Curable composition and method for producing the same

Abstract

The present invention provides a curable composition comprising a reactive silicon group-containing organic polymer, wherein the curability is improved and the composition exhibits a low modulus after curing. [Solution] A curable composition containing an organic polymer (A) having a reactive silicon group and a curing catalyst (B). The reactive silicon group is of formula:-SiR 1 3-a X a (R 1 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R 0 Represents a triorganosiloxy group represented as 3SiO-. 0 ) represents a hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a represents 1, 2, or 3. The curing catalyst (B) comprises a tin carboxylate compound (b1), a cyclic secondary amine compound (b2), and a β-dicarbonyl compound (b3), wherein compound (b2) has one or more skeletons selected from the group consisting of a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, and an azepane skeleton.

Description

Technical Field

[0001] The present invention relates to a curable composition containing 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 method for producing the same.

Background Art

[0002] It is known that an organic polymer having a reactive silicon group has a property that it can crosslink at room temperature by forming a siloxane bond accompanied by a hydrolysis reaction of a silyl group due to moisture or the like, and a rubber-like cured product can be obtained. Such an organic polymer having a reactive silicon group has already been industrially produced and is widely used in applications such as sealing materials, adhesives, paints, and waterproof materials.

[0003] In order to advance the curing reaction in a short time, a curing catalyst (also referred to as a silanol condensation catalyst) is usually blended in a curable composition containing an organic polymer having a reactive silicon group.

[0004] In Patent Document 1, it is disclosed that by using a combination of an organotin carboxylate such as tin octylate or an organolead carboxylate and an amine compound such as laurylamine as such a curing catalyst, the resilience of the obtained rubber-like cured product is improved.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] The curable composition containing a curing catalyst obtained by combining a tin carboxylate compound and an amine compound as disclosed in Patent Document 1 had insufficient curability and tended to require a long time for curing.

[0007] In contrast, the present inventors have found that when a cyclic secondary amine compound is used as the amine compound in a curing catalyst obtained by combining a tin carboxylate compound and an amine compound, the curability is improved. However, the curability has not yet reached a sufficient level, and there is still room for further improvement.

[0008] Further, when a curing catalyst obtained by combining a tin carboxylate compound and a cyclic secondary amine compound is used, the modulus after curing tends to increase. However, when the curable composition is used in applications such as a sealing material, it is required to exhibit a low modulus after curing.

[0009] In view of the above situation, an object of the present invention is to provide a curable composition containing a reactive silicon group-containing organic polymer, which has improved curability and exhibits a low modulus after curing.

Means for Solving the Problems

[0010] As a result of intensive studies to solve the above problems, the present inventors have found that by using a combination of a tin carboxylate compound, a cyclic secondary amine compound as the amine compound, and a β-dicarbonyl compound as a curing catalyst for a reactive silicon group-containing organic polymer, it is possible to achieve improved curability and a low modulus after curing, and thus have completed the present invention.

[0011] That is, the present invention is a curable composition containing an organic polymer (A) having a reactive silicon group and a curing catalyst (B), where the reactive silicon group is represented by the general formula (1): -SiR 1 3-a X a (1) (In the formula, R 1is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R 0 Represents a triorganosiloxy group represented as 3SiO-. 3 R 0 represents a hydrocarbon group having 1 to 20 carbon atoms, either identical or different. X represents a hydroxyl group or a hydrolyzable group. a represents 1, 2, or 3. R 1 Or, if there are multiple X's, they may be the same or different. ) The curing catalyst (B) comprises a tin carboxylate compound (b1), a cyclic secondary amine compound (b2), and a β-dicarbonyl compound (b3). The present invention relates to a curable composition in which the cyclic secondary amine compound (b2) has one or more skeletons selected from the group consisting of a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, and an azepane skeleton. The present invention also relates to a method for producing a curable composition containing an organic polymer (A) having a reactive silicon group and a curing catalyst (B), Tin carboxylate compound (b1), A cyclic secondary amine compound (b2) having one or more skeletons selected from the group consisting of a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, and an azepane skeleton, A step of mixing with a β-dicarbonyl compound (b3) to obtain a curing catalyst (B); and A manufacturing method comprising the step of mixing the curing catalyst (B) with an organic polymer (A) having a reactive silicon group represented by the general formula (1). [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a curable composition comprising a reactive silicon group-containing organic polymer, wherein the curability is improved and the curability is low after curing.

[0013] According to a preferred embodiment of the present invention, the various mechanical properties of the cured product obtained by curing the curable composition are also good. [Modes for carrying out the invention]

[0014] Hereinafter, embodiments of the present invention will be described in detail. One aspect of this embodiment relates to a curable composition containing an organic polymer (A) having a reactive silicon group and a curing catalyst (B).

[0015] (Organic polymer (A) containing reactive silicon group) The organic polymer (A) containing a reactive silicon group has a polymer backbone (also referred to as a main chain structure) and polymer chain terminals bonded to the polymer backbone. The polymer backbone is a structure in which a plurality of monomers are bonded by polymerization, condensation, etc. to form a continuous plurality of monomer units. The monomers may be of one type or a mixture of multiple types bonded together.

[0016] The polymer chain terminal refers to a site located at the terminal of the organic polymer (A) containing a reactive silicon group. When the polymer backbone is all linear, the number of polymer chain terminals of the organic polymer (A) containing a reactive silicon group is 2, and when the polymer backbone is all branched-chain, it is 3 or more. Also, when the polymer backbone is a mixture of linear and branched-chain, it can also be an average value between 2 and 3.

[0017] The reactive silicon group possessed by the organic polymer (A) may be present in the polymer backbone and / or in the polymer chain terminals. Also, there may be two or more reactive silicon groups in one polymer chain terminal. When the curable composition according to the present disclosure is used as an adhesive, a sealing material, an elastic coating agent, an adhesive, etc., the reactive silicon group is preferably contained in the polymer chain terminals of the organic polymer (A).

[0018] The organic polymer (A) has a reactive silicon group represented by the following general formula (1). -SiR 1 3-a X a (1) (In the formula, R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a triorganosiloxy group represented by R 0 3SiO-. The three R 0represents a hydrocarbon group having 1 to 20 carbon atoms, either identical or different. X represents a hydroxyl group or a hydrolyzable group. a indicates 1, 2, or 3. R 1 Or, if there are multiple X's, they may be the same or different.

[0019] R in general formula (1) 1 Examples include alkyl groups such as methyl and ethyl groups; alkyl groups with hetero-containing groups such as chloromethyl, methoxymethyl, and 3,3,3-trifluoropropyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl groups; aralkyl groups such as benzyl groups; R 0 R is a methyl group, a phenyl group, etc. 0 Examples include triorganosiloxy groups represented by 3SiO-. Preferably, these are alkyl groups or alkyl groups having hetero-containing groups, more preferably methyl groups, ethyl groups, chloromethyl groups, or methoxymethyl groups, even more preferably methyl groups or ethyl groups, and particularly preferably methyl groups. 1 If multiple instances exist, they may be identical or different from one another.

[0020] In general formula (1), X represents a hydroxyl group or a hydrolyzable group. The hydrolyzable group is not particularly limited and may be any known hydrolyzable group, such as a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, or an alkenyloxy group. Among these, alkoxy groups, acyloxy groups, ketoximate groups, and alkenyloxy groups are preferred. Alkoxy groups are more preferred because they are milder and easier to handle, methoxy groups and ethoxy groups are even more preferred, and methoxy groups are particularly preferred. If there are multiple Xs, they may be the same or different from each other.

[0021] a is 1, 2, or 3. It is preferable that a is 2 or 3. From the viewpoint of achieving better curing properties, it is particularly preferable that a is 3.

[0022] The reactive silicon group represented by general formula (1) is not particularly limited, but examples include trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, dimethoxyphenylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, and (N,N-diethylaminomethyl)diethoxysilyl group. Among these, dimethoxymethylsilyl group and trimethoxysilyl group are preferred because they are easy to synthesize. Trimethoxysilyl group and methoxymethyldimethoxysilyl group are preferred because they provide high curability. Trimethoxysilyl group and triethoxysilyl group are preferred because they yield cured products that exhibit high recovery rate and low water absorption.

[0023] (Main chain structure of reactive silicon group-containing organic polymer (A)) The main chain structure (also called the polymer backbone) of the reactive silicon group-containing organic polymer (A) is not particularly limited, and various main chain structures can be used. Specifically, polyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer; hydrocarbon polymers such as ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; and polymers obtained by condensation of dibasic acids such as adipic acid with glycols, or by ring-opening polymerization of lactones. Examples include ester polymers; (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 (meth)acrylic acid ester monomers, vinyl acetate, acrylonitrile, styrene, and other monomers; polysulfide polymers; polyamide polymers; polycarbonate polymers, diallyl phthalate polymers, etc. In the above description, (meth)acrylic refers to acrylic and / or methacrylic.

[0024] Of these, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth)acrylic acid ester polymers are preferred because they have relatively low glass transition temperatures and the resulting cured products have excellent cold resistance. One of these may be used alone, or two or more may be used in combination.

[0025] Polyoxyalkylene polymers and (meth)acrylic acid ester polymers are particularly preferred because they have high moisture permeability, excellent deep curing properties when used in a one-component curable composition, and also excellent adhesive properties. Polyoxyalkylene polymers are more preferred, and polyoxypropylene is even more preferred. It is also preferable to use polyoxyalkylene polymers and (meth)acrylic acid ester polymers in combination.

[0026] (Meth)acrylic acid ester polymers are useful because, by combining various monomer compositions that make up the polymer, effects such as improved adhesion, improved heat resistance and weather resistance, and reduced water absorption of cured products obtained by curing curable compositions can be obtained.

[0027] The polyoxyalkylene polymer is preferably a polymer having a repeating unit represented by -RO- (wherein R is a linear or branched alkylene group having 1 to 14 carbon atoms). More preferably, R is a linear or branched alkylene group having 2 to 4 carbon atoms. Specific examples of the repeating unit represented by -RO- include -CH2O-, -CH2CH2O-, -CH2CH(CH3)O-, -CH2CH(C2H5)O-, -CH2C(CH3)(CH3)O-, and -CH2CH2CH2CH2O-. The main chain structure of the polyoxyalkylene polymer may consist of only one type of repeating unit or of two or more types of repeating units.

[0028] In particular, when the curable composition according to this disclosure is used as a sealant, adhesive, etc., a polyoxypropylene polymer having oxypropylene repeating units at a concentration of 50% by weight or more, more preferably 80% by weight or more, of the polymer main chain structure is preferred because it is amorphous and has relatively low viscosity.

[0029] The main chain structure of the polyoxyalkylene polymer may be linear or branched. When branched, the number of branches is preferably 1 to 6 (i.e., 3 to 8 terminal hydroxyl groups), more preferably 1 to 4 (i.e., 3 to 6 terminal hydroxyl groups), and most preferably 1 (i.e., 3 terminal hydroxyl groups). Having branched chains improves the resilience of the cured product. It can also be expected to reduce the water absorption of the cured product. When branched chains are present and the reactive silicon group is a trimethoxysilyl group, a cured product with particularly low water absorption can be obtained.

[0030] Polyoxyalkylene polymers are preferably obtained by a ring-opening polymerization reaction of a cyclic ether compound using a polymerization catalyst in the presence of an initiator.

[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 the cyclic ether compounds, propylene oxide is particularly preferred because it yields amorphous and relatively low-viscosity polyether polymers.

[0032] 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 hydroxyl-terminated polyoxyalkylene polymers with a number average molecular weight of 300 to 4,000, such as polyoxypropylenediol, polyoxypropylenetriol, polyoxyethylenediol, and polyoxyethylenetriol.

[0033] Examples of synthesis methods for polyoxyalkylene polymers include, but are not limited to, polymerization methods using alkaline catalysts such as KOH, polymerization methods 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 methods using complex metal cyanide complex catalysts as shown in Japanese Patent Publication Nos. 46-27250, 59-15336, U.S. Patent Nos. 3278457, 3278458, 3278459, 3427256, 3427334, and 3427335, polymerization methods using catalysts consisting of polyphosphazene salts as exemplified in Japanese Patent Publication No. 10-273512, and polymerization methods 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] As the reactive silicon group-containing organic polymer (A), polyoxyalkylene polymers containing other bonds such as urethane bonds and urea bonds in the main chain structure may be used, as long as the effects of the invention are not significantly impaired. A specific example of such a polymer is a polyurethane prepolymer.

[0035] Polyurethane prepolymers can be obtained by known methods, for example, by reacting a polyol compound with a polyisocyanate compound.

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

[0037] Examples of polyisocyanate compounds include diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, methylene-bis(cyclohexyl isocyanate), isophorone diisocyanate, and hexamethylene diisocyanate. Furthermore, the polyurethane prepolymer may have either a hydroxyl group or an isocyanate group at its end.

[0038] In terms of obtaining a curable composition with excellent storage stability and workability, it is particularly preferable that the reactive silicon group-containing organic polymer (A) is a polyoxyalkylene polymer that does not contain urethane bonds, urea bonds, ester bonds, or amide bonds in its main chain structure.

[0039] The reactive silicon group-containing organic polymer (A) is preferably obtained by introducing reactive silicon groups into the polymer by any of the following methods (a) to (d). (a) After converting the terminal hydroxyl groups of the hydroxyl-terminated organic polymer to carbon-carbon unsaturated groups, HSiR 1 3-a X a (In the formula, R 1 A method for reacting X and a (where X and a are the same groups shown with respect to general formula (1)).

[0040] (b) OCN-W-SiR 1 3-a X a (In the formula, W is a divalent organic group. R 1 A method for reacting an isocyanate group-containing silane compound represented by (X, and a are the same groups shown with respect to general formula (1)).

[0041] (c) After converting the terminal hydroxyl groups of the hydroxyl-terminated organic polymer to carbon-carbon unsaturated groups, HS-W-SiR 1 3-a X a (In the formula, W is a divalent organic group. R 1 A method for reacting a mercapto group-containing silane compound represented by the same group as shown in general formula (1), where X and a are the same groups.

[0042] (d) After reacting the hydroxyl-terminated organic polymer with a polyisocyanate compound to synthesize an NCO-terminated organic polymer, HNR-W-SiR 1 3-a X a(In the formula, W is a divalent organic group. R is a hydrogen atom or an alkyl group. 1 X and a are the same groups shown with respect to general formula (1)) or HS-W-SiR 1 3-a X a (In the formula, W is a divalent organic group. R 1 A method for reacting a silane compound represented by the same group as shown in relation to general formula (1), where X and a are the same groups.

[0043] 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.

[0044] In each of the above methods, the reactive silicon group-containing organic polymer (A) obtained using a silane compound in which W is represented by a methylene group is preferred in that it exhibits very high curability.

[0045] Method (a) is preferred because it tends to yield a reactive silicon group-containing organic polymer (A) with good storage stability. Methods (b), (c), and (d) are preferred because they yield a high conversion rate with a relatively short reaction time.

[0046] The introduction of reactive silicon groups by method (a) is 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, U.S. Patent No. 4960844, etc. Examples include those described in Japanese Patent Publication Nos. 61-197631, 61-215622, 61-215623, and 61-218632, which introduce reactive silicon groups to polyoxypropylene polymers 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., and those proposed in Japanese Patent Publication No. 3-72527.

[0047] The molecular weight distribution (Mw / Mn) of the reactive silicon group-containing organic polymer (A) is not particularly limited, but is preferably 1.6 or less, more preferably 1.5 or less, and particularly preferably 1.4 or less. Furthermore, from the viewpoint of improving various mechanical properties such as the durability and elongation of the cured product, it is preferably 1.2 or less.

[0048] The number-average molecular weight of the reactive silicon group-containing organic polymer (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and particularly preferably 8,000 to 35,000, as polystyrene-equivalent molecular weight in GPC. When the number-average molecular weight is within these ranges, the cured product exhibits excellent mechanical properties, and the amount of reactive silicon groups introduced is appropriate, allowing for the production of an organic polymer (A) that exhibits good curability, has an easy-to-handle viscosity, and has excellent workability while keeping manufacturing costs within a reasonable range.

[0049] The molecular weight of reactive silicon-containing organic polymer (A) can also be expressed as the end group molecular weight, determined by directly measuring the end group concentration through 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 organic polymer (degree of branching determined by the polymerization initiator used). The end group-reduced molecular weight of organic polymer (A) can also 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] To obtain a good rubber-like cured product, it is preferable that the reactive silicon groups of the organic polymer (A) are located at the ends of the polymer chains. Since this exhibits good curability and readily shows rubber elastic behavior, the number of reactive silicon groups is preferably 0.5 or more on average per polymer chain end of the organic polymer (A), more preferably 0.6 or more, even more preferably 0.7 or more, and particularly preferably 0.8 or more.

[0051] The number of polymer chain ends per molecule of organic polymer (A) is preferably 2 to 8, more preferably 2 to 4, and particularly preferably 2 or 3. The number of reactive silicon groups in one molecule of organic polymer (A) is preferably 1 to 7 on average, more preferably 1 to 3.4, and particularly preferably 1 to 2.6.

[0052] When the reactive silicon group-containing organic polymer (A) is branched, the reactive silicon group may be located at the end of the main chain, at the end of a side chain (branched chain), or both. In particular, when the reactive silicon group is at the end of the main chain, it is preferable because the molecular weight between crosslinking points becomes longer, making it easier to obtain a rubbery cured product with high strength, high elongation, and low modulus of elasticity.

[0053] As described in International Publication No. 2013 / 180203, using an organic polymer having two or more carbon-carbon unsaturated bonds at the end of one polymer chain, the organic polymer (A) obtained by the above methods (a) and (c) has two or more reactive silicon groups at the end of one polymer chain. Such organic polymer (A) exhibits high curability, and the resulting cured product can be expected to have high strength and high resilience.

[0054] Specific product examples of reactive silicon group-containing organic polymers (A) include various reactive silicon group-containing polyoxypropylene products from Kaneka Corporation under the trademark names Kaneka MS Polymer or Kaneka Cyril, reactive silicon group-containing poly(meth)acrylic acid esters such as Kaneka TA Polymer or Kaneka XMAP, and reactive silicon group-containing polyisobutylene such as Kaneka EPION.

[0055] (Curing catalyst (B)) The curable composition according to this disclosure contains a curing catalyst (B) used to hydrolyze and condense the reactive silicon groups of an organic polymer (A) to form a cured product. The curing catalyst (B) contains a tin carboxylate compound (b1), a cyclic secondary amine compound (b2), and a β-dicarbonyl compound (b3). This makes it possible to provide a curable composition that exhibits improved curability and a low modulus after curing.

[0056] (Tin carboxylate compound (b1)) The tin carboxylate compound (b1) is preferably a tin salt of a carboxylic acid having one or more (preferably one) carboxyl groups (-COOH) in one molecule and 1 to 30 (preferably 2 to 20, more preferably 6 to 12) carbon atoms.

[0057] Specific examples of carboxylic acid compounds are not particularly limited, but aliphatic monocarboxylic acids include linear saturated fatty acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, and tridecyl acid; monoen unsaturated fatty acids such as acrylic acid and methacrylic acid; polyene unsaturated fatty acids; 2-methylbutyric acid, isobutyric acid, 2-ethylbutyric acid, pivalic acid, 2,2-dimethylbutyric acid, 2-ethyl-2-methylbutyric acid, and 2,2-dimethylbutyric acid. 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, octic acid, 2-ethylhexanoic acid, 2,2-dimethylhexanoic acid, neononanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, versatic acid, and neodecanoic acid; fatty acids with triple bonds; alicyclic carboxylic acids; oxygen-containing fatty acids; halogen-substituted monocarboxylic acids. Aliphatic dicarboxylic acids include chain-like dicarboxylic acids such as adipic acid, sebacic acid, oxalic acid, malonic acid, and succinic acid, as well as saturated dicarboxylic acids and unsaturated dicarboxylic acids. Examples of aliphatic polycarboxylic acids include chain-like tricarboxylic acids such as aconitic acid, citric acid, isocitric acid, 3-methylisocitric acid, and 4,4-dimethylaconitic acid.

[0058] Examples of aromatic carboxylic acids include aromatic monocarboxylic acids such as benzoic acid and salicylic acid; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid; and halogen-substituted aromatic carboxylic acids such as chlorobenzoic acid. In addition, carboxylic acid derivatives that produce carboxylic acids by hydrolysis of carboxylic acid anhydrides, esters, amides, nitriles, and acyl chlorides can also be used.

[0059] As the carboxylic acid compound, monocarboxylic acids are preferred, and fatty acid monocarboxylic acids are particularly preferred. As carboxylic acid compounds, carboxylic acids in which the carbon atom adjacent to the carbonyl group is a tertiary carbon (such as 2-ethylhexanoic acid) or a quaternary carbon (such as neodecanoic acid and pivalic acid) are preferred due to their fast curing rate, and carboxylic acids in which the carbon atom adjacent to the carbonyl group is a quaternary carbon are particularly preferred.

[0060] The tin that constitutes the tin carboxylate compound (b1) is not particularly limited as long as it is a tin that can form a salt with a carboxylic acid, and divalent tin or tetravalent tin can be used. From the viewpoint of improving resilience, divalent tin is preferred.

[0061] Specific examples of tin carboxylate compounds (b1) include, for example, divalent tin compounds such as tin octoate, tin neodecanoate, tin 2-ethylhexanoate, tin stearate, tin naphthenate, tin versatate, and tin pivalate; and tetravalent tin compounds such as dibutyltin dilaurate, dibutyltin maleate, and dibutyltin diacetate. One type of tin carboxylate compound (b1) may be used, or multiple compounds may be used in combination.

[0062] (Cyclic secondary amine compound (b2)) A cyclic secondary amine compound (b2) refers to a heterocyclic amine compound having a cyclic secondary amine skeleton and an NH group. By using (b2), the cured product can maintain good resilience, the curable composition can exhibit good curability, and the decrease in curability after storage can be suppressed.

[0063] The aforementioned cyclic secondary amine skeleton is a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, or an azepane skeleton. Among these, from the viewpoint of curability, the piperidine skeleton, piperazine skeleton, or azepane skeleton is preferred, the piperidine skeleton or azepane skeleton is more preferred, and the piperidine skeleton is particularly preferred. The cyclic secondary amine compound (b2) may be a single compound or a combination of multiple compounds.

[0064] The cyclic secondary amine compound (b2) may be a compound that does not have substituents on the carbon atoms of the cyclic secondary amine skeleton, or it may be a compound that has substituents. Examples of substituents include hydrocarbon groups, ester groups, and hydroxyl groups having 1 to 20 carbon atoms. The hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. The hydrocarbon group may also have substituents such as halogen atoms, ester groups, and hydroxyl groups.

[0065] Because it is highly effective in improving storage stability and its curability does not decrease easily even after storage, the cyclic secondary amine compound (b2) is preferably a compound having an ester group or a hydroxyl group.

[0066] A cyclic secondary amine compound (b2) having an ester group or a hydroxyl group can be represented, for example, by the following general formula (3) or (4). R 3 -R 4 -C(=O)-OR 5 (3) R 3 -R 4 -OH (4) In equations (3) and (4), R 3R represents a cyclic secondary amine skeleton. 4 R represents a directly bonded, substituted, or unsubstituted divalent hydrocarbon group with 1 to 20 carbon atoms. 5 This represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0067] R 3 The cyclic secondary amine skeleton represented by represents one of the following: pyrrolidine skeleton, piperidine skeleton, piperazine skeleton, or azepane skeleton. The carbon atoms constituting the ring of the cyclic secondary amine are R 4 It is preferable that the cyclic secondary amine skeleton is bonded to the ring, with -R 4 -C(=O)-OR 5 The group may have substituents other than those represented by , or it may not have substituents. Examples of substituents include hydrocarbon groups having 1 to 20 carbon atoms, halogen atoms, ester groups, hydroxyl groups, etc.

[0068] R 4 This represents a directly bonded, substituted, or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The hydrocarbon group may be aliphatic, alicyclic, or aromatic, but is preferably aliphatic. The hydrocarbon group may or may not have substituents such as halogen atoms, ester groups, or hydroxyl groups.

[0069] R 5 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The hydrocarbon group may be aliphatic, alicyclic, or aromatic, but is preferably aliphatic. The hydrocarbon group may or may not have substituents such as halogen atoms or hydroxyl groups.

[0070] The molecular weight of the cyclic secondary amine compound (b2) is not particularly limited, but may be, for example, around 100 to 1000. It may also be 120 to 500 or 150 to 200.

[0071] Specific examples of cyclic secondary amine compounds (b2) having an ester group include ester compounds of piperidinecarboxylic acids such as 4-piperidinecarboxylic acid, 2-piperidinecarboxylic acid, and 3-piperidinecarboxylic acid, and ester compounds of pyrrolidinecarboxylic acids such as 2-pyrrolidinecarboxylic acid. Specific examples of the ester compounds include methyl esters, ethyl esters, and propyl esters, but ethyl esters are particularly preferred from the viewpoint of curability.

[0072] From the viewpoint of availability, compatibility with organic polymer (A), and improved curability, ester compounds of piperidinecarboxylic acid are preferred, ester compounds of 4-piperidinecarboxylic acid are more preferred, methyl 4-piperidinecarboxylate and ethyl 4-piperidinecarboxylate are even more preferred, and ethyl 4-piperidinecarboxylate is particularly preferred.

[0073] Specific examples of cyclic secondary amine compounds (b2) having a hydroxyl group include hydroxypiperidines such as 4-hydroxypiperidine and 3-hydroxypiperidine, piperidine methanols such as 3-piperidine methanol, and piperidine ethanol.

[0074] Specific examples of cyclic secondary amine compounds (b2) that do not have an ester group or a hydroxyl group include pyrrolidine, piperidine, piperazine, azepane (hexamethyleneimine), methylpiperidine such as 4-methylpiperidine, dimethylpiperidine such as 3,5-dimethylpiperidine, and N-substituted piperazine such as N-methylpiperazine.

[0075] (β-Dicarbonyl compound (b3)) A β-dicarbonyl compound is a compound that has a structure in which two carbonyl groups are bonded with one carbon atom in between. The specific types of β-dicarbonyl compounds are not particularly limited as long as they have the above-mentioned structure, but examples include β-diketones, β-ketoesters, β-diesters, and the like.

[0076] Examples of the β-diketones include acetylacetone, trifluoroacetylacetone, 3-phenylacetylacetone, 1-phenyl-1,3-butanedione, 2,4-pentanedione, 2,4-hexanedione, 2,4-heptanedione, 2,4-pentadecanedione, dibenzoylmethane, 1,3-cyclohexanedionedimedone, cyclohexane-1,3-dione, and 2,2,6,6-tetramethyl-3,5-heptanedione. Examples include: 1-aryl-1,3-butanediones such as 1-phenyl-1,3-butanedione and 1-(4-methoxyphenyl)-1,3-butanedione; 1,3-diaryl-1,3-propanediones such as 1,3-diphenyl-1,3-propanedione, 1,3-bis(2-pyridyl)-1,3-propanedione and 1,3-bis(4-methoxyphenyl)-1,3-propanedione; and 3-benzyl-2,4-pentanedione. Among these, acetylacetone is preferred.

[0077] Examples of the β-ketoester include acetoacetates such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, and butyl acetoacetate; and methyl pivaloylacetate, methyl isobutyroylacetate, methyl caproylacetate, and methyl lauroylacetate. Among these, acetoacetates are preferred, methyl acetoacetate, ethyl acetoacetate, and propyl acetoacetate are more preferred, and ethyl acetoacetate is particularly preferred.

[0078] Examples of the β-diester include dimethyl malonate, diethyl malonate, diphenyl malonate, and meldrumic acid.

[0079] Examples of the β-ketoamide include N,N-dimethylacetacetamide, N,N-diethylacetacetamide, acetacetanilide, and N-methyl-3-oxo-N-phenylbutanamide.

[0080] As the β-dicarbonyl compound (b3), β-diketones and β-ketoesters are preferred from the viewpoint of improving curability and / or lowering the modulus, and β-ketoesters are more preferred.

[0081] When preparing the curable composition according to this disclosure, the tin carboxylate compound (b1), the cyclic secondary amine compound (b2), and the β-dicarbonyl compound (b3) may be added to and mixed individually with the organic polymer (A) without prior mixing.

[0082] However, from the viewpoint of catalytic activity, it is preferable to pre-mix (b1) to (b3) before adding them to the organic polymer (A). Pre-mixing (b1) to (b3) facilitates the formation of a complex through the interaction between (b1) and (b3). When this complex is mixed with the organic polymer (A), the curability can be further improved. Furthermore, by using a curing catalyst (B) obtained by mixing (b1) to (b3), it is possible to suppress the bleeding out of the curing catalyst from the surface of the cured product through the interaction between (b1) and (b3).

[0083] The method of mixing (b1) to (b3) is not particularly limited, but it is sufficient to mix (b1) to (b3) at room temperature or at a temperature below the decomposition temperature of each component and stir. The mixing may be carried out without a solvent, or in the presence of a solvent that is inert to both components. Furthermore, the mixing may be carried out in an inert gas atmosphere (nitrogen gas, argon gas) or in the presence of air. The time for mixing with stirring is not particularly limited, but for example, it may be from 1 hour to 3 days.

[0084] The order of mixing is not particularly limited, and (b1) to (b3) may be mixed simultaneously, but it is preferable to first mix (b1) and (b2) and then add and mix (b3). In this case, it is preferable to add (b3) after the exothermic reaction between (b1) and (b2) has subsided.

[0085] In a preferred embodiment, (b1) to (b3) can be pre-mixed to form a complex of (b1) to (b3). The term "complex" refers to a state in which (b1) to (b3) do not exist independently of each other, but rather a reaction proceeds to which two or more of (b1) to (b3) are combined, or the structure of any of (b1) to (b3) is altered. The complex can be formed by mixing (b1) to (b3) under stirring using the method described above. When mixed under stirring, the mixture becomes viscous and generates heat, thereby confirming the formation of the complex.

[0086] The curing catalyst (B) may consist only of a tin carboxylate compound (b1), a cyclic secondary amine compound (b2), and a β-dicarbonyl compound (b3), but may further contain a diluent. Using a diluent improves the handling properties of the curing catalyst (B), further improves the dispersibility of the curing catalyst (B) in the organic polymer (A), and improves the curability of the curable composition. Suitable diluents include solvents and plasticizers. Among these, plasticizers are preferred, ester group-containing plasticizers are more preferred, and phthalate ester compounds are particularly preferred. Specific examples of plasticizers are described below.

[0087] The diluent can be added before, during, or after the formation of the complex of (b1) to (b3). In particular, it is preferable to add it after the formation of the complex of (b1) to (b3).

[0088] The amount of diluent used can be set as appropriate, but the weight of the diluent relative to the total amount of (b1) to (b3) is preferably 0.1 to 10, more preferably 0.5 to 5, and even more preferably 1 to 3.

[0089] In the curable composition according to this disclosure, the content of the curing catalyst (B) can be appropriately determined considering the desired curability and the workability of the curable composition. For example, it may be about 0.001 to 20 parts by weight, preferably 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 1 to 8 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A). However, if the curing catalyst (B) contains the above-mentioned diluent, the amount of the diluent should not be included when calculating the content of the curing catalyst (B).

[0090] The ratio of the tin carboxylate compound (b1) to the cyclic secondary amine compound (b2) can be set as appropriate, but the weight ratio of (b2) to (b1) [(b2) / (b1)] may be 0.01 to 5. From the viewpoint of resilience, curability, and storage stability, it is preferably 0.05 to 1, more preferably 0.1 to 0.8, and even more preferably 0.2 to 0.5.

[0091] The ratio of the tin carboxylate compound (b1) to the β-dicarbonyl compound (b3) can be set as appropriate, but the weight ratio of (b3) to (b1) [(b3) / (b1)] may be 0.01 to 5. From the viewpoint of resilience, curability, and storage stability, it is preferably 0.05 to 1, more preferably 0.1 to 0.8, and even more preferably 0.2 to 0.5.

[0092] The curable composition according to this disclosure may further contain curing catalysts other than curing catalyst (B). Examples of such curing catalysts include metal carboxylate salts other than tin carboxylate compounds (b1), amine compounds other than cyclic secondary amine compounds (b2), carboxylic acids, metal alkoxides, and inorganic acids.

[0093] The content of curing catalysts other than curing catalyst (B) is not particularly limited and may be set as appropriate, but for example, it may be 0 to 10 parts by weight, or 0 to 5 parts by weight, or 0 to 3 parts by weight, or 0 to 1 part by weight, per 100 parts by weight of reactive silicon group-containing organic polymer (A).

[0094] The curable composition according to this embodiment may also contain other additives such as silicon compounds, adhesion promoters, plasticizers, solvents, diluents, silicates, fillers, anti-sagging agents, antioxidants, light stabilizers, UV absorbers, property modifiers, tackifying resins, compounds containing epoxy groups, photocurable substances, oxygen-curable substances, surface modifiers, epoxy resins, other resins, flame retardants, and foaming agents. Furthermore, the curable composition according to this embodiment may contain various additives as needed to adjust the properties of the composition or the cured product. Examples of such additives include curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments, and antifungal agents.

[0095] (Filler) Various fillers can be incorporated into the curable composition according to this embodiment. Examples of fillers include heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium dioxide, fumed silica, settling silica, crystalline silica, fused silica, anhydrous silicic acid, hydrated silicic acid, carbon black, ferric oxide, aluminum powder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fibers, and filaments.

[0096] The amount of filler used is preferably 1 to 300 parts by weight, and more preferably 10 to 250 parts by weight, per 100 parts by weight of the polymer according to this embodiment.

[0097] Organic balloons and inorganic balloons may be added to reduce the weight (lower specific gravity) of the composition. The balloons are spherical fillers with a hollow interior, and examples of materials for these balloons include inorganic materials such as glass, shirasu (volcanic ash), and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran.

[0098] The amount of balloon used is preferably 0.1 to 100 parts by weight, and more preferably 1 to 20 parts by weight, per 100 parts by weight of the polymer according to this embodiment.

[0099] (Adhesion-enhancing agent) Adhesion-imparting agents may be added to the curable composition according to this embodiment. As adhesion-imparting agents, silane coupling agents and reaction products of silane coupling agents may be added. Specific examples of silane coupling agents include amino group-containing silanes such as γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; as well as γ-isocyanatetopropyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane, and γ-iso Examples include isocyanate group-containing silanes such as cyanate-propylmethyldimethoxysilane, α-isocyanate-methyltrimethoxysilane, and α-isocyanate-methyldimethoxymethylsilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; and epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. In addition, condensates of various silane coupling agents, such as condensates of amino group-containing silanes and condensates of amino group-containing silanes and other alkoxysilanes; and reaction products of various silane coupling agents, such as reaction products of amino group-containing silanes and epoxy group-containing silanes and reaction products of amino group-containing silanes and (meth)acrylic group-containing silanes, can also be used. The above adhesion-imparting agents may be used individually or in combination of two or more types.

[0100] 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 the polymer according to this embodiment.

[0101] (Plasticizer) A plasticizer may be added to the curable composition according to this embodiment. Specific examples of plasticizers include phthalate ester compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate ester compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; non-phthalate ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; aliphatic polycarboxylic acid ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkyl sulfonate phenyl esters; phosphate ester compounds; trimellitic acid ester compounds; chlorinated paraffin; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; and epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

[0102] Furthermore, polymeric plasticizers can be used. Specific examples of polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol with a number average molecular weight of 500 or more, and polyethers such as derivatives obtained by converting the hydroxyl groups of these polyether polyols to ester groups, ether groups, etc.; polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, etc. Plasticizers may be used alone or in combination of two or more types.

[0103] 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 the polymer according to this embodiment.

[0104] (Solvents, diluents) A solvent or diluent may be added to the curable composition according to this embodiment. The solvent and diluent are not particularly limited, but aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, etc., can be used. When a solvent or diluent is used, 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, due to concerns about air pollution when the composition is used indoors. The above solvents or diluents may be used alone or in combination of two or more.

[0105] (Drip prevention agent) The curable composition according to this embodiment may contain, if necessary, an anti-sagging agent to prevent sagging and improve workability. The anti-sagging agent is not particularly limited, but examples include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents may be used individually or in combination of two or more.

[0106] The amount of anti-slip agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of the polymer according to this embodiment.

[0107] (Antioxidant) The curable composition according to this embodiment may contain an antioxidant (anti-aging agent). Using an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of antioxidants are also described in 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 the polymer according to this embodiment.

[0108] (Light stabilizer) A light stabilizer can be used in the curable composition according to this embodiment. Using a light stabilizer can prevent photo-oxidative degradation of the cured product. Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds, but hindered amine-based compounds are particularly preferred.

[0109] 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 the polymer according to this embodiment.

[0110] (UV absorber) A UV absorber can be used in the curable composition according to this embodiment. Using a UV absorber can improve the surface weather resistance of the cured product. Examples of UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, and metal chelate compounds. Benzotriazole-based compounds are particularly preferred, and examples include those with commercial names such as Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571, Tinuvin 1600, and Tinuvin B75 (all manufactured by BASF). The amount of ultraviolet 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 the polymer according to this embodiment.

[0111] (Property modifier) The curable composition according to this embodiment may contain a property modifier to adjust the tensile properties of the resulting cured product as needed. The property modifier is not particularly limited, but examples include alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilyl borates such as tris(trimethylsilyl)borate and tris(triethylsilyl)borate; silicone varnishes; and polysiloxanes. By using the above property modifier, the hardness of the curable composition according to this embodiment can be increased or decreased, resulting in increased elongation at break. The above property modifiers may be used alone or in combination of two or more.

[0112] In particular, compounds that produce compounds having a monovalent silanol group in their molecule upon hydrolysis have the effect of reducing the modulus of the cured product without worsening the stickiness of the surface of the cured product. Compounds that produce trimethylsilanol are especially preferred. Examples of compounds that produce compounds having a monovalent silanol group in their molecule upon hydrolysis include silicon compounds that are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol and produce silane monool upon hydrolysis. Specifically, examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.

[0113] The amount of property modifier used is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the polymer according to this embodiment.

[0114] (Adhesive-forming resin) The curable composition according to this embodiment may contain a tackifying resin to enhance adhesion to the substrate or as needed. There are no particular restrictions on the tackifying resin; commonly used resins can be used.

[0115] Specific examples 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 and their hydrogenated products, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, etc. These may be used individually or in combination of two or more types.

[0116] 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 the polymer according to this embodiment.

[0117] (Compounds containing epoxy groups) In the curable composition according to this embodiment, compounds containing epoxy groups can be used. 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, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, examples include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarbonoxylate (E-PS), epoxyoctyl stearate, epoxybutyl stearate, and the like. The epoxy compound is preferably used in an amount of 0.5 to 50 parts by weight per 100 parts by weight of the polymer according to this embodiment.

[0118] (light curing substance) A photocurable substance can be used in the curable composition according to this embodiment. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, improving the stickiness and weather resistance of the cured product. Many types of compounds of this kind are known, including organic monomers, oligomers, resins, or compositions containing them. Typical examples include unsaturated acrylic compounds, vinyl polycinnamates, or azidized resins, which are monomers, oligomers, or mixtures thereof having one or more acrylic or methacrylic unsaturated groups.

[0119] 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 the polymer according to this embodiment.

[0120] (oxygen curing substance) The curable composition according to this embodiment can use an oxygen-curable substance. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air. These react with oxygen in the air to form a cured film near the surface of the cured product, preventing 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, and various alkyd resins obtained by modifying these compounds; acrylic polymers, epoxy resins, and silicone resins modified with drying oils; and liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and polymers of C5-C8 dienes obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene. These may be used individually or in combination of two or more.

[0121] The amount of oxygen-curable substance used is preferably in the range of 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer according to this embodiment. As described in Japanese Patent Publication No. 3-160053, the oxygen-curable substance is preferably used in combination with the photocurable substance.

[0122] (Epoxy resin) An epoxy resin can be used in combination with the curable composition according to this embodiment. Compositions with added epoxy resin are particularly preferred as adhesives, especially adhesives for exterior wall tiles. Examples of epoxy resins include bisphenol A type epoxy resins or novolac type epoxy resins.

[0123] The ratio of epoxy resin to polymer according to this embodiment is preferably in the range of polymer / epoxy resin = 100 / 1 to 1 / 100 by weight. If the polymer / epoxy resin ratio according to this embodiment is less than 1 / 100, it becomes difficult to obtain the effect of improving the impact strength and toughness of the epoxy resin cured product, and if the polymer / epoxy resin ratio according to this embodiment exceeds 100 / 1, the strength of the polymer cured product becomes insufficient.

[0124] When an epoxy resin is added, a curing agent for curing the epoxy resin can be used in combination with the curable composition according to this embodiment. There are no particular restrictions on the epoxy resin curing agent that can be used; commonly used epoxy resin curing agents can be used.

[0125] When using a curing agent for epoxy resin, the amount used is preferably in the range of 0.1 to 300 parts by weight per 100 parts by weight of epoxy resin.

[0126] <<Preparation of Curable Composition>> The curable composition according to this embodiment can also be prepared as a one-component type, where all components are pre-mixed and sealed for storage, and cured by moisture in the air after application. Alternatively, it can be prepared as a two-component type, where components such as a curing catalyst, filler, plasticizer, and water are separately mixed as a curing agent, and these components are mixed with the organic polymer composition before use. However, since the curable composition according to this disclosure has excellent storage stability, it can preferably be configured as a one-component type curable composition.

[0127] 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 reducing pressure. 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.

[0128] (Application) The curable composition according to this disclosure can be used as a building sealant, industrial adhesive, waterproof coating, or adhesive raw material. It can also be used as a sealant for buildings, ships, automobiles, roads, etc. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, and resin molded products, either alone or with the help of a primer, it can also be used as various types of sealing and adhesive compositions. In addition to being an ordinary adhesive, it can also be used as a contact adhesive. Furthermore, it is useful as a food packaging material, casting rubber material, molding material, and paint.

[0129] The following sections list preferred embodiments of this disclosure, but the present invention is not limited to these sections. [Item 1] A curable composition containing an organic polymer (A) having a reactive silicon group and a curing catalyst (B), The aforementioned reactive silicon group is defined by general formula (1): -SiR 1 3-a X a (1) (In the formula, R 1 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R 0 Represents a triorganosiloxy group represented as 3SiO-. 3 R 0represents a hydrocarbon group having 1 to 20 carbon atoms, either identical or different. X represents a hydroxyl group or a hydrolyzable group. a represents 1, 2, or 3. R 1 Or, if there are multiple X's, they may be the same or different. ) The curing catalyst (B) comprises a tin carboxylate compound (b1), a cyclic secondary amine compound (b2), and a β-dicarbonyl compound (b3). A curable composition wherein the cyclic secondary amine compound (b2) has one or more skeletons selected from the group consisting of a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, and an azepane skeleton. [Item 2] The curable composition according to item 1, wherein the weight ratio of the cyclic secondary amine compound (b2) to the tin carboxylate compound (b1) is 0.1 to 0.8. [Item 3] The curable composition according to item 1 or 2, wherein the weight ratio of the β-dicarbonyl compound (b3) to the tin carboxylate compound (b1) is 0.1 to 0.8. [Item 4] The curable composition according to any one of items 1 to 3, wherein the curing catalyst (B) comprises a composite of the tin carboxylate compound (b1), the cyclic secondary amine compound (b2), and the β-dicarbonyl compound (b3). [Item 5] A method for producing a curable composition containing an organic polymer (A) having a reactive silicon group and a curing catalyst (B), Tin carboxylate compound (b1), A cyclic secondary amine compound (b2) having one or more skeletons selected from the group consisting of a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, and an azepane skeleton, A step of mixing with a β-dicarbonyl compound (b3) to obtain a curing catalyst (B); and A method for producing a product, comprising the step of mixing the curing catalyst (B) with an organic polymer (A) having a reactive silicon group represented by the general formula (1). [Examples]

[0130] The present invention will be described in more detail below with reference to specific examples, but the present invention is not limited to the following examples.

[0131] The number-average molecular weight in the examples is the GPC molecular weight measured under the following conditions. Liquid delivery system: Tosoh HLC-8120GPC Column: Tosoh TSKgel SuperH series Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40℃

[0132] The average number of silyl groups per terminal or per molecule of the polymers shown in the examples was calculated by 1H-NMR (measured in CDCl3 solvent using a Bruker AVANCE III HD-500).

[0133] <Synthesis of organic polymer (A)> (Synthesis example 1 (A-1)) Using polyoxypropylenediol with a molecular weight of approximately 2,000 as an initiator, propylene oxide was polymerized using a zinc hexacyanocobaltate grime complex catalyst to obtain polypropylene oxide with a number average molecular weight of approximately 28,500. Subsequently, 1.0 equivalent of a methanol solution of NaOMe was added to the hydroxyl groups of this hydroxyl-terminated polypropylene oxide, and the methanol was removed by distillation at 140°C. Then, 1.0 equivalent of allyl glycidyl ether was added and the reaction was carried out for 2 hours. Furthermore, allyl chloride was added to convert the terminal hydroxyl groups to allyl groups. As a result, an allyl polymer with multiple allyl groups at the terminals and a number average molecular weight of approximately 28,500 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, and the water was removed by centrifugation. Another 300 parts by weight of water was mixed and stirred into the obtained hexane solution, and the water was removed again by centrifugation, after which the hexane was removed by vacuum defoliation. The obtained allyl polymer was reacted with 0.8 molar equivalents of methyldimethoxysilane at 90°C for 5 hours using a 150 ppm isopropanol solution of a platinum vinylsiloxane complex with a platinum content of 3 wt% as a catalyst, to obtain methyldimethoxysilyl-terminated polypropylene oxide (A-1). The number of methyldimethoxysilyl groups was approximately 1.5 per polymer chain end.

[0134] (Synthesis example 2 (A-2)) A mixture of polyoxypropylene glycol with a number-average molecular weight of 14,600 and n-butanol in a weight ratio of 10:1 was used as an initiator, and polymerization of propylene oxide was carried out using a zinc hexacyanocobaltate grime complex catalyst to obtain a mixture of polypropylene oxides with a number-average molecular weight of 7,700 (polyoxypropylene glycol monobutyl ether with a number-average molecular weight of 6,500 and polyoxypropylene glycol with a number-average molecular weight of 18,000 (weight ratio of 9:1)). Subsequently, a methanol solution of NaOMe equivalent to 1.2 times the volume of the hydroxyl groups of this polypropylene oxide containing hydroxyl groups was added, and the methanol was removed by distillation. Furthermore, allyl chloride was added to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by vacuum defoliation to obtain unpurified polypropylene oxide containing allyl groups. To 100 parts by weight of the obtained unpurified polypropylene oxide having allyl groups, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred, and the water was removed by centrifugation. Another 300 parts by weight of water was mixed and stirred into the obtained hexane solution, and the water was removed again by centrifugation. Then, the hexane was removed from the obtained hexane solution by vacuum defloration. As a result, a mixture of polyoxypropylene polymers was obtained in which the main component was a component in which an allyl group was introduced only at one end, and the number average molecular weight in terms of polystyrene in GPC was approximately 7,700. To 100 parts by weight of the obtained polyoxypropylene polymer having allyl groups, 1.9 parts by weight of dimethoxymethylsilane was reacted with 1.9 parts by weight of dimethoxymethylsilane at 90°C for 2 hours using 36 ppm of an isopropanol solution of a platinum vinylsiloxane complex with a platinum content of 3 wt% as a catalyst to obtain polyoxypropylene polymer (A-2) having an average of 0.9 dimethoxymethylsilyl groups per molecule. Furthermore, the number-average molecular weight of the obtained polyoxypropylene polymer (A-2), calculated using GPC (Glycerin Propagation), was 7,700 in terms of polystyrene.

[0135] <Manufacturing of curing catalyst (B)> The compounds listed below were used in the preparation of complexes 1 to 11.

[0136] Tin carboxylate compounds (b1) U-28: Bis(neodecanoate)tin(II), (manufactured by Nitto Kasei Co., Ltd.) U-50: Tin(II) bis(octylate), (manufactured by Nitto Kasei Co., Ltd.)

[0137] Cyclic secondary amine (b2) 4-Methylpiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0138] Other amines N,N-diethyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0139] β-Dicarbonyl compound (b3) Ethyl acetoate (manufactured by Tokyo Chemical Industry Co., Ltd.) Acetylacetone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0140] <Production example 1 (complex 1)> 30 g of U-28 was added to a 100 ml round-bottom flask. While stirring the contents of the flask, 10 g of 4-methylpiperidine was slowly added dropwise to the flask. After the heat subsided, 10 g of ethyl acetoethyl was added and the mixture was stirred at room temperature for 2 hours to obtain 50 g of liquid complex 1.

[0141] <Production examples 2 to 11 (complexes 2 to 11)> Liquid complexes 2 to 11 were obtained in the same manner as in Production Example 1, except that the tin carboxylate compound (b1), cyclic secondary amine (b2) or other amine, and β-dicarbonyl compound (b3) listed in Table 1 were used in the weight ratios listed in Table 1.

[0142] [Table 1]

[0143] (Example 1) To 80 parts by weight of reactive silicon group-containing organic polymers (A-1) and 20 parts by weight of (A-2), the following were added in the amounts (parts by weight) shown in Table 2: colloidal calcium carbonate (Viscolite EL20), heavy calcium carbonate (Whiten SB), plasticizer DINP (manufactured by J-Plus Co., Ltd.), pigment (Typake R820), thixotropic agent (Crayvallac SL), antioxidant (Irganox 1010), UV absorber (Tinuvin 326), and light stabilizer (Tinuvin 770). After mixing with a spatula, the mixture was dispersed by passing it through a three-roll mill three times. Next, dehydration was performed under reduced pressure using a planetary mixer, and after cooling to below 50°C, 5 parts by weight of vinyltrimethoxysilane (manufactured by EVONIK, trade name: DynasylanVTMO) as a dehydrating agent and 3 parts by weight of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (manufactured by EVONIK, trade name: DynasylanDAMO) as an adhesion promoter were added to the resulting mixture and mixed. Subsequently, 5 parts by weight of Composite 1 was added to the resulting mixture as a curing catalyst, and the mixture was kneaded in a substantially moisture-free state to obtain the composition. The obtained composition was then sealed in a moisture-proof container, a cartridge, to obtain a one-component curable composition.

[0144] (evaluation) (Skinning time (hardening)) Each curable composition was stored at 23°C for 7 days in an atmosphere of 50% relative humidity. The resulting curable composition was then filled into a mold approximately 5 mm thick using a spatula, and the time it took to flatten the surface was defined as the curing start time. The time it took for the composition to no longer adhere to the spatula when touched was measured. The results are shown in Table 2 as "initial skinning time" (curing time). Furthermore, the curable composition was stored at 23°C for 7 days, then at 50°C for 28 days, and finally at 23°C for 1 day. Subsequently, the "skinning time after storage" (curing properties) was measured using the method described above. The obtained results are shown in Table 2 as "skinning time after storage".

[0145] (Tensile properties of dumbbells) Each curable composition was filled into a 3 mm thick sheet-like mold under constant temperature and humidity conditions of 23°C and 50% relative humidity. After curing at 23°C and 50% RH for 3 days, the mixture was cured in a 50°C dryer for 4 days to obtain a sheet-like cured product. The resulting hardened material was punched out into a No. 3 dumbbell shape according to JIS K 6251, and a tensile test (tensile speed 200 mm / min) was performed using an autograph to measure the stress at 50% elongation, stress at 100% elongation, stress at fracture, and elongation at fracture. The results are shown in Table 2.

[0146] (Tensile properties of H-type test specimens) Mortar or aluminum substrates were used as the adherends, and a commercially available primer (Sunrise Co., Ltd., product name: 1-component modified silicone LM dedicated primer) was used as the primer. Mortar or aluminum H-shaped test specimens with a joint width of 12 mm were prepared, and after curing at 23°C for 28 days (50% RH), measurements were taken according to the ISO 11600 standard for building sealants. The results are shown in Table 2.

[0147] (Adhesive failure state of H-type test specimen after tensile stress) CF: Cohesive failure of sealant, AF: Interfacial failure.

[0148] (Elastic recovery rate) The elastic recovery rate was measured for the one-component curable composition obtained above, according to the test procedure of JIS A1439 (2016 edition) 5.2 Elastic recovery test. Specifically, an H-shaped test specimen with a joint width of 12 mm was prepared using a mortar board as the substrate and a commercially available primer (Sunrise Co., Ltd., product name: 1-component modified silicone LM dedicated primer) as the primer, and cured at 23°C for 28 days (50% RH). After that, the H-shaped test specimen was held at 23°C for 24 hours with the joint width stretched to 100%. Then, the H-shaped test specimen was released at 23°C and left to stand on a float glass plate. The recovery rate after 1 hour was measured. The results are shown in Table 2. A higher recovery rate indicates better recovery performance.

[0149] (Comparative Example 1) Curable compositions were prepared and evaluated using the same method as in Example 1, except that the type of composite was changed as shown in Table 2. The results are shown in Table 2.

[0150] [Table 2]

[0151] (result) The curable composition of Example 1, which used complex 1 containing a tin carboxylate compound (b1), a cyclic secondary amine (b2), and a β-dicarbonyl compound (b3), showed improved curability compared to the curable composition of Comparative Example 1, which used complex 7 that did not contain the β-dicarbonyl compound (b3). Furthermore, surprisingly, the modulus decreased after curing. When using a curable composition as a sealant, a low modulus is a desirable property. Furthermore, the curable composition of Example 1 exhibited good storage stability, and the cured product obtained by curing the composition showed good tensile properties, adhesive properties, and elastic recovery properties.

[0152] (Example 2, Comparative Example 2) A curable composition was prepared and evaluated using the same method as in Example 1, except that the type of composite was changed as shown in Table 3. The results are shown in Table 3.

[0153] [Table 3]

[0154] (result) The curable composition of Example 2, which used complex 6 containing a tin carboxylate compound (b1), a cyclic secondary amine (b2), and a β-dicarbonyl compound (b3), showed improved curability and a lower modulus after curing compared to the curable composition of Comparative Example 2, which used complex 8 that did not contain the β-dicarbonyl compound (b3). Furthermore, the curable composition of Example 2 exhibited good storage stability, and the cured product obtained by curing the composition showed good tensile properties, adhesive properties, and elastic recovery properties.

[0155] (Comparative Examples 3-4) Curable compositions were prepared and evaluated using the same method as in Example 1, except that the type of composite was changed as shown in Table 4. The results are shown in Table 4.

[0156] [Table 4]

[0157] (result) The curable composition of Comparative Example 3, which used a composite 10 containing a tin carboxylate compound (b1), an amine other than a cyclic secondary amine (b2), and a β-dicarbonyl compound (b3), showed significantly reduced curability compared to the curable composition of Example 1 in Table 2. This indicates that the use of a cyclic secondary amine (b2) is essential to achieve improved curability. Furthermore, when Comparative Example 3 was compared with Comparative Example 4, which was under the same conditions except for the absence of the β-dicarbonyl compound (b3), no improvement in curability was observed due to the use of the β-dicarbonyl compound (b3), nor was there any change in the modulus after curing. From this, it can be seen that the effects of improved curability and lower modulus by the curable composition according to this disclosure are unique to the use of the β-dicarbonyl compound (b3) in combination with the cyclic secondary amine (b2), and cannot be achieved when the β-dicarbonyl compound (b3) is used in combination with amines other than (b2).

[0158] (Examples 3-6) Curable compositions were prepared and evaluated using the same method as in Example 1, except that the type of composite was changed as shown in Table 5. The results are shown in Table 5.

[0159] [Table 5]

[0160] (result) The curable compositions of Examples 3 to 6, which used composites 2 to 5 containing a tin carboxylate compound (b1), a cyclic secondary amine (b2), and a β-dicarbonyl compound (b3), all showed improved curability and a lower modulus after curing compared to Comparative Example 1 in Table 2. Furthermore, the curable compositions of Examples 3 to 6 exhibited good storage stability, and the cured products obtained by curing these compositions showed good tensile properties, adhesive properties, and elastic recovery properties.

Claims

1. A curable composition comprising an organic polymer (A) having a reactive silicon group and a curing catalyst (B), The reactive silicon group is defined by general formula (1): -SiR １ ３－ａ X ａ (1) (In the formula, R １ R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or ０ ３ Represents a triorganosiloxy group represented by SiO-. Three R ０ represents a hydrocarbon group having 1 to 20 carbon atoms, either identical or different. X represents a hydroxyl group or a hydrolyzable group. a represents 1, 2, or 3. R １ Or, if there are multiple X's, they may be the same or different.) The curing catalyst (B) comprises a tin carboxylate compound (b1), a cyclic secondary amine compound (b2), and a β-dicarbonyl compound (b3). A curable composition wherein the cyclic secondary amine compound (b2) has one or more skeletons selected from the group consisting of a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, and an azepane skeleton.

2. The curable composition according to claim 1, wherein the weight ratio of the cyclic secondary amine compound (b2) to the tin carboxylate compound (b1) is 0.1 to 0.

8.

3. The curable composition according to claim 1 or 2, wherein the weight ratio of the β-dicarbonyl compound (b3) to the tin carboxylate compound (b1) is 0.1 to 0.

8.

4. The curable composition according to claim 1 or 2, wherein the curing catalyst (B) comprises a complex of the tin carboxylate compound (b1), the cyclic secondary amine compound (b2), and the β-dicarbonyl compound (b3).

5. A method for producing a curable composition containing an organic polymer (A) having a reactive silicon group and a curing catalyst (B), Tin carboxylate compound (b1), A cyclic secondary amine compound (b2) having one or more skeletons selected from the group consisting of a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, and an azepane skeleton, A step of mixing with a β-dicarbonyl compound (b3) to obtain a curing catalyst (B); and The curing catalyst (B) and general formula (1): -SiR １ ３－ａ X ａ (1) (In the formula, R １ R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or ０ ３ Represents a triorganosiloxy group represented by SiO-. Three R ０ represents a hydrocarbon group having 1 to 20 carbon atoms, either identical or different. X represents a hydroxyl group or a hydrolyzable group. a represents 1, 2, or 3. R １ Or, if there are multiple X's, they may be the same or different. A step of mixing with an organic polymer (A) having reactive silicon groups represented by ). A manufacturing method that includes [details omitted].

Images