JP2018162387A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition that has high strength, excellent weather resistance and excellent chemical resistance, and can be used suitably as a waterproof material composition, a coating material composition, a sealant composition or an adhesive composition.SOLUTION: A curable composition contains a room-temperature-curable resin and a surface-treated barium sulfate.SELECTED DRAWING: None

Description

  The present invention relates to a curable composition having high strength and excellent weather resistance and chemical resistance.

  A curable composition containing a polyurethane resin, silicone resin, modified silicone resin, or polysulfide resin as a curing component is a sealing material composition for construction, civil engineering, automobile, etc., waterproof material composition, coating material composition, adhesion It is used as an agent composition. 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 a curable composition is used as a waterproofing composition for construction or civil engineering, it becomes a seamless coating, and even if the base is complex, it can secure waterproofness without gaps, and it can adhere to the base and the connecting member, and adhere to it. In recent years, the amount of its use has increased due to its good properties.

  When the waterproof material composition is used for a flooring material or a pavement material that can be walked or passed by a vehicle, a load is applied when walking or passing the vehicle, and the coating film may crack or swell over time. For this reason, what has the high-strength coating-film physical property is desired as a performance of a waterproof material composition. In order to obtain high-strength coating film properties, a method using an aromatic resin has also been studied. In this case, the resulting coating film has high strength, but the weather resistance is poor. After that, a top coat having excellent weather resistance is applied to the surface (for example, Patent Document 1). In this method, it is necessary to apply a waterproof material composition and a top coat, respectively. From the viewpoint of shortening the construction period and simplifying the construction, there is a demand for a waterproof material composition that has both high-strength coating film properties and weather resistance. Yes. In addition, building materials containing a waterproofing material composition have increased needs for longer life, and chemical resistance is also required in terms of ensuring reliability.

JP 2013-139559 A

  An object of the present invention is to provide a curable composition having high strength and excellent weather resistance and chemical resistance.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a curable composition containing a room temperature curable resin and a surface-treated barium sulfate has high strength, weather resistance, and chemical resistance. As a result, the present invention has been completed. That is, this invention has the aspect shown to following (1)-(8).
(1) A curable composition comprising a room temperature curable resin and a surface-treated barium sulfate.
(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 curable composition according to (1) or (2), wherein the surface-treated barium sulfate is barium sulfate surface-treated with a treatment agent containing silicon oxide and / or aluminum oxide. .
(4) The curability according to any one of (1) to (3), wherein the amount of the surface-treated barium sulfate is 10 to 200 parts by mass with respect to 100 parts by mass of the room temperature curable resin. Composition.
(5) The curable composition according to any one of (1) to (4), further comprising a block amine compound.
(6) Further, at least one selected from a curing accelerating catalyst, a plasticizer, a weathering stabilizer, a filler, a thixotropic agent, an adhesion improver, a storage stability improver (dehydrating agent), a colorant, and an organic solvent. The curable composition according to any one of (1) to (5), which contains at least one kind of additive.
(7) The curable composition according to any one of (1) to (6), wherein the curable composition is a curable composition for construction or civil engineering.
(8) The curing according to any one of (1) to (7), wherein the curable composition is a waterproofing material composition, a coating material composition, a sealing material composition, or an adhesive composition. Sex composition.

  Since the curable composition of the present invention has high strength and excellent weather resistance and chemical resistance, it is particularly suitable as a waterproofing composition, coating material composition, sealing material composition or adhesive composition for construction and civil engineering. Can be used for

  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 surface-treated barium sulfate. 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 or the like 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 are collectively or in a range in which the molar ratio of isocyanate group / active hydrogen is preferably 1.2 to 10, more preferably 1.2 to 5. It can be made to react so that isocyanate groups remain in the urethane prepolymer. When the molar ratio is less than 1.2, 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, 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, more preferably 0.3 to 10% 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 1,000 or more, more preferably 1,000 to 20,000, still more preferably 1,000 to 15,000, and particularly preferably 1,000 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). Examples of the method for measuring gel permeation chromatography (GPC) include the following methods.

<GPC measurement method>
Apparatus: HCL-8320GPC Tosoh Corporation Detector: RI (differential refractive index)
Solvent: THF (tetrahydrofuran)
Flow rate: 0.6 ml / min
Temperature: 40 ° C

  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. The method of making it react under stirring at 50-120 degreeC below 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, araliphatic 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 by which these polyols and the organic isocyanate compound are reacted with an excess of hydroxyl groups with respect to the isocyanate groups to make the molecular terminals hydroxyl groups.

  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. A polyoxyalkylene polyol synthesized using a double metal cyanide complex catalyst is preferred because it has a low total unsaturation and a low polyol viscosity.

  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. 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 low molecular weight polyol is a polyol having a number average molecular weight of less than 1,000, specifically, 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 glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, trimethylolpropane, glycerin, pentaerythritol, bisphenol skeleton-containing polyether polyol, polyester polyol, polycarbonate polyol, polyoxyalkylene polyol, Hydrocarbon-based polyol, animal and vegetable-based polyols, these copolyols can be mentioned. Any of these low molecular weight polyols can be used alone or in combination of two or more. Among the low-molecular polyols, bisphenol skeleton-containing polyether polyols can be suitably used because the tensile strength after curing of the curable composition is good. The content of the bisphenol skeleton-containing polyol is preferably 5 to 30% by mass, more preferably 5 to 20% by mass in the isocyanate group-containing urethane prepolymer.

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

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

Examples of the method for introducing the photoreactive unsaturated bond into the isocyanate group-containing urethane prepolymer include the following methods.
(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.
Among the above, the method (a) is preferable in terms of easy availability of raw materials and easy 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 is preferable, and 1.2 to 5 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 0.3 to 10% 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. 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 content of the photoreactive unsaturated bond in the isocyanate group-containing urethane prepolymer into which the photoreactive unsaturated bond is introduced is preferably 0.01 mmol / g or more, more preferably 0.03 to 1 mmol / g, 0.05 to 0.5 mmol / g is particularly 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 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 Japanese Patent Application Laid-Open No. 11-116763 and Japanese Patent Application Laid-Open No. 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.

（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。） 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.

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.

  The surface-treated barium sulfate will be described. The surface-treated barium sulfate is used in the curable composition of the present invention for the purpose of increasing the amount or reinforcing the physical properties of the cured product. In particular, in a curable composition in which surface-treated barium sulfate is blended in a room temperature curable resin, the cured composition has excellent chemical resistance (acid resistance and alkali resistance).

  The surface-treated barium sulfate is obtained by treating the surface of precipitated barium sulfate or fertile barium sulfate with a treatment agent containing silicon oxide and / or aluminum oxide. Hydrates and hydroxides may be contained in silicon oxide and aluminum oxide. When the surface of barium sulfate is treated with silicon oxide and aluminum oxide, the treatment steps can be performed simultaneously or individually. By treating the surface of barium sulfate with a treatment agent containing silicon oxide and / or aluminum oxide, the dispersibility when blended with a room temperature curable resin, a block amine compound, an additive, and the like described later is improved. When the surface of barium sulfate is treated with a treating agent containing silicon oxide and / or aluminum oxide and then the surface is further treated with an organic compound, the dispersibility with room temperature curable resins, block amine compounds, additives, etc. is particularly good. It becomes.

  Examples of the organic compound used for the surface treatment include amines, silicones, and alcohols. Any of these may be used alone or in combination of two or more.

  Examples of the amine include diethanolamine and triethanolamine. Examples of silicone include monomethyl polysiloxane and dimethyl polysiloxane. Examples of the alcohol include trimethylolpropane, ethylene glycol, glycerin, pentaerythritol, neopentyl glycol, polypropylene glycol, and polyethylene glycol.

  Examples of the surface treatment compound other than the above-described amine, silicone, and alcohol include carboxylic acid, metal soap, organic ester, silane, silane coupling agent, silylating agent, and siloxane.

  Although there is no restriction | limiting in particular as a manufacturing method of surface treatment barium sulfate, It can manufacture by the method described in patent 5924463 grade | etc.,. As a method for treating the surface of barium sulfate with silicon oxide, specifically, for example, sodium silicate or the like is added to an aqueous slurry of barium sulfate powder as it is or as an aqueous solution, and then an acid such as sulfuric acid is added to form silicon oxide. By precipitating, or by dispersing barium sulfate powder in alcohol or water or a mixed solvent of alcohol and water, adding alkoxysilane such as tetraethoxysilane, adding acid or base, or heating. The method of depositing silicon oxide is mentioned.

  Then, the surface-treated barium sulfate is obtained by performing filtration and drying. For the filtration, a device such as a filter press, a decanter, or a rotary filter can be used. For drying, a commonly used heating or vacuum drying apparatus can be used. Moreover, the surface-treated barium sulfate can also be obtained by using a spray dryer or the like without performing filtration. The treatment amount of silicon oxide is preferably 0.1 to 10 parts by mass of silicon oxide with respect to 100 parts by mass of barium sulfate.

  As a method for treating the surface of barium sulfate with aluminum oxide, specifically, for example, aluminum nitrate, aluminum sulfate, sodium aluminate or the like is added as it is or in an aqueous solution to a slurry of barium sulfate powder, and then acid or alkali is added. Is added to precipitate aluminum oxide. Subsequent filtration and drying can be performed in the same manner as in silicon oxide. The treatment amount of aluminum oxide is preferably 0.1 to 10 parts by mass of aluminum oxide with respect to 100 parts by mass of barium sulfate.

  Examples of treatment agents other than silicon oxide, aluminum oxide, and organic compounds include zinc oxide and zirconium oxide.

  The particle diameter of the surface-treated barium sulfate is preferably 0.01-5 μm, more preferably 0.01-2 μm. The particle diameter of the surface-treated barium sulfate can be determined as a 50% cumulative particle diameter by laser diffraction / scattering particle diameter distribution measurement.

  10-200 mass parts is preferable with respect to 100 mass parts of room temperature curable resin, and, as for the compounding quantity of surface treatment barium sulfate, 20-150 mass parts is more preferable.

  The curable composition of the present invention can further contain a block amine compound. A 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 can be suitably used when the room temperature curable resin is an isocyanate group-containing urethane prepolymer.

  The oxazolidine compound is a compound having one or more, preferably 1 to 6, more preferably 1 to 3, oxazolidine rings, which are saturated 5-membered heterocyclic rings 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. When this is described in detail, when the isocyanate group of the isocyanate group-containing resin reacts with water, a urea bond is formed and cured. At this time, carbon dioxide gas is also generated, and bubbles due to carbon dioxide gas are generated in the cured product. Problems such as deterioration of the appearance of the cured product, 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 isocyanate group of the organic polyisocyanate compound and the hydroxyl group of the compound having a hydroxyl group and an oxazolidine ring have an isocyanate group / hydroxyl molar ratio of 0.9 to 1.2, preferably 0.95. What is obtained by using it so that it may become 1.05 and making it react at the temperature of 50-120 degreeC in the presence or absence of an organic solvent is mentioned.

  The organic polyisocyanate used for the production of the urethane bond-containing oxazolidine compound may be the same as that used for the production of the urethane prepolymer. Among these, araliphatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate are preferable, and xylylene diisocyanate, hexamethylene diisocyanate, and isophorone 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 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 urethane bond-containing oxazolidine compound described above, a small amount of active hydrogen groups or isocyanate groups may remain in the molecule depending on the selection of the molar ratio. In this case, this is useful for achieving the object of the present invention. Can be considered not. The “small amount” means that the amount of active hydrogen 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, Furthermore, it is preferable to mix | blend so that it may become 0.3-1 mol, and it is preferable to set it as 0.5-1 mol especially. 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). Moreover, a hardening acceleration | stimulation catalyst can be used also as a reaction catalyst at the time of manufacture of the above-mentioned urethane prepolymer and a urethane bond containing oxazolidine compound. In addition, when it uses as a reaction catalyst at the time of manufacture of a urethane prepolymer and a urethane bond containing oxazolidine compound, the reaction catalyst which remains in them may act as a hardening acceleration catalyst of a curable composition.

  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. Examples of the metal chelate compound include a tin chelate compound, a zirconium chelate compound, a titanium chelate compound, an aluminum chelate compound, a bismuth chelate compound, and an iron chelate compound. Specifically, dibutyltin bis (acetylacetonate), tin chelate compound EXCESTAR C-501 manufactured by Asahi Glass Co., Ltd., zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate), aluminum tris (acetylacetonate) Aluminum tris (ethyl acetoacetate), bismuth tris (2-ethylhexanoate), 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 A salt with an organic acid, a salt with an organic tin and an organic acid, a salt with an organic bismuth and an organic acid, a tin chelate compound, a bismuth chelate compound and an iron chelate compound 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.

  In addition to the above-mentioned metal catalyst and amine catalyst, organic carboxylic acid catalyst, phosphate ester catalyst, p-toluenesulfonyl monoisocyanate, and a reaction product of p-toluenesulfonyl monoisocyanate and water can be used. Organic carboxylic acid catalyst, phosphoric acid ester catalyst, p-toluenesulfonyl monoisocyanate, reaction product of p-toluenesulfonyl monoisocyanate and water, when a block amine compound (for example, an oxazolidine compound) is blended with the curable composition And a hydrolysis promoting catalyst (ring-opening catalyst) for promoting hydrolysis of the oxazolidine ring of the oxazolidine compound. By the promotion of hydrolysis of the oxazolidine ring, the generated secondary amino group and alcoholic hydroxyl group (active hydrogen group) react with the isocyanate group of the urethane prepolymer to accelerate the curing of the curable composition.

  Examples of organic carboxylic acid catalysts include formic acid, acetic acid, propionic acid, caproic acid, oxalic acid, succinic acid, adipic acid, 2-ethylhexanoic acid (octylic acid), octenoic acid, lauric acid, oleic acid, stearic acid, etc. Α, β-unsaturated carboxylic acid such as aliphatic carboxylic acid, maleic acid, acrylic acid, aromatic carboxylic acid such as phthalic acid, benzoic acid, salicylic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride And alicyclic acid anhydrides such as methylhexahydrophthalic anhydride, methylnadic anhydride, and dimethylbutenyltetrahydrophthalic anhydride.

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

  The reaction product of p-toluenesulfonyl monoisocyanate and water may be one obtained by reacting p-toluenesulfonyl monoisocyanate and water in advance before blending with the curable composition of the present invention. Water may be added and reacted while toluenesulfonyl monoisocyanate is blended and prepared in the curable composition, or water present in the curable composition (water contained in the raw material). Etc.) may be reacted at the time of preparation or after adjustment.

  As for the usage-amount of a hydrolysis promotion catalyst (ring-opening catalyst), 0.001-5 mass parts is preferable with respect to 100 mass parts of block amine compounds.

  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 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 further 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 and reinforcing the physical properties of the cured product, like the surface-treated barium sulfate. 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; and organic thixotropic agents such as urea compounds, organic bentonites, and fatty acid amides. Any of these may be used alone or in combination of two or more.

  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.

  The urea compound is a compound having at least one urea bond (—NHCONH—) in the compound, and includes a reaction product of an organic isocyanate compound and an amine compound.

  As an organic isocyanate compound, the thing similar to the organic isocyanate compound at the time of manufacturing the above-mentioned urethane prepolymer can be mentioned.

  Examples of the amine compound include compounds having at least one amino group in the molecule. Examples of the amino group include a primary amino group and a secondary amino group. Monoamines having primary amino groups include butylamine, isobutylamine, hexylamine, heptylamine, 2-ethylhexylamine, octylamine, 3-methoxypropylamine, tetradecylamine, cetylamine, stearylamine, oleylamine, trimethylcyclohexylamine , Benzylamine, and aniline. Examples of the diamine having a primary amino group include ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 1,7-diaminoheptane, and trimethylhexamethylenediamine. 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, isophoronediamine, diaminodicyclohexylmethane, 3,9-bis (3-aminopropyl)- 2,4,8,10-tetraoxaspiro 5,5) undecane, xylene diamine, phenylene diamine, diaminodiphenylmethane, diaminodiphenyl diethyl phenyl methane, polyoxyethylene diamine, polyoxypropylene diamine. Examples of the triamine having a primary amino group include tri (methylamino) hexane. Examples of the monoamine having a secondary amino group include diethylamine, dipropylamine, diisopropylamine, dibutylamine, dihexylamine, di-2-ethylhexylamine, diphenylamine, dilaurylamine, distearylamine, and methyllaurylamine. Examples of the diamine having a secondary amino group include N, N′-dilaurylpropyldiamine, N, N′-distearylbutyldiamine, N-butyl-N′-laurylethyldiamine, and N-butyl-N′-lauryl. And propyldiamine and N-lauryl-N'-stearylbutyldiamine. Examples of the polyamine having a primary amino group and a secondary amino group include diethylenetriamine, triethylenetetramine, and methylaminopropylamine. Any of these amine compounds can be used alone or in combination of two or more.

  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 behenic acid. Examples of metal salts include sodium salts, potassium salts, calcium salts, aluminum salts, and organic salts include ammonium salts.

  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 adhesion.

  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.

  Since the curable composition of the present invention reacts with an active hydrogen-containing compound or the like (for example, water such as moisture) to be crosslinked and cured, it can be used as a one-pack type moisture curable composition. Moreover, the normal temperature curable resin in this invention can be used as a main ingredient, and a hardening | curing agent can be mix | blended with this and it can also be used as a two-component (multi-component) reaction curable composition.

  When used as a two-component reaction curable composition, an active hydrogen-containing compound such as a polyol, polyamine, or polysulfide can be used as the curing agent when an isocyanate group-containing resin is used as the main-temperature curable resin. Examples of the polyol and polyamine used in the curing agent include polyols and polyamines (for example, polymer polyols and polymer polyamines) that can be used when synthesizing an isocyanate group-containing urethane prepolymer.

As polysulfide, the formula in the main chain:
-(R ₁ O) _n-
[Wherein R ₁ is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 6 to 200], and a formula:
_{- (C 2 H 4 OC m} H 2m OC 2 H 4 -S x) - (a)
_{- (CH 2 CH (OH)} CH 2 -S x) - (b)
[Wherein m is an integer of 1 to 2 and x is an integer of 1 to 5], and the terminal is represented by the formula:
_{-C 2 H 4 OC m H 2m} OC 2 H 4 -SH and / or _{-CH 2 CH (OH) CH 2} -SH
[Wherein m is an integer of 1 to 2]. The number average molecular weight of polysulfide is preferably 600 to 200,000, more preferably 800 to 50,000. Commercially available products include “LP-282” (number average molecular weight 3,500) manufactured by Toray Fine Chemical Co., Ltd. The polyether portion of the polysulfide polymer and the structural units (a) and (b) can have an arbitrary arrangement, and the proportion occupied by the polyether portion is 2 to 95% by mass, and the structural unit (a): _{- (C 2 H 4 OC m} H 2m OC 2 H 4 -S x) - moiety is 3 to 70 mass%, and structural units _{(b) :-( CH 2 CH (} OH) CH 2 -S x) - moiety Is preferably 1 to 50% by mass. In addition, it is preferable that content of polysulfide bond _Sx is 1-60 mass%.

  In a two-component reaction curable composition, the reaction molar ratio (isocyanate group / active hydrogen) of an isocyanate group of a main component isocyanate group-containing resin and an active hydrogen (group) of an active hydrogen compound such as a polyol, polyamine, or polysulfide as a curing agent. ) Is preferably 0.9 to 1.5, more preferably 1 to 1.3.

  When a crosslinkable silyl group-containing resin is used as the curable resin as the main agent, 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.

  The surface-treated barium sulfate 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 the main agent and the curing agent, a predetermined amount may be measured and mixed together with the main agent and the curing agent.

  Even when used as a two-component reaction curable composition, in addition to the above-mentioned room temperature curable resin, surface-treated barium sulfate, and a curing agent, a block amine compound and an additive can be blended. 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, you may mix | blend when mixing a main ingredient and a hardening | curing agent.

  Examples of the mixing method of the two-component reaction curable composition include 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; woody material such as wood and plywood.

  It does not specifically limit as a manufacturing method of the curable composition of this invention, It can carry out by a well-known method. In the case of a one-pack type moisture curable composition, specifically, a room temperature curable resin, surface-treated barium sulfate, and, if necessary, a block amine compound and additives with a stirrer made of glass, stainless steel, iron, etc. Examples include a method of preparing a mixing (kneading) container, blocking water such as moisture, and stirring and mixing batchwise or continuously in a dry nitrogen stream. In the case of a two-component reactive curable composition, the above components are divided into a main agent and a curing agent, charged in a mixing (kneading) container with a stirrer, water such as moisture is shut off, and batchwise under a dry nitrogen stream And a method of stirring and mixing in a continuous manner.

  When the curable composition of the present invention is used as a one-pack type moisture curable composition, the room temperature curable resin may react with water such as moisture to thicken and cure, so that water such as moisture may be used. It is preferable to store it in a sealed container. The container is not particularly limited as long as it is a container that can block water such as moisture. Specific examples include metal and resin cans, aluminum bags, paper and resin cartridges. Even when it is used as a two-component reactive curable composition, it is preferable to store each component of the main agent and the curing agent in a container that can block water such as moisture and sealed.

  By setting the curable composition of the present invention to the components described above, the cured composition has high strength and excellent weather resistance and chemical resistance.

  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)
461.9 g of polyoxypropylene diol (Preminol S4001, hydroxyl value 56.4, manufactured by Asahi Glass Co., Ltd.) containing a bisphenol skeleton while flowing nitrogen gas through a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube and heating / cooling device 82.7 g of polyol (Adeka polyether BPX-33, hydroxyl value 196: polyether diol obtained by reacting 6 mol of propylene oxide to 1 mol of bisphenol A, manufactured by ADEKA) in one molecule Epoxide acrylate (epoxy ester 70PA: CH ₂ ═CHCOOCH ₂ CH (OH) CH ₂ OCH ₂ CH (CH ₃ ) OCH ₂ CH (OH) CH ₂ OCOCH═CH ₂ , hydroxyl value 338, Kyoeisha Chemical Co., Ltd. 16.6 g, naphthenic solvent (Swaclean 150, manufactured by Maruzen Petrochemical Co., Ltd.) 153.8 g each, while stirring, 285.0 g of isophorone diisocyanate, 0.05 g of inorganic bismuth (Neostan U-600, manufactured by Nitto Kasei Co., Ltd.) as a reaction catalyst After reacting at 75 to 80 ° C. for 3 hours, the reaction solution was cooled to room temperature to obtain an isocyanate group-containing urethane prepolymer PU-1. The reaction molar ratio of the isocyanate group-containing urethane prepolymer PU-1 (number of moles of isocyanate group as raw material / number of moles of hydroxyl group) is 3. The isocyanate group-containing urethane prepolymer has an isocyanate group content (theoretical value in the resin) of 8.5% by mass.

[Synthesis Example 2] (Synthesis of urethane bond-containing oxazolidine compound)
While flowing nitrogen gas through a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, ester tube and heating / cooling device, 420.0 g of diethanolamine (molecular weight 105), 177.0 g of toluene and isobutyraldehyde (molecular weight 72) .1) was charged with 317.0 g, heated while stirring, and reflux dehydration reaction was performed at 110 to 150 ° C. while removing by-product water (71.9 g) out of the system. After no water distilling was observed, the mixture was further heated under reduced pressure (50 to 70 hPa) to remove toluene and unreacted isobutyraldehyde, and N-hydroxyethyl-2-isopropyloxazolidine as an intermediate reaction product Got. Next, 336.0 g of hexamethylene diisocyanate (molecular weight: 168) was further added to 636.0 g of the obtained N-hydroxyethyl-2-isopropyloxazolidine, and the mixture was heated at 80 ° C. for 8 hours. The reaction was terminated when the amount reached 0% by mass, and a urethane bond-containing oxazolidine compound having two oxazolidine rings in one molecule was obtained. The urethane bond-containing oxazolidine compound O-1 was liquid at room temperature.

[Example 1]
410.5 g of the isocyanate group-containing urethane prepolymer PU-1 obtained in Synthesis Example 1 was charged into a kneading vessel equipped with a stirrer, a heating device, a cooling device, and a nitrogen seal tube while flowing nitrogen gas, and 100 to 110 ° C. in advance while stirring. Surface-treated barium sulfate (BARIACE B-34, treatment agent: SiO ₂ -Al ₂ O ₃ and organic compound, manufactured by Sakai Chemical Industry Co., Ltd.) having a moisture content of 0.05% by mass or less by drying with a dryer 205.0 g, 205.0 g of heavy calcium carbonate (Whiteon B, manufactured by Shiroishi Kogyo Co., Ltd.) and 13.7 g of titanium oxide were charged and kneaded until the contents were uniform. Next, 5.1 g of a hindered phenol-based antioxidant (IRGANOX245, manufactured by BASF Japan), 3.4 g of a hindered amine-based light stabilizer (ADK STAB LA-63P, manufactured by ADEKA), and urethane bond-containing oxazolidine of Synthesis Example 2 154.0 g of compound O-1 and 2.2 g of hydrophobic silica (Reorosil DM-10, manufactured by Tokuyama Corporation) were charged, kneaded for 30 minutes until uniform, and further iron (III) acetylacetonate (Wako Pure Chemical Industries, Ltd.). 0.08 g of alicyclic acid anhydride (HN-2200: methyl-1,2,3,6-tetrahydrophthalic anhydride, manufactured by Hitachi Chemical Co., Ltd.) was prepared and kneaded for 30 minutes. The curable composition (waterproofing composition) was prepared by degassing under reduced pressure at 50 to 100 hPa and filling and sealing in a square can container made of tin.

[Comparative Example 1]
A curable composition (waterproofing composition) was prepared in the same manner as in Example 1, except that the surface-treated barium sulfate was not blended and 410.0 g of heavy calcium carbonate was blended.

[Comparative Example 2]
In Example 1, the surface-treated barium sulfate was not blended, 205.0 g of heavy calcium carbonate, and 205.0 g of untreated barium sulfate (precipitated barium sulfate 100, Sakai Chemical Industry Co., Ltd.) were blended. Carried out the same operation to prepare a curable composition (waterproofing composition). However, barium sulfate that was not surface-treated could not be dispersed, and particulate matter was generated in the curable composition.

[Comparative Example 3]
In Example 1, the same operation was carried out except that no surface-treated barium sulfate was blended, and 410.0 g of untreated barium sulfate (precipitated barium sulfate 100, manufactured by Sakai Chemical Industry Co., Ltd.) was blended. A composition (waterproofing composition) was prepared. However, barium sulfate that was not surface-treated could not be dispersed, and particulate matter was generated in the curable composition.

  Using the curable compositions of Example 1 and Comparative Example 1, the following performance evaluation was performed. The evaluation results are shown in Table 1. Since the curable compositions of Comparative Examples 2 to 3 were poorly dispersed at the time of preparation, performance evaluation was not performed.

  The curable composition was placed in a mold that had been subjected to mold release treatment, and was cured at 23 ° C. and 50% RH for 96 hours. The curable composition was removed from the mold and further cured at 23 ° C. and 50% RH for 72 hours to prepare a cured sheet having a thickness of 2 mm.

1) Durometer Hardness Using a cured sheet, a type D durometer hardness test was performed in accordance with JIS K 6253-3: 2012 “How to find vulcanized rubber and thermoplastic rubber hardness Part 3: Durometer hardness”. The durometer hardness was determined.

2) Accelerated weather resistance JIS K 5658: 2010 “Weather-resistant top coat for construction” 7.16 In accelerated weather resistance, color difference and gloss after 2,500 hours of irradiation were the same except that a cured sheet was attached to a flexible plate. The retention rate and chalking grade were determined and evaluated. There is no cracking or swelling in the cured sheet after irradiation, the color difference value of the sample test piece is not large compared to the color difference value of the sample specimen, and the chalking grade is 1 or 0, and gloss When the retention rate is 80% or more (that is, when the accelerated weather resistance specified in JIS K 5658 conforms to the first grade), when either condition is not satisfied (that is, according to JIS K 5658) The case where the specified accelerated weather resistance does not conform to the first grade) was marked as x.

3) Foaming resistance The curable composition was put in a paper cup having an inner diameter of 5 mmΦ at the bottom so as to have a thickness of about 10 mm, followed by curing in an oven at 50 ° C. and 80% RH for 96 hours. After curing, take it out from the oven, leave it in an environment of 23 ° C. and 50% RH for 1 hour, then cut the paper cup and the curable composition vertically with a cutter, and visually observe the cut surface of the curable composition. The case where there was no bubble on the cut surface was marked as ◯, and the case where there was a bubble on the cut surface was marked as x.

4) Tensile performance Using a cured product sheet, a JIS K 6251: 2010 “Method of obtaining tensile properties of vulcanized rubber and thermoplastic rubber” 6.1 A dumbbell-shaped test specimen of dumbbell-shaped specimen 3 was produced.
The test body was measured by a tensile performance test at 23 ° C. according to JIS A 6021: 2011 “Building Waterproofing Material for Buildings” 6.6.1, and the tensile strength before treatment and the elongation at break were determined.

5) Tensile properties after treatment Using cured sheet, JIS K 6251: 2010 “How to find vulcanized rubber and thermoplastic rubber tensile properties” 6.1 Dumbbell-shaped test piece of No. 3 type specimen did. After the heat treatment, alkali treatment, and acid treatment shown below, the specimen was measured in a tensile performance test at 23 ° C. according to JIS A 6021: 2011 “Waterproofing Material for Architectural Coatings”. The strength and elongation at break were determined. Further, the tensile strength ratio was determined from the tensile strength before and after the treatment.
Heat treatment: The specimen was heat-treated under the conditions of JIS A 6021: 2011 “Building paint waterproofing material” 6.9.3a). The heating temperature is 80 ° C. and the treatment time is 168 hours.
Alkali treatment: The test specimen was alkali-treated under the conditions of JIS A 6021: 2011 “Waterproofing material for architectural coatings” 6.9.3c). The processing time is 168 hours.
Acid treatment :: The test specimen was acid-treated under the conditions of JIS A 6021: 2011 “Building paint waterproof material” (6.3.3d). The processing time is 168 hours.

Table 1 shows the blending contents and test results of Example 1 and Comparative Examples 1 to 3. For reference, JIS standard values are also shown in the table.

  From the results of Table 1, since the curable composition of Example 1 is excellent in weather resistance, it is not necessary to apply a top coat (top coat) for the purpose of imparting weather resistance to the surface of the curable composition, and the construction is simple. And shortening the construction period can be realized. Moreover, it turns out that the curable composition of Example 1 has high hardness and favorable foaming resistance. Furthermore, the curable composition of Example 1 has a high elongation at break before treatment, and has high strength and high elongation tensile performance (rubber physical properties). In particular, the elongation at break after heat treatment, and the tensile strength ratio after alkali treatment and acid treatment and the elongation at break are high, indicating that the heat resistance and chemical resistance are excellent.

  On the other hand, the curable composition of Comparative Example 1 has a low elongation at break after heat treatment, a tensile strength ratio after alkali treatment and after acid treatment, and a low elongation at break, so that the roof is specified in JIS A 6021. It does not conform to the performance of waterproofing coating film (urethane rubber type, high strength type).

  Since the curable composition of the present invention conforms to the performance (urethane rubber type, high strength type) of the waterproof coating film for roofs specified in JIS A 6021 in tensile performance, the curable composition for construction and civil engineering use. It can be suitably used as a product and has high industrial value. Moreover, the curable composition of this invention can be used as a waterproofing material composition, a coating material composition, a sealing material composition, or an adhesive composition.

Claims (8)

  A curable composition comprising a room temperature curable resin and a surface-treated barium sulfate.   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 curable composition according to claim 1 or 2, wherein the surface-treated barium sulfate is barium sulfate surface-treated with a treatment agent containing silicon oxide and / or aluminum oxide.   The curable composition according to any one of claims 1 to 3, wherein the amount of the surface-treated barium sulfate is 10 to 200 parts by mass with respect to 100 parts by mass of the room temperature curable resin.   Furthermore, a block amine compound is contained, The curable composition as described in any one of Claims 1-4 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 1-5 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 1-6 characterized by the above-mentioned.   The curable composition according to any one of claims 1 to 7, wherein the curable composition is a waterproofing material composition, a coating material composition, a sealing material composition, or an adhesive composition. object.