Curable composition and production method therefor

Abstract

This curable composition comprises an organic polymer (A) having a reactive silicon group and a curing catalyst (B), wherein: the curing catalyst (B) contains a carboxylic acid metal compound (b1) and a cyclic secondary amine compound (b2); the carboxylic acid metal compound (b1) contains at least one metal selected from the group consisting of tin, titanium, bismuth, zirconium, iron, aluminum, and zinc; and the cyclic secondary amine compound (b2) has at least one skeleton selected from the group consisting of a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, and an azepane skeleton.

Description

Curable composition and method for producing the same

[0001] The present invention relates to a curable composition containing an organic polymer having a silicon group (hereinafter also referred to as a "reactive silicon group") that has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and that can form a crosslink by forming a siloxane bond, and a method for producing the same.

[0002] It is known that organic polymers having reactive silicon groups have the property of crosslinking even at room temperature through the formation of siloxane bonds accompanied by hydrolysis of the silyl groups due to moisture, etc., to give rubber-like cured products. Such organic polymers having reactive silicon groups are already produced industrially and are widely used in applications such as sealants, adhesives, paints, and waterproofing materials.

[0003] To allow the curing reaction to proceed in a short period of time, a curing catalyst (also called a silanol condensation catalyst) is usually blended into a curable composition containing an organic polymer having a reactive silicon group.

[0004] Patent Document 1 discloses that the recovery properties of the resulting rubber-like cured product are improved by using, as such a curing catalyst, an organic tin carboxylate such as tin octoate or an organic lead carboxylate in combination with an amine compound such as laurylamine.

[0005] Special Publication No. 61-060867

[0006] The use of a curing catalyst that combines a conventional carboxylic acid metal compound and an amine compound as disclosed in Patent Document 1 can improve the recovery properties of a rubber-like cured product. However, curable compositions containing such curing catalysts tend to have low curability, requiring a long time for curing, or to have low storage stability, resulting in a decrease in curability when attempting to cure after long-term storage.

[0007] In view of the above-described current situation, an object of the present invention is to provide a curable composition containing a reactive silicon group-containing organic polymer, which is capable of forming a cured product having good recovery properties, has good curability, and is inhibited from decreasing in curability due to storage.

[0008] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that, in a curing catalyst combining a metal carboxylic acid compound and an amine compound, by using a cyclic secondary amine compound as the amine compound, good curability can be achieved while maintaining good recovery properties, and deterioration of curability after storage can be suppressed, thereby completing the present invention.

[0009] That is, the present invention provides a curable composition containing an organic polymer (A) having a reactive silicon group and a curing catalyst (B), wherein the reactive silicon group is represented by the general formula (1): -SiR １ ３－ａ X ａ (1) (wherein, R １ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ０ ３ It represents a triorganosiloxy group represented by SiO—. ０ are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a represents 1, 2, or 3. R １ or when a plurality of X's are present, they may be the same or different.), wherein the curing catalyst (B) comprises a metal carboxylate compound (b1) and a cyclic secondary amine compound (b2), wherein the metal carboxylate compound (b1) comprises one or more metals selected from the group consisting of tin, titanium, bismuth, zirconium, iron, aluminum, and zinc, and the cyclic secondary amine compound (b2) has one or more skeletons selected from the group consisting of a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, and an azepane skeleton. The present invention also relates to a method for producing a curable composition containing an organic polymer (A) having a reactive silicon group and a curing catalyst (B), the method comprising: mixing the metal carboxylate compound (b1) and the cyclic secondary amine compound (b2) to obtain the curing catalyst (B); and mixing the curing catalyst (B) with the organic polymer (A) having a reactive silicon group represented by the general formula (1).

[0010] According to the present invention, it is possible to provide a curable composition containing a reactive silicon group-containing organic polymer, which is capable of forming a cured product having good recovery properties, has good curability, and is inhibited from decreasing in curability due to storage.

[0011] According to a preferred embodiment of the present invention, the cured product obtained by curing the curable composition also has good mechanical properties.

[0012] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS One aspect of the present invention relates to a curable composition containing an organic polymer (A) having a reactive silicon group and a curing catalyst (B).

[0013] (Reactive silicon group-containing organic polymer (A)) The reactive silicon group-containing organic polymer (A) has a polymer skeleton (also referred to as a main chain structure) and a polymer chain end bonded to the polymer skeleton. The polymer skeleton is a structure in which a plurality of monomer units are formed consecutively by bonding a plurality of monomers by polymerization, condensation, or the like. The monomer may be of one type, or a mixture of a plurality of types may be bonded.

[0014] The polymer chain end refers to a site located at the end of the reactive silicon group-containing organic polymer (A). The number of polymer chain ends of the reactive silicon group-containing organic polymer (A) is 2 when the polymer skeleton is entirely linear, and 3 or more when the polymer skeleton is entirely branched. Furthermore, when the polymer skeleton is a mixture of linear and branched chains, the average number can be between 2 and 3.

[0015] The reactive silicon group of the organic polymer (A) may be present in the polymer backbone and / or at the polymer chain end. Two or more reactive silicon groups may be present at one polymer chain end. When the curable composition according to the present disclosure is used for adhesives, sealants, elastic coating agents, pressure-sensitive adhesives, etc., the reactive silicon group is preferably contained at the polymer chain end of the organic polymer (A).

[0016] The organic polymer (A) has a reactive silicon group represented by the following general formula (1): —SiR １ ３－ａ X ａ(1) (wherein, R １ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ０ ３ It represents a triorganosiloxy group represented by SiO—. ０ are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a represents 1, 2, or 3. R １ Or, when there are multiple X's, they may be the same or different.

[0017] R in general formula (1) １ Examples of the alkyl group include alkyl groups such as methyl and ethyl groups; alkyl groups having hetero groups such as chloromethyl, methoxymethyl, and 3,3,3-trifluoropropyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl groups; aralkyl groups such as benzyl groups; and R ０ is a methyl group, a phenyl group, etc. ０ ３ Examples include triorganosiloxy groups represented by SiO-. Preferred are alkyl groups or alkyl groups having a hetero-containing group, more preferred are methyl groups, ethyl groups, chloromethyl groups, and methoxymethyl groups, even more preferred are methyl groups and ethyl groups, and particularly preferred is methyl group. R １ When there are a plurality of groups, they may be the same or different.

[0018] X in general formula (1) represents a hydroxyl group or a hydrolyzable group. The hydrolyzable group is not particularly limited and may be a known hydrolyzable group, such as a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, or an alkenyloxy group. Among these, an alkoxy group, an acyloxy group, a ketoximate group, or an alkenyloxy group is preferred. Because of their mild hydrolysis and ease of handling, an alkoxy group is more preferred, a methoxy group or an ethoxy group is even more preferred, and a methoxy group is particularly preferred. When multiple Xs are present, they may be the same or different.

[0019] a is 1, 2, or 3. a is preferably 2 or 3. From the viewpoint of obtaining better curability, a is particularly preferably 3.

[0020] The reactive silicon group represented by general formula (1) is not particularly limited, but examples include trimethoxysilyl, triethoxysilyl, tris(2-propenyloxy)silyl, triacetoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethoxyethylsilyl, dimethoxyphenylsilyl, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N-diethylaminomethyl)dimethoxysilyl, and (N,N-diethylaminomethyl)diethoxysilyl. Among these, dimethoxymethylsilyl and trimethoxysilyl groups are preferred due to their ease of synthesis. Trimethoxysilyl and methoxymethyldimethoxysilyl groups are preferred because they provide high curability. Trimethoxysilyl and triethoxysilyl groups are preferred because they provide cured products with high recovery rates and low water absorption.

[0021] (Main Chain Structure of Reactive Silicon Group-Containing Organic Polymer (A)) The main chain structure (also referred to as polymer skeleton) of the reactive silicon group-containing organic polymer (A) is not particularly limited, and various main chain structures can be used. Specific examples include polyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymers, and polyoxypropylene-polyoxybutylene copolymers; hydrocarbon polymers such as ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; polyolefins obtained by condensation of dibasic acids such as adipic acid with glycols, or by ring-opening polymerization of lactones; Examples of suitable ester polymers include (meth)acrylic acid ester polymers obtained by radical polymerization of (meth)acrylic acid ester monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and stearyl (meth)acrylate; vinyl copolymers obtained by radical polymerization of monomers such as (meth)acrylic acid ester monomers, vinyl acetate, acrylonitrile, and styrene; polysulfide polymers; polyamide polymers; polycarbonate polymers; and diallyl phthalate polymers. In the above description, (meth)acrylic refers to acrylic and / or methacrylic.

[0022] Among these, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth)acrylic acid ester polymers are preferred because they have relatively low glass transition temperatures and the resulting cured products have excellent cold resistance. Only one of these may be used, or two or more may be used in combination.

[0023] Polyoxyalkylene polymers and (meth)acrylic acid ester polymers are particularly preferred because they have high moisture permeability, excellent deep curing properties when made into a one-component curable composition, and excellent adhesive properties. Polyoxyalkylene polymers are more preferred, and polyoxypropylene is even more preferred. It is also preferred to use a polyoxyalkylene polymer and a (meth)acrylic acid ester polymer in combination.

[0024] (Meth)acrylic acid ester-based polymers are useful because, by combining various monomer compositions constituting the polymer, effects such as improved adhesiveness, improved heat resistance and weather resistance, and reduced water absorption of a cured product obtained by curing a curable composition can be obtained.

[0025] The polyoxyalkylene polymer is preferably a polymer having a repeating unit represented by -R-O- (wherein R is a linear or branched alkylene group having 1 to 14 carbon atoms). R is more preferably a linear or branched alkylene group having 2 to 4 carbon atoms. Specific examples of the repeating unit represented by -R-O- include -CH ２ O-, -CH ２ CH ２ O-, -CH ２ CH (CH ３ ) O—, —CH ２ CH(C ２ H ５ ) O—, —CH ２ C(CH ３ ) (CH ３ ) O—, —CH ２ CH ２ CH ２ CH ２ The main chain structure of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.

[0026] In particular, when the curable composition according to the present disclosure is used as a sealant, adhesive, or the like, a polyoxypropylene-based polymer having oxypropylene repeating units in an amount of 50% by weight or more, more preferably 80% by weight or more, of the polymer main chain structure is preferred because it is amorphous and has a relatively low viscosity.

[0027] The main chain structure of the polyoxyalkylene polymer may be linear or may have a branched chain. When the polymer has a branched chain, the number of branches is preferably 1 to 6 (i.e., 3 to 8 terminal hydroxyl groups), more preferably 1 to 4 (i.e., 3 to 6 terminal hydroxyl groups), and most preferably 1 (i.e., 3 terminal hydroxyl groups). The presence of a branched chain can improve the restorability of the cured product. It can also be expected to reduce the water absorption of the cured product. When the polymer has a branched chain and the reactive silicon group is a trimethoxysilyl group, a cured product with particularly low water absorption can be obtained.

[0028] The polyoxyalkylene polymer is preferably one obtained by ring-opening polymerization of a cyclic ether compound in the presence of an initiator using a polymerization catalyst.

[0029] Examples of cyclic ether compounds include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more. Among the cyclic ether compounds, propylene oxide is particularly preferred because it can produce an amorphous polyether polymer with a relatively low viscosity.

[0030] Specific examples of the initiator include alcohols such as butanol, ethylene glycol, propylene glycol, propylene glycol monoalkyl ether, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, and sorbitol; and hydroxyl group-terminated polyoxyalkylene polymers having a number average molecular weight of 300 to 4,000, such as polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene diol, and polyoxyethylene triol.

[0031] Examples of synthesis methods for polyoxyalkylene polymers include, but are not limited to, polymerization methods using an alkali catalyst such as KOH, polymerization methods using a transition metal compound-porphyrin complex catalyst such as the complex obtained by reacting an organoaluminum compound with porphyrin disclosed in JP-A-61-215623, polymerization methods using a composite metal cyanide complex catalyst disclosed in JP-B-46-27250, JP-B-59-15336, U.S. Pat. Nos. 3,278,457, 3,278,458, 3,278,459, 3,427,256, 3,427,334, and 3,427,335, polymerization methods using a catalyst made of a polyphosphazene salt exemplified in JP-A-10-273512, and polymerization methods using a catalyst made of a phosphazene compound exemplified in JP-A-11-060722. A polymerization method using a composite metal cyanide complex catalyst is more preferred for reasons such as production costs and the fact that a polymer with a narrow molecular weight distribution can be obtained.

[0032] The reactive silicon group-containing organic polymer (A) may be a polyoxyalkylene polymer containing other bonds such as urethane bonds or urea bonds in the main chain structure, provided that the effects of the present invention are not significantly impaired. Specific examples of such polymers include polyurethane prepolymers.

[0033] The polyurethane prepolymer can be obtained by a known method, for example, by reacting a polyol compound with a polyisocyanate compound.

[0034] Specific examples of the polyol compound include polyether polyol, polyester polyol, polycarbonate polyol, and polyether polyester polyol.

[0035] Specific examples of polyisocyanate compounds include diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, methylene-bis(cyclohexyl isocyanate), isophorone diisocyanate, hexamethylene diisocyanate, etc. The polyurethane prepolymer may be terminated with either a hydroxyl group or an isocyanate group.

[0036] From the viewpoint of obtaining a curable composition having excellent storage stability and workability, it is particularly preferred that the reactive silicon group-containing organic polymer (A) is a polyoxyalkylene polymer that does not contain a urethane bond, a urea bond, an ester bond, or an amide bond in the main chain structure.

[0037] The reactive silicon group-containing organic polymer (A) is preferably obtained by introducing reactive silicon groups into a polymer by any of the following methods (a) to (d): (a) converting the terminal hydroxyl groups of a hydroxyl group-terminated organic polymer into carbon-carbon unsaturated groups, and then forming HSiR １ ３－ａ X ａ (In the formula, R １ , X, and a are the same as the groups shown in general formula (1).

[0038] (b) OCN-W-SiR １ ３－ａ X ａ (Wherein, W is a divalent organic group. R １ , X, and a are the same as the groups shown in general formula (1),

[0039] (c) After converting the terminal hydroxyl groups of the hydroxyl-terminated organic polymer into carbon-carbon unsaturated groups, HS-W-SiR １ ３－ａ X ａ (Wherein, W is a divalent organic group. R １ , X, and a are the same as the groups shown in general formula (1),

[0040] (d) A hydroxyl-terminated organic polymer is reacted with a polyisocyanate compound to synthesize an NCO-terminated organic polymer, and then HNR-W-SiR １ ３－ａ X ａ (Wherein, W is a divalent organic group. R is a hydrogen atom or an alkyl group. R １ , X, and a are the same as the groups shown in general formula (1)) or HS—W—SiR １ ３－ａ X ａ (Wherein, W is a divalent organic group. R１ , X, and a are the same as the groups shown in general formula (1),

[0041] In the above methods (a) and (c), examples of the terminal carbon-carbon unsaturated group include a vinyl group, an allyl group, a methallyl group, an allenyl group, and a propargyl group.

[0042] In each of the above methods, the reactive silicon group-containing organic polymer (A) obtained using a silane compound in which W is a methylene group is preferred in that it exhibits very high curability.

[0043] Method (a) is preferred because it tends to produce a reactive silicon group-containing organic polymer (A) with good storage stability, while methods (b), (c), and (d) are preferred because they can achieve high conversion in a relatively short reaction time.

[0044] The introduction of reactive silicon groups by the method (a) has been proposed in Japanese Patent Publication Nos. 45-36319, 46-12154, Japanese Patent Laid-Open Nos. 50-156599, 54-6096, 55-13767, 55-13468, 57-164123, Japanese Patent Publication No. 3-2450, U.S. Pat. Nos. 3,632,557, 4,345,053, 4,366,307, and 4,960,844. Examples include those proposed in JP-A Nos. 61-197631, 61-215622, 61-215623, and 61-218632 in which reactive silicon groups are introduced by hydrosilylation or the like into polyoxypropylene polymers having a high molecular weight and narrow molecular weight distribution, with a number average molecular weight of 6,000 or more and an Mw / Mn ratio of 1.6 or less, and those proposed in JP-A No. 3-72527.

[0045] The molecular weight distribution (Mw / Mn) of the reactive silicon group-containing organic polymer (A) is not particularly limited, but is preferably 1.6 or less, more preferably 1.5 or less, and particularly preferably 1.4 or less, and from the viewpoint of improving various mechanical properties such as durability and elongation of the cured product, it is preferably 1.2 or less.

[0046] The number average molecular weight of the reactive silicon group-containing organic polymer (A), as calculated as polystyrene by GPC, is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and particularly preferably 8,000 to 35,000. When the number average molecular weight is within these ranges, the cured product has excellent mechanical properties, and since the amount of reactive silicon groups introduced is appropriate, it is possible to obtain an organic polymer (A) that exhibits good curability, has a manageable viscosity, and is excellent in workability, while keeping production costs within an appropriate range.

[0047] The molecular weight of the reactive silicon group-containing organic polymer (A) can also be expressed as an end group molecular weight calculated by directly measuring the end group concentration by titration analysis based on the principles of the hydroxyl value measurement method specified in JIS K 1557 and the iodine value measurement method specified in JIS K 0070, and taking into consideration the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). The end group-converted molecular weight of the organic polymer (A) can also be calculated by preparing a calibration curve of the number average molecular weight determined by general GPC measurement of a polymer precursor and the end group-converted molecular weight, and converting the number average molecular weight determined by GPC of the organic polymer (A) into an end group-converted molecular weight.

[0048] In order to obtain a good rubber-like cured product, the reactive silicon groups of the organic polymer (A) are preferably present at the polymer chain terminals. In order to show good curability and easily exhibit rubber elastic behavior, the number of reactive silicon groups per polymer chain terminal of the organic polymer (A) is preferably 0.5 or more, more preferably 0.6 or more, even more preferably 0.7 or more, and particularly preferably 0.8 or more, on average.

[0049] The number of polymer chain ends per molecule of the organic polymer (A) is preferably 2 to 8, more preferably 2 to 4, and particularly preferably 2 or 3. The number of reactive silicon groups per molecule of the organic polymer (A) is preferably 1 to 7 on average, more preferably 1 to 3.4, and particularly preferably 1 to 2.6.

[0050] When the reactive silicon group-containing organic polymer (A) is branched, the reactive silicon group may be located at the end of the main chain of the organic polymer, at the end of a side chain (branched chain), or at both. In particular, when the reactive silicon group is located at the end of the main chain, the molecular weight between crosslinking points becomes longer, which makes it easier to obtain a rubber-like cured product that has high strength, high elongation, and a low elastic modulus, which is preferred.

[0051] As described in WO 2013 / 180203, an organic polymer (A) obtained by methods (a) and (c) using an organic polymer having two or more carbon-carbon unsaturated bonds at one polymer chain end has two or more reactive silicon groups at one polymer chain end. Such organic polymer (A) exhibits high curability, and the resulting cured product can be expected to have high strength and high recovery.

[0052] Specific examples of reactive silicon group-containing organic polymers (A) include various reactive silicon group-containing polyoxypropylene products under the trade names Kaneka MS Polymer or Kaneka Silyl, reactive silicon group-containing poly(meth)acrylic acid esters such as Kaneka TA Polymer or Kaneka XMAP, and reactive silicon group-containing polyisobutylenes such as Kaneka EPION, all of which are available from Kaneka Corporation.

[0053] (Curing Catalyst (B)) The curable composition according to the present disclosure contains a curing catalyst (B) used to form a cured product by hydrolyzing and condensing the reactive silicon groups of the organic polymer (A). The curing catalyst (B) contains a carboxylic acid metal compound (b1) and a cyclic secondary amine compound (b2). This makes it possible to provide a curable composition that is capable of forming a cured product with good recovery, has good curability, and is inhibited from decreasing in curability due to storage.

[0054] (Carboxylic Acid Metal Compound (b1)) The carboxylic acid metal compound (b1) is preferably a metal salt of a carboxylic acid having one or more (preferably one) carboxyl groups (—COOH) in one molecule and 1 to 30 (preferably 2 to 20, more preferably 6 to 12) carbon atoms.

[0055] Specific examples of the carboxylic acid compound are not particularly limited, and examples of the aliphatic monocarboxylic acid include straight-chain saturated fatty acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, and tridecylic acid; monoene unsaturated fatty acids such as acrylic acid and methacrylic acid; polyene unsaturated fatty acids; 2-methylbutyric acid, isobutyric acid, 2-ethylbutyric acid, pivalic acid, 2,2-dimethylbutyric acid, 2-ethyl-2-methylbutyric acid, and 2,2-dimethylbutyric acid. Examples of the fatty acids include branched fatty acids such as ethyl butyric acid, 2-phenyl butyric acid, isovaleric acid, 2,2-dimethyl valeric acid, 2-ethyl-2-methyl valeric acid, 2,2-diethyl valeric acid, octylic acid, 2-ethyl hexanoic acid, 2,2-dimethyl hexanoic acid, neononanoic acid, 2,2-diethyl hexanoic acid, 2,2-dimethyl octanoic acid, 2-ethyl-2,5-dimethyl hexanoic acid, versatic acid, and neodecanoic acid; fatty acids having a triple bond; alicyclic carboxylic acids; oxygen-containing fatty acids; and halogen-substituted monocarboxylic acids. Examples of the aliphatic dicarboxylic acids include chain dicarboxylic acids such as adipic acid, sebacic acid, oxalic acid, malonic acid, and succinic acid, saturated dicarboxylic acids, and unsaturated dicarboxylic acids. Examples of the aliphatic polycarboxylic acids include chain tricarboxylic acids such as aconitic acid, citric acid, isocitric acid, 3-methylisocitric acid, and 4,4-dimethylaconitic acid.

[0056] Examples of aromatic carboxylic acids include aromatic monocarboxylic acids such as benzoic acid and salicylic acid, aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid, and halogen-substituted aromatic carboxylic acids such as chlorobenzoic acid. Also usable are carboxylic acid derivatives that produce carboxylic acids upon hydrolysis, such as carboxylic acid anhydrides, esters, amides, nitriles and acyl chlorides.

[0057] As the carboxylic acid compound, a monocarboxylic acid is preferred, and a fatty acid monocarboxylic acid is particularly preferred. As the carboxylic acid compound, a carboxylic acid in which the carbon atom adjacent to the carbonyl group is a tertiary carbon (e.g., 2-ethylhexanoic acid) or a carboxylic acid in which the carbon atom adjacent to the carbonyl group is a quaternary carbon (e.g., neodecanoic acid, pivalic acid) is preferred because of its fast curing rate, and a carboxylic acid in which the carbon atom adjacent to the carbonyl group is a quaternary carbon is particularly preferred.

[0058] The metal constituting the carboxylic acid metal compound (b1) is one or more selected from the group consisting of tin, titanium, bismuth, zirconium, iron, aluminum, and zinc. Among them, tin and / or titanium are preferred because they provide high catalytic activity, and tin is particularly preferred. As tin, divalent tin is preferred from the viewpoint of improving recovery.

[0059] Specific examples of the carboxylate metal compound (b1) include divalent tin compounds such as tin octoate, tin neodecanoate, tin 2-ethylhexanoate, tin stearate, tin naphthenate, tin versatate, and tin pivalate; tetravalent tin compounds such as dibutyltin dilaurate, dibutyltin maleate, and dibutyltin diacetate; titanium carboxylate, bismuth carboxylate, zirconium carboxylate, iron carboxylate, aluminum carboxylate, and zinc carboxylate. One type of carboxylate metal compound (b1) may be used, or multiple compounds may be used in combination.

[0060] (Cyclic secondary amine compound (b2)) The cyclic secondary amine compound (b2) refers to a heterocyclic amine compound having a cyclic secondary amine skeleton and an NH group. By using (b2), the curable composition exhibits good curability and can suppress a decrease in curability after storage, while the cured product maintains good recovery.

[0061] The cyclic secondary amine skeleton is a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, or an azepane skeleton. Among them, from the viewpoint of curability, a piperidine skeleton, a piperazine skeleton, or an azepane skeleton is preferred, a piperidine skeleton or an azepane skeleton is more preferred, and a piperidine skeleton is particularly preferred. The cyclic secondary amine compound (b2) may be used alone or in combination with a plurality of compounds.

[0062] The cyclic secondary amine compound (b2) may be a compound having no substituent on the carbon atom of the cyclic secondary amine skeleton, or may be a compound having a substituent. Examples of the substituent include a hydrocarbon group having 1 to 20 carbon atoms, an ester group, a hydroxyl group, etc. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The hydrocarbon group may also have a substituent such as a halogen atom, an ester group, or a hydroxyl group.

[0063] The cyclic secondary amine compound (b2) is preferably a compound having an ester group or a hydroxyl group, since it has an excellent effect of improving storage stability and the curability is less likely to decrease even during storage.

[0064] The cyclic secondary amine compound (b2) having an ester group or a hydroxyl group can be represented, for example, by the following general formula (3) or (4): ３ -R ４ -C(=O)-OR ５ (3) R ３ -R ４ —OH (4) In formulas (3) and (4), R ３ represents a cyclic secondary amine skeleton, R ４ represents a direct bond or a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms. ５ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0065] R ３ The cyclic secondary amine skeleton represented by the formula (I) represents a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, or an azepane skeleton.４ In addition, the cyclic secondary amine skeleton preferably has a bond with -R ４ -C(=O)-OR ５ The substituent may or may not have a substituent other than the group represented by the formula: Examples of the substituent include a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, an ester group, and a hydroxyl group.

[0066] R ４ represents a direct bond or a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. The hydrocarbon group may be aliphatic, alicyclic, or aromatic, but is preferably aliphatic. The hydrocarbon group may or may not have a substituent such as a halogen atom, an ester group, or a hydroxyl group.

[0067] R ５ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. The hydrocarbon group may be aliphatic, alicyclic, or aromatic, but is preferably aliphatic. The hydrocarbon group may or may not have a substituent such as a halogen atom or a hydroxyl group.

[0068] The molecular weight of the cyclic secondary amine compound (b2) is not particularly limited, but may be, for example, about 100 to 1,000. It may also be 120 to 500, or 150 to 200.

[0069] Specific examples of the cyclic secondary amine compound (b2) having an ester group include ester compounds of piperidine carboxylic acids such as 4-piperidine carboxylic acid, 2-piperidine carboxylic acid, and 3-piperidine carboxylic acid, and ester compounds of pyrrolidine carboxylic acids such as 2-pyrrolidine carboxylic acid, etc. Specific examples of the ester compounds include methyl esters, ethyl esters, and propyl esters, with ethyl esters being particularly preferred from the viewpoint of curability.

[0070] From the viewpoints of availability, compatibility with the organic polymer (A), and improvement of curability, an ester compound of piperidine carboxylic acid is preferred, an ester compound of 4-piperidine carboxylic acid is more preferred, methyl 4-piperidine carboxylate and ethyl 4-piperidine carboxylate are even more preferred, and ethyl 4-piperidine carboxylate is particularly preferred.

[0071] Specific examples of the hydroxyl group-containing cyclic secondary amine compound (b2) include hydroxypiperidines such as 4-hydroxypiperidine and 3-hydroxypiperidine, piperidinemethanols such as 3-piperidinemethanol, and piperidineethanol.

[0072] Specific examples of the cyclic secondary amine compound (b2) having no ester group or hydroxyl group include pyrrolidine, piperidine, piperazine, azepane (hexamethyleneimine), methylpiperidines such as 4-methylpiperidine, dimethylpiperidines such as 3,5-dimethylpiperidine, and N-substituted piperazines such as N-methylpiperazine.

[0073] When producing the curable composition according to the present disclosure, the carboxylic acid metal compound (b1) and the cyclic secondary amine compound (b2) may be added and mixed separately to the organic polymer (A) without previously mixing the carboxylic acid metal compound (b1) and the cyclic secondary amine compound (b2).

[0074] However, from the viewpoint of catalytic activity, it is preferable to premix (b1) and (b2) and then add and mix them with the organic polymer (A). Premixing (b1) and (b2) facilitates the formation of a complex through the interaction between (b1) and (b2). Mixing this complex with the organic polymer (A) can further improve curability. Furthermore, by using the curing catalyst (B) obtained by mixing (b1) and (b2), the interaction between (b1) and (b2) can prevent the curing catalyst from bleeding out from the surface of the cured product.

[0075] The method for mixing the carboxylic acid metal compound (b1) and the cyclic secondary amine compound (b2) is not particularly limited, but may involve mixing and stirring both components at room temperature or at an elevated temperature below the decomposition temperature of each component. The mixing may be performed without a solvent, or in the presence of a solvent inert to both components. Furthermore, the mixing may be performed in an inert gas (nitrogen gas, argon gas) atmosphere, or in the presence of air. The time for mixing under stirring is not particularly limited, but may be, for example, about 1 hour to 3 days.

[0076] According to a preferred embodiment, a complex of (b1) and (b2) can be formed by premixing a metal carboxylate compound (b1) and a cyclic secondary amine compound (b2). The complex refers to a state in which (b1) and (b2) do not exist independently of each other, but rather involve a reaction in which (b1) and (b2) are bonded together or the structure of (b1) and / or (b2) is changed. The complex can be formed by mixing (b1) and (b2) under stirring using the method described above. When mixed under stirring, the mixture becomes viscous and generates heat, allowing the formation of the complex to be confirmed.

[0077] The curing catalyst (B) may be composed only of a carboxylic acid metal compound (b1) and a cyclic secondary amine compound (b2), but preferably further contains a diluent. The use of a diluent improves the handleability of the curing catalyst (B), and further improves the dispersibility of the curing catalyst (B) in the organic polymer (A) and the curability of the curable composition. As the diluent, a solvent or a plasticizer can be suitably used. Among these, plasticizers are preferred, ester group-containing plasticizers are more preferred, and phthalate ester compounds are particularly preferred. Specific examples of plasticizers are described below.

[0078] The diluent can be added before, during, or after the formation of the complex of (b1) and (b2), and is preferably added after the formation of the complex of (b1) and (b2).

[0079] The amount of diluent used can be set appropriately, but the weight ratio of the diluent to the total amount of (b1) and (b2) is preferably 0.1 to 10, more preferably 0.5 to 5, and even more preferably 1 to 3.

[0080] In the curable composition according to the present disclosure, the content of the curing catalyst (B) can be appropriately determined taking into consideration the desired curability and the workability of the curable composition, and may be, for example, about 0.001 to 20 parts by weight, preferably 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 1 to 8 parts by weight, relative to 100 parts by weight of the reactive silicon group-containing organic polymer (A). However, when the curing catalyst (B) contains the above-mentioned diluent, the amount of the diluent is not included in the calculation of the content of the curing catalyst (B).

[0081] The ratio of the carboxylic acid metal compound (b1) to the cyclic secondary amine compound (b2) can be set appropriately, and the weight ratio of (b2) to (b1) [(b2) / (b1)] may be 0.01 to 5. From the viewpoints of recovery, curability, and storage stability, it is preferably 0.05 to 1, more preferably 0.1 to 0.8, and even more preferably 0.2 to 0.5.

[0082] The curable composition according to the present disclosure may further contain a curing catalyst other than the curing catalyst (B). Examples of such a curing catalyst include a metal carboxylate other than the metal carboxylate compound (b1), an amine compound other than the cyclic secondary amine compound (b2), a carboxylic acid, a metal alkoxide, and an inorganic acid.

[0083] The content of the curing catalyst other than the curing catalyst (B) is not particularly limited and may be set appropriately. For example, it may be 0 to 10 parts by weight, 0 to 5 parts by weight, 0 to 3 parts by weight, or 0 to 1 part by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0084] The curable composition according to this embodiment may contain other additives, such as silicon compounds, adhesion promoters, plasticizers, solvents, diluents, silicates, fillers, anti-sagging agents, antioxidants, light stabilizers, UV absorbers, physical property adjusters, tackifier resins, epoxy group-containing compounds, photocurable substances, oxygen-curable substances, surface property improvers, epoxy resins, other resins, flame retardants, and foaming agents. Furthermore, various additives may be added to the curable composition according to this embodiment as needed to adjust the physical properties of the composition or the cured product. Examples of such additives include curability adjusters, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, and mildew inhibitors.

[0085] (Filler) The curable composition according to the present embodiment may contain various fillers, such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, silicic anhydride, hydrated silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc white, PVC powder, PMMA powder, glass fiber, and filament.

[0086] The amount of filler used is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, based on 100 parts by weight of the polymer according to this embodiment.

[0087] Organic or inorganic balloons may be added to the composition to reduce its weight (lower its specific gravity). The balloons are hollow spherical fillers, and examples of the materials for the balloons include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran.

[0088] The amount of balloons used is preferably 0.1 to 100 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the polymer according to this embodiment.

[0089] (Adhesion Imparting Agent) An adhesion imparting agent can be added to the curable composition according to this embodiment. As the adhesion imparting agent, a silane coupling agent or a reaction product of a silane coupling agent can be added. Specific examples of the silane coupling agent include amino group-containing silanes such as γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-isopropyltriethoxysilane; Examples of suitable adhesion promoters include isocyanate group-containing silanes such as cyanatepropylmethyldimethoxysilane, α-isocyanatomethyltrimethoxysilane, and α-isocyanatomethyldimethoxymethylsilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; and epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Condensates of various silane coupling agents, such as condensates of amino group-containing silanes and condensates of amino group-containing silanes with other alkoxysilanes, and reaction products of various silane coupling agents, such as reaction products of amino group-containing silanes and epoxy group-containing silanes and reaction products of amino group-containing silanes and (meth)acrylic group-containing silanes, can also be used. The adhesion promoters may be used alone or in combination.

[0090] The amount of the adhesion promoter used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer according to this embodiment.

[0091] (Plasticizer) A plasticizer may be added to the curable composition according to this embodiment. Specific examples of plasticizers include phthalate ester compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate ester compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; non-phthalate ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; aliphatic polycarboxylic acid ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and acetyl tributyl citrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkylsulfonic acid phenyl esters; phosphate ester compounds; trimellitic acid ester compounds; chlorinated paraffins; hydrocarbon oils such as alkyl diphenyls and partially hydrogenated terphenyls; process oils; and epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

[0092] Furthermore, a polymer plasticizer can be used. Specific examples of the polymer plasticizer include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more, and polyethers such as derivatives in which the hydroxy groups of these polyether polyols are converted into ester groups, ether groups, etc.; polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, etc. The plasticizers may be used alone or in combination of two or more.

[0093] The amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and even more preferably 20 to 100 parts by weight, relative to 100 parts by weight of the polymer according to this embodiment.

[0094] (Solvent, Diluent) A solvent or diluent can be added to the curable composition according to this embodiment. The solvent and diluent are not particularly limited, but aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, etc. can be used. When using a solvent or diluent, in view of the problem of air pollution when the composition is used indoors, the boiling point of the solvent is preferably 150°C or higher, more preferably 200°C or higher, and particularly preferably 250°C or higher. The above solvents or diluents may be used alone or in combination of two or more.

[0095] (Anti-sagging agent) If necessary, an anti-sagging agent may be added to the curable composition according to this embodiment in order to prevent sagging and improve workability. The anti-sagging agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents may be used alone or in combination of two or more.

[0096] The amount of the anti-sagging agent used is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the polymer according to this embodiment.

[0097] (Antioxidant) An antioxidant (antiaging agent) can be used in the curable composition according to this embodiment. Use of an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731. The amount of antioxidant used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polymer according to this embodiment.

[0098] (Light Stabilizer) A light stabilizer can be used in the curable composition according to this embodiment. The use of a light stabilizer can prevent photo-oxidative degradation of the cured product. Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds, with hindered amine-based compounds being particularly preferred.

[0099] The amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polymer according to this embodiment.

[0100] (UV Absorber) An UV absorber can be used in the curable composition according to this embodiment. The use of a UV absorber can improve the surface weather resistance of the cured product. Examples of UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, and metal chelate-based compounds. Benzotriazole-based compounds are particularly preferred, and examples thereof include those commercially available under the names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571, Tinuvin 1600, and Tinuvin B75 (all manufactured by BASF). The amount of UV absorber used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polymer according to this embodiment.

[0101] (Physical Property Modifier) ​​A physical property modifier may be added to the curable composition according to this embodiment as needed to adjust the tensile properties of the resulting cured product. The physical property modifier is not particularly limited, but examples include alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as tris(trimethylsilyl)borate and tris(triethylsilyl)borate; silicone varnishes; and polysiloxanes. The use of the physical property modifier can increase the hardness of the curable composition according to this embodiment when cured, or conversely, decrease the hardness and increase the elongation at break. The physical property modifiers may be used alone, or two or more types may be used in combination.

[0102] In particular, compounds that upon hydrolysis produce compounds having monovalent silanol groups in the molecule have the effect of reducing the modulus of the cured product without increasing the stickiness of the surface of the cured product. Compounds that produce trimethylsilanol are particularly preferred. Examples of compounds that upon hydrolysis produce compounds having monovalent silanol groups in the molecule include silicon compounds that are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol and that produce silane monool upon hydrolysis. Specific examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.

[0103] The amount of the physical property adjuster used is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the polymer according to this embodiment.

[0104] (Tackifying Resin) A tackifying resin can be added to the curable composition according to the present embodiment for the purpose of improving adhesion or adhesion to a substrate, or as otherwise required. The tackifying resin is not particularly limited, and any commonly used tackifying resin can be used.

[0105] Specific examples include terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and hydrogenated products thereof, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, etc. These may be used alone or in combination of two or more.

[0106] The amount of the tackifier resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, and even more preferably 5 to 30 parts by weight, relative to 100 parts by weight of the polymer according to this embodiment.

[0107] (Epoxy Group-Containing Compound) A compound containing an epoxy group can be used in the curable composition according to this embodiment. The use of a compound containing an epoxy group can improve the recovery of the cured product. Examples of compounds containing an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. Specific examples include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, and epoxy butyl stearate. The epoxy compound is preferably used in an amount of 0.5 to 50 parts by weight per 100 parts by weight of the polymer according to this embodiment.

[0108] (Photocurable Substance) A photocurable substance can be used in the curable composition according to this embodiment. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, improving the stickiness and weather resistance of the cured product. Many compounds of this type are known, including organic monomers, oligomers, resins, and compositions containing them. Representative examples include unsaturated acrylic compounds, which are monomers or oligomers having one or more acrylic or methacrylic unsaturated groups, or mixtures thereof, polyvinyl cinnamates, and azido resins.

[0109] The amount of the photocurable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer according to this embodiment.

[0110] (Oxygen-Curable Substance) An oxygen-curable substance can be used in the curable composition according to this embodiment. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, which react with oxygen in the air to form a cured film near the surface of the cured product, preventing stickiness of the surface and adhesion of dirt and dust to the surface of the cured product. Specific examples of oxygen-curable substances include drying oils such as tung oil and linseed oil, and various alkyd resins obtained by modifying such compounds; acrylic polymers, epoxy resins, and silicone resins modified with drying oils; and liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and polymers of C5 to C8 dienes obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene. These substances may be used alone or in combination of two or more.

[0111] The amount of the oxygen-curable substance used is preferably in the range of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer according to this embodiment. As described in JP-A-3-160053, the oxygen-curable substance is preferably used in combination with a photo-curable substance.

[0112] (Epoxy Resin) The curable composition according to the present embodiment can be used in combination with an epoxy resin. A composition containing an epoxy resin is particularly suitable as an adhesive, particularly as an adhesive for exterior wall tiles. Examples of the epoxy resin include bisphenol A epoxy resins and novolac epoxy resins.

[0113] The ratio by weight of the epoxy resin to the polymer according to this embodiment is preferably in the range of polymer according to this embodiment / epoxy resin = 100 / 1 to 1 / 100. If the ratio of polymer according to this embodiment / epoxy resin is less than 1 / 100, it becomes difficult to obtain the effect of improving the impact strength and toughness of the cured epoxy resin product, and if the ratio of polymer according to this embodiment / epoxy resin exceeds 100 / 1, the strength of the cured polymer product becomes insufficient.

[0114] When an epoxy resin is added, a curing agent for curing the epoxy resin can be used in combination with the curable composition according to this embodiment. There are no particular limitations on the epoxy resin curing agent that can be used, and any commonly used epoxy resin curing agent can be used.

[0115] When a curing agent for an epoxy resin is used, the amount used is preferably in the range of 0.1 to 300 parts by weight per 100 parts by weight of the epoxy resin.

[0116] <<Preparation of Curable Composition>> The curable composition according to this embodiment can be prepared as a one-component composition in which all ingredients are mixed in advance and stored in a sealed container, and then cured by moisture in the air after application. Alternatively, it can be prepared as a two-component composition in which ingredients such as a curing catalyst, filler, plasticizer, and water are mixed separately as a curing agent, and the ingredients are mixed with the organic polymer composition before use. However, since the curable composition according to the present disclosure has excellent storage stability, it can be suitably used as a one-component curable composition.

[0117] When the curable composition is a one-component type, all of the components are blended in advance, and therefore it is preferable to dehydrate and dry the components containing water before use, or to dehydrate them under reduced pressure during blending and kneading. In addition to the dehydration and drying method, the storage stability can be further improved by adding an alkoxysilane compound such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, or γ-glycidoxypropyltrimethoxysilane.

[0118] (Applications) The curable composition according to the present disclosure can be used as a construction sealant, industrial adhesive, waterproof coating, pressure-sensitive adhesive raw material, etc. It can also be used as a sealant for buildings, ships, automobiles, roads, etc. Furthermore, since it can adhere to a wide range of substrates, such as glass, porcelain, wood, metal, and resin moldings, either alone or with the aid of a primer, it can also be used as various types of sealing and adhesive compositions. In addition to ordinary adhesives, it can also be used as a contact adhesive. It is also useful as a food packaging material, cast rubber material, molding material, and paint.

[0119] The following items are preferred embodiments of the present disclosure, but the present invention is not limited to the following items. [Item 1] A curable composition containing an organic polymer (A) having a reactive silicon group and a curing catalyst (B), wherein the reactive silicon group is represented by the general formula (1): -SiR １ ３－ａ X ａ (1) (wherein, R １ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ０ ３ It represents a triorganosiloxy group represented by SiO—. ０ are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a represents 1, 2, or 3. R １or when a plurality of X's are present, they may be the same or different.), wherein the curing catalyst (B) comprises a metal carboxylate compound (b1) and a cyclic secondary amine compound (b2), wherein the metal carboxylate compound (b1) comprises one or more metals selected from the group consisting of tin, titanium, bismuth, zirconium, iron, aluminum, and zinc, and the cyclic secondary amine compound (b2) has one or more skeletons selected from the group consisting of a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, and an azepane skeleton. [Item 2] The curable composition according to Item 1, wherein the curing catalyst (B) further comprises a plasticizer. [Item 3] The curable composition according to Item 1 or 2, wherein the metal carboxylate compound (b1) comprises tin and / or titanium. [Item 4] The curable composition according to any one of Items 1 to 3, wherein the weight ratio of the cyclic secondary amine compound (b2) to the metal carboxylate compound (b1) is 0.1 to 0.8. [Item 5] The curable composition according to any one of Items 1 to 4, wherein the curing catalyst (B) comprises a complex of the carboxylic acid metal compound (b1) and the cyclic secondary amine compound (b2). [Item 6] The curable composition according to any one of Items 1 to 5, wherein the cyclic secondary amine compound (b2) has an ester group or a hydroxyl group. [Item 7] A method for producing a curable composition containing an organic polymer (A) having a reactive silicon group and a curing catalyst (B), the method comprising the steps of: mixing the carboxylic acid metal compound (b1) with the cyclic secondary amine compound (b2) to obtain the curing catalyst (B); and mixing the curing catalyst (B) with the organic polymer (A) having a reactive silicon group represented by the general formula (1). [Item 8] The production method according to Item 7, wherein a plasticizer is further mixed in the step of obtaining the curing catalyst (B). [Item 9] A cured product obtained by curing the curable composition according to any one of Items 1 to 6.

[0120] The present invention will be described in more detail below with reference to specific examples, but the present invention is not limited to these examples. The number average molecular weight in the examples is a GPC molecular weight measured under the following conditions: Solution delivery system: HLC-8120GPC manufactured by Tosoh Corporation Column: TSKgel Super H series manufactured by Tosoh Corporation Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40°C

[0121] The average number of silyl groups per terminal or per molecule of the polymers shown in the examples was determined by H-NMR (using an AVANCE III HD-500 manufactured by Bruker) using CDCl ３ The values ​​were calculated based on measurements using a fluorine-containing solvent.

[0122] Synthesis of Organic Polymer (A) (Synthesis Example 1 (A-1)) Using a polyoxypropylene diol having a molecular weight of approximately 2,000 as an initiator, propylene oxide was polymerized in the presence of a zinc hexacyanocobaltate glyme complex catalyst to obtain polypropylene oxide having a number average molecular weight of approximately 28,500. Subsequently, a methanol solution of 1.0 equivalent of NaOMe relative to the hydroxyl groups of this hydroxyl-terminated polypropylene oxide was added, and the methanol was distilled off at 140°C. Next, 1.0 equivalent of allyl glycidyl ether was added and the reaction was carried out for 2 hours. Further, allyl chloride was added to convert the terminal hydroxyl groups to allyl groups. As a result, an allyl polymer having a number average molecular weight of approximately 28,500 and having multiple terminal allyl groups was obtained. 100 parts by weight of the resulting unpurified allyl-terminated polypropylene oxide was mixed and stirred with 300 parts by weight of n-hexane and 300 parts by weight of water, and the water was then removed by centrifugation. The resulting hexane solution was further mixed and stirred with 300 parts by weight of water, and the water was again removed by centrifugation, after which the hexane was removed by devolatilization under reduced pressure. The resulting allyl polymer was reacted with 0.8 molar equivalents of methyldimethoxysilane relative to the allyl groups of the allyl-terminated polypropylene oxide at 90°C for 5 hours using 150 ppm of an isopropanol solution of a platinum vinylsiloxane complex containing 3 wt% platinum as a catalyst, to yield methyldimethoxysilyl-terminated polypropylene oxide (A-1). The number of methyldimethoxysilyl groups per polymer chain end was approximately 1.5.

[0123] Synthesis Example 2 (A-2) Using a mixture of polyoxypropylene glycol having a number average molecular weight of 14,600 and n-butanol in a weight ratio of 10:1 as an initiator, propylene oxide was polymerized in the presence of a zinc hexacyanocobaltate glyme complex catalyst to obtain a mixture of polypropylene oxide having a number average molecular weight of 7,700 (polyoxypropylene glycol monobutyl ether having a number average molecular weight of 6,500 and polyoxypropylene glycol having a number average molecular weight of 18,000 (weight ratio of 9:1)). Subsequently, a methanol solution of NaOMe in an amount 1.2 times the equivalent of the hydroxyl groups of this hydroxyl-containing polypropylene oxide was added, and the methanol was distilled off. Allyl chloride was then added to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by devolatilization under reduced pressure to obtain unpurified polypropylene oxide having allyl groups. 100 parts by weight of the resulting unpurified allyl group-containing polypropylene oxide was mixed and stirred with 300 parts by weight of n-hexane and 300 parts by weight of water, and the mixture was then centrifuged to remove the water. An additional 300 parts by weight of water was mixed with the resulting hexane solution and stirred, and the water was again removed by centrifugation. The hexane was then removed from the resulting hexane solution by devolatilization under reduced pressure. As a result, a polyoxypropylene polymer mixture was obtained, the main component of which was a component having an allyl group introduced only at one end, and the polystyrene-equivalent number average molecular weight measured by GPC was approximately 7,700. 100 parts by weight of the resulting allyl group-containing polyoxypropylene polymer was reacted with 1.9 parts by weight of dimethoxymethylsilane at 90°C for 2 hours using 36 ppm of an isopropanol solution of a platinum vinylsiloxane complex containing 3 wt% platinum as a catalyst, to obtain a polyoxypropylene polymer (A-2) having an average of 0.9 dimethoxymethylsilyl groups per molecule. The polyoxypropylene polymer (A-2) thus obtained had a number average molecular weight of 7,700 as calculated on polystyrene standards by GPC.

[0124] Synthesis Example 3 (A-3) Using a polyoxypropylene diol having a molecular weight of approximately 2,000 as an initiator, propylene oxide was polymerized in the presence of a zinc hexacyanocobaltate glyme complex catalyst to obtain hydroxyl-terminated polypropylene oxide having a number average molecular weight of approximately 16,000. Subsequently, a methanol solution of NaOMe in an amount 1.2 times the equivalent of the hydroxyl groups of this hydroxyl-terminated polypropylene oxide was added, and the methanol was distilled off. Allyl chloride was then added to convert the terminal hydroxyl groups to allyl groups. As a result, an allyl polymer having a number average molecular weight of approximately 16,000 and terminated with allyl groups was obtained. The allyl polymer was purified using the same procedure as in Synthesis Example 1. 100 parts by weight of the obtained allyl polymer was reacted with 0.7 molar equivalents of methyldimethoxysilane relative to the allyl groups of the allyl-terminated polypropylene oxide at 90°C for 2 hours using 150 ppm of an isopropanol solution of platinum divinyldisiloxane containing 3 wt% platinum as a catalyst to obtain methyldimethoxysilyl-terminated polypropylene oxide (A-3). The number of methyldimethoxysilyl groups per polymer chain end was approximately 0.6.

[0125] Synthesis Example 4 (A-4) Using a polyoxypropylene diol having a molecular weight of approximately 2,000 as an initiator, propylene oxide was polymerized in the presence of a zinc hexacyanocobaltate glyme complex catalyst to obtain hydroxyl-terminated polypropylene oxide having a number average molecular weight of 28,500. Subsequently, a methanol solution of NaOMe in an amount 1.2 times the equivalent of the hydroxyl groups of this hydroxyl-terminated polypropylene oxide was added, and the methanol was distilled off. Allyl chloride was then added to convert the terminal hydroxyl groups to allyl groups. As a result, an allyl polymer having a number average molecular weight of approximately 28,500 and terminated with allyl groups was obtained. The allyl polymer was purified using the same procedure as in Synthesis Example 1. 100 parts by weight of the obtained allyl-terminated polypropylene oxide was reacted with 0.7 molar equivalents of methyldimethoxysilane relative to the allyl groups of the allyl-terminated polypropylene oxide at 90°C for 2 hours using 150 ppm of an isopropanol solution of platinum divinyldisiloxane containing 3 wt% platinum as a catalyst to obtain methyldimethoxysilyl-terminated polypropylene oxide (A-4). The number of methyldimethoxysilyl groups per polymer chain end was approximately 0.7.

[0126] Synthesis Example 5 (E-1) 52.1 parts by weight of isobutyl alcohol was placed in a four-neck flask equipped with a stirrer and heated to 90°C under a nitrogen atmosphere. A mixed solution obtained by dissolving 14.5 parts by weight of methyl methacrylate, 68.2 parts by weight of butyl acrylate, 14.9 parts by weight of stearyl methacrylate, 2.4 parts by weight of 3-(dimethoxymethylsilyl)propyl methacrylate, and 0.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 12.4 parts by weight of isobutyl alcohol was added dropwise thereto over 7 hours. Polymerization was further carried out at 90°C for 2 hours to obtain an isobutyl alcohol solution (solids content 60% by weight) of poly(meth)acrylic acid ester (E-1) having an average of 1.8 methyldimethoxysilyl groups per molecule, a number average molecular weight of 17,000, and a weight average molecular weight of 48,000.

[0127] Synthesis Example 6 (A-5) 70 parts by weight of the polyoxypropylene (A-4) obtained in Synthesis Example 4 and 50 parts by weight of the isobutyl alcohol solution of the poly(meth)acrylic acid ester (E-1) obtained in Synthesis Example 5 were mixed, and the isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture (A-5) in which the weight ratio of polyoxypropylene (A-4) / poly(meth)acrylic acid ester (E-1) was 70 / 30.

[0128] Synthesis Example 7 (A-6) Using polyoxypropylene glycol having a molecular weight of approximately 2,500 as an initiator, propylene oxide was polymerized in the presence of a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene having a number average molecular weight of 25,000. Subsequently, a methanol solution of NaOMe in an amount 1.2 times the equivalent of the hydroxyl groups of this hydroxyl-terminated polyoxypropylene was added. After distilling off the methanol by vacuum devolatilization, allyl chloride was added to convert the terminal hydroxyl groups to allyl groups, and unreacted allyl chloride was removed by vacuum devolatilization. The obtained unpurified polyoxypropylene was mixed and stirred with n-hexane and water, and the water was removed by centrifugation. The hexane was then devolatilized under reduced pressure from the resulting hexane solution to remove metal salts from the polymer. In this manner, polyoxypropylene having allyl groups at its termini was obtained. To this polymer was added 36 ppm of a platinum divinyldisiloxane complex solution (a 2-propanol solution containing 3% by weight of platinum), and 0.9 parts by weight of dimethoxymethylsilane was slowly added dropwise while stirring. The mixture was reacted at 90°C for 2 hours, and then unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (A-6) having terminal dimethoxymethylsilyl groups and a number-average molecular weight of approximately 25,500. The number of dimethoxymethylsilyl groups per polymer chain end was approximately 0.7.

[0129] Synthesis Example 8 (A-7) 70 parts by weight of the polyoxypropylene (A-6) obtained in Synthesis Example 7 and 50 parts by weight of the isobutyl alcohol solution of the poly(meth)acrylic acid ester (E-1) obtained in Synthesis Example 5 were mixed, and the isobutyl alcohol was distilled off under reduced pressure to obtain a polymer mixture (A-7) in which the weight ratio of polyoxypropylene (A-6) / poly(meth)acrylic acid ester (E-1) was 70 / 30.

[0130] <Preparation of Conjugates> The compounds described below were used in the preparation of Conjugates 1 to 14. Carboxylic acid metal compounds (b1) U-50: tin(II) bis(octoate) (manufactured by Nitto Chemical Industry Co., Ltd.) U-28: tin(II) bis(neodecanoate) (manufactured by Nitto Chemical Industry Co., Ltd.) Cyclic secondary amines (b2) Ethyl 4-piperidinecarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 4-methylpiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) Hexamethyleneimine (manufactured by Tokyo Chemical Industry Co., Ltd.) 4-hydroxypiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) 3-hydroxypiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) 3-piperidinemethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) N-methylpiperazine (manufactured by Tokyo Chemical Industry Co., Ltd.) 3,5-dimethylpiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) Methyl 4-piperidinecarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.) Other amines N,N-diethyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) Laurylamine (Tokyo Chemical Industry Co., Ltd.)

[0131] Production Example 1 (Composite 1) 30 g of U-50 was added to a 200 ml recovery flask. While stirring the contents of the flask, 10 g of ethyl 4-piperidinecarboxylate was slowly added dropwise to the flask. After the heat subsided, 60 g of plasticizer DINP (diisononyl phthalate, manufactured by J-Plus Corporation) was added, and the mixture was stirred at room temperature for 2 hours to obtain 100 g of liquid Composite 1.

[0132] <Production Examples 2 to 14 (Composites 2 to 14)> Liquid composites 2 to 14 were obtained in the same manner as in Production Example 1, except that the carboxylic acid metal compound (b1), the cyclic secondary amine (b2) or other amine, and the plasticizer DINP shown in Table 1 were used in the weight ratios shown in Table 1.

[0133]

[0134] Example 1 To 70 parts by weight of an organic polymer (A-1) having a reactive silicon group and 30 parts by weight of an organic polymer (A-2), colloidal calcium carbonate (Hakuenka CCR), heavy calcium carbonate (Whiten SB), plasticizer DINP (manufactured by J-Plus Corporation), pigment (Tipake R820), thixotropy imparting agent (Crayvallac SL), antioxidant (Irganox 1010), ultraviolet absorber (Tinuvin 326), and light stabilizer (Tinuvin 770) were added in the amounts (parts by weight) shown in Table 2, respectively, and the mixture was mixed using a spatula, and then dispersed by passing the mixture through a three-roll mill three times. After this, the mixture was dehydrated under reduced pressure using a planetary mixer and cooled to below 50°C. To the resulting mixture, 3 parts by weight of vinyltrimethoxysilane (manufactured by EVONIK, trade name: Dynasylan VTMO) as a dehydrating agent and 2 parts by weight of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (manufactured by EVONIK, trade name: Dynasylan DAMO) as an adhesion promoter were added and mixed. Then, 10 parts by weight of Composite 1 was added to the resulting mixture as a curing catalyst, and the mixture was kneaded in a state substantially free of moisture to obtain a composition. The resulting composition was then sealed in a moisture-proof container, a cartridge, to obtain a one-component curable composition.

[0135] (Evaluation) (Skinning Time (Curability)) Each curable composition was stored at 23°C for 7 days in an atmosphere of 50% relative humidity. Thereafter, the obtained curable composition was filled into a mold of approximately 5 mm thickness using a spatula, and the time when the surface was smoothed to a flat surface was recorded as the curing initiation time. The surface was touched with the spatula, and the time when the composition no longer adhered to the spatula was measured. The obtained results are shown in Table 2 as "initial skinning time" (curability). Furthermore, the curable compositions were stored at 23°C for 7 days, then further stored at 50°C for 28 days, and then stored at 23°C for 1 day. Thereafter, the skinning time was measured using the method described above. The obtained results are shown in Table 2 as "skinning time after storage" (curability).

[0136] (Dumbbell Tensile Properties) Each curable composition was filled into a 3 mm thick sheet mold under constant temperature and humidity conditions of 23°C and 50% relative humidity. After curing for 3 days at 23°C and 50% RH, the composition was aged in a 50°C dryer for 4 days to obtain a sheet-like cured product. The resulting cured product was punched into a No. 3 dumbbell shape in accordance with JIS K 6251, and a tensile test (tensile speed 200 mm / min) was performed using an autograph to measure the stress at 50% elongation, stress at 100% elongation, stress at break, and elongation at break. The results are shown in Table 2.

[0137] (Elastic recovery rate) The elastic recovery rate of the one-component curable composition obtained above was measured according to the elastic recovery test procedure specified in JIS A1439 (2016 edition) 5.2. That is, an H-type specimen with a joint width of 12 mm was prepared using a mortar board as the adherend and a commercially available primer (manufactured by Sunrise, product name: One-component modified silicone LM dedicated primer) as the primer, and cured at 23 ° C. for 28 days (50% RH). Then, the H-type specimen was held at 23 ° C. for 24 hours with the joint width of the specimen stretched to 100%. Then, the H-type specimen was opened at 23 ° C. and placed on a float glass plate. The elastic recovery rate was measured after leaving it for 1 hour. The results are shown in Table 2. A larger value of elastic recovery rate indicates better recovery.

[0138] (Examples 2 to 9, Comparative Examples 1 and 2) Curable compositions were prepared and evaluated in the same manner as in Example 1, except that the type of composite was changed as shown in Table 2. The results are shown in Table 2.

[0139]

[0140] (Results) The curable compositions of Examples 1 to 9, which used composites 1 to 9 containing a metal carboxylic acid compound and a cyclic secondary amine, exhibited good curability both before and after storage, and showed good storage stability with little decrease in curability due to storage. On the other hand, the curable composition of Comparative Example 1, which used composite 10 containing a metal carboxylic acid compound and an amine other than a cyclic secondary amine, exhibited poor curability and storage stability after storage, and the curable composition of Comparative Example 2, which used composite 11, exhibited poor curability both before and after storage. All of the cured products obtained by curing the curable compositions containing the organic polymer (A) and each composite exhibited good tensile properties and recovery.

[0141] (Example 10, Comparative Examples 3 and 4) Curable compositions were prepared and evaluated in the same manner as in Example 1, except that the type of composite was changed as shown in Table 3. The results are shown in Table 3.

[0142]

[0143] (Results) The curable composition of Example 10, which used Composite 12 containing a metal carboxylic acid compound and a cyclic secondary amine, exhibited good curability both before and after storage, and showed good storage stability with little decrease in curability due to storage. On the other hand, the curable composition of Comparative Example 3, which used Composite 13 containing a metal carboxylic acid compound and an amine other than a cyclic secondary amine, exhibited poor curability and storage stability after storage, and the curable composition of Comparative Example 4, which used Composite 14, exhibited poor curability both before and after storage.

[0144] Example 11 A curable composition was prepared and evaluated in the same manner as in Example 2, except that Viscolite EL20 was used instead of Hakuenka CCR as the colloidal calcium carbonate. The results are shown in Table 4.

[0145]

[0146] (Results) The curable composition of Example 11, which used Composite 2 containing a metal carboxylate compound and a cyclic secondary amine, exhibited good curability both before and after storage, and exhibited good storage stability with little deterioration in curability due to storage. Furthermore, the cured product obtained by curing the curable composition exhibited good tensile properties and recovery.

[0147] <Production Examples 15 to 17 (Composites 15 to 17)> Liquid composites 15 to 16 were obtained in the same manner as in Production Example 1, except that the carboxylic acid metal compound (b1), cyclic secondary amine (b2), and plasticizer DINP shown in Table 5 were used in the weight ratios shown in Table 5. Liquid composite 17 was also obtained in the same manner as in Production Example 1, except that the plasticizer DINP was not used.

[0148]

[0149] (Example 12) Curable compositions were prepared and evaluated in the same manner as in Example 11, except that the mixing ratio of the organic polymer and the blending amount of the adhesion promoter were changed as shown in Table 6. The results are shown in Table 6.

[0150] (Example 13) A curable composition was prepared and evaluated in the same manner as in Example 12, except that Dynasylan AMMO (3-aminopropyltrimethoxysilane, manufactured by EVONIK) was used instead of the adhesion promoter Dynasylan DAMO. The results are shown in Table 6.

[0151] Example 14 Curable compositions were prepared and evaluated in the same manner as in Example 13, except that the type of organic polymer was changed as shown in Table 6. The results are shown in Table 6.

[0152] (Examples 15 to 18) Curable compositions were prepared and evaluated in the same manner as in Example 11, except that the type of organic polymer or the type and amount of the composite were changed as shown in Table 6. The results are shown in Table 6.

[0153]

[0154] (Results) The curable compositions of Examples 12 to 18, which used a composite containing a metal carboxylate compound and a cyclic secondary amine, exhibited good curability both before and after storage, and showed good storage stability with little deterioration in curability due to storage. Furthermore, all of the cured products obtained by curing the curable compositions exhibited good tensile properties and recovery.

Claims

1. A curable composition comprising an organic polymer (A) having a reactive silicon group and a curing catalyst (B), wherein the reactive silicon group is represented by the general formula (1): -SiR １ ３－ａ X ａ (1) (wherein, R １ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ０ ３ Three R ０ are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a represents 1, 2, or 3. R １ or when a plurality of X's are present, they may be the same or different; the curing catalyst (B) comprises a metal carboxylic acid compound (b1) and a cyclic secondary amine compound (b2); the metal carboxylic acid compound (b1) comprises one or more metals selected from the group consisting of tin, titanium, bismuth, zirconium, iron, aluminum, and zinc; and the cyclic secondary amine compound (b2) has one or more skeletons selected from the group consisting of a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, and an azepane skeleton.

2. The curable composition of claim 1, wherein the curing catalyst (B) further comprises a plasticizer.

3. The curable composition according to claim 1 or 2, wherein the metal carboxylate compound (b1) contains tin and / or titanium.

4. The curable composition according to claim 1 or 2, wherein the weight ratio of the cyclic secondary amine compound (b2) to the carboxylic acid metal compound (b1) is 0.1 to 0.

8.

5. The curable composition according to claim 1 or 2, wherein the curing catalyst (B) comprises a complex of the carboxylic acid metal compound (b1) and the cyclic secondary amine compound (b2).

6. The curable composition according to claim 1 or 2, wherein the cyclic secondary amine compound (b2) has an ester group or a hydroxyl group.

7. A method for producing a curable composition containing an organic polymer (A) having a reactive silicon group and a curing catalyst (B), comprising the steps of: mixing a metal carboxylate compound (b1) containing one or more metals selected from the group consisting of tin, titanium, bismuth, zirconium, iron, aluminum, and zinc with a cyclic secondary amine compound (b2) having one or more skeletons selected from the group consisting of a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, and an azepane skeleton to obtain the curing catalyst (B); and mixing the curing catalyst (B) with a cyclic secondary amine compound (b2) represented by the general formula (1): -SiR １ ３－ａ X ａ (1) (wherein, R １ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ０ ３ Three R ０ are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a represents 1, 2, or 3. R １ or when a plurality of X's are present, they may be the same or different; and a reactive silicon group-containing organic polymer (A) represented by the following formula (I):

8. The manufacturing method according to claim 7, wherein a plasticizer is further mixed in the step of obtaining the curing catalyst (B).

9. A cured product obtained by curing the curable composition according to claim 1 or 2.

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