Curable composition and method for producing same

Abstract

Provided is a method for producing a curable composition containing: an organic polymer (A) having a reactive silicon group; an amidine structure-containing compound (b1); a titanium compound or a condensate thereof (b2); and a silane compound (b3) having a hydrolyzable silicon group and an amino group and having a molecular weight of 100-1,500. A catalyst-containing composition (B) obtained by mixing (b1), (b2), and (b3) is prepared, and the organic polymer (A) and the catalyst-containing composition (B) are mixed. The weight ratio (b3) / (b2) is 0.1-2.

Description

Curable composition and method for producing the same

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

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

[0003] To accelerate the curing reaction in a short time, curable compositions containing organic polymers having reactive silicon groups usually contain a curing catalyst (also called a silanol condensation catalyst), such as an organotin compound having a carbon-tin bond, typified by dibutyltin bis(acetylacetonate). However, from the viewpoint of environmental safety, caution is required when using organotin compounds.

[0004] For this reason, curing catalysts other than organotin compounds are being investigated. Patent Document 1 describes the use of a titanium compound, such as a titanium alkoxide or a titanium chelate compound, in combination with an amine compound, such as DBU (1,8-diazabicyclo[5.4.0]-7-undecene), as a curing catalyst for an organic polymer having a reactive silicon group. Paragraph

[0220] of this document describes adding a titanium compound and an amine compound separately to an organic polymer having a reactive silicon group, and then mixing them together.

[0005] On the other hand, it is known that by blending a low-molecular-weight silane compound (a so-called silane coupling agent) having a hydrolyzable silicon group and a reactive group such as an amino group or a vinyl group with a curable composition containing an organic polymer having a reactive silicon group, the adhesion to various adherends and storage stability can be improved.

[0006] JP 2014-114434 A

[0007] The curing catalyst disclosed in Patent Document 1 is formed by adding a titanium compound and an amine compound to a reactive silicon group-containing organic polymer. In contrast, the present inventors investigated mixing the titanium compound and the amine compound before adding them to the polymer, and using the resulting mixture as the curing catalyst.

[0008] However, it has been found that a mixture of a titanium compound and an amine compound may become discolored due to the reaction between the two components, and the color deepens over time after mixing. Such a darkening is undesirable in terms of the appearance of the mixture, which is a curing catalyst, or the curable composition or cured product.

[0009] In view of the above-described current situation, an object of the present invention is to provide a method for producing a curable composition containing a reactive silicon group-containing organic polymer, in which the curing catalyst mixture of a titanium compound and an amine compound can be prevented from darkening over time while maintaining its function as a curing catalyst.

[0010] As a result of extensive research into solving the above-mentioned problems, the present inventors have found that by further adding an amino group-containing silane compound to a mixture of a titanium compound and an amine compound, it is possible to suppress the darkening of the mixture over time, and that when the compound is added to a reactive silicon group-containing organic polymer, good curability can be achieved, thereby completing the present invention.

[0011] That is, the present invention provides a compound represented by the following general formula (1): -SiR １ ３－ａ X ａ (1) (wherein, R １ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ０ ３ It represents a triorganosiloxy group represented by SiO—. ０ are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a represents 1, 2, or 3. R １and an organic polymer (A) having a reactive silicon group represented by the following general formula (2): R ２ N=CR ３ -NR ４ ２ (2) (wherein, R ２ , R ３ , and R ４ are the same or different and represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ４ may be the same or different. ２ , R ３ , and two R ４ Any two or more of these may be bonded to form a cyclic structure.) ５ ) ｄ Y ４－ｄ (3) (wherein, R ５represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a chelate coordination compound. d represents 0 or an integer of 1 to 4. The present invention also relates to a method for producing a curable composition containing a titanium compound represented by the formula (b2) or a condensate thereof, and a silane compound (b3) having a molecular weight of 100 to 1,500 and having a hydrolyzable silicon group and an amino group, the method comprising: a preparation step of mixing the amidine structure-containing compound (b1), the titanium compound or the condensate thereof (b2), and the silane compound (b3), to prepare a catalyst-containing composition (B), and a mixing step of mixing the organic polymer (A) with the catalyst-containing composition (B), wherein the weight ratio (b3) / (b2) of the silane compound (b3) to the titanium compound or condensate thereof (b2) is 0.1 to 2. The present invention also relates to a curable composition comprising the reactive silicon group-containing organic polymer (A) and a catalyst-containing composition (B), wherein the catalyst-containing composition (B) comprises a complex of the amidine structure-containing compound (b1) represented by the general formula (2), the titanium compound or condensate thereof (b2) represented by the general formula (3), and a silane compound (b3) having a molecular weight of 100 to 1,500 and containing a hydrolyzable silicon group and an amino group, wherein the weight ratio (b3) / (b2) of the silane compound (b3) to the titanium compound or condensate thereof (b2) is 0.1 to 2. The present invention also relates to a curable composition and a cured product obtained by curing the curable composition. The present invention also relates to a catalyst-containing composition (B) for an organic polymer (A) having a reactive silicon group, which comprises a complex of an amidine structure-containing compound (b1) represented by the general formula (2), a titanium compound or a condensate thereof (b2) represented by the general formula (3), and a silane compound (b3) having a molecular weight of 100 to 1,500 and having a hydrolyzable silicon group and an amino group, wherein the weight ratio (b3) / (b2) of the silane compound (b3) to the titanium compound or the condensate thereof (b2) is 0.1 to 2.

[0012] The present invention provides a method for producing a curable composition containing a reactive silicon group-containing organic polymer, in which the mixture of a titanium compound and an amine compound serving as a curing catalyst can be inhibited from darkening over time while retaining its function as a curing catalyst.

[0013] Furthermore, the present invention provides a non-tin catalyst-containing composition that is inhibited from darkening over time and that can achieve good curing properties as a curing catalyst for reactive silicon-containing organic polymers. In a preferred embodiment, a colorless and transparent catalyst-containing composition can be provided.

[0014] According to one aspect of the present invention, a curable composition can be provided in which bleed-out of the compound on the surface of the cured product obtained by curing is suppressed. Furthermore, according to one aspect of the present invention, a curable composition can be provided in which delay in curing due to storage is suppressed and which exhibits good storage stability in terms of curability. Furthermore, according to one aspect of the present invention, a curable composition can be provided in which good adhesive properties are obtained. Furthermore, according to one aspect of the present invention, a curable composition can be provided in which good tensile properties are obtained after curing.

[0015] Hereinafter, embodiments of the present invention will be described in detail.

[0016] (Reactive silicon group-containing organic polymer (A)) The reactive silicon group-containing organic polymer (A) has a polymer skeleton (also referred to as a main chain structure) and a polymer chain end bonded to the polymer skeleton. The polymer skeleton is a structure in which a plurality of monomer units are formed consecutively by bonding a plurality of monomers by polymerization, condensation, or the like. The monomer may be of one type, or a mixture of a plurality of types may be bonded.

[0017] The polymer chain end refers to a site located at the end of the reactive silicon group-containing organic polymer (A). The number of polymer chain ends of the reactive silicon group-containing organic polymer (A) is 2 when the polymer skeleton is entirely linear, and 3 or more when the polymer skeleton is entirely branched. Furthermore, when the polymer skeleton is a mixture of linear and branched chains, the average number can be between 2 and 3.

[0018] The reactive silicon group of the organic polymer (A) may be present in the polymer backbone and / or at the polymer chain end. Two or more reactive silicon groups may be present at one polymer chain end. When the curable composition according to the present disclosure is used for adhesives, sealants, elastic coating agents, pressure-sensitive adhesives, etc., the reactive silicon group is preferably contained at the polymer chain end of the organic polymer (A).

[0019] The organic polymer (A) has a reactive silicon group represented by the following general formula (1): —SiR １ ３－ａ X ａ (1) (wherein, R １ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ０ ３ It represents a triorganosiloxy group represented by SiO—. ０ are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a represents 1, 2, or 3. R １ Or, when there are multiple X's, they may be the same or different.

[0020] R in general formula (1) １ Examples of the alkyl group include alkyl groups such as methyl and ethyl groups; alkyl groups having hetero groups such as chloromethyl, methoxymethyl, and 3,3,3-trifluoropropyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl groups; aralkyl groups such as benzyl groups; and R ０ is a methyl group, a phenyl group, etc. ０ ３ Examples include triorganosiloxy groups represented by SiO-. Preferred are alkyl groups or alkyl groups having a hetero-containing group, more preferred are methyl groups, ethyl groups, chloromethyl groups, and methoxymethyl groups, even more preferred are methyl groups and ethyl groups, and particularly preferred is methyl group. R １ When there are a plurality of groups, they may be the same or different.

[0021] X in general formula (1) represents a hydroxyl group or a hydrolyzable group. The hydrolyzable group is not particularly limited and may be a known hydrolyzable group, such as a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, or an alkenyloxy group. Among these, an alkoxy group, an acyloxy group, a ketoximate group, or an alkenyloxy group is preferred. Because of their mild hydrolysis and ease of handling, an alkoxy group is more preferred, a methoxy group or an ethoxy group is even more preferred, and a methoxy group is particularly preferred. When multiple Xs are present, they may be the same or different.

[0022] a is 1, 2, or 3. a is preferably 2 or 3. From the viewpoint of obtaining better curability, a is particularly preferably 3.

[0023] The reactive silicon group represented by general formula (1) is not particularly limited, but examples include trimethoxysilyl, triethoxysilyl, tris(2-propenyloxy)silyl, triacetoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethoxyethylsilyl, dimethoxyphenylsilyl, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N-diethylaminomethyl)dimethoxysilyl, and (N,N-diethylaminomethyl)diethoxysilyl. Among these, dimethoxymethylsilyl and trimethoxysilyl groups are preferred due to their ease of synthesis. Trimethoxysilyl and methoxymethyldimethoxysilyl groups are preferred because they provide high curability. Trimethoxysilyl and triethoxysilyl groups are preferred because they provide cured products with high recovery rates and low water absorption.

[0024] (Main Chain Structure of Reactive Silicon Group-Containing Organic Polymer (A)) The main chain structure (also referred to as polymer skeleton) of the reactive silicon group-containing organic polymer (A) is not particularly limited, and various main chain structures can be used. Specific examples include polyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymers, and polyoxypropylene-polyoxybutylene copolymers; hydrocarbon polymers such as ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; polyolefins obtained by condensation of dibasic acids such as adipic acid with glycols, or by ring-opening polymerization of lactones; Examples of suitable ester polymers include (meth)acrylic acid ester polymers obtained by radical polymerization of (meth)acrylic acid ester monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and stearyl (meth)acrylate; vinyl copolymers obtained by radical polymerization of monomers such as (meth)acrylic acid ester monomers, vinyl acetate, acrylonitrile, and styrene; polysulfide polymers; polyamide polymers; polycarbonate polymers; and diallyl phthalate polymers. In the above description, (meth)acrylic refers to acrylic and / or methacrylic.

[0025] Among these, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth)acrylic acid ester polymers are preferred because they have relatively low glass transition temperatures and the resulting cured products have excellent cold resistance. Only one of these may be used, or two or more may be used in combination.

[0026] Polyoxyalkylene polymers and (meth)acrylic acid ester polymers are particularly preferred because they have high moisture permeability, excellent deep curing properties when made into a one-component curable composition, and also excellent adhesive properties. Polyoxyalkylene polymers are more preferred, and polyoxypropylene is even more preferred.

[0027] (Meth)acrylic acid ester-based polymers are useful because, by combining various monomer compositions constituting the polymer, effects such as improved adhesiveness, improved heat resistance and weather resistance, and reduced water absorption of a cured product obtained by curing a curable composition can be obtained.

[0028] The polyoxyalkylene polymer is preferably a polymer having a repeating unit represented by -R-O- (wherein R is a linear or branched alkylene group having 1 to 14 carbon atoms). R is more preferably a linear or branched alkylene group having 2 to 4 carbon atoms. Specific examples of the repeating unit represented by -R-O- include -CH ２ O-, -CH ２ CH ２ O-, -CH ２ CH (CH ３ ) O—, —CH ２ CH(C ２ H ５ ) O—, —CH ２ C(CH ３ ) (CH ３ ) O—, —CH ２ CH ２ CH ２ CH ２ The main chain structure of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.

[0029] In particular, when the curable composition according to the present disclosure is used as a sealant, adhesive, or the like, a polyoxypropylene-based polymer having oxypropylene repeating units in an amount of 50% by weight or more, more preferably 80% by weight or more, of the polymer main chain structure is preferred because it is amorphous and has a relatively low viscosity.

[0030] The main chain structure of the polyoxyalkylene polymer may be linear or may have a branched chain. When the polymer has a branched chain, the number of branches is preferably 1 to 6 (i.e., 3 to 8 terminal hydroxyl groups), more preferably 1 to 4 (i.e., 3 to 6 terminal hydroxyl groups), and most preferably 1 (i.e., 3 terminal hydroxyl groups). The presence of a branched chain can improve the restorability of the cured product. It can also be expected to reduce the water absorption of the cured product. When the polymer has a branched chain and the reactive silicon group is a trimethoxysilyl group, a cured product with particularly low water absorption can be obtained.

[0031] The polyoxyalkylene polymer is preferably one obtained by ring-opening polymerization of a cyclic ether compound in the presence of an initiator using a polymerization catalyst.

[0032] Examples of cyclic ether compounds include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more. Among the cyclic ether compounds, propylene oxide is particularly preferred because it can produce an amorphous polyether polymer with a relatively low viscosity.

[0033] Specific examples of the initiator include alcohols such as butanol, ethylene glycol, propylene glycol, propylene glycol monoalkyl ether, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, and sorbitol; and hydroxyl group-terminated polyoxyalkylene polymers having a number average molecular weight of 300 to 4,000, such as polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene diol, and polyoxyethylene triol.

[0034] Examples of synthesis methods for polyoxyalkylene polymers include, but are not limited to, polymerization methods using an alkali catalyst such as KOH, polymerization methods using a transition metal compound-porphyrin complex catalyst such as the complex obtained by reacting an organoaluminum compound with porphyrin disclosed in JP-A-61-215623, polymerization methods using a composite metal cyanide complex catalyst disclosed in JP-B-46-27250, JP-B-59-15336, U.S. Pat. Nos. 3,278,457, 3,278,458, 3,278,459, 3,427,256, 3,427,334, and 3,427,335, polymerization methods using a catalyst made of a polyphosphazene salt exemplified in JP-A-10-273512, and polymerization methods using a catalyst made of a phosphazene compound exemplified in JP-A-11-060722. A polymerization method using a composite metal cyanide complex catalyst is more preferred for reasons such as production costs and the fact that a polymer with a narrow molecular weight distribution can be obtained.

[0035] The reactive silicon group-containing organic polymer (A) may be a polyoxyalkylene polymer containing other bonds such as urethane bonds or urea bonds in the main chain structure, provided that the effects of the present invention are not significantly impaired. Specific examples of such polymers include polyurethane prepolymers.

[0036] The polyurethane prepolymer can be obtained by a known method, for example, by reacting a polyol compound with a polyisocyanate compound.

[0037] Specific examples of the polyol compound include polyether polyol, polyester polyol, polycarbonate polyol, and polyether polyester polyol.

[0038] Specific examples of polyisocyanate compounds include diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, methylene-bis(cyclohexyl isocyanate), isophorone diisocyanate, hexamethylene diisocyanate, etc. The polyurethane prepolymer may be terminated with either a hydroxyl group or an isocyanate group.

[0039] From the viewpoint of obtaining a curable composition having excellent storage stability and workability, it is particularly preferred that the reactive silicon group-containing organic polymer (A) is a polyoxyalkylene polymer that does not contain a urethane bond, a urea bond, an ester bond, or an amide bond in the main chain structure.

[0040] The reactive silicon group-containing organic polymer (A) is preferably obtained by introducing reactive silicon groups into a polymer by any of the following methods (a) to (d): (a) converting the terminal hydroxyl groups of a hydroxyl group-terminated organic polymer into carbon-carbon unsaturated groups, and then forming HSiR １ ３－ａ X ａ (In the formula, R １ , X, and a are the same as the groups shown in general formula (1).

[0041] (b) OCN-W-SiR １ ３－ａ X ａ (Wherein, W is a divalent organic group. R １ , X, and a are the same as the groups shown in general formula (1),

[0042] (c) After converting the terminal hydroxyl groups of the hydroxyl-terminated organic polymer into carbon-carbon unsaturated groups, HS-W-SiR １ ３－ａ X ａ (Wherein, W is a divalent organic group. R １ , X, and a are the same as the groups shown in general formula (1),

[0043] (d) A hydroxyl-terminated organic polymer is reacted with a polyisocyanate compound to synthesize an NCO-terminated organic polymer, and then HNR-W-SiR １ ３－ａ X ａ (Wherein, W is a divalent organic group. R is a hydrogen atom or an alkyl group. R １ , X, and a are the same as the groups shown in general formula (1)) or HS—W—SiR １ ３－ａ X ａ (Wherein, W is a divalent organic group. R１ , X, and a are the same as the groups shown in general formula (1),

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

[0045] In each of the above methods, the reactive silicon group-containing organic polymer (A) obtained using a silane compound in which W is a methylene group is preferred in that it exhibits very high curability.

[0046] Method (a) is preferred because it tends to produce a reactive silicon group-containing organic polymer (A) with good storage stability, while methods (b), (c), and (d) are preferred because they can achieve high conversion in a relatively short reaction time.

[0047] The introduction of reactive silicon groups by the method (a) has been proposed in Japanese Patent Publication Nos. 45-36319, 46-12154, Japanese Patent Laid-Open Nos. 50-156599, 54-6096, 55-13767, 55-13468, 57-164123, Japanese Patent Publication No. 3-2450, U.S. Pat. Nos. 3,632,557, 4,345,053, 4,366,307, and 4,960,844. Examples include those proposed in JP-A Nos. 61-197631, 61-215622, 61-215623, and 61-218632 in which reactive silicon groups are introduced by hydrosilylation or the like into polyoxypropylene polymers having a high molecular weight and narrow molecular weight distribution, with a number average molecular weight of 6,000 or more and an Mw / Mn ratio of 1.6 or less, and those proposed in JP-A No. 3-72527.

[0048] The molecular weight distribution (Mw / Mn) of the reactive silicon group-containing organic polymer (A) is not particularly limited, but is preferably 1.6 or less, more preferably 1.5 or less, and particularly preferably 1.4 or less, and from the viewpoint of improving various mechanical properties such as durability and elongation of the cured product, it is preferably 1.2 or less.

[0049] The number average molecular weight of the reactive silicon group-containing organic polymer (A), as calculated as polystyrene by GPC, is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and particularly preferably 8,000 to 35,000. When the number average molecular weight is within these ranges, the cured product has excellent mechanical properties, and since the amount of reactive silicon groups introduced is appropriate, it is possible to obtain an organic polymer (A) that exhibits good curability, has a manageable viscosity, and is excellent in workability, while keeping production costs within an appropriate range.

[0050] The molecular weight of the reactive silicon group-containing organic polymer (A) can also be expressed as an end group molecular weight calculated by directly measuring the end group concentration by titration analysis based on the principles of the hydroxyl value measurement method specified in JIS K 1557 and the iodine value measurement method specified in JIS K 0070, and taking into consideration the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). The end group-converted molecular weight of the organic polymer (A) can also be calculated by preparing a calibration curve of the number average molecular weight determined by general GPC measurement of a polymer precursor and the end group-converted molecular weight, and converting the number average molecular weight determined by GPC of the organic polymer (A) into an end group-converted molecular weight.

[0051] In order to obtain a good rubber-like cured product, the reactive silicon groups of the organic polymer (A) are preferably present at the polymer chain terminals. In order to show good curability and easily exhibit rubber elastic behavior, the number of reactive silicon groups per polymer chain terminal of the organic polymer (A) is preferably 0.5 or more, more preferably 0.6 or more, even more preferably 0.7 or more, and particularly preferably 0.8 or more, on average.

[0052] The number of polymer chain ends per molecule of the organic polymer (A) is preferably 2 to 8, more preferably 2 to 4, and particularly preferably 2 or 3. The number of reactive silicon groups per molecule of the organic polymer (A) is preferably 1 to 7 on average, more preferably 1 to 3.4, and particularly preferably 1 to 2.6.

[0053] When the reactive silicon group-containing organic polymer (A) is branched, the reactive silicon group may be located at the end of the main chain of the organic polymer, at the end of a side chain (branched chain), or at both. In particular, when the reactive silicon group is located at the end of the main chain, the molecular weight between crosslinking points becomes longer, which makes it easier to obtain a rubber-like cured product that has high strength, high elongation, and a low elastic modulus, which is preferred.

[0054] As described in WO 2013 / 180203, an organic polymer (A) obtained by methods (a) and (c) using an organic polymer having two or more carbon-carbon unsaturated bonds at one polymer chain end has two or more reactive silicon groups at one polymer chain end. Such organic polymer (A) exhibits high curability, and the resulting cured product can be expected to have high strength and high recovery.

[0055] Specific examples of reactive silicon group-containing organic polymers (A) include various reactive silicon group-containing polyoxypropylene products under the trade names Kaneka MS Polymer or Kaneka Silyl, reactive silicon group-containing poly(meth)acrylic acid esters such as Kaneka TA Polymer or Kaneka XMAP, and reactive silicon group-containing polyisobutylenes such as Kaneka EPION, all of which are available from Kaneka Corporation.

[0056] (Catalyst-Containing Composition (B)) The curable composition according to the present disclosure contains a catalyst-containing composition (B) used to form a cured product by hydrolyzing and condensing the reactive silicon groups of the organic polymer (A). The catalyst-containing composition (B) is composed of an amidine structure-containing compound (b1), a titanium compound or a condensate thereof (b2), and an amino group-containing silane compound (b3), and is a premix of at least these three components. The phrase "premixed" refers to mixing the amidine structure-containing compound (b1), the titanium compound or a condensate thereof (b2), and the amino group-containing silane compound (b3) in the absence of the organic polymer (A) before adding them to and mixing them with the organic polymer (A). This is intended to distinguish from the method described in Patent Document 1, in which each component is added to the organic polymer (A) and then mixed all at once.

[0057] When the amidine structure-containing compound (b1) is mixed with the titanium compound or its condensate (b2), some active species is formed by the interaction between (b1) and (b2), and it is presumed that this active species is mixed with the organic polymer (A), thereby improving the curability. In addition, by mixing (b1) and (b2) in advance, the interaction between (b1) and (b2) can also prevent (b1) from bleeding out from the surface of the cured product.

[0058] However, due to the reaction between the amidine structure-containing compound (b1) and the titanium compound or its condensate (b2), the mixture of (b1) and (b2) becomes colored, and the color tends to deepen if time passes before the mixture is added to the organic polymer (A).

[0059] In this embodiment, an amino group-containing silane compound (b3) is mixed with an amidine structure-containing compound (b1) and a titanium compound or its condensate (b2). This prevents the resulting mixture from darkening over time. This is thought to be because (b3) mediates the interaction between (b1) and (b2), suppressing the reaction that causes coloration.

[0060] The method for mixing the amidine structure-containing compound (b1), the titanium compound or its condensate (b2), and the amino group-containing silane compound (b3) is not particularly limited, but the components may be mixed and stirred at room temperature or at an elevated temperature below the decomposition temperature of each component. The mixing may be performed without a solvent or in the presence of a solvent inert to both components. Furthermore, the mixing may be performed in an inert gas atmosphere (e.g., nitrogen gas, argon gas) or in the presence of air. The time for mixing under stirring is not particularly limited, but may be, for example, about 1 hour to 3 days.

[0061] The order in which the three components are mixed is not particularly limited. The three components may be added individually and mixed at once, or (b1) and (b2) may be mixed and then (b3) may be added and mixed. Alternatively, (b1) and (b3) may be mixed and then (b2) may be added and mixed, or (b2) and (b3) may be mixed and then (b1) may be added and mixed.

[0062] According to a preferred embodiment, an amidine structure-containing compound (b1), a titanium compound or its condensate (b2), and an amino group-containing silane compound (b3) can be premixed to form a complex of (b1), (b2), and (b3). The complex refers to a state in which (b1), (b2), and (b3) do not exist independently of each other, but rather a state in which a reaction has progressed, forming a chemical bond between at least two of (b1), (b2), and (b3), or a structural change in at least one of (b1), (b2), and (b3). The complex can be formed by mixing (b1), (b2), and (b3) under stirring using the method described above. The mixture becomes viscous when mixed under stirring, allowing the formation of the complex to be confirmed.

[0063] (Amidine structure-containing compound (b1)) The amidine structure-containing compound can be represented by the following general formula (2): ２ N=CR ３ -NR ４ ２ (2) (wherein, R ２ , R ３ , and R ４ are the same or different and represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ４ may be the same or different. ２ , R ３ , and two R ４ Any two or more of these may be bonded to form a cyclic structure.)

[0064] R ２ is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group in which the carbon atom adjacent to the nitrogen atom (the carbon atom at the α-position) does not have an unsaturated bond, in order to enhance the curability of the curable composition. ２ The number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, because they are readily available.

[0065] R ３ is a hydrogen atom or —NR ６ ２Preferably, the organic group is represented by —NR ６ ２ It is more preferable that the organic group is an organic group represented by the following formula: ６ each independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. In this case, the compound represented by general formula (2) is called a guanidine compound.

[0066] Also, R ３ Since the physical properties of the resulting cured product are good, -NR ７ -C(=NR ８ )-NR ９ ２ , or -N=C(NR １０ ２ )-NR １１ ２ Preferably, R is an organic group represented by the formula: ７ , R ８ and two R ９ each independently represents a hydrogen atom or an organic group having 1 to 6 carbon atoms. １０ and two R １１ each independently represents a hydrogen atom or an organic group having 1 to 6 carbon atoms. In this case, the compound represented by general formula (2) is called a biguanide compound.

[0067] Two R in general formula (2) ４ preferably represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, because they are easily available and enhance the curability of the curable composition.

[0068] The number of carbon atoms contained in the amidine structure-containing compound is preferably 2 or more, more preferably 6 or more, and particularly preferably 7 or more. There is no particular upper limit to the number of carbon atoms, but it is preferably 10,000 or less.

[0069] The molecular weight of the amidine structure-containing compound is preferably at least 60, more preferably at least 120, and particularly preferably at least 130. There is no particular upper limit to the molecular weight, but it is preferably at most 100,000.

[0070] The amidine structure-containing compound (b1) is not particularly limited, and examples thereof include pyrimidine compounds such as pyrimidine, 2-aminopyrimidine, 6-amino-2,4-dimethylpyrimidine, 2-amino-4,6-dimethylpyrimidine, 1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1-ethyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-diethyl-1,4,5,6-tetrahydropyrimidine, 1-n-propyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 2-hydroxy-4,6-dimethylpyrimidine, 1,3-diazanaphthalene, and 2-hydroxy-4-aminopyrimidine; Imidazoline compounds such as 2-imidazoline, 2-methyl-2-imidazoline, 2-ethyl-2-imidazoline, 2-propyl-2-imidazoline, 2-vinyl-2-imidazoline, 1-(2-hydroxyethyl)-2-methyl-2-imidazoline, 1,3-dimethyl-2-iminoimidazolidine, and 1-methyl-2-iminoimidazolidin-4-one; amidine compounds such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 2,9-diazabicyclo[4.3.0]nona-1,3,5,7-tetraene, and 6-(dibutylamino)-1,8-diazabicyclo[5,4.0]undecene-7 (DBA-DBU);Guanidine, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, 1,1-dimethylguanidine, 1,3-dimethylguanidine, 1,2-diphenylguanidine, 1,1,2-trimethylguanidine, 1,2,3-trimethylguanidine, 1,1,3,3-tetramethylguanidine, 1,1,2,3,3-pentamethylguanidine, 2-ethyl-1,1,3,3-tetramethylguanidine, 1,1,3,3-tetramethyl-2-n-propylguanidine, 1,1,3,3-tetramethyl-2-isopropylguanidine, 2-n-butyl-1,1,3,3-tetramethylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, 1,2,3-Tricyclohexylguanidine, 1-benzyl-2,3-dimethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-ethyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-propyl-1,5,7-triazabicyclo[4.4.0] guanidine compounds such as dec-5-ene, 7-isopropyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-cyclohexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 7-n-octyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene;Biguanide, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-(2-ethylhexyl)biguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, 1-morpholinobiguanide, Examples of the amidine structure-containing compound (b1) include biguanide compounds such as 1-n-butyl-N2-ethylbiguanide, 1,1'-ethylenebisbiguanide, 1,5-ethylenebiguanide, 1-[3-(diethylamino)propyl]biguanide, 1-[3-(dibutylamino)propyl]biguanide, and N',N''-dihexyl-3,12-diimino-2,4,11,13-tetraazatetradecanediamidine. Only one type of compound may be used, or two or more types may be used in combination.

[0071] The amidine structure-containing compound (b1) is preferably an amidine compound or a guanidine compound, more preferably DBU, DBA-DBU, DBN, or phenylguanidine, further preferably DBU, DBA-DBU, or DBN, and particularly preferably DBU, because this improves curability.

[0072] (Titanium Compound or Condensate Thereof (b2)) The titanium compound (b2) is represented by the following general formula (3): Ti(OR ５ ) ｄ Y ４－ｄ (3) (wherein, R ５ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; Y represents a chelate coordination compound; and d represents 0 or an integer of 1 to 4.

[0073] A condensate of a titanium compound represented by the general formula (3) can also be used as (b2). The condensate can be obtained by adding water to a titanium compound and allowing it to react. In order to exhibit better curability, (b2) is preferably a condensate of a titanium compound. Furthermore, a titanium compound and a condensate of a titanium compound may be used in combination.

[0074] R ５The substituted or unsubstituted hydrocarbon group represented by the formula (I) is preferably a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and more preferably an aliphatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include saturated or unsaturated hydrocarbon groups. Examples of the saturated hydrocarbon group include linear or branched alkyl groups. The hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.

[0075] R ５ Examples of the hydrocarbon group represented by the formula (R) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, and decyl. Examples of the substituent that the hydrocarbon group may have include a methoxy group, an ethoxy group, a hydroxyl group, and an acetoxy group. ５ When there are a plurality of groups, they may be the same or different.

[0076] The chelate coordination compound represented by Y may be a known compound that is known to coordinate to titanium. Examples of the chelate coordination compound include, but are not limited to, 1-aryl-1,3-butanediones such as 2,4-pentanedione, 2,4-hexanedione, 2,4-pentadecanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 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; 3-benzyl Examples of suitable amines include diketones such as 2,4-pentanedione; ketoesters such as methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, t-butyl acetoacetate, and ethyl 3-oxohexanoate; ketoamides such as N,N-dimethyl acetoacetamide, N,N-diethyl acetoacetamide, and acetoacetanilide; malonic acid esters such as dimethyl malonate, diethyl malonate, and diphenyl malonate; and malonic acid amides such as N,N,N',N'-tetramethylmalonamide and N,N,N',N'-tetraethylmalonamide. Among these, diketones and ketoesters are preferred. When multiple Ys are present, they may be the same or different.

[0077] d represents 0 or an integer of 1 to 4. Because the curable composition according to the present disclosure can exhibit better curability and also exhibit greater elongation after curing, d preferably represents 0 or an integer of 1 to 3, more preferably an integer of 1 to 3, and particularly preferably 2.

[0078] Specific examples of the titanium compound represented by general formula (3) or a condensate thereof include tetramethoxytitanium, trimethoxyethoxytitanium, trimethoxyisopropoxytitanium, trimethoxybutoxytitanium, dimethoxydiethoxytitanium, dimethoxydiisopropoxytitanium, dimethoxydibutoxytitanium, methoxytriethoxytitanium, methoxytriisopropoxytitanium, methoxytributoxytitanium, tetraethoxytitanium, triethoxyisopropoxytitanium, triethoxybutoxytitanium, diethoxydiisopropoxytitanium, and diethoxydibutoxytitanium. Examples of titanium alkoxide condensates include titanium alkoxides such as ethoxytitanium, ethoxytriisopropoxytitanium, ethoxytributoxytitanium, tetraisopropoxytitanium, triisopropoxybutoxytitanium, diisopropoxydibutoxytitanium, tetrabutoxytitanium, tetra-tert-butoxytitanium, diisopropoxytitanium bis(acetylacetonate), diisopropoxytitanium bis(ethylacetoacetate), diisobutoxytitanium bis(ethylacetoacetate); tetrabutoxytitanium dimer, tetrabutoxytitanium tetramer, etc. One type of titanium compound or a condensate thereof may be used alone, or two or more types may be used in combination.

[0079] The titanium compound represented by general formula (3) is preferably a compound containing a chelate coordination compound represented by Y, since this allows for good curability and large elongation after curing. Specifically, diisopropoxytitanium bis(acetylacetonate), diisopropoxytitanium bis(ethylacetoacetate), and diisobutoxytitanium bis(ethylacetoacetate) are particularly preferred.

[0080] (Amino group-containing silane compound (b3)) The amino group-containing silane compound (b3) is a silane compound having a molecular weight of 100 to 1500 and containing a hydrolyzable silicon group and an amino group. This compound is also known as a silane coupling agent, and is usually used as an adhesion promoter to improve the adhesion of curable compositions to various adherends. In this embodiment, this is a component that suppresses the darkening of the catalyst-containing composition (B) over time.

[0081] The hydrolyzable silicon group contained in the amino group-containing silane compound (b3) refers to a silicon atom-containing group to which a hydrolyzable group is bonded, and can also be expressed by the general formula (1) described above for the reactive silicon group contained in the organic polymer (A).

[0082] The hydrolyzable group contained in the hydrolyzable silicon group is not particularly limited and examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkenyloxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, etc. Among these, alkoxy groups such as a methoxy group and an ethoxy group are more preferred because of their mild hydrolysis and ease of handling, and a methoxy group and an ethoxy group are particularly preferred.

[0083] The number of hydrolyzable groups bonded to silicon atoms in the amino group-containing silane compound (b3) may be preferably 3 to ensure good adhesion, or 2 to ensure storage stability of the curable composition.

[0084] The molecular weight of the amino group-containing silane compound (b3) may be in the range of 100 to 1,500. The lower limit of the molecular weight may be 150 or more. The upper limit may be 1,000 or less, or 500 or less.

[0085] The amino group-containing silane compound (b3) is a compound having a hydrolyzable silicon group and a substituted or unsubstituted amino group, and is sometimes called an aminosilane. The substituent of the substituted amino group is not particularly limited, and examples thereof include an alkyl group, an aralkyl group, and an aryl group.

[0086] Specific examples of the amino group-containing silane compound (b3) 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-ureido ... amino group-containing silanes such as iodopropyltriethoxysilane, 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 silanes such as N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine. In addition, partial hydrolysis condensates of the amino group-containing silanes mentioned above, and partial hydrolysis condensates of amino group-containing silanes and other alkoxysilanes (for example, reaction products of amino group-containing silanes and epoxy group-containing silanes, reaction products of amino group-containing silanes and (meth)acrylic group-containing silanes) can also be used. Only one type of amino group-containing silane compound (b3) can be used, or two or more types can be used in combination.

[0087] In order to achieve good adhesion, the amino group-containing silane compound (b3) is preferably γ-aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, or γ-(2-aminoethyl)aminopropylmethyldimethoxysilane. Silane coupling agents oligomerized by partial condensation of hydrolyzable silicon groups are suitable for use in terms of safety and stability. The silane coupling agents to be condensed may be a single type or multiple types. Examples of oligomerized silane coupling agents include Dynasylan 1146 from Evonik. In order to ensure the storage stability of the curable composition, γ-aminopropyltrimethoxysilane and γ-(2-aminoethyl)aminopropylmethyldimethoxysilane are preferred.

[0088] The amount of amino group-containing silane compound (b3) used is defined in relation to the titanium compound or its condensate (b2), and the weight ratio of (b3) to (b2), (b3) / (b2), is within the range of 0.1 to 2. Within this range, darkening of the catalyst-containing composition (B) over time is suppressed, and good curing properties as a curing catalyst for reactive silicon group-containing organic polymers can be achieved. If (b3) / (b2) is less than 0.1, it becomes difficult to suppress darkening over time.

[0089] From the viewpoint of suppressing darkening, the lower limit of (b3) / (b2) is preferably 0.15 or more, more preferably 0.2 or more, and even more preferably 0.25 or more. Also, since a colorless and transparent catalyst-containing composition (B) is obtained, the lower limit is preferably 0.3 or more, more preferably 0.5 or more. On the other hand, from the viewpoint of improving curability, the upper limit of (b3) / (b2) is preferably 1.5 or less, preferably 1 or less, and even more preferably 0.8 or less.

[0090] In the curable composition according to the present disclosure, the content of the catalyst-containing composition (B) can be appropriately determined depending on the desired curability, and may be, for example, about 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 0.75 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).

[0091] The amount of the amidine structure-containing compound (b1) contained in the curable composition according to the present disclosure can be appropriately adjusted within the above range, but in order to improve the bleed-out suppression effect of (b1), it is preferably 2 parts by weight or less, more preferably 1 part by weight or less, and even more preferably 0.7 parts by weight or less, relative to 100 parts by weight of the reactive silicon group-containing organic polymer (A). Also, from the viewpoint of curability, the lower limit of the amount of (b1) is preferably 0.1 parts by weight or more, more preferably 0.3 parts by weight or more, even more preferably 0.4 parts by weight or more, and particularly preferably 0.5 parts by weight or more.

[0092] The ratio of the amidine structure-containing compound (b1) to the titanium compound or its condensate (b2) can be set appropriately, but the weight ratio of (b2) / (b1) may be, for example, about 0.1 to 20, preferably 0.5 to 15, more preferably 0.8 to 12, and even more preferably 1.0 to 10. Since the effect of improving curability is particularly excellent, the upper limit of the weight ratio is preferably 9 or less, more preferably 6 or less, even more preferably 5 or less, and particularly preferably 4 or less. Furthermore, since the effect of suppressing bleed-out of (b1) is improved, the lower limit of the weight ratio is preferably 1.5 or more, more preferably 2 or more, and even more preferably 2.6 or more.

[0093] The curable composition according to the present disclosure may contain a curing catalyst other than the catalyst-containing composition (B). Examples of such a curing catalyst include organotin compounds, metal carboxylates, amine compounds other than the amidine structure-containing compound (b1), carboxylic acids, metal alkoxides other than the titanium compounds or condensates thereof (b2), and inorganic acids.

[0094] The content of the curing catalyst other than the catalyst-containing composition (B) is not particularly limited and may be set appropriately, and may be, for example, 0 to 10 parts by weight, 0 to 5 parts by weight, 0 to 3 parts by weight, or 0 to 1 part by weight, relative to 100 parts by weight of the reactive silicon group-containing organic polymer (A). In particular, from the viewpoint of environmental safety, it is preferable to use a small amount of organotin compounds, preferably 0 to 1 part by weight, and more preferably 0 to 0.1 part by weight.

[0095] (Silane Compound (C) and / or Silane Compound (D)) The curable composition according to the present disclosure preferably further contains a silane compound (C) having a hydrolyzable silicon group and an amino group and a molecular weight of 100 to 1500, and / or a silane compound (D) having a hydrolyzable silicon group but no amino group and a molecular weight of 100 to 1500. These silane compounds are also known as silane coupling agents.

[0096] By blending these silane compounds (C) and / or (D), the adhesiveness of the curable composition to various adherends and storage stability can be improved. The curable composition according to the present disclosure may contain only the silane compound (C), may contain only the silane compound (D), or may contain both the silane compound (C) and the silane compound (D). However, it is also possible to not contain either the silane compound (C) or the silane compound (D).

[0097] Details of the silane compound (C) are the same as those of the amino group-containing silane compound (b3) described above, and therefore will not be described here. In this application, the amino group-containing silane compound contained in the catalyst-containing composition (B) is referred to as (b3), and the amino group-containing silane compound not contained in the catalyst-containing composition (B) but blended in the curable composition is referred to as (C). However, the same compound or different compounds may be used as (b3) and (C).

[0098] On the other hand, the silane compound (D) having a hydrolyzable silicon group but no amino group may be a compound having a hydrolyzable silicon group and a reactive group other than an amino group, or may be a compound having no reactive groups other than a hydrolyzable silicon group.

[0099] The type and number of hydrolyzable silicon groups contained in the silane compound (D) and the molecular weight of (D) are the same as those described above for the amino group-containing silane compound (b3), and therefore will not be described here.

[0100] Specific examples of the silane compound (D) include epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltriethoxysilane; isocyanate group-containing silanes such as γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, (isocyanatemethyl)trimethoxysilane, and (isocyanatemethyl)dimethoxymethylsilane; Mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and mercaptomethyltriethoxysilane; carboxysilanes such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis(2-methoxyethoxy)silane, and N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane; vinyl type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and vinyltriethoxysilane; (meth)acrylic type unsaturated group-containing silanes such as γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropylmethyltriethoxysilane, and γ-acryloxypropyltrimethoxysilane; Examples include reactive group-free silanes such as methyltrimethoxysilane, dimethyldimethoxysilane, n-propyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, dimethoxydiphenylsilane, hexyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, (methoxymethyl)trimethoxysilane, and p-styryltrimethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; and isocyanurate silanes such as tris(trimethoxysilyl)isocyanurate.The silane compound (D) may be used alone or in combination of two or more. Partial hydrolysis condensates of the above-listed silane compounds may also be used. Examples include Dynasylan 6490 and Dynasylan 6498 manufactured by Evonik.

[0101] In order to achieve good adhesion, the silane compound (D) is preferably γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, or γ-glycidoxypropylmethyldimethoxysilane.

[0102] In order to achieve good storage stability, the silane compound (D) is preferably vinyltrimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, or (methoxymethyl)trimethoxysilane, more preferably vinyltrimethoxysilane or (methoxymethyl)trimethoxysilane, and particularly preferably vinyltrimethoxysilane.

[0103] In order to exhibit better curability, the silane compound (D) is preferably a condensate of a silane compound having a hydrolyzable silicon group and a vinyl group. The condensate of the silane compound refers to a silane oligomer, which is a partial hydrolysis condensate of a silane compound, and has a vinyl group. At least a part of the silane compound as a raw material may have a vinyl group.

[0104] The blending amounts of the silane compound (C) and the silane (D) are not particularly limited and can be appropriately set depending on the desired physical properties of the silane compounds used. However, each blending amount is preferably 0 to 20 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 organic polymer (A).

[0105] The curable composition according to the present disclosure can incorporate a large amount of silane compound (C) and / or (D), which has been a factor in reducing the curability of conventional curable compositions. From this viewpoint, the amount of silane compound (C) incorporated is preferably 3 parts by weight or more, more preferably 4 parts by weight or more, and even more preferably 5 parts by weight or more, per 100 parts by weight of organic polymer (A). The amount of silane compound (D) incorporated is also preferably 3 parts by weight or more, more preferably 4 parts by weight or more, and even more preferably 5 parts by weight or more, per 100 parts by weight of organic polymer (A). Furthermore, the total content of silane compound (C) and the silane compound (D) is preferably 5 to 20 parts by weight, more preferably 6 to 15 parts by weight, and even more preferably 7 to 12 parts by weight, per 100 parts by weight of organic polymer (A).

[0106] (Method for producing curable composition) The curable composition according to the present disclosure can be produced by mixing an amidine structure-containing compound (b1), a titanium compound or a condensate thereof (b2), and an amino group-containing silane compound (b3) to obtain a catalyst-containing composition (B), and then adding the catalyst-containing composition (B) to an organic polymer (A) and mixing the two components. This can improve the curability of the produced curable composition.

[0107] The method for mixing the organic polymer (A) and the catalyst-containing composition (B) is not particularly limited as long as it can be mixed uniformly, and can be carried out using a conventionally known device. The temperature during mixing is not particularly limited, and may be room temperature. The catalyst-containing composition (B) can also be purchased and used if it is manufactured by another company.

[0108] The order in which the silane compound (C) and / or silane compound (D) are mixed with the organic polymer (A) is not particularly limited. The catalyst-containing composition (B) and the silane compound (C) and / or (D) may be added in parallel to the organic polymer (A) and then mixed. Alternatively, the organic polymer (A) and the silane compound (C) and / or (D) may be mixed first, and then the catalyst-containing composition (B) may be added and mixed. Alternatively, the organic polymer (A) and the catalyst-containing composition (B) may be mixed first, and then the silane compound (C) and / or (D) may be added and mixed. The order in which the silane compound (C) and the silane compound (D) are mixed is also not particularly limited. The method and temperature for performing the mixing are the same as those described above and are not particularly limited.

[0109] The timing of mixing the other compounding ingredients described below is not particularly limited, and may be the same as in the case of mixing the silane compound (C) and / or the silane compound (D). However, it is preferable to mix the catalyst-containing composition (B) and the silane compound (C) and / or the silane compound (D) after mixing the organic polymer (A) with the other compounding ingredients.

[0110] (Other Compounding Agents) The curable composition according to the present disclosure may contain, as necessary, a plasticizer, a filler, a physical property adjusting agent, an anti-sagging agent (a thixotropy imparting agent), a stabilizer, and the like.

[0111] The curable composition according to the present disclosure may contain a plasticizer. The addition of a plasticizer makes it possible to adjust the viscosity and slump of the curable composition, as well as the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the curable composition. 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 (specifically, product name: EASTMAN 168 (manufactured by EASTMAN CHEMICAL)); and non-phthalate ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester (specifically, product name: Hexamoll DINCH (manufactured by BASF); aliphatic polycarboxylic acid ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and acetyl tributyl citrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkylsulfonic acid phenyl esters (specifically, trade name: Mesamoll (manufactured by LANXESS)); phosphate ester compounds such as tricresyl phosphate and tributyl phosphate; trimellitic acid ester compounds; chlorinated paraffin; hydrocarbon oils such as alkyl diphenyls and partially hydrogenated terphenyls; process oil; epoxidized soybean oil, and epoxy plasticizers such as benzyl epoxy stearate. Among these, cured products obtained from curable compositions using aliphatic carboxylic acid esters such as 1,2-cyclohexanedicarboxylic acid diisononyl ester are preferred because they tend to have low water absorption.

[0112] Furthermore, polymeric plasticizers can be used. The use of polymeric plasticizers allows the initial physical properties to be maintained for a longer period of time than when low-molecular-weight plasticizers, which are plasticizers that do not contain polymer components in the molecule, are used. Furthermore, the drying properties (paintability) of the cured product when coated with an alkyd paint can be improved. Specific examples of polymer plasticizers include vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols 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; polyethers such as polyether polyols having a number average molecular weight of 500 or more, and even 1,000 or more, such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, or derivatives in which the hydroxy groups of these polyether polyols are converted to ester groups, ether groups, or the like; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, and polychloroprene, but are not limited to these.

[0113] Among these polymeric plasticizers, those compatible with the reactive silicon group-containing organic polymer (A) are preferred. From this viewpoint, polyethers and vinyl polymers are preferred. Furthermore, the use of polyethers as plasticizers is preferred because it improves surface curability and deep curability and does not cause delay in curing after storage, and polypropylene glycol is more preferred. Furthermore, vinyl polymers are preferred in terms of compatibility, weather resistance, and heat resistance. Among vinyl polymers, acrylic polymers and / or methacrylic polymers are preferred, with acrylic polymers such as polyacrylic acid alkyl esters being more preferred. The polymer is preferably synthesized by living radical polymerization, which has a narrow molecular weight distribution and can be made low viscosity, and atom transfer radical polymerization is even more preferred. Furthermore, it is preferred to use a polymer obtained by the so-called SGO process, which is described in JP-A-2001-207157, in which an acrylic acid alkyl ester monomer is obtained by continuous bulk polymerization at high temperature and high pressure.

[0114] The number average molecular weight of the polymer plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, even more preferably 1,000 to 8,000, and particularly preferably 1,000 to 5,000. It is most preferably 1,000 to 3,000. If the molecular weight is too low, the plasticizer will leach out over time due to heat or rain, making it impossible to maintain the initial physical properties over a long period of time. Furthermore, if the molecular weight is too high, the viscosity will increase, resulting in poor workability.

[0115] The molecular weight distribution of the polymeric plasticizer is not particularly limited, but is preferably narrow, and 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.

[0116] The number average molecular weight of the polymer plasticizer is measured by GPC in the case of a vinyl polymer, and by end group analysis in the case of a polyether polymer. The molecular weight distribution (Mw / Mn) is measured by GPC (polystyrene equivalent).

[0117] Furthermore, the polymer plasticizer may or may not have a reactive silicon group. When it has a reactive silicon group, it acts as a reactive plasticizer and can prevent the plasticizer from migrating from the cured product. When it has a reactive silicon group, it is preferable that the number of reactive silicon groups is 1 or less, more preferably 0.8 or less, on average per molecule. When using a plasticizer having a reactive silicon group, particularly a polyether polymer having a reactive silicon group, it is desirable that its number average molecular weight is lower than that of the reactive silicon group-containing organic polymer (A).

[0118] 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 reactive silicon group-containing organic polymer (A). Within such a range, the plasticizer's effects can be exhibited while maintaining the mechanical strength of the cured product. The plasticizers may be used alone or in combination of two or more types. A low-molecular-weight plasticizer and a polymeric plasticizer may also be used in combination. These plasticizers can also be added during polymer production.

[0119] The curable composition according to the present disclosure may contain a filler. Examples of fillers include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic acid anhydride, hydrated silicic acid, and carbon black; fillers such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc oxide, PVC powder, and resin powders such as PMMA powder; and fibrous fillers such as asbestos, glass fiber, and filaments. When a filler is used, the amount thereof is preferably 1 to 300 parts by weight, more preferably 10 to 200 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0120] When a high-strength cured product is desired using these fillers, fillers selected from the group consisting of fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic acid anhydride, hydrated silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and activated zinc oxide are preferably used. Favorable results can be obtained by using 1 to 200 parts by weight of a filler per 100 parts by weight of the reactive silicon group-containing organic polymer (A). Furthermore, when a low-strength cured product with high elongation at break is desired, favorable results can be obtained by using 5 to 200 parts by weight of a filler selected from the group consisting of titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloons per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0121] The curable composition according to the present disclosure may contain spherical hollow bodies such as balloons to reduce the weight (specific gravity) of the composition. Balloons are hollow spherical fillers. Examples of balloon materials include, but are not limited to, inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, saran, and acrylonitrile. Inorganic and organic materials can also be combined or laminated to form multiple layers. Inorganic, organic, or composite balloons can be used. The balloons used may be the same or a mixture of multiple balloons made of different materials. Furthermore, the balloons may be surface-treated or coated, or may be surface-treated with various surface treatment agents. For example, organic balloons may be coated with calcium carbonate, talc, titanium oxide, or the like, or inorganic balloons may be surface-treated with a silane coupling agent.

[0122] The particle size of the balloons is preferably 3 to 200 μm, and particularly preferably 10 to 110 μm. If the particle size is less than 3 μm, the contribution to weight reduction is small, and a large amount must be added, while if the particle size is 200 μm or more, the surface of the cured sealant tends to become uneven and the elongation tends to decrease.

[0123] The amount of the hollow spheres used is preferably 0.01 to 30 parts by weight per 100 parts by weight of the reactive silicon group-containing organic polymer (A). The lower limit is more preferably 0.1 part by weight, and the upper limit is more preferably 20 parts by weight. Within this range, the elongation and breaking strength of the cured product can be maintained while improving workability.

[0124] The curable composition according to the present disclosure may contain, as necessary, a physical property modifier for adjusting the tensile properties of the cured product. Examples of the physical property modifier include, but are not limited to, alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane; alkoxysilanes having a functional group such as γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; silicone varnishes; and polysiloxanes. The physical property modifier can be used to increase the hardness of the cured product obtained by curing the curable composition, or conversely, to decrease the hardness and increase the elongation at break. The physical property modifiers can be used alone or in combination of two or more.

[0125] In particular, compounds that hydrolyze to form a compound having a monovalent silanol group in the molecule have the effect of reducing the modulus of the cured product without increasing the stickiness of the surface of the cured product. Compounds that form trimethylsilanol are particularly preferred. Examples of compounds that hydrolyze to form a compound having a monovalent silanol group in the molecule include the compounds described in JP-A-5-117521. Other examples include compounds that are derivatives of alkyl alcohols such as hexanol, octanol, and decanol, which form silicon compounds that form trialkylsilanols such as trimethylsilanol upon hydrolysis, and compounds described in JP-A-11-241029, which are derivatives of polyhydric alcohols with three or more hydroxyl groups, such as trimethylolpropane, glycerin, pentaerythritol, and sorbitol, which form silicon compounds that form trialkylsilanols such as trimethylsilanol upon hydrolysis. Specific examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.

[0126] Other examples include compounds that are derivatives of oxyalkylene polymers and produce silicon compounds that produce trialkylsilanols such as trimethylsilanol upon hydrolysis, as described in JP-A-7-258534. Furthermore, polymers having crosslinkable hydrolyzable silicon-containing groups and silicon-containing groups that can be converted to monosilanol-containing compounds upon hydrolysis, as described in JP-A-6-279693, can also be used.

[0127] The physical property adjusting agent is preferably used in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0128] The curable composition according to the present disclosure may contain an anti-sagging agent, if necessary, to prevent sagging and improve workability. The anti-sagging agent is not particularly limited, but examples thereof include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents may be used alone or in combination of two or more.

[0129] The anti-sagging agent is preferably used in an amount of 0.1 to 20 parts by weight per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0130] The curable composition according to the present disclosure may contain an antioxidant (antiaging agent). The use of an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Examples include Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330, and Irganox 1520 (all manufactured by BASF); SONGNOX 1076 (manufactured by SONGWON); and BHT. Similarly, hindered amine light stabilizers such as TINUVIN 622LD, TINUVIN 144, TINUVIN 292, CHIMASSORB 944LD, and CHIMASSORB 119FL (all manufactured by BASF); Adeka STAB LA-57, Adeka STAB LA-62, Adeka STAB LA-67, Adeka STAB LA-63, and Adeka STAB LA-68 (all manufactured by ADEKA Corporation); Sanol LS-2626, Sanol LS-1114, and Sanol LS-744 (all manufactured by Sankyo Lifetech Co., Ltd.); and Nocrac CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) can also be used. Other antioxidants that can be used include SONGNOX 4120, Nauguard 445, and OKABEST CLX050. Specific examples of antioxidants are also described in Japanese Patent Application Laid-Open Nos. 4-283259 and 9-194731.

[0131] The amount of antioxidant used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0132] The curable composition according to the present disclosure may contain a light stabilizer. The use of a light stabilizer can prevent photooxidative degradation of the cured product. Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds, with hindered amine-based compounds being particularly preferred. Specific examples of light stabilizers are also described in JP-A-9-194731.

[0133] The amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0134] When a photocurable substance is blended into the curable composition according to the present disclosure, particularly when an unsaturated acrylic compound is used, it is preferable to use a tertiary amine-containing hindered amine light stabilizer as the hindered amine light stabilizer, as described in JP-A-5-70531, in order to improve the storage stability of the composition. Examples of tertiary amine-containing hindered amine light stabilizers include TINUVIN 123, TINUVIN 144, TINUVIN 249, TINUVIN 292, TINUVIN 312, TINUVIN 622LD, TINUVIN 765, TINUVIN 770, TINUVIN 880, TINUVIN 5866, TINUVIN B97, CHIMASSORB 119FL, and CHIMASSORB 944LD (all manufactured by BASF); ADK STAB LA-57, LA-62, LA-63, LA-67, and LA-68 (all manufactured by ADEKA Corporation); SANOL LS-292, LS-2626, LS-765, LS-744, and LS-1114 (all manufactured by Sankyo Lifetech Co., Ltd.), SABOSTAB UV91, SABOSTAB Examples of light stabilizers include UV119, SONGSORB CS5100, SONGSORB CS622, SONGSORB CS944 (all manufactured by SONGWON), and NOCRAC CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.).

[0135] The curable composition according to the present disclosure may contain an ultraviolet absorber. The use of an ultraviolet absorber can improve the surface weather resistance of the cured product. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, triazine-based, substituted acrylonitrile-based, and metal chelate-based compounds, with benzotriazole-based compounds being particularly preferred. Examples include Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 350, Tinuvin 571, Tinuvin 900, Tinuvin 928, Tinuvin 1130, and Tinuvin 1600 (all manufactured by BASF); and SONGSORB 3290 (manufactured by SONGWON). Examples of triazine compounds include TINUVIN 400, TINUVIN 405, TINUVIN 477, and TINUVIN 1577ED (all manufactured by BASF), SONGSORB CS400 and SONGSORB 1577 (manufactured by SONGWON), etc. Examples of benzophenone compounds include SONGSORB 8100 (manufactured by SONGWON).

[0136] The amount of the UV absorber used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A). It is preferred to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer, and a benzotriazole UV absorber in combination.

[0137] Addworks IBC760 (manufactured by Clariant) can also be used as a product containing a mixture of antioxidants, light stabilizers, and UV absorbers.

[0138] The curable composition according to the present disclosure may contain an epoxy resin. A composition containing an epoxy resin is particularly suitable as an adhesive, particularly as an adhesive for exterior wall tiles. Examples of the epoxy resin include bisphenol A epoxy resins and novolac epoxy resins.

[0139] The ratio of the organic polymer (A) to the epoxy resin is not particularly limited, but it is preferable that the weight ratio of organic polymer (A) / epoxy resin is in the range of 100 / 1 to 1 / 100.

[0140] When an epoxy resin is blended, the curable composition according to the present disclosure preferably uses a curing agent for curing the epoxy resin. There are no particular limitations on the epoxy resin curing agent that can be used, and any commonly used epoxy resin curing agent can be used. When an epoxy resin curing agent is used, the amount used is preferably in the range of 0.1 to 300 parts by weight per 100 parts by weight of the epoxy resin.

[0141] The curable composition according to the present disclosure may contain various additives as needed to adjust the physical properties of the curable composition or the cured product. Examples of such additives include flame retardants, curability regulators, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, foaming agents, solvents, and antifungal agents. Examples of flame retardants include aluminum hydroxide and magnesium hydroxide. These various additives may be used alone or in combination of two or more. Specific examples of additives other than those listed in this specification are described, for example, in JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, and JP-A-2001-72854.

[0142] The curable composition according to the present disclosure can be prepared as a one-component curable composition in which all ingredients are mixed in advance and stored in a sealed container, and then cured by moisture in the air after application. Alternatively, it can be prepared as a two-component curable composition in which a curing agent containing ingredients such as a curing catalyst, a filler, a plasticizer, and water is prepared separately from a base agent containing a reactive silicon group-containing organic polymer (A), and the base agent and curing agent are mixed before use.

[0143] When the curable composition is a one-component type, all ingredients are premixed, so it is preferable to dehydrate and dry the ingredients containing water before use, or to dehydrate them under reduced pressure during blending and kneading. When the curable composition is a two-component type, there is no need to add a curing catalyst to the base compound containing the reactive silicon group-containing organic polymer (A). Therefore, even if a small amount of water is contained in the ingredients, the risk of gelation is low. However, when long-term storage stability is required, dehydration and drying are preferable. As for the dehydration and drying method, heat drying is preferable for solid substances such as powders, and reduced pressure dehydration or dehydration methods using synthetic zeolite, activated alumina, silica gel, etc. is preferable for liquid substances. Alternatively, a small amount of an isocyanate compound may be added and dehydrated by reacting the isocyanate group with water. In addition to such dehydration drying methods, storage stability can be further improved by adding lower alcohols such as methanol and ethanol, or alkoxysilane compounds such as methyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, phenyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Partially condensed silane compounds such as Evonik's Dynasylan 6490 can also be used as dehydrating agents from the standpoints of safety and stability.

[0144] The amount of the dehydrating agent, particularly a silicon compound capable of reacting with water such as vinyltrimethoxysilane, used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0145] The curable compositions according to the present disclosure can be used as architectural sealants, industrial adhesives, waterproof coatings, adhesive raw materials, and the like. They can also be used as sealants for buildings, ships, automobiles, roads, and the like. Furthermore, because they can adhere to a wide range of substrates, such as glass, porcelain, wood, metal, and resin moldings, either alone or with the aid of a primer, they can also be used as various types of sealing and adhesive compositions. In addition to conventional adhesives, they can also be used as contact adhesives. Furthermore, they are useful as food packaging materials, cast rubber materials, molding materials, and paints.

[0146] The following items are preferred embodiments of the present disclosure, but the present invention is not limited to the following items. [Item 1] A compound represented by the following general formula (1): -SiR １ ３－ａ X ａ (1) (wherein, R １ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ０ ３ It represents a triorganosiloxy group represented by SiO—. ０ are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a represents 1, 2, or 3. R １ and an organic polymer (A) having a reactive silicon group represented by the following general formula (2): R ２ N=CR ３ -NR ４ ２ (2) (wherein, R ２ , R ３ , and R ４ are the same or different and represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ４ may be the same or different. ２ , R ３ , and two R ４ Any two or more of these may be bonded to form a cyclic structure.) ５) ｄ Y ４－ｄ (3) (where R ５represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a chelate coordination compound. d represents 0 or an integer of 1 to 4. A method for producing a curable composition containing a titanium compound represented by the formula (b2) or a condensate thereof, and a silane compound (b3) having a molecular weight of 100 to 1,500 and having a hydrolyzable silicon group and an amino group, the method comprising: a preparation step of mixing the amidine structure-containing compound (b1), the titanium compound or the condensate thereof (b2), and the silane compound (b3), to prepare a catalyst-containing composition (B), and a mixing step of mixing the organic polymer (A) with the catalyst-containing composition (B), wherein the weight ratio (b3) / (b2) of the silane compound (b3) to the titanium compound or condensate thereof (b2) is 0.1 to 2. [Item 2] A method for producing a curable composition according to Item 1, wherein the weight ratio (b2) / (b1) of the titanium compound or condensate thereof (b2) to the amidine structure-containing compound (b1) is 2.6 to 9. [Item 3] A method for producing a curable composition according to Item 1 or 2, wherein the content of the amidine structure-containing compound (b1) is 0.3 to 0.7 parts by weight per 100 parts by weight of the organic polymer (A). [Item 4] A method for producing a curable composition according to any one of Items 1 to 3, wherein the curable composition further contains a silane compound (D) having a hydrolyzable silicon group, no amino group, and a molecular weight of 100 to 1,500. [Item 5] A method for producing a curable composition according to Item 4, wherein the silane compound (D) is a condensate of a silane compound having a hydrolyzable silicon group and a vinyl group. [Item 6] A curable composition comprising an organic polymer (A) having a reactive silicon group represented by the general formula (1) and a catalyst-containing composition (B), wherein the catalyst-containing composition (B) comprises a complex of an amidine structure-containing compound (b1) represented by the general formula (2), a titanium compound or a condensate thereof represented by the general formula (3) (b2), and a silane compound (b3) having a molecular weight of 100 to 1500 and having a hydrolyzable silicon group and an amino group, wherein the weight ratio (b3) / (b2) of the silane compound (b3) to the titanium compound or condensate thereof (b2) is 0.1 to 2. [Item 7] A cured product obtained by curing the curable composition according to Item 6.[Item 8] A catalyst-containing composition (B) for an organic polymer (A) having a reactive silicon group, comprising a complex of an amidine structure-containing compound (b1) represented by the general formula (2), a titanium compound or a condensate thereof represented by the general formula (3) (b2), and a silane compound (b3) having a molecular weight of 100 to 1500 and having a hydrolyzable silicon group and an amino group, wherein the weight ratio (b3) / (b2) of the silane compound (b3) to the titanium compound or the condensate thereof (b2) is 0.1 to 2.

[0147] 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.

[0148] The number average molecular weight in the examples is a GPC molecular weight measured under the following conditions: Solution delivery system: HLC-8120GPC manufactured by Tosoh Corporation Column: TSKgel Super H series manufactured by Tosoh Corporation Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40°C

[0149] The average number of silyl groups per terminal or per molecule of the polymers shown in the examples was determined by H-NMR (using an AVANCE III HD-500 manufactured by Bruker) using CDCl ３ The values ​​were calculated based on measurements using a fluorine-containing solvent.

[0150] Synthesis of Organic Polymer (A) (Synthesis Example 1 (A-1)) Using a polyoxypropylene diol having a molecular weight of approximately 2,000 as an initiator, propylene oxide was polymerized in the presence of a zinc hexacyanocobaltate glyme complex catalyst to obtain polypropylene oxide having a number average molecular weight of 28,500. Subsequently, a methanol solution of 1.2 molar equivalents of NaOMe relative to the hydroxyl groups of this hydroxyl-terminated polypropylene oxide was added, and the methanol was distilled off. Allyl chloride was then added to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by devolatilization under reduced pressure. 100 parts by weight of the resulting unpurified allyl-terminated polypropylene oxide was mixed and stirred with 300 parts by weight of n-hexane and 300 parts by weight of water, and the water was then removed by centrifugation. An additional 300 parts by weight of water was then mixed and stirred with the resulting hexane solution, and the water was again removed by centrifugation. The hexane was then removed by devolatilization under reduced pressure. As a result, a bifunctional polypropylene oxide having an allyl group at the end and a number average molecular weight of approximately 28,500 was obtained. 100 parts by weight of the obtained allyl-terminated polypropylene oxide was reacted with 0.8 molar equivalents of trimethoxysilane relative to the allyl groups of the allyl-terminated polypropylene oxide at 90°C for 5 hours using 150 ppm of a 2-propanol solution of a platinum vinylsiloxane complex containing 3 wt% platinum as a catalyst, to obtain trimethoxysilyl-terminated polyoxypropylene (A-1). The number of trimethoxysilyl groups per polymer chain end was approximately 0.8.

[0151] The following compounds were used in the production of each composite: TC-750: titanium diisopropoxybis(ethylacetoacetate), (manufactured by Matsumoto Fine Chemical Co., Ltd.) Tyzor IBAY: titanium diisobutoxybis(ethylacetoacetate), (manufactured by Dorf Ketal) Ti(O ｉ Pr) ４ : Titanium tetraisopropoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) Ti(OBu) ４: tetrabutoxy titanium (manufactured by Tokyo Chemical Industry Co., Ltd.) Tyzor 9000: titanium tetratertiary butoxide (manufactured by Dorf Ketal) Hexabutoxy-μ-oxoditanium (manufactured by Tokyo Chemical Industry Co., Ltd.) DBU: 1,8-diazabicyclo[5.4.0]-7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) Dynasylan AMMO (γ-aminopropyltrimethoxysilane, manufactured by Evonik) Dynasylan 1146 (condensate of diamino group-containing silane and alkyl group-containing silane, manufactured by Evonik)

[0152] <Production Example 1 (Reference Complex 1)> 20 g of TC-750 was added to a 200 ml recovery flask. While stirring the contents of the flask, 0.1 g of DBU was slowly added dropwise to the flask. After the addition was complete, the flask was capped and the contents were stirred at room temperature for 24 hours, yielding 20.1 g of liquid Reference Complex 1.

[0153] <Production Examples 2 to 17 (Reference Composites 2 to 17)> Liquid Reference Composites 2 to 17 were obtained in the same manner as in Production Example 1, except that the amidine compound (b1) and titanium compound (b2) shown in Table 1 were used in the weight ratio shown in Table 1.

[0154]

[0155] (Reference Examples 1 to 17) (Preparation of Main Component) Colloidal calcium carbonate (Shiraishi Industrial Co., Ltd., trade name: Hakuenka CCR), heavy calcium carbonate (Shiraishi Calcium Co., Ltd., trade name: Whiten SB), plasticizer (BASF, trade name: Hexamoll DINCH), pigment (Ishihara Sangyo Kaisha, Ltd., trade name: Typek R820), thixotropic agent (ARKEMA, trade name: Crayvallac), and the like were added in the amounts (parts by weight) shown in Table 2 to 100 parts by weight of the organic polymer (A-1) having a reactive silicon group. SLT), an antioxidant (BASF, trade name: Irganox 1010), an ultraviolet absorber (BASF, trade name: Tinuvin 326), and a light stabilizer (BASF, trade name: Tinuvin 770) were added and mixed using a spatula, and the mixture was then passed through a three-roll mill three times to disperse. Thereafter, the mixture was dehydrated under reduced pressure using a planetary mixer, and the blend was filled into a moisture-proof cartridge to form the base compound.

[0156] (Preparation of Curable Compositions) In an atmosphere of 23°C and 50% relative humidity, the base resin was extruded from the cartridge and weighed into a plastic container. Dynasylan VTMO (silane compound (D): vinyltrimethoxysilane, manufactured by Evonik) and Dynasylan AMMO (silane compound (C): γ-aminopropyltrimethoxysilane, manufactured by Evonik) were added and mixed in the amounts shown in Table 2. Subsequently, Reference Composites 1 to 17 prepared in Production Examples 1 to 17 were added as curing catalysts in the amounts shown in Table 2 and mixed to obtain curable compositions.

[0157] (Evaluation) (Skinning time (curability)) The obtained curable composition was filled into a mold about 5 mm thick using a spatula, and the time when the surface was smoothed to a flat surface was recorded as the curing initiation time. The surface was touched with the spatula, and the time when the composition no longer adhered to the spatula was measured as the skinning time (curability). The measurement results are shown in Table 2.

[0158] (Presence or absence of bleeding) Each curable composition was formed into a sheet using a spatula on a cardboard board under constant temperature and humidity conditions of 23°C and 50% or 70% relative humidity, and the surface was smoothed. After leaving the sheet for 7 days under conditions of 23°C and 50% or 70% relative humidity, the surface of the curable composition was touched with a fingertip to check whether the liquid compound derived from DBU had bled onto the surface of the cured product. The results are shown in Table 2.

[0159]

[0160] (Results) In Reference Examples 1 to 17, a reference composite consisting of (b1) and (b2) was used as the curing catalyst. Reference Examples 1 to 11, which used Reference Composites 3 to 7, 11 to 15, or 17, in which the (b2) / (b1) weight ratio was within the range of 2.6 to 9, exhibited relatively good curability, and no bleeding was observed on the surface of the cured product. On the other hand, Reference Examples 12 and 13, which used Reference Composite 1 or 2, in which the (b2) / (b1) weight ratio was high at 9 or more, exhibited a long skinning time and reduced curability. Furthermore, Reference Examples 14 to 17, which used Reference Composites 8 to 10 and 16, in which the (b2) / (b1) weight ratio was low at 2.6 or less, exhibited bleeding on the surface of the cured product under humid conditions.

[0161] Example 1 (Composite 18) In a 200 ml recovery flask, Ti(O ｉ Pr) ４ 20 g of the above was added. While stirring the contents of the flask, 5 g of DBU was slowly added dropwise to the flask. Subsequently, 3 g of Dynasylan AMMO was slowly added dropwise to the flask. After the heat subsided, the flask was capped and the contents were stirred at room temperature for 24 hours, yielding 28 g of liquid complex 18.

[0162] Examples 2 to 12 (Composites 19 to 29) and Comparative Example 1 (Comparative Composite 30) Liquid composites 19 to 29 or comparative composite 30 were obtained in the same manner as in Example 1, except that the amidine compound (b1), titanium compound (b2), and amino group-containing silane (b3) shown in Table 3 were used in the weight ratios shown in Table 3.

[0163] (Evaluation) (Storage Stability) After each composite was prepared, it was sealed in a transparent container and stored under constant temperature and humidity conditions of 23°C and 50% relative humidity for 1 day or 30 days, after which its color was visually confirmed. If it was colorless and transparent, it was rated as "1", if it exhibited a pale yellow color, it was rated as "2", if it exhibited a yellow color, it was rated as "3", and if it exhibited a red color, it was rated as "4". A lower rating is more desirable, but a rating of up to "3" was considered acceptable. The measurement results are shown in Table 3.

[0164]

[0165] (Results) It can be seen that the composites 18 to 29 (Examples 1 to 12) of the amidine compound (b1), the titanium compound (b2), and the amino group-containing silane (b3) have a weight ratio of (b3) / (b2) in the range of 0.1 to 2, and that the increase in coloration over time is suppressed. On the other hand, in the comparative composite 30 (Comparative Example 1), in which the amount of the amino group-containing silane (b3) used is small and the weight ratio of (b3) / (b2) is less than 0.1, and in the reference composite 13 (Comparative Example 2), in which no amino group-containing silane (b3) is used, the color changed from pale yellow after 1 day to red after 30 days, indicating that the color deepened over time.

[0166] (Examples 13 to 27) First, a base resin was prepared in the same manner as in Reference Examples 1 to 17. Next, in the amounts shown in Table 4, Dynasylan 6490 (a condensate of a vinyltrimethoxysilane compound, manufactured by Evonik) as the silane compound (D), and Dynasylan AMMO, Dynasylan DAMO (2-aminoethyl-3-aminopropyltrimethoxysilane, manufactured by Evonik), or Dynasylan 1146 as the silane compound (C) were added and mixed. Subsequently, the composites 19 to 22 or 26 to 29 prepared in Examples 2 to 5 or 9 to 12 were added and mixed in the amounts shown in Table 4, and then filled into a cartridge, which is a moisture-proof container, to obtain a one-component curable composition. Each curable composition was stored at 23°C for 7 days in an atmosphere of 50% relative humidity, and then the skinning time (curability) was measured and the presence or absence of bleeding was confirmed in the same manner as in Reference Examples 1 to 17. The measurement results are shown in Table 4.

[0167]

[0168] (Results) In Examples 13 to 27, by using a composite of an amidine compound (b1), a titanium compound (b2), and an amino group-containing silane (b3) in which the weight ratio of (b3) / (b2) was in the range of 0.1 to 2, good curability was exhibited and no bleeding was observed on the surface of the cured product.

[0169] Examples 28 to 32 (Composites 31 to 35) Liquid composites 31 to 35 were obtained in the same manner as in Example 1, except that the amidine compound (b1), titanium compound (b2), and amino group-containing silane (b3) shown in Table 5 were used in the weight ratios shown in Table 5.

[0170]

[0171] (Examples 33 to 39) To 100 parts by weight of the organic polymer (A-1) having a reactive silicon group, colloidal calcium carbonate (Hakuenka CCR), heavy calcium carbonate (Whiten SB), plasticizer (Hexamoll DINCH), pigment (Tipake R820), thixotropy imparting agent (Crayvallac SLT), antioxidant (Irganox 1010), ultraviolet absorber (Tinuvin 326), and light stabilizer (Tinuvin 770) were added in the amounts (parts by weight) shown in Table 6, respectively, and mixed using a spatula. The mixture was then passed through a three-roll mill three times to be dispersed. Thereafter, the mixture was dehydrated under reduced pressure using a planetary mixer, cooled to 50°C or less, and then Dynasylan VTMO (vinyltrimethoxysilane, manufactured by Evonik) as the silane compound (D) and Dynasylan AMMO as the silane compound (C) were added and mixed in the amounts shown in Table 6. Subsequently, composites 31 to 35, 19, or 26 prepared in Examples 28 to 32, 2, or 9 were added and mixed in the amounts shown in Table 6, and then the mixture was filled into a moisture-proof cartridge to obtain a one-component curable composition.

[0172]

[0173] (Evaluation) (Skinning time (curing property)) Each curable composition was stored at 23°C for 7 days in an atmosphere of 50% relative humidity. Thereafter, the skinning time (curing property) was measured by the method described above. The obtained results are shown in Table 6 as "skinning time before storage." Furthermore, the curable composition was stored at 23°C for 7 days, then further stored at 50°C for 28 days, and then stored at 23°C for 1 day. Thereafter, the skinning time (curing property) was measured by the method described above. The obtained results are shown in Table 6 as "skinning time after storage."

[0174] The curable compositions of Examples 33 to 39 containing the organic polymer (A) and each composite exhibited good curability both before and after storage. There was substantially no delay in curing due to storage, and they exhibited good storage stability.

[0175] (Presence or absence of bleeding) Each curable composition was formed into a sheet using a spatula on a cardboard board under constant temperature and humidity conditions of 23°C and 50% or 70% relative humidity, and the surface was smoothed. After leaving the sheet for 7 days under conditions of 23°C and 50% or 70% relative humidity, the surface of the curable composition was touched with a fingertip to check whether the liquid compound derived from DBU had bled onto the surface of the cured product. The results are shown in Table 6.

[0176] No bleeding of the liquid compound was observed on the surface of any of the cured products obtained by curing the curable compositions of Examples 33 to 39 containing the organic polymer (A) and each composite.

[0177] (Adhesion) Each curable composition was applied to the surface of various substrates shown in Table 6 and cured for 7 days under constant temperature and humidity conditions of 23°C and 50% relative humidity. The resulting cured products were subjected to a 90° hand peel test and the state of failure was visually observed. The state of failure was rated as CF for cohesive failure (failure at the cured product) and AF for interfacial failure (peel at the interface between the cured product and the substrate). The results are shown in Table 6.

[0178] All of the curable compositions of Examples 33 to 39 containing the organic polymer (A) and each composite exhibited good adhesion to various substrates.

[0179] (Dumbbell Tensile Properties) Each curable composition was filled into a 3 mm thick sheet mold under constant temperature and humidity conditions of 23°C and 50% relative humidity. After curing for 3 days at 23°C and 50% RH, the composition was aged in a 50°C dryer for 4 days to obtain a sheet-like cured product. The resulting cured product was punched into a No. 3 dumbbell shape 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 break, and elongation at break. The results are shown in Table 6.

[0180] All of the cured products obtained by curing the curable compositions of Examples 33 to 39 containing the organic polymer (A) and each composite exhibited good tensile properties.

Claims

1. 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 ３ SiO-. Three Rs ０ are the same or different and each 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. When there are a plurality of Rs １ or X, they may be the same or different.) An organic polymer (A) having a reactive silicon group represented by the following general formula (2): R ２ N = CR ３ -NR ４ ２ (2) (In the formula, R ２ 、R ３ 、and R ４ are the same or different and each represents a hydrogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Two Rs ４ may be the same or different. Any two or more of R ２ 、R ３ 、and two Rs ４ may combine to form a cyclic structure.) An amidine structure-containing compound (b1) represented by the following general formula (3): Ti(OR ５ ) ｄ Y ４－ｄ (3) (In the formula, R ５ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a chelate coordination compound. d represents 0 or an integer of 1 to 4.) A method for producing a curable composition containing a titanium compound represented by the formula or a condensate thereof (b2), and a silane compound (b3) having a hydrolyzable silicon group and an amino group and having a molecular weight of 100 to 1500, comprising: a preparation step of preparing a catalyst-containing composition (B) obtained by mixing the amidine structure-containing compound (b1), the titanium compound or a condensate thereof (b2), and the silane compound (b3); and a mixing step of mixing the organic polymer (A) and the catalyst-containing composition (B), wherein the weight ratio (b3) / (b2) of the silane compound (b3) to the titanium compound or a condensate thereof (b2) is 0.1 to 2.

2. The method for producing a curable composition according to claim 1, wherein the weight ratio (b2) / (b1) of the titanium compound or its condensate (b2) to the amidine structure-containing compound (b1) is 2.6 to 9.

3. The method for producing a curable composition according to claim 1 or 2, wherein the content of the amidine structure-containing compound (b1) is 0.3 to 0.7 parts by weight with respect to 100 parts by weight of the organic polymer (A).

4. The method for producing a curable composition according to claim 1 or 2, wherein the curable composition further contains a silane compound (D) having a hydrolyzable silicon group and no amino group and having a molecular weight of 100 to 1500.

5. The method for producing a curable composition according to claim 4, wherein the silane compound (D) is a condensate of a silane compound having a hydrolyzable silicon group and a vinyl group.

6. 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 ３ SiO-. Three Rs ０ are the same or different and each 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. When there are a plurality of Rs １ or X, they may be the same or different.) An organic polymer (A) having a reactive silicon group represented by the formula, and a curable composition containing a catalyst-containing composition (B), wherein the catalyst-containing composition (B) has the following general formula (2): R ２ N = CR ３ -NR ４ ２ (2) (In the formula, R ２ , R ３ , and R ４ are the same or different and each represents a hydrogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Two Rs ４ may be the same or different. Any two or more of R ２ , R ３ , and two Rs ４ may be bonded to form a cyclic structure.) An amidine structure-containing compound (b1) represented by the formula, and the following general formula (3): Ti(OR ５ ) ｄ Y ４－ｄ (3) (In the formula, R ５ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a chelate coordination compound. d represents 0, or an integer of 1 to 4.) A complex of a titanium compound or a condensate thereof (b2) and a silane compound (b3) having a hydrolyzable silicon group and an amino group and having a molecular weight of 100 to 1500, wherein the weight ratio (b3) / (b2) of the silane compound (b3) to the titanium compound or its condensate (b2) is 0.1 to 2. A curable composition.

7. A cured product obtained by curing the curable composition according to claim 6.

8. A catalyst-containing composition (B) for an organic polymer (A) having a reactive silicon group, represented by the following general formula (2): R ２ N═CR ３ −NR ４ ２ (2) (In the formula, R ２ , R ３ , and R ４ are the same or different and each represents a hydrogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Two R ４ may be the same or different. Any two or more of R ２ , R ３ , and two R ４ may be bonded to form a cyclic structure.) An amidine structure-containing compound (b1) represented by the following general formula (3): Ti(OR ５ ) ｄ Y ４－ｄ (3) (In the formula, R ５ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a chelate coordination compound. d represents 0 or an integer of 1 to 4.) A complex of a titanium compound or a condensate thereof (b2) and a silane compound (b3) having a hydrolyzable silicon group and an amino group and having a molecular weight of 100 to 1500, wherein the weight ratio (b3) / (b2) of the silane compound (b3) to the titanium compound or a condensate thereof (b2) is 0.1 to 2, the catalyst-containing composition (B).

Images