Method for manufacturing a one-component curable composition for working joints, method for manufacturing a joint structure, and method for construction.

Abstract

Provided is a curable composition that is excellent in compression recovery rate, displacement followability, and durability, and can provide a cured product that can be used as a sealing material for working joints in buildings. [Solution] A one-component curable composition for working joints contains a polyoxyalkylene polymer having an average of 1.2 to 5 specific reactive silicon groups per molecule, a specific silane compound, and a specific amount of a tetravalent organotin compound.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a one-component curable composition for working joints, a method for producing a joint structure, and a method for constructing a joint structure, all of which include a polyoxyalkylene polymer having a reactive silicon group (particularly a trialkoxysilyl group). [Background technology]

[0002] Polyoxyalkylene polymers containing reactive silicon groups (also known as "modified silicones") are known to have the property of being able to obtain a rubbery cured product by crosslinking through the formation of siloxane bonds, which involves hydrolysis reactions of reactive silicon groups due to moisture, even at room temperature. Polyoxyalkylene polymers containing reactive silicon groups are already produced industrially and are widely used as raw material resins for applications such as sealants, adhesives, and paints.

[0003] Polyoxyalkylene polymers having reactive silicon groups can have their cured properties improved by adding various compounds such as reactive plasticizers and silane compounds (Patent Documents 1-2).

[0004] Curable compositions containing polyoxyalkylene polymers with reactive silicon groups are widely used as sealants for joints in the construction and civil engineering fields. Based on their curing method, sealants are classified into two types: one-component types that cure using moisture in the air, and two-component types that cure by mixing a main component and a hardener.

[0005] Of these, the one-component type offers superior workability because it eliminates the need to mix the main component and hardener, and there are no curing failures due to measurement errors.

[0006] On the one hand, in a building, there are large joints, called working joints, due to (a) expansion and contraction of exterior members caused by changes in sunlight exposure and temperature changes such as air temperature, or (b) displacement and movement (movement) between exterior members due to effects such as various vibrations and wind pressure. As a sealing material for this working joint, a two-component type is generally used. This is because the two-component type cures throughout the curable composition and does not cause damage to the surface and interior of the cured product even if the joint is greatly displaced during curing, that is, because it has excellent displacement followability during curing.

[0007] On the other hand, since the one-component type cures from the surface in contact with moisture in the air, when it undergoes large displacement during curing, a stress difference occurs between the cured part on the surface and the uncured part inside, which is considered to lead to damage such as cracks in the cured product. That is, the one-component type is considered to have poor displacement followability during curing. For this reason, conventionally, the one-component type has not been used as a sealing material for working joints with large displacements.

[0008] So far, various one-component or two-component curable compositions containing a polyoxyalkylene polymer having a reactive silicon group and applicable to working joints have been studied (Patent Documents 3 to 12).

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

[0010] However, the above-mentioned conventional technologies are not sufficient from the viewpoints of compression restoration rate, displacement followability, and durability, and there is room for further improvement.

[0011] One embodiment of the present invention has been made in view of the above problems, and its object is to provide a cured product excellent in compression restoration rate, displacement followability, and durability and usable as a sealing material for a working joint of a building, and to provide a novel one-component curable composition containing a polyoxyalkylene polymer having a reactive silicon group. [Means for Solving the Problems] <>

[0012] As a result of intensive studies to solve the above problems, the present inventor has completed the present invention.

[0013] That is, a method for producing a curable composition according to one embodiment of the present invention is a method for producing a one-component curable composition for working joints, comprising the steps of: (A) a polyoxyalkylene polymer having an average of 1.2 to 5 reactive silicon groups per molecule represented by general formula (1); (D) a silane compound obtained by partially condensing aminosilane compounds having reactive silicon groups, or a silane compound obtained by partially condensing an aminosilane compound having reactive silicon groups with an alkoxysilane compound other than aminosilane; and (E) a tetravalent organotin compound, in an amount of 0.05 parts by weight or more and less than 1 part by weight per 100 parts by weight of component (A); and kneading the resulting mixture: -SiX3···(1) (In the formula, X independently represents either a hydroxyl group or a hydrolyzable group.)

[0014] That is, a curable composition according to one embodiment of the present invention is a one-component curable composition for working joints characterized by comprising: (A) a polyoxyalkylene polymer having an average of 1.2 to 5 reactive silicon groups represented by general formula (1) per molecule; (D) a silane compound obtained by partially condensing aminosilane compounds having reactive silicon groups, or a silane compound obtained by partially condensing an aminosilane compound having reactive silicon groups with an alkoxysilane compound other than aminosilane; and (E) a tetravalent organotin compound in an amount of 0.05 parts by weight or more and less than 1 part by weight per 100 parts by weight of component (A): -SiX3···(1) (In the formula, X independently represents either a hydroxyl group or a hydrolyzable group.) [Effects of the Invention]

[0015] According to one embodiment of the present invention, a one-component curable composition can be obtained that includes a polyoxyalkylene polymer having a reactive silicon group, which has excellent compression recovery rate, displacement following ability, and durability, and can provide a cured product that can be applied as a sealing material for working joints in buildings. [Modes for carrying out the invention]

[0016] One embodiment of the present invention will be described in detail below.

[0017] One embodiment of the present invention is described below, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications are possible within the scope of the claims. Furthermore, embodiments or examples obtained by appropriately combining the technical means disclosed in different embodiments or examples are also included in the technical scope of the present invention. Moreover, new technical features can be formed by combining the technical means disclosed in each embodiment. All academic and patent documents mentioned herein are incorporated herein by reference. Furthermore, unless otherwise specified herein, "A to B" representing a numerical range means "A or greater (including A and greater than A) and B or less (including B and less than B)."

[0018] [1. Technical Concept of One Embodiment of an Embodiment] As a result of the inventor's diligent research, the technologies described in the aforementioned prior art documents 3 to 12 had room for improvement in terms of displacement-following ability and durability. In other words, no sealing material has been found that possesses sufficient displacement-following ability and durability and is applicable to working joints with large displacements.

[0019] The inventors have conducted diligent studies to solve the above problems and have now, to their surprise, succeeded in creating a one-component curable composition for working joints that can be used as a sealing material for working joints in buildings. This composition is obtained by including a polyoxyalkylene polymer having an average of 1.2 to 5 reactive silicon groups per molecule represented by the above general formula (1), a silane compound obtained by partially condensing aminosilane compounds having reactive silicon groups, or a silane compound obtained by partially condensing an aminosilane compound having reactive silicon groups with an alkoxysilane compound other than aminosilane, and a tetravalent organotin compound in an amount of 0.05 parts by weight or more and less than 1 part by weight per 100 parts by weight of the above polyoxyalkylene polymer, which, even though it is a one-component type, passes the durability category 9030 of JIS A5758, exhibits excellent compression recovery rate and displacement following ability, and can be used as a sealing material for working joints in buildings.

[0020] [2. Curable composition] A curable composition according to one embodiment of the present invention comprises (A) a polyoxyalkylene polymer having an average of 1.2 to 5 reactive silicon groups represented by general formula (1) per molecule, (D) a silane compound obtained by partially condensing aminosilane compounds having reactive silicon groups, or a silane compound obtained by partially condensing an aminosilane compound having reactive silicon groups with an alkoxysilane compound other than aminosilane, and (E) a tetravalent organotin compound in an amount of 0.05 parts by weight or more and less than 1 part by weight per 100 parts by weight of component (A): -SiX3···(1) (In the formula, X independently represents either a hydroxyl group or a hydrolyzable group.) Furthermore, the curable composition according to one embodiment of the present invention is a one-component curable composition for working joints.

[0021] In this specification, "curable composition according to one embodiment of the present invention" is also referred to simply as "this curable composition." In this specification, "(A) a polyoxyalkylene polymer having an average of 1.2 to 5 reactive silicon groups represented by general formula (1) per molecule" is also referred to simply as "component (A)." In this specification, "(D) a silane compound obtained by partially condensing aminosilane compounds having reactive silicon groups, or a silane compound obtained by partially condensing an aminosilane compound having reactive silicon groups with an alkoxysilane compound other than aminosilane" is also referred to simply as "component (D)." In this specification, "(E) a tetravalent organotin compound" is also referred to simply as "component (E)."

[0022] Because this curable composition has the above-described structure, even when used as a one-component sealant, it has the advantage of providing a cured product that meets the durability classification 9030 of JIS A5758 and exhibits excellent compression recovery rate and displacement-following properties. Therefore, this curable composition is suitable as a sealant for working joints in buildings.

[0023] (2-1. Component (A)) In one embodiment of the present invention, the reactive silicon group of component (A) is a reactive silicon group represented by the following general formula (1). -SiX3···(1) (In the formula, X independently represents either a hydroxyl group or a hydrolyzable group.)

[0024] The hydrolyzable group is not particularly limited and any conventionally known hydrolyzable group is acceptable. Examples of hydrolyzable groups include hydrogen atoms, halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups. Among these hydrolyzable groups, hydrogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups are preferred. From the viewpoint of mild hydrolysis and ease of handling, alkoxy groups are more preferred as hydrolyzable groups. Among alkoxy groups, methoxy groups, ethoxy groups, and isopropoxy groups are even more preferred as hydrolyzable groups, with methoxy groups being the most preferred.

[0025] The three hydrolyzable groups (X) bonded to the silicon atom may be the same or different.

[0026] The reactive silicon group represented by general formula (1) is not particularly limited. Among the reactive silicon groups represented by general formula (1), the trialkoxysilyl group is preferred due to its high activity and good curability. Specifically, the trialkoxysilyl group is more preferably trimethoxysilyl, triethoxysilyl, or triisopropoxysilyl, with the trimethoxysilyl group being the most preferred.

[0027] This section describes the case in which a trialkoxysilyl group is used as the reactive silicon group represented by general formula (1) (case a) and the case in which an alkyldialkoxysilyl group is used as the reactive silicon group outside the range of general formula (1) (case b). In case a, compared to case b, curing proceeds more quickly to the interior of the curable composition, even when the curable composition containing component (A) is used as a one-component type. That is, compared to reactive silicon groups outside the range of general formula (1), such as alkyldialkoxysilyl groups, reactive silicon groups represented by general formula (1), such as trialkoxysilyl groups, contribute more to improved resilience, durability, and creep resistance.

[0028] Component (A) preferably contains an average of 1.2 to 5 reactive silicon groups per molecule, more preferably 1.2 to 4, and even more preferably 1.2 to 3. If the number of reactive silicon groups in component (A) is less than 1.2 per molecule on average, the curability of the resulting curable composition will be insufficient. As a result, the cured product provided by the curable composition will not have good rubber elasticity, and the restorability, durability, and creep resistance of the cured product will be difficult to achieve. The reactive silicon groups may be located at the main chain ends or side chain ends of component (A), or at both the main chain ends and side chain ends. In particular, when the reactive silicon groups are located only at the main chain ends of component (A), the effective network length in the final cured product becomes longer, which is preferable because it makes it easier to obtain a rubbery cured product with high strength, high elongation, and low modulus of elasticity.

[0029] The method for introducing reactive silicon groups into polyoxyalkylene polymers can be carried out by known methods. For example, the following methods I to III can be cited.

[0030] Method I: An organic polymer having a functional group such as a hydroxyl group is reacted with a compound having an active group that is reactive to this functional group and an unsaturated group to obtain an organic polymer having an unsaturated group. Then, the obtained organic polymer having an unsaturated group is reacted with a hydrosilane compound having a reactive silicon group by hydrosilylation.

[0031] Examples of compounds having reactive and unsaturated groups used in Method I include allyl chloride, methallyl chloride, and unsaturated group-containing epoxy compounds such as allyl glycidyl ether.

[0032] Examples of hydrosilane compounds used in Method I include, but are not limited to, halogenated silanes, alkoxysilanes, asyloxysilanes, and ketoximate silanes.

[0033] Examples of halogenated silanes include trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane.

[0034] Examples of alkoxysilanes include trimethoxysilane, triethoxysilane, triisopropoxysilane, 1-[2-(trimethoxysilyl)ethyl]-1,1,3,3-tetramethyldisiloxane, diethoxymethylsilane, dimethoxymethylsilane, and phenyldimethoxysilane.

[0035] Examples of asilocysilanes include methyldiacetoxysilane and phenyldiacetoxysilane.

[0036] Examples of ketoximate silanes include bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane.

[0037] Among these hydrosilane compounds, when obtaining component (A) having a reactive silicon group of general formula (1), trialkoxysilanes are preferred in terms of hydrolyzability and mildness of reaction, and trimethoxysilane and triethoxysilane are more preferred.

[0038] Furthermore, to obtain component (A) having a trimethoxysilyl group, it is preferable to synthesize a polymer having a triethoxysilyl group using triethoxysilane as a raw material, as described in WO2007-040143 and JP 2008-285585, and then convert the triethoxysilyl group to a trimethoxysilyl group with methanol. This is because trimethoxysilane is a very unstable compound and may undergo disproportionation reactions, producing a low-boiling-point, spontaneously combustible monosilane. In addition, trimethoxysilane is extremely dangerous to humans, especially to the eyes, making it difficult to handle and obtain.

[0039] Method II: This method involves introducing a compound having a mercapto group and a reactive silicon group into the unsaturated group moiety of an organic polymer having an unsaturated group, obtained in the same manner as in Method I, by a radical addition reaction in the presence of a radical initiator and / or a radical source.

[0040] Examples of compounds having a mercapto group and a reactive silicon group used in Method II include, but are not limited to, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, and mercaptomethyltriethoxysilane.

[0041] Method III: An organic polymer having a functional group such as a hydroxyl group, epoxy group, or isocyanate group in its molecule is reacted with a compound having a functional group that is reactive to this functional group and a reactive silicon group.

[0042] Method III involves reacting an organic polymer having a hydroxyl group with a compound having an isocyanate group and a reactive silicon group that are reactive to the hydroxyl group. Examples of such methods include, but are not limited to, the method shown in Japanese Patent Application Publication No. 3-47825.

[0043] Examples of compounds having an isocyanate group and a reactive silicon group used in Method III include, but are not limited to, γ-isocyanate-propyltrimethoxysilane, γ-isocyanate-propyltriethoxysilane, isocyanate-methyltrimethoxysilane, and isocyanate-methyltriethoxysilane.

[0044] When using γ-mercaptopropyltrimethoxysilane and γ-isocyanatetopropyltrimethoxysilane, the disproportionation reaction that occurs when using trimethoxysilane does not proceed. For this reason, it is preferable to use the method of Method II or Method III rather than using trimethoxysilane in Method I.

[0045] On the other hand, silane compounds represented by the following general formula (3) do not undergo disproportionation reactions: H-(SiR 2 20) m SiR 2 2-R 3 -SiX3···(3) (In the formula, X is the same as in general formula (1). 2m+2 R 2 Each of these independently represents a hydrocarbon group. 3 (where m represents an integer between 0 and 19)

[0046] Therefore, when introducing a group in which three hydrolyzable groups are bonded to one silicon atom in Method I, it is preferable to use a silane compound represented by general formula (3). From the standpoint of availability and cost, 2m+2 R 2 Each of these is independently preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 8 carbon atoms, and even more preferably a hydrocarbon group having 1 to 4 carbon atoms. 3 A divalent hydrocarbon group having 1 to 12 carbon atoms is preferred, a divalent hydrocarbon group having 2 to 8 carbon atoms is more preferred, and a divalent hydrocarbon group having 2 carbon atoms is even more preferred. m is most preferably 1.

[0047] Examples of silane compounds represented by general formula (3) include 1-[2-(trimethoxysilyl)ethyl]-1,1,3,3-tetramethyldisiloxane, 1-[2-(trimethoxysilyl)propyl]-1,1,3,3-tetramethyldisiloxane, and 1-[2-(trimethoxysilyl)hexyl]-1,1,3,3-tetramethyldisiloxane.

[0048] Among the above Method I or Method III, the method of reacting an organic polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group is preferable because a high conversion rate can be obtained in a relatively short reaction time. On the other hand, the organic polymer having a reactive silicon group obtained by Method I has a lower viscosity than the organic polymer having a reactive silicon group obtained by Method III, and a curable composition with good workability can be obtained. In addition, the organic polymer having a reactive silicon group obtained by Method II may have a strong odor based on mercaptosilane. For this reason, Method I is particularly preferable.

[0049] In one embodiment of the present invention, the polyoxyalkylene-based polymer which is the main chain structure of component (A) is preferably a polymer having a repeating unit represented by the following general formula (4): -R 4 -O-···(4) (In the formula, R 4 represents a linear or branched alkylene group having 1 to 14 carbon atoms, and a linear or branched alkylene group having 2 to 4 carbon atoms is more preferable).

[0050] Examples of the repeating unit represented by the general formula (4) include -CH2O-, -CH2CH2O-, -CH2CH(CH3)O-, -CH2CH(C2H5)O-, -CH2C(CH3)2O-, -CH2CH2CH2CH2O- and the like.

[0051] In component (A), the main chain of the polyoxyalkylene-based polymer may consist of only one type of repeating unit or may consist of two or more types of repeating units. Particularly when the curable composition according to one embodiment of the present invention is used as a sealing material or the like, the polyoxyalkylene-based polymer which is the main chain structure of component (A) is more preferably a polyoxypropylene-based polymer which is amorphous and has a relatively low viscosity.

[0052] Examples of synthesis methods for polyoxyalkylene polymers include (a) polymerization using an alkaline catalyst such as KOH, (b) polymerization using a transition metal compound-porphyrin complex catalyst such as a complex obtained by reacting an organoaluminum compound and porphyrin as shown in Japanese Patent Publication No. 61-215623, (c) Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US No. 3278457, US No. 3278458, US No. 3278459, US No. 3427 Polymerization methods include, but are not limited to, (d) polymerization using a complex metal cyanide catalyst (e.g., zinc hexacyanocobaltate-grime complex catalyst) as shown in Japanese Patent Publication No. 256, US No. 3427334, US No. 3427335, etc., (d) polymerization using a catalyst consisting of a polyphosphazene salt as shown in Japanese Patent Publication No. 10-273512, and (e) polymerization using a catalyst consisting of a phosphazene compound as shown in Japanese Patent Publication No. 11-060722. Among these synthesis methods, polymerization in which an alkylene oxide is reacted with an initiator in the presence of a complex metal cyanide catalyst is preferred because it can produce polymers with a narrow molecular weight distribution.

[0053] Examples of complex metal cyanide catalysts include Zn3[Co(CN)6]2 (zinc hexacyanocobaltate complex). Catalysts in which an alcohol and / or ether are coordinated as an organic ligand to a zinc hexacyanocobaltate complex can also be used.

[0054] As an initiator, a compound having at least two active hydrogen groups (hereinafter also referred to as an "active hydrogen-containing compound") is preferred. Examples of active hydrogen-containing compounds include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin, and linear and / or branched polyether compounds with a number average molecular weight of 500 to 20,000.

[0055] Examples of alkylene oxides include ethylene oxide, propylene oxide, and isobutylene oxide.

[0056] Examples of polyoxyalkylene polymers having a reactive silicon group represented by general formula (1) are those proposed in the following publications: (a) Japanese Patent Publication No. 45-36319, Japanese Patent Publication No. 46-12154, Japanese Unexamined Patent Publication No. 50-156599, Japanese Unexamined Patent Publication No. 54-6096, Japanese Unexamined Patent Publication No. 55-13767, Japanese Unexamined Patent Publication No. 55-13468, Japanese Unexamined Patent Publication No. 57-164123, Japanese Unexamined Patent Publication No. 3-2450, US No. 3632557, US No. 4345053, US No. 4366307, US No. 4960844, etc. Examples include polymers such as (b) polyoxyalkylene polymers having a high molecular weight of 6,000 or more and a molecular weight distribution (Mw / Mn) of 1.6 or less, a narrow molecular weight distribution, and reactive silicon groups, as proposed in Japanese Patent Publication Nos. (b) 61-197631, 61-215622, 61-215623, 61-218632, 3-72527, 3-47825, and 8-231707. Such polyoxyalkylene polymers having reactive silicon groups may be used individually or in combination of two or more.

[0057] The polyoxyalkylene polymer having a reactive silicon group represented by general formula (1) may be linear or branched. The number-average molecular weight (Mn) of the polyoxyalkylene polymer having a reactive silicon group represented by general formula (1) is measured by gel permeation chromatography (GPC) (in polystyrene terms) and is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 3,000 to 35,000. If the above number-average molecular weight is (a) less than 1,000, the elongation of the cured product tends to be insufficient, and if it exceeds 100,000, the curable composition tends to be highly viscous, which is inconvenient in terms of workability. The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer having a reactive silicon group represented by general formula (1), as measured by GPC, is preferably 2 or less, more preferably 1.5 or less, and even more preferably 1.4 or less.

[0058] Component (A) of one embodiment of the present invention may contain other components, such as urethane bonding components, to the extent that they do not impair the effects of one embodiment of the present invention. The urethane bonding component is not particularly limited, but examples include groups produced by the reaction of an isocyanate group with an active hydrogen group (hereinafter also referred to as an amide-containing group).

[0059] The amide-containing group is a group represented by the following general formula (5). -NR 5 -C(=O)-···(5) (In the formula, R 5 (This indicates an organic group or a hydrogen atom.)

[0060] Specifically, amide-containing groups can be formed by reactions such as the reaction of an isocyanate group with a hydroxyl group, an isocyanate group with an amino group, an isocyanate group with another isocyanate group, or an isocyanate group with a mercapto group. Also, the R of general formula (5) 5 Those formed by the reaction of an amide bond site containing an active hydrogen atom with an isocyanate group are also included in the amide-containing groups represented by general formula (5).

[0061] An industrially easy method for producing organic polymers having amide-containing groups and reactive silicon groups is, for example, to produce a polyurethane polymer having isocyanate groups at the terminals by reacting an excess of polyisocyanate compound with an organic polymer having an active hydrogen-containing group at the terminals, and then simultaneously reacting all or part of the terminal isocyanate groups with the W group of a silicon compound represented by the following general formula (6). WR 6 -SiR 1 3-a X a ...(6) (In the formula, R 1 X and a are the same as in general formula (2) described later. 6represents a divalent organic group, with hydrocarbon groups having 1 to 20 carbon atoms being more preferred. (W represents an active hydrogen-containing group selected from hydroxyl groups, carboxyl groups, mercapto groups, and amino groups (primary or secondary)).

[0062] Examples of silicon compounds represented by general formula (6) include amino group-containing silane compounds, hydroxyl group-containing silane compounds, and mercapto group-containing silane compounds.

[0063] Among these, the following silane compounds can be used to obtain component (A) having a reactive silicon group where a in general formula (6) is 3.

[0064] Examples of amino group-containing silane compounds include γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, (N-phenyl)-γ-aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, and N-phenylaminomethyltrimethoxysilane.

[0065] Examples of hydroxyl group-containing silane compounds include γ-hydroxypropyltrimethoxysilane.

[0066] Examples of mercapto group-containing silane compounds include γ-mercaptopropyltrimethoxysilane.

[0067] Furthermore, as described in Japanese Patent Publication No. 6-211879 (US5364955), Japanese Patent Publication No. 10-53637 (US5756751), Japanese Patent Publication No. 10-204144 (EP0831108), Japanese Patent Publication No. 2000-169544, and Japanese Patent Publication No. 2000-169545, Michael addition products of various α,β-unsaturated carbonyl compounds and primary amino group-containing silane compounds, or Michael addition products of various (meth)acryloyl group-containing silane compounds and primary amino group-containing compounds can also be used as silicon compounds represented by general formula (6).

[0068] Related literature on this manufacturing method includes, for example, Japanese Patent Publication No. 46-12154 (US No. 3632557), Japanese Unexamined Patent Publication No. 58-109529 (US No. 4374237), Japanese Unexamined Patent Publication No. 62-13430 (US No. 4645816), Japanese Unexamined Patent Publication No. 8-53528 (EP0676403), Japanese Unexamined Patent Publication No. 10-204144 (EP0831108), and Japanese Patent Publication No. 2003-508561 (US No. 6197912). Examples include Japanese Patent Publication No. 6-211879 (US No. 5364955), Japanese Patent Publication No. 10-53637 (US No. 5756751), Japanese Patent Publication No. 11-100427, Japanese Patent Publication No. 2000-169544, Japanese Patent Publication No. 2000-169545, Japanese Patent Publication No. 2002-212415, Japanese Patent No. 3313360, US No. 4067844, US No. 3711445, and Japanese Patent Publication No. 2001-323040.

[0069] Furthermore, polymers having amide-containing groups and reactive silicon groups include, for example, polymers produced by reacting an organic polymer having an active hydrogen-containing group at its terminal with a reactive silicon-containing isocyanate compound represented by the following general formula (7). O=C=NR 6 -SiR 1 3-a X a ...(7) (In the formula, R 6 , R 1 (where X and a are the same as in general formula (6)).

[0070] Examples of reactive silicon group-containing isocyanate compounds represented by general formula (7) include, but are not limited to, γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, γ-methyldimethoxysilylpropyl isocyanate, γ-methyldiethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, and diethoxymethylsilylmethyl isocyanate. Furthermore, as described in Japanese Patent Application Publication No. 2000-119365 (US Patent No. 6046270), compounds obtained by reacting a silicon compound of general formula (6) with an excess of the polyisocyanate compound can also be used as reactive silicon group-containing isocyanate compounds represented by general formula (7).

[0071] Examples of literature related to this manufacturing method include Japanese Patent Publication No. 11-279249 (US No. 5990257), Japanese Patent Publication No. 2000-119365 (US No. 6046270), Japanese Patent Publication No. 58-29818 (US No. 4345053), Japanese Patent Publication No. 3-47825 (US No. 5068304), Japanese Patent Publication No. 11-60724, Japanese Patent Publication No. 2002-155145, Japanese Patent Publication No. 2002-249538, WO03 / 018658, and WO03 / 059981.

[0072] Examples of organic polymers having active hydrogen-containing groups at their terminals include polyoxyalkylene polymers (polyether polyols), polyacrylic polyols, polyester polyols, saturated hydrocarbon polymers (polyolefin polyols), polythiol compounds, and polyamine compounds, all of which have hydroxyl groups at their terminals. Among these, polyether polyols, polyacrylic polyols, and polyolefin polyols are preferred because the resulting organic polymers have relatively low glass transition temperatures, and the resulting cured products have excellent cold resistance. Polyether polyols are particularly preferred because the resulting organic polymers have low viscosity, good workability, and exhibit good deep curing properties of the curable composition and good adhesion of the cured products. Polyacrylic polyols and saturated hydrocarbon polymers are even more preferred because the resulting cured products have good weather resistance and heat resistance.

[0073] While there are no particular limitations on the polyether polyol, those having at least 0.7 hydroxyl groups per molecular end on average across all molecules are preferred. Examples of polyether polyols include polyoxyalkylene polymers produced using conventional alkali metal catalysts, and polyoxyalkylene polymers produced by reacting an alkylene oxide with an initiator such as a polyhydroxy compound having at least two hydroxyl groups in the presence of a complex metal cyanide catalyst or a cesium catalyst.

[0074] Among the polymerization methods described above, the polymerization method using a complex metal cyanide catalyst is preferred because it is possible to obtain polyoxyalkylene polymers with a lower degree of unsaturation, a narrower molecular weight distribution (Mw / Mn), lower viscosity, and high acid resistance and weather resistance.

[0075] Examples of the polyacrylic polyol include polyols having an alkyl (meth)acrylate (co)polymer as the main chain and containing hydroxyl groups within the molecule. The synthesis method for this polymer is preferably living radical polymerization, and more preferably atom transfer radical polymerization, due to its narrow molecular weight distribution and the ability to achieve low viscosity. Furthermore, it is preferable to use the polymer described in Japanese Patent Application Publication No. 2001-207157, specifically a polymer obtained by continuous bulk polymerization of alkyl acrylate monomers at high temperature and pressure.

[0076] Examples of the polyisocyanate compounds include aromatic polyisocyanates and aliphatic polyisocyanates.

[0077] Examples of aromatic polyisocyanates include toluene(trylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate.

[0078] Examples of aliphatic polyisocyanates include isophorone diisocyanate and hexamethylene diisocyanate.

[0079] (2-2.(B) component) The curable composition preferably further contains a reactive plasticizer which is a polyoxyalkylene polymer having an average of 0.5 to less than 1.2 reactive silicon groups represented by general formula (2) per molecule: -SiR 1 3-a X a ...(2) (In the formula, R 1 Each of these independently represents an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, and an aralkyl group with 7 to 20 carbon atoms. X is the same as in general formula (1). a represents an integer from 1 to 3.

[0080] According to the above configuration, the resulting curable composition will have low viscosity and excellent workability. In this specification, "(B) a reactive plasticizer which is a polyoxyalkylene polymer having an average of 0.5 to less than 1.2 reactive silicon groups represented by general formula (2) per molecule" is also simply referred to as "component (B)".

[0081] Component (B) according to one embodiment of the present invention can improve the brittle mechanical properties of a cured product provided by a curable composition containing only component (A) by forming a crosslinked structure with the reactive silicon group in component (A). Furthermore, by using a low molecular weight component (B), component (B) can function as a reactive plasticizer or diluent, thereby reducing the viscosity of the composition and improving its workability.

[0082] As the reactive silicon group in component (B) according to one embodiment of the present invention, a reactive silicon group represented by the following general formula (2) can be used. -SiR 1 3-a X a ...(2) (In the formula, R 1 Each of these independently represents an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, and an aralkyl group with 7 to 20 carbon atoms. X is the same as in general formula (1). a represents an integer from 1 to 3. The reactive silicon group in component (B) is not particularly limited, but specifically, examples include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, diethoxyethylsilyl group, diisopropoxymethylsilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, and methoxydimethylsilyl group.

[0083] In general formula (2), a reactive silicon group in which a is 2 is more preferable because it has a high effect in improving the brittleness of the cured product provided by a curable composition having component (A) alone, that is, it can moderately lower the modulus of the cured product, ensure good elongation, and also make it easier to ensure the storage stability of the curable composition. Specifically, as the reactive silicon group in general formula (2) in which a is 2, for example, dimethoxymethylsilyl group, diethoxymethylsilyl group, diethoxyethylsilyl group, diisopropoxymethylsilyl group, etc. are preferred, dimethoxymethylsilyl group and diethoxymethylsilyl group are more preferred, and dimethoxymethylsilyl group is particularly preferred.

[0084] In general formula (2), a reactive silicon group in which a is 3 is preferred because it can improve the balance between low viscosity and mechanical properties while maintaining the rapid curing properties of component (A). Specifically, preferred reactive silicon groups in general formula (2) where a is 3 include trimethoxysilyl group, triethoxysilyl group, and triisopropoxysilyl group, with trimethoxysilyl group being particularly preferred due to its high hydrolysis activity.

[0085] In one embodiment of the present invention, in order to improve the brittleness of the cured product, moderately reduce the modulus of the cured product, ensure good elongation, and improve durability and creep properties, the component (B) is preferably a reactive silicon group in which a is 2 in general formula (2), and a dimethoxymethylsilyl group is particularly preferred.

[0086] In one embodiment of the present invention, the polyoxyalkylene polymer that is the main chain structure of component (B) can use the repeating unit represented by the general formula (4).

[0087] In component (B), the main chain of the polyoxyalkylene polymer may consist of only one type of repeating unit, or it may consist of two or more types of repeating units. In particular, when the curable composition according to one embodiment of the present invention is used as a sealant or the like, it is more preferable that the polyoxyalkylene polymer, which is the main chain structure of component (B), is an amorphous and relatively low-viscosity polyoxypropylene polymer.

[0088] The method for introducing reactive silicon groups into component (B) can be the same as the method for introducing reactive silicon groups into component (A) described above (Methods I to III). However, the number of reactive silicon groups introduced into component (B) is preferably 0.5 to less than 1.2 per molecule on average, more preferably 0.5 to 1.1, and even more preferably 0.5 to 1.

[0089] Specifically, Method I involves reacting a hydrosilane compound with a polyoxyalkylene polymer having allyl groups at both ends. Method II involves reacting a mercaptosilane compound with a polyoxyalkylene polymer having allyl groups at both ends. Method III involves reacting an isocyanate silane compound with a polyoxyalkylene polymer having hydroxyl groups at both ends.

[0090] However, similar to the method for introducing component (A) described above, Method I is preferred in terms of the ease of removing residual raw materials and reactivity. Furthermore, Method I is preferred because the resulting organic polymer does not have structures such as urethane bonds and urea bonds that may lead to a decrease in heat resistance.

[0091] When reactive silicon groups are introduced using the method described above, molecules with an average of multiple reactive silicon groups, molecules with one reactive silicon group, and molecules with no reactive silicon groups are produced simultaneously, probabilistically. Molecules with an average of multiple reactive silicon groups have little effect in improving the brittleness of the cured product according to one embodiment of the present invention, and may maintain or improve the modulus of the cured product provided by a curable composition containing component (A) alone. Molecules with one reactive silicon group or none of the reactive silicon groups can impart flexibility to the cured product according to one embodiment of the present invention and have the effect of lowering the modulus of the cured product provided by a curable composition containing component (A) alone. However, molecules with no reactive silicon groups at all are unreactive and may leach out onto the surface of the cured product over time from a cured product using the curable composition according to one embodiment of the present invention, potentially causing problems such as coating contamination.

[0092] Therefore, in this curable composition, it is preferable that component (B) contains a polyoxyalkylene polymer having one reactive silicon group represented by general formula (2) per molecule (B1). It is more preferable that component (B) is mainly composed of "(B1) a polyoxyalkylene polymer having one reactive silicon group represented by general formula (2) per molecule". That is, a preferred component (B) can be obtained, for example, by selectively reacting "(B') a polyoxyalkylene precursor polymer having only one functional group into which a reactive silicon group can be introduced" with one reactive silicon group-containing compound represented by general formula (2) in the aforementioned methods I to III for introducing reactive silyl groups.

[0093] In this specification, "(B1) a polyoxyalkylene polymer having one reactive silicon group represented by general formula (2) in one molecule" is also simply referred to as "component (B1)". A specific method for obtaining component (B1) is to react a "(B') polyoxyalkylene precursor polymer having only one functional group into which a reactive silicon group can be introduced" with an initiator having only one hydroxyl group in one molecule, in the presence of a catalyst such as a complex metal cyanide complex, with alkylene oxides such as propylene oxide and ethylene oxide, and then react a hydrosilane compound having a reactive silicon group represented by general formula (2).

[0094] In this curable composition, it is preferable that component (B) is obtained by reacting an alkylene oxide with an initiator having only one hydroxyl group in one molecule, and then introducing a reactive silicon group represented by general formula (2) into a polyoxyalkylene precursor polymer having only one functional group capable of introducing a reactive silicon group (B').

[0095] Furthermore, a specific method for obtaining component (B1) is to react a hydrosilane compound having a reactive silicon group represented by general formula (2) with a "polyoxyalkylene precursor polymer mixture having a functional group that can introduce a reactive silicon group, obtained by reacting a mixture of an initiator having only one hydroxyl group per molecule and an initiator having two or more hydroxyl groups per molecule with alkylene oxides such as propylene oxide and ethylene oxide in the presence of a catalyst such as a complex metal cyanide complex." When obtaining component (B1) by this method, it is preferable that the reaction product contains 50% or more of component (B1), more preferably 60% or more, and even more preferably 70% or more. If it is less than 50% by weight, the effect of improving the stainability of the cured surface is insufficient, or the modulus is high, making it unsuitable as a building sealant.

[0096] In this curable composition, it is preferable that component (B) is obtained by introducing a reactive silicon group represented by general formula (2) into a polyoxyalkylene precursor polymer mixture having a functional group capable of introducing a reactive silicon group, which is obtained by reacting an alkylene oxide with an initiator having only one hydroxyl group per molecule of (B) and an initiator having two or more hydroxyl groups per molecule.

[0097] Examples of initiators having only one hydroxyl group per molecule include (a) monohydric primary, secondary, and tertiary alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, and decanol; and (b) monohydric unsaturated group-containing alcohols such as allyl alcohol, methallyl alcohol, and propenyl alcohol. Furthermore, examples include, but are not limited to, monohydric unsaturated group-containing alcohols such as monoallyl etherified diol compounds such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,4-cyclohexanediol, as well as monovinyl etherified diol compounds, as well as monohydric saturated alcohols such as monoalkyl etherified diol compounds, as well as monohydric saturated alcohols such as monoalkyl etherified diol compounds.

[0098] When using the above-mentioned monovalent unsaturated group-containing alcohol, we will specifically describe the case where a polyoxyalkylene precursor polymer having an unsaturated group and a hydroxyl group at separate ends is used. In this case, for example, a polyoxyalkylene polymer in which one reactive silicon group is introduced per molecule can be obtained by (a) reacting an isocyanate silane with a hydroxyl group, or (b) reacting a hydrosilane compound with an unsaturated group in an almost quantitative manner. In the reaction of a polyoxyalkylene precursor polymer having an unsaturated group and a hydroxyl group at separate ends with a hydrosilane compound, the hydrosilane compound can react with the unsaturated group almost quantitatively, although there is a slight introduction of a hydroxyl group (reaction with the hydroxyl group).

[0099] Alcohols are preferred as initiators due to their excellent reactivity and availability, with alcohols having 3 to 7 carbon atoms being the most preferred. Alcohols with 1 to 2 carbon atoms are unsuitable as initiators because they have low boiling points and are not stable as liquids. On the other hand, alcohols with 8 or more carbon atoms tend to have low reactivity when reactive silicon groups are introduced into the resulting precursor polymer. Among alcohols, n-butanol is the most preferred.

[0100] Examples of initiators having two or more hydroxyl groups in one molecule include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin, and linear and / or branched polyether compounds with a number average molecular weight of 500 to 20,000.

[0101] Examples of hydrosilane compounds having a reactive silicon group include trimethoxysilane, triethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane.

[0102] There are no restrictions on the number average molecular weight of component (B), but it is preferably between 1,000 and 15,000, more preferably between 3,000 and 10,000, and particularly preferably between 3,000 and 8,000 or less. If the number average molecular weight of component (B) is (a) less than 1,000, it may flow onto the surface of the cured product and contaminate the coating surface, and if it is (b) greater than 15,000, the effect of lowering the viscosity of the composition and improving workability may be reduced. Furthermore, due to the effect of lowering viscosity, the number average molecular weight of component (B) is preferably 1,000 or more less than the number average molecular weight of component (A), and more preferably 3,000 or more less. Note that the number average molecular weight of component (B) is a value measured by GPC (polystyrene equivalent).

[0103] (B) There are no particular limitations on the amount of component used, but 15 to 200 parts by weight is preferred, 20 to 100 parts by weight is more preferred, and 25 to 80 parts by weight is particularly preferred, per 100 parts by weight of component (A). If the amount of component (B) used is (a) less than 15 parts by weight per 100 parts by weight of component (A), the effects of one embodiment of the present invention may not be obtained, and if it exceeds (b) 200 parts by weight, the resilience, durability, and creep resistance of the curable composition may be impaired.

[0104] Component (B) is reactive with component (A) and can form a cross-linked structure. Therefore, when using a low molecular weight component (B), it is expected to improve the plasticizer contamination of the sealant compared to when a large amount of conventional plasticizer is used. It is also expected to reduce the tack on the surface of the cured product, making it more difficult for dust and dirt to adhere to the surface. Furthermore, it is expected to improve the workability of the composition, and in particular improve stringiness at low temperatures.

[0105] In this curable composition, it is preferable that the polyoxyalkylene polymers of component (A) and component (B) are polyoxypropylene polymers.

[0106] (2-3.(C) component) A curable composition according to one embodiment of the present invention may contain "(C) a plasticizer without a reactive silicon group represented by general formula (1) or general formula (2)" for purposes such as viscosity adjustment and workability improvement. In this specification, "(C) a plasticizer without a reactive silicon group represented by general formula (1) or general formula (2)" is also simply referred to as "component (C)".

[0107] Examples of component (C) include "(C1) a polyether-based plasticizer without a reactive silicon group represented by general formula (1) or general formula (2)", "(C2) a phthalate ester-based plasticizer", and polymer plasticizers. In this specification, "(C1) a polyether-based plasticizer without a reactive silicon group represented by general formula (1) or general formula (2)" is also simply referred to as "(C1) component". In this specification, "(C2) a phthalate ester-based plasticizer" is also simply referred to as "(C2) component".

[0108] Examples of component (C1) include (a) polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, or (b) derivatives obtained by converting the hydroxyl groups of these polyether polyols to ester groups, ether groups, etc. Using these (C1) components is preferable because it improves the surface curability and deep curability of the resulting curable composition and suppresses curing delay after storage of the curable composition. Among these (C1) components, polypropylene glycol is particularly preferred.

[0109] Examples of the (C2) component include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, din-rectal hexyl phthalate, bis(2-ethylhexyl) phthalate, din-rectal octyl phthalate, diisononyl phthalate, dinonyl phthalate, diisodecyl phthalate, diisoundecyl phthalate, and bis-butylbenzyl phthalate.

[0110] Examples of polymeric plasticizers include (a) vinyl polymers obtained by polymerizing vinyl monomers in various ways; (b) esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; (c) polyester plasticizers obtained from dibasic acids such as sebaic acid, adipic acid, azelaic acid, and phthalic acid, and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol; (d) polystyrenes such as polystyrene and poly-α-methylstyrene; and (e) polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, and polychloroprene.

[0111] Among polymeric plasticizers, those compatible with the polymers of components (A) and (B) are preferred, and vinyl polymers are preferred from the viewpoint of weather resistance and heat resistance. Among vinyl polymers, acrylic polymers and / or methacrylic polymers are more preferred, and acrylic polymers such as alkyl polyacrylates are particularly preferred. As for the synthesis method of these polymers, living radical polymerization is preferred because it allows for a narrow molecular weight distribution and low viscosity, and atom transfer radical polymerization is even more preferred. Furthermore, it is preferable to use polymers obtained by the so-called SGO process, which is obtained by continuous bulk polymerization of alkyl acrylate monomers described in Japanese Patent Application Publication No. 2001-207157 at high temperature and high pressure. This polymer (plasticizer) obtained by the SGO process is sold by Toagosei Co., Ltd. under the trade name Alphon.

[0112] The curable composition preferably further contains a polyether-based plasticizer that does not have a reactive silicon group represented by general formula (1) or general formula (2) (C1). The case in which component (C1) or a polymer plasticizer is used (case c) will be described below. In case c, the initial physical properties can be maintained for a long period of time compared to when a low-molecular-weight plasticizer, which is a plasticizer that does not contain polymer components in its molecule, is used. Furthermore, in case c, the drying properties (also called paintability) when an alkyd paint is applied to the cured product of the curable composition according to one embodiment of the present invention can be improved.

[0113] The number average molecular weight of component (C1) or polymer plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, even more preferably 1,000 to 8,000, particularly preferably 1,000 to 5,000, and most preferably 1,000 to 3,000. If the number average molecular weight of component (C1) or polymer plasticizer is too low (e.g., less than 500), the plasticizer will leach out over time due to heat or rainfall, preventing the initial physical properties from being maintained for a long period and preventing improvement in alkyd coating properties. Also, if the number average molecular weight of component (C1) or polymer plasticizer is too high (e.g., more than 15,000), the viscosity will increase, resulting in poor workability. The molecular weight distribution of component (C1) or polymer plasticizer is not particularly limited, but is preferably less than 1.8, more preferably 1.6 or less, even more preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less.

[0114] The amount of component (C1) or polymeric plasticizer used is preferably 0 to 200 parts by weight, more preferably 30 to 170 parts by weight, and particularly preferably 50 to 150 parts by weight, per 100 parts by weight of the total amount of component (A) and component (B).

[0115] (C) The number-average molecular weight of component (C) is measured by GPC (polystyrene equivalent) for vinyl polymers and by end-group analysis for polyether polymers. The molecular weight distribution (Mw / Mn) is also measured by GPC (polystyrene equivalent).

[0116] Other components (C) include, for example, (a) non-aromatic dibasic acid esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and diisodecyl succinate; (b) aliphatic esters such as butyl oleate and methyl acetylricylinoleate; (c) phosphate esters such as tricresyl phosphate and tributyl phosphate; (d) trimellitic acid esters; (e) chlorinated paraffins; (f) hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; (g) process oils; (h) epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate; and (i) cyclohexane dicarboxylates obtained by hydrogenating the above phthalate esters.

[0117] The relatively low molecular weight plasticizers mentioned above may contaminate the surrounding substrate to which the curable composition is applied, so it is desirable to use them in small amounts. Contamination is particularly likely to occur in porous stone materials, such as granite, marble, and siding boards, where plasticizers tend to leach out, which can impair the aesthetic appearance. To suppress such deterioration of aesthetic appearance, the amount of low molecular weight plasticizer such as "(C2) phthalate ester plasticizer" used is preferably 200 parts by weight or less, more preferably 100 parts by weight or less, and even more preferably 50 parts by weight or less, per 100 parts by weight of the total amount of components (A) and (B). If it is desirable to obtain a curable composition that does not cause contamination, it is most desirable not to use any low molecular weight plasticizers at all.

[0118] When applying a paint to a curable composition, it is preferable to use a (C2) phthalate ester plasticizer to the extent that it does not reduce staining properties. This is because using a (C2) phthalate ester plasticizer improves the adhesion between the cured product obtained from the curable composition and the paint film, thereby improving the problem of peeling. Specifically, the amount of (C2) phthalate ester plasticizer used is preferably 1 to 30 parts by weight, more preferably 2 to 25 parts by weight, and particularly preferably 3 to 20 parts by weight, per 100 parts by weight of the total amount of component (A) and component (B).

[0119] These (C) components can be added either during the production of the curable composition or during the production of the polymer.

[0120] When this curable composition is used for working joints, the amount of component (C) used is preferably 10 to 200 parts by weight, more preferably 30 to 170 parts by weight, and particularly preferably 50 to 150 parts by weight, per 100 parts by weight of the total amount of components (A) and (B). If the amount of component (C) used is within the above range, the amount of component (C2) used is preferably 10 to 200 parts by weight, more preferably 10 to 170 parts by weight, and particularly preferably 15 to 150 parts by weight, per 100 parts by weight of the total amount of components (A) and (B).

[0121] Component (C) may be used alone or in combination of two or more types. Alternatively, component (C1) and / or a polymer plasticizer may be used in combination with component (C2). When using two or more types in combination, the combination of component (C1) and component (C2) is particularly preferred. In this case, it is preferable to add more component (C1) and / or a polymer plasticizer than component (C2) in order to suppress curability and the migration of the plasticizer to the surface.

[0122] (2-4.(D) component) Component (D) according to one embodiment of the present invention has the effect of improving the restorability of the curable composition.

[0123] Component (D) can also be described as a silane compound obtained by partially condensing the reactive silicon group of (D)aminosilane, either alone or with other alkoxysilane compounds.

[0124] Component (D) may be a silane compound containing either "(D1) a silane compound obtained by partially condensing aminosilane compounds having reactive silicon groups" (hereinafter also referred to as "component (D1)") or "(D2) a silane compound obtained by partially condensing an aminosilane compound having reactive silicon groups with an alkoxysilane compound other than aminosilane" (hereinafter also referred to as "component (D2)"). In component (D1), one type of aminosilane compound having reactive silicon groups may be used, or two or more types may be used in combination. The condensation of component (D1) is preferably a partial condensation of the reactive silicon groups of the aminosilane compounds having reactive silicon groups. In component (D2), one type of aminosilane compound having reactive silicon groups may be used, or two or more types may be used in combination. In component (D2), one type of alkoxysilane compound may be used, or two or more types may be used in combination. The condensation of component (D2) is preferably a partial condensation between the reactive silicon group of the aminosilane compound having a reactive silicon group and the alkoxy group of the alkoxysilane compound.

[0125] Component (D) is preferably a silane compound obtained by partially condensing aminosilane compounds having a reactive silicon group represented by the general formula (2) described above, or a silane compound obtained by partially condensing an aminosilane compound having a reactive silicon group represented by the general formula (2) described above with an alkoxysilane compound other than aminosilane.

[0126] Examples of aminosilane compounds having a reactive silicon group include N-2-aminoethyl-3-aminopropyltrimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-1-aminomethyltriethoxysilane, and Nn-butyl-3-aminopropyltrimethoxysilane. One of these aminosilane compounds having a reactive silicon group may be used, or two or more may be used in combination.

[0127] Examples of alkoxysilane compounds include (a) methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and methyltriacetoxysilane. (b) Silicate compounds such as hydrocarbon group-containing silanes; (c) Silicate compounds such as tetramethyl orthosilicate (tetramethoxysilane or methyl silicate), tetraethyl orthosilicate (tetraethoxysilane or ethyl silicate), tetrapropyl orthosilicate, and tetrabutyl orthosilicate; (d) 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl (d) Silanes containing epoxy groups such as xyl(ethyltrimethoxysilane) and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; (g) Silanes containing vinyl-type unsaturated groups such as vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acrylooxypropyltrimethoxysilane, and methacryloyloxymethyltrimethoxysilane; (e) Silanes containing mercapto groups such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, and mercaptomethyltriethoxysilane; (f) Isocyanurate silanes such as 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate; (g) or partially hydrolyzed condensates thereof, etc. As for the alkoxysilane compounds, one or more of these can be used in combination.

[0128] (D)Specific examples of component include X-40-2651 (manufactured by Shin-Etsu Chemical Co., Ltd.), MS3301 (manufactured by JNC Corporation), MS3302 (manufactured by JNC Corporation), and DYNASYLAN1146 (manufactured by EVONIK).

[0129] The amount of component (D) used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, and even more preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the total of components (A) and (B). If the amount of component (D) used is less than (a) 0.1 parts by weight, based on 100 parts by weight of the total of components (A) and (B), the resilience tends to be insufficient, and if it exceeds 10 parts by weight, the curability tends to decrease.

[0130] (2-5.(E) component) Component (E) according to one embodiment of the present invention is used as a curing catalyst (silanol condensation catalyst) for component (A). By using a tetravalent tin compound, a one-component curable composition with excellent curing speed and storage stability can be easily obtained.

[0131] (E)Specific examples of component include, for example, dimethyltin diacetate, dimethyltin bis(acetylacetonate), dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis(2-ethylhexanoate), dibutyltin bis(methyl maleate), dibutyltin bis(ethyl maleate), dibutyltin bis(butyl maleate), dibutyltin bis(octyl maleate), dibutyltin bis(tridecyl maleate), dibutyltin bis(benzyl maleate), dibutyltin diacetate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate) Examples of tetravalent organotin compounds include, but are not limited to, dibutyltin dimethoxide, dibutyltin bis(nonylphenoxide), dibutyltin oxide, dibutyltin bis(acetylacetonate) (also called "dibutyltin diacetylacetonate"), dibutyltin bis(ethylacetonate), reaction products of dibutyltin oxide and silicate compounds, reaction products of dibutyltin oxide and phthalate esters, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin bis(acetylacetonate), and reaction products of dioctyltin oxide and silicate compounds.

[0132] Among these tetravalent organotin compounds, dibutyltin compounds or dioctyltin compounds are preferred due to their excellent availability, curability, and adhesive properties, and dioctyltin compounds are more preferred due to their lower toxicity. Among dioctyltin compounds, dioctyltin dicarboxylate is even more preferred in terms of workability, and dioctyltin dilaurate is particularly preferred.

[0133] The amount of component (E) used is preferably 0.05 parts by weight or more and less than 1 part by weight, more preferably 0.1 to 0.7 parts by weight, and even more preferably 0.1 to 0.5 parts by weight, per 100 parts by weight of the total of components (A) and (B). If the amount of component (E) used is (a) less than 0.05 parts by weight per 100 parts by weight of the total of components (A) and (B), the catalytic function may not be sufficiently expressed, and there is a risk that the curing rate may be affected due to weighing errors. If it is 1 part by weight or more, the surface of the resulting curable composition will harden quickly, and if it undergoes a large displacement during curing, strain may occur between the surface and the interior of the curable composition, which may cause cracks in the cured product.

[0134] (2-6. Various Additives) In the curable composition according to one embodiment of the present invention, various additives other than those mentioned above may be added for the purpose of adjusting the various physical properties of the curable composition or cured product. Examples of such additives include fillers, adhesion promoters, solvents, diluents, anti-sagging agents, antioxidants, light stabilizers, ultraviolet absorbers, property modifiers, tackifying resins, compounds containing epoxy groups, photocurable substances, oxygen-curable substances, epoxy resins, surface modifiers, foaming agents, curing modifiers, flame retardants, silicates, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments, foaming agents, termite repellents, and fungicides.

[0135] A filler may be added to the curable composition according to one embodiment of the present invention. Examples of fillers include reinforcing fillers such as fume silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrated silicic acid, and carbon black; fillers such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium dioxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc oxide, shirasu balloons, glass microballoons, organic microballoons of phenolic resin and vinylidene chloride resin, and resin powders such as PVC powder and PMMA powder; and fibrous fillers such as glass fibers and filaments.

[0136] When using a filler, the amount of filler used is preferably 1 to 250 parts by weight, and more preferably 10 to 200 parts by weight, per 100 parts by weight of the total of components (A) and (B).

[0137] When a hardened product with high strength is to be obtained by using these fillers, fillers selected mainly from fume silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrated silicic acid and carbon black, surface-treated fine calcium carbonate, calcined clay, clay and activated zinc oxide are preferred, and favorable results can be obtained by using 1 to 200 parts by weight of such fillers per 100 parts by weight of the total of components (A) and (B).

[0138] Furthermore, if a cured product with low strength and high elongation at break is desired, a favorable result can be obtained by using 5 to 200 parts by weight of a filler selected mainly from titanium dioxide, calcium carbonate such as heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloons, per 100 parts by weight of the total of components (A) and (B).

[0139] Generally speaking, the greater the specific surface area of ​​calcium carbonate, the greater the improvement in the fracture strength, elongation at fracture, and adhesion of the cured material. These fillers may be used individually or in combination of two or more types.

[0140] When using calcium carbonate, it is desirable to use a combination of surface-treated fine calcium carbonate and calcium carbonate with a larger particle size, such as heavy calcium carbonate. The particle size of the surface-treated fine calcium carbonate is preferably 0.5 μm or less, and the surface treatment is preferably with fatty acids and / or fatty acid salts. The particle size of the calcium carbonate with a larger particle size is preferably 1 μm or more, and untreated calcium carbonate can be used.

[0141] In the curable composition according to one embodiment of the present invention, balloons (preferably with an average particle size of 0.1 mm or more) can be used. By using balloons, a surface with a rough texture resembling sand or sandstone can be created, and the weight can be reduced.

[0142] A balloon is a spherical, hollow filler. Examples of balloon materials include inorganic materials such as glass, shirasu (volcanic ash), and silica, as well as organic materials such as phenolic resin, urea resin, polystyrene, and saran. However, the materials are not limited to these; inorganic and organic materials can be combined, or multiple layers can be formed by lamination. Furthermore, the balloons used may be identical, or multiple types of balloons made of different materials may be used in combination. Additionally, the balloons may have their surfaces processed or coated, or their surfaces treated with various surface treatment agents. For example, organic balloons may be coated with calcium carbonate, talc, or titanium dioxide, while inorganic balloons may be surface-treated with adhesion promoters.

[0143] To obtain a surface with a rough texture resembling sand or sandstone, the balloons preferably have a particle size of 0.1 mm or larger, more preferably 0.2 to 5.0 mm, and even more preferably 0.5 to 5.0 mm. If the balloon particle size is less than 0.1 mm, even if a large amount is added, it may only increase the viscosity of the composition without obtaining the desired rough texture. The amount of balloons to be added can be easily determined depending on the desired degree of roughness resembling sand or sandstone. Typically, it is preferable to add balloons with a particle size of 0.1 mm or larger in a volume concentration of 5 to 25 vol%, and more preferably 8 to 22 vol%, to the curable composition. If the volume concentration of balloons is less than 5 vol%, there will be no rough texture, and if it exceeds 25 vol%, the viscosity of the curable composition will increase, making it difficult to work with, and the modulus of the cured product will also increase, which tends to impair the basic performance of the curable composition. Note that "vol%" refers to "volume %".

[0144] When using balloons, an anti-slip agent as described in Japanese Patent Publication No. 2000-154368, and an amine compound for creating an uneven and matte surface on the cured product as described in Japanese Patent Publication No. 2001-164237, particularly primary and / or secondary amines with a melting point of 35°C or higher, can be added.

[0145] Specific examples of balloons are described in various patent publications such as Japanese Patent Publication No. 2-129262, Japanese Patent Publication No. 4-8788, Japanese Patent Publication No. 4-173867, Japanese Patent Publication No. 5-1225, Japanese Patent Publication No. 7-113073, Japanese Patent Publication No. 9-53063, Japanese Patent Publication No. 10-251618, Japanese Patent Publication No. 2000-154368, Japanese Patent Publication No. 2001-164237, and WO97 / 05201.

[0146] The curable composition according to one embodiment of the present invention can use a flaky or granular substance with a diameter of 0.1 mm or more, preferably 0.1 to 5.0 mm. Using a flaky substance results in an uneven surface due to its flaky nature. Using a granular substance results in a surface with a rough texture resembling sand or sandstone.

[0147] The preferred diameter, amount, and material of the flake-like or granular substance can be appropriately referenced from those described in Japanese Patent Publication No. 9-53063.

[0148] The diameter of the flake-like or granular material is preferably 0.1 mm or more, more preferably 0.1 to 5.0 mm, even more preferably 0.2 to 5.0 mm, and particularly preferably 0.5 to 5.0 mm. The optimal size is used according to the material and pattern of the exterior wall. In the case of flake-like material, a thickness of 1 / 10 to 1 / 5 of the diameter (0.01 to 1.00 mm) is preferred.

[0149] It is preferable to use 1 to 200 parts by weight of the flaky or granular material per 100 parts by weight of the curable composition. The amount of flaky or granular material to be blended is appropriately selected depending on the size of each flaky or granular material, the material and pattern of the exterior wall, etc. As flaky or granular material, natural materials such as silica sand and mica, and inorganic materials such as synthetic rubber, synthetic resin, and alumina can be used. In order to enhance the aesthetic appearance when filled into joints, the material is colored to the optimal color according to the material and pattern of the exterior wall, etc.

[0150] Even when the curable composition according to one embodiment of the present invention contains cured material particles of the curable composition, it is possible to form irregularities on the surface of the cured material and improve its design properties. The preferred diameter, amount, and material of the cured material particles of the curable composition are as described in Japanese Patent Application Publication No. 2001-115142. The diameter of the cured material particles of the curable composition is preferably 0.1 to 1 mm, and more preferably 0.2 to 0.5 mm. The amount of cured material particles of the curable composition is preferably 5 to 100% by weight, and more preferably 20 to 50% by weight, in the curable composition.

[0151] A silicate can be used in the curable composition according to one embodiment of the present invention. The silicate acts as a crosslinking agent and has the function of improving the resilience, durability, and creep resistance of the organic polymer which is component (A) according to one embodiment of the present invention. The silicate also has the effect of improving the adhesion, water-resistant adhesion, and adhesive durability under high temperature and high humidity conditions of the cured product.

[0152] Specific examples of silicates include tetraalkoxysilanes (tetraalkyl silicates) such as tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, and tetra-t-butoxysilane, as well as their partial hydrolysis condensates.

[0153] Partial hydrolysis condensates of tetraalkoxysilanes are more preferable than tetraalkoxysilanes because they offer greater improvements in resilience, durability, and creep resistance.

[0154] Examples of the partially hydrolyzed condensate of the tetraalkoxysilane include those obtained by adding water to tetraalkoxysilane using a conventional method, causing partial hydrolysis and condensation.

[0155] When using silicate, the amount used is preferably 0.1 to 8 parts by weight, and more preferably 0.5 to 3 parts by weight, per 100 parts by weight of the total of components (A) and (B).

[0156] The curable composition according to one embodiment of the present invention may contain adhesion promoters other than component (D). A silane coupling agent can be added as the adhesion promoter.

[0157] Specific examples of silane coupling agents include amino group-containing silanes such as γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; γ-isocyanatetopropyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane, and γ-isocyanatetopropyltriethoxysilane. Examples include isocyanate group-containing silanes such as anetopropylmethyldimethoxysilane, α-isocyanatemethyltrimethoxysilane, and α-isocyanatemethyldimethoxymethylsilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; and epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0158] The above-mentioned adhesion-improving agents may be used individually or in combination of two or more types.

[0159] The amount of adhesion promoter used is preferably 0 to 10 parts by weight, more preferably 0 to 5 parts by weight, and even more preferably 0 to 3 parts by weight, per 100 parts by weight of the total of components (A) and (B). Since adhesion promoters tend to reduce the durability of the cured product, it is preferable to use a small amount, and preferably to have virtually no adhesion promoter at all.

[0160] An antioxidant (anti-aging agent) can be used in the curable composition according to one embodiment of the present invention. Using an antioxidant can improve the heat resistance of the cured product.

[0161] Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Hindered phenols are particularly preferred as antioxidants. Specific examples of antioxidants are also described in Japanese Patent Publication No. 4-283259 and Japanese Patent Publication No. 9-194731.

[0162] The amount of antioxidant used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the total of components (A) and (B).

[0163] A light stabilizer can be used in the curable composition according to one embodiment of the present invention. Using a light stabilizer can prevent photo-oxidative degradation of the cured product.

[0164] Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds. Hindered amine-based compounds are particularly preferred as light stabilizers.

[0165] The amount of light stabilizer used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the total of components (A) and (B). Specific examples of light stabilizers are also described in Japanese Patent Publication No. 9-194731.

[0166] A UV absorber can be used in the curable composition according to one embodiment of the present invention. Using a UV absorber can improve the surface weather resistance of the cured product.

[0167] Examples of UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate compounds. Benzotriazole-based UV absorbers are particularly preferred.

[0168] The amount of UV absorber used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the total of components (A) and (B).

[0169] A photocurable substance can be used in the curable composition according to one embodiment of the present invention. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, improving the stickiness and weather resistance of the cured product. A photocurable substance is a substance whose molecular structure undergoes a chemical change in a relatively short time when exposed to light, resulting in physical changes such as curing. Many types of compounds of this kind are known, including organic monomers, oligomers, resins, or compositions containing them, and any commercially available one can be used. Typical examples include unsaturated acrylic compounds, polyvinyl polycinnamates, or azidized resins.

[0170] Examples of unsaturated acrylic compounds include monomers, oligomers, or mixtures thereof having one or more acrylic or methacrylic unsaturated groups, such as monomers or oligoesters with a molecular weight of 10,000 or less, including propylene (or butylene, ethylene) glycol di(meth)acrylate and neopentyl glycol di(meth)acrylate. Specifically, examples include the (bifunctional) special acrylates Aronics M-210, Aronics M-215, Aronics M-220, Aronics M-233, Aronics M-240, and Aronics M-245; the (trifunctional) Aronics M-305, Aronics M-309, Aronics M-310, Aronics M-315, Aronics M-320, Aronics M-325; and the (polyfunctional) Aronics M-400. Compounds containing acrylic functional groups are particularly preferred, and compounds containing an average of three or more of these functional groups per molecule are also preferred. (All of the above Aronics products are manufactured by Toagosei Co., Ltd.)

[0171] Examples of polyvinyl polycinnamates include photosensitive resins with cinnamoyl groups as photosensitive groups, which are obtained by esterifying polyvinyl alcohol with cinnamic acid, as well as many polyvinyl polycinnamate derivatives.

[0172] Azidated resins are known as photosensitive resins that use azide groups as photosensitive groups. They are typically used in rubber photosensitive solutions to which diazide compounds are added as photosensitive agents. Detailed examples can be found in "Photosensitive Resins" (published March 17, 1972, by the Printing Society Publishing Department, pp. 93, 106, and 117), and these can be used individually or in combination, with sensitizers added as needed. The effect may be enhanced by adding sensitizers such as ketones and nitro compounds, or accelerators such as amines.

[0173] The amount of photocurable material 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 total of components (A) and (B). If the amount of photocurable material used is less than 0.1 parts by weight, there is no effect in improving weather resistance, and if it exceeds 20 parts by weight, the cured product may become too hard and crack.

[0174] An oxygen-curable substance can be used in the curable composition according to one embodiment of the present invention. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, and by reacting with oxygen in the air, they form a cured film near the surface of the cured product, which prevents stickiness of the surface and the adhesion of dirt and dust to the surface of the cured product.

[0175] Examples of oxygen-curable substances include drying oils such as tuna oil and linseed oil, and various alkyd resins obtained by modifying these compounds; acrylic polymers, epoxy resins, and silicone resins modified with drying oils; liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and C5-C8 dienes obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene; liquid copolymers such as NBR and SBR obtained by copolymerizing these diene compounds with monomers such as acrylonitrile and styrene, so that the diene compounds are the main component; and various modified products thereof (maleinated modified products, boiled oil modified products, etc.). These may be used individually or in combination of two or more. Among these, tuna oil and liquid diene polymers are particularly preferred. Furthermore, the effect may be enhanced by using catalysts or metal dryers to promote the oxidative curing reaction. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octoate, and zirconium octoate, as well as amine compounds.

[0176] The amount of oxygen-curable 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 total of components (A) and (B). If the amount of oxygen-curable substance used is less than 0.1 parts by weight, the improvement in stainability will not be sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product may be impaired.

[0177] In the curable composition according to one embodiment of the present invention, a thixotropic agent (anti-sagging agent) may be used to prevent sagging and improve workability.

[0178] The anti-sagging agent is not particularly limited, but examples include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Furthermore, using rubber powder with a particle size of 10 to 500 μm, as described in Japanese Patent Publication No. 11-349916, or organic fibers, as described in Japanese Patent Publication No. 2003-155389, can yield a composition with high thixotropy and good workability. These thixotropy-imparting agents (anti-sagging agents) may be used individually or in combination of two or more.

[0179] The amount of thixotropic agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of the total of components (A) and (B).

[0180] A compound containing an epoxy group in one molecule can be used in the curable composition according to one embodiment of the present invention. Using a compound having an epoxy group can improve the resilience of the cured product.

[0181] Examples of compounds containing epoxy groups include epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, examples include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarbonoxylate (E-PS), epoxyoctyl stearate, and epoxybutyl stearate. Among these, E-PS is particularly preferred as a compound containing epoxy groups.

[0182] The amount of epoxy compound used is preferably 0.5 to 50 parts by weight per 100 parts by weight of the total of components (A) and (B).

[0183] The curable composition according to one embodiment of the present invention may contain phosphorus-based plasticizers such as ammonium polyphosphate and tricresyl phosphate, flame retardants such as aluminum hydroxide and magnesium hydroxide, and thermally expandable graphite. One of the flame retardants may be used alone, or two or more may be used in combination.

[0184] The amount of flame retardant used is preferably 5 to 200 parts by weight, and more preferably 10 to 100 parts by weight, per 100 parts by weight of the total of components (A) and (B).

[0185] A tackifier can be used in the curable composition according to one embodiment of the present invention. The tackifier resin is not particularly limited as long as it is one that is commonly used, whether solid or liquid at room temperature. Specifically, examples include styrene block copolymers, their hydrogenated derivatives, phenolic resins, modified phenolic resins (e.g., cashew oil-modified phenolic resins, tall oil-modified phenolic resins, etc.), terpene phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins and their hydrogenated derivatives (e.g., styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylenebutylene-styrene block copolymer (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), styrene-isobutylene-styrene block copolymer (SIBS), etc.), petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, terpene resins, DCPD resin petroleum resins, etc. These may be added individually or in combination with multiple other types.

[0186] The amount of tackifier used is preferably 5 to 100 parts by weight per 100 parts by weight of the total of components (A) and (B).

[0187] In the curable composition according to one embodiment of the present invention, a solvent may be used for the purpose of reducing the viscosity of the composition, increasing its thixotropy, and improving its workability. There are no particular limitations on the solvent, and various compounds can be used. Specific examples of solvents include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and petroleum solvents; halogen solvents such as trichloroethylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, and isopropyl alcohol; and silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. These solvents may be used individually or in combination of two or more.

[0188] If the amount of solvent is high, the toxicity to the human body may increase, and volume shrinkage of the cured product may occur. Therefore, the amount of solvent is preferably 3 parts by weight or less, more preferably 1 part by weight or less, and most preferably substantially absent, per 100 parts by weight of the total of components (A) and (B).

[0189] In a curable composition according to one embodiment of the present invention, a property modifier may be used to adjust the tensile properties and hardness of the cured product. The property modifier is not particularly limited, but examples include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane; silicone varnishes; and polysiloxanes. The property modifier may be used alone or in combination of two or more.

[0190] In the curable composition according to one embodiment of the present invention, a compound that "produces a compound having a monovalent silanol group in the molecule by hydrolysis" can be used. By using such a compound, the modulus of the cured product can be reduced without worsening the stickiness of the surface of the cured product. Compounds that produce trimethylsilanol are particularly preferred. Examples of compounds that produce a compound having a monovalent silanol group in the molecule by hydrolysis include the compounds described in Japanese Patent Application Publication No. 5-117521. Other examples include silicon compounds that are derivatives of alkyl alcohols such as hexanol, octanol, and decanol and produce R3SiOH such as trimethylsilanol by hydrolysis, and silicon compounds that are derivatives of polyhydric alcohols having 3 or more hydroxyl groups, such as trimethylolpropane, glycerin, pentaerythritol, or sorbitol, as described in Japanese Patent Application Publication No. 11-241029, and produce R3SiOH such as trimethylsilanol by hydrolysis.

[0191] Furthermore, silicon compounds that are derivatives of oxypropylene polymers, such as those described in Japanese Patent Publication No. 7-258534, and that produce R3SiOH such as trimethylsilanol upon hydrolysis can also be mentioned. In addition, polymers having a crosslinkable reactive silicon-containing group and a silicon-containing group that can become a monosilanol-containing compound upon hydrolysis can also be used, as described in Japanese Patent Publication No. 6-279693.

[0192] The amount of the compound that generates a compound having a monovalent silanol group in its molecule by hydrolysis 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 total of components (A) and (B).

[0193] The curable composition according to one embodiment of the present invention can be prepared as a one-component type that hardens at room temperature due to moisture in the air after application, by pre-mixing and sealing all the components and storing them.

[0194] When the curable composition is a one-component type, all components are pre-mixed, so it is preferable to dehydrate and dry any components containing water before use, or to dehydrate them by reducing pressure during mixing. When the curable composition is a two-component type, there is no need to mix a curing catalyst into the main component containing a polymer having reactive silicon groups, so even if the compound contains some water, there is little concern about gelation. However, if long-term storage stability is required, it is preferable to dehydrate and dry the compound.

[0195] For dehydration and drying, for solid materials such as powders, heat drying or vacuum dehydration is preferred, while for liquid materials, vacuum dehydration or dehydration using synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide, etc. is preferred. In addition to such dehydration and drying methods, alkoxysilane compounds such as n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methyl silicate, ethyl silicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane may be added and reacted with water to dehydrate. Alternatively, oxazolidine compounds such as 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine may be added and reacted with water to dehydrate. Furthermore, a small amount of isocyanate compound may be added and the isocyanate group may react with water to dehydrate. The storage stability of the curable composition is improved by the addition of alkoxysilane compounds, oxazolidine compounds, and isocyanate compounds.

[0196] There are no particular limitations on the method for preparing the curable composition according to one embodiment of the present invention. For example, conventional methods can be used, such as (1) a method of blending the above-mentioned components and kneading them at room temperature or under heating using a mixer, roll and kneader, or (2) a method of dissolving each component using a small amount of a suitable solvent and mixing the dissolved products of each component.

[0197] A curable composition according to one embodiment of the present invention, after being exposed to the atmosphere, forms a three-dimensional network structure due to the action of moisture in the atmosphere, and hardens into a solid (cured product) having rubber-like elasticity.

[0198] The curable composition according to one embodiment of the present invention can be used as an adhesive, sealant, molding agent, vibration damper, soundproofing material, foaming material, paint, spray material, etc. Examples of sealants include those for buildings, ships, automobiles, and roads. The cured product obtained by curing the curable composition according to one embodiment of the present invention has low modulus, high elongation, and high resilience, so this curable composition can be suitably used as a building sealant, particularly a working joint sealant, among these.

[0199] A one-component curable composition according to one embodiment of the present invention is suitable for use as a sealant for curtain walls, balcony window frames, stone, and bridges. It is also suitable as a joint sealant for exterior materials such as siding boards, which are widely used in construction.

[0200] This curable composition exhibits excellent compression recovery. When this curable composition is used as a one-component curable composition in a working joint, a higher compression recovery value is preferable. The compression recovery of this curable composition is more preferably 10% or more, even more preferably exceeding 10%, and particularly preferably 15% or more. When the compression recovery is 10% or more, the expansion and contraction of the cured material can easily follow the expansion and contraction of the exterior member due to long-term daily and seasonal fluctuations, thus preventing damage such as cracking of the cured material and delamination between the cured material and the member.

[0201] [3. Joint structure] A joint structure according to one embodiment of the present invention is a joint structure obtained by filling a working joint of a building with the one-component curable composition for working joints described in section [2. Curable Composition] and curing it. Because the joint structure according to one embodiment of the present invention has the above configuration, it is excellent in compression recovery rate, displacement following ability and durability.

[0202] The method for manufacturing a joint structure according to one embodiment of the present invention, specifically the method for filling with a curable composition, is not particularly limited and known methods can be used. Examples of methods for filling with a curable composition include using a manual caulking gun, an electric caulking gun, and a pneumatic caulking gun. Since the curable composition according to one embodiment of the present invention is a one-component type, after being filled, i.e., after being exposed to the atmosphere, it can form a three-dimensional network structure due to the action of moisture in the atmosphere, thereby forming a cured product, i.e., a joint structure.

[0203] [4. Wall] A wall according to one embodiment of the present invention has a joint structure obtained by filling the working joint of a building with the one-component curable composition for working joints described in section [2. Curable Composition] and curing it. Because the wall according to one embodiment of the present invention has the above configuration, it is excellent in durability, weather resistance and waterproofing.

[0204] A method for manufacturing a wall according to one embodiment of the present invention, specifically a method for manufacturing a joint structure, is the method described in [3. Joint Structure].

[0205] [5. Construction method] A construction method according to one embodiment of the present invention comprises the step of filling the working joint of a building with a one-component curable composition for working joints described in section [2. Curable Composition] and curing it. Because the construction method according to one embodiment of the present invention has the above configuration, it can provide a building (for example, a joint structure and a wall) with excellent durability, weather resistance and waterproofing.

[0206] The actual operation in the construction method according to one embodiment of the present invention can be described as filling with a curable composition. An example of a method for filling with a curable composition is the method described in [3. Joint Structure].

[0207] One embodiment of the present invention may have the following configuration:

[0208] [1] (A) A polyoxyalkylene polymer having an average of 1.2 to 5 reactive silicon groups represented by general formula (1) per molecule, (D) A silane compound obtained by partially condensing aminosilane compounds having reactive silicon groups, or a silane compound obtained by partially condensing an aminosilane compound having reactive silicon groups with an alkoxysilane compound other than aminosilane, and (E) A tetravalent organotin compound in an amount of 0.05 parts by weight or more and less than 1 part by weight per 100 parts by weight of component (A). A one-component curable composition for working joints, characterized by containing: -SiX3···(1) (In the formula, X independently represents either a hydroxyl group or a hydrolyzable group.)

[0209] [2] The one-component curable composition for working joints according to [1], further comprising (B) a reactive plasticizer which is a polyoxyalkylene polymer having an average of 0.5 to less than 1.2 reactive silicon groups represented by general formula (2) per molecule: -SiR 1 3-a X a ...(2) (In the formula, R 1 Each of these independently represents an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, and an aralkyl group with 7 to 20 carbon atoms. X is the same as in general formula (1). a represents an integer from 1 to 3. [3] The one-component curable composition for working joints according to [1] or [2], characterized in that component (B) contains a polyoxyalkylene polymer having one reactive silicon group represented by general formula (2) in one molecule of (B1).

[0210] [4] The one-component curable composition for working joints according to any one of [1] to [3], characterized in that component (B) is obtained by reacting an alkylene oxide with an initiator having only one hydroxyl group in one molecule to which a reactive silicon group (B') can be introduced into a polyoxyalkylene precursor polymer having only one functional group to which a reactive silicon group can be introduced.

[0211] [5] The one-component curable composition for working joints according to any one of [1] to [4], characterized in that component (B) is obtained by introducing a reactive silicon group represented by general formula (2) into a polyoxyalkylene precursor polymer mixture having a functional group into which a reactive silicon group can be introduced, obtained by reacting an alkylene oxide with a mixture of an initiator having only one hydroxyl group in one molecule of (B") and an initiator having two or more hydroxyl groups in one molecule.

[0212] [6] A one-component curable composition for working joints according to any one of [1] to [5], characterized in that the polyoxyalkylene polymers of component (A) and component (B) are polyoxypropylene polymers.

[0213] [7] A one-component curable composition for working joints according to any one of [1] to [6], further comprising (C1) a polyether-based plasticizer that does not have a reactive silicon group represented by general formula (1) or general formula (2).

[0214] A joint structure obtained by filling a working joint of a building with a one-component curable composition for working joints described in any one of [8], [1], to [7] and allowing it to harden.

[0215] A wall having a joint structure obtained by filling the working joints of a building with a one-component curable composition for working joints described in any one of [9], [1], to [7] and curing it.

[0216] A construction method characterized by comprising the step of filling a working joint of a building with a one-component curable composition for working joints described in any one of [1] to [7] and allowing it to harden.

[0217] Another embodiment of the present invention may have the following configuration.

[0218] [X1] (A) A polyoxyalkylene polymer having an average of 1.2 to 5 reactive silicon groups represented by general formula (1) per molecule, (D) Silane compounds obtained by partially condensing aminosilane compounds having reactive silicon groups, or silane compounds obtained by partially condensing an aminosilane compound having reactive silicon groups with an alkoxysilane compound other than aminosilane, and A method for producing a one-component curable composition for working joints, comprising the steps of (E) mixing a tetravalent organotin compound in an amount of 0.05 parts by weight or more and less than 1 part by weight per 100 parts by weight of component (A), and kneading the resulting mixture: -SiX3···(1) (In the formula, X independently represents either a hydroxyl group or a hydrolyzable group.)

[0219] [X2] The step of the above step is to mix in (B) a reactive plasticizer which is a polyoxyalkylene polymer having an average of 0.5 to less than 1.2 reactive silicon groups represented by general formula (2) per molecule, in addition to the components (A), (D), and (E), and to knead the resulting mixture, the method for producing a one-component curable composition for working joints according to [X1]: -SiR 1 3-a X a ...(2) (In the formula, R 1 Each of these independently represents an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, and an aralkyl group with 7 to 20 carbon atoms. X is the same as in general formula (1). a represents an integer from 1 to 3. [X3] A method for producing a one-component curable composition for working joints according to [X1] or [X2], wherein the component (B) comprises a polyoxyalkylene polymer having one reactive silicon group represented by general formula (2) in one molecule of (B1).

[0220] [X4] A method for producing a one-component curable composition for working joints according to any one of [X1] to [X3], wherein the component (B) is obtained by reacting an alkylene oxide with an initiator having only one hydroxyl group in one molecule, and introducing a reactive silicon group represented by general formula (2) into a polyoxyalkylene precursor polymer having only one functional group into which a reactive silicon group (B') can be introduced.

[0221] [X5] A method for producing a one-component curable composition for working joints according to any one of [X1] to [X4], wherein the component (B) is obtained by introducing a reactive silicon group represented by general formula (2) into a polyoxyalkylene precursor polymer mixture having a functional group into which a reactive silicon group can be introduced, obtained by reacting an alkylene oxide with a mixture of an initiator having only one hydroxyl group in one molecule of (B") and an initiator having two or more hydroxyl groups in one molecule.

[0222] [X6] A method for producing a one-component curable composition for working joints according to any one of [X1] to [X5], wherein the polyoxyalkylene polymer of component (A) and component (B) is a polyoxypropylene polymer.

[0223] [X7] The step of mixing component (A), component (D), and component (E), or component (A), component (B), component (D), and component (E), with (C1) a polyether plasticizer that does not have a reactive silicon group represented by general formula (1) or general formula (2), and kneading the resulting mixture, as described in any one of [X1] to [X6].

[0224] A method for manufacturing a joint structure, comprising the step of filling a working joint with a one-component curable composition for working joints obtained by a method for manufacturing a one-component curable composition for working joints described in any one of [X8], [X1] to [X7], and curing it in the working joints of a building.

[0225] A construction method comprising the step of filling a working joint with a one-component curable composition for working joints obtained by a method for producing a one-component curable composition for working joints described in any one of [X9], [X1], to [X7], and curing it in the working joints of a building. [Examples]

[0226] One embodiment of the present invention will be specifically described by examples and comparative examples, but the present invention is not limited thereto. In the following description, an X-group-terminated Y polymer refers to a Y polymer having an X group at its terminus.

[0227] (Synthesis Example 1) Using polypropylene glycol with a number-average molecular weight of approximately 3,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate-grime complex catalyst to obtain a hydroxyl-terminated polyoxypropylene polymer with a number-average molecular weight of approximately 29,000, calculated from the amount of hydroxyl groups. Subsequently, a methanol solution of sodium methoxide (NaOMe) in an amount equivalent to 1.2 times the amount of hydroxyl groups of this hydroxyl-terminated polyoxypropylene polymer was added, and the methanol was removed by distillation. Then, an amount equivalent to 1.3 times the amount of allyl chloride was added to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by defoliation under reduced pressure to obtain an unpurified allyl-terminated polyoxypropylene polymer.

[0228] To 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene polymer, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred, and the water was removed by centrifugation. Another 300 parts by weight of water was mixed and stirred into the obtained hexane solution, and the water was removed again by centrifugation. Subsequently, hexane was removed from the obtained hexane solution by vacuum defloration. The allyl-terminated polyoxypropylene polymer was thus obtained.

[0229] To obtain a triethoxysilyl-terminated polyoxypropylene polymer, 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer was reacted with triethoxysilane at 90°C for 2 hours using 150 ppm of an isopropanol solution of a platinum vinylsiloxane complex with a platinum content of 3 wt% as a catalyst. 1 Measurements using 1H-NMR (measured in CDCl3 solvent using JEOL JNM-LA400) confirmed that the obtained triethoxysilyl-terminated polyoxypropylene polymer contained an average of 1.7 terminal triethoxysilyl groups per molecule.

[0230] To the obtained triethoxysilyl-terminated polyoxypropylene polymer, methanol was added using a 0.5 wt% methanol solution of hydrochloric acid as a catalyst, and the mixture was stirred at 70°C for 2 hours to convert the terminal triethoxysilyl groups to trimethoxysilyl groups. Finally, methanol was removed by defoliation under reduced pressure. Thus, trimethoxysilyl-terminated polyoxypropylene polymer (a1) was obtained. 1 Measurements using 1H-NMR (measured in CDCl3 solvent using JEOL JNM-LA400) confirmed that the obtained trimethoxysilyl-terminated polyoxypropylene polymer (a1) had an average of 1.7 terminal trimethoxysilyl groups per molecule. The number-average molecular weight of the obtained trimethoxysilyl-terminated polyoxypropylene polymer (a1) in terms of polystyrene, calculated by GPC, was 29,000. The trimethoxysilyl-terminated polyoxypropylene polymer (a1) is component (A) in one embodiment of the present invention.

[0231] (Synthesis Example 2) Using polypropylene glycol with a number-average molecular weight of approximately 3,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate-grime complex catalyst to obtain a hydroxyl-terminated polyoxypropylene polymer with a number-average molecular weight of approximately 29,000, calculated from the amount of hydroxyl groups. Subsequently, a methanol solution of NaOMe in an equivalent volume of 1.2 times the amount of hydroxyl groups of this hydroxyl-terminated polyoxypropylene polymer was added, and the methanol was removed by distillation. Then, an equivalent volume of allyl chloride was added in an equivalent volume to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by defoliation under reduced pressure to obtain an unpurified allyl-terminated polyoxypropylene polymer.

[0232] To 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene polymer, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred, and the water was removed by centrifugation. Another 300 parts by weight of water was mixed and stirred into the obtained hexane solution, and the water was removed again by centrifugation. Subsequently, hexane was removed from the obtained hexane solution by vacuum defloration. By these steps, an allyl-terminated polyoxypropylene polymer was obtained.

[0233] To obtain a triethoxysilyl-terminated polyoxypropylene polymer, 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer was reacted with triethoxysilane at 90°C for 2 hours using 150 ppm of an isopropanol solution of a platinum vinylsiloxane complex with a platinum content of 3 wt% as a catalyst. 1 Measurements using 1H-NMR (measured in CDCl3 solvent using JEOL JNM-LA400) confirmed that the obtained triethoxysilyl-terminated polyoxypropylene polymer contained an average of 1.4 terminal triethoxysilyl groups per molecule.

[0234] To the obtained triethoxysilyl-terminated polyoxypropylene polymer, methanol was added using a 0.5 wt% methanol solution of hydrochloric acid as a catalyst, and the mixture was stirred at 70°C for 2 hours to convert the terminal triethoxysilyl groups to trimethoxysilyl groups. Finally, methanol was removed by defoliation under reduced pressure. Thus, trimethoxysilyl-terminated polyoxypropylene polymer (a2) was obtained. 1 Measurements using 1H-NMR (measured in CDCl3 solvent using JEOL JNM-LA400) confirmed that the obtained trimethoxysilyl-terminated polyoxypropylene polymer (a2) had an average of 1.4 terminal trimethoxysilyl groups per molecule. The number-average molecular weight of the obtained trimethoxysilyl-terminated polyoxypropylene polymer (a2) in terms of polystyrene, calculated by GPC, was 29,000. The trimethoxysilyl-terminated polyoxypropylene polymer (a2) is component (A) in one embodiment of the present invention.

[0235] (Synthesis Example 3) Using polypropylene glycol with a number-average molecular weight of approximately 3,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate-grime complex catalyst to obtain a hydroxyl-terminated polyoxypropylene polymer with a number-average molecular weight of approximately 29,000, calculated from the amount of hydroxyl groups. Subsequently, a methanol solution of NaOMe in an equivalent volume of 1.2 times the amount of hydroxyl groups of this hydroxyl-terminated polyoxypropylene polymer was added, and the methanol was removed by distillation. Then, an equivalent volume of allyl chloride was added to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by defoliation under reduced pressure to obtain an unpurified allyl-terminated polyoxypropylene polymer.

[0236] To 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene polymer, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred, and the water was removed by centrifugation. Another 300 parts by weight of water was mixed and stirred into the obtained hexane solution, and the water was removed again by centrifugation. Subsequently, hexane was removed from the obtained hexane solution by vacuum defloration. By these steps, an allyl-terminated polyoxypropylene polymer was obtained.

[0237] To 100 parts by weight of the obtained allyl-terminated polyoxypropylene polymer, a 150 ppm isopropanol solution of a platinum vinylsiloxane complex with a platinum content of 3 wt% was used as a catalyst to react the allyl-terminated polyoxypropylene polymer with dimethoxymethylsilane at 90°C for 2 hours to obtain dimethoxymethylsilyl-terminated polyoxypropylene polymer (a3). 1 Measurements using 1H-NMR (measured in CDCl3 solvent using JEOL JNM-LA400) confirmed that the obtained dimethoxymethylsilyl-terminated polyoxypropylene polymer (a3) ​​had an average of 1.8 terminal dimethoxymethylsilyl groups per molecule. Furthermore, the number-average molecular weight of the obtained dimethoxymethylsilyl-terminated polyoxypropylene polymer (a3), calculated using GPC on a polystyrene basis, was 29,000.

[0238] (Synthesis Example 4) A mixture of polyoxypropylene glycol with a number-average molecular weight of 14,600 and n-butanol in a weight ratio of 10:1 was used as an initiator, and polymerization of propylene oxide was carried out using a zinc hexacyanocobaltate grime complex catalyst to obtain a mixture of polypropylene oxides with a number-average molecular weight of 7,700 (polyoxypropylene glycol monobutyl ether with a number-average molecular weight of 6,500 and polyoxypropylene glycol with a number-average molecular weight of 18,000 (weight ratio of 9:1)). Subsequently, a methanol solution of NaOMe equivalent to 1.2 times the volume of the hydroxyl groups of this polypropylene oxide containing hydroxyl groups was added, and the methanol was removed by distillation. Furthermore, allyl chloride was added to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by vacuum defoliation to obtain unpurified polypropylene oxide containing allyl groups. To 100 parts by weight of the obtained unpurified polypropylene oxide having allyl groups, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred, and the water was removed by centrifugation. Another 300 parts by weight of water was mixed and stirred into the obtained hexane solution, and the water was removed again by centrifugation. Then, the hexane was removed from the obtained hexane solution by vacuum defloration. As a result, a mixture of polyoxypropylene polymers was obtained in which the main component was a component in which an allyl group was introduced only at one end, and the number average molecular weight in terms of polystyrene in GPC was approximately 7,700. To 100 parts by weight of the obtained polyoxypropylene polymer having allyl groups, 1.9 parts by weight of dimethoxymethylsilane was reacted with 1.9 parts by weight of dimethoxymethylsilane at 90°C for 2 hours using 36 ppm of an isopropanol solution of a platinum vinylsiloxane complex with a platinum content of 3 wt% as a catalyst to obtain polyoxypropylene polymer (b1) having an average of 0.9 dimethoxymethylsilyl groups per molecule. Furthermore, the number-average molecular weight of the obtained polyoxypropylene polymer (b1) in terms of polystyrene, calculated by GPC, was 7,700. The polyoxypropylene polymer (b1) having a dimethoxymethylsilyl group is component (B) in one embodiment of the present invention.

[0239] (Synthesis Example 5) Using polypropylene glycool with a number average molecular weight of approximately 2,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate-grime complex catalyst to obtain a hydroxyl-terminated polyoxypropylene polymer with a number average molecular weight of approximately 16,000. Subsequently, a methanol solution of NaOMe in an equivalent volume of 1.2 times the amount of the hydroxyl groups of this hydroxyl-terminated polyoxypropylene polymer was added, and the methanol was removed by distillation. Then, an equivalent volume of allyl chloride was added to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by defoliation under reduced pressure to obtain an unpurified allyl-terminated polyoxypropylene polymer.

[0240] To 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene polymer, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred, and the water was removed by centrifugation. Another 300 parts by weight of water was mixed and stirred into the obtained hexane solution, and the water was removed again by centrifugation. Subsequently, hexane was removed from the obtained hexane solution by vacuum defloration. By these steps, an allyl-terminated polyoxypropylene polymer was obtained.

[0241] To obtain the allyl-terminated polyoxypropylene polymer, 100 parts by weight was reacted with dimethoxymethylsilane at 90°C for 2 hours using 150 ppm of an isopropanol solution of a platinum vinylsiloxane complex with a platinum content of 3 wt% as a catalyst, thereby obtaining dimethoxymethylsilyl-terminated polyoxypropylene polymer (a4). 1 Measurements using 1H-NMR (measured in CDCl3 solvent using JEOL JNM-LA400) confirmed that the obtained dimethoxymethylsilyl-terminated polyoxypropylene polymer (a4) had an average of 1.3 terminal dimethoxymethylsilyl groups per molecule. The number-average molecular weight of the obtained dimethoxymethylsilyl-terminated polyoxypropylene polymer (a4) in terms of polystyrene, calculated by GPC, was 16,200.

[0242] (Example 1) (A) Component: 70 parts by weight of trimethoxysilyl group-terminated polyoxypropylene polymer (a1) obtained in Synthesis Example 1; (B) Component: 30 parts by weight of polyoxypropylene polymer (b1) having an average of 0.9 dimethoxymethylsilyl groups per molecule obtained in Synthesis Example 4; (C1) Component: Polyether-based plasticizer (manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd., trade name: Actcol) 90 parts by weight of P-23 (number average molecular weight 3,000), 15 parts by weight of diisodecylphthalate plasticizer (manufactured by J-Plus Co., Ltd., product name: DIDP) as component (C2), 130 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Shiraishi Industries Co., Ltd., product name: Shirotsuya CCR-B), 64 parts by weight of heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., product name: Whiteon SB), 1 part by weight of benzotriazole-based UV absorber (manufactured by BASF, product name: Tinuvin 326), 1 part by weight of hindered amine-based light stabilizer (manufactured by BASF, product name: Tinuvin 770), and 1 part by weight of hindered phenol-based antioxidant (manufactured by BASF, product name: Irganox 1010) were weighed and mixed with a spatula. The resulting mixture was then passed through three paint rolls three times to uniformly disperse it. Subsequently, the obtained mixture was dehydrated under reduced pressure at 120°C for 2 hours, cooled to below 50°C, and then 4 parts by weight of vinyltrimethoxysilane (manufactured by MOMENTIVE, trade name: A-171) and 1 part by weight of silane compound (manufactured by EVONIK, trade name: DYNASYLAN1146), component (D), were added to the mixture as dehydrating agents and mixed. Then, 0.2 parts by weight of dioctyl tin dilaurate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-810), component (E), was added to the obtained mixture as a curing catalyst, and the mixture was kneaded in a substantially moisture-free state to obtain the composition. The obtained composition was then sealed in a moisture-proof container, a cartridge, to obtain a one-component curable composition.

[0243] (Example 2) (A) Component: 100 parts by weight of the trimethoxysilyl group-terminated polyoxypropylene polymer (a2) obtained in Synthesis Example 2, and (C1) Component: Polyether-based plasticizer (manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd., trade name: Actcol) 90 parts by weight of P-23 (number average molecular weight 3,000), 15 parts by weight of diisodecylphthalate plasticizer (manufactured by J-Plus Co., Ltd., product name: DIDP) as component (C2), 160 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Shiraishi Industries Co., Ltd., product name: Shirotsuya CCR-B), 64 parts by weight of heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., product name: Whiteon SB), 1 part by weight of benzotriazole-based UV absorber (manufactured by BASF, product name: Tinuvin 326), 1 part by weight of hindered amine-based light stabilizer (manufactured by BASF, product name: Tinuvin 770), and 1 part by weight of hindered phenol-based antioxidant (manufactured by BASF, product name: Irganox 1010) were weighed and mixed with a spatula. The resulting mixture was then passed through three paint rolls three times to uniformly disperse it. Subsequently, the obtained mixture was dehydrated under reduced pressure at 120°C for 2 hours, cooled to below 50°C, and then 4 parts by weight of vinyltrimethoxysilane (manufactured by MOMENTIVE, trade name: A-171) and 1 part by weight of silane compound (manufactured by EVONIK, trade name: DYNASYLAN1146), component (D), were added to the mixture as dehydrating agents and mixed. Then, 0.2 parts by weight of dioctyl tin dilaurate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-810), component (E), was added to the obtained mixture as a curing catalyst, and the mixture was kneaded in a substantially moisture-free state to obtain the composition. The obtained composition was then sealed in a moisture-proof container, a cartridge, to obtain a one-component curable composition.

[0244] (Comparative Example 1) (A) Component: 90 parts by weight of trimethoxysilyl group-terminated polyoxypropylene polymer (a1) obtained in Synthesis Example 1; (B) Component: 10 parts by weight of polyoxypropylene polymer (b1) having an average of 0.9 dimethoxymethylsilyl groups per molecule obtained in Synthesis Example 4; (C2) Component: 90 parts by weight of diisodecylphthalate plasticizer (manufactured by J-Plus Co., Ltd., product name: DIDP); Surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., product name: Shirotsuya) 170 parts by weight of Hua CCR-B, 64 parts by weight of heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: Whiteon SB), 1 part by weight of benzotriazole-based ultraviolet absorber (manufactured by BASF, trade name: Tinuvin 326), 1 part by weight of hindered amine-based light stabilizer (manufactured by BASF, trade name: Tinuvin 770), and 1 part by weight of hindered phenol-based antioxidant (manufactured by BASF, trade name: Irganox 1010) were weighed and mixed with a spatula. The resulting mixture was then passed through three paint rolls three times to ensure uniform dispersion. After this, the resulting mixture was dehydrated under reduced pressure at 120°C for 2 hours, cooled to below 50°C, and then 3 parts by weight of vinyltrimethoxysilane (manufactured by MOMENTIVE, trade name: A-171) and 3 parts by weight of adhesion promoter (manufactured by MOMENTIVE Co., Ltd., trade name: A-1120) were added to the mixture as a dehydrating agent and mixed. Subsequently, 0.2 parts by weight of dioctyl tin dilaurate (manufactured by Nitto Chemical Co., Ltd., trade name: Neostan U-810), component (E), was added as a curing catalyst, and the mixture was kneaded in a substantially moisture-free state to obtain the composition. The obtained composition was then sealed in a moisture-proof container, a cartridge, to obtain a one-component curable composition.

[0245] (Comparative Example 2) 100 parts by weight of the dimethoxymethylsilyl group-terminated polyoxypropylene polymer (a3) ​​obtained in Synthesis Example 3, 90 parts by weight of the polyether-based plasticizer (C1) manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd., trade name: Actcol P-23, number average molecular weight 3,000), 15 parts by weight of the diisodecylphthalate plasticizer (C2) manufactured by J-Plus Co., Ltd., trade name: DIDP, and surface-treated colloidal calcium carbonate (Shiraishi Industries Co., Ltd., trade name: Viscolite). 130 parts by weight of (OS), 64 parts by weight of heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: Whiteon SB), 1 part by weight of benzotriazole-based ultraviolet absorber (manufactured by BASF, trade name: Tinuvin 326), 1 part by weight of hindered amine-based light stabilizer (manufactured by BASF, trade name: Tinuvin 770), and 1 part by weight of hindered phenol-based antioxidant (manufactured by BASF, trade name: Irganox 1010) were weighed and mixed with a spatula. The resulting mixture was then passed through three paint rolls three times to ensure uniform dispersion. After this, the resulting mixture was dehydrated under reduced pressure at 120°C for 2 hours, cooled to below 50°C, and then 4 parts by weight of vinyltrimethoxysilane (manufactured by MOMENTIVE, trade name: A-171) and 1 part by weight of silane compound (manufactured by EVONIK, trade name: DYNASYLAN 1146) of component (D) were added to the mixture as dehydrating agents and mixed. Subsequently, 0.5 parts by weight of component (E), dibutyltin diacetylacetonate (manufactured by Nitto Chemical Co., Ltd., trade name: Neostan U-220H), was added to the obtained mixture as a curing catalyst, and the mixture was kneaded in a substantially moisture-free state to obtain the composition. The obtained composition was then sealed in a moisture-proof container, a cartridge, to obtain a one-component curable composition.

[0246] (Example 3) (A) Component: 70 parts by weight of trimethoxysilyl group-terminated polyoxypropylene polymer (a1) obtained in Synthesis Example 1; (B) Component: 30 parts by weight of polyoxypropylene polymer (b1) having an average of 0.9 dimethoxymethylsilyl groups per molecule obtained in Synthesis Example 4; (C1) Component: 90 parts by weight of polyether-based plasticizer (manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd., product name: Actcol P-23, number average molecular weight 3,000); (C2) Component: 15 parts by weight of diisodecylphthalate plasticizer (manufactured by J-Plus Co., Ltd., product name: DIDP); (A) Component: 70 parts by weight of trimethoxysilyl group-terminated polyoxypropylene polymer (a1) obtained in Synthesis Example 1; (B) Component: 30 parts by weight of polyoxypropylene polymer (b1) obtained in Synthesis Example 4; (C1) Component: 90 parts by weight of polyether-based plasticizer (manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd., product name: Actcol P-23, number average molecular weight 3,000); (C2) Component: 15 parts by weight of diisodecylphthalate plasticizer (manufactured by J-Plus Co., Ltd., product name: DIDP); (C2) Component: 160 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Shiraishi Industries Co., Ltd., product name: Shiratsuka CCR-B); (C2) Component: 64 parts by weight of heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., product name: Whiteon SB); (C3) Component: 10 parts by weight of titanium dioxide (manufactured by Ishihara Industries Co., Ltd., product name: Typeque R820) Parts by weight of the product, 2 parts by weight of a sagging prevention agent (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil R972), 1 part by weight of a benzotriazole-based ultraviolet absorber (manufactured by BASF, trade name: Tinuvin 326), 1 part by weight of a hindered amine-based light stabilizer (manufactured by BASF, trade name: Tinuvin 770), and 1 part by weight of a hindered phenol-based antioxidant (manufactured by BASF, trade name: Irganox 1010) were weighed and mixed with a spatula. The resulting mixture was then passed through three paint rolls three times to ensure uniform dispersion. After this, the resulting mixture was dehydrated under reduced pressure at 120°C for 2 hours, cooled to below 50°C, and then 4 parts by weight of vinyltrimethoxysilane (manufactured by MOMENTIVE, trade name: A-171) and 1 part by weight of the silane compound of component (D) (manufactured by EVONIK, trade name: DYNASYLAN 1146) were added to the mixture as dehydrating agents and mixed. Subsequently, 0.2 parts by weight of dioctyl tin dilaurate (manufactured by Nitto Chemical Co., Ltd., trade name: Neostan U-810), component (E), was added to the obtained mixture as a curing catalyst, and the mixture was kneaded in a substantially moisture-free state to obtain the composition. The obtained composition was then sealed in a moisture-proof container, a cartridge, to obtain a one-component curable composition.

[0247] (Example 4) Instead of 70 parts by weight of the polymer (a1) of component (A) and 30 parts by weight of the polymer (b1) of component (B), a one-component curable composition was obtained in the same manner as in Example 3, except that 100 parts by weight of the trimethoxysilyl group-terminated polyoxypropylene polymer (a2) obtained in Synthesis Example 2 was used as component (A).

[0248] (Example 5) Instead of 90 parts by weight of the polyether plasticizer (Actocol P-23) of component (C1) and 15 parts by weight of the diisodecyl phthalate plasticizer (DIDP) of component (C2), a one-component curable composition was obtained in the same manner as in Example 3, except that 105 parts by weight of the diisodecyl phthalate plasticizer (DIDP) of component (C2) was used.

[0249] (Example 6) Instead of 0.2 parts by weight of dioctyltin dilaurate (Neo-Stann U-810) of component (E), a one-component curable composition was obtained in the same manner as in Example 3, except that 0.1 parts by weight of dibutyltin diacetylacetonate (manufactured by Nitto Kasei Co., Ltd., trade name: Neo-Stann U-220H) of component (E) was used.

[0250] (Comparative Example 3) Instead of 70 parts by weight of the polymer (a1) of component (A), a one-component curable composition was obtained in the same manner as in Example 3, except that 70 parts by weight of the dimethoxymethylsilyl group-terminated polyoxypropylene polymer (a5) obtained in Synthesis Example 5 was used.

[0251] (Comparative Example 4) 70 parts by weight of the polymer (a5) was used instead of 70 parts by weight of the polymer (a1) of component (A). Further, instead of 0.2 parts by weight of dioctyltin dilaurate (Neo-Stann U-810) of component (E), a one-component curable composition was obtained in the same manner as in Example 3, except that 0.5 parts by weight of dibutyltin diacetylacetonate (Neo-Stann U-220H) of component (E) was used.

[0252] (Comparative Example 5) A one-component curable composition was obtained in the same manner as in Example 3, except that 2 parts by weight of an aminosilane compound (N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, manufactured by MOMENTIVE, trade name: A-1120) was used instead of 1 part by weight of component (DYNASYLAN1146).

[0253] (Comparative Example 6) A one-component curable composition was obtained in the same manner as in Example 3, except that 1 part by weight of dioctyl tin dilaurate (Neostan U-810) of component (E) was used instead of 0.2 parts by weight of dioctyl tin dilaurate (Neostan U-810) of component (E).

[0254] (Example 7) A one-component curable composition was obtained in the same manner as in Example 3, except that 0.1 parts by weight of dioctyl tin dilaurate (Neostan U-810) of component (E) was used instead of 0.2 parts by weight of dioctyl tin dilaurate (Neostan U-810) of component (E).

[0255] (Example 8) A one-component curable composition was obtained in the same manner as in Example 3, except that 0.07 parts by weight of dioctyl tin dilaurate (Neostan U-810) of component (E) was used instead of 0.2 parts by weight of dioctyl tin dilaurate (Neostan U-810) of component (E).

[0256] (Example 9) A one-component curable composition was obtained in the same manner as in Example 3, except that 0.05 parts by weight of dioctyl tin dilaurate (Neostan U-810) of component (E) was used instead of 0.2 parts by weight of dioctyl tin dilaurate (Neostan U-810) of component (E).

[0257] (Comparative Example 7) A one-component curable composition was obtained in the same manner as in Example 3, except that 0.01 parts by weight of dioctyl tin dilaurate (Neostan U-810) of component (E) was used instead of 0.2 parts by weight of dioctyl tin dilaurate (Neostan U-810) of component (E).

[0258] (Leather stretching time) The one-component curable composition obtained above was filled into a mold approximately 3 mm thick, and the surface was leveled to a flat surface. The time at which the surface leveling was completed was defined as the curing start time, and the time at which the curable composition no longer adhered to the micro-spatula when the surface was touched was defined as the skinning time. The skinning time was measured under conditions of 23°C (50% RH). The test results are shown in Tables 1 to 4.

[0259] (deep hardening) The one-component curable composition obtained above was filled into a 12 mm diameter polyethylene cylindrical container, ensuring no air bubbles were present, and the surface was smoothed to prepare a test specimen. The test specimen was left to stand at 23°C (50% RH) for 1 day and then for 7 days. After 1 day and 7 days, the cured portion of the test specimen was removed, any uncured portions attached were removed, and the thickness of the cured portion was measured using calipers. If there was no cured portion (uncured), it was recorded as "unmeasurable." The test results are shown in Tables 1-3.

[0260] (Workability) The one-component curable composition obtained above was conditioned by standing in a constant temperature bath set to 5°C for more than 5 hours. Then, the curable composition was filled into 100 ml containers, ensuring no air bubbles were present. Next, an 8 mm diameter glass rod was quickly inserted into the curable composition, and the glass rod was withdrawn from the composition at a tensile speed of 1000 mm / min using a tensile testing machine with a constant temperature bath set to 5°C. The length of the curable composition hanging from the tip of the glass rod was measured upon withdrawal. The test results are shown in Tables 1-3. The workability can be described as stringiness.

[0261] (Tensile test) The one-component curable composition obtained above was filled into a polyethylene mold to a thickness of 3 mm, ensuring no air bubbles were present, and cured at 23°C and 50% RH for 3 days, followed by 50°C for 4 days. From the resulting 3 mm thick cured sheet, a No. 3 dumbbell-shaped test specimen was punched out. Using this test specimen, a tensile test (tensile speed 200 mm / min) was performed at 23°C (50% RH), and the 50% modulus, 100% modulus, strength at break (breaking strength), and elongation at break (elongation at break) were measured. If curing did not occur (uncured), it was recorded as "unmeasurable". The test results are shown in Tables 1-4.

[0262] (Compression recovery rate) The one-component curable composition obtained above was subjected to test procedures 1 to 6 of durability category 9030 as described in Table 2 - Durability Test Procedure of JIS A1439 (2016 edition) 5.12. The measured values ​​thereafter were used to calculate the following formula.

[0263] Specifically, an H-shaped test specimen with a joint width of 12 mm was prepared using an aluminum plate as the substrate and a commercially available primer (Cemedine, product name: MP-1000) as the primer, and cured at 23°C for 14 days (50% RH) + 30°C for 14 days. Next, the H-shaped test specimen was immersed in 50°C hot water for 24 hours, and then left at 23°C for 24 hours (50% RH). After that, the H-shaped test specimen was compressed by 30% and fixed at 90°C for 7 days (168 hours). After that, the H-shaped test specimen was released at 23°C (i.e., the compression was released) and left for 24 hours (50% RH), and the recovery rate was measured. A higher recovery rate indicates better recovery performance. If hardening did not occur (uncured), it was recorded as "unmeasurable". The test results are shown in Tables 1 to 4.

[0264] Compression recovery rate (%) = (L2 - L1 / L0 - L1) × 100 Here, L0: Thickness of the curable composition in the compression direction before heating and compression. L1: Thickness of the curable composition in the compression direction during heat compression. L2: Conduct Test Procedures 1 to 6 of JIS A1439 Durability Classification 9030, and measure the thickness in the compression direction of the curable composition after leaving it standing at 23°C and 50% RH for 1 day (24 hours).

[0265] (Durability Test) For the one-component curable composition obtained above, an aluminum plate was used as the adherend and a commercially available primer (manufactured by Cemedine, product name: MP-1000) was used as the primer, and the test was conducted in accordance with Durability Classification 9030 described in Table 2 - Durability Test Procedures of JIS A1439 (2016 Edition) 5.12 Durability Test.

[0266] For the evaluation of the durability test, after conducting Test Procedures 1 to 9 described in the above JIS, the state of cracks at the adhesion interface between the adherend and the cured product was visually observed. Those without cracks were judged as qualified, and those with cracks were judged as unqualified. The test results are shown in Tables 1 to 4.

[0267] [Table 1]

[0268] [Table 2] [[ID=CHINESE]]

[0269] [Table 3]

[0270] [Table 4]

[0271] As can be seen from Tables 1 to 4, it can be seen that the curable compositions according to one embodiment of the present invention (Examples 1 to 9) pass Durability Classification 9030 in Table 4 - Durability of JIS A5758 (2016 Edition) 4.2 C). Furthermore, it can be seen that the compression recovery rate is also good. [Industrial Applicability]

[0272] A curable composition according to one embodiment of the present invention exhibits excellent compression recovery rate, displacement following ability, and durability, and can provide a cured product applicable as a sealing material for working joints in buildings. Therefore, the curable composition according to one embodiment of the present invention can be suitably used as an adhesive, sealing material, bonding agent, molding agent, vibration damping material, soundproofing material, foaming material, paint, spray material, etc. In particular, the curable composition according to one embodiment of the present invention can be suitably used as a one-component curable composition for working joints.

Claims

1. (A) General formula (1): -SiX ３ ・・・(1) (In the formula, X independently represents either a hydroxyl group or a hydrolyzable group.) A polyoxyalkylene polymer having an average of 1.2 to 5 reactive silicon groups per molecule, represented by [the formula shown]. (D) Silane compounds obtained by partially condensing aminosilane compounds having reactive silicon groups, or silane compounds obtained by partially condensing an aminosilane compound having reactive silicon groups with an alkoxysilane compound other than aminosilane, and (E) Tetravalent organotin compounds, Optionally, (B) General formula (2): -SiR 1 3-a X a ... (2) (In the formula, R1 independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. X is the same as in general formula (1). a represents an integer from 1 to 3.) A reactive plasticizer which is a polyoxyalkylene polymer having an average of 0.5 to less than 1.2 reactive silicon groups per molecule, represented by [the formula shown]. A method for producing a curable composition for working joints, comprising: The polyoxyalkylene polymer of component (A) has a trimethoxysilyl terminus, Mix the aforementioned component (A), the aforementioned component (D), optionally the aforementioned component (B), and the aforementioned component (E) in an amount of 0.05 parts by weight or more and less than 1 part by weight per 100 parts by weight of the total of the aforementioned components (A) and (B). A method comprising the step of kneading the obtained mixture to prepare a one-component type (excluding component (D) that has not condensed during mixing).

2. The method according to claim 1, wherein component (B) is added in the above step.

3. The method according to claim 2, wherein the polyoxyalkylene polymer of component (B) has one reactive silicon group represented by general formula (2) in one molecule.

4. The method according to claim 2 or 3, wherein component (B) is obtained by reacting an alkylene oxide with an initiator having only one hydroxyl group in one molecule, and then introducing a reactive silicon group represented by general formula (2) into a polyoxyalkylene precursor polymer having only one functional group capable of introducing a reactive silicon group (B').

5. The method according to any one of claims 2 to 4, wherein the component (B) is obtained by introducing a reactive silicon group represented by general formula (2) into a polyoxyalkylene precursor polymer mixture having a functional group capable of introducing a reactive silicon group, which is obtained by reacting an alkylene oxide with a mixture of an initiator having only one hydroxyl group in one molecule and an initiator having two or more hydroxyl groups in one molecule.

6. A method for manufacturing a joint structure, comprising the step of filling a working joint of a building with a one-component curable composition for working joints obtained by the method described in any one of claims 1 to 5, and curing it.

7. A construction method comprising the step of filling a working joint of a building with a one-component curable composition for working joints obtained by the method described in any one of claims 1 to 5, and allowing it to harden.

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