Hardening components

Abstract

To provide a curable composition containing a reactive silicon group-containing organic polymer that exhibits favorable fast curability in spite of containing a non-organic tin-based curing catalyst.SOLUTION: In a curable composition containing an organic polymer having a reactive silicon group, a curing catalyst is used that contains a carboxylic acid or a metal salt thereof (b1), an amine compound (b2), a specific metal compound (b3), and a carboxylic acid ester compound (b4). Preferably, the carboxylic acid ester compound (b4) is a compound that can form an intramolecular hydrogen bond between the hydroxyl group of the hydroxyl group-containing carboxylic acid ester and the carbonyl group in the ester bond.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] An organic polymer having at least one reactive silicon group in the molecule can crosslink by forming a siloxane bond accompanied by a hydrolysis reaction of a silyl group due to moisture or the like even at room temperature. It is known that an organic polymer having a reactive silicon group has a property of giving a rubbery cured product by such a crosslinking reaction.

[0003] As these organic polymers having a reactive silicon group, organic polymers having a main chain structure of polyoxyalkylene, polyacrylate ester, or polyisobutylene have already been industrially produced and are widely used in applications such as sealing materials, adhesives, paints, waterproof materials, etc. (Patent Document 1), (Patent Document 2), (Patent Document 3(MA)), (Patent Document 4(XMAP)).

[0004] When an organic polymer having a reactive silicon group is used as a curable composition such as a sealing material, an adhesive, a paint, or a waterproof material, various properties such as curability, adhesiveness, workability, mechanical properties of the cured product, and waterproofness are required for the curable composition.

[0005] A curable composition containing an organic polymer having a reactive silicon group is usually cured using a silanol condensation catalyst such as an organic tin compound having a carbon-tin bond, represented by dibutyltin bis(acetylacetonate). A silanol condensation catalyst is also referred to as a curing catalyst. In recent years, the toxicity of organotin compounds has been pointed out, and attention is required for their use from the viewpoint of environmental safety.

[0006] For this reason, the use of tin carboxylates and other metal carboxylate salts, organic salts using carboxylic acids and amine compounds in combination, and metal complexes such as titanium compounds has been proposed as curing catalysts other than organotin compounds (Patent Document 3), (Patent Document 4), (Patent Document 5), (Patent Document 6). [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 52-73998 [Patent Document 2] Japanese Patent Application Publication No. 63-6041 [Patent Document 3] Japanese Patent Application Publication No. 55-9669 [Patent Document 4] Japanese Patent Publication No. 2003-206410 [Patent Document 5] Japanese Patent Application Publication No. 5-117519 [Patent Document 6] International Publication No. 2005 / 108499 [Overview of the project] [Problems that the invention aims to solve]

[0008] However, the conventional technologies described above had room for improvement in terms of the rapid curing properties of the curable composition.

[0009] Therefore, the present invention aims to provide a curable composition containing a reactive silicon group-containing organic polymer that exhibits good rapid curing properties even when containing a non-organotin curing catalyst. [Means for solving the problem]

[0010] As a result of diligent research to solve the aforementioned problems, the inventors of the present invention discovered that a rapidly curing curable composition can be obtained by using an organic polymer having a reactive silicon group and a specific curing catalyst, and thus completed the present invention.

[0011] That is, the present invention is a curable composition containing an organic polymer (A) and a curing catalyst (B), where the organic polymer (A) has the following formula (1): -SiR , , , f , 3-a X a (1) (In formula (1), R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a triorganosiloxy group represented by R 0 3SiO-, and the three Rs 0 are hydrocarbon groups having 1 to 20 carbon atoms, and they may be the same or different. X represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. R 1 , and for each of X, when there are a plurality of them, they may be the same or different.) and has a reactive silicon group represented by the curing catalyst (B) contains a carboxylic acid or its metal salt (b1), an amine compound (b2), a metal compound (b3), and a carboxylic acid ester compound having a hydroxyl group (b4). Two or more selected from the carboxylic acid or its metal salt (b1), the amine compound (b2), the metal compound (b3), and the carboxylic acid ester compound having a hydroxyl group (b4) may react with each other. The amine compound (b2) is a compound that does not fall under an amidine compound and a guanidine compound. The metal compound (b3) has the following formula (2): M(O) d (OR 2 ) e Y f (2) (In formula (2), M is Ti, Al, Zr, Hf, or V. d is 0 or 1, and e and f are each independently an integer of 0 or more, provided that (2d + e + f) is the valence of M. When M is Ti, Al, Zr, or Hf, d is 0. If M is V, then d is 1, R 2 This is a hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. Y is a chelate-coordinating compound. This relates to a curable composition, which is a compound represented by [the formula shown]. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a curable composition containing a reactive silicon group-containing organic polymer that exhibits good rapid curing properties even when it contains a non-organotin curing catalyst. [Modes for carrying out the invention]

[0013] The present invention will be described in detail below.

[0014] ≪Curable composition≫ The curable composition comprises an organic polymer (A) and a curing catalyst (B). The organic polymer (A) is given by the following formula (1): -SiR 1 3-a X a (1) (In formula (1), R 1 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R 0 It shows a triorganosiloxy group represented as 3SiO-, and 3 R 0 These are hydrocarbon groups having 1 to 20 carbon atoms, and they may be the same or different. X represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. R 1 (For each of X, if there are multiple instances of them, they may be the same or different.) It has a reactive silicon group represented by . The curing catalyst (B) comprises a carboxylic acid or its metal salt (b1), an amine compound (b2), a metal compound (b3), and a carboxylic acid ester compound having a hydroxyl group (b4).

[0015] Amine compound (b2) is a compound that does not fall under the categories of amidine compounds or guanidine compounds. The metal compound (b3) is given by the following formula (2): M(O) d (OR 2 ) e Y f (2) (In equation (2), M is Ti, Al, Zr, Hf, or V, d is 0 or 1, e and f are each independent non-negative integers, where (2d+e+f) is the valence of M. If M is Ti, Al, Zr, or Hf, then d is 0. If M is V, then d is 1, R 2 This is a hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. Y is a chelate-coordinating compound. It is a compound represented by [formula]. The above curing composition exhibits excellent rapid curing properties.

[0016] The following describes the essential and optional components that the curable composition may contain.

[0017] <Organic polymer (A)> The organic polymer has reactive silicon groups of a predetermined structure, as described later. Organic polymer (A) has a polymer skeleton and polymer chain ends bonded to the polymer skeleton. In the specification and claims of this application, the polymer skeleton is also referred to as the "main chain structure". The polymer skeleton is a structure in which multiple structural units derived from monomers are continuously bonded together. There may be one type of monomer or multiple types.

[0018] Polymer chain ends are the parts located at the ends of an organic polymer (A). The number of polymer chain ends in an organic polymer (A) is 2 if the main chain structure is linear, and 3 or more if the polymer backbone is branched. If organic polymer (A) is a mixture of a polymer with a linear main chain structure and a polymer with a branched main chain structure, the number of polymer chain ends is, on average, between 2 and 3.

[0019] Reactive silicon groups can be present in the polymer backbone and at the polymer chain ends. Furthermore, two or more reactive silicon groups may be present at the polymer chain ends. When using a curable composition in adhesives, sealants, elastic coatings, or other adhesives, it is preferable that the reactive silicon groups in the organic polymer (A) are present at the polymer chain ends.

[0020] The organic polymer (A) is not particularly limited as long as it is an organic polymer having a reactive silicon group represented by the following formula (1).

[0021] -SiR 1 3-a X a (1) (In formula (1), R 1 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R 0 It is a triorganosiloxy group represented by 3SiO-. 0 It is a hydrocarbon group with 1 to 20 carbon atoms. 3 R 0 They may be the same or different. X is a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. R 1 , or when there are multiple X, multiple R 1 (Or, multiple X's may be the same or different.)

[0022] R in equation (1) 1Specific examples include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, 2-ethylhexyl, and n-dodecyl; unsaturated hydrocarbon groups such as vinyl, isopropenyl, and allyl; alkoxymethyl groups such as methoxymethyl; halogenated methyl groups such as chloromethyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, toluyl, and 1-naphthyl; and aralkyl groups such as benzyl. Among these groups, alkyl groups and aryl groups are preferred, methyl, ethyl, and phenyl groups are more preferred, methyl and ethyl groups are even more preferred, and methyl groups are particularly preferred. 1 If multiple R 1 These may be the same group, or a combination of two or more different groups.

[0023] In formula (1), X is a hydroxyl group or a hydrolyzable group. The hydrolyzable group is not particularly limited and may be any known hydrolyzable group. Specific examples of hydrolyzable groups include hydrogen atoms, halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups. Among these, alkoxy groups, acyloxy groups, ketoximate groups, and alkenyloxy groups are preferred, and alkoxy groups such as methoxy groups and ethoxy groups are more preferred because they are mildly hydrolyzable and easy to handle.

[0024] The reactive silicon group represented by formula (1) is not particularly limited. Specific examples of the reactive silicon group represented by formula (1) include dimethoxymethylsilyl group, diethoxymethylsilyl group, trimethoxysilyl group, triethoxysilyl group, dimethoxyphenylsilyl group, methoxymethyldimethoxysilyl group, methoxymethyldiethoxysilyl group, triisopropenyloxysilyl group, and triacetoxysilyl group. Among these, the dimethoxymethylsilyl group and the trimethoxysilyl group are preferred because they facilitate the synthesis of organic polymer (A). The trimethoxysilyl group and the methoxymethyldimethoxysilyl group are preferred because they exhibit excellent curability.

[0025] (Regarding the main chain structure of organic polymer (A)) The main chain structure of organic polymer (A) is not particularly limited and may be various known main chain structures. Specific examples of main chain structures include polyoxyalkylene polymers such as polyoxyethylene polymers, polyoxypropylene polymers, polyoxybutylene polymers, polyoxytetramethylene polymers, polyoxyethylene-polyoxypropylene copolymers, and polyoxypropylene-polyoxybutylene copolymers; hydrocarbon polymers such as ethylene-propylene copolymers, polyisobutylene, isobutylene-isoprene copolymers, polybutadiene, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; polycondensates of dibasic acids such as adipic acid and glycols, and Examples include polyester polymers such as ring-opening polymers of lactones; (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 two or more monomers selected from (meth)acrylic acid ester monomers, vinyl acetate, acrylonitrile, and styrene; polysulfide polymers; and diallyl phthalate polymers. Note that (meth)acrylic acid ester refers to both acrylic acid esters and methacrylic acid esters.

[0026] Due to their high moisture permeability, these one-component compositions exhibit excellent deep curing properties and superior adhesion. Therefore, polyoxyalkylene polymers and (meth)acrylic acid ester polymers are particularly preferred as the main chain structure. Polyoxyalkylene polymers are more preferred as the main chain structure, and polyoxypropylene is even more preferred.

[0027] (Meth)acrylic acid ester polymers are also useful as a main chain structure because by varying the composition of the monomers that make up the polymer, it is possible to improve adhesion and reduce the heat resistance, weather resistance, and water absorption of the cured product. The main chain structure of organic polymer (A) may be one of the above or a combination of several. For example, organic polymer (A) whose main chain structure is a polyoxypropylene polymer and organic polymer (A) whose main chain structure is a (meth)acrylic acid ester polymer are uniformly compatible with each other, and the resulting cured product has a good balance of elasticity, mechanical strength, adhesive strength, etc. In this respect, it is also preferable to use a combination of organic polymer (A) whose main chain structure is a polyoxypropylene polymer and organic polymer (A) whose main chain structure is a (meth)acrylic acid ester polymer.

[0028] Polyoxyalkylene polymers are -R 3 It is a polymer having repeating units represented by -O-. 3 R is a linear or branched alkylene group having 1 to 14 carbon atoms. 3 As such, linear or branched alkylene groups having 2 to 4 carbon atoms are more preferred. -R 3Specific examples of repeating units represented by -O- include -CH2O-, -CH2CH2O-, -CH2CH(CH3)O-, -CH2CH(C2H5)O-, -CH2C(CH3)(CH3)O-, and -CH2CH2CH2CH2O-. The main chain structure of a polyoxyalkylene polymer may consist of only one type of repeating unit or of two or more types of repeating units. In particular, when the curable composition is used as a sealant, adhesive, etc., a polyoxypropylene polymer having 50% or more, preferably 80% or more by weight of oxypropylene repeating units in the polymer main chain structure is preferred as the polyoxyalkylene polymer. This is because such a polyoxyalkylene polymer is amorphous and has relatively low viscosity.

[0029] The main chain structure of the polyoxyalkylene polymer may be linear or branched.

[0030] As for polyoxyalkylene polymers, polymers obtained by a ring-opening polymerization reaction of cyclic ether compounds using a polymerization catalyst in the presence of an initiator are preferred.

[0031] Examples of cyclic ether compounds include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used individually or in combination of two or more. Among these cyclic ether compounds, propylene oxide is particularly preferred because it yields amorphous and relatively low-viscosity polyether polymers.

[0032] Specific examples of initiators 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 polyoxyalkylene polymers such as polyoxypropylenediol, polyoxypropylenetriol, polyoxyethylenediol, and polyoxyethylenetriol.

[0033] The method for synthesizing polyoxyalkylene polymers is not particularly limited. Examples of synthesis methods for polyoxyalkylene polymers include polymerization using alkaline catalysts such as KOH, polymerization using transition metal compound-porphyrin complex catalysts such as the complex obtained by reacting an organoaluminum compound with porphyrin as shown in Japanese Patent Publication No. 61-215623, polymerization using complex metal cyanide complex catalysts as shown in Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, U.S. Patent No. 3278457, U.S. Patent No. 3278458, U.S. Patent No. 3278459, U.S. Patent No. 3427256, U.S. Patent No. 3427334, and U.S. Patent No. 3427335, etc., polymerization using catalysts consisting of polyphosphazene salts as exemplified in Japanese Patent Publication No. 10-273512, and polymerization using catalysts consisting of phosphazene compounds as exemplified in Japanese Patent Publication No. 11-060722. Polymerization using complex metal cyanide catalysts is more preferable due to reasons such as lower manufacturing costs and the ability to obtain polymers with a narrow molecular weight distribution.

[0034] The main chain structure of the organic polymer (A) may be a polyoxyalkylene polymer containing urethane bonds and other bonds other than ether bonds, such as urea bonds, to the extent that the desired effect is not significantly impaired. Specific examples of polymers having such a main chain structure include polyurethane prepolymers and polyurea prepolymers.

[0035] Polyurethane prepolymers can be obtained by known methods, such as reacting a polyol compound with a polyisocyanate compound. Polyurea prepolymers can be obtained by known methods, such as reacting a polyamine compound with a polyisocyanate compound. The main chain structure may be a prepolymer having a combination of urethane and urea bonds, obtained by reacting a polyol compound and a polyamine compound with a polyisocyanate compound.

[0036] Specific examples of polyol compounds include polyether polyols, polyester polyols, polycarbonate polyols, and polyether polyester polyols.

[0037] Specific examples of polyisocyanate compounds include diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, methylene-bis(cyclohexyl isocyanate), isophorone diisocyanate, and hexamethylene diisocyanate.

[0038] The ends of the polyurethane prepolymer may be either hydroxyl groups or isocyanate groups. The ends of the polyurea prepolymer may be either amino groups or isocyanate groups.

[0039] In curable compositions containing an organic polymer (A) having one or more bonds selected from urethane bonds, urea bonds, and ester bonds in its main chain structure, the strength of the cured product may decrease due to the cleavage of urethane bonds, urea bonds, or ester bonds in the main chain structure caused by heat or other factors.

[0040] When polymers containing amide bonds in their main chain structure are used as organic polymers, the curability of the curable composition may be improved. For example, amide bonds can be represented as -NR. 4 It is represented as -C(=O)-. 4This is an organic group that may have a hydrogen atom or a substituent. When the amount of amide bonds in the main chain structure is within an appropriate range, the viscosity of the polymer is low, and the decrease in strength of the cured product due to cleavage of amide bonds due to heat, etc., and the increase in viscosity of the curable composition due to storage are less likely to occur, resulting in good workability of the curable composition.

[0041] When the organic polymer (A) contains amide bonds in its main chain structure, the number of amide bonds is preferably 1 to 10, more preferably 1.5 to 5, and even more preferably 2 to 3, on average per molecule. When the number of amide bonds on average per molecule is within this range, the curability of the curable composition is good, the viscosity of the organic polymer (A) is low, and the organic polymer (A) and the curable composition are easy to handle.

[0042] Of the organic polymers (A) described above, polyoxyalkylene polymers that do not contain urethane bonds, urea bonds, ester bonds, or amide bonds in their main chain structure are most preferred, in terms of obtaining a curable composition with excellent storage stability and workability.

[0043] As the organic polymer (A), a polymer obtained by introducing reactive silicon groups into the polymer by any of the following methods (a) to (d) is preferred. (a) After converting the terminal hydroxyl groups of the hydroxyl-terminated organic polymer to carbon-carbon unsaturated groups, the carbon-carbon unsaturated groups are converted to HSiR 1 3-a X a A method of hydrosilylation using a hydrosilane represented by R. 1 X and a are the same as those in general formula (1), respectively. (b) OCN-W-SiR 1 3-a X a A method for reacting an isocyanate alkylsilane compound represented by . W is a divalent organic group. R 1 X and a are the same as those in general formula (1), respectively. (c) After converting the terminal hydroxyl groups of the hydroxyl-terminated organic polymer to carbon-carbon unsaturated groups, the carbon-carbon unsaturated groups and HS-W-SiR 1 3-a X a A method for carrying out an en-thiol reaction with a mercaptoalkylsilane compound represented by . W is a divalent organic group. R 1 X and a are the same as those in general formula (1), respectively. (d) After synthesizing an NCO group-terminated organic polymer by reacting a hydroxyl group-terminated organic polymer with a polyisocyanate compound, the terminal NCO group is HNR 5 -W-SiR 1 3-a X a , or HS-W-SiR 1 3-a X a A method of reacting with a silane compound represented by . W is a divalent organic group. R 5 R is a hydrogen atom or an alkyl group. 1 X and a are the same as those in general formula (1), respectively.

[0044] In the methods described in (a) and (c) above, examples of terminal carbon-carbon unsaturated groups include vinyl groups, allyl groups, methallyl groups, allenyl groups, and propargyl groups.

[0045] In any of the methods (b) to (d) above, the organic polymer (A) obtained using a silane compound in which W is methylene exhibits very high curability.

[0046] Method (a) is preferred because it is easy to obtain an organic polymer (A) with good storage stability. Methods (b), (c), and (d) are preferred because a high conversion rate can be obtained with a relatively short reaction time.

[0047] Methods for introducing reactive silicon groups by method (a) are proposed in the following publications: Japanese Patent Publication Nos. 45-36319, 46-12154, Japanese Patent Publication Nos. 50-156599, 54-6096, 55-13767, 55-13468, 57-164123, Japanese Patent Publication No. 3-2450, U.S. Patent No. 3632557, U.S. Patent No. 4345053, U.S. Patent No. 4366307, and U.S. Patent No. 4960844. Examples include the methods described, or the method proposed in Japanese Patent Publication Nos. 61-197631, 61-215622, 61-215623, and 61-218632, which introduce reactive silicon groups to a polyoxypropylene polymer with a high molecular weight and narrow molecular weight distribution, having a number average molecular weight of 6,000 or more and an Mw / Mn ratio of 1.6 or less, by hydrosilylation, etc., or the method proposed in Japanese Patent Publication No. 3-72527.

[0048] The number-average molecular weight of organic polymer (A) is not particularly limited. The number-average molecular weight of organic polymer (A), as polystyrene-equivalent molecular weight in GPC, is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000. When the number-average molecular weight is within the above range, the amount of hydrolyzable silyl groups introduced is appropriate, making it easy to obtain polymer (A) with a manageable viscosity and excellent workability while keeping manufacturing costs within a reasonable range.

[0049] The molecular weight of organic polymer (A) can also be expressed as the molecular weight of the end group, determined by directly measuring the end group concentration of the polymer precursor before the introduction of hydrolyzable silyl groups using 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 considering the structure of the polymer (degree of branching determined by the polymerization initiator used). Alternatively, the molecular weight of organic polymer (A) can be determined by creating a calibration curve between the number average molecular weight obtained by general GPC measurement of the polymer precursor and the above-mentioned end group-reduced molecular weight, and then converting the number average molecular weight obtained by GPC of organic polymer (A) to the end group-reduced molecular weight.

[0050] The molecular weight distribution (Mw / Mn) of the organic polymer (A) is not particularly limited. A narrow molecular weight distribution of the organic polymer (A) is preferred. Specifically, the molecular weight distribution is preferably 1.6 or less, more preferably 1.4 or less, even more preferably 1.3 or less, and particularly preferably 1.2 or less. The molecular weight distribution of the organic polymer (A) can be determined from the number-average molecular weight and weight-average molecular weight obtained by GPC measurement.

[0051] To obtain a good rubber-like cured product, it is preferable that the reactive silicon groups of the organic polymer (A) are present at the ends of the polymer chains. The number of reactive silicon groups is preferably 0.5 or more on average per polymer chain end, more preferably 0.6 or more, even more preferably 0.7 or more, and particularly preferably 0.8 or more. When the number of reactive silicon groups is 0.5 or more, the curability of the organic polymer (A) and the curable composition is good, and the cured product of the curable composition has good rubber elasticity.

[0052] The number of reactive silicon groups in one molecule is preferably 1 to 7 on average, more preferably 1 to 4, and particularly preferably 1 to 3.

[0053] Furthermore, as described in Publication No. WO2013 / 180203, organic polymers having two or more reactive silicon groups at the ends of the polymer chain can also be used as organic polymer (A). Such organic polymers (A) exhibit high curability, and the resulting cured product can be expected to have high strength and high resilience.

[0054] Specific examples of commercially available organic polymer (A) products include various reactive silicon group-containing polyoxypropylene products such as Kaneka MS Polymer (registered trademark) and Kaneka Cyryl (registered trademark), reactive silicon group-containing poly(meth)acrylic acid ester products such as Kaneka TA Polymer (registered trademark) and KANEKA XMAP (registered trademark), and reactive silicon group-containing polyisobutylene products such as EPION (registered trademark). All of these commercially available organic polymers (A) are products of Kaneka Corporation.

[0055] <Curing catalyst (B)> The curable composition contains a curing catalyst (B) that cures an organic polymer (A) by hydrolysis condensation. The curing catalyst (B) comprises a carboxylic acid or its metal salt (b1), an amine compound (b2), a metal compound (b3), and a carboxylic acid ester compound having a hydroxyl group (b4). Amine compound (b2) is a compound that does not fall under the categories of amidine compounds or guanidine compounds. The metal compound (b3) is given by the following formula (2): M(O) d (OR 2 ) e Y f (2) (In equation (2), M is Ti, Al, Zr, Hf, or V, d is 0 or 1, e and f are each independent non-negative integers, where (2d+e+f) is the valence of M. If M is Ti, Al, Zr, or Hf, then d is 0. If M is V, then d is 1, R 2 This is a hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. Y is a chelate-coordinating compound. It is a compound represented by [formula]. Two or more compounds selected from carboxylic acids or their metal salts (b1), amine compounds (b2), metal compounds (b3), and carboxylic acid ester compounds having a hydroxyl group (b4) may be reacted with each other.

[0056] Amine compounds having a carboxyl group can be used as a carboxylic acid or its metal salt (b1), or as an amine compound (b2). However, amine compounds having a carboxyl group are used in combination with a carboxylic acid or its metal salt (b1) that does not fall under the category of an amine compound, or with an amine compound without a carboxyl group (b2). In other words, the carboxylic acid or its metal salt (b1) and the amine compound (b2) cannot both be amine compounds having a carboxyl group.

[0057] Of the carboxylic acid or its metal salt (b1), the carboxylic acid is not particularly limited as long as it is an organic compound having a carboxyl group. The carboxylic acid may be a monocarboxylic acid compound having one carboxyl group, or a polycarboxylic acid compound having two or more carboxyl groups. Examples of carboxylic acids include aliphatic monocarboxylic acids, aliphatic dicarboxylic acids, aliphatic polycarboxylic acids with a valency of three or more, and aromatic carboxylic acids.

[0058] Specific examples of aliphatic monocarboxylic acids 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, tridecyl acid, myristic acid, pentadecyl acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, and laxeric acid; undecylenic acid, lindelic acid, tuzic acid, phyzeteric acid, myristoleic acid, 2-hexadecenoic acid, Monoenenusaturated fatty acids such as 6-hexadecenoic acid, 7-hexadecenoic acid, palmitoleic acid, petroseric acid, oleic acid, elaidic acid, asclepic acid, vaccenic acid, gadolic acid, gondouic acid, cetoleic acid, erucic acid, brassic acid, ceracoleic acid, xymenic acid, lumecitric acid, acrylic acid, methacrylic acid, angelic acid, crotonic acid, isocrotonic acid, and 10-undecenoic acid; linoleidic acid, linoleic acid, 10,12-octadecadienoic acid, hiragonic acid, α-eleostearic acid, β-eleostearic acid Polyene unsaturated fatty acids such as thearic acid, punicic acid, linolenic acid, 8,11,14-eicosatrienoic acid, 7,10,13-docosatrienoic acid, 4,8,11,14-hexadecatetraenoic acid, moloctic acid, stearidonic acid, arachidonic acid, 8,12,16,19-docosatetraenoic acid, 4,8,12,15,18-eicosapentaenoic acid, sardine acid, herring acid, and docosahexaenoic acid; 2-methylbutyric acid, isobutyric acid, 2-ethylbutyric acid, pivalic acid, 2,2-dimethylbutyric acid, 2-ethyl-2-methylbutyric acid, 2,2-methylbutyric acid Branched fatty acids such as ethyl butyric acid, 2-phenyl butyric acid, isovaleric acid, 2,2-dimethylvaleric acid, 2-ethyl-2-methylvaleric acid, 2,2-diethylvaleric acid, 2-ethylhexanoic acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, versatic acid, neodecanoic acid, and tubercurostearic acid; fatty acids with triple bonds such as propiolic acid, tali-phosphate, stearolic acid, krepenic acid, ximenic acid, and 7-hexadecinic acid;Alicyclic carboxylic acids such as naphthenic acid, malvalumic acid, sterkric acid, hydnocarpus acid, schormugric acid, goronic acid, 1-methylcyclopentanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 1-adamantanecarboxylic acid, bicyclo[2.2.2]octane-1-carboxylic acid, and bicyclo[2.2.1]heptane-1-carboxylic acid; acetoacetic acid, ethoxyacetic acid, glyoxylic acid, glycolic acid, gluconic acid, sabinic acid, 2-hydroxytetradecanoic acid, iprolic acid, 2-hydroxyhexadecanoic acid, jalapinolic acid, uniperinic acid, ambrette Examples include oxygen-containing fatty acids such as tall acid, allulite acid, 3-hydroxyisoacetic acid, 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, 2,2-dimethyl-3-hydroxypropionic acid, ricinoleic acid, camlorenic acid, lycanic acid, feronic acid, and cerebronic acid; halogen-substituted monocarboxylic acids such as chloroacetic acid and 2-chloroacrylic acid; and piperidine carboxylic acids such as piperidine-2-carboxylic acid, piperidine-3-carboxylic acid, and piperidine-4-carboxylic acid. Aliphatic monocarboxylic acids are not limited to the compounds listed above. Of the compounds listed above, piperidinecarboxylic acid or its metal salt may also be used as amine compound (b2).

[0059] Examples of aliphatic dicarboxylic acids include linear dicarboxylic acids such as adipic acid, azelaic acid, pimelic acid, suberic acid, sebacic acid, glutaric acid, oxalic acid, malonic acid, ethyl malonic acid, dimethyl malonic acid, ethyl methyl malonic acid, diethyl malonic acid, succinic acid, 2,2-dimethyl succinic acid, 2,2-diethyl succinic acid, and 2,2-dimethyl glutaric acid; saturated dicarboxylic acids such as 1,2,2-trimethyl-1,3-cyclopentanedicarboxylic acid and oxydiacetic acid; and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, acetylenedicarboxylic acid, and itaconic acid. Aliphatic dicarboxylic acids are not limited to the compounds listed above.

[0060] Examples of trivalent or higher aliphatic polycarboxylic acids include aconitic acid, citric acid, isocitric acid, 3-methylisocitric acid, and chain-like tricarboxylic acids such as 4,4-dimethylaconitic acid. However, trivalent or higher aliphatic polycarboxylic acids are not limited to the compounds listed above.

[0061] Examples of aromatic carboxylic acids include aromatic monocarboxylic acids such as benzoic acid, chlorobenzoic acid, 9-anthracenecarboxylic acid, atrolactinic acid, anisic acid, isopropylbenzoic acid, salicylic acid, and toluic acid; and aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, carboxyphenylacetic acid, and pyromellitic acid. Aromatic dicarboxylic acids are not limited to the compounds listed above.

[0062] Furthermore, carboxylic acid derivatives that produce carboxylic acids by hydrolysis of carboxylic acid anhydrides, esters, amides, nitriles, acyl chlorides, etc., can also be used as carboxylic acids.

[0063] In terms of rapid curing properties, it is preferable that the carboxylic acid or its metal salt (b1) is a carboxylic acid having a carboxyl group bonded to a tertiary carbon atom or a secondary carbon atom, or a metal salt of a carboxylic acid having a carboxyl group bonded to a tertiary carbon atom or a secondary carbon atom. As the carboxylic acid or its metal salt (b1), a carboxylic acid having a carboxyl group bonded to a tertiary carbon atom, and a metal salt of a carboxylic acid having a carboxyl group bonded to a tertiary carbon atom are more preferred. Suitable examples of carboxylic acids having a carboxyl group bonded to a tertiary or secondary carbon atom include 2-methylbutyric acid, isobutyric acid, 2-ethylbutyric acid, pivalic acid, 2,2-dimethylbutyric acid, 2-ethyl-2-methylbutyric acid, 2,2-diethylbutyric acid, 2,2-dimethylvaleric acid, 2-ethyl-2-methylvaleric acid, 2,2-diethylvaleric acid, 2-ethylhexanoic acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, and neodecanoic acid. Among these, pivalic acid, 2,2-dimethylbutyric acid, 2-ethyl-2-methylbutyric acid, 2,2-diethylbutyric acid, 2,2-dimethylvaleric acid, 2-ethyl-2-methylvaleric acid, 2,2-diethylvaleric acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, and neodecanoic acid are preferred, with neodecanoic acid being more preferred.

[0064] Specific examples of metal carboxylic acid salts include salts of alkali metals such as lithium, sodium, and potassium; and salts of alkaline earth metals such as calcium, strontium, barium, and magnesium. The metal salt of the carboxylic acid may also be a metal such as aluminum, titanium, zirconium, hafnium, and vanadium.

[0065] Among these, 2-ethylhexanoic acid, octyl acid, neodecanoic acid, oleic acid, and naphthenic acid are preferred due to their easy availability, low cost, and good compatibility with reactive silicon group-containing organic polymers (A). Neodecanoic acid is particularly preferred because it is easy to obtain high catalytic activity. The carboxylic acid or its metal salt (b1) may be a single component or a combination of multiple components.

[0066] In terms of rapid curing properties, the amount of carboxylic acid or its metal salt (b1) used is preferably 0.5 parts by weight or more and 10.0 parts by weight or less, more preferably 1.0 part by weight or more and 8.0 parts by weight or less, and even more preferably 2.0 parts by weight or more and 6.0 parts by weight or less, per 100 parts by weight of organic polymer (A).

[0067] Specific examples of amine compounds (b2) include aliphatic primary monoamines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, cyclohexylamine, monoethanolamine, 3-hydroxypropylamine, 3-methoxypropylamine, and 3-lauryloxypropylamine; dimethylamine, die Tylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, di(2-ethylhexyl)amine, didecylamine, dilaurylamine, dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine, pyrrolidine, piperidine, 2-methylpiperidine, 4-methylpiperidine, 3,5-dimethylpiperidine, 1,3-bis(4-piperidyl)propane, piperidine 2-carboxylic acid, piperidine 3-carboxylic acid Aliphatic secondary monoamines such as benzoic acid, piperidine 4-carboxylic acid, hexamethyleneimine, and diethanolamine; Aliphatic tertiary monoamines such as triamylamine, trihexylamine, trioctylamine, and triethanolamine; Aliphatic unsaturated amines such as triallylamine and oleylamine; Aromatic amines such as aniline, laurylaniline, stearylaniline, and triphenylamine; Ethylenediamine, propylenediamine, hexamethylenediamine, N-methyl-1,3-propanediamine, N,N Examples include aliphatic diamines such as dimethyl-1,3-propanediamine, 2-(2-aminoethylamino)ethanol, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine, and 3-morpholinopropylamine; polyhydric amines of trivalent or higher valencies such as diethylenetriamine, triethylenetetramine, and 2-(1-piperazinyl)ethylamine; and other amines such as benzylamine, xylylenediamine, and 2,4,6-tris(dimethylaminomethyl)phenol. Among the compounds listed above, piperidine carboxylic acids such as piperidine 2-carboxylic acid, piperidine 3-carboxylic acid, and piperidine 4-carboxylic acid can also be used as carboxylic acid (b1).

[0068] From the standpoint of availability, compatibility with organic polymer (A), and curability, among these, laurylamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine, hexamethyleneimine, and 4-methylpiperidine are preferred. The amine compound (b2) may be a single component or a combination of multiple components.

[0069] The amine compound (b2) may form a salt with the carboxylic acid, such as the aforementioned carboxylic acid or its metal salt (b1), in the curable composition.

[0070] In terms of rapid curing properties, the amount of amine compound (b2) used is preferably 0.1 parts by weight or more and 3.0 parts by weight or less, more preferably 0.3 parts by weight or more and 2.5 parts by weight or less, and even more preferably 0.5 parts by weight or more and 2.0 parts by weight or less, per 100 parts by weight of organic polymer (A).

[0071] The metal compound (b3) is given by the following formula (2): M(O) d (OR 2 ) e Y f (2) (In equation (2), M is Ti, Al, Zr, Hf, or V, d is 0 or 1, e and f are each independent non-negative integers, where (2d+e+f) is the valence of M. If M is Ti, Al, Zr, or Hf, then d is 0. If M is V, then d is 1, R 2 This is a hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. Y is a chelate-coordinating compound. It is a compound represented by [formula].

[0072] R 2 The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. 2 If the hydrocarbon group is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may have one or more unsaturated bonds. 2 If the hydrocarbon group is an aliphatic hydrocarbon group, the structure of the aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination of these structures.

[0073] As the chelate coordination compound for Y, a bidentate organic ligand is preferred. Examples of chelate coordination compounds include β-diketones and β-ketoesters. Specific examples of β-diketones include acetylacetone (ACAC), trifluoroacetylacetone, hexafluoroacetylacetone, benzoylacetone, tenoyltrifluoroacetone, dipivaloylmethane, dibenzoylmethane, and ascorbic acid. Specific examples of β-ketoesters include methyl acetoacetate, ethyl acetoacetate, allyl acetoacetate, benzyl acetoacetate, n-propyl acetoacetate, iso-propyl acetoacetate, n-butyl acetoacetate, iso-butyl acetoacetate, tert-butyl acetoacetate, 2-methoxyethyl acetoacetate, and methyl 3-oxopentanoate.

[0074] Specific examples of metal compounds (b3) include tetramethoxytitanium, trimethoxyethoxytitanium, trimethoxyisopropoxytitanium, trimethoxybutoxytitanium, dimethoxydiethoxytitanium, dimethoxydiisopropoxytitanium, dimethoxydibutoxytitanium, methoxytriethoxytitanium, methoxytriisopropoxytitanium, methoxytributoxytitanium, tetraethoxytitanium, triethoxyisopropoxytitanium, triethoxybutoxytitanium, diethoxydiisopropoxytitanium, diethoxydibutoxytitanium, ethoxytriisopropoxytitanium, ethoxytributoxytitanium, tetraisopropoxytitanium, triisopropoxybutoxytitanium, diisopropoxydibutoxytitanium, tetrabutoxytitanium, tetratert-butoxytitanium, bis Examples include titanium compounds such as (acetylacetonate)diisopropoxytitanium, bis(ethylacetoacetate)diisopropoxytitanium, and bis(ethylacetoacetate)diisobutoxytitanium; aluminum compounds such as triisopropoxyaluminum, tritert-butoxyaluminum, trisec-butoxyaluminum, trin-butoxyaluminum, aluminum tris(acetylacetonate), aluminum tris(ethylacetoacetate), and diisopropoxyaluminum ethylacetoacetate; zirconium compounds such as tetrapropoxyzirconium and zirconium tetrakis(acetylacetonate); hafnium compounds such as tetrabutoxyhafnium; and vanadium compounds such as vanadium(V)oxytriisopropoxide.

[0075] From the viewpoints of availability, compatibility with organic polymer (A), and curability, tetraisopropoxytitanium, tetratert-butoxytitanium, bis(acetylacetonate)diisopropoxytitanium, bis(ethylacetoacetate)diisopropoxytitanium, triisopropoxyaluminum, trisec-butoxyaluminum, tetrapropoxyzirconium, and vanadium(V) oxytriisopropoxide are more preferred, and tetraisopropoxytitanium, tetratert-butoxytitanium, and bis(ethylacetoacetate) are particularly preferred. Triisopropoxyaluminum and trisec-butoxyaluminum are particularly preferred in terms of activity and non-coloring. The metal compound (b3) may be a single component or a combination of multiple components.

[0076] In terms of rapid curing properties, the amount of metal compound (b3) used is preferably 0.1 parts by weight or more and 5.0 parts by weight or less, more preferably 0.5 parts by weight or more and 4.5 parts by weight or less, and even more preferably 1.0 part by weight or more and 4.0 parts by weight or less, per 100 parts by weight of organic polymer (A).

[0077] The carboxylic acid ester compound (b4) having a hydroxyl group is not particularly limited as long as it is a compound having both a hydroxyl group and a carboxylic acid ester group. The carboxylic acid ester compound may be a chain-like aliphatic carboxylic acid ester compound having a hydroxyl group, such as hydroxypropionic acid ester or hydroxybutyrate ester; it may be an alicyclic carboxylic acid ester compound having a hydroxyl group, such as hydroxycyclopentane carboxylic acid ester or hydroxycyclohexane carboxylic acid ester; or it may be an aromatic compound, such as hydroxybenzoic acid ester or hydroxynaphthalene carboxylic acid ester.

[0078] The organic group bonded to the non-carbonyl oxygen in the ester bond of the carboxylic acid ester compound (b4) is not particularly limited as long as the desired effect is not impaired. Such an organic group may be a hydrocarbon group or an organic group containing heteroatoms such as N, O, S, P, or halogen atoms. The structure of such an organic group may be linear, branched, cyclic, or a combination thereof. Such an organic group may have one or more unsaturated bonds. Such organic groups are preferably hydrocarbon groups, more preferably hydrocarbon groups having 1 to 10 carbon atoms, and even more preferably hydrocarbon groups having 1 to 6 carbon atoms. The carboxylic acid ester compound is preferably typically a methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, isobutyl ester, n-amyl ester, isoamyl ester, n-hexyl ester, 2-ethylhexyl ester, cyclopentyl ester, cyclohexyl ester, 3,3,5-trimethylcyclohexyl ester, or phenyl ester.

[0079] In terms of rapid curing properties, the carboxylic acid ester compound (b4) is preferably a compound that can form an intramolecular hydrogen bond between the hydroxyl group of the carboxylic acid ester having a hydroxyl group and the carbonyl group in the ester bond. Examples of such carboxylic acid ester compounds (b4) include compounds having a hydroxyl group and a carboxylic acid ester group adjacent to each other on the aromatic ring, and β-hydroxycarboxylic acid esters having a hydroxyl group at the β position. Preferred compounds having a hydroxyl group and a carboxylic acid ester group adjacent to each other on the aromatic ring include salicylic acid esters, 2-hydroxy-1-naphthoate esters, 1-hydroxy-2-naphthoate esters, and 2-hydroxy-3-naphthoate esters. In other words, the carboxylic acid ester compound (b4) is preferably one or more selected from the group consisting of salicylic acid esters, 2-hydroxy-1-naphthoate esters, 1-hydroxy-2-naphthoate esters, 2-hydroxy-3-naphthoate esters, and β-hydroxyaliphatic carboxylic acid esters. Among these carboxylic acid ester compounds (b4), salicylic acid esters are particularly preferred in terms of rapid curing properties.

[0080] Specific examples of carboxylic acid ester compounds (b4) include salicylate esters such as methyl salicylate, ethyl salicylate, isopropyl salicylate, isobutyl salicylate, isoamyl salicylate, 2-ethylhexyl salicylate, 3,3,5-trimethylcyclohexyl salicylate, and phenyl salicylate; and ethyl m-hydroxybenzoate, isobutyl m-hydroxybenzoate, isoamyl m-hydroxybenzoate, and 2-ethyl m-hydroxybenzoate. m-hydroxybenzoic acid esters such as xyl; p-hydroxybenzoic acid esters such as ethyl p-hydroxybenzoate, isobutyl p-hydroxybenzoate, isoamyl p-hydroxybenzoate, and 2-ethylhexyl p-hydroxybenzoate; 2-hydroxy-1-naphthoate ethyl 2-hydroxy-1-naphthoate, isobutyl 2-hydroxy-1-naphthoate, isoamyl 2-hydroxy-1-naphthoate, and 2-ethylhexyl 2-hydroxy- 1-Naphthoate esters; 1-hydroxy-2-naphthoate esters such as ethyl 1-hydroxy-2-naphthoate, isobutyl 1-hydroxy-2-naphthoate, isoamyl 1-hydroxy-2-naphthoate, and 2-ethylhexyl 1-hydroxy-2-naphthoate; ethyl 2-hydroxy-3-naphthoate, isobutyl 2-hydroxy-3-naphthoate, isoamyl 2-hydroxy-3-naphthoate, and 2-ethylhexyl 2-hydroxy-3-naphthoate Examples include 2-hydroxy-3-naphthoate esters such as 3-hydroxybutyrate, isobutyl 3-hydroxybutyrate, isoamyl 3-hydroxybutyrate, and 2-ethylhexyl 3-hydroxybutyrate; and 3-hydroxypropionate esters such as ethyl 3-hydroxypropionate, isobutyl 3-hydroxypropionate, isoamyl 3-hydroxypropionate, and 2-ethylhexyl 3-hydroxypropionate.

[0081] Among these, salicylate esters such as methyl salicylate, ethyl salicylate, isopropyl salicylate, isobutyl salicylate, isoamyl salicylate, 2-ethylhexyl salicylate, 3,3,5-trimethylcyclohexyl salicylate, and phenyl salicylate; 2-hydroxy-1-naphthoate esters such as ethyl 2-hydroxy-1-naphthoate, isobutyl 2-hydroxy-1-naphthoate, isoamyl 2-hydroxy-1-naphthoate, and 2-ethylhexyl 2-hydroxy-1-naphthoate; ethyl 1-hydroxy-2-naphthoate, 1-hydroxy-2-naphthoate Preferred are 1-hydroxy-2-naphthoate esters such as butyl, isoamyl 1-hydroxy-2-naphthoate, and 2-ethylhexyl 1-hydroxy-2-naphthoate; 2-hydroxy-3-naphthoate esters such as ethyl 2-hydroxy-3-naphthoate, isobutyl 2-hydroxy-3-naphthoate, isoamyl 2-hydroxy-3-naphthoate, and 2-ethylhexyl 2-hydroxy-3-naphthoate; and 3-hydroxybutyrate esters such as ethyl 3-hydroxybutyrate, isobutyl 3-hydroxybutyrate, isoamyl 3-hydroxybutyrate, and 2-ethylhexyl 3-hydroxybutyrate.

[0082] Among these, salicylic acid esters such as methyl salicylate, ethyl salicylate, isopropyl salicylate, isobutyl salicylate, isoamyl salicylate, 2-ethylhexyl salicylate, 3,3,5-trimethylcyclohexyl salicylate, and phenyl salicylate are preferred; 3-hydroxybutyrate esters such as ethyl 3-hydroxybutyrate, isobutyl 3-hydroxybutyrate, isoamyl 3-hydroxybutyrate, and 2-ethylhexyl 3-hydroxybutyrate are preferred.

[0083] In terms of rapid curing properties, the amount of carboxylic acid ester compound (b4) used is preferably 0.1 parts by weight or more and 10.0 parts by weight or less, more preferably 0.5 parts by weight or more and 9.0 parts by weight or less, and even more preferably 1.0 part by weight or more and 8.0 parts by weight or less, per 100 parts by weight of organic polymer (A).

[0084] <Other additives> The curable composition may contain other additives besides the organic polymer (A) and the curing catalyst (B), to the extent that the desired effect is not impaired. Examples of other additives include silanol condensation catalysts other than the curing catalyst (B), fillers, adhesion promoters, plasticizers, solvents, diluents, anti-sagging agents, antioxidants, light stabilizers, UV absorbers, property modifiers, tackifying resins, compounds containing epoxy groups, photocurable substances, oxygen-curable substances, epoxy resins, other resins, surface modifiers, foaming agents, curing modifiers, flame retardants, silicates, radical inhibitors, metal deactivators, phosphorus-based peroxide decomposers, lubricants, pigments, and antifungal agents.

[0085] (Silanol condensation catalyst) The curable composition may contain a silanol condensation catalyst other than the curing catalyst (B) described above, for the purpose of promoting the hydrolysis condensation reaction between reactive silicon groups of the organic polymer (A) and extending or crosslinking the polymer chain. Examples of such condensation catalysts include organotin compounds, metal carboxylate salts, amine compounds, carboxylic acids, metal alkoxides, and inorganic acids. The silanol condensation catalyst may be used in combination with two or more different catalysts. The amount of silanol condensation catalyst used is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and particularly preferably 0.01 to 10 parts by weight, per 100 parts by weight of organic polymer (A).

[0086] (Filler) Various fillers may be added to the curable composition. Examples of fillers include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrated silicic acid, and carbon black; fillers such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium dioxide, bentonite, organic bentonite, ferric oxide, aluminum powder, flint powder, zinc oxide, activated zinc oxide, and resin powder; and fibrous fillers such as asbestos, glass fibers, and filaments. Examples of resin powders include PVC powder and PMMA powder. When using a filler, the amount of filler used is preferably 1 to 300 parts by weight, and more preferably 10 to 200 parts by weight, per 100 parts by weight of organic polymer (A).

[0087] When a hardened product with high strength is desired using these fillers, fillers selected from fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrated silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and activated zinc oxide are preferably used. In terms of the strength of the cured product, the preferred amount of these fillers to use is 1 to 200 parts by weight per 100 parts by weight of organic polymer (A). Furthermore, if it is desired to obtain a cured product with low strength and high elongation at break, fillers selected mainly from titanium dioxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloons can be preferably used. In terms of the elongation at break of the cured product, the preferred amount of these fillers to use is 5 to 200 parts by weight per 100 parts by weight of organic polymer (A).

[0088] The curable composition may contain spherical hollow bodies, such as balloons, for the purpose of reducing the weight (specific gravity) of the cured product. A balloon is a hollow, spherical filler. Examples of balloon materials include inorganic materials such as glass, shirasu (volcanic ash), and silica, and organic materials such as phenolic resin, urea resin, polystyrene, saran, and acrylonitrile. However, the balloon material is not limited to these materials. The balloon material may be a composite material consisting of inorganic and organic materials. Furthermore, the balloon material may consist of multiple layers laminated together. In addition, a single type of balloon may be used, or two or more types may be used in combination. The surface of the balloon may be surface-treated, coated, or treated with various surface treatment agents. For example, organic balloons coated with calcium carbonate, talc, titanium dioxide, etc., or inorganic balloons surface-treated with silane coupling agents can be used.

[0089] The balloon particle size is preferably 3 to 200 μm, and particularly preferably 10 to 110 μm. When the balloon particle size is within the above range, the cured product can be made lighter to the desired extent by using an appropriate amount of balloons, and the cured product can be formed while suppressing the occurrence of surface irregularities and a decrease in elongation.

[0090] The amount of spherical hollow body (balloon) used is preferably 0.01 to 30 parts by weight per 100 parts by weight of organic polymer (A). The lower limit is more preferably 0.1 parts by weight, and the upper limit is more preferably 20 parts by weight. Using an amount of spherical hollow body within the above range results in a good curable composition and makes it easy to form a cured product with excellent elongation and tensile strength.

[0091] (Adhesion-enhancing agent) The curable composition may contain an adhesion promoter. An example of an adhesion promoter is a silane coupling agent. Silane coupling agents are compounds that have a hydrolyzable silicon group and a functional group other than a hydrolyzable silicon group in their molecule. The effect of improving adhesion to various substrates is particularly remarkable when using silane coupling agents. In addition to the above functions, silane coupling agents can also function as dehydrating agents, property modifiers, and dispersibility improvers for inorganic fillers.

[0092] The hydrolyzable groups in the hydrolyzable silicon groups of the silane coupling agent are not particularly limited. Examples of hydrolyzable groups include hydrogen atoms, halogen atoms, alkoxy groups, aryloxy groups, alkenyloxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, and mercapto groups. Among these, alkoxy groups such as methoxy and ethoxy groups are more preferred because they are mildly hydrolyzable and easy to handle, with methoxy and ethoxy groups being particularly preferred. The number of hydrolyzable groups bonded to the silicon atoms in the silane coupling agent may be preferably three to ensure good adhesion. Alternatively, two may be preferable to ensure the storage stability of the curable composition.

[0093] When using a silane coupling agent as an adhesion promoter, an aminosilane coupling agent having a hydrolyzable silicon group and a substituted or unsubstituted amino group is preferred because it has a greater adhesion-improving effect. The substituent on the substituted amino group is not particularly limited. Examples of such substituents include alkyl groups, aralkyl groups, and aryl groups.

[0094] Specific examples of aminosilane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, γ-(2-(2-aminoethyl)aminoethyl)aminopropyltrimethoxysilane, γ-(6-aminohexyl)aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureido Examples of amino group-containing silanes include propyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, N-butylaminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, and bis(trimethoxysilylpropyl)amine; and ketimine-type silanes such as N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine.

[0095] Of these, γ-aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and γ-(2-aminoethyl)aminopropylmethyldimethoxysilane are preferred in terms of good adhesion of the cured product. One aminosilane coupling agent may be used alone, or two or more may be used in combination. Silane coupling agents obtained by partially condensing hydrolyzable silicon groups to oligomerize them can be suitably used in terms of safety and stability. The silane coupling agents to be condensed may be one or more types. Examples of oligomerized silane coupling agents include Dynasylan 1146 from Evonik. In terms of good storage stability of the curable composition, γ-aminopropyltrimethoxysilane and γ-(2-aminoethyl)aminopropylmethyldimethoxysilane are preferred.

[0096] Specific examples of silane coupling agents other than aminosilane coupling agents include epoxy group-containing silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltriethoxysilane; isocyanate group-containing silane coupling agents such as γ-isocyanatetopropyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane, γ-isocyanatetopropylmethyldiethoxysilane, γ-isocyanatetopropylmethyldimethoxysilane, (isocyanatemethyl)trimethoxysilane, and (isocyanatemethyl)dimethoxymethylsilane; and γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane. Examples include mercapto group-containing silane coupling agents such as γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and mercaptomethyltriethoxysilane; carboxysilane coupling agents such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis(2-methoxyethoxy)silane, and N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane; vinyl-type unsaturated group-containing silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-acryloyloxypropylmethyltriethoxysilane; halogen-containing silane coupling agents such as γ-chloropropyltrimethoxysilane; and isocyanurate silane coupling agents such as tris(trimethoxysilyl)isocyanurate. In addition, condensates obtained by partially condensing the above silane coupling agents can also be used. Examples of such condensates include Dynasylan6490 and Dynasylan6498 from Evonik.Furthermore, modified derivatives of these, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, and silylated polyesters, can also be used as silane coupling agents.

[0097] Of these, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane are preferred in terms of good adhesion of the cured product.

[0098] The above silane coupling agents may be used individually or in combination of two or more types. The amount of silane coupling agent used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of organic polymer (A).

[0099] (Plasticizer) The curable composition may contain a plasticizer. By adding a plasticizer, the viscosity and slump of the curable composition, as well as the mechanical properties of the cured product, such as tensile strength and elongation, can be adjusted.

[0100] 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; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and diylurea succinate. Examples include aliphatic polycarboxylic acid ester compounds such as sodecyl and tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkyl sulfonate phenyl esters; phosphate ester compounds such as tricresyl phosphate and tributyl phosphate; trimellitic acid ester compounds; chlorinated paraffin; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate. A specific example of a terephthalate ester compound is EASTMAN 168 (trade name, manufactured by EASTMAN CHEMICAL). A specific example of a non-phthalate ester compound is Hexamoll DINCH (trade name, manufactured by BASF). A specific example of an alkylsulfonate phenyl ester is Mesamoll (trade name, manufactured by LANXESS).

[0101] High molecular weight plasticizers can also be used. Using high molecular weight plasticizers allows the initial properties of the cured product to be maintained over a longer period compared to using low molecular weight plasticizers. Furthermore, the drying properties (coatability) when alkyd paint is applied to the cured product are improved.

[0102] Specific examples of polymeric plasticizers include vinyl polymers, which are polymers of vinyl monomers; esters of polyalkylene glycols and polyols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid, and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol; polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol with a number average molecular weight of 500 or more, and even 1,000 or more; derivatives of these polyether polyols obtained by converting the hydroxyl groups to ester groups, ether groups, etc.; polystyrenes such as polystyrene and poly-α-methylstyrene; and polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, and polychloroprene. Polymeric plasticizers are not limited to these.

[0103] The polymeric plasticizer is preferably compatible with the organic polymer (A). From this point of view, polyethers and vinyl polymers are preferred. When polyethers are used as plasticizers, surface curability and deep curability are improved, and curing delay after storage does not occur. Among polyethers, polypropylene glycol is more preferred. Vinyl polymers are also preferred from the viewpoint of compatibility with the organic polymer (A), and the weather resistance and heat resistance of the cured product. Among vinyl polymers, acrylic polymers and / or methacrylic polymers are preferred, and acrylic polymers such as alkyl polyacrylates are even more preferred. As a synthesis method for vinyl polymers, living radical polymerization is preferred, and atom transfer radical polymerization is even more preferred, as it yields polymers with a narrow molecular weight distribution and low viscosity. The so-called SGO process, described in Japanese Patent Application Publication No. 2001-207157, which involves continuous bulk polymerization of alkyl acrylate monomers at high temperature and high pressure, is also a preferred method for producing vinyl polymers.

[0104] The number-average molecular weight of the polymeric plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, even more preferably 1,000 to 8,000, particularly preferably 1,000 to 5,000, and most preferably 1,000 to 3,000. When the number-average molecular weight of the polymeric plasticizer is within the above range, the leaching of the plasticizer from the cured product over time due to heat, rainfall, etc., can be suppressed, the initial physical properties of the cured product can be maintained for a long period of time, the curable composition has an appropriate viscosity, and the curable composition has good workability. The molecular weight distribution of the polymeric plasticizer is not particularly limited, but a narrow distribution is preferred. Specifically, the molecular weight distribution is preferably less than 1.80, more preferably 1.70 or less, even more preferably 1.60 or less, still more preferably 1.50 or less, particularly preferably 1.40 or less, and most preferably 1.30 or less.

[0105] The number-average molecular weight of vinyl polymers is measured by GPC (Geomorphic Spectroscopy). The number-average molecular weight of polyether polymers is measured by end-group analysis. Furthermore, the molecular weight distribution (Mw / Mn) is measured by GPC (polystyrene equivalent).

[0106] The polymeric plasticizer may or may not have reactive silicon groups. When the polymeric plasticizer has reactive silicon groups, it acts as a reactive plasticizer, preventing the migration of the plasticizer from the cured product. When the polymeric plasticizer has reactive silicon groups, the number of reactive silicon groups is preferably one or less on average per molecule, and more preferably 0.8 or less. When using a plasticizer having reactive silicon groups, especially a polyether polymer having reactive silicon groups, its number-average molecular weight must be lower than that of the organic polymer (A).

[0107] The amount of 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, per 100 parts by weight of organic polymer (A). When the amount of plasticizer used is within the above range, it is possible to form a cured product with excellent mechanical strength while fully obtaining the desired effect of using the plasticizer. The plasticizer may be used alone or in combination of two or more types. A low molecular weight plasticizer and a high molecular weight plasticizer may be used in combination. These plasticizers may be blended into organic polymer (A) when manufacturing organic polymer (A).

[0108] (Solvents, diluents) The curable composition may contain a solvent or a diluent. The solvent and diluent are not particularly limited. Examples of solvents and diluents include aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, and ethers. When using a solvent or diluent, to address the issue of air pollution when the curable 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 solvent or diluent may be used alone or in combination of two or more.

[0109] (Drip prevention agent) The curable composition may contain a drip inhibitor as needed to prevent dripping and improve workability. The drip inhibitor is not particularly limited. Examples of drip inhibitors include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These drip inhibitors may be used alone or in combination of two or more. The amount of anti-slip agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of organic polymer (A).

[0110] (Antioxidant) The curable composition may contain an antioxidant (anti-aging agent). Using an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenol compounds, monophenol compounds, bisphenol compounds, and polyphenol compounds, with hindered phenol compounds being particularly preferred. Examples of antioxidants include Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330, Irganox 1520 (all manufactured by BASF); SONGNOX 1076 (manufactured by SONGWON); and BHT. Hindered amine-based light stabilizers such as Chinuvin 622LD, Chinuvin 144, Chinuvin 292, CHIMASSORB944LD, CHIMASSORB119FL (all manufactured by BASF); Adekastab LA-57, Adekastab LA-62, Adekastab LA-67, Adekastab LA-63, Adekastab LA-68 (all manufactured by ADEKA Corporation); Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all manufactured by Sankyo Life Tech Co., Ltd.); and Nocrack CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) can also be used. Other antioxidants such as SONGNOX4120, Nowguard445, and OKABEST CLX050 can also be used. Specific examples of antioxidants are also described in Japanese Patent Publication No. 4-283259 and Japanese Patent Publication No. 9-194731. The amount of antioxidant used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of organic polymer (A).

[0111] (Light stabilizer) The curable composition may contain a light stabilizer. Using a light stabilizer can prevent photo-oxidative degradation of the cured product. Examples of light stabilizers include benzotriazole compounds, hindered amine compounds, and benzoate compounds. Hindered amine compounds are particularly preferred as light stabilizers. The amount of light stabilizer used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of organic polymer (A). Specific examples of light stabilizers are described, for example, in Japanese Patent Publication No. 9-194731.

[0112] When a photocurable substance is incorporated into a curable composition, particularly when an unsaturated acrylic compound is used, it is preferable to use a tertiary amine-containing hindered amine-based light stabilizer as a hindered amine-based light stabilizer, as described in Japanese Patent Publication No. 5-70531, in order to improve the storage stability of the curable composition. Examples of tertiary amine-containing hindered amine light stabilizers include: Chinuvin 123, Chinuvin 144, Chinuvin 249, Chinuvin 292, Chinuvin 312, Chinuvin 622LD, Chinuvin 765, Chinuvin 770, Chinuvin 880, Chinuvin 5866, Chinuvin B97, CHIMASSORB119FL, CHIMASSORB944LD (all manufactured by BASF); Adeka Stab LA-57, LA-62, LA-63, LA-67, LA-68 (all manufactured by ADEKA Corporation); Sanol LS-292, LS-2626, LS-765, LS-744, LS-1114 (all manufactured by Sankyo Life Tech Co., Ltd.), SABOSTAB UV91, SABOSTAB UV119, SONGSORB CS5100, SONGSORB CS622, SONGSORB Examples include CS944 (all manufactured by SONGWON) and Nocrack CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.).

[0113] (UV absorber) The curable composition may contain an ultraviolet absorber. Using an ultraviolet absorber can improve the surface weather resistance of the cured product. Examples of ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, salicylate compounds, triazine compounds, substituted tolyl compounds, and metal chelate compounds. Among these, benzotriazole compounds are particularly preferred. Specific examples of benzotriazole compounds include tinubine 234, tinubine 326, tinubine 327, tinubine 328, tinubine 329, tinubine 350, tinubine 571, tinubine 900, tinubine 928, tinubine 1130, tinubine 1600 (all manufactured by BASF); and SONGSORB 3290 (manufactured by SONGWON). Specific examples of triazine compounds include Tinuvin 400, Tinuvin 405, Tinuvin 477, and Tinuvin 1577ED (all manufactured by BASF); and SONGSORB CS400 and SONGSORB 1577 (manufactured by SONGWON). Specific examples of benzophenone compounds include SONGSORB 8100 (manufactured by SONGWON). The amount of UV absorber used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of organic polymer (A). It is preferable to use a combination of a phenolic antioxidant or a hindered phenolic antioxidant, a hindered amine light stabilizer, and a benzotriazole UV absorber. AddworksIBC760 (manufactured by Clariant) can be used as a product containing antioxidants, light stabilizers, and UV absorbers.

[0114] (Property modifier) The curable composition may optionally contain a property modifier to adjust the tensile properties of the cured product. The property modifier is not particularly limited. Examples of property modifiers include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane; alkoxysilanes having functional groups such as γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; silicone varnishes; and polysiloxanes. By using property modifiers, it is possible to increase the hardness of the cured product or, conversely, decrease its hardness and increase its elongation at break. These property modifiers may be used alone or in combination of two or more types.

[0115] In particular, compounds that produce a compound having a monovalent silanol group in the molecule upon hydrolysis have the effect of lowering the modulus of the cured product without worsening the stickiness of the surface of the cured product. Among the compounds that produce a compound having a monovalent silanol group in the molecule upon hydrolysis, compounds that produce trimethylsilanol are particularly preferred. Examples of compounds that produce a compound having a monovalent silanol group in the molecule upon hydrolysis include the compounds described in Japanese Patent Publication No. 5-117521. In addition, examples of compounds that produce trialkylsilanols such as trimethylsilanol upon hydrolysis include derivatives of alkyl alcohols such as hexanol, octanol, and decanol, and derivatives of polyhydric alcohols having 3 or more hydroxyl groups such as trimethylolpropane, glycerin, pentaerythritol, or sorbitol, which produce trialkylsilanols such as trimethylsilanol upon hydrolysis, as described in Japanese Patent Publication No. 11-241029. Examples include derivatives of oxyalkylene polymers that produce silicon compounds that generate trialkylsilanols such as trimethylsilanol upon hydrolysis, as described in Japanese Patent Publication No. 7-258534. Furthermore, polymers having a crosslinkable hydrolyzable silicon-containing group and a silicon-containing group that can become a monosilanol-containing compound upon hydrolysis, as described in Japanese Patent Publication No. 6-279693, can also be used. The property modifier is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the organic polymer (A).

[0116] (Adhesive-granting resin) The curable composition may contain a tackifying resin for purposes such as improving the adhesion and bonding of the cured product to the substrate. There are no particular restrictions on the tackifying resin, and any tackifying resin commonly used in various curable compositions can be used. Specific examples of tackifying resins include terpene resins, aromatically 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, hydrogenated styrene block copolymers, petroleum resins, hydrogenated petroleum resins, and DCPD resins. Examples of petroleum resins include C5 hydrocarbon resins, C9 hydrocarbon resins, and C5C9 hydrocarbon copolymer resins. These may be used individually or in combination of two or more types. The amount of tackifying 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, per 100 parts by weight of organic polymer (A). Using an amount of tackifying resin within this range allows for the formation of a cured product with good adhesion and bonding to the substrate. The curable composition has an appropriate viscosity and is easy to handle.

[0117] (Compounds containing epoxy groups) The curable composition may contain compounds containing epoxy groups. Using compounds with epoxy groups can improve the resilience of the cured product. Examples of compounds with epoxy groups include epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. Specific examples of compounds with epoxy groups include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarbonoxylate (E-PS), epoxyoctyl stearate, and epoxybutyl stearate. The amount of epoxy group-containing compound used is preferably 0.5 to 50 parts by weight per 100 parts by weight of organic polymer (A).

[0118] (Epoxy resin) The curable composition may contain an epoxy resin. Curable compositions containing an epoxy resin are preferred as adhesives, particularly as adhesives for exterior wall tiles. Examples of epoxy resins include bisphenol A type epoxy resins and novolac type epoxy resins. The ratio of the weight of organic polymer (A) to the weight of epoxy resin is preferably in the range of 100 / 1 to 1 / 100, expressed as (weight of organic polymer (A)) / (weight of epoxy resin). When organic polymer (A) and epoxy resin are used in the above ratio, it is easy to form a high-strength cured product with excellent impact strength and toughness. When using epoxy resin, the curing composition may contain a curing agent along with the epoxy resin. The type of curing agent is not particularly limited, and commonly used curing agents can be used. The amount of hardener used is preferably 0.1 to 300 parts by weight per 100 parts by weight of epoxy resin.

[0119] (light curing substance) The curable composition may contain a photocurable substance. Using a photocurable substance forms a film of the photocurable substance on the surface of the cured product, improving the stickiness and weather resistance of the cured product. Various compounds such as organic monomers, oligomers, and resins are known as photocurable substances. Numerous compositions containing photocurable substances are also known. Representative photocurable substances include unsaturated acrylic compounds, polyvinyl polycinnamates, and azidized resins. Examples of unsaturated acrylic compounds include monomers, oligomers, or mixtures thereof having one or more acrylic or methacrylic unsaturated groups. The amount of photocurable substance used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of organic polymer (A). When an amount of photocurable substance within this range is used, it is easy to form a flexible cured product with excellent weather resistance and suppressed cracking.

[0120] (oxygen curing substance) The curable composition may contain an oxygen-curable substance. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air. When the curable composition contains an oxygen-curable substance, the oxygen-curable substance reacts with oxygen in the air to form a cured film near the surface of the cured product. The formation of a cured film on the surface of the cured product prevents stickiness and the 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; various alkyd resins obtained by modifying drying oils; acrylic polymers, epoxy resins, and silicone resins modified with drying oils; and liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, or polymers of C5-C8 dienes obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, or 1,3-pentadiene. These may be used individually or in combination of two or more. The amount of oxygen-curable substance used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of organic polymer (A). Using an amount of oxygen-curable substance within this range makes it easier to form a cured product that is less susceptible to contamination by dirt and dust on the surface and has excellent mechanical properties such as tensile strength. As described in Japanese Patent Publication No. 3-160053, the oxygen-curable substance is preferably used in combination with a photocurable substance.

[0121] <Preparation of curable composition> The curable composition can be prepared as a one-component type, where all components are pre-mixed and sealed for storage, and then cured by moisture in the air after application. Alternatively, the curing agent composition can be prepared as a two-component type, where a curing agent mixture containing a curing catalyst (B), a filler, a plasticizer, and water, and a separately prepared organic polymer (A) are mixed before use. From the viewpoint of workability, the one-component type is preferred. When the curable composition is a one-component type, all components are pre-mixed. Therefore, it is preferable to dehydrate and dry any components containing water before use, or to dehydrate them during mixing by reduced pressure or other means. In addition to dehydration and drying, the storage stability can be further improved by adding alkoxysilane compounds such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Partially condensed silane compounds such as Evonik's Dynasylan 6490 can also be suitably used as dehydrating agents from the viewpoint of safety and stability. The amount of dehydrating agent, particularly a silicon compound that can react with water such as vinyltrimethoxysilane, is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of organic polymer (A).

[0122] The order in which a carboxylic acid or its metal salt (b1), an amine compound (b2), a metal compound (b3), and a carboxylic acid ester compound (b4) are added to a compound constituting a one-component curable composition or a two-component curable composition is not particularly limited, as long as the desired effect is not impaired. Since it is easy to obtain a curable composition with excellent rapid curing properties, it is preferable that the carboxylic acid ester compound (b4), metal compound (b3), carboxylic acid or its metal salt (b1), and amine compound (b2) are added in this order.

[0123] Curable compositions can be used as building sealants, industrial adhesives, waterproof coating formation compositions, and adhesive raw materials. They can also be used as sealants for buildings, ships, automobiles, and roads. Furthermore, curable compositions can adhere to a wide range of substrates, including glass, porcelain, wood, metal, and resin molded products, either alone or with the help of a primer. Therefore, curable compositions can be used as various types of sealing and adhesive compositions. In addition to being ordinary adhesives, curable compositions can also be used as contact adhesives. Moreover, curable compositions are useful as food packaging materials, casting rubber materials, molding materials, and paints. The cured products of the above curable compositions exhibit low water absorption. Therefore, the above curable compositions and their cured products are particularly suitable for use as waterproofing materials such as sealants, waterproofing adhesives, and waterproof coatings.

[0124] The present invention is not limited to the embodiments described above, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0125] In other words, one aspect of the present invention includes the following:

[0126] <1> A curable composition comprising an organic polymer (A) and a curing catalyst (B), Organic polymer (A) is given by the following formula (1): -SiR 13-a X a (1) (In formula (1), R 1 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R 0 It shows a triorganosiloxy group represented as 3SiO-, and 3 R 0 These are hydrocarbon groups having 1 to 20 carbon atoms, and they may be the same or different. X represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. R 1 (For each of X, if there are multiple instances of them, they may be the same or different.) It has a reactive silicon group represented by, The curing catalyst (B) comprises a carboxylic acid or its metal salt (b1), an amine compound (b2), a metal compound (b3), and a carboxylic acid ester compound having a hydroxyl group (b4). Two or more compounds selected from carboxylic acids or their metal salts (b1), amine compounds (b2), metal compounds (b3), and carboxylic acid ester compounds having a hydroxyl group (b4) may be reacted with each other. Amine compound (b2) is a compound that does not fall under the category of amidine compounds or guanidine compounds. The metal compound (b3) is given by the following formula (2): M(O) d (OR 2 ) e Y f (2) (In equation (2), M is Ti, Al, Zr, Hf, or V, d is 0 or 1, e and f are each independent non-negative integers, where (2d+e+f) is the valence of M. If M is Ti, Al, Zr, or Hf, then d is 0. If M is V, then d is 1, R 2 This is a hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. Y is a chelate-coordinating compound. A curable composition, which is a compound represented by [the formula shown]. <2> The main chain structure of the organic polymer (A) is one or more selected from the group consisting of polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic acid ester polymers. <1> The curable composition described above. <3> The main chain structure of organic polymer (A) is a polyoxyalkylene polymer. <2> The curable composition described above. <4> The carboxylic acid ester compound (b4) is a compound that can form an intramolecular hydrogen bond between the hydroxyl group of a carboxylic acid ester having a hydroxyl group and the carbonyl group in the ester bond. <1> ~ <3> A curable composition as described in any one of the following. <5> The carboxylic acid ester compound (b4) is one or more selected from the group consisting of salicylic acid esters, 2-hydroxy-1-naphthoate esters, 1-hydroxy-2-naphthoate esters, 2-hydroxy-3-naphthoate esters, and β-hydroxyaliphatic carboxylic acid esters. <4> The curable composition described above. <6> The carboxylic acid or its metal salt (b1) is a carboxylic acid having a carboxyl group bonded to a tertiary carbon atom or a secondary carbon atom, or a metal salt of a carboxylic acid having a carboxyl group bonded to a tertiary carbon atom or a secondary carbon atom. <1> ~ <5> A curable composition as described in any one of the following. <7> <1> ~ <5> A cured product of any one of the curable compositions described in any one of the above. <8> <1> ~ <5> A waterproofing material using a curable composition described in any one of the above, or a cured product of a curable composition. [Examples]

[0127] The present invention will be described in more detail below with reference to specific examples. The present invention is not limited to the following examples.

[0128] <Examples of catalyst synthesis> [Catalyst synthesis example 1: Catalyst (B-1)] 8 g of aluminum trisec-butoxide (Al(OsBu)3, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a nitrogen-purged glass flask. While stirring the contents of the flask, 24 g of 2-ethylhexyl salicylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly added dropwise to the flask. After the addition was complete, the contents of the flask were stirred at room temperature for 30 minutes. Then, the flask was immersed in an 80°C oil bath, and the pressure inside the flask was reduced using an evaporator for 45 minutes to remove volatile components from the flask. After that, the contents of the flask were cooled to obtain catalyst (B-1).

[0129] [Catalyst Synthesis Example 2: Al(nda)3] 8 g of aluminum sec-butoxide (Al(OsBu)3, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a nitrogen-purged glass flask. While stirring the contents of the flask, 16.5 g of neodecanoic acid (manufactured by Hexion, trade name: Neodecanoic Acid (Versatic 10, nda)) was slowly added dropwise to the flask. After the addition was complete, the contents of the flask were stirred at room temperature for 30 minutes. Then, the flask was immersed in an 80°C oil bath, and the inside of the flask was depressurized using an evaporator for 45 minutes to remove volatile components from the flask. After that, the contents of the flask were cooled to obtain aluminum trineodecanoate (Al(nda)3).

[0130] [Catalyst Synthesis Example 3: Ti(nda)4] 9 g of titanium tetraisopropoxide (Ti(OiPr)4, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to a nitrogen-purged glass flask. While stirring the contents of the flask, 22 g of neodecanoic acid (manufactured by Hexion, trade name: Neodecanoic Acid (Versatic 10, nda)) was slowly added dropwise to the flask. After the addition was complete, the contents of the flask were stirred at room temperature for 30 minutes. Then, the flask was immersed in an 80°C oil bath, and the inside of the flask was depressurized using an evaporator for 45 minutes to remove volatile components from the flask. After that, the contents of the flask were cooled to obtain titanium tetraneodecanoate (Ti(nda)4).

[0131] [Catalyst Synthesis Example 4: Zr(nda)4] 15 g of Zr(OPr)4, approximately 75% by weight propanol solution, manufactured by Tokyo Chemical Industry Co., Ltd., was added to a nitrogen-purged glass flask. While stirring the contents of the flask, 22 g of neodecanoic acid (manufactured by Hexion, trade name: Neodecanoic Acid (Versatic 10, nda)) was slowly added dropwise to the flask. After the addition was complete, the contents of the flask were stirred at room temperature for 30 minutes. Then, the flask was immersed in an 80°C oil bath, and the inside of the flask was depressurized using an evaporator for 45 minutes to remove volatile components from the flask. After that, the contents of the flask were cooled to obtain zirconium tetraneodecanoate (Zr(nda)4).

[0132] <Example of synthesis of organic polymer (A)> The following number-average molecular weights are GPC molecular weights measured under the following conditions. Liquid delivery system: Tosoh HLC-8420GPC Column: Tosoh TSKgel SuperH series Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40℃

[0133] The molecular weights in the examples, calculated using end-group ratios, were determined by measuring the hydroxyl value according to the JIS K 1557 method and the iodine value according to the JIS K 0070 method, taking into account the structure of the organic polymer. The degree of branching determined by the polymerization initiator used was considered when determining the structure of the organic polymer.

[0134] The average number of silyl groups per terminal or per molecule of the polymers shown in the examples 1 The results were calculated by 1H-NMR (measured in CDCl3 solvent using a Bruker AVANCE III HD-500).

[0135] [Preparation Example 1: Synthesis of Organic Polymer (A-1)] Polypropylene oxide was polymerized using polyoxypropylenediol with a molecular weight of approximately 2,000 as an initiator and a zinc hexacyanocobaltate-grime complex catalyst to obtain hydroxyl-terminated polypropylene oxide with a number average molecular weight of 28,500. Subsequently, 1.2 molar equivalents of a methanol solution of NaOMe was added to the hydroxyl groups of this hydroxyl-terminated polypropylene oxide. After distilling off the methanol from the reaction mixture, allyl chloride was added to the reaction mixture to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by defoliation under reduced pressure. 100 parts by weight of the obtained unpurified allyl-terminated polypropylene oxide was mixed with 300 parts by weight of n-hexane and 300 parts by weight of water, and then stirred. Next, the mixture was separated into an aqueous phase and a hexane phase by centrifugation, and the aqueous phase was removed. 300 parts by weight of water was mixed into the obtained hexane phase and stirred. The mixture was separated into an aqueous phase and a hexane phase again by centrifugation, and the aqueous phase was removed. Subsequently, hexane was removed from the hexane phase by vacuum defloration. This yielded a bifunctional polypropylene oxide with a number-average molecular weight of approximately 28,500, with allyl groups at the ends. To 100 parts by weight of the obtained allyl-terminated polypropylene oxide, 150 ppm of a 2-propanol solution of a platinum vinylsiloxane complex with a platinum content of 3 wt% was added as a catalyst. Next, 0.8 molar equivalents of trimethoxysilane relative to the allyl groups of the allyl-terminated polypropylene oxide were added, and the allyl-terminated groups and trimethoxysilane were reacted at 90°C for 5 hours to obtain a trimethoxysilyl-terminated polyoxypropylene polymer (A-1). The number of trimethoxysilyl groups was approximately 0.7 per polymer chain end.

[0136] [Preparation Example 2: Synthesis of Organic Polymer (A-2)] Polymerization of propylene oxide was carried out using an equiweight mixture of polyoxypropylenediol with a molecular weight of approximately 2,000 and polyoxypropylenetriol with a molecular weight of approximately 3,000 as initiators, and a zinc hexacyanocobaltate glyme complex catalyst, to obtain hydroxyl-terminated polypropylene oxide with a number average molecular weight of approximately 19,000. Subsequently, a methanol solution of NaOMe in an amount equivalent to 1.2 times the hydroxyl group of this hydroxyl-terminated polypropylene oxide was added. After distilling off the methanol from the reaction mixture, allyl chloride was added to the reaction mixture to convert the terminal hydroxyl groups to allyl groups. Thus, polypropylene oxide with allyl groups at the ends and a number average molecular weight of approximately 19,000 was obtained. To 100 parts by weight of the obtained unpurified allyl-terminated polypropylene oxide, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred. The mixture was then separated into an aqueous phase and a hexane phase by centrifugation, and the aqueous phase was removed. To the obtained hexane phase, 300 parts by weight of water were mixed and stirred. The mixture was again separated into an aqueous phase and a hexane phase by centrifugation, and the aqueous phase was removed. Subsequently, hexane was removed from the hexane phase by vacuum defloration. Thus, polypropylene oxide with allyl groups at the end was obtained. To 100 parts by weight of the obtained allyl-terminated polypropylene oxide, 150 ppm of an isopropanol solution of a platinum vinylsiloxane complex with a platinum content of 3 wt% was added as a catalyst. Next, 0.7 molar equivalents of methyldimethoxysilane were added to the allyl-terminated polypropylene oxide relative to the allyl group, and the allyl-terminated group and methyldimethoxysilane were reacted at 90°C for 5 hours to obtain methyldimethoxysilyl-terminated polypropylene oxide (A-3). The number of methyldimethoxysilyl groups was approximately 0.7 per polymer chain end. Polymer (A-2) has both linear and branched main chain structures.

[0137] Below, a curable composition was prepared using the organic polymer and catalyst obtained by the above method, and the curability of the curable composition was confirmed. The details of components (b2) and (b4) described in Tables 1 and 2 below are as follows: ((b2) component) 3-Dimethylaminopropylamine: Manufactured by Fujifilm Wako Pure Chemical Corporation 3-Diethylaminopropylamine: Manufactured by Tokyo Chemical Industry Co., Ltd. 3-Dibutylaminopropylamine: Manufactured by Tokyo Chemical Industry Co., Ltd. ((b4) component) Isobutyl salicylate: Manufactured by Tokyo Chemical Industry Co., Ltd. Isoamyl salicylate: Manufactured by Tokyo Chemical Industry Co., Ltd. 2-Ethylhexyl salicylate: Manufactured by Tokyo Chemical Industry Co., Ltd. DL-3-Hydroxybutyrate Ethyl: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0138] [Examples 1-10 and Comparative Examples 1-4] 100 parts by weight of the type of organic polymer (A) listed in Table 1, 160 parts by weight of colloidal calcium carbonate (Imery, trade name: Winnofil SPM), 54 parts by weight of heavy calcium carbonate (Imery, trade name: Imerseal 36S), 5 parts by weight of balloon (Matsumoto Oil & Fat Pharmaceutical Co., Ltd., trade name: MFL-81GCA), 120 parts by weight of plasticizer (BASF, trade name: Hexamoll DINCH), 5 parts by weight of pigment (Sachtleben, trade name: R-FK-2), and thixotropic agent (ARKEMA, trade name: Crayvallac 5 parts by weight of SL, 1 part by weight of antioxidant (BASF, product name: Irganox 1010), 1 part by weight of UV absorber (BASF, product name: Tinuvin 326), and 1 part by weight of light stabilizer (BASF, product name: Tinuvin 770) were mixed using a spatula. The resulting mixture was dispersed by passing it through a three-roll mill three times to obtain the main component.

[0139] (Skinning time (hardening evaluation)) Under an atmosphere of 23°C and 50% relative humidity, the carboxylic acid ester compound (b4) (component (b4)) and the metal compound (b3) (component (b3)) in the amounts listed in Table 1 were added to the main component in a 100 ml plastic container, in that order. Subsequently, the dehydrating agent (manufactured by Evonik, trade name: Dynasylan VTMO, vinyltrimethoxysilane), the adhesion promoter (manufactured by Evonik, trade name: Dynasylan AMMO, γ-aminopropyltrimethoxysilane), the type and amount of carboxylic acid or its metal salt (b1) (component (b1)) and the type and amount of amine compound (b2) (component (b2)) listed in Table 1 were added to the main component in that order, in the amounts listed in Table 1, to obtain a curable composition. The values ​​listed in Table 1 for each component represent the amount (parts by weight) used for each component. In Comparative Example 1, component (b4) was not used. In Comparative Example 2, component (b3) was not used. In Comparative Example 3, component (b1) was not used. In Comparative Example 4, component (b2) was not used.

[0140] Under conditions of 23°C and 50% relative humidity, the obtained curable composition was filled into a mold approximately 5 mm thick. The curing time (curing properties) was then measured by touching the curable composition inside the mold with a spatula and determining the time until no more of the mixture adhered to the spatula, which was defined as the skinning time.

[0141] [Table 1]

[0142] A comparison of Examples 1-10 with Comparative Examples 1-4 shows that when a curable composition containing an organic polymer (A) having a reactive silicon group is combined with predetermined components (b1), (b2), (b3), and (b4) as a curing catalyst (B), the curable composition hardens rapidly.

[0143] [Examples 11-25] 100 parts by weight of the type of organic polymer (A) listed in Table 2, 160 parts by weight of colloidal calcium carbonate (Imery, trade name: Winnofil SPM), 54 parts by weight of heavy calcium carbonate (Imery, trade name: Imerseal 36S), 90 parts by weight of plasticizer (BASF, trade name: Hexamoll DINCH), 5 parts by weight of pigment (Sachtleben, trade name: R-FK-2), 5 parts by weight of thixotropic agent (ARKEMA, trade name: Crayvallac SLT), 1 part by weight of antioxidant (BASF, trade name: Irganox 1010), 1 part by weight of ultraviolet absorber (BASF, trade name: Tinuvin 326), and 1 part by weight of light stabilizer (BASF, trade name: Tinuvin 770) were mixed using a spatula. The resulting mixture was dispersed by passing it through a three-roll mill three times to obtain the main component.

[0144] (Skinning time (hardening evaluation)) Under an atmosphere of 23°C and 50% relative humidity, the main component in a 100 ml plastic container was prepared by adding the carboxylic acid ester compound (b4) (component (b4)), which is a compound capable of forming an intramolecular hydrogen bond between the hydroxyl group of the carboxylic acid having a hydroxyl group and the carbonyl group in the ester bond, and the metal compound (b3) (component (b3)), in the order listed in Table 2. Subsequently, the main component was prepared by adding the dehydrating agent (manufactured by Evonik, trade name: Dynasylan VTMO, vinyltrimethoxysilane), the adhesion promoter (manufactured by Evonik, trade name: Dynasylan AMMO, γ-aminopropyltrimethoxysilane), the type and amount of carboxylic acid or its metal salt (b1) (component (b1)), and the type and amount of amine compound (b2) (component (b2)), in the order listed in Table 2, in the order listed in Table 2, to obtain a curable composition. In Comparative Example 5, component (b4) was not used. The values ​​listed in Table 2 for each component represent the amount (parts by weight) used for each component. In Table 2, component (b3) is as follows: When component (b3) is isopropanol or a 1-propanol solution, the values ​​listed in Table 2 represent the total amount of solids and solvent in component (b3). Ti(OiPr)4: Tetraisopropoxytitanium (manufactured by Tokyo Chemical Industry Co., Ltd.) Ti(acac)2(OiPr)2 / iPrOH: Isopropanol solution of bis(acetylacetonate)diisopropoxytitanium at a concentration of 75% by mass (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Al(OsBu)3: Trisec-butoxyaluminum: Manufactured by Tokyo Chemical Industry Co., Ltd. VO(OiPr)3: Vanadium (V) oxytriisopropoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) Zr(OPr)4 / PrOH: A 1-propanol solution of tetrapropoxyzirconium with a concentration of approximately 70% by mass (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0145] Under conditions of 23°C and 50% relative humidity, the obtained curable composition was filled into a mold approximately 5 mm thick. The curing time (curing properties) was then measured by touching the curable composition inside the mold with a spatula and determining the time until no more of the mixture adhered to the spatula, which was defined as the skinning time.

[0146] [Table 2]

[0147] A comparison of Examples 11-25 with Comparative Example 5 shows that when a curable composition containing an organic polymer (A) having a reactive silicon group is combined with a predetermined curing catalyst (B) consisting of components (b1), (b2), (b3), and (b4), the curable composition hardens rapidly.

Claims

1. A curable composition comprising an organic polymer (A) and a curing catalyst (B), The aforementioned organic polymer (A) is given by the following formula (1): -SiR １ ３－ａ X ａ (1) (In formula (1), R １ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ０ ３ It shows a triorganosiloxy group represented by SiO- and three R ０ These are hydrocarbon groups having 1 to 20 carbon atoms, and they may be the same or different. X represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. R １ (For each of X, if there are multiple instances of them, they may be the same or different.) It has a reactive silicon group represented by, The curing catalyst (B) comprises a carboxylic acid or its metal salt (b1), an amine compound (b2), a metal compound (b3), and a carboxylic acid ester compound having a hydroxyl group (b4). Two or more compounds selected from the carboxylic acid or its metal salt (b1), the amine compound (b2), the metal compound (b3), and the carboxylic acid ester compound (b4) may be reacted with each other. The amine compound (b2) is a compound selected from the group consisting of aliphatic secondary monoamines, aliphatic tertiary monoamines, aromatic amines, aliphatic diamines, and polyhydric amines of trivalent or higher. The amine compound (b2) is a compound that does not fall under the category of amidine compounds or guanidine compounds. The aforementioned metal compound (b3) is given by the following formula (2): M(O) ｄ (OR ２ ) ｅ Y ｆ (2) (In formula (2), M is Ti, Al, Zr, Hf, or V, d is 0 or 1, e and f are each independent integers of 0 or greater, where (2d + e + f) is the valence of M. If M is Ti, Al, Zr, or Hf, then d is 0. If M is V, then d is 1, R ２ This is a hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. Y is a chelate-coordinating compound. A curable composition, which is a compound represented by [the formula shown].

2. The curable composition according to claim 1, wherein the main chain structure of the organic polymer (A) is one or more selected from the group consisting of polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic acid ester polymers.

3. The curable composition according to claim 2, wherein the main chain structure of the organic polymer (A) is the polyoxyalkylene polymer.

4. The curable composition according to any one of claims 1 to 3, wherein the carboxylic acid ester compound (b4) is a compound that can form an intramolecular hydrogen bond between the hydroxyl group of the carboxylic acid ester having a hydroxyl group and the carbonyl group in the ester bond.

5. The curable composition according to claim 4, wherein the carboxylic acid ester compound (b4) is one or more selected from the group consisting of salicylic acid esters, 2-hydroxy-1-naphthoate esters, 1-hydroxy-2-naphthoate esters, 2-hydroxy-3-naphthoate esters, and β-hydroxyaliphatic carboxylic acid esters.

6. The curable composition according to any one of claims 1 to 3, wherein the carboxylic acid or its metal salt (b1) is a carboxylic acid having a carboxyl group bonded to a tertiary carbon atom or a secondary carbon atom, or a metal salt of a carboxylic acid having a carboxyl group bonded to a tertiary carbon atom or a secondary carbon atom.

7. A cured product of the curable composition according to any one of claims 1 to 3.

8. A waterproofing material using a curable composition according to any one of claims 1 to 3, or a cured product of the curable composition.

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