Curing composition and method for producing the same

Abstract

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 condensed product 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. The method includes: preparing a catalyst-containing composition (B) obtained by mixing (b1), (b2), and (b3), and mixing the organic polymer (A) with the catalyst-containing composition (B). The weight ratio (b3) / (b2) is 0.1 to 2.

Description

Technical Field

[0001] The present invention relates to curable compositions comprising organic polymers having hydroxyl or hydrolyzable groups bonded to silicon atoms and having a silicon-based (hereinafter also referred to as "reactive silicon-based") capable of forming crosslinks by forming siloxane bonds, and methods thereof. Background Technology

[0002] Organic polymers with reactive silicon groups are known to exhibit the following property: at room temperature, they can crosslink through the formation of siloxane bonds, such as those resulting from the hydrolysis of silanes due to moisture absorption, to obtain rubber-like cured products. Such organic polymers with reactive silicon groups are already industrially produced and widely used in sealing materials, adhesives, coatings, waterproofing materials, and other applications.

[0003] To enable the curing reaction to proceed quickly, curing catalysts, such as organotin compounds with carbon-tin bonds (also known as silanol condensation catalysts), are typically incorporated into curing compositions containing organic polymers with reactive silicon groups. However, the use of organotin compounds requires caution from an environmental safety perspective.

[0004] Therefore, curing catalysts other than organotin compounds were investigated. Patent Document 1 describes the use of titanium compounds such as titanium alkoxides and titanium chelate compounds, and amine compounds such as DBU (1,8-diazabicyclo[5.4.0]-7-undecene), as curing catalysts for organic polymers with reactive silicon groups. Paragraph

[0220] of that document describes the addition of titanium compounds and amine compounds to the organic polymers with reactive silicon groups, followed by mixing.

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

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2014-114434 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] The curing catalyst disclosed in Patent Document 1 is constructed by adding a titanium compound and an amine compound to an organic polymer containing reactive silicon groups, respectively. In this regard, the inventors conducted the following research: the titanium compound and the amine compound were pre-mixed before being added to the polymer, and the resulting mixture was used as a curing catalyst.

[0011] However, mixtures of titanium compounds and amine compounds can sometimes become discolored due to the reaction between the two components, and their color may darken over time after mixing. Such darkening is undesirable from the perspective of the appearance of the mixture, the curable composition, or the cured product, which serves as a curing catalyst.

[0012] In view of the above, the object of the present invention is to provide a method for manufacturing a curable composition comprising an organic polymer containing a reactive silicon group, wherein the mixture of a titanium compound and an amine compound as a curing catalyst can suppress darkening over time while maintaining its function as a curing catalyst.

[0013] Problem Solving Methods

[0014] In order to solve the above problems, the inventors conducted in-depth research and found that by further adding amino-silane compounds to the mixture of titanium compounds and amine compounds, the darkening of the mixture over time can be suppressed. Furthermore, if added to an organic polymer containing reactive silicon groups, good curability can be achieved, thus completing the present invention.

[0015] That is, the present invention also relates to a method for manufacturing a curable composition, said curable composition comprising: an organic polymer (A) having a reactive silicon group represented by the following general formula (1), an amidine-containing compound (b1) represented by the following general formula (2), a titanium compound or its condensate represented by the following general formula (3) (b2), and a silane compound (b3) having a molecular weight of 100 to 1500 having a hydrolyzable silicon group and an amino group.

[0016] -SiR 1 3-a X a (1)

[0017] (where R is in the formula) 1 Indicates a hydrocarbon group with 1 to 20 carbon atoms, whether substituted or unsubstituted, or R 0 3SiO- represents a triorganosilylankyl group. (3 Rs) 0 Same or different, indicating hydrocarbon groups with 1 to 20 carbon atoms. X indicates a hydroxyl group or a hydrolyzable group. a indicates 1, 2, or 3. In the presence of multiple R... 1 (When X is used, they can be the same or different.)

[0018] R 2 N=CR3 -NR 4 twenty two)

[0019] (where R is in the formula) 2 R 3 and R 4 Same or different, indicating a hydrocarbon group with 1 to 20 hydrogen atoms, or substituted or unsubstituted carbon atoms. Two Rs 4 They can be the same or different. R 2 R 3 and 2 Rs 4 (Any two or more of these can be optionally bonded to form a ring structure.)

[0020] Ti(OR 5 ) d Y 4-d (3)

[0021] (where R is in the formula) 5 Represents a hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted. Y represents a chelated coordination compound. d represents 0 or an integer from 1 to 4.

[0022] The method includes:

[0023] A preparation step for preparing a catalyst-containing composition (B) by mixing the above-mentioned amidine-structured compound (b1), the above-mentioned titanium compound or its condensate (b2), and the above-mentioned silane compound (b3); and

[0024] The mixing process of mixing the above-mentioned organic polymer (A) with the above-mentioned catalyst-containing composition (B)

[0025] The weight ratio of the silane compound (b3) to the titanium compound or its condensate (b2) is 0.1 to 2.

[0026] In addition, the present invention also relates to a curable composition comprising the above-mentioned organic polymer having a reactive silicon group (A) and a catalyst-containing composition (B).

[0027] The catalyst-containing composition (B) described above comprises a complex of an amidine-containing compound (b1) represented by general formula (2), a titanium compound or its condensate (b2) represented by general formula (3), and a silane compound (b3) having a molecular weight of 100 to 1500 and having hydrolyzable silicon and amino groups.

[0028] The weight ratio (b3) / (b2) of the silane compound (b3) to the titanium compound or its condensate (b2) is 0.1 to 2. Furthermore, a cured product is also described, which is a cured product obtained by curing the curable composition.

[0029] Furthermore, the present invention also relates to a catalyst-containing composition (B), which is a catalyst-containing composition (B) for use with an organic polymer (A) having a reactive silicon group.

[0030] The catalyst-containing composition (B) comprises a complex of an amidine-containing compound (b1) represented by general formula (2), a titanium compound or its condensate (b2) represented by general formula (3), and a silane compound (b3) having a molecular weight of 100-1500 and having hydrolyzable silicon and amino groups.

[0031] The weight ratio of the silane compound (b3) to the titanium compound or its condensate (b2) is 0.1 to 2.

[0032] The effects of the invention

[0033] According to the present invention, a method for manufacturing a curable composition is provided, which is a method for manufacturing a curable composition comprising an organic polymer containing a reactive silicon group, wherein a mixture of a titanium compound and an amine compound as a curing catalyst can suppress darkening over time while maintaining its function as a curing catalyst.

[0034] Furthermore, according to the present invention, a non-tin-based catalyst-containing composition can be provided that suppresses darkening over time and achieves good curability as a curing catalyst for reactive silicon-containing organic polymers. According to a preferred embodiment, a colorless and transparent catalyst-containing composition can be provided.

[0035] According to one aspect of the present invention, it is possible to provide a curable composition that inhibits the exudation of complexes at the surface of a cured product obtained by curing.

[0036] In addition, according to one aspect of the present invention, a curable composition that suppresses curing delay caused by storage and exhibits good storage stability in terms of curability can be provided.

[0037] Furthermore, according to one aspect of the present invention, a curable composition with good adhesion can be provided.

[0038] In addition, according to one aspect of the present invention, it is possible to provide a cured composition that exhibits good tensile properties after curing. Detailed Implementation

[0039] The embodiments of the present invention will now be described in detail.

[0040] (Organic polymers containing reactive silicon groups (A))

[0041] Organic polymers (A) containing reactive silicon groups have a polymer backbone (also called the main chain structure) and polymer chain ends bonded to the polymer backbone. The polymer backbone is a structure formed by multiple monomer units continuously formed by polymerization, condensation, and other bonding processes. The monomers can be a single type or a mixture of multiple monomers bonded together.

[0042] The aforementioned polymer chain ends refer to the terminal portions of the organic polymer (A) containing reactive silicon groups. The number of polymer chain ends in the organic polymer (A) containing reactive silicon groups is 2 when the polymer backbone is entirely linear, and 3 or more when the polymer backbone is entirely branched. Additionally, in the case of a mixture of linear and branched polymer backbones, the average value may be between 2 and 3.

[0043] The reactive silicon in the organic polymer (A) can be present in the polymer backbone and / or at the ends of the polymer chains. Additionally, sometimes two or more reactive silicon groups are present at the end of one polymer chain. When the curable composition of this disclosure is used in adhesives, sealants, elastic coatings, bonding agents, etc., the aforementioned reactive silicon groups are preferably contained at the ends of the polymer chains of the organic polymer (A).

[0044] The organic polymer (A) has a reactive silicon group represented by the following general formula (1).

[0045] -SiR 1 3-a X a (1)

[0046] (where R is in the formula) 1 Indicates a hydrocarbon group with 1 to 20 carbon atoms, whether substituted or unsubstituted, or R 0 3SiO- represents a triorganosilylankyl group. (3 Rs) 0 Same or different, indicating hydrocarbon groups with 1 to 20 carbon atoms. X indicates a hydroxyl group or a hydrolyzable group. a indicates 1, 2, or 3. In the presence of multiple R... 1 (When X is used, they can be the same or different.)

[0047] R in general formula (1) 1 Examples include: alkyl groups such as methyl and ethyl; alkyl groups containing heteroatoms such as chloromethyl, methoxymethyl, and 3,3,3-trifluoropropyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl; aralkyl groups such as benzyl; R 0 R for methyl, phenyl, etc. 0 3SiO- represents triorganosylsiloxy groups, etc. Preferably alkyl, or alkyl having a heteroatom group, more preferably methyl, ethyl, chloromethyl, methoxymethyl, further preferably methyl, ethyl, and particularly preferably methyl. In the presence of multiple R...1 In certain circumstances, they can be the same or different.

[0048] In general formula (1), X represents a hydroxyl group or a hydrolyzable group. The hydrolyzable group is not particularly limited and can be any known hydrolyzable group, such as: hydrogen atom, halogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, alkenoxy group, etc. Among these, alkoxy, acyloxy, ketoximate, and alkenoxy groups are preferred. Alkoxy groups are more preferred due to their hydrolytic stability and ease of handling, methoxy groups are even more preferred, ethoxy groups are particularly preferred, and methoxy groups are especially preferred. When multiple X groups are present, they can be the same or different.

[0049] a can be 1, 2, or 3. a is preferably 2 or 3. From the viewpoint of better curing properties, a is particularly preferably 3.

[0050] The reactive silicon group represented by general formula (1) is not particularly limited, and examples include: trimethoxysilyl, triethoxysilyl, tri(2-propenyloxy)silyl, triacetyloxysilyl, 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 are preferred for ease of synthesis. Trimethoxysilyl and methoxymethyldimethoxysilyl are preferred for high curability. Trimethoxysilyl or triethoxysilyl compounds are preferred in order to obtain cured products that exhibit high recovery rate and low water absorption rate.

[0051] (Main chain structure of organic polymer (A) containing reactive silicon groups)

[0052] There are no particular restrictions on the main chain structure (also known as the polymer backbone) of organic polymers (A) containing reactive silicon groups, and various main chain structures can be used. Specifically, examples include: polyoxyethylene, polyoxypropylene, polyoxybutene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutene copolymer, and other polyoxyolefin polymers; hydrocarbon polymers such as ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; polyester polymers obtained by condensation of dicarboxylic acids such as adipic acid with diols, or by ring-opening polymerization of lactones; (meth)acrylate polymers obtained by free radical polymerization of (meth)acrylate monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and stearate methacrylate; vinyl copolymers obtained by free radical polymerization of (meth)acrylate monomers, vinyl acetate, acrylonitrile, styrene, and other monomers; polysulfide polymers; polyamide polymers; polycarbonate polymers; and diallyl phthalate polymers. It should be noted that in the above description, (meth)acrylic acid refers to acrylic acid and / or methacrylic acid.

[0053] Among these, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, as well as polyoxyethylene polymers and (meth)acrylate polymers, are preferred due to their relatively low glass transition temperature and excellent cold resistance of the resulting cured products. Only one of these polymers may be used, or two or more may be used in combination.

[0054] Polyoxyethylene polymers and (meth)acrylate polymers are particularly preferred due to their high moisture permeability, excellent deep curing properties when formulated as a one-liquid curable composition, and consequently, excellent adhesion. Polyoxyethylene polymers are more preferred, and polyoxypropylene polymers are even more preferred.

[0055] (Meth)acrylate polymers are useful because they can be combined with various monomers that make up the polymer to achieve effects such as improved adhesion, improved heat resistance, weather resistance, and reduced water absorption of the cured product obtained by curing the curing composition.

[0056] Polyoxyalkylene polymers are preferably polymers having repeating units represented by -RO- (where 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 repeating units represented by -RO- include -CH2O-, -CH2CH2O-, -CH2CH(CH3)O-, -CH2CH(C2H5)O-, -CH2C(CH3)(CH3)O-, and -CH2CH2CH2CH2O-. The main chain structure of polyoxyalkylene polymers may consist of only one type of repeating unit or two or more types of repeating units.

[0057] In particular, when the curable composition disclosed herein is used in sealants, adhesives, etc., polyoxypropylene polymers having 50% or more, more preferably 80% or more of oxypropylene repeating units in the polymer backbone structure are preferred because they are amorphous and have relatively low viscosity.

[0058] The main chain structure of polyoxyethylene polymers can be linear or branched. When branched, it is preferable to have 1 to 6 branches (i.e., 3 to 8 terminal hydroxyl groups), more preferably 1 to 4 branches (i.e., 3 to 6 terminal hydroxyl groups), and most preferably 1 branch (i.e., 3 terminal hydroxyl groups). By having branches, the resilience of the cured product can be improved. Furthermore, it is also expected to reduce the water absorption of the cured product. When the polymer has branches and the reactive silicon group is trimethoxysilyl, a cured product with particularly low water absorption can be obtained.

[0059] Polyoxyolefin polymers are preferably obtained by ring-opening polymerization of cyclic ether compounds using a polymerization catalyst in the presence of an initiator.

[0060] Examples of cyclic ether compounds include ethylene oxide, propylene oxide, butane oxide, tetramethylene oxide, and tetrahydrofuran. One type of these cyclic ether compounds may be used, or two or more may be used in combination. Among cyclic ether compounds, propylene oxide is particularly preferred because it yields amorphous polyether polymers with relatively low viscosity.

[0061] Initiators include: butanol, ethylene glycol, propylene glycol, propylene glycol monoalkyl ethers, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, and other alcohols; and hydroxyl-terminated polyoxyethylene polymers with a number average molecular weight of 300-4000, such as polyoxypropylene glycol, polyoxypropylene triol, polyoxyethylene glycol, and polyoxyethylene triol.

[0062] Examples of methods for synthesizing polyoxyethylene polymers include: polymerization using a base catalyst such as KOH; polymerization using a transition metal compound-porphyrin complex catalyst, as shown in Japanese Patent Application Publication No. 61-215623, which utilizes a complex obtained by reacting an organoaluminum compound with a porphyrin; polymerization using a complex metal cyanide complex catalyst, as shown in Japanese Patent Publication Nos. 46-27250, 59-15336, US Patent Nos. 3278457, 3278458, 3278459, 3427256, 3427334, and 3427335; polymerization using a catalyst containing a polyphosphazene salt, as exemplified in Japanese Patent Application Publication No. 10-273512; and polymerization using a catalyst containing a phosphazene compound, as exemplified in Japanese Patent Application Publication No. 11-060722. No particular limitation is specified. For reasons such as manufacturing cost and the availability of polymers with narrow molecular weight distribution, polymerization methods using composite metal cyanide complex catalysts are preferred.

[0063] As an organic polymer containing reactive silicon groups (A), a polyoxyalkylene polymer that includes other bonds such as urethane bonds and urea bonds in its main chain structure can be used, without significantly impairing the effect of the invention. A specific example of such a polymer is a polyurethane prepolymer.

[0064] Polyurethane prepolymers can be obtained by known methods, for example, by reacting polyol compounds with polyisocyanate compounds.

[0065] Examples of polyol compounds include: polyether polyols, polyester polyols, polycarbonate polyols, and polyether polyester polyols.

[0066] Examples of polyisocyanate compounds include: diphenylmethane diisocyanate, toluene diisocyanate, phenyl dimethyl diisocyanate, methylene bis(cyclohexyl isocyanate), isophorone diisocyanate, hexamethylene diisocyanate, etc.

[0067] It should be noted that the ends of polyurethane prepolymers can be any group, including hydroxyl and isocyanate groups.

[0068] From the viewpoint of obtaining a curable composition with excellent storage stability and workability, the organic polymer (A) containing reactive silicon groups is particularly preferred to be a polyoxyethylene polymer that does not contain urethane bonds, urea bonds, ester bonds and amide bonds in its main chain structure.

[0069] The organic polymer (A) containing reactive silicon groups is preferably obtained by introducing reactive silicon groups into the polymer through any of the methods described in (a) to (d) below.

[0070] (a) After converting the terminal hydroxyl groups of the hydroxyl-terminated organic polymer into carbon-carbon unsaturated groups, HSiR 1 3-a X a (where R is in the formula) 1 The method of reacting (X, and a are the same as those shown for the groups in general formula (1)).

[0071] (b) Make OCN-W-SiR 1 3-a X a (In the formula, W is a divalent organic group. R) 1 A method for reacting isocyanate-containing silane compounds (represented by X, and a, which are the same as the groups shown in general formula (1)) with the terminal hydroxyl groups of hydroxyl-terminated organic polymers.

[0072] (c) Converting the terminal hydroxyl groups of the hydroxyl-terminated organic polymer into carbon-carbon unsaturated groups to form HS-W-SiR 1 3- a X a (In the formula, W is a divalent organic group. R) 1 A method for reacting a mercaptosilane compound represented by (X, and a are the same as the groups shown in general formula (1)).

[0073] (d) After synthesizing an NCO-terminated organic polymer by reacting a hydroxyl-terminated organic polymer with a polyisocyanate compound, HNR-W-SiR was then used. 1 3-a X a (In the formula, W is a divalent organic group. R is hydrogen or alkyl.) 1 X, and a are the same as those shown for the groups in general formula (1) or HS-W-SiR 1 3-a X a (In the formula, W is a divalent organic group. R) 1 A method for reacting silane compounds represented by (X, and a) with the same groups shown in general formula (1).

[0074] In the methods described in (a) and (c) above, examples of terminal carbon-carbon unsaturated groups include vinyl, allyl, methylallyl, propadienyl, propargyl, etc.

[0075] Of the methods described above, the organic polymer (A) containing reactive silicon groups obtained by using W, which is a silane compound represented by methylene, is preferred from the perspective of exhibiting very high curability.

[0076] Method (a) tends to yield a reactive silicon-based organic polymer (A) with good storage stability, and is therefore preferred. Methods (b), (c) and (d) are preferred because they can achieve high conversion rates in relatively short reaction times.

[0077] Examples of the introduction of reactive silicon-based materials based on method (a) include Japanese Patent Publication Nos. 45-36319, 46-12154, 50-156599, 54-6096, 55-13767, 55-13468, 57-164123, 3-2450, U.S. Patent Nos. 3,632,557, 4,345,053, and 4,366,307. The methods proposed in US Patent No. 4,960,844 and other publications, as well as the methods proposed in Japanese Patent Application Publications Nos. 61-197,631, 61-215,622, 61-215,623, and 61-218,632, which introduce reactive silicon groups into high molecular weight polyoxypropylene polymers with a number average molecular weight of 6,000 or more and a Mw / Mn ratio of 1.6 or less, and the method proposed in Japanese Patent Application Publication No. 3-72,527, which introduce reactive silicon groups into high molecular weight polyoxypropylene polymers with a number average molecular weight of 6,000 or more and a Mw / Mn ratio of 1.6 or less, through hydrogenation silylation or the like, are all examples of methods.

[0078] The molecular weight distribution (Mw / Mn) of the organic polymer (A) containing reactive silicon groups is not particularly limited, but is preferably 1.6 or less, more preferably 1.5 or less, and particularly preferably 1.4 or less. Furthermore, from the viewpoint of improving the durability, elongation, and other mechanical properties of the cured product, it is preferably 1.2 or less.

[0079] The number-average molecular weight of the organic polymer (A) containing reactive silicon groups, converted from the molecular weight of polystyrene in 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 mechanical properties of the cured product are excellent. Furthermore, by appropriately introducing the reactive silicon groups, the manufacturing cost can be controlled within a reasonable range, and an organic polymer (A) exhibiting good curability, easily handleable viscosity, and excellent workability can be obtained.

[0080] The molecular weight of the organic polymer (A) containing reactive silicon groups can also be expressed by the terminal group molecular weight, which is determined as follows: by titration analysis based on the principles of the hydroxyl value determination method of JIS K 1557 and the iodine value determination method specified in JIS K 0070, directly determining the terminal group concentration, and considering the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). The terminal group-converted molecular weight of the organic polymer (A) can also be determined as follows: by converting the number-average molecular weight obtained by general GPC determination of the polymer precursor to the terminal group-converted molecular weight using a calibration curve of the above-mentioned terminal group-converted molecular weight, and then converting the number-average molecular weight obtained by GPC of the organic polymer (A) to the terminal group-converted molecular weight.

[0081] To obtain a good rubbery cured product, the reactive silica groups of the organic polymer (A) are preferably present at the ends of the polymer chains. Since it exhibits good curability and readily displays rubber-like elastic behavior, the number of reactive silica groups is preferably 0.5 or more on average per polymer chain end of the organic polymer (A), more preferably 0.6 or more, even more preferably 0.7 or more, and particularly preferably 0.8 or more.

[0082] The number of polymer chain ends per molecule of organic polymer (A) is preferably 2 to 8, more preferably 2 to 4, and particularly preferably 2 or 3.

[0083] The number of reactive silicon groups in one molecule of organic polymer (A) is preferably 1 to 7 on average, more preferably 1 to 3.4, and particularly preferably 1 to 2.6.

[0084] When the organic polymer (A) containing reactive silicon groups is branched, the reactive silicon groups can be located at the ends of the main chain, the ends of the side chains (branches), or any of these two ends. In particular, when the reactive silicon groups are located at the ends of the main chain, the molecular weight between the crosslinking points increases, thus it is easy to obtain a rubber-like cured material with high strength, high elongation, and low elastic modulus, which is therefore preferred.

[0085] As described in International Publication No. 2013 / 180203, an organic polymer (A) obtained by methods (a) and (c) described above uses an organic polymer having two or more carbon-carbon unsaturated bonds at the end of one polymer chain. Such an organic polymer (A) exhibits high curability, and the resulting cured product is expected to have high strength and high resilience.

[0086] Specific examples of organic polymers (A) containing reactive silicon groups include various polyoxypropylene products containing reactive silicon groups under the trademarks KANEKA MS Polymer or KANEKA Silyl, KANEKATA Polymer or KANEKA XMAP, poly(meth)acrylates containing reactive silicon groups, and polyisobutylene containing reactive silicon groups such as KANEKA EPION.

[0087] (Containing catalyst composition (B))

[0088] The curable composition disclosed herein contains a catalyst-containing composition (B) used to hydrolyze / condense the reactive silicon groups of the organic polymer (A) to form a cured product.

[0089] The catalyst-containing composition (B) comprises an amidine-containing compound (b1), a titanium compound or its condensate (b2), and an aminosilane compound (b3), wherein at least these three components are premixed. "Premixing" means that the amidine-containing compound (b1), the titanium compound or its condensate (b2), and the aminosilane compound (b3) are mixed in the absence of the organic polymer (A) before being added to and mixed with it, intended to distinguish this from the method described in Patent Document 1, where each component is added separately to the organic polymer (A) and then mixed together.

[0090] It is hypothesized that if an amidine-containing compound (b1) is mixed with a titanium compound or its condensate (b2), an active species is formed through the interaction between (b1) and (b2). This active species, when mixed with the organic polymer (A), can improve curability. Furthermore, by pre-mixing (b1) and (b2), the exudation of (b1) from the surface of the cured product can also be suppressed through the interaction between (b1) and (b2).

[0091] However, the mixture of (b1) and (b2) is colored by the reaction between the amidine-containing compound (b1) and the titanium compound or its condensate (b2), and if it is added to the organic polymer (A) after a period of time, its color tends to become more intense.

[0092] In this embodiment, an aminosilane compound (b3) is mixed in addition to an amidine-containing compound (b1) and a titanium compound or its condensate (b2). This suppresses the darkening of the resulting mixture over time. It is believed that this is because (b3) acts between (b1) and (b2), suppressing the reaction that causes the coloring.

[0093] The method for mixing the amidine-containing compound (b1), the titanium compound or its condensate (b2), and the aminosilane-containing compound (b3) is not particularly limited, as long as the components are mixed and stirred at room temperature or under heating below the decomposition temperature of each component. Furthermore, the above mixing can be carried out under solvent-free conditions or in the presence of a solvent inert to both components. Additionally, the above mixing can be carried out in an inert gas atmosphere (e.g., nitrogen, argon) or in the presence of air. The mixing time under stirring is not particularly limited, and can be, for example, from approximately 1 hour to 3 days.

[0094] There is no particular order in which the three components are mixed. Components can be added separately and then mixed together, or (b1) and (b2) can be mixed first, followed by (b3). Alternatively, (b1) and (b3) can be mixed first, followed by (b2), or (b2) and (b3) can be mixed first, followed by (b1).

[0095] According to a preferred embodiment, a complex of (b1), (b2), and (b3) can be obtained by pre-mixing an amidine-containing compound (b1), a titanium compound or its condensate (b2), and an aminosilane-containing compound (b3). This complex refers to a state where (b1), (b2), and (b3) do not exist independently of each other, but rather involve a reaction, the formation of chemical bonds between at least two of (b1), (b2), and (b3), or a structural change in at least one of (b1), (b2), and (b3). This complex can be formed by mixing (b1), (b2), and (b3) under stirring using the method described above. If mixing under stirring, the mixture becomes viscous, thus confirming the formation of the complex.

[0096] (Compound containing amidine structure (b1))

[0097] Compounds containing amidine structures can be represented by the following general formula (2).

[0098] R 2 N=CR 3 -NR 4 twenty two)

[0099] (where R is in the formula) 2 R 3 and R 4 Same or different, indicating a hydrocarbon group with 1 to 20 hydrogen atoms, or substituted or unsubstituted carbon atoms. Two Rs 4 They can be the same or different. R 2 R 3 and 2 Rs 4 (Any two or more of these can be optionally bonded to form a ring structure.)

[0100] In order to improve the curability of the above-mentioned curable composition, R 2 Preferably, it is a hydrocarbon group with 1 to 20 hydrogen atoms or carbon atoms, 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. For ease of acquisition, R... 2 The number of carbon atoms is preferably 1 to 10, more preferably 1 to 6.

[0101] Due to the curability of the above-mentioned curable composition, R 3 Preferably hydrogen atoms or -NR 6 The organic group represented by 2, more preferably -NR 6 2 represents an organic group. Wherein, there are two R... 6 Each of the above can be an organic group representing 1 to 20 hydrogen or carbon atoms. In this case, the compound represented by general formula (2) is called a guanidine compound.

[0102] In addition, due to the good physical properties of the obtained cured product, R 3 Preferred is -NR 7 -C(=NR 8 )-NR 9 2. Or -N = C(NR) 10 2)-NR 11 2 represents an organic group. Wherein, R 7 R 8 and 2 Rs 9 Each of the two R groups independently represents an organic group with 1 to 6 hydrogen or carbon atoms. 10 and 2 Rs 11 Each of the above can be an organic group consisting of 1 to 6 hydrogen or carbon atoms. In this case, the compound represented by general formula (2) is called a biguanide compound.

[0103] For ease of acquisition and to improve the curability of the above-mentioned curable composition, the two Rs in general formula (2) 4 Preferably, the hydrocarbon group represents 1 to 20 hydrogen atoms or carbon atoms, and more preferably, the hydrocarbon group represents 1 to 10 hydrogen atoms or carbon atoms.

[0104] The number of carbon atoms in the above-mentioned amidine-containing compounds is preferably 2 or more, more preferably 6 or more, and particularly preferably 7 or more. There is no particular limitation on the upper limit of the number of carbon atoms, but it is preferably 10,000 or less.

[0105] Furthermore, the molecular weight of the aforementioned midanidine-containing compound is preferably 60 or more, more preferably 120 or more, and particularly preferably 130 or more. There is no particular limitation on the upper limit of the molecular weight, but it is preferably 100,000 or less.

[0106] As a compound containing an amidine structure (b1), there is no particular limitation, and examples include: pyrimidines, 2-aminopyrimidines, 6-amino-2,4-dimethylpyrimidines, 2-amino-4,6-dimethylpyrimidines, 1,4,5,6-tetrahydropyrimidines, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidines, 1-ethyl-2-methyl-1,4,5,6-tetrahydropyrimidines, 1,2-diethyl-1,4,5,6-tetrahydropyrimidines, 1-n-propyl-2-methyl-1,4,5,6-tetrahydropyrimidines, 2-hydroxy-4,6-dimethylpyrimidines, 1,3-diazanaphthalenes, 2-hydroxy-4-aminopyrimidines, and other pyrimidine compounds;

[0107] 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-iminoimidazoline, and 1-methyl-2-iminoimidazoline-4-one;

[0108] 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]non-1,3,5,7-tetraene, 6-(dibutylamino)-1,8-diazabicyclo[5,4,0]undecene-7 (DBA-DBU) and other amidine compounds;

[0109] 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-Terbutyl-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]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, 7-n-octyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene and other guanidine compounds;

[0110] Biguanides, 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, 1-n-butyl-N2-ethylbiguanide, 1,1'-ethylenebiguanide, 1,5-ethylenebiguanide, 1-[3-(diethylamino)propyl]biguanide, 1-[3-(dibutylamino)propyl]biguanide, N',N''-dihexyl-3,12-diimino-2,4,11,13-tetraazatetradecanediamidinium, and other biguanide compounds. As an amidine-containing compound (b1), only one type can be used, or two or more types can be used in combination.

[0111] For better curability, the amidine-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.

[0112] (Titanium compound or its condensate (b2))

[0113] The above titanium compound (b2) is represented by the following general formula (3).

[0114] Ti(OR5 ) d Y 4-d (3)

[0115] (where R is in the formula) 5 Represents a hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted. Y represents a chelated coordination compound. d represents 0 or an integer from 1 to 4.

[0116] The condensate of the titanium compound represented by the above general formula (3) can also be used as (b2). This condensate can be obtained by reacting the titanium compound with water. Since it exhibits better curability, (b2) is preferably a condensate of the titanium compound. In addition, the titanium compound can be used in combination with the condensate of the titanium compound.

[0117] R 5 The substituted or unsubstituted hydrocarbon group is preferably a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and more preferably an aliphatic hydrocarbon group. Examples of aliphatic hydrocarbon groups include saturated or unsaturated hydrocarbon groups. As a saturated hydrocarbon group, a straight-chain or branched alkyl group is preferred. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

[0118] As R 5 Examples of hydrocarbon groups that can be represented include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, etc. Substituents that can be optionally present on the above hydrocarbon groups include: methoxy, ethoxy, hydroxyl, acetoxy, etc. In the presence of multiple R... 5 In certain circumstances, they can be the same or different.

[0119] The chelating coordination compound represented by Y can be any known compound that coordinates with titanium. There are no particular limitations; examples include: 2,4-pentanedione, 2,4-hexanedione, 2,4-pentadecanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1-phenyl-1,3-butanedione, 1-(4-methoxyphenyl)-1,3-butanedione, etc., 1-aryl-1,3-butanedione, 1,3-diphenyl-1,3-propanedione, 1,3-bis(2-pyridyl)-1,3-propanedione, 1,3-bis(4-methoxyphenyl)-1,3-propanedione, etc., 1,3-diaryl- Diketones such as 1,3-propanedione and 3-benzyl-2,4-pentanedione; ketone esters such as methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, tert-butyl acetoacetate, and ethyl 3-oxohexanoate; ketone amides such as N,N-dimethylacetoacetamide, N,N-diethylacetoacetamide, and acetoacetanilide; malonate esters such as dimethyl malonate, diethyl malonate, and diphenyl malonate; and malonamides such as N,N,N',N'-tetramethylmalonamide and N,N,N',N'-tetraethylmalonamide. Among these, diketones and ketone esters are preferred. When multiple Y groups are present, they can be the same or different.

[0120] d represents 0 or an integer from 1 to 4. In order for the curable composition of this disclosure to exhibit better curability and, in addition, to exhibit a large elongation after curing, d preferably represents 0 or an integer from 1 to 3, more preferably an integer from 1 to 3, and particularly preferably 2.

[0121] Specific examples of titanium compounds or their condensates represented by general formula (3) include tetramethoxytitanium, trimethoxyethoxydititanium, trimethoxyisopropoxytitanium, trimethoxybutoxytitanium, dimethoxydiethoxytitanium, dimethoxydiisopropoxytitanium, dimethoxydibutoxytitanium, methoxytriethoxytitanium, methoxytriisopropoxytitanium, methoxytributoxytitanium, tetraethoxytitanium, triethoxyisopropoxytitanium, triethoxybutoxytitanium, diethoxydiisopropoxytitanium, diethoxydibutoxytitanium, ethoxytriisopropoxytitanium, ethoxytributoxytitanium, tetraisopropoxytitanium, triisopropoxydibutoxytitanium, diisopropoxydibutoxytitanium, tetrabutoxytitanium, tetratert-butoxytitanium, bis(acetylacetone)diisopropoxytitanium, bis(ethyl acetoacetate)diisopropoxytitanium, bis(ethyl acetoacetate)diisobutoxytitanium; condensates of titanium alkoxides such as tetrabutoxytitanium dimer and tetrabutoxytitanium tetramer. As a titanium compound or its condensate, only one type can be used, or two or more types can be used in combination.

[0122] In order to obtain good curability and exhibit large elongation after curing, the titanium compound represented by general formula (3) is preferably a compound containing a chelating coordination compound represented by Y, and particularly preferably bis(acetylacetone)diisopropoxy titanium, bis(ethyl acetoacetate)diisopropoxy titanium, or bis(ethyl acetoacetate)diisobutoxy titanium.

[0123] (Contains aminosilane compound (b3))

[0124] The amino-containing silane compound (b3) is a silane compound with a molecular weight of 100-1500 having hydrolyzable silicon and amino groups. It is also known as a so-called silane coupling agent and is typically used as an adhesive enhancer to improve the adhesion of curable compositions to various substrates. In this embodiment, it is the component that inhibits the time-induced darkening of the catalyst-containing composition (B).

[0125] The hydrolytic silicon group in aminosilane compounds (b3) refers to a silicon-containing atomic group bonded with a hydrolytic group, or it can be represented by the general formula (1) described above for the reactive silicon group in organic polymers (A).

[0126] The hydrolyzable groups contained in the aforementioned hydrolyzable silicon group are not particularly limited, and examples include: hydrogen atoms, halogen atoms, alkoxy groups, aryloxy groups, alkenoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, etc. Among these, alkoxy groups such as methoxy and ethoxy are more preferred for their hydrolytic stability and ease of handling, and methoxy and ethoxy groups are particularly preferred.

[0127] To ensure good adhesion, the number of hydrolyzable groups bonded to silicon atoms in the aminosilane compound (b3) is sometimes preferably three. Additionally, to ensure the storage stability of the cured composition, two groups are sometimes desirable.

[0128] The molecular weight of aminosilane compounds (b3) only needs to be between 100 and 1500. The lower limit of this molecular weight can be above 150, and the upper limit can be below 1000 or below 500.

[0129] Aminosilane compounds (b3) are compounds having a hydrolyzable silicon group and a substituted or unsubstituted amino group, and are sometimes referred to as aminosilanes. The substituents present as the substituted amino group are not particularly limited, and examples include alkyl, aralkyl, and aryl groups.

[0130] Specific examples of aminosilane-containing compounds (b3) include: γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-(2-aminoethyl)aminoethyl)aminopropyltrimethoxysilane, γ-(6-aminohexyl)aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, γ-ureapropyltrimethoxysilane, etc. Methoxysilanes, γ-ureapropyltriethoxysilanes, N-phenyl-γ-aminopropyltrimethoxysilanes, N-benzyl-γ-aminopropyltrimethoxysilanes, N-vinylbenzyl-γ-aminopropyltriethoxysilanes, N-cyclohexylaminomethyltriethoxysilanes, N-cyclohexylaminomethyldiethoxymethylsilanes, N-phenylaminomethyltrimethoxysilanes, N-butylaminopropyltrimethoxysilanes, (2-aminoethyl)aminomethyltrimethoxysilanes, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis(trimethoxysilylpropyl)amine, etc., containing aminosilanes; N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propaneamine, etc., ketimine-type silanes. Alternatively, partially hydrolyzed condensates of aminosilanes, partially hydrolyzed condensates of aminosilanes and other alkoxysilanes (e.g., reactants of aminosilanes and epoxysilanes, reactants of aminosilanes and (meth)acrylate silanes) can also be used. One aminosilane compound (b3) can be used alone, or two or more can be used in combination.

[0131] To achieve good adhesion, the amino-containing silane compound (b3) is preferably γ-aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, or γ-(2-aminoethyl)aminopropylmethyldimethoxysilane. Silane coupling agents formed by condensing and oligomerizing hydrolyzed silicon groups are suitable for use from the perspective of safety and stability. The condensed silane coupling agent can be a single agent or multiple agents. Examples of oligomerized silane coupling agents include Dynasylan 1146 from Evonik. To ensure the storage stability of the cured composition, γ-aminopropyltrimethoxysilane or γ-(2-aminoethyl)aminopropylmethyldimethoxysilane are preferred.

[0132] The amount of aminosilane compound (b3) is defined by its relationship with the titanium compound or its condensate (b2), and the weight ratio of (b3) to (b2) (b3) / (b2) is in the range of 0.1 to 2. Within this range, good curability can be achieved as a curing catalyst for organic polymers containing reactive silicon groups while suppressing the time-dependent darkening of the catalyst-containing composition (B). If (b3) / (b2) is less than 0.1, it is difficult to suppress the time-dependent darkening.

[0133] 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. Furthermore, to obtain a colorless and transparent catalyst-containing composition (B), it 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, more preferably 1 or less, and even more preferably 0.8 or less.

[0134] In the curable composition disclosed herein, the content of the catalyst composition (B) can be appropriately determined according to the desired curability. For example, it can be about 0.1 to 20 parts by weight relative to 100 parts by weight of the organic polymer (A) containing reactive silicon groups, 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.

[0135] The amount of the amidine-containing compound (b1) in the curable composition disclosed herein can be appropriately adjusted within the above-mentioned range. To achieve good exudation inhibition 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 silicone-based organic polymer (A). Furthermore, 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.

[0136] The ratio of the amidine-containing compound (b1) to the titanium compound or its condensate (b2) can be appropriately set. The weight ratio of (b2) / (b1) can 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 above 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, in order to make the exudation inhibition effect of (b1) good, the lower limit of the above weight ratio is preferably 1.5 or more, more preferably 2 or more, and even more preferably 2.6 or more.

[0137] The curable composition disclosed herein may contain a curing catalyst other than the catalyst-containing composition (B). Examples of such curing catalysts include: organotin compounds, metal salts of carboxylic acids, amine compounds other than compounds containing an amidine structure (b1), carboxylic acids, metal alkoxides other than titanium compounds or their condensates (b2), inorganic acids, etc.

[0138] The content of the curing catalyst, excluding the catalyst composition (B), is not particularly limited and can be appropriately set. For example, it can be 0 to 10 parts by weight relative to 100 parts by weight of the reactive silicon-based organic polymer (A), or it can be 0 to 5 parts by weight, 0 to 3 parts by weight, or 0 to 1 part by weight. In particular, from the viewpoint of environmental safety, the lower the amount of organotin compound used, the better, preferably 0 to 1 part by weight, and more preferably 0 to 0.1 parts by weight.

[0139] (Silane compound (C) and / or silane compound (D))

[0140] The curable composition disclosed herein preferably further contains a silane compound (C) having a molecular weight of 100-1500 and having a hydrolyzable silicon group and an amino group, and / or a silane compound (D) having a molecular weight of 100-1500 and having a hydrolyzable silicon group but not an amino group. These silane compounds are compounds also known as silane coupling agents.

[0141] By incorporating these silane compounds (C) and / or (D), the adhesion and storage stability of the curable composition to various substrates can be improved. The curable composition disclosed herein may contain only silane compound (C), only silane compound (D), or both silane compound (C) and silane compound (D). Alternatively, it may not contain either silane compound (C) or silane compound (D).

[0142] The details of silane compound (C) are the same as those of amino-containing silane compound (b3) described above, and therefore will not be described further. In this application, the amino-containing silane compound contained in the catalyst-containing composition (B) is described as (b3), and the amino-containing silane compound not contained in the catalyst-containing composition (B) but incorporated into the curable composition is described as (C). However, (b3) and (C) may be the same compound or different compounds.

[0143] On the other hand, a silane compound (D) having a hydrolyzable silicon group and not having an amino group can be a compound having a hydrolyzable silicon group and reactive groups other than an amino group, or it can be a compound not having reactive groups other than a hydrolyzable silicon group.

[0144] The types and number of hydrolyzable silicon groups in silane compound (D) are the same as those described above for amino-containing silane compound (b3), so they are omitted here.

[0145] Specific examples of silane compounds (D) include: γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and other epoxy-containing silanes;

[0146] γ-isocyanate propyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-isocyanate propylmethyldiethoxysilane, γ-isocyanate propylmethyldimethoxysilane, (isocyanate methyl)trimethoxysilane, (isocyanate methyl)dimethoxymethylsilane and other isocyanate-containing silanes;

[0147] γ-Mercaptopropyltrimethoxysilane, γ-Mercaptopropyltriethoxysilane, γ-Mercaptopropylmethyldimethoxysilane, γ-Mercaptopropylmethyldiethoxysilane, mercaptomethyltriethoxysilane, and other mercaptosilanes containing mercaptosilyl groups;

[0148] Carboxysilanes such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis(2-methoxyethoxy)silane, and N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane;

[0149] Vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, and other silanes containing vinyl-type unsaturated groups;

[0150] Silanes containing (meth)acrylic acid type unsaturated groups, such as γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropylmethyltriethoxysilane, and γ-acryloxypropyltrimethoxysilane.

[0151] Silanes that do not contain reactive groups, such as methyltrimethoxysilane, dimethyldimethoxysilane, n-propyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, dimethoxydiphenylsilane, hexyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, (methoxymethyl)trimethoxysilane, and p-styryltrimethoxysilane.

[0152] Halogenated silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris(trimethoxysilyl)isocyanurate. Silane compound (D) can be used alone or in combination of two or more. Alternatively, partially hydrolyzed condensates of the silane compounds mentioned above can also be used. Examples include Dynasylan 6490 and Dynasylan 6498 from Evonik.

[0153] To achieve good adhesion, the silane compound (D) is preferably γ-epoxypropoxypropyltrimethoxysilane, γ-epoxypropoxypropyltriethoxysilane, or γ-epoxypropoxypropylmethyldimethoxysilane.

[0154] 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.

[0155] To exhibit better curability, the silane compound (D) is preferably a condensate of a silane compound having hydrolyzable silicon groups and vinyl groups. It should be noted that the silane compound condensate refers to a silane oligomer that is a partially hydrolyzed condensate of the silane compound and has vinyl groups. It is sufficient that at least a portion of the silane compound used as a raw material has vinyl groups.

[0156] The amount of silane compound (C) and the amount of silane (D) are not particularly limited and can be appropriately set according to the target properties of the silane compound used. They are preferably 0 to 20 parts by weight relative to 100 parts by weight of organic polymer (A), more preferably 0.1 to 10 parts by weight, and even more preferably 1 to 8 parts by weight.

[0157] The curable composition disclosed herein can incorporate a large amount of silane compound (C) and / or (D), which are the main causes of reduced curability in existing curable compositions. From this viewpoint, the amount of silane compound (C) relative to 100 parts by weight of organic polymer (A) 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. Similarly, the amount of silane compound (D) relative to 100 parts by weight of organic polymer (A) 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. Furthermore, the total content of silane compound (C) and the aforementioned silane compound (D) relative to 100 parts by weight of organic polymer (A) 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.

[0158] (Method for manufacturing curable compositions)

[0159] The curable composition disclosed herein can be manufactured as follows: a catalyst-containing composition (B) is obtained by mixing an amidine-containing compound (b1), a titanium compound or its condensate (b2), and an aminosilane-containing compound (b3), and then the catalyst-containing composition (B) is added to an organic polymer (A), and the two components are mixed to manufacture the composition. This improves the curability of the manufactured curable composition.

[0160] The method for mixing the organic polymer (A) and the catalyst-containing composition (B) is not particularly limited as long as uniform mixing can be achieved, and existing known equipment can be used. Furthermore, the mixing temperature is not particularly limited and can be room temperature. The catalyst-containing composition (B) can also be a commercially available product.

[0161] The order in which silane compound (C) and / or silane compound (D) are mixed with organic polymer (A) is not particularly limited. The catalyst-containing composition (B) can be added simultaneously with silane compound (C) and / or (D) to organic polymer (A) and then mixed; alternatively, organic polymer (A) can be mixed with silane compound (C) and / or (D) first, followed by the addition of catalyst-containing composition (B) and mixing. Furthermore, the mixing order of silane compound (C) and silane compound (D) is not particularly limited. Similarly, the method and temperature for performing this mixing are not particularly limited.

[0162] Furthermore, the timing of mixing other complexing agents, as described later, is not particularly limited and can be the same as in the case of silane compound (C) and / or silane compound (D). However, it is preferable to mix the catalyst-containing composition (B), as well as the silane compound (C) and / or the aforementioned silane compound (D), after mixing the organic polymer (A) with the other complexing agents.

[0163] (Other compounding agents)

[0164] As needed, the curable compositions disclosed herein may contain plasticizers, fillers, property modifiers, anti-sagging agents (thixotropic agents), stabilizers, etc.

[0165] The curable composition disclosed herein may contain a plasticizer. By adding a plasticizer, the viscosity, flowability, and mechanical properties such as tensile strength and elongation of the cured product obtained by curing the composition can be adjusted. Specific examples of plasticizers include: phthalate compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate compounds such as bis(2-ethylhexyl)-1,4-benzenediacarboxylate (specifically, trade name: EASTMAN 168 (manufactured by EASTMAN CHEMICAL)); and non-phthalate compounds such as diisononyl 1,2-cyclohexanedicarboxylate (specifically, trade name: Hexamoll). The composition includes: DINCH (manufactured by BASF); aliphatic polycarboxylic acid esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and acetyl tributyl citrate; unsaturated fatty acid esters such as butyl oleate and acetyl ricinoleate; alkyl sulfonates (specifically, trade name: Mesamoll (manufactured by LANXESS)); phosphate esters such as tricresyl phosphate and tributyl phosphate; trimellitic acid esters; chlorinated paraffins; hydrocarbon oils such as alkyl biphenyls and partially hydrogenated terphenyls; processing oils; and epoxy plasticizers such as epoxidized soybean oil and benzyl epoxidized stearate. Among these, cured compositions made using aliphatic carboxylic acid esters such as diisononyl 1,2-cyclohexanedicarboxylate are preferred as they readily exhibit low water absorption.

[0166] Alternatively, polymeric plasticizers can be used. When polymeric plasticizers are used, the initial physical properties can be maintained for a longer period compared to the use of low-molecular-weight plasticizers, which are plasticizers that do not contain polymer components in their molecules. Furthermore, the drying properties (coating properties) can be improved when alkyd coatings are applied to the cured material. Specific examples of polymeric plasticizers include vinyl polymers obtained by polymerizing vinyl monomers through various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; polyester plasticizers obtained by reacting dicarboxylic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid with diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol; polyethers such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol with a number average molecular weight of 500 or higher, and further 1000 or higher; polyethers such as derivatives obtained by converting the hydroxyl groups of these polyether polyols into ester groups or ether groups; polystyrene such as polystyrene and poly-α-methylstyrene; and polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, and polychloroprene, but not limited to these.

[0167] Among these polymeric plasticizers, those compatible with organic polymers (A) containing reactive silicon groups are preferred. From this perspective, polyether-based and vinyl-based polymers are preferred. Furthermore, using polyether-based plasticizers improves surface curing and deep curing properties and prevents delayed curing after storage, making them preferred, with polypropylene glycol being more preferred. Additionally, vinyl-based polymers are preferred from the perspectives of compatibility, weather resistance, and heat resistance. Among vinyl-based polymers, acrylic polymers and / or methacrylic polymers are preferred, and acrylic polymers such as alkyl polyacrylates are more preferred. Regarding the synthesis method of this polymer, since its narrow molecular weight distribution allows for low viscosity, living radical polymerization is preferred, and atom transfer radical polymerization is more preferred. Furthermore, polymers obtained by continuous bulk polymerization of alkyl polyacrylate monomers under high temperature / high pressure using the so-called SGO process, as described in Japanese Patent Application Publication No. 2001-207157, are preferred.

[0168] The number average molecular weight of the polymeric plasticizer is preferably 500-15000, more preferably 800-10000, further preferably 1000-8000, and particularly preferably 1000-5000. Most preferably, it is 1000-3000. If the molecular weight is too low, the plasticizer will flow out over time due to heat or rainfall, and cannot maintain its initial physical properties for a long period. Furthermore, if the molecular weight is too high, the viscosity increases, and the workability deteriorates.

[0169] The molecular weight distribution of the polymeric plasticizer is not particularly limited, but a narrow distribution is preferred, preferably less than 1.80. More preferably, it is 1.70 or less, further preferably 1.60 or less, even more preferably 1.50 or less, particularly preferably 1.40 or less, and most preferably 1.30 or less.

[0170] The number-average molecular weight of the polymeric plasticizer was determined by GPC for vinyl-based polymers and by end-group analysis for polyether-based polymers. Furthermore, the molecular weight distribution (Mw / Mn) was determined by GPC (polystyrene conversion).

[0171] Furthermore, polymeric plasticizers may or may not have reactive silicone groups. When reactive silicone groups are present, they can function as reactive plasticizers, preventing the plasticizer from migrating from the cured product. When reactive silicone groups are present, the number of reactive silicone groups is preferably 1 or less per molecule, more preferably 0.8 or less. When using plasticizers with reactive silicone groups, particularly polyether polymers with reactive silicone groups, it is desirable that their number-average molecular weight is lower than that of organic polymers (A) containing reactive silicone groups.

[0172] The amount of plasticizer used relative to 100 parts by weight of the reactive silicone-based organic polymer (A) 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. Within this range, the effect of acting as a plasticizer can be achieved while maintaining the mechanical strength of the cured product. The plasticizer can be used alone or in combination of two or more types. Furthermore, low-molecular-weight plasticizers can be used in combination with high-molecular-weight plasticizers. It should be noted that these plasticizers can also be incorporated into the polymer manufacturing process.

[0173] The curable composition disclosed herein may contain fillers. Examples of fillers include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silica, hydrated silica, and carbon black; resin powders such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium dioxide, bentonite, organobentonite, iron oxide, aluminum micropowder, flint powder, zinc oxide, active zinc oxide, PVC powder, and PMMA powder; and fibrous fillers such as asbestos, glass fiber, and filaments. When using fillers, their amount relative to 100 parts by weight of the reactive silicon-based organic polymer (A) is preferably 1 to 300 parts by weight, more preferably 10 to 200 parts by weight.

[0174] When it is desirable to obtain a cured product with high strength by using these fillers, it is preferable to primarily use fillers selected from fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silica, hydrated silica, carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and active zinc oxide. Preferred results can be obtained by using fillers in the range of 1 to 200 parts by weight relative to 100 parts by weight of the reactive silicon-based organic polymer (A). Furthermore, when it is desirable to obtain a cured product with low strength and high elongation at break, preferred results can be obtained by primarily using fillers selected from titanium dioxide, calcium carbonate, magnesium carbonate, talc, iron oxide, zinc oxide, and Shirasu hollow spheres in the range of 5 to 200 parts by weight relative to 100 parts by weight of the reactive silicon-based organic polymer (A).

[0175] For the purpose of making the composition lighter (lower specific gravity), the curable composition disclosed herein may contain spherical hollow bodies such as hollow spheres.

[0176] Hollow spheres refer to substances that are hollow inside a spherical filler. Examples of materials for hollow spheres include inorganic materials such as glass, white sand, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, styrene, and acrylonitrile. However, these are not limited to these materials; inorganic and organic materials can be combined, or layered to form multilayers. Hollow spheres can be made from inorganic, organic, or composite materials. Furthermore, the same type of hollow spheres can be used, or a mixture of hollow spheres from different materials can be used. Additionally, hollow spheres can be made from materials obtained by surface processing or coating, or from materials obtained by surface treatment with various surface treatment agents. Examples include coating organic hollow spheres with calcium carbonate, talc, or titanium dioxide, or surface treating inorganic hollow spheres with silane coupling agents.

[0177] The particle size of the hollow spheres is preferably 3~200μm, and particularly preferably 10~110μm. If it is less than 3μm, the contribution to lightweighting is small, so a large amount needs to be added. If it is greater than 200μm, the surface of the cured sealing material becomes uneven, or there is a tendency for the elongation to decrease.

[0178] The amount of the spherical hollow body is preferably 0.01 to 30 parts by weight relative to 100 parts by weight of the organic polymer (A) containing reactive silicon groups. The lower limit is preferably 0.1 parts by weight, and the upper limit is more preferably 20 parts by weight. Within this range, the workability can be improved while maintaining the elongation and tensile strength of the cured product.

[0179] As needed, the curable compositions disclosed herein may contain property modifiers to adjust the tensile properties of the cured product. Property modifiers are not particularly limited, and examples include: alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; alkylisopropoxysilanes such as dimethyldiisopropoxysilane, methyltriisopropoxysilane, and γ-glycidoxypropylmethyldiisopropoxysilane; alkylalkoxysilanes with functional groups such as γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; organosilicon varnishes; and polysiloxanes. By using the above-mentioned property modifiers, the hardness of the cured product obtained by curing the curable composition can be increased, or conversely, the hardness can be decreased, exhibiting elongation at break. The above-mentioned property modifiers can be used alone or in combination of two or more.

[0180] In particular, compounds that generate a monovalent silanol group within the molecule through hydrolysis do not worsen the stickiness of the cured material's surface and have the effect of reducing the modulus of the cured material. Compounds that generate trimethylsilanol are particularly preferred. Examples of compounds that generate a monovalent silanol group within the molecule through hydrolysis include those described in Japanese Patent Application Publication No. 5-117521. Additionally, derivatives of alkyl alcohols such as hexanol, octanol, and decanol, which are silicon compounds that generate trialkylsilanols such as trimethylsilanol through hydrolysis, are also examples. Derivatives of polyols with 3 or more hydroxyl groups, such as trimethylolpropane, glycerol, pentaerythritol, or sorbitol, as described in Japanese Patent Application Publication No. 11-241029, are also examples of silicon compounds that generate trialkylsilanols such as trimethylsilanol through hydrolysis. Specifically, examples include phenoxytrimethylsilane and tris(trimethylsiloxymethyl)propane.

[0181] Additionally, derivatives of olefin oxide polymers disclosed in Japanese Patent Application Publication No. 7-258534 can be cited as examples. These derivatives are silicon compounds that generate trialkylsilanols such as trimethylsilanol through hydrolysis. Furthermore, polymers with crosslinkable hydrolyzable silicon-containing groups and silicon-containing groups that can generate monosilanol compounds through hydrolysis, as disclosed in Japanese Patent Application Publication No. 6-279693, can also be used.

[0182] The property modifier is preferably used in an amount of 0.1 to 20 parts by weight relative to 100 parts by weight of the organic polymer (A) containing reactive silicon groups, and more preferably in an amount of 0.5 to 10 parts by weight.

[0183] As needed, to prevent sagging and improve workability, the curable compositions disclosed herein may contain anti-sagging agents. Furthermore, there are no particular limitations on anti-sagging agents; examples include: polyamide waxes; hydrogenated castor oil derivatives; and metallic soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents can be used alone or in combination of two or more.

[0184] The anti-sagging agent is preferably used in the range of 0.1 to 20 parts by weight relative to 100 parts by weight of the organic polymer (A) containing reactive silicone groups.

[0185] The curable compositions disclosed herein may contain antioxidants (anti-aging agents). Using antioxidants improves the weather resistance of the cured product. Examples of antioxidants include hindered phenolic, monophenolic, bisphenolic, and polyphenolic compounds, with hindered phenolic compounds 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 Corporation); and NocRac CD (manufactured by Ouchi Shinsei Chemical Co., Ltd.) can also be used. In addition, antioxidants such as SOGNOX 4120, Naugard 445, and OKABEST CLX050 can also be used. Specific examples of antioxidants are also recorded in Japanese Patent Application Publication No. 4-283259 and Japanese Patent Application Publication No. 9-194731.

[0186] The amount of antioxidant used is preferably 0.1 to 10 parts by weight relative to 100 parts by weight of the reactive silicone-based organic polymer (A), more preferably 0.2 to 5 parts by weight.

[0187] The curable composition disclosed herein may contain a light stabilizer. Using a light stabilizer can prevent photo-oxidative degradation of the cured product. Examples of light stabilizers include benzotriazole compounds, hindered amine compounds, and benzoate compounds, with hindered amine compounds being particularly preferred. Specific examples of light stabilizers are also described in Japanese Patent Application Publication No. 9-194731.

[0188] The amount of light stabilizer used is preferably 0.1 to 10 parts by weight relative to 100 parts by weight of the reactive silicon-based organic polymer (A), more preferably 0.2 to 5 parts by weight.

[0189] When a light-curing substance is incorporated into the curable composition disclosed herein, especially when an unsaturated acrylic compound is used, it is preferable to use a hindered amine light stabilizer containing a tertiary amine, as described in Japanese Patent Application Publication No. 5-70531, as the hindered amine light stabilizer for improving the storage stability of the composition. Examples of hindered amine light stabilizers containing tertiary amines include Tinuvin 123, Tinuvin 144, Tinuvin 249, Tinuvin 292, Tinuvin 312, Tinuvin 622LD, Tinuvin 765, Tinuvin 770, Tinuvin 880, Tinuvin 5866, Tinuvin B97, Chimassor B119FL, and Chimassor B944LD (all manufactured by BASF); ADEKA 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 Corporation), SABOSTAB UV91, SABOSTAB UV119, and SONGSORB. Light stabilizers such as CS5100, SONGSORB CS622, SONGSORB CS944 (all manufactured by SONGWON), and NocRac CD (manufactured by Ouchi Shinshin Chemical Industry Co., Ltd.).

[0190] The curable compositions disclosed herein may contain a UV absorber. Using a UV absorber improves the surface weather resistance of the cured product. Examples of UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, triazine-based, substituted acrylonitrile-based, and metal chelate 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). In addition, examples of triazine compounds include: Tinuvin 400, Tinuvin 405, Tinuvin 477, and Tinuvin 1577ED (all manufactured by BASF); and SONGSORB CS400 and SONGSORB 1577 (manufactured by SONGWON). Examples of benzophenone compounds include SONGSORB 8100 (manufactured by SONGWON).

[0191] The amount of ultraviolet absorber relative to 100 parts by weight of the reactive silicon-based organic polymer (A) is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight. It is preferable to use a combination of phenolic, hindered phenolic antioxidants, hindered amine light stabilizers and benzotriazole ultraviolet absorbers.

[0192] Addworks IBC760 (manufactured by Clariant) can also be used as a product that combines antioxidants, light stabilizers, and UV absorbers.

[0193] The curable compositions disclosed herein may contain epoxy resin. Compositions containing epoxy resin are particularly preferred as adhesives, especially for exterior wall tiles. Examples of epoxy resins include bisphenol A type epoxy resins and phenolic varnish type epoxy resins.

[0194] There is no particular limitation on the ratio of organic polymer (A) to epoxy resin, but the preferred ratio by weight is in the range of 100 / 1 to 1 / 100.

[0195] When used in conjunction with epoxy resin, the curable composition of this disclosure preferably incorporates a curing agent for curing the epoxy resin. There are no particular limitations on the epoxy resin curing agent that can be used; commonly used epoxy resin curing agents can be employed. When using an epoxy resin curing agent, its amount is preferably in the range of 0.1 to 300 parts by weight relative to 100 parts by weight of the epoxy resin.

[0196] For the purpose of adjusting various physical properties of the curable composition or cured product, the curable composition disclosed herein may contain various additives as needed. Examples of such additives include: flame retardants, curing modifiers, polymerization inhibitors, metal passivators, ozone degrading agents, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, solvents, and mildew inhibitors. 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 other than those described in this specification are described in Japanese Patent Application Publication Nos. 4-69659, 7-108928, 63-254149, 64-22904, and 2001-72854.

[0197] Alternatively, all the ingredients can be pre-mixed and sealed for preservation, forming a single-component curable composition that cures upon application due to moisture in the air. Alternatively, a two-component curable composition can be prepared by separately preparing a curing agent containing a curing catalyst, filler, plasticizer, water, etc., and a main agent containing a reactive silicone-based organic polymer (A), mixing these main agents and the curing agent before use.

[0198] When the curable composition is a single-component form, all compounding components are pre-formulated. Therefore, it is preferable to use the compounding components containing moisture after pre-dehydration and drying, or to dehydrate them during compounding by means of reduced pressure. When the above-mentioned curable composition is a two-component form, since it is not necessary to incorporate a curing catalyst into the main agent containing the organic polymer (A) with reactive silicon groups, the possibility of gelation is small even if the compounding agent contains some moisture. When long-term storage stability is required, dehydration and drying are preferred. As dehydration and drying methods, in the case of solid substances such as powders, heating drying is preferred. In the case of liquid substances, reduced pressure dehydration or dehydration methods using synthetic zeolites, activated alumina, silica gels, etc. are preferred. Alternatively, a small amount of isocyanate compound may be incorporated to react the isocyanate groups with water and dehydrate them. In addition to the dehydration and drying methods mentioned above, storage stability can be further improved by adding lower alcohols such as methanol and ethanol, and alkoxysilane compounds such as methyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, phenyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-epoxypropoxypropyltrimethoxysilane. From a safety and stability perspective, partially condensed silane compounds such as Dynasylan 6490 from Evonik can also be appropriately used as dehydrating agents.

[0199] The amount of the dehydrating agent, particularly a silicon compound such as vinyltrimethoxysilane that can react with water, is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the organic polymer (A) containing reactive silicon groups.

[0200] The curable compositions disclosed herein can be used as sealing materials for construction, adhesives for industrial use, waterproof coatings, and adhesive raw materials. Additionally, they can be used as sealants for buildings, ships, automobiles, roads, etc. Furthermore, because they can bond well with a wide range of substrates such as glass, porcelain, wood, metal, and resin molded products, either alone or with the aid of a primer, they can also be used as various types of sealing and adhesive compositions. As adhesives, in addition to general adhesives, they can also be used in the form of contact adhesives. Furthermore, they are useful as food packaging materials, casting rubber materials, molding materials, and coatings.

[0201] In the following items, preferred embodiments of this disclosure are listed, but the invention is not limited to the following items.

[0202] [Project 1]

[0203] A method for manufacturing a curable composition, said curable composition comprising: an organic polymer (A) having a reactive silicon group represented by the following general formula (1), an amidine-containing compound (b1) represented by the following general formula (2), a titanium compound or its condensate represented by the following general formula (3) (b2), and a silane compound (b3) having a hydrolyzable silicon group and an amino group and a molecular weight of 100-1500.

[0204] -SiR 1 3-a X a (1)

[0205] In the formula, R 1 Indicates a hydrocarbon group with 1 to 20 carbon atoms, whether substituted or unsubstituted, or R 0 3SiO- represents three organosilasilyloxy groups, with three R groups. 0 Same or different, indicating hydrocarbon groups with 1 to 20 carbon atoms, X indicates a hydroxyl group or a hydrolyzable group, a indicates 1, 2 or 3, and multiple R are present. 1 When X or , they can be the same or different.

[0206] R 2 N=CR 3 -NR 4 twenty two)

[0207] In the formula, R 2 R 3 and R 4Same or different, indicating a hydrocarbon group with 1 to 20 hydrogen atoms, or substituted or unsubstituted carbon atoms, and two Rs. 4 They can be the same or different, R 2 R 3 and 2 Rs 4 Any two or more of them can be selectively bonded to form a ring structure.

[0208] Ti(OR 5 ) d Y 4-d (3)

[0209] (where R is in the formula) 5 The group represents a hydrocarbon group with 1 to 20 carbon atoms, whether substituted or unsubstituted; Y represents a chelated coordination compound; and d represents 0 or an integer from 1 to 4.

[0210] The method includes:

[0211] A preparation step for preparing a catalyst-containing composition (B) by mixing the above-mentioned amidine-structured compound (b1), the above-mentioned titanium compound or its condensate (b2), and the above-mentioned silane compound (b3); and

[0212] The mixing process of mixing the above-mentioned organic polymer (A) with the above-mentioned catalyst-containing composition (B)

[0213] The weight ratio of the silane compound (b3) to the titanium compound or its condensate (b2) is 0.1 to 2.

[0214] [Project 2]

[0215] According to the method for manufacturing the curable composition described in Project 1, wherein,

[0216] The weight ratio (b2) / (b1) of the above titanium compound or its condensate (b2) to the above amidine-containing compound (b1) is 2.6 to 9.

[0217] [Project 3]

[0218] The method for manufacturing the curable composition according to item 1 or 2, wherein,

[0219] The content of the above-mentioned amidine-containing compound (b1) is 0.3 to 0.7 parts by weight relative to 100 parts by weight of the above-mentioned organic polymer (A).

[0220] [Project 4]

[0221] The method for manufacturing the curable composition according to any one of items 1 to 3, wherein,

[0222] The above-mentioned curable composition further contains a silane compound (D) with a molecular weight of 100 to 1500 that has a hydrolyzable silicon group and does not have an amino group.

[0223] [Project 5]

[0224] According to the method for manufacturing the curable composition described in Project 4, wherein,

[0225] The aforementioned silane compound (D) is a condensation of a silane compound having hydrolyzable silicon and vinyl groups.

[0226] [Project 6]

[0227] A curable composition comprising an organic polymer (A) having a reactive silicon group represented by the above general formula (1), and a catalyst-containing composition (B),

[0228] The catalyst-containing composition (B) described above comprises a complex of an amidine-containing compound (b1) represented by general formula (2), a titanium compound or its condensate (b2) represented by general formula (3), and a silane compound (b3) having a molecular weight of 100 to 1500 and having hydrolyzable silicon and amino groups.

[0229] The weight ratio of the silane compound (b3) to the titanium compound or its condensate (b2) is 0.1 to 2.

[0230] [Project 7]

[0231] A cured product obtained by curing the curable composition described in item 6.

[0232] [Project 8]

[0233] A catalyst-containing composition (B) is used with an organic polymer (A) having a reactive silicon group.

[0234] The catalyst-containing composition (B) comprises a complex of an amidine-containing compound (b1) represented by general formula (2), a titanium compound or its condensate (b2) represented by general formula (3), and a silane compound (b3) having a molecular weight of 100-1500 and having hydrolyzable silicon and amino groups.

[0235] The weight ratio of the silane compound (b3) to the titanium compound or its condensate (b2) is 0.1 to 2.

[0236] Example

[0237] The present invention will be described in more detail below with specific examples, but the present invention is not limited to the following examples.

[0238] The number-average molecular weights in the examples are GPC molecular weights measured under the following conditions.

[0239] Liquid delivery system: Tosoh HLC-8120GPC

[0240] Pillar: Tosoh TSKgel SuperH series

[0241] Solvent: THF

[0242] Molecular weight: Polystyrene conversion

[0243] Measurement temperature: 40℃

[0244] The average number of silyl groups per terminal or per molecule of the polymers shown in the examples was calculated by H-NMR measurements (using a Bruker AVANCE III HD-500 in CDCl3 solvent).

[0245] <Synthesis of Organic Polymer (A)>

[0246] (Synthetic Example 1(A-1))

[0247] Polypropylene glycol with a molecular weight of approximately 2000 was used as an initiator to polymerize propylene oxide using a zinc hexacyanocobaltate ethylene glycol dimethyl ether complex catalyst, yielding polypropylene oxide with a number average molecular weight of 28500. Next, 1.2 molar equivalents of NaOMe in a methanol solution were added relative to the hydroxyl groups of this hydroxyl-terminated polypropylene oxide. The methanol was removed by distillation, and allyl chloride was further added to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by vacuum devolatilization. Relative to 100 parts by weight of the resulting unpurified allyl-terminated polypropylene oxide, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred. The water was removed by centrifugation. The resulting hexane solution was then further mixed with 300 parts by weight of water and stirred. The water was removed again by centrifugation, and the hexane was removed by vacuum devolatilization. Through these operations, a difunctional polypropylene oxide with an allyl-terminated molecular weight of approximately 28500 was obtained. Relative to 100 parts by weight of the obtained allyl-terminated polypropylene oxide, a 150 ppm solution of 2-propanol containing 3 wt% platinum of the platinum vinylsiloxane complex was used as a catalyst to react trimethoxysilane with an allyl group equivalent of 0.8 molar equivalent relative to the allyl-terminated polypropylene oxide at 90 °C for 5 hours, yielding trimethoxysilyl-terminated polypropylene oxide (A-1). The number of trimethoxysilyl groups was approximately 0.8 per polymer chain terminus on average.

[0248] The following compounds were used in the manufacture of each complex.

[0249] TC-750: Di(ethyl acetoacetate) diisopropoxy titanium (Matsumoto Fine Chemical Co., Ltd.)

[0250] Tyzor IBAY: Bis(ethyl acetoacetate) diisobutoxytitanium, (manufactured by Dorf Ketal)

[0251] Ti(O i Pr)4: Tetraisopropoxy titanium (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0252] Ti(OBu)4: Tetrabutoxytitanium (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0253] Tyzor 9000: Tetratert-butoxytitanium (manufactured by Dorf Ketal)

[0254] Hexabutoxy-μ-oxotitanium (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0255] DBU: 1,8-diazabicyclo[5.4.0]-7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0256] Dynasylan AMMO (γ-aminopropyltrimethoxysilane, manufactured by Evonik)

[0257] Dynasylan 1146 (a condensate of diaminosilane and alkylsilane, manufactured by Evonik)

[0258] <Manufacturing Example 1 (Reference Composite 1)>

[0259] Add 20g of TC-750 to a 200ml round-bottom flask. While stirring the contents of the flask, slowly add 0.1g of DBU dropwise. After the addition is complete, cap the flask and stir the contents at room temperature for 24 hours to obtain 20.1g of liquid reference complex 1.

[0260] <Manufacturing Examples 2-17 (Refer to Composites 2-17)>

[0261] Using the amidine compound (b1) and titanium compound (b2) listed in Table 1 at the weight ratios specified in Table 1, liquid reference complexes 2-17 were obtained by the same method as in manufacturing example 1.

[0262] [Table 1]

[0263]

[0264] (Refer to Examples 1-17)

[0265] (Preparation of the main ingredient)

[0266] Relative to 100 parts by weight of the reactive silicon-based organic polymer (A-1), the following were added in the amounts (parts by weight) listed in Table 2: colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., trade name: Shirai Enka CCR), heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: Whiton SB), plasticizer (manufactured by BASF, trade name: Hexamoll DINCH), pigment (manufactured by Ishihara Sangyo Co., Ltd., trade name: TIPAQUE R820), thixotropic agent (manufactured by ARKEMA, trade name: Crayvallac SLT), antioxidant (manufactured by BASF, trade name: Irganox 1010), ultraviolet absorber (manufactured by BASF, trade name: Tinuvin 326), and light stabilizer (manufactured by BASF, trade name: Tinuvin 770). After mixing with a scraper, the mixture was dispersed by passing it through a three-roll mill three times. Then, a planetary mixer was used to dehydrate the mixture under reduced pressure, and the mixture was filled into a cartridge, which served as a moisture-proof container, to produce the main agent.

[0267] (Preparation of curable compositions)

[0268] The main agent was extruded from the barrel and metered in a plastic container at 23°C and 50% relative humidity. Dynasylan VTMO (silane compound (D): vinyltrimethoxysilane, manufactured by Evonik) and Dynasylan AMMO (silane compound (C): γ-aminopropyltrimethoxysilane, manufactured by Evonik) were added to the container in the amounts specified in Table 2 and mixed.

[0269] Next, as a curing catalyst, reference composites 1 to 17 prepared in manufacturing examples 1 to 17 were added in the amounts recorded in Table 2 and mixed to obtain curable compositions.

[0270] (evaluate)

[0271] (Skin formation time (curing time))

[0272] The obtained curable composition was filled into a mold frame with a thickness of approximately 5 mm using a scraper. The time it took for the surface to become flat was taken as the curing start time. The time it took for the composition to no longer adhere to the scraper after contacting the surface was taken as the skinning time (curing time). The results are shown in Table 2.

[0273] (Presence or absence of seepage)

[0274] Under constant temperature and humidity conditions of 23°C and 50% or 70% relative humidity, each curing composition was sheeted onto corrugated cardboard using a scraper to smooth the surface. Then, after being left at 23°C and 50% or 70% relative humidity for 7 days, the surface of the cured composition was touched with a fingertip to confirm whether the liquid compound from DBU had seeped out onto the cured surface. The results are shown in Table 2.

[0275] [Table 2]

[0276]

[0277] (result)

[0278] In Reference Examples 1-17, a reference composite consisting of (b1) and (b2) was used as a curing catalyst. Reference Examples 1-11, which used reference composites 3-7, 11-15, or 17 with a (b2) / (b1) weight ratio in the range of 2.6-9, exhibited relatively good curing properties, and no exudation was observed on the surface of the cured product. On the other hand, Reference Examples 12-13, which used reference composites 1 or 2 with a (b2) / (b1) weight ratio as high as 9 or more, showed a long skinning time and reduced curing properties. Furthermore, Reference Examples 14-17, which used reference composites 8-10 and 16 with a (b2) / (b1) weight ratio as low as 2.6 or less, experienced exudation on the surface of the cured product under humid conditions.

[0279] <Example 1 (Composite 18)>

[0280] Add 20g of Ti(O) to a 200ml round-bottom flask. i Pr)4. While stirring the contents of the flask, 5g of DBU was slowly added dropwise to the flask. Then, 3g of Dynasylan AMMO was slowly added dropwise to the flask. After the heat dissipated, the flask was capped, and the contents of the flask were stirred at room temperature for 24 hours to obtain 28g of liquid complex 18.

[0281] <Examples 2-12 (complexes 19-29) and Comparative Example 1 (comparative complex 30)>

[0282] The amidine compound (b1), titanium compound (b2), and aminosilane (b3) listed in Table 3 were used in the weight ratios specified in Table 3. Otherwise, liquid complexes 19-29 or comparative complex 30 were obtained by the same method as in Example 1.

[0283] (evaluate)

[0284] (Storage stability)

[0285] After preparing each composite, it was sealed in a transparent container and stored under constant temperature and humidity conditions of 23°C and 50% for 1 day or 30 days. Its color was then visually assessed. Colorless and transparent was rated "1", pale yellow was rated "2", yellow was rated "3", and red was rated "4". Lower ratings were preferred, and values ​​up to "3" were considered acceptable. The results are shown in Table 3.

[0286] [Table 3]

[0287]

[0288] (result)

[0289] It was found that when the weight ratio of (b3) / (b2) of the amidine compound (b1), titanium compound (b2), and aminosilane-containing complexes 18-29 (Examples 1-12) was in the range of 0.1-2, the increase in coloring over time was suppressed. On the other hand, it was found that in comparative complex 30 (Comparative Example 1), which used a small amount of aminosilane-containing compound (b3) and had a weight ratio of (b3) / (b2) of less than 0.1, and in reference complex 13 (Comparative Example 2), which did not use aminosilane-containing compound (b3), the pale yellow complex turned red after 30 days, and the color deepened over time.

[0290] (Examples 13-27)

[0291] First, the main agent was prepared in the same manner as in Reference Examples 1-17.

[0292] Next, Dynasylan 6490 (a condensate of vinyltrimethoxysilane compound, manufactured by Evonik) as silane compound (D), and Dynasylan AMMO, Dynasylan DAMO (2-aminoethyl-3-aminopropyltrimethoxysilane, manufactured by Evonik), or Dynasylan 1146 as silane compound (C), were added and mixed according to the amounts specified in Table 4.

[0293] Next, the composites 19-22 or 26-29 prepared in Examples 2-5 or 9-12 were added in the amounts recorded in Table 4 and mixed. The mixture was then filled into a cylinder serving as a moisture-proof container to obtain a single-agent curable composition.

[0294] After storing each curing composition for 7 days in an atmosphere with a relative humidity of 50% at 23°C, the skinning time (curing properties) was measured using the same method as in Reference Examples 1-17 to confirm the presence or absence of exudation. The results are shown in Table 4.

[0295] [Table 4]

[0296]

[0297] (result)

[0298] In Examples 13-27, good curability was observed by using a composite of amidine compound (b1), titanium compound (b2), and aminosilane (b3) with a weight ratio of (b3) / (b2) of the composite in the range of 0.1 to 2, and no exudation was detected on the surface of the cured product.

[0299] <Examples 28-32 (Compounds 31-35)>

[0300] The amidine compound (b1), titanium compound (b2), and aminosilane (b3) listed in Table 5 were used in the weight ratios specified in Table 5. Otherwise, liquid composites 31-35 were obtained by the same method as in Example 1.

[0301] [Table 5]

[0302]

[0303] (Examples 33-39)

[0304] Relative to 100 parts by weight of the reactive silicon-based organic polymer (A-1), colloidal calcium carbonate (Baiyanhua CCR), heavy calcium carbonate (Whiton SB), plasticizer (HexamollDINCH), pigment (TIPAQUE R820), thixotropic agent (Crayvallac SLT), antioxidant (Irganox 1010), UV absorber (Tinuvin 326), and light stabilizer (Tinuvin 770) were added in the amounts (parts by weight) listed in Table 6. After mixing with a scraper, the mixture was dispersed by passing it through a three-roll mill three times. Then, it was dehydrated under reduced pressure using a planetary mixer and cooled to below 50°C. Dynasylan VTMO (vinyltrimethoxysilane, manufactured by Evonik) as silane compound (D) and Dynasylan AMMO as silane compound (C) were added in the amounts listed in Table 6 and mixed.

[0305] Next, the composites 31-35, 19, or 26 prepared in Examples 28-32, 2, or 9 were added in the amounts recorded in Table 6 and mixed. The mixture was then filled into a cylinder serving as a moisture-proof container to obtain a single-agent curable composition.

[0306] [Table 6]

[0307]

[0308] (evaluate)

[0309] (Skin formation time (curing time))

[0310] Each curing composition was stored for 7 days at 23°C in an atmosphere with 50% relative humidity. Then, the skinning time (curing time) was determined using the method described above. The results are shown in Table 6 as "Skinning Time Before Storage".

[0311] Furthermore, after storing the above-mentioned curing composition at 23°C for 7 days, it was further stored at 50°C for 28 days, and then at 23°C for 1 day. The skinning time (curing time) was then determined using the above method. The results are shown in Table 6 as "Skinning Time After Storage".

[0312] The curable compositions of Examples 33-39, containing the organic polymer (A) and the various composites, exhibited good curability both before and after storage. No storage-induced curing delay occurred, demonstrating good storage stability.

[0313] (Presence or absence of seepage)

[0314] Under constant temperature and humidity conditions of 23°C and 50% or 70% relative humidity, each curing composition was sheeted onto corrugated cardboard using a scraper to smooth the surface. Then, after being left at 23°C and 50% or 70% relative humidity for 7 days, the surface of the cured composition was touched with a fingertip to confirm whether the liquid compound from DBU had seeped out onto the cured surface. The results are shown in Table 6.

[0315] No seepage of liquid compounds was observed on the surface of the cured compositions of Examples 33-39, which contained organic polymer (A) and various composites, which were cured by curing.

[0316] (Adhesion)

[0317] Each curable composition was coated onto 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. A 90° manual peel test was performed on the resulting cured products, and the state of failure was observed visually. For the state of failure, cohesion failure (failure occurring at the cured portion) was defined as CF, and interfacial failure (peeling at the interface between the cured product and the substrate) was defined as AF. The results are shown in Table 6.

[0318] The curable compositions of Examples 33-39, which contain organic polymer (A) and various composites, all exhibit good adhesion to a variety of substrates.

[0319] (Dumbbell stretching properties)

[0320] Under constant temperature and humidity conditions of 23°C and 50% relative humidity, the various curable compositions were filled into a 3mm thick sheet mold. After curing for 3 days at 23°C and 50%RH, the cured sheet was aged for 4 days in a dryer at 50°C to obtain the cured sheet.

[0321] According to JIS K 6251, the cured material was punched into a No. 3 dumbbell shape and tensile tests were performed using Autograph (tensile speed 200 mm / min). The stress at 50% extension, stress at 100% extension, stress at fracture, and elongation at fracture were measured. The results are shown in Table 6.

[0322] The cured products obtained by curing the curable compositions of Examples 33-39 containing organic polymer (A) and various composites all exhibited good tensile properties.

Claims

1. A method for manufacturing a curable composition, said curable composition comprising: Organic polymers having reactive silicon groups represented by the following general formula (1) (A), compounds containing amidine structures represented by the following general formula (2) (b1), titanium compounds or their condensates represented by the following general formula (3) (b2), and silane compounds having hydrolyzable silicon groups and amino groups with a molecular weight of 100 to 1500 (b3), -SiR 1 3-a X a (1) In the formula, R 1 Indicates a hydrocarbon group with 1 to 20 carbon atoms, whether substituted or unsubstituted, or R 0 3SiO- represents three organosilasilyloxy groups, with three R groups. 0 Same or different, indicating hydrocarbon groups with 1 to 20 carbon atoms, X indicates a hydroxyl group or a hydrolyzable group, a indicates 1, 2 or 3, and multiple R are present. 1 When X or , they can be the same or different. R 2 N=CR 3 -NR 4 2 (2) In the formula, R 2 R 3 and R 4 Same or different, indicating a hydrocarbon group with 1 to 20 hydrogen atoms, or substituted or unsubstituted carbon atoms, and two Rs. 4 They can be the same or different, R 2 R 3 and 2 Rs 4 Any two or more of them can be optionally bonded to form a ring structure. Ti(OR 5 ) d AND 4-d (3) In the formula, R 5 The group represents a hydrocarbon group with 1 to 20 carbon atoms, whether substituted or unsubstituted; Y represents a chelated coordination compound; and d represents 0 or an integer from 1 to 4. The method includes: A preparation step for preparing a catalyst-containing composition (B) by mixing the amidine-containing compound (b1), the titanium compound or its condensate (b2), and the silane compound (b3); as well as The mixing process of mixing the organic polymer (A) with the catalyst-containing composition (B) The weight ratio of the silane compound (b3) to the titanium compound or its condensate (b2) is 0.1 to 2.

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

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

4. The method for manufacturing the curable composition according to claim 1 or 2, wherein, The curable composition further contains a silane compound (D) with a molecular weight of 100-1500 that has a hydrolyzable silicon group and does not have an amino group.

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

6. A curable composition comprising an organic polymer (A) having a reactive silicon group represented by the following general formula (1), and a catalyst-containing composition (B), -SiR 1 3-a X a (1) In the formula, R 1 Indicates a hydrocarbon group with 1 to 20 carbon atoms, whether substituted or unsubstituted, or R 0 3SiO- represents three organosilasilyloxy groups, with three R groups. 0 Same or different, indicating hydrocarbon groups with 1 to 20 carbon atoms, X indicates a hydroxyl group or a hydrolyzable group, a indicates 1, 2 or 3, and multiple R are present. 1 When X or , they can be the same or different. The catalyst-containing composition (B) comprises a complex of an amidine-containing compound (b1) represented by general formula (2), a titanium compound or its condensate (b2) represented by general formula (3), and a silane compound (b3) having a molecular weight of 100-1500 and having hydrolyzable silicon and amino groups. R 2 N=CR 3 -NR 4 2 (2) In the formula, R 2 R 3 and R 4 Same or different, indicating a hydrocarbon group with 1 to 20 hydrogen atoms, or substituted or unsubstituted carbon atoms, and two Rs. 4 They can be the same or different, R 2 R 3 and 2 Rs 4 Any two or more of them can be selectively bonded to form a ring structure. Ti(OR 5 ) d AND 4-d (3) In the formula, R 5 The group represents a hydrocarbon group with 1 to 20 carbon atoms, whether substituted or unsubstituted; Y represents a chelated coordination compound; and d represents 0 or an integer from 1 to 4. The weight ratio of the silane compound (b3) to the titanium compound or its condensate (b2) is 0.1 to 2.

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

8. A catalyst-containing composition (B) for use with an organic polymer (A) having a reactive silicon group, The catalyst-containing composition (B) comprises: a complex of an amidine-containing compound (b1) represented by general formula (2), a titanium compound or its condensate (b2) represented by general formula (3), and a silane compound (b3) having a molecular weight of 100-1500 and having hydrolyzable silicon and amino groups. R 2 N=CR 3 -NR 4 2 (2) In the formula, R 2 R 3 and R 4 Same or different, indicating a hydrocarbon group with 1 to 20 hydrogen atoms, or substituted or unsubstituted carbon atoms, and two Rs. 4 They can be the same or different, R 2 R 3 and 2 Rs 4 Any two or more of them can be selectively bonded to form a ring structure. Ti(OR 5 ) d AND 4-d (3) In the formula, R 5 The group represents a hydrocarbon group with 1 to 20 carbon atoms, whether substituted or unsubstituted; Y represents a chelated coordination compound; and d represents 0 or an integer from 1 to 4. The weight ratio of the silane compound (b3) to the titanium compound or its condensate (b2) is 0.1 to 2.

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