface and dried and cured, and then the curable composition (sealing material composition) is applied. A test specimen was cast and cured.

From the results of Table 1, it can be seen that the curable composition of Example 1 has excellent extrudability and excellent workability during use, and excellent anti-staining properties of the top coat (coating film) on the surface of the cured product.
Furthermore, it can be seen that the curable composition of Example 1 has good weather resistance over a long period of time without cracks on the surface of the cured product even after 2,500 hours in the weather resistance test. On the other hand, in the curable composition using a hindered amine light stabilizer or the like, cracks occurred by 2,500 hours.

  From the results of Table 2, it can be seen that the curable composition of Example 2 has low modulus and high elongation in tensile adhesiveness (rubber physical properties) after curing.

  As described above, the curable composition of the present invention is excellent in workability (extrusion property), antifouling property, weather resistance, and rubber physical property (tensile adhesiveness), and is a sealing material composition, waterproof material composition, coating. It can be suitably used as a material composition. Moreover, the curable composition of this invention can be used conveniently for construction use and civil engineering.

Claims (7)

  A curable composition comprising a room temperature curable resin and a compound having a nitroxide free radical having a number average molecular weight of 2,000 or more.   The curable composition according to claim 1, wherein the room temperature curable resin is an isocyanate group-containing resin or a crosslinkable silyl group-containing resin.   The curing according to claim 1 or 2, wherein the compound having a nitroxide free group having a number average molecular weight of 2,000 or more is a compound having a nitroxide free group having a number average molecular weight of 2,000 or more and a piperidine ring. Sex composition.   The compound having a nitroxide free group having a number average molecular weight of 2,000 or more is a polyoxyalkylene compound having a nitroxide free group having a number average molecular weight of 2,000 or more and / or a nitroxide free group having a number average molecular weight of 2,000 or more. It is a poly (meth) acrylic-type compound which has, 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. Additives are 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 said curable composition is a sealing material composition, a waterproof material composition, or a coating material composition, The curable composition as described in any one of Claims 1-6 characterized by the above-mentioned.