Curable composition and cured product thereof

Abstract

Provided is a non-organic tin-based curable composition containing: (A) an organic polymer having a reactive silicon group–containing structure represented by at least one among specific general formulas (1) to (6); (B) an amidine compound having a melting point below 23°C; and (C) an acid anhydride and / or a carboxylic acid having a pKa value of 3 to 5. The amount of the amidine compound (B) is preferably 0.1 to 15 parts by weight and the amount of the acid anhydride and / or carboxylic acid (C) is preferably 0.1 to 15 parts by weight per 100 parts by weight of the organic polymer (A).

Description

[Technical field]

[0001] The present invention relates to a curable composition containing an organic polymer having a reactive silicon group, and a cured product thereof. [Background technology]

[0002] Reactive silicon group-containing organic polymers are known as moisture-reactive polymers, and are used in a wide range of fields, being included in many industrial products such as adhesives, sealants, coatings, paints, pressure sensitive adhesives, etc. Known examples of such reactive silicon group-containing organic polymers include various polymers whose main chain skeleton is a polyoxyalkylene-based polymer, a saturated hydrocarbon-based polymer, or a (meth)acrylic acid ester-based copolymer.

[0003] Such curable compositions containing reactive silicon group-containing organic polymers generally contain a curing catalyst (also called a silanol condensation catalyst) for accelerating the curing reaction of the polymer. As a curing catalyst, organotin catalysts having a carbon-tin bond, such as dibutyltin bis(acetylacetonate), are widely used. However, in recent years, the toxicity of organotin compounds has been pointed out, and there is a demand for the development of non-organotin catalysts.

[0004] As such a non-organotin catalyst, a technology using an amine compound such as 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) has been reported (see, for example, Patent Documents 1 to 3). However, an amine compound such as DBU has low catalytic activity when used alone, and Patent Documents 1 and 2 disclose that good curability can be achieved by using an amine compound in combination with a Lewis acid such as boron trifluoride. Furthermore, Patent Document 3 discloses that a reactive silicon-group-containing organic polymer exhibiting fast curing properties is prepared by introducing a specific substituent onto the silicon atom in a reactive silicon group, and that an amine compound is used as a curing catalyst for the polymer. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2006-199730 A [Patent Document 2] International Publication No. 2008 / 099858 [Patent Document 3] JP 2013-213229 A Summary of the Invention [Problem to be solved by the invention]

[0006] As described in Patent Document 3, when an amine compound is added to a reactive silicon group-containing organic polymer that exhibits fast curing properties, good curing properties can be achieved without the concomitant use of a Lewis acid. However, the inventors' investigations revealed that when an amine compound such as DBU is used as a curing catalyst to produce a cured product of a reactive silicon group-containing organic polymer, a liquid substance appears on the surface of the cured product as time passes after curing, giving rise to the problem of bleed-out.

[0007] In view of the above-mentioned current situation, an object of the present invention is to provide a curable composition which contains a reactive silicon group-containing organic polymer and an amine compound, and which exhibits good curability while suppressing bleed-out after curing.

[0008] As a result of investigations aimed at solving the above-mentioned problems, the present inventors discovered that by blending an acid anhydride and / or a specific carboxylic acid with a non-organotin-based curable composition containing an organic polymer having a specific reactive silicon group-containing structure and a specific amine compound, it is possible to achieve good curability while suppressing bleed-out after curing, thereby arriving at the present invention.

[0009] That is, the present invention provides: (A) an organic polymer having a reactive silicon group-containing structure represented by at least one of general formulas (1) to (6); (B) amidine compounds having a melting point below 23°C, and (C) Acid anhydride and / or carboxylic acid having a pKa of 3 to 5 The present invention relates to a non-organotin based curable composition comprising: [ka] (In formula (1), R 1 R represents a divalent linking group which may contain a heteroatom. 2 represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. [ka] (In formula (2), R 1 , R 2 , and X are the same as above. R 3 R represents a hydrocarbon group having 1 to 5 carbon atoms and having an electron-withdrawing group on the carbon atom at position 1. 4 represents an unsubstituted hydrocarbon group having 1 to 5 carbon atoms; a is 1 or 2, b is 0 or 1, and c is 1 or 2, provided that a+b+c=3 is satisfied. [ka] (In formula (3), R 5 represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain a heteroatom. X is the same as above. Y is -O-, -S-, -N(R 6 )-, -OC(=O)-N(R 6 )-, -N(R 6 )-C(=O)-O-, and -N(R 6 )-C(=O)-N(R 6 R represents a divalent group selected from the group consisting of 6 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain a heteroatom. d is 1, 2, or 3. [ka] [ka] [ka] (In formulas (4)-(6), R 7 represents a hydrocarbon group having 1 to 20 carbon atoms, which may contain a heteroatom. X is the same as above. e is 1, 2, or 3. R 8 , and R 9 R each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a silyl group. 10 represents a divalent linking group, 10 Each of the two bonds of is bonded to a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom in the linking group. Preferably, general formulas (4) to (6) are represented by general formulas (7) to (9), respectively. [ka] [ka] [ka] (In formulas (7)-(9), R 7 , X, and e are the same as the groups in formulas (4) to (6). Preferably, the main chain skeleton of the organic polymer (A) is at least one selected from the group consisting of polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic acid ester polymers. Preferably, the amidine compound (B) is represented by the general formula (10). R 11 N=CR 12 -NR 13 2(10) (In formula (10), R 11 , R 12, and two R 13 R each independently represents a hydrogen atom or an organic group. 11 , R 12 , and two R 13 Any two or more of these may be bonded to form a cyclic structure.) Preferably, the content of the amidine compound (B) is 0.1 to 15 parts by weight, and the content of the acid anhydride and / or carboxylic acid (C) is 0.1 to 15 parts by weight, based on 100 parts by weight of the organic polymer (A). Preferably, the component (C) contains an acid anhydride. The present invention also relates to a cured product obtained by curing the non-organotin curable composition. The present invention also relates to a method for suppressing bleed-out on the surface of a cured product, comprising mixing an organic polymer (A) having a reactive silicon group-containing structure represented by at least one of the general formulas (1) to (6) above, an amidine compound (B) having a melting point of less than 23°C, and an acid anhydride and / or a carboxylic acid (C) having a pKa of 3 to 5, and then curing the mixture to obtain a cured product. Effect of the Invention

[0010] According to the present invention, it is possible to provide a curable composition that contains a reactive silicon group-containing organic polymer and an amine compound, and exhibits good curability while suppressing bleed-out after curing. The curable composition according to the present invention uses a reactive silicon group-containing organic polymer that exhibits fast curing properties, and therefore can achieve good curability without blending a Lewis acid. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, an embodiment of the present invention will be described in detail. The curable composition according to the present disclosure contains an organic polymer (A) having a reactive silicon group (hereinafter also referred to as reactive silicon group-containing organic polymer (A) or simply as polymer (A)) as a curable resin, and further contains an amidine compound (B) and an acid anhydride and / or a carboxylic acid (C).

[0012] <<Reactive silicon group-containing organic polymer (A)>> The reactive silicon group-containing organic polymer (A) has a polymer skeleton composed of a plurality of repeating units and a terminal structure bonded to the end of the polymer skeleton. The polymer skeleton refers to a polymer main chain composed of a plurality of repeating units. The polymer skeleton of the polymer (A) may be linear or branched. A linear polymer skeleton is preferred in that the cured product of the curable composition has high elongation, and a branched polymer skeleton is preferred in that the cured product of the curable composition has high strength. When the polymer skeleton of the polymer (A) is a polyoxyalkylene polymer, the linear polymer skeleton can be formed by using an initiator having one or two hydroxyl groups in one molecule in the polymerization method for forming the polymer skeleton, and the branched polymer skeleton can be formed by using an initiator having three or more hydroxyl groups in one molecule.

[0013] The polymer skeleton is preferably a polymer skeleton consisting of only a plurality of repeating units linked together, or a polymer skeleton consisting of only the repeating units and including a structure derived from an initiator used during polymerization. When the polymer skeleton of the polymer (A) is a polyoxyalkylene polymer, the repeating unit refers to an oxyalkylene unit, for example, an oxyalkylene unit having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

[0014] The terminal structure refers to a portion that does not contain a repeating unit constituting the polymer skeleton and is bonded to the end of the polymer skeleton. When the polymer skeleton of the polymer (A) is a polyoxyalkylene polymer, the terminal structure is preferably bonded to an oxyalkylene unit located at the end of the polymer skeleton via an oxygen atom. In addition, the reactive silicon group possessed by the polymer (A) and the reactive silicon group-containing structure described below are preferably contained in the terminal structure. In this case, each terminal structure may contain a reactive silicon group, or a terminal structure containing a reactive silicon group and a terminal structure not containing a reactive silicon group may coexist.

[0015] The reactive silicon group-containing organic polymer (A) preferably has reactive silicon groups at two or more ends of the polymer backbone. When the polymer backbone of the polymer (A) is linear, the polymer (A) can be said to have reactive silicon groups at both ends of the polymer backbone. In this case, the polymer (A) is preferably a polymer component composed of polymer molecules having reactive silicon groups at two or more ends of the polymer backbone, but the entire polymer (A) may contain, in addition to the polymer molecules, polymer molecules having reactive silicon groups at only one end of the polymer backbone and / or polymer molecules having no reactive silicon groups.

[0016] The number of reactive silicon groups per molecule of the reactive silicon group-containing organic polymer (A) is preferably more than 1 on average, more preferably 1.1 or more, even more preferably 1.3 or more, and particularly preferably 1.5 or more. The upper limit is preferably 5 or less, more preferably 4 or less.

[0017] In addition, the average ratio of the number of reactive silicon groups to the number of terminals of the polymer backbone in one molecule of the organic polymer (A) is not particularly limited, and may be 1.0 or less, or may be more than 1.0. The numerical value of the average ratio can be determined by the method described in the Examples. In addition to the method described in the Examples, the numerical value of the average ratio can also be calculated from the results of GPC measurement and NMR measurement of the reactive silicon group-containing organic polymer (A).

[0018] In the present specification, the average ratio of the number of reactive silicon groups to the number of polymer backbone ends refers to the number of reactive silicon groups contained on average per terminal structure of the polymer backbone, and is expressed as the average number of reactive silicon groups in one polymer molecule / the number of polymer backbone ends in one polymer molecule. The number of polymer backbone ends in one polymer molecule is 2 when the polymer backbone is entirely linear, and 3 or more when the polymer backbone is entirely branched. In addition, when the polymer backbone is a mixture of linear and branched, it can be between 2 and 3.

[0019] <Reactive silicon group-containing structure> The organic polymer (A) has a reactive silicon group-containing structure represented by at least one of the general formulas (1) to (6). The following formulas will be explained below.

[0020] [ka]

[0021] In formula (1), R 1 R represents a divalent linking group which may contain a heteroatom. 2 represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. R 1 is not particularly limited, but may be, for example, -O-, -S-, -N(R 6 )-, -OC(=O)-N(R 6 )-, -N(R 6 )-C(=O)-O-, and -N(R 6 )-C(=O)-N(R 6 )- are listed. R 6 More on this later.

[0022] R 2 R is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. 2 As the alkyl group, a hydrogen atom, a methyl group, or an ethyl group is preferable, and a hydrogen atom or a methyl group is more preferable.

[0023] Examples of X include a hydroxyl group, a hydrogen atom, a halogen, 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, and an alkenyloxy group. Among these, an alkoxy group is preferred because it is mildly hydrolyzable and easy to handle, a methoxy group and an ethoxy group are more preferred, and a methoxy group is particularly preferred.

[0024] [ka]

[0025] In formula (2), R 1 , R 2 , and X are the same as above. R 3 R represents a hydrocarbon group having 1 to 5 carbon atoms and having an electron-withdrawing group on the carbon atom at position 1. 4 represents an unsubstituted hydrocarbon group having 1 to 5 carbon atoms, a is 1 or 2, b is 0 or 1, and c is 1 or 2, provided that a+b+c=3 is satisfied.

[0026] R 3 The hydrocarbon group represented by the formula: preferably has 1 to 4 carbon atoms, more preferably 1 to 3, further preferably 1 or 2, and particularly preferably 1. R 3 The hydrocarbon group represented by the formula (2) has an electron-withdrawing group on the carbon atom at position 1 (i.e., the carbon atom adjacent to the silicon atom shown in formula (2)). The electron-withdrawing group is not particularly limited, and examples thereof include halogen atoms; oxygen-based substituents such as alkoxy groups and acyloxy groups; nitrogen-based substituents such as amino groups, alkylamino groups, and ureido groups; acyl groups, alkoxycarbonyl groups, nitro groups, cyano groups, isocyanato groups, sulfonyl groups, perfluoroalkyl groups, and electron-withdrawing aryl groups. More specifically, the electron-withdrawing group may be a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group, a 1-propoxy group, a 2-propoxy group, a 1-butoxy group, a 2-butoxy group, a tert-butyloxy group, an octoxy group, a lauryloxy group, a phenoxy group, or a benzyloxy group; an acyloxy group such as an acetoxy group, a propanoyloxy group, or a benzoyloxy group; a substituted amino group such as an amino group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a propylamino group, a dipropylamino group, or a diphenylamino group; a ureido group, a carbame acyl groups such as acetyl, propanoyl, octanoyl, lauryl, and benzoyl; alkoxycarbonyl groups such as methoxycarbonyl and tert-butyloxycarbonyl; nitro, cyano, and isocyanato groups; sulfonyl groups such as methylsulfonyl and toluenesulfonyl; perfluoroalkyl groups such as trifluoromethyl, pentafluoroethyl, perfluoropropyl, perfluorohexyl, and perfluorooctyl; and electron-withdrawing aryl groups such as difluorophenyl and pentafluorophenyl. As the electron-withdrawing group, a halogen atom, an alkoxy group, a substituted or unsubstituted amino group, or a trifluoromethyl group is preferred, since the polymer (A) exhibits high curability, and a halogen atom, an alkoxy group, or a substituted or unsubstituted amino group is more preferred.

[0027] R 3 Specific examples of the alkyl group include, but are not limited to, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a bromomethyl group, an iodomethyl group, a methoxymethyl group, an ethoxymethyl group, a phenoxymethyl group, an aminomethyl group, an N-methylaminomethyl group, an N,N-dimethylaminomethyl group, an N-ethylaminomethyl group, an N,N-diethylaminomethyl group, an acetoxymethyl group, and a methyl carbamate group.

[0028] R 4represents a hydrocarbon group having no substituent and has 1 to 5 carbon atoms, preferably 1 to 4, more preferably 1 to 3, further preferably 1 or 2, and particularly preferably 1. R 4 The hydrocarbon group having 1 to 5 carbon atoms as the alkyl group is not particularly limited, and examples thereof include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl groups; alkenyl groups such as vinyl, 2-propenyl, 3-butenyl, and 4-pentenyl groups; and cycloalkyl groups such as cyclopropyl, cyclobutyl, and cyclopentyl groups. Among these, alkyl groups are preferred, with methyl or ethyl groups being more preferred, and methyl groups being particularly preferred.

[0029] In formula (2), a is 1 or 2, b is 0 or 1, and c is 1 or 2 (but the total is 3), and it is preferable that a is 1, b is 0, and c is 2, in order to improve the curability of the organic polymer (A).

[0030] [ka]

[0031] In formula (3), R 5 represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain a heteroatom. X is the same as above. Y is -O-, -S-, -N(R 6 )-, -OC(=O)-N(R 6 )-, -N(R 6 )-C(=O)-O-, and -N(R 6 )-C(=O)-N(R 6 R represents a divalent group selected from the group consisting of 6 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may contain a heteroatom. d is 1, 2, or 3.

[0032] R 5 R is a hydrocarbon group having 1 to 20 carbon atoms.5 The number of carbon atoms in the hydrocarbon group as the substituent is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 4. The hydrocarbon group may be an unsubstituted hydrocarbon group, or a hydrocarbon group having a substituent.

[0033] R 5 The hetero-containing group which the hydrocarbon group may have as a substituent is a group containing a hetero atom, where an atom other than carbon and hydrogen atoms is defined as a hetero atom. Suitable examples of the heteroatom include N, O, S, P, Si, and halogen atoms. In the hetero-containing group, the total number of carbon atoms and heteroatoms is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. Suitable examples of the hetero-containing group include a hydroxyl group; a mercapto group; halogen atoms such as Cl, Br, I, and F; a nitro group; a cyano group; alkoxy groups such as a methoxy group, an ethoxy group, an n-propyloxy group, and an isopropyloxy group; alkylthio groups such as a methylthio group, an ethylthio group, an n-propylthio group, and an isopropylthio group; acyl groups such as an acetyl group, a propionyl group, and a butanoyl group; acyloxy groups such as an acetyloxy group, a propionyloxy group, and a butanoyloxy group; substituted or unsubstituted amino groups such as an amino group, a methylamino group, an ethylamino group, a dimethylamino group, and a diethylamino group; substituted or unsubstituted aminocarbonyl groups such as an aminocarbonyl group, a methylaminocarbonyl group, an ethylaminocarbonyl group, a dimethylaminocarbonyl group, and a diethylaminocarbonyl group; and a cyano group.

[0034] R 5 When R is a hydrocarbon group substituted with a hetero-containing group, 5 The total number of carbon atoms and heteroatoms in is preferably 2 to 30, more preferably 2 to 18, further preferably 2 to 10, and particularly preferably 2 to 6.

[0035] R 5Specific examples of the hydrocarbon group as the alkyl group include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethyl-n-hexyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group; alkenyl groups such as cyclopentyl, 3-butenyl, and 4-pentenyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; aryl groups such as phenyl, naphthalene-1-yl, naphthalene-2-yl, o-phenylphenyl, m-phenylphenyl, and p-phenylphenyl; and aralkyl groups such as benzyl, phenethyl, naphthalene-1-ylmethyl, and naphthalene-2-ylmethyl. These hydrocarbon groups may also be substituted with the hetero-containing groups described above. 5 As preferred.

[0036] R 5 Suitable examples of R include alkyl groups such as methyl and ethyl groups; alkyl groups having a hetero-containing group such as chloromethyl and methoxymethyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl groups; and aralkyl groups such as benzyl groups. 5 As the alkyl group, a methyl group, a methoxymethyl group, and a chloromethyl group are preferable, a methyl group and a methoxymethyl group are more preferable, and a methyl group is further preferable.

[0037] Y is -O-, -S-, -N(R 6 )-, -OC(=O)-N(R 6 )-, -N(R 6 )-C(=O)-O-, and -N(R 6 )-C(=O)-N(R 6Y represents a divalent group selected from the group consisting of -S-, -OC(=O)-N(R 6 )- is preferred, and -OC(=O)-N(R 6 )- is more preferred.

[0038] R 6 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain a heteroatom. 5 Examples of R include the same as those mentioned above, such as alkyl groups such as methyl, ethyl, n-propyl, and isopropyl, alkyl groups having a hetero-containing group such as chloromethyl and methoxymethyl, cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl and naphthyl, and aralkyl groups such as benzyl. 6 is preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and further preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. 6 )-C(=O)-N(R 6 )-Two R's in 6 may be the same or different.

[0039] In the formula (3), d is 1, 2 or 3, with 2 or 3 being preferred from the viewpoint of curability.

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] In formulas (4)-(6), R 7 represents a hydrocarbon group having 1 to 20 carbon atoms, which may contain a heteroatom. X is the same as above. e is 1, 2, or 3. R 8 , and R 9 R each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a silyl group. 10 represents a divalent linking group, 10 Each of the two bonds of is bonded to a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom in the linking group.

[0044] R 7 is the aforementioned R 5 is the same as R 5 The above statements apply to R 8 , and R 9 are each independently any one of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a silyl group. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 4. The number of carbon atoms in the aryl group is preferably 6 to 12, and more preferably 6 to 10. The number of carbon atoms in the aralkyl group is preferably 7 to 12.

[0045] R 8 , and R 9 Specific examples of the alkyl group include a hydrogen atom, alkyl groups such as a methyl group, an ethyl group, and a cyclohexyl group, aryl groups such as a phenyl group and a tolyl group, aralkyl groups such as a benzyl group and a phenethyl group, and silyl groups such as a trimethylsilyl group. Among these, a hydrogen atom, a methyl group, and a trimethylsilyl group are preferred, a hydrogen atom and a methyl group are more preferred, and a hydrogen atom is even more preferred.

[0046] R 10 is a divalent linking group. 10Each of the two bonds of is bonded to a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom in the linking group. Here, R 10 The two bonds of R are bonded to a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom in the linking group, respectively. 10 means that the two bonds in the formula (I) are present on a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom in the linking group. Specific examples of the divalent linking group include -(CH2) n -, -O-(CH2) n -, -S-(CH2) n -, -N(R 6 )-(CH2) n -, -OC(=O)-N(R 6 )-(CH2) n -, -N(R 6 )-C(=O)-N(R 6 )-(CH2) n Among these, -O-(CH2) n -, -OC(=O)-N(R 6 )-(CH2) n -, -N(R 6 )-C(=O)-N(R 6 )-(CH2) n - is preferred, and -O-CH2- is more preferred because the raw material is easily available. 6 is the same as above. n is preferably an integer of 0 to 10, more preferably an integer of 0 to 5, still more preferably an integer of 0 to 2, particularly preferably 0 or 1, and most preferably 1.

[0047] In the formulas (4) to (6), e is 1, 2, or 3, with 2 or 3 being preferred from the viewpoint of curability.

[0048] Formulas (4) to (6) are preferably represented by general formulas (7) to (9), respectively.

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] In formulas (7)-(9), R 7 , X, and e are the same as the respective groups in formulae (4) to (6).

[0053] Specific examples of reactive silicon groups in the structures represented by formulas (1)-(6) include, but are not limited to, trimethoxysilyl, triethoxysilyl, tris(2-propenyloxy)silyl, triacetoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethoxyethylsilyl, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N-diethylaminomethyl)dimethoxysilyl, and (N,N-diethylaminomethyl)diethoxysilyl.

[0054] <Main chain structure> The main chain structure of the reactive silicon group-containing organic polymer (A) may be linear or may have a branched chain. There is no particular restriction on the main chain skeleton of the reactive silicon group-containing organic polymer (A). Polymers having various main chain skeletons can be used as the reactive silicon group-containing organic polymer (A). Examples of the main chain skeleton of the reactive silicon group-containing organic polymer (A) include polyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymers, and polyoxypropylene-polyoxybutylene copolymers; ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, etc., polychloroprene, polyisoprene, copolymers of isoprene or butadiene and acrylonitrile and / or styrene, copolymers of polybutadiene, isoprene or butadiene and acrylonitrile and styrene, etc., and copolymers of these polyoxyalkylene polymers. Examples of the organic polymers include saturated hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating olefin polymers; polyester polymers; vinyl polymers such as (meth)acrylic acid ester polymers obtained by radical polymerization of (meth)acrylic acid ester monomers such as ethyl (meth)acrylate and butyl (meth)acrylate, and polymers obtained by radical polymerization of monomers such as (meth)acrylic acid monomers, vinyl acetate, acrylonitrile, and styrene; graft polymers obtained by polymerizing vinyl monomers in the above-mentioned polymers; polysulfide polymers; polyamide polymers; polycarbonate polymers; and diallyl phthalate polymers. The above-mentioned polymers may be mixed in block form, graft form, etc. Among these, saturated hydrocarbon polymers, polyoxyalkylene polymers, and (meth)acrylic acid ester polymers are preferred because they have a relatively low glass transition temperature and the obtained cured product has excellent cold resistance, polyoxyalkylene polymers are more preferred, and polyoxypropylene is particularly preferred.

[0055] The reactive silicon group-containing organic polymer (A) may be a polymer having any one of the above-mentioned various main chain skeletons, or a mixture of polymers having different main chain skeletons. The mixture may be a mixture of polymers produced separately, or a mixture produced simultaneously to have any mixture composition.

[0056] The number average molecular weight of the reactive silicon group-containing organic polymer (A) is not particularly limited, but is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000, as calculated based on polystyrene standards by GPC. When the number average molecular weight is within the above range, the amount of reactive silicon groups introduced is appropriate, and it is easy to obtain a reactive silicon group-containing organic polymer (A) that has an easy-to-handle viscosity and excellent workability while keeping production costs within an appropriate range.

[0057] The molecular weight of the reactive silicon group-containing organic polymer (A) can also be expressed as an end group-converted molecular weight obtained by directly measuring the end group concentration of the polymer precursor before the introduction of the reactive silicon group by titration analysis based on the principle of the hydroxyl value measurement method of JIS K 1557 and the iodine value measurement method specified in JIS K 0070, and taking into consideration the structure of the polymer (the degree of branching determined by the polymerization initiator used). The end group-converted molecular weight of the reactive silicon group-containing organic polymer (A) can also be obtained by preparing a calibration curve of the number average molecular weight obtained by general GPC measurement of the polymer precursor and the above-mentioned end group-converted molecular weight, and converting the number average molecular weight obtained by GPC of the reactive silicon group-containing organic polymer (A) into the end group-converted molecular weight.

[0058] The molecular weight distribution (Mw / Mn) of the reactive silicon group-containing organic polymer (A) is not particularly limited, but is preferably narrow. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, and particularly preferably 1.4 or less. The molecular weight distribution of the reactive silicon group-containing organic polymer (A) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.

[0059] <Method for producing reactive silicon group-containing organic polymer (A)> Next, a method for producing the reactive silicon group-containing organic polymer (A) will be described. The reactive silicon group-containing organic polymer (A) can be produced by introducing a reactive silicon group into a precursor polymer to which a reactive silicon group can be introduced. Various embodiments of the method for producing the reactive silicon group-containing organic polymer (A) in which the main chain is a polyoxyalkylene polymer will be described in detail below, but the method for producing the reactive silicon group-containing organic polymer (A) is not limited to the following description.

[0060] According to a first embodiment of the method for producing the reactive silicon group-containing organic polymer (A), the organic polymer (A) whose main chain is a polyoxyalkylene polymer and has a reactive silicon group-containing structure represented by any one of general formulas (1) or (2), or (4) to (6) can be produced by introducing a carbon-carbon unsaturated bond into a polyoxyalkylene polymer (D) having a hydroxyl group at its terminal, utilizing the reactivity of the hydroxyl group, to obtain a precursor polymer having a carbon-carbon unsaturated bond, and then reacting the precursor polymer with a reactive silicon group-containing compound that is reactive with the carbon-carbon unsaturated bond to introduce the reactive silicon group.

[0061] (polymerization) The polymer skeleton of the polyoxyalkylene polymer can be formed by polymerizing an epoxy compound with an initiator having a hydroxyl group by a conventionally known method, thereby obtaining a polyoxyalkylene polymer (D) having a hydroxyl group at its terminal. Although the specific polymerization method is not particularly limited, a polymerization method using a composite metal cyanide complex catalyst such as zinc hexacyanocobaltate glyme complex is preferred because it can obtain a hydroxyl-terminated polymer with a small molecular weight distribution (Mw / Mn).

[0062] The initiator having a hydroxyl group is not particularly limited, but examples thereof include ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, low molecular weight polyoxypropylene triol, butanol, allyl alcohol, low molecular weight polyoxypropylene monoallyl ether, and low molecular weight polyoxypropylene monoalkyl ether.

[0063] The epoxy compound is not particularly limited, but examples thereof include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and butyl glycidyl ether, etc. Propylene oxide is preferred.

[0064] (Reaction with alkali metal salts) When introducing a carbon-carbon unsaturated bond into a polyoxyalkylene polymer (D) having a hydroxyl group at the end, it is preferable to first react an alkali metal salt with the polyoxyalkylene polymer (D) to convert the terminal hydroxyl group into a metaloxy group. Also, a composite metal cyanide complex catalyst can be used instead of the alkali metal salt. In this manner, a metaloxy group-terminated polyoxyalkylene polymer (E) is formed.

[0065] The alkali metal salt is not particularly limited, and examples thereof include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. From the viewpoint of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred, and sodium methoxide and sodium tert-butoxide are more preferred. From the viewpoint of availability, sodium methoxide is preferred. The alkali metal salt may be dissolved in a solvent and then subjected to the reaction.

[0066] (Reaction with electrophile (F)) The metaloxy group-terminated polyoxyalkylene polymer (E) obtained as described above can be converted into a structure containing a carbon-carbon unsaturated bond by reacting an electrophilic agent (F) having a carbon-carbon unsaturated bond, thereby forming a polyoxyalkylene polymer (G) having a carbon-carbon unsaturated bond in the terminal structure.

[0067] The electrophile (F) having a carbon-carbon unsaturated bond is not particularly limited as long as it is a compound that can react with the metaloxy group in the polyoxyalkylene polymer (E) and introduce a carbon-carbon unsaturated bond into the polyoxyalkylene polymer. Examples of the electrophile (F) having a carbon-carbon unsaturated bond include an organic halide (F1) having a carbon-carbon unsaturated bond and an epoxy compound (F2) having a carbon-carbon unsaturated bond.

[0068] An organic halide (F1) having a carbon-carbon unsaturated bond, which is one embodiment of the electrophile (F), reacts with the metaloxy group through a halogen substitution reaction to form an ether bond, and can introduce a structure containing a carbon-carbon unsaturated bond as a terminal structure of a polyoxyalkylene polymer.

[0069] The organic halide (F1) having a carbon-carbon unsaturated bond is preferably a halogenated hydrocarbon compound having a carbon-carbon double bond. The polyoxyalkylene polymer (G) obtained by reacting the compound has a carbon-carbon double bond at the end of the polymer skeleton. When a reactive silicon group is introduced into such a polymer (G), a reactive silicon group-containing structure represented by the general formula (1) or (2) can be formed. In this case, R in formula (1) or (2) 1 is an oxygen atom.

[0070] The halogenated hydrocarbon compound having a carbon-carbon double bond is not particularly limited, and examples thereof include allyl chloride, methallyl chloride, allyl bromide, methallyl bromide, allyl iodide, and methallyl iodide. Allyl chloride and methallyl chloride are preferred from the viewpoint of ease of handling. Furthermore, methallyl chloride, methallyl bromide, and methallyl iodide are preferred from the viewpoint of improving the average ratio of the number of reactive silicon groups to the number of terminals of the polymer skeleton.

[0071] The organic halide (F1) having a carbon-carbon unsaturated bond may be a halogenated hydrocarbon compound having a carbon-carbon triple bond. The polyoxyalkylene polymer (G) obtained by reacting the compound has a carbon-carbon triple bond at the end of the polymer skeleton. When a reactive silicon group is introduced into such a polymer (G), the atom adjacent to the reactive silicon group has a carbon-carbon double bond, and a reactive silicon group-containing structure represented by any one of the general formulas (4) to (6) can be formed.

[0072] The halogenated hydrocarbon compound having a carbon-carbon triple bond is not particularly limited, and examples thereof include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne, 1-chloro-2-pentyne, 1,4-dichloro-2-butyne, 5-chloro-1-pentyne, 6-chloro-1-hexyne, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, Examples of the halogenated hydrocarbon compound include 1-bromo-2-octyne, 1-bromo-2-pentyne, 1,4-dibromo-2-butyne, 5-bromo-1-pentyne, 6-bromo-1-hexyne, propargyl iodide, 1-iodo-2-butyne, 4-iodo-1-butyne, 1-iodo-2-octyne, 1-iodo-2-pentyne, 1,4-diiodo-2-butyne, 5-iodo-1-pentyne, and 6-iodo-1-hexyne. Among these, propargyl chloride, propargyl bromide, and propargyl iodide are more preferred. In addition, the halogenated hydrocarbon compound having a carbon-carbon double bond may be used together with the halogenated hydrocarbon compound having a carbon-carbon triple bond.

[0073] An epoxy compound (F2) having a carbon-carbon unsaturated bond, which is another embodiment of the electrophile (F), can react with the metaloxy group through a ring-opening addition reaction of the epoxy group to form an ether bond, thereby introducing a structure containing a carbon-carbon unsaturated bond and a hydroxyl group as a terminal structure of the polyoxyalkylene polymer. In the ring-opening addition reaction, one or more epoxy compounds (F2) can be added to one metaloxy group by adjusting the amount of epoxy compound (F2) used relative to the metaloxy group and the reaction conditions.

[0074] The epoxy compound (F2) having a carbon-carbon unsaturated bond is not particularly limited, but is preferably an epoxy compound having a carbon-carbon double bond. For example, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and butadiene monoxide are more preferable in terms of reaction activity, and allyl glycidyl ether is particularly preferable.

[0075] As described above, when the epoxy compound (F2) having a carbon-carbon unsaturated bond is reacted with the metaloxy group-terminated polyoxyalkylene polymer (E), a new metaloxy group is generated by ring-opening of the epoxy group. Therefore, after the reaction with the epoxy compound (F2), the above-mentioned halogenated hydrocarbon compound having a carbon-carbon double bond can be continuously reacted. The same compounds as those described above can be used as the halogenated hydrocarbon compound having a carbon-carbon double bond used in this embodiment. This method is preferable because it can further increase the amount of carbon-carbon unsaturated bonds and the amount of reactive silicon groups introduced into the polymer.

[0076] (Introduction of reactive silicon groups) The polyoxyalkylene polymer (G) (precursor polymer) having a carbon-carbon unsaturated bond in the terminal structure obtained as above can be subjected to a hydrosilylation reaction with a hydrosilane compound (H) having a reactive silicon group to introduce a reactive silicon group into the polymer. This allows the production of an organic polymer (A) whose main chain is a polyoxyalkylene polymer and has a reactive silicon group-containing structure represented by any one of general formulas (1) or (2), or (4) to (6). In this case, when forming the reactive silicon group-containing structure represented by general formula (1) or the reactive silicon group-containing structure represented by general formula (2), the hydrosilane compound (H) having a reactive silicon group may be appropriately selected.

[0077] Specific examples of the hydrosilane compound (H) having a reactive silicon group include halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, and bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, and diethoxymethysilane; silane, dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, bis(chloromethyl)methoxysilane, (methoxymethyl)methylmethoxysilane, (methoxymethyl)dimethoxysilane, bis(methoxymethyl)methoxysilane, (methoxymethyl)diethoxysilane, (ethoxymethyl)diethoxysilane, (3,3,3-trifluoroethylene)silane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, [(chloromethyl)dimethoxysilyloxy]dimethylsilane, [(chloromethyl)diethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(methoxymethyl)diemethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilyloxy]dimethylsilane, [(3,3,3-trimethoxysilane], alkoxysilanes such as [fluoropropyl]dimethoxysilyloxy]dimethylsilane; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; ketoximate silanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane; and isopropenyloxysilanes (deacetone type) such as triisopropenyloxysilane, (chloromethyl)diisopropenyloxysilane, and (methoxymethyl)diisopropenyloxysilane.

[0078] The hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst in order to promote the reaction. As the specific hydrosilylation catalyst, a known one can be appropriately used.

[0079] According to a second embodiment of the method for producing a reactive silicon group-containing organic polymer (A), a method can also be applied in which a compound (I) having a reactive silicon group and an isocyanate group in one molecule is allowed to react with a polyoxyalkylene polymer (D) (precursor polymer) having a hydroxyl group at its terminal to form a urethane bond and introduce a reactive silicon group. According to this embodiment, an organic polymer (A) having a reactive silicon group-containing structure represented by any one of general formulas (1) to (3) can be produced. At this time, R in formula (1) or (2) 1 , and Y in formula (3) is the above-mentioned -OC(=O)-N(R 6 )-can be.

[0080] The compound (I) having a reactive silicon group and an isocyanate group in one molecule is not particularly limited as long as it is a compound having both an isocyanate group capable of undergoing a urethane reaction with a hydroxyl group in the polyoxyalkylene polymer (D) and a reactive silicon group in one molecule. Specific examples include (3-isocyanatepropyl)trimethoxysilane, (3-isocyanatepropyl)dimethoxymethylsilane, (3-isocyanatepropyl)triethoxysilane, (3-isocyanatepropyl)diethoxymethylsilane, (isocyanatemethyl)trimethoxysilane, (isocyanatemethyl)triethoxysilane, (isocyanatemethyl)dimethoxymethylsilane, and (isocyanatemethyl)diethoxymethylsilane.

[0081] The urethanization reaction may be carried out without using a urethanization catalyst, but may be carried out in the presence of a urethanization catalyst in order to improve the reaction rate or the reaction rate. As such a urethanization catalyst, for example, a conventionally known urethanization catalyst such as the catalysts listed in Polyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963, may be used. Specific examples of the urethanization catalyst include, but are not limited to, base catalysts such as organic tin compounds, bismuth compounds, and organic amines.

[0082] According to a third embodiment of the method for producing the reactive silicon group-containing organic polymer (A), a method can also be applied in which an excess of a polyisocyanate compound (J) is reacted with a polyoxyalkylene polymer (D) having a hydroxyl group at the end to produce a polymer (precursor polymer) having an isocyanate group at the end, and then the precursor polymer is reacted with a compound (K) having a group reactive with an isocyanate group (e.g., an amino group, a hydroxyl group, etc.) and a reactive silicon group. According to this embodiment, an organic polymer (A) having a reactive silicon group-containing structure represented by any one of general formulas (1) to (3) can be produced. At this time, R in formula (1) or (2) 1 , and Y in formula (3) is the above-mentioned -N(R 6 )-C(=O)-N(R 6 )- or -N(R 6 )-C(=O)-O-, etc.

[0083] Examples of the polyisocyanate compound (J) include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; and aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate.

[0084] Examples of the compound (K) having a group reactive with an isocyanate group and a reactive silicon group include γ-aminopropyltrimethoxysilane, γ-aminopropyldimethoxymethylsilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyldimethoxymethylsilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, γ-(N-phenyl)aminopropyltrimethoxysilane, γ-(N-phenyl)aminopropyldimethoxysilane, amino group-containing silanes such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyldimethoxymethylsilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyldimethoxymethylsilane; and the like.

[0085] According to a fourth embodiment of the method for producing a reactive silicon group-containing organic polymer (A), a method can also be applied in which a compound (L) having a reactive silicon group and a mercaptan group in one molecule is allowed to act on a polyoxyalkylene polymer (G) (precursor polymer) having a carbon-carbon unsaturated bond in its terminal structure, and a sulfide bond is formed by addition of the mercaptan group to the carbon-carbon unsaturated bond, thereby introducing a reactive silicon group. According to this embodiment, an organic polymer (A) having a reactive silicon group-containing structure represented by any one of general formulas (1) to (3) can be produced. At this time, when R in formula (1) or (2) 1 and Y in formula (3) is a sulfur atom.

[0086] The compound (L) having a reactive silicon group and a mercaptan group in one molecule is not particularly limited as long as it is a compound having both a mercaptan group capable of addition reaction with the carbon-carbon unsaturated bond of the polyoxyalkylene polymer (G) and a reactive silicon group in one molecule. Specific examples include (3-mercaptopropyl)methyldimethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)methyldiethoxysilane, (3-mercaptopropyl)triethoxysilane, (mercaptomethyl)methyldimethoxysilane, (mercaptomethyl)trimethoxysilane, (mercaptomethyl)methyldiethoxysilane, (mercaptomethyl)triethoxysilane, and the like.

[0087] The addition reaction of the mercaptan group to the carbon-carbon unsaturated bond may be carried out without using a radical initiator, but may be carried out in the presence of a radical initiator in order to improve the reaction rate or the reaction rate. As such a radical initiator, a conventionally known initiator may be used. Specific examples include, but are not limited to, azo-based initiators and peroxide-based initiators.

[0088] Among known radical initiators, catalysts with low activity toward reactive silicon groups are preferred, and from this viewpoint, azo initiators such as 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile) (V-59), and 2,2'-azobis(1-methylcyclohexanecarbonitrile) (V-40) are particularly preferred.

[0089] ((Meth)acrylic acid ester polymer) When the main chain of the reactive silicon group-containing organic polymer (A) is a (meth)acrylic acid ester polymer, examples of the method for producing the reactive silicon group-containing organic polymer (A) include (I) a method in which a compound having a polymerizable unsaturated group and a reactive functional group (e.g., acrylic acid, 2-hydroxyethyl acrylate) is copolymerized with a monomer having a (meth)acrylic structure to obtain a polymer, and then a carbon-carbon unsaturated bond is introduced to the terminal of the obtained polymer, and then a reactive silicon group-containing hydrosilane compound is added to the carbon-carbon unsaturated bond by a hydrosilylation reaction; and (II) a method in which a monomer having a (meth)acrylic structure is polymerized by a living radical polymerization method such as atom transfer radical polymerization to obtain a polymer, and then a carbon-carbon unsaturated bond is introduced to the terminal of the obtained polymer, and then a reactive silicon group-containing hydrosilane compound is added to the carbon-carbon unsaturated bond by a hydrosilylation reaction.

[0090] (Saturated Hydrocarbon Polymer) When the main chain of the reactive silicon group-containing organic polymer (A) is a saturated hydrocarbon polymer, examples of a method for producing the reactive silicon group-containing organic polymer (A) include a method in which an olefin compound having 2 to 6 carbon atoms, such as ethylene, propylene, 1-butene, or isobutylene, is polymerized as the main monomer to obtain a polymer, and then a carbon-carbon unsaturated bond is introduced into the terminal of the obtained polymer, and then a reactive silicon group-containing hydrosilane compound is added to the carbon-carbon unsaturated bond by a hydrosilylation reaction.

[0091] <<Amidine Compounds (B)>> The amidine compound (B) has a melting point of less than 23°C, that is, it is a compound that is liquid at 23°C. By blending the amidine compound (B) with the reactive silicon group-containing organic polymer (A), the curable composition can achieve practical curability. In addition, amidine compounds that are liquid at 23°C are generally prone to bleeding out over time after curing, but it is possible to suppress bleeding out by using the compound in combination with the component (C) described below.

[0092] The amidine compound (B) can be represented by general formula (10). R 11 N=CR 12 -NR 13 2(10) In formula (10), R 11 , R 12 , and two R 13 R each independently represents a hydrogen atom or an organic group. 11 , R 12 , and two R 13 Any two or more of these may be bonded to form a cyclic structure.

[0093] R 11 R is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group in which the carbon atom adjacent to the nitrogen atom (the carbon atom at the α-position) does not have an unsaturated bond, in order to enhance the curability of the reactive silicon group-containing organic polymer (A). 11 The number of carbon atoms is preferably 1 to 10, and more preferably 1 to 6, because these are easily available.

[0094] R 12 enhances the curing property of the reactive silicon group-containing organic polymer (A), and therefore is preferably a hydrogen atom or -NR 14 2, and preferably an organic group represented by -NR 14 It is more preferable that the organic group represented by the formula: 14 each independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. R 12 Ga-NR 14 When the organic group represented by the general formula (10) is an organic group represented by the general formula (10), the amidine compound represented by the general formula (10) is called a guanidine compound. The guanidine compound is easily available and has a large effect of enhancing the curability of the reactive silicon group-containing organic polymer (A), and therefore R 14 is preferably represented by a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably represented by a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0095] R 12Since the adhesiveness of the resulting cured product is good, -NR 15 -C(=NR 16 )-NR 17 2 (However, R 15 , R 16 and two R 17 each independently represents a hydrogen atom or an organic group having 1 to 6 carbon atoms; or -N=C(NR 18 2)-NR 19 2 (However, 2 R 18 and two R 19 each independently represents a hydrogen atom or an organic group having 1 to 6 carbon atoms. In this case, the amidine compound represented by the general formula (10) is called a biguanide compound.

[0096] R 12 Ga-NR 15 -C(=NR 16 )-NR 17 As the biguanide compound represented by R2, the following is preferred because it is easily available and the resulting cured product has good adhesiveness. 15 , R 16 and two R 17 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Furthermore, in order to further improve the adhesiveness of the obtained cured product, it is preferable that R 11 , 2 R 13 , R 15 , R 16 and two R 17 It is particularly preferred that one or more of:

[0097] R 12 -N=C(NR 18 2)-NR 19 As the biguanide compound represented by R2, the following is preferred because it is easily available and the resulting cured product has good adhesiveness. 11 , 2 R 13 , R 18 , and two R 19 It is preferable that each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

[0098] Two R in the general formula (10) 13 Preferably, represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, because they are easily available and because they enhance the curability of the reactive silicon group-containing organic polymer (A).

[0099] The number of carbon atoms contained in the amidine compound (B) is preferably 2 or more, more preferably 6 or more, and particularly preferably 7 or more. If the number of carbon atoms in the amidine compound (B) is less than 2, the volatility of the compound increases, and the working environment tends to deteriorate. The upper limit of the number of carbon atoms contained in the amidine compound (B) is not particularly limited, but is preferably 10,000 or less. In addition, the molecular weight of the amidine compound (B) is preferably 60 or more, more preferably 120 or more, and particularly preferably 130 or more, for the same reasons as above. The upper limit of the molecular weight of the amidine compound (B) is not particularly limited, but is generally preferably 100,000 or less.

[0100] Examples of the amidine compound (B) include, but are not limited to, pyrimidine compounds such as pyrimidine, 2-aminopyrimidine, 6-amino-2,4-dimethylpyrimidine, 2-amino-4,6-dimethylpyrimidine, 1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1-ethyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-diethyl-1,4,5,6-tetrahydropyrimidine, 1-n-propyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 2-hydroxy-4,6-dimethylpyrimidine, 1,3-diazanaphthalene, and 2-hydroxy-4-aminopyrimidine; imidazoline compounds such as 2-imidazoline, 2-methyl-2-imidazoline, 2-ethyl-2-imidazoline, 2-propyl-2-imidazoline, 2-vinyl-2-imidazoline, 1-(2-hydroxyethyl)-2-methyl-2-imidazoline, 1,3-dimethyl-2-iminoimidazolidine, and 1-methyl-2-iminoimidazolidine-4-one; amidine compounds such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 2,9-diazabicyclo[4.3.0]nona-1,3,5,7-tetraene, and 6-(dibutylamino)-1,8-diazabicyclo[5,4,0]undec-7-ene (DBA-DBU); Guanidine, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, 1,1-dimethylguanidine, 1,3-dimethylguanidine, 1,2-diphenylguanidine, 1,1,2-trimethylguanidine, 1,2,3-trimethylguanidine, 1,1,3,3-tetramethylguanidine, 1,1,2,3,3-pentamethylguanidine, 2-ethyl-1,1,3,3-tetramethylguanidine, 1,1,3,3-tetramethyl-2-n-propylguanidine, 1,1,3,3-tetramethyl-2-isopropylguanidine, 2-n-butyl-1,1,3,3-tetramethylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, 1,2,3-Tricyclohexylguanidine, 1-benzyl-2,3-dimethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-ethyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-propyl-1,5,7-triazabicyclo[4.4.0] guanidine compounds such as dec-5-ene, 7-isopropyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-cyclohexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-octyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene; Biguanide, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-(2-ethylhexyl)biguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, 1-morpholinobiguanide, Examples of the biguanide compounds include 1-n-butyl-N2-ethylbiguanide, 1,1'-ethylenebisbiguanide, 1,5-ethylenebiguanide, 1-[3-(diethylamino)propyl]biguanide, 1-[3-(dibutylamino)propyl]biguanide, and N',N''-dihexyl-3,12-diimino-2,4,11,13-tetraazatetradecanediamidine; and the like. Among these, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is preferred due to its good curability.

[0101] The content of the amidine compound (B) in the curable composition is not particularly limited, but is preferably 0.1 to 15 parts by weight based on 100 parts by weight of the reactive silicon group-containing organic polymer (A). In this range, the curable composition can have a practical curing speed while suppressing bleeding out after curing. More preferably, it is 0.3 to 10 parts by weight, and even more preferably, it is 0.5 to 5 parts by weight.

[0102] <<Acid anhydride and / or carboxylic acid (C)>> The component (C) is an acid anhydride or a carboxylic acid. An acid anhydride and a carboxylic acid may be used in combination. By using the component (C) in combination with the amidine compound (B), the curable composition can have good curability and suppress bleeding out after curing. Since the curability is improved, it is preferable that the component (C) contains an acid anhydride.

[0103] The acid anhydride is preferably a carboxylic acid anhydride. The acid anhydride may be a compound having a cyclic structure or may not have a cyclic structure. In addition, it may be a compound having a carbon-carbon double bond or may not have a carbon-carbon double bond. Specifically, acetic anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, benzoic anhydride, maleic anhydride, phthalic anhydride, pyromellitic anhydride, 4,4-biphthalic anhydride, 4,4-oxydiphthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhimic anhydride, nadic anhydride, trimellitic anhydride, trialkyl phthalic anhydride, dodecylsuccinic anhydride, methylnadic anhydride, chlorendic anhydride, etc. may be mentioned.

[0104] The carboxylic acid is preferably a carboxylic acid having a pKa of 3 to 5. When the pKa of the carboxylic acid is within the above range, both good curability and suppression of bleed-out after curing can be achieved. When the pKa of the carboxylic acid is less than 3, the curability tends to be insufficient, and when it exceeds 5, the suppression of bleed-out becomes insufficient. Note that, when a carboxylic acid having two pKa values ​​has a lower pKa value within the range of 3 to 5, the carboxylic acid corresponds to a carboxylic acid having a pKa of 3 to 5. The lower limit of the pKa of the carboxylic acid is preferably 3.0, more preferably 3.2, and even more preferably 3.4.

[0105] Carboxylic acids having a pKa of 3 to 5 are not particularly limited, but examples thereof include fatty acids such as formic acid (pKa=3.8), acetic acid (pKa=4.8), propionic acid (pKa=4.9), butyric acid (pKa=4.8), and 2-ethylhexanoic acid (pKa=4.9), aromatic carboxylic acids such as benzoic acid (pKa=4.2), and hydroxy acids such as malic acid (pKa1=3.4, pKa2=5.1).

[0106] The content of the acid anhydride and / or carboxylic acid (C) in the curable composition is not particularly limited, but is preferably 0.1 to 15 parts by weight in total relative to 100 parts by weight of the reactive silicon group-containing organic polymer (A). Within this range, the curable composition can have a practical curing speed while suppressing bleed-out after curing. More preferably, it is 0.3 to 10 parts by weight, and even more preferably, it is 0.5 to 5 parts by weight.

[0107] The content ratio of the amidine compound (B) to the acid anhydride and / or carboxylic acid (C) is not particularly limited, but from the viewpoint of achieving both good curability and suppression of bleed-out after curing, the ratio of the number of moles of carboxy groups contained in the (C) component to the number of moles of the amidine compound (B) is preferably 0.1 to 10, more preferably 0.5 to 5, and even more preferably 0.7 to 1.5. When the (C) component is an acid anhydride, the number of moles of carboxy groups is twice the number of moles of the acid anhydride.

[0108] <<Curable composition>> The curable composition contains a reactive silicon group-containing organic polymer (A) that exhibits fast curing properties, and therefore can achieve good curability, even though an amidine compound (B) is used as a curing catalyst, rather than an organotin compound. The curable composition has good curability even without Lewis acids such as metal halides and boron halides, which are disclosed in Patent Documents 1 and 2 as components that improve curability, and therefore the curable composition may be free of Lewis acids. Lewis acids require special handling, so it is preferable that the curable composition does not contain Lewis acids.

[0109] The curable composition may contain various additives, if necessary, in addition to the reactive silicon group-containing organic polymer (A), the amidine compound (B), and the acid anhydride and / or carboxylic acid (C). Examples of the additives include silanol condensation catalysts other than the components (B) and (C), fillers, adhesion promoters, plasticizers, anti-sagging agents, antioxidants, light stabilizers, UV absorbers, physical property adjusters, compounds containing epoxy groups, photocurable substances, oxygen-curable substances, and resins other than the reactive silicon group-containing organic polymer (A).

[0110] In addition, in order to adjust various physical properties of the curable composition or the cured product, additives other than those described above may be added to the curable composition as necessary. Examples of such additives include tackifier resins, solvents, diluents, epoxy resins, surface improvers, foaming agents, curability regulators, flame retardants, silicates, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, and fungicides. Representative additives will be described below.

[0111] <Silanol condensation catalyst> The curable composition may contain a silanol condensation catalyst other than components (B) and (C). Examples of silanol condensation catalysts other than components (B) and (C) include organotin compounds, metal carboxylates, amine compounds other than component (B), carboxylic acids other than component (C), and alkoxy metals.

[0112] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dioctyltin bis(acetylacetonate), reaction products of dibutyltin oxide with silicate compounds, reaction products of dioctyltin oxide with silicate compounds such as dioctyltin bis(triethoxysilicate), and reaction products of dibutyltin oxide with phthalic acid esters.

[0113] Specific examples of the metal carboxylate include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, and iron carboxylate. As the metal carboxylate, salts of the following carboxylic acids combined with various metals can be used.

[0114] Specific examples of amine compounds other than component (B) include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; amino group-containing silane coupling agents; and ketimine compounds.

[0115] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis(acetylacetonate), and diisopropoxytitanium bis(ethylacetoacetate), aluminum compounds such as aluminum tris(acetylacetonate), and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis(acetylacetonate).

[0116] Other silanol condensation catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0117] The use of silanol condensation catalysts other than the components (B) and (C) is not required, but if used, the amount used is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 5 parts by weight, even more preferably 0.001 to 1 part by weight, and particularly preferably 0.001 to 0.5 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A). However, it is preferable that the curable composition does not substantially contain an organotin compound. Specifically, the content of the organotin compound in the curable composition is preferably 0 to 0.5 parts by weight, more preferably 0 to 0.1 parts by weight, and even more preferably 0 to 0.01 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0118] The curable composition may contain a compound having a Si-F bond, but may not substantially contain a compound having a Si-F bond. It is known that the compound having a Si-F bond can act as a curing catalyst for the reactive silicon group-containing organic polymer. The curable composition according to the present disclosure can suppress bleeding out after curing while exhibiting good curability even if it does not substantially contain a compound having a Si-F bond. Examples of the compound having a Si-F bond include a low molecular weight compound having a fluorosilyl group and an organic polymer having a fluorosilyl group. Here, the fact that the curable composition does not substantially contain a compound having a Si-F bond means that the amount of the compound having a Si-F bond relative to 100 parts by weight of the reactive silicon group-containing organic polymer (A) is 0 parts by weight or more and less than 0.1 parts by weight, preferably 0 to 0.01 parts by weight.

[0119] <Filling agent> Various fillers can be blended into the curable composition. Examples of the fillers include ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, kaolin, silicin, calcined silicin, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc oxide, PVC powder, PMMA powder, glass fiber and filament. The amount of the filler used is preferably from 1 to 300 parts by weight, particularly preferably from 10 to 250 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0120] For the purpose of reducing the weight (density) of the cured product formed using the curable composition, balloons (hollow fillers) such as organic balloons and inorganic balloons may be added. The balloons are spherical fillers with a hollow interior. Balloon materials include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran. The amount of balloons used is preferably 0.1 to 100 parts by weight, particularly preferably 1 to 20 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0121] <Adhesion promoter> An adhesion promoter may be added to the curable composition. As the adhesion promoter, a silane coupling agent or a reaction product of a silane coupling agent may be added. Specific examples of the silane coupling agent include amino group-containing silanes such as γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropyltriethoxysilane, Examples of the adhesion promoter include isocyanate group-containing silanes such as α-isocyanate methyl trimethoxy silane, α-isocyanate methyl dimethoxy methyl silane, mercapto group-containing silanes such as γ-mercapto propyl trimethoxy silane, γ-mercapto propyl triethoxy silane, and γ-mercapto propyl methyl dimethoxy silane, and epoxy group-containing silanes such as γ-glycidoxy propyl trimethoxy silane and β-(3,4-epoxy cyclohexyl) ethyl trimethoxy silane. The adhesion promoter may be used alone or in combination of two or more. Also, the reaction products of various silane coupling agents may be used as adhesion promoters. The amount of the silane coupling agent used is preferably from 0.1 to 20 parts by weight, particularly preferably from 0.5 to 10 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0122] <Plasticizer> A plasticizer may be added to the curable composition. Specific examples of the plasticizer include phthalate compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl)phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; non-phthalate compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; aliphatic polycarboxylic acid ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and acetyl tributyl citrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetyl ricinoleate; alkylsulfonic acid phenyl ester; phosphate ester compounds; trimellitic acid ester compounds; chlorinated paraffin; hydrocarbon oils such as alkyl diphenyls and partially hydrogenated terphenyls; process oils; epoxidized soybean oil, and epoxy plasticizers such as epoxy benzyl stearate. The plasticizers may be used alone or in combination of two or more kinds.

[0123] Also, a polymer plasticizer can be used. Specific examples of the polymer plasticizer include vinyl polymers, polyester plasticizers, polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more, polyethers such as derivatives in which the hydroxyl groups of these polyether polyols are converted to ester groups, ether groups, etc., polystyrenes, polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, and polychloroprene.

[0124] The amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and particularly preferably 20 to 100 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0125] <Anti-sagging agent> In order to prevent sagging and improve workability, a sagging prevention agent may be added to the curable composition as necessary. The sagging prevention agent is not particularly limited. Examples of the sagging prevention agent include polyamide waxes, hydrogenated castor oil derivatives, and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These sagging prevention agents may be used alone or in combination of two or more. The amount of the sagging prevention agent used is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0126] <Antioxidants> An antioxidant (antiaging agent) can be used in the curable composition. The use of an antioxidant can improve the weather resistance of the cured product. Examples of the antioxidant include hindered phenol-based, monophenol-based, bisphenol-based, diarylamine-based, and polyphenol-based antioxidants. Specific examples of antioxidants are described in, for example, JP-A-4-283259 and JP-A-9-194731. The amount of the antioxidant used is preferably from 0.1 to 10 parts by weight, particularly preferably from 0.2 to 5 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0127] <Light stabilizer> A light stabilizer can be used in the curable composition. The use of a light stabilizer can prevent photo-oxidative deterioration of the cured product. Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds. As the light stabilizer, a hindered amine-based compound is particularly preferred. The amount of the light stabilizer used is preferably from 0.1 to 10 parts by weight, particularly preferably from 0.2 to 5 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0128] <Ultraviolet absorbing agent> The curable composition may contain an ultraviolet absorber. The use of an ultraviolet absorber may improve the surface weather resistance of the cured product. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds. Benzotriazole-based ultraviolet absorbers are particularly preferred. Specific examples of suitable benzotriazole-based ultraviolet absorbers include those commercially available under the names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (all manufactured by BASF). The amount of the ultraviolet absorber used is preferably from 0.1 to 10 parts by weight, particularly preferably from 0.2 to 5 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0129] <Physical property adjusters> If necessary, a physical property adjuster for adjusting the tensile properties of the resulting cured product may be added to the curable composition. There is no particular limitation on the physical property adjuster. Examples of the physical property adjuster include alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as tris(trimethylsilyl)borate and tris(triethylsilyl)borate; silicone varnishes; and polysiloxanes. By using a physical property adjuster, the hardness of the cured product of the curable composition can be increased, or conversely, the hardness can be decreased to provide a breaking elongation. The physical property adjuster may be used alone or in combination of two or more kinds.

[0130] In particular, compounds that generate a compound having a monovalent silanol group in the molecule by hydrolysis have the effect of lowering the modulus of the cured product without worsening the stickiness of the surface of the cured product. In particular, compounds that generate trimethylsilanol are preferred. Examples of compounds that generate a compound having a monovalent silanol group in the molecule by hydrolysis include silicon compounds that are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, and generate silane monool by hydrolysis. Specific examples include phenoxytrimethylsilane, tris((trimethylsiloxy)methyl)propane, etc.

[0131] The amount of the physical property adjusting agent used is preferably from 0.1 to 10 parts by weight, particularly preferably from 0.5 to 5 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0132] <Compounds containing epoxy groups> In the curable composition, a compound containing an epoxy group can be used. The use of a compound containing an epoxy group can improve the restorability of the cured product. Examples of compounds containing an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, and epichlorohydrin derivatives, and mixtures thereof. Specific examples include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, and epoxy butyl stearate. The amount of the epoxy compound used is preferably 0.5 to 50 parts by weight based on 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0133] <Photocurable substance> A photocurable material can be used in the curable composition. When a photocurable material is used, a film of the photocurable material is formed on the surface of the cured product, improving the stickiness and weather resistance of the cured product. Many materials are known as this type of material, such as organic monomers, oligomers, resins, and compositions containing them. Representative materials that can be used include unsaturated acrylic compounds, which are monomers or oligomers having one or several acrylic or methacrylic unsaturated groups, or mixtures thereof, polyvinyl cinnamates, or azido resins. The amount of the photocurable substance used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0134] <Oxygen curing substance> An oxygen-curable substance can be used in the curable composition. Examples of the oxygen-curable substance include unsaturated compounds that can react with oxygen in the air. The oxygen-curable substance reacts with oxygen in the air to form a cured film near the surface of the cured product, thereby preventing the surface from becoming sticky and preventing dirt and dust from adhering to the surface of the cured product.

[0135] Specific examples of oxygen-curable substances include drying oils such as tung oil and linseed oil, various alkyd resins obtained by modifying these compounds, acrylic polymers, epoxy resins, silicone resins, and other resins modified with drying oils, and liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene. These may be used alone or in combination of two or more.

[0136] The amount of the oxygen-curable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A). As described in JP-A-3-160053, the oxygen-curable substance is preferably used in combination with a photocurable substance.

[0137] <<Preparation of Curable Composition>> The curable composition can be prepared as a one-component type in which all ingredients are mixed in advance, sealed, and stored, and then cured by moisture in the air after application. Alternatively, it can be prepared as a two-component type in which ingredients such as (B) ingredient, (C) ingredient, other silanol condensation catalyst, filler, plasticizer, and water are mixed as a curing agent, and the curing agent and the base agent containing the reactive silicon group-containing organic polymer (A) are mixed before use. From the viewpoint of workability, the one-component type is preferable.

[0138] When the curable composition is of one-component type, all the ingredients are mixed in advance, and therefore, it is preferable that the ingredients containing water are dehydrated and dried before use, or dehydrated by reducing pressure during mixing and kneading. In addition to the dehydration and drying method, the storage stability can be further improved by adding a silicon compound capable of reacting with water, such as n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane, as a dehydrating agent.

[0139] The amount of the dehydrating agent, particularly the silicon compound capable of reacting with water such as vinyltrimethoxysilane, used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the reactive silicon group-containing organic polymer (A).

[0140] <<Manufacturing method of the cured product>> Prior to curing, the curable composition is formed into a desired shape by a method such as coating, casting, or filling. The curable composition that has been coated, cast, or filled and formed into a desired shape can be cured at room temperature or under heating.

[0141] <<Application>> The curable composition can be used as an adhesive, a sealant for sealing construction in buildings, ships, automobiles, roads, etc., a mold release agent, an adhesive, a paint, a spraying agent, etc. The cured product obtained by curing the curable composition is preferably used as a waterproof material, a coating waterproof material, a vibration-proof material, a vibration-damping material, a sound-proof material, a foam material, etc. Since the obtained cured product has excellent flexibility and adhesiveness, the curable composition is more preferably used as a sealant or adhesive among the above uses. EXAMPLES

[0142] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0143] The number average molecular weight in the examples is a GPC molecular weight measured under the following conditions. Liquid delivery system: Tosoh HLC-8220GPC Column: Tosoh TSKgel SuperH series Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40℃

[0144] The terminal-converted molecular weight in the examples is a molecular weight calculated by determining the hydroxyl value according to the measurement method of JIS K 1557 and the iodine value according to the measurement method of JIS K 0070, taking into consideration the structure of the organic polymer (the degree of branching determined by the polymerization initiator used).

[0145] The average number of silyl groups per terminal or per molecule of the polymer shown in the examples was calculated by NMR measurement.

[0146] (Synthesis example 1) A-1 A mixture of 60% and 40% by weight of polyoxypropylene glycol having a number average molecular weight of approximately 4,500 and polyoxypropylene triol having a number average molecular weight of approximately 4,500 was used as an initiator, and propylene oxide was polymerized using a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (P-1) having a number average molecular weight of 17,300 and a molecular weight distribution Mw / Mn = 1.28 with hydroxyl groups at the terminals. Sodium methoxide was added in an amount of 1.1 molar equivalents to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene (P-1) as a 28% methanol solution. After distilling off the methanol by vacuum devolatilization, 1.2 molar equivalents of propargyl bromide were added to the hydroxyl groups of the polymer (P-1) to convert the terminal hydroxyl groups to propargyl groups. Unreacted propargyl bromide was removed by devolatilization under reduced pressure. The obtained unpurified propargyl-terminated polyoxypropylene was mixed and stirred with n-hexane and water, and then the water was removed by centrifugation. The hexane was devolatilized under reduced pressure from the obtained hexane solution to remove the metal salts in the polymer. As a result, polyoxypropylene (Q-1) having propargyl groups at the terminal sites was obtained. To 500 g of this polymer (Q-1), 50 μL of platinum divinyldisiloxane complex (3 wt % isopropanol solution calculated as platinum) and 8.0 g of trimethoxysilane were added to carry out a hydrosilylation reaction. After reacting at 90° C. for 2 hours, unreacted trimethoxysilane was distilled off under reduced pressure to obtain polyoxypropylene (A-1) having a number average molecular weight of 19,900 and trimethoxysilyl groups at the ends. It was found that the polymer (A-1) had an average of 0.6 trimethoxysilyl groups at each end. The polymer (A-1) has a reactive silicon group-containing structure represented by at least one of the general formulas (4) to (6) at the end of the polymer skeleton.

[0147] (Synthesis example 2) A-2 Sodium methoxide was added in an amount of 1.2 molar equivalents to the hydroxyl groups of the polymer (P-1) obtained in Synthesis Example 1 as a 28% methanol solution. After distilling off the methanol by vacuum devolatilization, 1.5 molar equivalents of allyl chloride were added to the hydroxyl groups of the polymer (P-1) to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by devolatilization under reduced pressure. The obtained unpurified allyl-terminated polyoxypropylene was mixed and stirred with n-hexane and water, and then the water was removed by centrifugation. The hexane was devolatilized under reduced pressure from the obtained hexane solution to remove the metal salts in the polymer. As a result, polyoxypropylene (Q-2) having allyl groups at the terminal sites was obtained. To 500 g of this polymer (Q-2), 36 ppm of platinum divinyldisiloxane complex (3 wt% isopropanol solution calculated as platinum) and 8.7 g of methoxymethyldimethoxysilane were added to carry out a hydrosilylation reaction. After reacting at 90°C for 2 hours, unreacted methoxymethyldimethoxysilane was distilled off under reduced pressure to obtain polyoxypropylene (A-2) having a number average molecular weight of 19,900 and methoxymethyldimethoxysilyl groups at the ends. It was found that polymer (A-2) had an average of 0.7 methoxymethyldimethoxysilyl groups at each end. Polymer (A-2) has a reactive silicon group-containing structure represented by general formula (2) at the end of the polymer skeleton.

[0148] (Synthesis example 3) A-3 Using polyoxypropylene triol with a number average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (P-2) with a number average molecular weight of 24,600 (terminal group equivalent molecular weight 17,400) having hydroxyl groups at the ends and a molecular weight distribution Mw / Mn = 1.31. Sodium methoxide was added in an amount of 1.2 molar equivalents to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene (P-2) as a 28% methanol solution. After the methanol was distilled off by vacuum devolatilization, 1.5 molar equivalents of allyl chloride was added to the hydroxyl groups of the polymer (P-2) to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by devolatilization under reduced pressure. The obtained unpurified polyoxypropylene was mixed with n-hexane and water and stirred, after which the water was removed by centrifugation, and the metal salts in the polymer were removed by devolatilizing the hexane from the obtained hexane solution under reduced pressure. As a result, polyoxypropylene (Q-3) having allyl groups at its terminals was obtained. 50 μL of platinum divinyldisiloxane complex solution (3% by weight of platinum in isopropanol solution) was added to 500 g of the obtained polymer (Q-3), and 8.5 g of trimethoxysilane was slowly added dropwise while stirring. After reacting at 100°C for 2 hours, unreacted trimethoxysilane was distilled off under reduced pressure to obtain polyoxypropylene (A-3) having a number average molecular weight of 26,200 and trimethoxysilyl groups at the ends. It was found that the polymer (A-3) had an average of 0.7 trimethoxysilyl groups at one end and an average of 2.1 trimethoxysilyl groups per molecule. The polymer (A-3) has a reactive silicon group-containing structure represented by the general formula (1) at the end of the polymer skeleton.

[0149] (Synthesis example 4) N-1 Sodium methoxide was added in an amount of 1.2 molar equivalents to the hydroxyl groups of the polymer (P-1) obtained in Synthesis Example 1 as a 28% methanol solution. After the methanol was distilled off by vacuum devolatilization, 1.5 molar equivalents of allyl chloride was added to the hydroxyl groups of the polymer (P-1) to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by devolatilization under reduced pressure. The obtained unpurified allyl-terminated polyoxypropylene was mixed and stirred with n-hexane and water, and then the water was removed by centrifugation. The hexane was devolatilized under reduced pressure from the obtained hexane solution to remove the metal salts in the polymer. As a result, polyoxypropylene (Q-4) having allyl groups at the terminal sites was obtained. To 500 g of this polymer (Q-4), 50 μL of platinum divinyldisiloxane complex (3 wt% isopropanol solution calculated as platinum) and 6.5 g of dimethoxymethylsilane were added to carry out a hydrosilylation reaction. After reacting at 90° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (N-1) having a number average molecular weight of 19,900 and dimethoxymethylsilyl groups at the terminals. It was found that the polymer (N-1) had an average of 0.7 dimethoxymethylsilyl groups at each terminal. The polymer (N-1) is a comparative polymer having a reactive silicon group-containing structure that does not correspond to any of the general formulas (1) to (6).

[0150] (Examples 1 to 12, Comparative Examples 1 to 6) According to the composition shown in Table 1, 50 parts by weight of surface-treated gelatinous calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., product name: Whiten SB), 50 parts by weight of surface-untreated heavy calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., product name: Hakuenka CCR), and 2 parts by weight of an anti-sagging agent (manufactured by Kusumoto Chemical Co., Ltd., product name: Disparlon 6500) were weighed out per 100 parts by weight of the organic polymer having a reactive silicon group obtained in each synthesis example or a commercially available organic polymer having a reactive silicon group, and the mixture was thoroughly dispersed using three paint rolls, and then dehydrated under reduced pressure at 120°C for 2 hours to obtain the main component.

[0151] Under constant temperature and humidity conditions of 23°C and 50%, a silane coupling agent having a vinyl group (manufactured by Momentive, product name: A-171) as a dehydrating agent, a silane coupling agent having an amino group (manufactured by Dow Koning Toray Co., Ltd., product name: A-1110) as an adhesion promoter, a silane coupling agent having an epoxy group (manufactured by Dow Koning Toray Co., Ltd., product name: A-187) and an acid anhydride were added in the ratios (parts by weight) shown in Table 1 to the main component, and then DBU (Tokyo Chemical Industry Co., Ltd., 1,8-diazabicyclo[5,4,0]undecene-7), an amidine compound with a melting point of less than 23°C, was added as a curing catalyst. The mixture was kneaded with a spatula for 2 minutes and air bubbles in the mixture were thoroughly degassed to prepare a curable composition.

[0152] (Commercially available organic polymers containing reactive silicon groups) Polymer (A-4): Manufactured by Wacker Chemie, trade name GENIOSIL STP-E10: polyoxyalkylene having methyldimethoxysilylmethylcarbamate (urethane bond) at the end (polymer having a reactive silicon group-containing structure represented by formula (3) at the end of the polymer skeleton) Polymer (A-5): Manufactured by Wacker Chemie, trade name GENIOSIL STP-E35: polyoxyalkylene having trimethoxysilylpropyl carbamate (urethane bond) at the end (polymer having a reactive silicon group-containing structure represented by formula (1) at the end of the polymer skeleton)

[0153] (acid anhydride) Acetic Anhydride Tokyo Chemical Industry Co., Ltd. cis-1,2-Cyclohexanedicarboxylic Anhydride Tokyo Chemical Industry Co., Ltd. Benzoic Anhydride Tokyo Chemical Industry Co., Ltd. Maleic Anhydride Tokyo Chemical Industry Co., Ltd. Phthalic Anhydride Tokyo Chemical Industry Co., Ltd. Pyromellitic Anhydride Tokyo Chemical Industry Co., Ltd. 4,4-Biphthalic Anhydride Tokyo Chemical Industry Co., Ltd. 4,4-Oxydiphthalic Anhydride Tokyo Chemical Industry Co., Ltd.

[0154] (Skinning time) The obtained curable composition was applied to a polyethylene sheet under constant temperature and humidity conditions of 23°C and 50%, and the time when the surface was smoothed to a thickness of 3 mm was defined as the curing start time, and the time when the curable composition no longer adhered to the spatula when the surface was touched with a spatula was defined as the skinning time, and the curing time was measured. The results are shown in Table 1.

[0155] (bleed out) The obtained curable composition was applied onto a polyethylene sheet, spread to a thickness of 3 mm, and smoothed to prepare a cured product. The cured product was left for the number of days shown in each table under constant temperature and humidity conditions of 23°C and 50%, and then, when the surface of the cured product was touched with a finger, if the liquid compound did not come off the hand, it was judged as "no bleed-out", and if the liquid compound came off the hand, it was judged as "yes bleed-out". The results are shown in Table 1.

[0156] [Table 1-1]

[0157] [Table 1-2]

[0158] As is clear from Table 1, in Examples 1 to 12, which used an organic polymer (A) having a reactive silicon group-containing structure represented by at least one of the general formulas (1) to (6), an amidine compound (B) having a melting point of less than 23°C, and an acid anhydride (C), the curability was good and no bleeding of the liquid compound onto the surface of the cured product was observed. On the other hand, in Comparative Examples 1 to 5, which are the same as each Example in that no acid anhydride was used, the curability was good, but bleeding of the liquid compound onto the surface of the cured product occurred. In Comparative Example 6, which used an organic polymer (N-1) having a reactive silicon group-containing structure not corresponding to any of the general formulas (1) to (6) and an amidine compound (B), the curability was insufficient and the product did not cure even after 48 hours.

[0159] (Examples 13 to 20, Comparative Examples 7 to 14) According to the composition shown in Table 2, 50 parts by weight of surface-treated gelatinous calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., product name: Whiten SB), 50 parts by weight of surface-untreated heavy calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., product name: Hakuenka CCR), and 2 parts by weight of an anti-sagging agent (manufactured by Kusumoto Chemical Co., Ltd., product name: Disparlon 6500) were weighed out per 100 parts by weight of the organic polymer having a reactive silicon group obtained in each synthesis example or a commercially available organic polymer having a reactive silicon group, and the mixture was thoroughly dispersed using three paint rolls, followed by dehydration under reduced pressure at 120°C for 2 hours to obtain the main component.

[0160] Under constant temperature and humidity conditions of 23°C and 50%, a silane coupling agent having a vinyl group (manufactured by Momentive, product name: A-171) as a dehydrating agent, a silane coupling agent having an amino group (manufactured by Dow Koning Toray Co., Ltd., product name: A-1110) as an adhesion promoter, a silane coupling agent having an epoxy group (manufactured by Dow Koning Toray Co., Ltd., product name: A-187), and a carboxylic acid were added in the proportions (parts by weight) shown in Table 2 to the main component, and then DBU (Tokyo Chemical Industry Co., Ltd., 1,8-diazabicyclo[5,4,0]undecene-7), an amidine compound with a melting point of less than 23°C, was added as a curing catalyst. The mixture was kneaded with a spatula for 2 minutes and air bubbles in the mixture were thoroughly defoamed to prepare a curable composition. The skinning time was measured and bleeding out was evaluated in the same manner as above using the prepared curable composition. The results are shown in Table 2.

[0161] (Carboxylic Acid) DL-Malic acid (50% by weight in methanol solution): pKa1 (in H2O) = 3.4, pKa2 (in H2O) = 5.1 Tokyo Chemical Industry Co., Ltd. Acetic acid: pKa(in H2O)=4.76 Tokyo Chemical Industry Co., Ltd. Propionic acid: pKa(in H2O)=4.88 Tokyo Chemical Industry Co., Ltd. Salicylic acid: pKa(in H2O)=2.98 Kishida Chemical Co., Ltd.

[0162] [Table 2-1]

[0163] [Table 2-2]

[0164] As is clear from Table 2, in Examples 13 to 20, in which an organic polymer (A) having a reactive silicon group-containing structure represented by at least one of the general formulas (1) to (6), an amidine compound (B) having a melting point of less than 23°C, and a carboxylic acid (C) having a pKa in the range of 3 to 5 were used, the curability was good, and no bleeding out of the liquid compound onto the surface of the cured product was observed. On the other hand, in Comparative Examples 7 to 11, which are the same as each Example except that no carboxylic acid was used, the curability was good, but bleeding out of the liquid compound onto the surface of the cured product occurred. In Comparative Example 12, in which a carboxylic acid having a pKa of less than 3 was used without using a carboxylic acid (C) having a pKa of 3 to 5, the curability was significantly reduced compared to Examples 14 to 17 and Comparative Example 8, in which the same polymer (A-2) was used ...8 and Comparative Example 9, in which a carboxylic acid having a pKa of less than 3 was used without using a carboxylic acid (C) having a pKa of 3 to 5, and a carboxylic acid having a pKa of less than 3 was used. Similarly, in Comparative Example 13, in which a carboxylic acid having a pKa of less than 3 was used without using a carboxylic acid (C) having a pKa of 3 to 5, the curability was significantly reduced compared to Examples 18 and Comparative Example 9, in which the same polymer (A-3) was used, and the curing did not take place even after 3 hours. In Comparative Example 14, in which an organic polymer (N-1) having a reactive silicon group-containing structure not corresponding to any of the general formulas (1) to (6) and an amidine compound (B) were used, the curability was insufficient and the composition did not cure even after 48 hours.

Claims

1. (A) an organic polymer having a reactive silicon group-containing structure represented by at least one of general formulas (1) to (6), (B) amidine compounds having a melting point of less than 23° C., and (C) Acid anhydride and / or carboxylic acid having a pKa of 3 to 5 A non-organotin based curable composition comprising: 【Chemistry 1】 (In formula (1), R １ R represents a divalent linking group which may contain a heteroatom. ２ represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. 【Chemistry 2】 (In formula (2), R １ , R ２ , and X are the same as above. ３ R represents a hydrocarbon group having 1 to 5 carbon atoms and having an electron-withdrawing group on the carbon atom at position 1. ４ represents an unsubstituted hydrocarbon group having 1 to 5 carbon atoms; a is 1 or 2, b is 0 or 1, and c is 1 or 2, provided that a+b+c=3 is satisfied. 【Chemistry 3】 (In formula (3), R ５ represents a hydrocarbon group having 1 to 20 carbon atoms, which may contain a heteroatom. X is the same as above. Y is -O-, -S-, -N(R ６ )-, -OC(=O)-N(R ６ ) -, -N(R ６ )-C(=O)-O-, and -N(R ６ )-C(=O)-N(R ６ R represents a divalent group selected from the group consisting of ６ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain a heteroatom; and d is 1, 2, or 3. 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 (In formulas (4) to (6), R ７ represents a hydrocarbon group having 1 to 20 carbon atoms, which may contain a heteroatom. X is the same as above. e is 1, 2, or 3. R ８ , and R ９ R each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a silyl group. １０ represents a divalent linking group, １０ Each of the two bonds of is bonded to a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom in the linking group.

2. The non-organotin curable composition according to claim 1, wherein general formulas (4) to (6) are represented by general formulas (7) to (9), respectively. 【Chemistry 7】 【Chemistry 8】 【Chemistry 9】 (In formulas (7) to (9), R ７ , X, and e are the same as the groups in formulas (4) to (6).

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

4. The non-organotin curable composition according to any one of claims 1 to 3, wherein the amidine compound (B) is represented by general formula (10). R １１ N=CR １２ -NR １３ ２ (10) (In formula (10), R １１ , R １２ , and two R １３ R each independently represents a hydrogen atom or an organic group. １１ , R １２ , and two R １３ Any two or more of these may be bonded to form a cyclic structure.)

5. The non-organotin curable composition according to any one of claims 1 to 4, wherein the content of the amidine compound (B) is 0.1 to 15 parts by weight, and the content of the acid anhydride and / or carboxylic acid (C) is 0.1 to 15 parts by weight, relative to 100 parts by weight of the organic polymer (A).

6. The non-organotin curable composition according to any one of claims 1 to 5, wherein component (C) comprises an acid anhydride.

7. A cured product obtained by curing the non-organotin curable composition according to any one of claims 1 to 6.

8. A method for suppressing bleed-out on the surface of a cured product, comprising mixing an organic polymer (A) having a reactive silicon group-containing structure represented by at least one of general formulas (1) to (6) defined in any one of claims 1 to 6, an amidine compound (B) having a melting point of less than 23°C, and an acid anhydride and / or a carboxylic acid (C) having a pKa of 3 to 5, and then curing the mixture to obtain a cured product.

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