Method for producing curable composition

Abstract

The method comprises a dehydration step in which an amidine structure-containing compound (B) and an alkoxysilane-containing dehydrating agent (C) are added to a system containing an organic polymer (A) having a reactive silicon group represented by -SiR1 3-aXa and the mixture is stirred at 10-90°C under an atmospheric pressure at which (C) substantially does not volatilize and a devolatilization step in which the volatile components contained in the system containing (A) after the dehydration step are devolatilized under reduced pressure . The amount of (C) added is such that the total number of moles of alkoxy groups directly bonded to silicon atoms contained in (C) is 200 mol% or more relative to 100 mol% of the moisture content of the system containing (A) before the dehydration step.

Description

Method for manufacturing a curable composition

[0001] The present invention relates to a method for producing a curable composition containing an organic polymer having a silicon group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom (hereinafter also referred to as a "reactive silicon group").

[0002] Organic polymers containing reactive silicon groups are known to crosslink at room temperature through the formation of siloxane bonds, accompanied by hydrolysis reactions of silyl groups due to moisture, etc., resulting in a rubbery cured product. Such organic polymers containing reactive silicon groups are already produced industrially and are widely used in applications such as sealants, adhesives, paints, and waterproofing materials.

[0003] To expedite the curing reaction, curable compositions containing organic polymers with reactive silicon groups typically incorporate a curing catalyst (also known as a silanol condensation catalyst). Such curing catalysts include organotin compounds with carbon-tin bonds, such as dibutyltinbis(acetylacetonate). However, due to environmental safety concerns, non-tin curing catalysts are being investigated.

[0004] Patent Document 1 discloses the use of an amidine structure-containing compound such as DBU (1,8-diazabicyclo[5.4.0]-7-undecene) as a non-tin curing catalyst.

[0005] On the other hand, when producing a curable composition containing an organic polymer having a reactive silicon group, in order to ensure the storage stability of the curable composition, the organic polymer having a reactive silicon group is first mixed with additives such as fillers and plasticizers, and then moisture is removed under reduced pressure while heated to 100°C or higher, after which a curing catalyst and adhesion promoter are added (see, for example, paragraphs

[0179] to

[0180] of Patent Document 1).

[0006] Furthermore, it is known that alkoxysilane-containing dehydrating agents such as vinyltrimethoxysilane may be incorporated as dehydrating agents (see, for example, paragraph

[0171] of Patent Document 1).

[0007] International Publication No. 2007-037483

[0008] As described above, the storage stability of curable compositions containing organic polymers with reactive silicon groups can be improved by removing moisture under reduced pressure conditions while heated, or by incorporating an alkoxysilane-containing dehydrating agent. However, curable compositions obtained in this way tend to have low curability and require a long time to cure, especially when an organotin-based curing catalyst is not included.

[0009] In view of the above situation, the present invention aims to provide a method for producing a curable composition containing a reactive silicon group-containing organic polymer that has good storage stability while improving curability.

[0010] As a result of diligent research to solve the above problems, the present inventors have found that when preparing a curable composition containing a reactive silicon group-containing organic polymer, the curability of the curable composition can be improved while maintaining good storage stability by adding an amidine structure-containing compound together with an alkoxysilane-containing dehydrating agent to a system containing the reactive silicon group-containing organic polymer, performing dehydration by stirring, and then performing defloration under reduced pressure. This has led to the completion of the present invention.

[0011] In other words, the present invention relates to the following general formula (1): -SiR １ ３－ａ X ａ (1) (wherein, R １ R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or ０ ３ Represents a triorganosiloxy group represented by SiO-. Three R ０ represents a hydrocarbon group having 1 to 20 carbon atoms, either identical or different. X represents a hydroxyl group or a hydrolyzable group. a indicates 1, 2, or 3. R １A method for producing a curable composition containing an organic polymer (A) having a reactive silicon group represented by (or, when there are multiple X's, they may be the same or different), comprising: a dehydration step of adding an amidine structure-containing compound (B) and an alkoxysilane-containing dehydrating agent (C) to a system containing the organic polymer (A), and stirring at 10 to 90°C under pressure in which the alkoxysilane-containing dehydrating agent (C) does not substantially volatilize; and a defoliation step of defoliating the volatile components contained in the system containing the organic polymer (A) after the dehydration step under reduced pressure, wherein the amount of alkoxysilane-containing dehydrating agent (C) added is such that the total number of moles of alkoxy groups directly attached to silicon atoms in the alkoxysilane-containing dehydrating agent (C) is 200 mol% or more, relative to the 100 mol% water content of the system containing the organic polymer (A) before the dehydration step.

[0012] According to the present invention, it is possible to provide a method for producing a curable composition containing a reactive silicon group-containing organic polymer that has improved curability while having good storage stability.

[0013] According to the present invention, it is possible to provide a curable composition in which the progression of thickening due to storage is suppressed, exhibits good storage stability, and has improved curability. Furthermore, according to a preferred embodiment of the present invention, it is possible to provide a curable composition that exhibits good tensile properties and / or adhesive properties after curing.

[0014] Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the embodiments described below, and various modifications are possible within the scope defined in the claims. Furthermore, the configurations described below can be combined in any way, and such combinations may also constitute an embodiment of the present invention.

[0015] (Reactive Silicon Group-Containing Organic Polymer (A)) The curable composition according to the present disclosure contains, as a curable resin, a reactive silicon group-containing organic polymer (A). The reactive silicon group-containing organic polymer (A) has a polymer backbone (also referred to as a main chain structure) and polymer chain terminals bonded to the polymer backbone. The polymer backbone is a structure in which a plurality of monomers are bonded by polymerization, condensation, etc. and a plurality of monomer units are continuously formed. The monomer may be of one type, or a plurality of types may be mixed and bonded.

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

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

[0018] The organic polymer (A) has a reactive silicon group represented by the following general formula (1). -SiR １ ３－ａ X ａ (1) (In the formula, R １ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a triorganosiloxy group represented by R ０ ３ SiO-. The three Rs ０ are the same or different and represent hydrocarbon groups having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a represents 1, 2, or 3. When there are a plurality of Rs １ or X, they may be the same or different.)

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

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

[0021] a is 1, 2, or 3. It is preferable that a is 2 or 3. It is particularly preferable that a is 2 because the method for producing the curable composition according to this disclosure is excellent in achieving good storage stability and improved curability.

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

[0023] (Main chain structure of reactive silicon group-containing organic polymer (A)) The main chain structure (also called the polymer backbone) of reactive silicon group-containing organic polymer (A) is not particularly limited, and various main chain structures can be used. Specifically, polyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer; hydrocarbon polymers such as ethylene-propylene copolymer, polyisobutylene, copolymers of isobutylene and isoprene, and hydrogenated polyolefin polymers obtained by hydrogenation of these polyolefin polymers; and polyolefins obtained by condensation of dibasic acids such as adipic acid with glycol, or by ring-opening polymerization of lactones. Examples include ester polymers; (meth)acrylic acid ester polymers obtained by radical polymerization of (meth)acrylic acid ester monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and stearyl (meth)acrylate; vinyl copolymers obtained by radical polymerization of (meth)acrylic acid ester monomers, vinyl acetate, acrylonitrile, styrene, and other monomers; polysulfide polymers; polyamide polymers; polycarbonate polymers, diallyl phthalate polymers, etc. In the above description, (meth)acrylic refers to acrylic and / or methacrylic.

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

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

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

[0027] The polyoxyalkylene polymer is preferably a polymer having a repeating unit represented by -R-O- (wherein R is a linear or branched alkylene group having 1 to 14 carbon atoms). More preferably, R is a linear or branched alkylene group having 2 to 4 carbon atoms. A specific example of the repeating unit represented by -R-O- is -CH ２ O-, -CH ２ CH ２ O-, -CH ２ CH (CH ３ ) O-, -CH ２ CH(C ２ H ５ ) O-, -CH ２ C (CH ３ ) (CH ３ ) O-, -CH ２ CH ２ CH ２ CH ２ Examples include O-. The main chain structure of the polyoxyalkylene polymer may consist of only one type of repeating unit, or it may consist of two or more types of repeating units.

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

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

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

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

[0032] Examples of initiators include alcohols such as butanol, ethylene glycol, propylene glycol, propylene glycol monoalkyl ether, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, and sorbitol; and hydroxyl-terminated polyoxyalkylene polymers with a number average molecular weight of 300 to 4,000, such as polyoxypropylenediol, polyoxypropylenetriol, polyoxyethylenediol, and polyoxyethylenetriol.

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

[0034] As the reactive silicon group-containing organic polymer (A), polyoxyalkylene polymers containing other bonds such as urethane bonds and urea bonds in the main chain structure may be used, as long as the effects of the invention are not significantly impaired. A specific example of such a polymer is a polyurethane prepolymer.

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

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

[0037] Examples of polyisocyanate compounds include diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, methylene-bis(cyclohexyl isocyanate), isophorone diisocyanate, and hexamethylene diisocyanate. The polyurethane prepolymer may have either hydroxyl or isocyanate groups at its ends.

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

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

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

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

[0042] (d) After reacting a hydroxyl-terminated organic polymer with a polyisocyanate compound to synthesize an NCO-terminated organic polymer, HNR-W-SiR １ ３－ａ X ａ (In the formula, W is a divalent organic group. R is a hydrogen atom or an alkyl group. １ X and a are the same groups shown with respect to general formula (1)) or HS-W-SiR １ ３－ａ X ａ (In the formula, W is a divalent organic group. R１ A method for reacting a silane compound represented by (X, and a are the same groups shown with respect to general formula (1)).

[0043] In the methods described in (a) and (c) above, examples of terminal carbon-carbon unsaturated groups include vinyl groups, allyl groups, methallyl groups, allenyl groups, and propargyl groups.

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

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

[0046] The introduction of reactive silicon groups by method (a) has been proposed in various publications, including Japanese Patent Publication Nos. 45-36319, 46-12154, Japanese Patent Publication Nos. 50-156599, 54-6096, 55-13767, 55-13468, 57-164123, Japanese Patent Publication No. 3-2450, U.S. Patent No. 3632557, U.S. Patent No. 4345053, U.S. Patent No. 4366307, and U.S. Patent No. 4960844. Examples include those described in Japanese Patent Publication Nos. 61-197631, 61-215622, 61-215623, and 61-218632, which introduce reactive silicon groups to polyoxypropylene polymers with a high molecular weight and narrow molecular weight distribution, having a number average molecular weight of 6,000 or more and an Mw / Mn ratio of 1.6 or less, by hydrosilylation, etc., and those proposed in Japanese Patent Publication No. 3-72527.

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

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

[0049] The molecular weight of reactive silicon-containing organic polymer (A) can also be expressed as the molecular weight of the end groups, determined by directly measuring the end group concentration by titration analysis based on the principles of the hydroxyl value measurement method specified in JIS K 1557 and the iodine value measurement method specified in JIS K 0070, and considering the structure of the organic polymer (degree of branching determined by the polymerization initiator used). The molecular weight of the end groups of organic polymer (A) can also be determined by creating a calibration curve between the number average molecular weight obtained by general GPC measurement of the polymer precursor and the above-mentioned molecular weight of the end groups, and then converting the number average molecular weight obtained by GPC of organic polymer (A) to the molecular weight of the end groups.

[0050] To obtain a good rubber-like cured product, it is preferable that the reactive silicon groups of the organic polymer (A) are located at the ends of the polymer chains. Since this exhibits good curability and readily shows rubber elastic behavior, the number of reactive silicon groups is preferably 0.5 or more on average per polymer chain end of the organic polymer (A), more preferably 0.6 or more, even more preferably 0.7 or more, and particularly preferably 0.8 or more.

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

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

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

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

[0055] (Amidine structure-containing compound (B) or (B')) In the method for producing the curable composition according to the present disclosure, an amidine structure-containing compound is used. The amidine structure-containing compound used in the dehydration step is denoted as (B), and the amidine structure-containing compound used in the mixing step is denoted as (B'). Component (B) and component (B') may be the same amidine structure-containing compound or different amidine structure-containing compounds.

[0056] The amidine structure-containing compound is not particularly limited as long as it contains an amidine structure, but it can be represented by the following general formula (2). ２ N = CR ３ -NR ４ ２ (2) (wherein, R ２ , R ３ , and R ４These represent, either identical or different, a hydrogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ４ They may be the same or they may be different. ２ , R ３ , and two R ４ Any two or more of these may be joined together to form a ring structure.

[0057] R ２ Since this enhances the curability of the curable composition, it is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group in which the carbon atom adjacent to the nitrogen atom (the carbon atom at the α-position) does not have an unsaturated bond. ２ The number of carbon atoms is preferably 1 to 10, and more preferably 1 to 6, due to their availability.

[0058] R ３ This enhances the curability of the curable composition, and therefore hydrogen atoms or -NR ６ ２ It is preferable that the organic group is represented by -NR ６ ２ It is more preferable that the organic group is represented by , provided that there are two R ６ Each of these independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. In this case, the compound represented by general formula (2) is called a guanidine compound.

[0059] Also, R ３ Because the resulting cured product has good physical properties, -NR ７ -C (=NR ８ ) - NR ９ ２ , or -N = C(NR １０ ２ ) - NR １１ ２ It is preferable that the organic group is represented by R. ７ , R ８ and two R ９ Each of these independently represents a hydrogen atom or an organic group with 1 to 6 carbon atoms. １０ and two R １１Each independently represents a hydrogen atom or an organic group having 1 to 6 carbon atoms. In this case, the compound represented by the general formula (2) is called a biguanide compound.

[0060] Two Rs in the general formula (2) ４ Preferably represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, because they are easily available and enhance the curability of the curable composition.

[0061] The number of carbon atoms contained in the amidine structure-containing compound is preferably 2 or more, more preferably 6 or more, and particularly preferably 7 or more. The upper limit of the number of carbon atoms is not particularly limited, but preferably 10,000 or less.

[0062] Also, the molecular weight of the amidine structure-containing compound is preferably 60 or more, more preferably 120 or more, and particularly preferably 130 or more. The upper limit of the molecular weight is not particularly limited, but preferably 100,000 or less.

[0063] The amidine structure-containing compounds are not particularly limited, but examples include pyrimidine compounds such as pyrimidine, 2-aminopyrimidine, 6-amino-2,4-dimethylpyrimidine, 2-amino-4,6-dimethylpyrimidine, 1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1-ethyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-diethyl-1,4,5,6-tetrahydropyrimidine, 1-n-propyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 2-hydroxy-4,6-dimethylpyrimidine, 1,3-diazanaphthalene, and 2-hydroxy-4-aminopyrimidine; Imidazolin compounds such as 2-imidazoline, 2-methyl-2-imidazoline, 2-ethyl-2-imidazoline, 2-propyl-2-imidazoline, 2-vinyl-2-imidazoline, 1-(2-hydroxyethyl)-2-methyl-2-imidazoline, 1,3-dimethyl-2-iminoimidazolidine, and 1-methyl-2-iminoimidazolidine-4-one; amidine compounds such as 1,8-diazabicyclo[5.4.0]undeca-7-ene (DBU), 1,5-diazabicyclo[4.3.0]nona-5-ene (DBN), 2,9-diazabicyclo[4.3.0]nona-1,3,5,7-tetraene, and 6-(dibutylamino)-1,8-diazabicyclo[5,4,0]undecene-7 (DBA-DBU);Guanidine, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, 1,1-dimethylguanidine, 1,3-dimethylguanidine, 1,2-diphenylguanidine, 1,1,2-trimethylguanidine, 1,2,3-trimethylguanidine, 1,1,3,3-tetramethylguanidine, 1,1,2,3,3-pentamethylguanidine, 2-ethyl-1,1,3,3-tetramethylguanidine, 1,1,3,3-tetramethyl-2-n-propylguanidine, 1,1,3,3-tetramethyl-2-isopropylguanidine, 2-n-butyl-1,1,3,3-tetramethylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, 1,2,3-Tricyclohexylguanidine, 1-Benzyl-2,3-dimethylguanidine, 1,5,7-Triazabicyclo[4.4.0]deca-5-ene, 7-Methyl-1,5,7-Triazabicyclo[4.4.0]deca-5-ene, 7-Ethyl-1,5,7-Triazabicyclo[4.4.0]deca-5-ene, 7-n-Propyl-1,5,7-Triazabicyclo[4.4.0] Guanidine compounds such as deca-5-ene, 7-isopropyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-n-butyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-cyclohexyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, and 7-n-octyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene;Biguanides, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-(2-ethylhexyl) biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, 1-morpholinobiguanide, Examples include biguanide compounds such as 1-n-butyl-N2-ethyl biguanide, 1,1'-ethylenebisbiguanide, 1,5-ethylene biguanide, 1-[3-(diethylamino)propyl]biguanide, 1-[3-(dibutylamino)propyl]biguanide, and N',N''-dihexyl-3,12-diimino-2,4,11,13-tetraazatetradecanediamidine. Only one type of amidine structure-containing compound may be used, or two or more types may be used in combination.

[0064] The amidine structure-containing compound is preferably an amidine compound or a guanidine compound, with DBU, DBA-DBU, DBN, or phenylguanidine being more preferred, DBU, DBA-DBU, or DBN being even more preferred, and DBU being particularly preferred.

[0065] (Alkoxysilane-containing dehydrating agent (C)) Alkoxysilane-containing dehydrating agent (C) refers to an alkoxysilane compound that functions as a dehydrating agent. This alkoxysilane compound is a compound having an alkoxy group directly attached to a silicon atom, and the alkoxy group reacts with water to hydrolyze and produce an alcohol, thereby reducing the water content of the system containing the organic polymer (A). However, alkoxysilane compounds having an amino group do not qualify as alkoxysilane-containing dehydrating agents (C) because, although they function as dehydrating agents, they have the problem of adhering to the walls of the mixer during the dehydration process and being difficult to remove.

[0066] In the alkoxysilane-containing dehydrating agent (C), the number of carbon atoms in the alkoxy group directly bonded to the silicon atom is not particularly limited, but is usually around 1 to 3. The alkoxy group is preferably a methoxy group or an ethoxy group, and more preferably a methoxy group.

[0067] The molecular weight of the alkoxysilane-containing dehydrating agent (C) is not particularly limited, but is usually in the range of 100 to 1,500. The lower limit of the molecular weight may be 150 or more. The upper limit may be 1,000 or less, or 500 or less.

[0068] The alkoxysilane-containing dehydrating agent (C) may be a compound having an alkoxy group directly attached to a silicon atom and a reactive group other than an amino group, or it may be a compound that does not have a reactive group other than an alkoxy group directly attached to a silicon atom.

[0069] Specific examples of alkoxysilane-containing dehydrating agents (C) include epoxy-containing silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltriethoxysilane; and isocyanate-containing silanes such as γ-isocyanatetopropyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane, γ-isocyanatetopropylmethyldiethoxysilane, γ-isocyanatetopropylmethyldimethoxysilane, (isocyanatemethyl)trimethoxysilane, and (isocyanatemethyl)dimethoxymethylsilane; Silanes containing mercapto groups such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and mercaptomethyltriethoxysilane; carboxysilanes such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis(2-methoxyethoxy)silane, and N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane; silanes containing vinyl-type unsaturated groups such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and vinyltriethoxysilane; silanes containing (meth)acrylic-type unsaturated groups such as γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropylmethyltriethoxysilane, and γ-acryloxypropyltrimethoxysilane; Examples include silanes without reactive groups such as methyltrimethoxysilane, dimethyldimethoxysilane, n-propyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, dimethoxydiphenylsilane, hexyltrimethoxysilane, 1,6-bis(trimethoxylyl)hexane, (methoxymethyl)trimethoxysilane, and p-styryltrimethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; and isocyanurate silanes such as tris(trimethoxysilyl)isocyanurate.The alkoxysilane-containing dehydrating agent (C) may be used alone or in combination of two or more types. In addition, partially hydrolyzed condensates of the silane compounds listed above can also be used. Examples include Evonik's Dynasylan 6490 and Dynasylan 6498.

[0070] Because it exhibits good dehydration performance, the alkoxysilane-containing dehydrating agent (C) is preferably vinyltrimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, or (methoxymethyl)trimethoxysilane, more preferably vinyltrimethoxysilane or (methoxymethyl)trimethoxysilane, and particularly preferably vinyltrimethoxysilane.

[0071] (Curing Catalyst) The curable composition according to this disclosure contains a curing catalyst to promote the hydrolysis and condensation reaction of the reactive silicon groups of the organic polymer (A). The curing catalyst may contain only an amidine structure-containing compound (B), or it may further contain other curing catalysts in addition to the amidine structure-containing compound (B). Examples of curing catalysts other than component (B) include organotin compounds, metal carboxylate salts, amine compounds other than amidine structure-containing compounds, carboxylic acids, metal alkoxides, and inorganic acids.

[0072] However, when an organotin compound is incorporated into the curable composition according to this disclosure, the storage stability may decrease. For this reason, it is preferable to use a non-tin curing catalyst. Here, a non-tin curing catalyst refers to a curing catalyst that does not contain tin.

[0073] As the non-tin curing catalyst, one can be selected from the curing catalysts described above, but it is particularly preferable to use a titanium compound or its condensate (D'), or a composite of an amidine structure-containing compound (B') and component (D'). Details of these are described below.

[0074] (Titanium compound or its condensate (D) or (D')) In the method for producing the curable composition according to the present disclosure, a titanium compound or its condensate may be used as a curing catalyst. (D) is appended to the titanium compound or its condensate used in the dehydration step, and (D') is appended to the titanium compound or its condensate used in the mixing step. The (D) component and the (D') component may be the same compound or different compounds.

[0075] The titanium compound is represented by the following general formula (3). Ti(OR ５ ) ｄ Y ４－ｄ (3) (In the formula, R ５ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y represents a chelate coordination compound. d represents 0 or an integer of 1 to 4.)

[0076] The condensate of the titanium compound represented by the general formula (3) can also be used as the (D) or (D') component. The condensate can be obtained by adding water to the titanium compound and reacting them. Also, a titanium compound and a condensate of the titanium compound may be used in combination.

[0077] The substituted or unsubstituted hydrocarbon group represented by R ５ is preferably a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and an aliphatic hydrocarbon group is preferred. Examples of the aliphatic hydrocarbon group include saturated or unsaturated hydrocarbon groups. As the saturated hydrocarbon group, a linear or branched alkyl group is preferred. The number of carbon atoms of the hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

[0078] Examples of the hydrocarbon group represented by R ５ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, etc. Examples of the substituent that the hydrocarbon group may have include a methoxy group, an ethoxy group, a hydroxyl group, an acetoxy group, etc. When there are a plurality of R ５ , they may be the same as each other or different from each other.

[0079] The chelate-coordinating compound represented by Y may be any known compound that is known to coordinate to titanium. While not particularly limited, examples include 1-aryl-1,3-butanedione such as 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, 1,3-diaryl-1,3-propanedione such as 1,3-diphenyl-1,3-propanedione, 1,3-bis(2-pyridyl)-1,3-propanedione, and 3-benzyl Examples include diketones such as -2,4-pentanedione; ketoesters such as methyl acetate, ethyl acetate, butyl acetate, t-butyl acetate, and ethyl 3-oxohexanoate; ketoamides such as N,N-dimethylacetate, N,N-diethylacetate, and acetacetanilide; malonic acid esters such as dimethyl malonate, diethyl malonate, and diphenyl malonate; and malonic acid amides such as N,N,N',N'-tetramethylmalonamide and N,N,N',N'-tetraethylmalonamide. Among these, diketones and ketoesters are preferred. If there are multiple Ys, they may be the same or different from each other.

[0080] d represents 0 or an integer from 1 to 4. In order for the curable composition according to this disclosure to exhibit better curability and to exhibit greater elongation after curing, d is preferably 0 or an integer from 1 to 3, more preferably an integer from 1 to 3, and particularly preferably 2.

[0081] Specific examples of titanium compounds or condensates represented by general formula (3) include tetramethoxytitanium, trimethoxyethoxytitanium, trimethoxyisopropoxytitanium, trimethoxybutoxytitanium, dimethoxydiethoxytitanium, dimethoxydiisopropoxytitanium, dimethoxydibutoxytitanium, methoxytriethoxytitanium, methoxytriisopropoxytitanium, methoxytributoxytitanium, tetraethoxytitanium, triethoxyisopropoxytitanium, triethoxybutoxytitanium, diethoxydiisopropoxytitanium, diethoxydibutoxytitanium Examples include toxicitamin, ethoxytriisopropoxytitamin, ethoxytributoxytitamin, tetraisopropoxytitamin, triisopropoxybutoxytitamin, diisopropoxydibutoxytitamin, tetrabutoxytitamin, tetratert-butoxytitamin, diisopropoxytitamin bis(acetylacetonate), diisopropoxytitamin bis(ethylacetoacetate), diisobutoxytitamin bis(ethylacetoacetate); and condensates of titanium alkoxides such as tetrabutoxytitamin dimer and tetrabutoxytitamin tetramer. Only one type of titanium compound or its condensate may be used, or two or more types may be used in combination.

[0082] Because good curability can be obtained and large elongation can be observed after curing, the titanium compound represented by general formula (3) is preferably a compound containing a chelate coordination compound represented by Y, and specifically, diisopropoxytitanium bis(acetylacetonate), diisopropoxytitanium bis(ethylacetoacetate), and diisobutoxytitanium bis(ethylacetoacetate) are particularly preferred.

[0083] (Composite of component (B') and component (D')) As one embodiment of the curing catalyst, a composite of an amidine structure-containing compound (B') and a titanium compound or its condensate (D') can be used. This composite refers to a composite formed by mixing component (B') and component (D') in the absence of the organic polymer (A) before adding and mixing them into a system containing the organic polymer (A). In this composite, when component (B') and component (D') are mixed, some reaction proceeds, causing component (B') and component (D') to bond or the structure of component (B') and / or component (D') to change.

[0084] By pre-mixing components (B') and (D') to form a composite, and then adding this composite to a system containing organic polymer (A), the curability can be improved compared to adding components (B') and (D') individually to the system. Furthermore, the bleed-out of component (B') from the surface of the cured product can be suppressed.

[0085] The composite can be formed by mixing component (B') and component (D') under stirring. When mixed under stirring, the mixture becomes viscous, which confirms the formation of the composite.

[0086] The method for mixing component (B') and component (D') is not particularly limited, but the two components may be mixed and stirred at room temperature or at a temperature below the decomposition temperature of each component. The mixing may be carried out without a solvent, or in the presence of a solvent that is inert to both components. Furthermore, the mixing may be carried out in an inert gas atmosphere (nitrogen gas, argon gas) or in the presence of air. The mixing time with stirring is not particularly limited, but may be, for example, 1 hour to 3 days.

[0087] The ratio of the amidine structure-containing compound (B') to the titanium compound or its condensate (D') in the composite can be set as appropriate, but the weight ratio of component (D') / component (B') may be, for example, about 0.1 to 20, preferably 0.5 to 15, more preferably 0.8 to 12, and even more preferably 1.0 to 10. Since the effect of improving curability is particularly excellent, the upper limit of the weight ratio is preferably 9 or less, more preferably 6 or less, even more preferably 5 or less, and especially preferably 4 or less. Furthermore, since the bleed-out suppression effect of component (B') is improved, the lower limit of the weight ratio is preferably 1.5 or more, more preferably 2 or more, and even more preferably 2.6 or more.

[0088] (Adhesion-imparting agent) The curable composition according to this disclosure does not need to contain an adhesion-imparting agent, but it is preferable that it contains one. By incorporating an adhesion-imparting agent, the adhesion of the cured product obtained by curing the curable composition to various substrates can be improved.

[0089] Examples of adhesion-imparting agents include silane compounds (also called aminosilanes) having a hydrolyzable silicon group and a substituted or unsubstituted amino group. The hydrolyzable silicon group refers to a silicon atom-containing group to which a hydrolyzable group is bonded, and the reactive silicon group of the organic polymer (A) can also be represented by the general formula (1) described above.

[0090] The hydrolyzable groups included in the hydrolyzable silicon group are not particularly limited, and examples include hydrogen atoms, halogen atoms, alkoxy groups, aryloxy groups, alkenyloxy groups, acyloxy groups, ketoxymate groups, amino groups, amide groups, acid amide groups, aminooxy groups, and mercapto groups. Among these, alkoxy groups such as methoxy groups and ethoxy groups are more preferred because they are mildly hydrolyzable and easy to handle, with methoxy groups and ethoxy groups being particularly preferred.

[0091] In order to ensure good adhesion, it is sometimes preferable to have three hydrolyzable groups bonded to silicon atoms in the silane compound, which is an adhesion-imparting agent. Alternatively, two groups may be preferable to ensure the storage stability of the curable composition.

[0092] The substituents on the substituted amino group are not particularly limited and include, for example, alkyl groups, aralkyl groups, and aryl groups.

[0093] The molecular weight of the silane compound used as an adhesion promoter is not particularly limited, but is usually in the range of 100 to 1,500. The lower limit of the molecular weight may be 150 or more. The upper limit may be 1,000 or less, or 500 or less.

[0094] Specific examples of silane compounds that act as adhesion promoters include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, γ-(2-(2-aminoethyl)aminoethyl)aminopropyltrimethoxysilane, γ-(6-aminohexyl)aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyl Examples of amino group-containing silanes include Idopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, N-butylaminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, and bis(trimethoxysilylpropyl)amine; and ketimine-type silanes such as N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine. In addition, partially hydrolyzed condensates of the amino group-containing silanes mentioned above, or partially hydrolyzed condensates of amino group-containing silanes with other alkoxysilanes (for example, reaction products of amino group-containing silane and epoxy group-containing silane, reaction products of amino group-containing silane and (meth)acrylic group-containing silane), etc., can also be used. Only one type of silane compound may be used, or two or more types may be used in combination.

[0095] To achieve good adhesion, the silane compound used as the adhesion imparting agent is preferably γ-aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, or γ-(2-aminoethyl)aminopropylmethyldimethoxysilane. Silane coupling agents obtained by partially condensing hydrolyzable silicon groups to oligomerize them are suitable in terms of safety and stability. The silane coupling agents to be condensed may be a single type or multiple types. Examples of oligomerized silane coupling agents include Dynasylan 1146 from Evonik. To ensure the storage stability of the curable composition, γ-aminopropyltrimethoxysilane and γ-(2-aminoethyl)aminopropylmethyldimethoxysilane are preferred.

[0096] (Dehydration step) In the method for producing a curable composition according to the present disclosure, first, an organic polymer (A) is prepared, and after adding any additive such as a plasticizer or filler to the organic polymer (A), a dehydration step is performed. This reduces the water content of the system containing the organic polymer (A) and improves the storage stability of the curable composition according to the present disclosure.

[0097] Conventional methods, such as those described in the examples of Patent Document 1, involved a dehydration step in which water was evaporated by heating to a high temperature of 100°C or higher and under reduced pressure. However, while curable compositions obtained by such physical dehydration had good storage stability, they sometimes lacked sufficient curability.

[0098] In contrast to such conventional methods, the method for producing a curable composition according to this disclosure involves chemical dehydration using an alkoxysilane-containing dehydrating agent (C). In this chemical dehydration, the alkoxy groups in the alkoxysilane-containing dehydrating agent (C) react with water and undergo hydrolysis to produce alcohol, thereby reducing the water content of the system containing the organic polymer (A). The curable composition obtained by the production method including chemical dehydration according to this disclosure can have significantly improved curability compared to a curable composition obtained by physical dehydration in the conventional method.

[0099] In the manufacturing method described herein, since chemical dehydration is performed, it is preferable not to perform a physical dehydration step that involves heating to a high temperature of 100°C or higher. This makes it possible to reduce the energy and costs required for physical dehydration.

[0100] The amount of alkoxysilane-containing dehydrating agent (C) added in the dehydration step is set so that the total number of moles of alkoxy groups directly attached to silicon atoms in the alkoxysilane-containing dehydrating agent (C) is 200 mol% or more, relative to 100 mol% of the water content of the system containing the organic polymer (A) before the dehydration step. If the total number of moles of alkoxy groups relative to 100% of the moles of water is less than 200 mol%, the amount of dehydrating agent present is insufficient, making it difficult to sufficiently reduce the water content of the system and thus preventing the achievement of good storage stability. Preferably, the total number of moles of alkoxy groups is 250 mol% or more.

[0101] The upper limit of the total number of moles of the alkoxy groups is not particularly limited, but since the dehydration effect achieved by adding component (C) will plateau, it may be, for example, 5,000 mol% or less, 2,000 mol% or less, 1,000 mol% or less, or 500 mol% or less.

[0102] In the dehydration step, an amidine structure-containing compound (B) is added to the system containing the organic polymer (A) in addition to an alkoxysilane-containing dehydrating agent (C). The amidine structure-containing compound (B) functions as a catalyst (i.e., a dehydration catalyst) that promotes the reaction between component (C) and water, efficiently reducing the water content of the system and improving the storage stability of the curable composition. Furthermore, component (B) can also function as a curing catalyst when curing the curable composition.

[0103] Even when using only an alkoxysilane-containing dehydrating agent (C) without adding the amidine structure-containing compound (B), the water content of the system does not decrease sufficiently, and good storage stability or curability cannot be achieved. Similarly, the same result occurs when amine compounds other than component (B) are added, and good storage stability or curability cannot be achieved.

[0104] The amount of the amidine structure-containing compound (B) added in the dehydration process can be appropriately set from the viewpoint of promoting the reaction between component (C) and water and promoting the curing reaction. Specifically, from the viewpoint of improving storage stability and curability by adding component (B), it is preferable that the amount is 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, even more preferably 0.3 parts by weight or more, even more preferably 0.5 parts by weight or more, and particularly preferably 0.8 parts by weight or more, per 100 parts by weight of the organic polymer (A).

[0105] (B) There is no particular upper limit to the amount of component added, but since the dehydration promoting effect achieved by adding component (B) plateaus, it is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, even more preferably 3 parts by weight or less, and particularly preferably 2 parts by weight or less.

[0106] The amidine structure-containing compound (B) and the alkoxysilane-containing dehydrating agent (C) are added to the system containing the organic polymer (A). The "system containing the organic polymer (A)" may consist only of the organic polymer (A), but it is preferable that it is a mixture containing the organic polymer (A) and additives such as plasticizers and fillers.

[0107] As additives that can be incorporated into the above mixture, additives known to be incorporated into curable compositions containing organic polymers having reactive silicon groups can be used as appropriate. Specifically, these include, but are not limited to, plasticizers, fillers, property modifiers, anti-sagging agents (thixotropic agents), antioxidants, light stabilizers, UV absorbers, conductive fillers, flame retardants, curing modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments, foaming agents, solvents, and antifungal agents. Any of these additives can be any component, but it is preferable to use at least one selected from the group consisting of plasticizers and fillers.

[0108] When adding the amidine structure-containing compound (B) and the alkoxysilane-containing dehydrating agent (C) to a system containing the organic polymer (A), they may be added sequentially or simultaneously. Furthermore, the order of sequential addition is not particularly limited. Alternatively, components (B) and (C) may be mixed beforehand before being added to the system containing the organic polymer (A).

[0109] In the dehydration step, in addition to components (B) and (C), a titanium compound or its condensate (D) may be added. This embodiment also allows the reaction between component (C) and water to proceed efficiently. Furthermore, with this embodiment, good curability can be achieved without adding a curing catalyst after the defoliation step.

[0110] After adding components (B) and (C) to a system containing organic polymer (A), the system is stirred for a predetermined time to allow the reaction between component (C) and water to proceed and reduce the water content of the system. The stirring method is not particularly limited and can be carried out using conventionally known apparatus.

[0111] During the stirring process, the temperature of the system should be within the range of 10 to 90°C. If the temperature is below 10°C, the reaction between component (C) and water may not proceed sufficiently, making it difficult to sufficiently reduce the water content of the system. Conversely, if the temperature exceeds 90°C, it may also be difficult to sufficiently reduce the water content of the system. The lower limit of the temperature is preferably 20°C or higher, more preferably 30°C or higher, even more preferably 40°C or higher, even more preferably 50°C or higher, and particularly preferably 60°C or higher. The upper limit of the temperature is preferably 80°C or lower, more preferably 70°C or lower.

[0112] The stirring is preferably carried out under pressure at which component (C) does not substantially volatilize. Stirring under pressure at which component (C) volatilizes does not sufficiently achieve the effect of reducing the water content of the system. Here, pressure at which component (C) does not substantially volatilize means pressure at which, during stirring that satisfies the above temperature conditions, the amount of reduction of component (C) due to volatilization is 10% or less (preferably 1% or less).

[0113] Examples of atmospheric pressure at which component (C) does not substantially volatilize include atmospheric pressure or above, or a reduced pressure to the extent that component (C) does not substantially volatilize. Preferably, it is atmospheric pressure or above, and more preferably atmospheric pressure.

[0114] The time for which the stirring is performed is preferably the time required for the reaction between component (C) and water to proceed and for the water content of the system to be sufficiently reduced. Typically, such dehydration takes longer than the time required for stirring aimed solely at uniformly mixing each component. The stirring time required for dehydration can be determined by measuring the water content of the system and depends on the temperature and pressure conditions, but is usually preferably 10 minutes or more, more preferably 20 minutes or more, and even more preferably 30 minutes or more. There is no particular upper limit to the stirring time, but since the progress of the reaction due to stirring will plateau, it may be, for example, 120 minutes or less, 90 minutes or less, or 60 minutes or less.

[0115] The dehydration process described above can reduce the water content of the system containing the organic polymer (A). From the viewpoint of achieving good storage stability, the water content of the system after the dehydration process is preferably 700 ppm or less, and more preferably 500 ppm or less.

[0116] On the other hand, the water content of the system containing the organic polymer (A) before the dehydration step is not particularly limited, but since applying the manufacturing method according to this disclosure has great significance in improving storage stability, it is preferably 1,000 ppm or more, more preferably 1,500 ppm or more, and particularly preferably 1,800 ppm or more. The upper limit is not particularly limited, but for example, it may be 10,000 ppm or less, 5,000 ppm or less, or 3,000 ppm or less.

[0117] In the method for producing a curable composition according to this disclosure, the alkoxysilane-containing dehydrating agent (C) may be added only once during the dehydration step. That is, the alkoxysilane-containing dehydrating agent (C) does not need to be added in a step after the dehydration step (for example, the mixing step described later). If the alkoxysilane-containing dehydrating agent (C) is added once during the dehydration step, a curable composition exhibiting good storage stability can be obtained without additional additions.

[0118] (Devolatilization Step) In the method for producing a curable composition according to the present disclosure, following the dehydration step described above, a defoliation step is performed to defoliate volatile components contained in the system containing the organic polymer (A) under reduced pressure. Since alcohol is generated by the reaction of component (C) with water in the dehydration step, the system after the dehydration step will contain alcohol. In the defoliation step, this alcohol is removed by volatilization. Furthermore, if the system after the dehydration step contains unreacted component (C), this component (C) can also be removed by volatilization. Moreover, by removing the alcohol product, the reaction between component (C) and water will proceed further, and it can be expected that the water content of the system will be further reduced.

[0119] If the defoliation process is not performed, the curable composition will contain volatile components such as alcohol, which raises concerns about hazards due to these volatile components. Furthermore, there is a concern that the sealed container may expand when the curable composition is stored in a sealed container, especially in high temperatures such as during the summer.

[0120] The defoliation process is carried out under reduced pressure. The degree of reduced pressure is not particularly limited; it should be sufficient to cause the alcohol produced in the dehydration process to volatilize, depending on the type of alcohol produced.

[0121] The temperature in the defoliation process is not particularly limited and can be determined according to the type of alcohol product and the degree of reduced pressure, but it may be within the range of approximately 10 to 90°C. The upper limit of the temperature may be 70°C or less, or 50°C or less. The temperature may also be room temperature (approximately 15 to 25°C).

[0122] (Mixing step) The system containing the organic polymer (A) after the defoliation step may be used as the curable composition, but it is preferable to perform a step of mixing a curing catalyst and / or an adhesion promoter with the system containing the organic polymer (A) after the defoliation step.

[0123] As the curing catalyst added in the mixing step, the curing catalysts described above can be used as appropriate, but as mentioned above, it is preferable to use a non-tin curing catalyst because it can achieve good storage stability. Among non-tin curing catalysts, it is particularly preferable to use a titanium compound or its condensate (D'), or a composite of an amidine structure-containing compound (B') and a titanium compound or its condensate (D').

[0124] The amount of curing catalyst added in the mixing step is not particularly limited and can be set according to the type of curing catalyst and the desired curability. For example, it may be 15 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less per 100 parts by weight of reactive silicon group-containing organic polymer (A). The lower limit is also not particularly limited and may be 0 parts by weight or more, 0.1 parts by weight or more, 0.5 parts by weight or more, or 1 part by weight or more.

[0125] The addition of the curing catalyst in the mixing step may be omitted. In particular, as mentioned above, if a titanium compound or its condensate (D) is added in the dehydration step, the addition of the curing catalyst in the mixing step can be omitted.

[0126] In the mixing step, it is preferable to mix an adhesion promoter into the system containing the organic polymer (A). This improves the adhesion of the cured product obtained by curing the curable composition to various substrates. The above-mentioned aminosilane can be used as the adhesion promoter.

[0127] The amount of adhesion promoter added is not particularly limited and can be set appropriately depending on the type of adhesion promoter and the desired adhesion, but it is preferably 0 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 1 to 8 parts by weight per 100 parts by weight of organic polymer (A).

[0128] By sealing the curable composition obtained through the processes described above into a sealable container, it is possible to prepare a one-component curable composition that hardens due to moisture in the air after application. According to the method for producing a curable composition of this disclosure, the moisture content of the system can be reduced by the dehydration process, so a one-component curable composition with good storage stability can be provided.

[0129] Furthermore, it is also possible to prepare a two-component curable composition by preparing the curable composition obtained through the processes described above as the main component, and separately preparing a curing agent containing components such as a curing catalyst and water, thereby mixing the main component and curing agent before use.

[0130] The curable composition according to this disclosure can be used as a building sealant, industrial adhesive, waterproof coating, or adhesive raw material. It can also be used as a sealant for buildings, ships, automobiles, roads, etc. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, and resin molded products, either alone or with the help of a primer, it can also be used as various types of sealing and adhesive compositions. In addition to being an ordinary adhesive, it can also be used as a contact adhesive. Furthermore, it is useful as a food packaging material, casting rubber material, molding material, and paint.

[0131] The following sections list preferred embodiments of this disclosure, but the present invention is not limited to these sections. [Section 1] The following general formula (1): -SiR １ ３－ａ X ａ (1) (wherein, R １ R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or ０ ３ Represents a triorganosiloxy group represented by SiO-. Three R ０ represents a hydrocarbon group having 1 to 20 carbon atoms, either identical or different. X represents a hydroxyl group or a hydrolyzable group. a indicates 1, 2, or 3. R １A method for producing a curable composition containing an organic polymer (A) having a reactive silicon group represented by (or, when there are multiple X, they may be the same or different), comprising: a dehydration step of adding an amidine structure-containing compound (B) and an alkoxysilane-containing dehydrating agent (C) to a system containing the organic polymer (A), and stirring at 10 to 90°C under pressure in which the alkoxysilane-containing dehydrating agent (C) does not substantially volatilize; and a defoliation step of defoliating the volatile components contained in the system containing the organic polymer (A) after the dehydration step under reduced pressure, wherein the amount of alkoxysilane-containing dehydrating agent (C) added is such that the total number of moles of alkoxy groups directly attached to silicon atoms in the alkoxysilane-containing dehydrating agent (C) is 200 mol% or more, relative to the water content of the system containing the organic polymer (A) before the dehydration step (100 mol%). [Item 2] The method for producing a curable composition according to Item 1, wherein the stirring time in the dehydration step is 20 minutes or more. [Item 3] The manufacturing method according to Item 1 or 2, wherein the temperature in the dehydration step is 40°C or higher. [Item 4] The manufacturing method according to any one of Items 1 to 3, wherein the amount of the amidine structure-containing compound (B) added is 0.2 parts by weight or more per 100 parts by weight of the organic polymer (A). [Item 5] The amidine structure-containing compound (B) is the following general formula (2): R ２ N = CR ３ -NR ４ ２ (2) (wherein, R ２ , R ３ , and R ４ These represent, either identical or different, a hydrogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. ４ They may be the same or they may be different. ２ , R ３ , and two R ４A manufacturing method according to any one of items 1 to 4, wherein any two or more of the following may be bonded together to form a cyclic structure. [Item 6] A manufacturing method according to any one of items 1 to 5, wherein the addition of the alkoxysilane-containing dehydrating agent (C) is performed only once in the dehydration step. [Item 7] A manufacturing method according to any one of items 1 to 6, further comprising a mixing step of mixing a curing catalyst and / or an adhesion imparting agent into the system containing the organic polymer (A) after the defoliation step. [Item 8] A manufacturing method according to item 7, wherein the curing catalyst is a non-tin curing catalyst. [Item 9] The non-tin curing catalyst is represented by the following general formula (3): Ti(OR ５ ) ｄ Y ４－ｄ (3) (wherein, R ５ The method for producing the product according to item 8, comprising a titanium compound represented by (D') or a condensate thereof (D'), or a composite of an amidine structure-containing compound (B') and the titanium compound or condensate thereof (D'), in the dehydration step, wherein the system containing the organic polymer (A) is subjected to the following general formula (3): Ti(OR ５ ) ｄ Y ４－ｄ (3) (wherein, R ５ The method for producing titanium compounds or condensates thereof (D) represented by (1 to 20 carbon atoms) is further added, wherein (1) represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. (Y) represents a chelate coordination compound. (d) represents 0 or an integer from 1 to 4. [Item 11] The method for producing titanium compounds or condensates thereof (D) represented by (1) represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. [Item 12] The method for producing titanium compounds or condensates thereof (D) represented by (1) represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. [Item 11] The method for producing titanium compounds or condensates thereof (D) represented by (1) represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. (Y) represents a chelate coordination compound. (d) represents 0 or an integer from 1 to 4. [Item 12] The method for producing titanium compounds or condensates thereof (D) represented by (1) represents a titanium compound or condensate thereof (D) represented by (1) represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. [Item 13] The method for producing titanium compounds or condensates4] The method for producing titanium compounds or condensates thereof (D) represented by (1) represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. [Item 13] The method for producing titanium compounds or condensates thereof (D) represented by (1) represents a chelate coordination compound. [Item 14] The method for producing titanium compounds or condensates thereof (D) represented by (1) represents a chelate coordination compound. [Item 15] The method for producing titanium compounds or

[0132] The present invention will be described in more detail below with reference to specific examples, but the present invention is not limited to the following examples.

[0133] The number-average molecular weight in the examples is the GPC molecular weight measured under the following conditions: Liquid delivery system: Tosoh HLC-8420GPC Column: Tosoh TSKgel SuperH series Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40°C

[0134] The average number of silyl groups per terminal or per molecule of the polymers shown in the examples was determined by 1H-NMR (using a Bruker AVANCE III HD-500) using CDClone. ３ The results were calculated by measurement (measured in a solvent).

[0135] <Synthesis of Organic Polymers> (Synthesis Example 1 (A-1)) A 1 / 1 (weight ratio) mixture of polyoxypropylenediol with a molecular weight of approximately 2,000 and polyoxypropylenetriol with a molecular weight of approximately 3,000 was used as an initiator, and polymerization of propylene oxide was carried out using a zinc hexacyanocobaltate glyme complex catalyst to obtain polypropylene oxide with a number average molecular weight of approximately 19,000 (polystyrene-equivalent molecular weight measured using a Tosoh HLC-8120GPC liquid delivery system, a Tosoh TSK-GEL H type column, and THF as the solvent). Subsequently, a methanol solution of NaOMe in an amount equivalent to 1.2 times the hydroxyl group of this hydroxyl-terminated polypropylene oxide was added, and the methanol was removed by distillation. Furthermore, allyl chloride was added to convert the terminal hydroxyl groups to allyl groups. As a result, polypropylene oxide with a number average molecular weight of approximately 19,000 and terminal allyl groups was obtained. To 100 parts by weight of the obtained unpurified allyl-terminated polypropylene oxide, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred. The water was then removed by centrifugation, and another 300 parts by weight of water was mixed and stirred into the resulting hexane solution. The water was removed again by centrifugation, and the hexane was removed by vacuum defloration to obtain purified allyl-terminated polypropylene oxide (hereinafter referred to as allyl polymer). To 100 parts by weight of the obtained allyl polymer, 0.7 molar equivalents of methyldimethoxysilane were reacted with the allyl groups of the allyl-terminated polypropylene oxide at 90°C for 2 hours using 150 ppm of an isopropanol solution of a platinum vinylsiloxane complex with a platinum content of 3 wt% as a catalyst, to obtain methyldimethoxysilyl-terminated polypropylene oxide (A-1). There were approximately 0.7 methyldimethoxysilyl groups per polymer chain end.

[0136] (Synthesis Example 2 (A-2)) Using polyoxypropylenediol with a molecular weight of approximately 2,000 as an initiator, propylene oxide was polymerized using a zinc hexacyanocobaltate grime complex catalyst to obtain polypropylene oxide with a number average molecular weight of approximately 16,000. Subsequently, a methanol solution of NaOMe in an amount equivalent to 1.2 times the hydroxyl group of this hydroxyl-terminated polypropylene oxide was added, and the methanol was removed by distillation. Furthermore, allyl chloride was added to convert the terminal hydroxyl groups to allyl groups. As a result, an allyl polymer with a number average molecular weight of approximately 16,000 and terminal allyl groups was obtained. The allyl polymer was purified using the same procedure as in Synthesis Example 1. To 100 parts by weight of the obtained allyl polymer, 0.7 molar equivalents of methyldimethoxysilane were reacted with 150 ppm of an isopropanol solution containing 3 wt% platinum of the platinum vinylsiloxane complex as a catalyst, at 90°C for 2 hours, to obtain methyldimethoxysilyl-terminated polypropylene oxide (A-2). The number of methyldimethoxysilyl groups was approximately 0.6 per polymer chain end.

[0137] (Synthesis Example 3 (A-3)) Using polyoxypropylenediol with a molecular weight of approximately 2,000 as an initiator, propylene oxide was polymerized using a zinc hexacyanocobaltate grime complex catalyst to obtain a hydroxyl-terminated polypropylene oxide with a number average molecular weight of 28,500. Subsequently, a methanol solution of NaOMe in an amount equivalent to 1.2 times the hydroxyl group of this hydroxyl-terminated polypropylene oxide was added, and the methanol was removed by distillation. Furthermore, allyl chloride was added to convert the terminal hydroxyl groups to allyl groups. As a result, an allyl polymer with a number average molecular weight of approximately 28,500 and terminal allyl groups was obtained. The allyl polymer was purified by the same procedure as in Synthesis Example 1. To 100 parts by weight of the obtained allyl-terminated polypropylene oxide, 0.7 molar equivalents of methyldimethoxysilane were reacted with 150 ppm of an isopropanol solution of platinum divinyldisiloxane with a platinum content of 3 wt% at 90°C for 2 hours, using this as a catalyst, to obtain methyldimethoxysilyl-terminated polypropylene oxide (A-3). The number of methyldimethoxysilyl groups was approximately 0.7 per polymer chain end.

[0138] (Synthesis Example 4 (a-1)) 52.1 parts by weight of isobutyl alcohol were placed in a four-necked flask equipped with a stirrer and heated to 90°C under a nitrogen atmosphere. A mixed solution of 14.5 parts by weight of methyl methacrylate, 68.2 parts by weight of butyl acrylate, 14.9 parts by weight of stearyl methacrylate, 2.4 parts by weight of 3-(dimethoxymethylsilyl)propyl methacrylate, and 0.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 12.4 parts by weight of isobutyl alcohol was added dropwise over 7 hours. Polymerization was then carried out at 90°C for 2 hours to obtain an isobutyl alcohol solution (60% by weight) of poly(meth)acrylic acid ester (a-1) having an average of 1.8 methyldimethoxysilyl groups per molecule, a number average molecular weight of 1700, and a weight average molecular weight of 4800.

[0139] (Synthesis Example 5 (A-4)) 70 parts by weight of polyoxypropylene (A-3) obtained in Synthesis Example 3 and 50 parts by weight of an isobutyl alcohol solution of poly(meth)acrylic acid ester (a-1) obtained in Synthesis Example 4 were mixed, and the isobutyl alcohol was removed by vacuum distillation to obtain a polymer mixture (A-4) in which the weight ratio of polyoxypropylene (A-3) to poly(meth)acrylic acid ester (a-1) was 70 / 30.

[0140] (Synthesis Example 6 (A-5)) Using polyoxypropylene glycol with a number average molecular weight of approximately 2,500 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate-grime complex catalyst to obtain hydroxyl-terminated polypropylene oxide with a number average molecular weight of 25,000. Subsequently, 1.2 molar equivalents of sodium methoxide in a 28% methanol solution were added to the hydroxyl groups of this hydroxyl-terminated polyoxypropylene. After removing methanol by vacuum defoliation, an additional 1.5 molar equivalents of allyl chloride were added to the hydroxyl groups of the polymer to convert the terminal hydroxyl groups to allyl groups, and the unreacted allyl chloride was removed by vacuum defoliation. The obtained unpurified polyoxypropylene was mixed and stirred with n-hexane and water, and the water was removed by centrifugation. The metal salts in the polymer were removed by vacuum defoliation of the hexane from the obtained hexane solution. Thus, polyoxypropylene having allyl groups at the ends was obtained. To this polymer, 36 ppm of a platinum divinyldisiloxane complex solution (a 2-propanol solution equivalent to 3% by weight of platinum) was added, and 0.9 parts by weight of dimethoxymethylsilane were slowly added dropwise while stirring. The mixture was reacted at 90°C for 2 hours, and then the unreacted dimethoxymethylsilane was removed under reduced pressure to obtain polyoxypropylene (A-5) with a number-average molecular weight of approximately 25,500 and methyldimethoxysilyl groups at the ends. The number of methyldimethoxysilyl groups was approximately 0.7 per polymer chain end.

[0141] (Synthesis Example 7 (A-6)) 70 parts by weight of polyoxypropylene (A-5) obtained in Synthesis Example 6 and 50 parts by weight of an isobutyl alcohol solution of poly(meth)acrylic acid ester (a-1) obtained in Synthesis Example 4 were mixed, and the isobutyl alcohol was removed by vacuum distillation to obtain a polymer mixture (A-6) in which the weight ratio of polyoxypropylene (A-5) to poly(meth)acrylic acid ester (a-1) was 70 / 30.

[0142] (Preparation of Complex 1) 60 g of TC-750 (titanium diisopropoxybis(ethyl acetate), manufactured by Matsumoto Fine Chemicam Co., Ltd.) was added to a 100 ml round-bottom flask. While stirring the contents of the flask, 10 g of DBU (1,8-diazabicyclo[5.4.0]-7-undecene, manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly added dropwise to the flask. After the addition was complete, the contents of the flask were stirred at room temperature for 24 hours to obtain 70.0 g of a reddish-brown liquid complex 1.

[0143] (Preparation of Complex 2) 60 g of TC-750 (titanium diisopropoxybis(ethyl acetate), manufactured by Matsumoto Fine Chemicam Co., Ltd.) was added to a 100 ml round-bottom flask. While stirring the contents of the flask, 20 g of DBU (1,8-diazabicyclo[5.4.0]-7-undecene, manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly added dropwise to the flask. After the addition was complete, the contents of the flask were stirred at room temperature for 24 hours to obtain 80.0 g of a reddish-brown liquid complex 2.

[0144]

[0145] (One-component curable composition) (Example 1) <Main component preparation> For polymer (A-1), prepare the following amounts of colloidal calcium carbonate (manufactured by Shiraishi Industries Co., Ltd., product name: Shiratsuka CCR), heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., product name: Whiteon SB), pigment (manufactured by Ishihara Industries Co., Ltd., product name: Typeque R820), plasticizer (manufactured by J-Plus Co., Ltd., product name: DINP, diisononyl phthalate), and thixotropic agent (manufactured by ARKEMA, product name: Crayvallac) as shown in Table 2 (unless otherwise specified, the unit is parts by weight; the same applies hereinafter). SLT, an antioxidant (BASF, trade name: Irganox 1010), a UV absorber (BASF, trade name: Tinuvin 571), and a light stabilizer (BASF, trade name: Tinuvin 770) were added and mixed using a spatula. The mixture was then dispersed by passing it through a three-roll mill three times to obtain the main component. After this, a Karl Fischer moisture meter (EBU-610: Kyoto Electronics Manufacturing Co., Ltd.) was used to determine the concentration of Aquamicron titration solution SS 3 mg (potency 2.5-3.5 mgH). ２0 / mL (manufactured by Mitsubishi Chemical Corporation), and Aquamicron dehydrating agent CM (moisture content 0.3 mgH) ２ The water content in the main component was measured using a device manufactured by Mitsubishi Chemical Corporation (for use with a water content of 0 / mL or less).

[0146] <Dehydration Process> To the main component described above, the amounts of Dynasylan VTMO (alkoxysilane-containing dehydrating agent (C): vinyltrimethoxysilane, manufactured by Evonik) and DBU (amidine structure-containing compound (B): 1,8-diazabicyclo[5.4.0]-7-undecene, manufactured by Tokyo Chemical Industry Co., Ltd.) listed in Table 2 were added, and dehydration was carried out by stirring at 60°C under atmospheric pressure for 30 minutes using a planetary mixer. After this, a Karl Fischer moisture meter (EBU-610: manufactured by Kyoto Electronics Manufacturing Co., Ltd.) was used to determine the concentration of Aquamicron titration solution SS 3 mg (potency 2.5-3.5 mgH). ２ 0 / mL (manufactured by Mitsubishi Chemical Corporation), and Aquamicron dehydrating agent CM (moisture content 0.3 mgH) ２ The moisture content after the dehydration process was measured using a device manufactured by Mitsubishi Chemical Corporation (for use with a moisture content of 0 / mL or less).

[0147] <Devolatilization Process> After the dehydration process, defoliation was carried out for 30 minutes under room temperature and reduced pressure to remove unreacted Dynasylan VTMO with methanol.

[0148] <Mixing Process> Next, the amount of Dynasylan DAMO (adhesion agent, 3-(2-aminoethylamino)propyltrimethoxysilane, manufactured by Evonik) listed in Table 2 and Complex 1 were added and mixed. The resulting curable composition was filled into a moisture-proof cartridge and sealed to obtain a one-component curable composition.

[0149] (Comparative Example 1) <Main component preparation> To polymer (A-1), the amounts of colloidal calcium carbonate (manufactured by Shiraishi Industries Co., Ltd., trade name: Shiratsuka CCR), heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: Whiteon SB), pigment (manufactured by Ishihara Industries Co., Ltd., trade name: Typake R820), plasticizer (manufactured by J-Plus Co., Ltd., trade name: DINP, diisononyl phthalate), thixotropic agent (manufactured by ARKEMA, trade name: Crayvallac SL), antioxidant (manufactured by BASF, trade name: Irganox 1010), ultraviolet absorber (manufactured by BASF, trade name: Tinuvin 571), and light stabilizer (manufactured by BASF, trade name: Tinuvin 770) listed in Table 2 were added, and the mixture was mixed using a spatula. The mixture was then dispersed by passing it through a three-roll mill three times to obtain the main component. After that, the water content in the main component was measured in the same manner as in Example 1. <Dehydration Process> Next, dehydration was performed by stirring at 120°C under reduced pressure for 120 minutes using a planetary mixer. After that, the moisture content after the dehydration process was measured in the same manner as in Example 1. <Devaporation Process> After the dehydration process, defoliation was performed in the same manner as in Example 1.

[0150] <Mixing Process> Next, the amounts of Dynasylan VTMO, Dynasylan DAMO, and Composite 2 listed in Table 2 were added and mixed. The resulting curable composition was filled into a moisture-proof cartridge and sealed to obtain a one-component curable composition.

[0151] (Evaluation) (Skinning time (curing properties)) The one-component curable composition was stored for 7 days in an atmosphere of 23°C and 50% relative humidity. The time it took to fill a mold with a thickness of approximately 5 mm with the obtained curable composition and smooth the surface was defined as the curing start time. The time it took for the composition to no longer adhere to the spatula when touched was measured. The results obtained are shown in Table 2 as "Skinning time (curing properties) before storage". Furthermore, the one-component curable composition was stored at 23°C for 7 days, then at 50°C for 28 days, and then at 23°C for 1 day. After that, the skinning time (curing properties) was measured using the method described above. The results obtained are shown in Table 2 as "Skinning time after storage".

[0152] (Viscosity) The one-component curable composition was stored at 23°C for 7 days, and then its viscosity was measured at 2 rpm using a BS-type viscometer, rotor No. 7, manufactured by Tokyo Keiki Co., Ltd., under an atmosphere of 23°C and 50% relative humidity. The results obtained are shown in Table 2 as "viscosity before storage". The one-component curable composition was also stored at 23°C for 7 days, then further stored at 50°C for 28 days, and then stored at 23°C for 1 day. After that, the viscosity was measured at 2 rpm using the same method. The results obtained are shown in Table 2 as "viscosity after storage".

[0153] (Storage Stability) Based on the results obtained above, the rate of change of viscosity after storage relative to the viscosity before storage (viscosity after storage / viscosity before storage) was calculated. The results are shown in Table 2. The closer the rate of change is to 100%, the better the storage stability. The results are shown in Table 2.

[0154] (Dumbbell Tensile Properties) Under constant temperature and humidity conditions of 23°C and 50% relative humidity, the curable composition was filled into a 3 mm thick sheet-like mold. After curing at 23°C and 50% RH for 3 days, it was cured in a 50°C dryer for 4 days to obtain a sheet-like cured material. The obtained cured material was punched out into a No. 3 dumbbell shape according to JIS K 6251, and a tensile test (tensile speed 200 mm / min) was performed using an autograph to measure the stress at 50% elongation, stress at 100% elongation, stress at fracture, and elongation at fracture. The results are shown in Table 2.

[0155] (Adhesion) The curable composition was applied to various substrates shown in Table 2 to ensure close adhesion, and cured for 7 days under constant temperature and humidity conditions of 23°C and 50% relative humidity. A 90° hand peel test was performed on the resulting cured material, and the fracture state was observed. The fracture state was defined as cohesive fracture (failure in the curable composition portion) as CF and interfacial fracture (peeling at the interface between the curable composition and the substrate) as AF, and confirmed visually. The results are shown in Table 2.

[0156]

[0157] (Evaluation Results) The curable composition (Example 1), prepared by adding an alkoxysilane-containing dehydrating agent (C) and an amidine structure-containing compound (B) in the dehydration step, stirring at 60°C and atmospheric pressure, and then performing a defoliation step under reduced pressure, showed faster curing properties compared to the curable composition (Comparative Example 1) prepared by physical dehydration (stirring at 120°C and under reduced pressure for 120 minutes) without using the alkoxysilane-containing dehydrating agent (C) and the amidine structure-containing compound (B). Furthermore, it also showed good storage stability, dumbbell tensile properties, and adhesive properties.

[0158] (Comparative Example 2) A one-component curable composition was prepared in the same manner as in Example 1, except that Dynasylan DAMO was used instead of DBU in the dehydration step, and composite 2 was used instead of composite 1 in the mixing step.

[0159] (Comparative Example 3) A one-component curable composition was prepared in the same manner as in Comparative Example 2, except that Dynasylan DAMO was not used in the dehydration step.

[0160]

[0161] (Evaluation Results) The one-component curable composition of Comparative Example 2 gelled in the cartridge after being stored at 23°C for 7 days, making it impossible to evaluate its curability. It is presumed that the storage stability was poor because, in the dehydration process, a less active Dynasylan DAMO was used instead of the amidine structure-containing compound (B), resulting in inefficient dehydration and a large amount of unreacted alkoxysilane-containing dehydrating agent (C) remaining, which was removed in the defoliation process.

[0162] The one-component curable composition of Comparative Example 3 also gelled in the cartridge after being stored at 23°C for 7 days, making it impossible to evaluate its curability. It is presumed that the storage stability was poor because the amidine structure-containing compound (B) was not used in the dehydration process, resulting in inefficient dehydration, and a large amount of unreacted alkoxysilane-containing dehydrating agent (C) remained, which was removed in the defoliation process.

[0163] (Comparative Example 4) A one-component curable composition was prepared in the same manner as in Example 1, except that the amount of Dynasilan VTMO (alkoxysilane-containing dehydrating agent (C)) used in the dehydration step was changed as shown in Table 4.

[0164]

[0165] (Evaluation Results) In Comparative Example 4, the amount of alkoxysilane-containing dehydrating agent (C) added relative to the water content in the main component was small, and the one-component curable composition gelled in the cartridge after storage, resulting in poor storage stability.

[0166] (Example 2) As shown in Table 5, a one-component curable composition was prepared in the same manner as in Example 1, except that the amounts of Dynasylan VTMO (alkoxysilane-containing dehydrating agent (C)) and DBU (amidine structure-containing compound (B)) were changed, and TC-750 (titanium diisopropoxybis(ethyl acetate), manufactured by Matsumoto Fine Chemicam Co., Ltd.) was used instead of complex 1.

[0167] (Example 3) As shown in Table 5, a one-component curable composition was prepared in the same manner as in Example 2, except that Tyzor KE-6 (titanium diisobutoxybis(ethyl acetate, manufactured by Dorf Ketal)) was added instead of TC-750.

[0168] (Example 4) A one-component curable composition was prepared in the same manner as in Example 1, except that the amount of Dynasylan VTMO (alkoxysilane-containing dehydrating agent (C)) used was changed, as shown in Table 5.

[0169] (Examples 5-6) As shown in Table 5, one-component curable compositions were prepared in the same manner as in Example 1, except that the amount of Dynasilan VTMO (alkoxysilane-containing dehydrating agent (C)) used was changed and TC-750 was used instead of Composite 1. Measurements were performed in the same manner as in Example 1. The results obtained are shown in Table 5.

[0170]

[0171] (Evaluation Results) The one-component curable compositions (Examples 2-6) prepared by performing a dehydration step and a defoliation step in the same manner as in Example 1 showed good curability, storage stability, dumbbell tensile properties, and adhesive properties.

[0172] (Examples 7-9) As shown in Table 6, one-component curable compositions were prepared in the same manner as in Example 1, except that the temperature in the dehydration step was changed. Measurements were performed in the same manner as in Example 1. The results obtained are shown in Table 6.

[0173]

[0174] (Evaluation Results) The one-component curable compositions (Examples 7-9) prepared by changing the dehydration temperature to 40°C, 60°C, or 80°C showed good curability, storage stability, dumbbell tensile properties, and adhesive properties.

[0175] (Example 10) As shown in Table 7, a one-component curable composition was prepared in the same manner as in Example 1, except that the temperature and time in the dehydration step were changed, and TC-750 (titanium compound (D)) was added in addition to Dynasylan VTMO and DBU in the dehydration step. Measurements were performed in the same manner as in Example 1. The obtained results are shown in Table 7.

[0176]

[0177] (Evaluation Results) The one-component curable composition (Example 10) prepared using DBU and TC-750 in the dehydration process exhibited good curability, storage stability, dumbbell tensile properties, and adhesive properties.

[0178] (Examples 11-13) One-component curable compositions were prepared in the same manner as in Example 1, except that the type of organic polymer (A) was changed as shown in Table 8. Measurements were performed in the same manner as in Example 1. The results obtained are shown in Table 8.

[0179]

[0180] (Evaluation Results) The one-component curable compositions (Examples 11-13) prepared by adding an alkoxysilane-containing dehydrating agent (C) and an amidine structure-containing compound (B) in the dehydration step, stirring at 60°C and atmospheric pressure, and then performing a defoliation step, exhibited good curability, storage stability, dumbbell tensile properties, and adhesive properties.

Claims

1. The following general formula (1): -SiR １ ３－ａ X ａ (1) (wherein, R １ R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or ０ ３ Represents a triorganosiloxy group represented by SiO-. Three R ０ represents a hydrocarbon group having 1 to 20 carbon atoms, either identical or different. X represents a hydroxyl group or a hydrolyzable group. a indicates 1, 2, or 3. R １ A method for producing a curable composition containing an organic polymer (A) having a reactive silicon group represented by (or, when there are multiple X, they may be the same or different), comprising: a dehydration step of adding an amidine structure-containing compound (B) and an alkoxysilane-containing dehydrating agent (C) to a system containing the organic polymer (A), and stirring at 10 to 90°C under pressure in which the alkoxysilane-containing dehydrating agent (C) does not substantially volatilize; and a defoliation step of defoliating the volatile components contained in the system containing the organic polymer (A) after the dehydration step under reduced pressure, wherein the amount of the alkoxysilane-containing dehydrating agent (C) added is such that the total number of moles of alkoxy groups directly attached to silicon atoms in the alkoxysilane-containing dehydrating agent (C) is 200 mol% or more, relative to the water content of the system containing the organic polymer (A) before the dehydration step (100 mol%).

2. The manufacturing method according to claim 1, wherein the stirring time in the dewatering step is 20 minutes or more.

3. The manufacturing method according to claim 1, wherein the temperature in the dehydration step is 40°C or higher.

4. The manufacturing method according to claim 1, wherein the amount of the amidine structure-containing compound (B) added is 0.2 parts by weight or more per 100 parts by weight of the organic polymer (A).

5. The amidine structure-containing compound (B) is represented by the following general formula (2): R ２ N = CR ３ -NR ４ ２ (2) (In the formula, R ２ , R ３ , and R ４ are the same or different and each represents a hydrogen atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Two R ４ may be the same or different. Any two or more of R ２ , R ３ , and two R ４ may combine to form a cyclic structure.) The production method according to claim 1.

6. The manufacturing method according to claim 1, wherein the addition of the alkoxysilane-containing dehydrating agent (C) is performed only once in the dehydration step.

7. The manufacturing method according to claim 1, further comprising a mixing step of mixing a curing catalyst and / or an adhesion promoter into the system containing the organic polymer (A) after the defoliation step.

8. The manufacturing method according to claim 7, wherein the curing catalyst is a non-tin curing catalyst.

9. The non-tin curing catalyst is defined by the following general formula (3): Ti(OR ５ ) ｄ Y ４－ｄ (3) (wherein, R ５ The method for producing the product according to claim 8, comprising a titanium compound represented by (D') or a condensate thereof (D'), or a composite of an amidine structure-containing compound (B') and the titanium compound or condensate thereof (D').

10. In the dehydration step, the following general formula (3): Ti(OR ５ ) ｄ Y ４－ｄ (3) (wherein, R ５ The manufacturing method according to claim 1, further comprising adding a titanium compound represented by (D) or a condensate thereof (D), wherein (A) represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. (Y) represents a chelate coordination compound. (d) represents 0 or an integer from 1 to 4.

11. The manufacturing method according to claim 1, wherein the alkoxysilane-containing dehydrating agent (C) is a vinyl-type unsaturated group-containing silane.

12. The manufacturing method according to claim 11, wherein the alkoxysilane-containing dehydrating agent (C) is vinyltrimethoxysilane.

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