Curable composition

Abstract

Provided are a curable composition exhibiting good curability, and a cured product of the curable composition.　This curable composition comprises a polyoxyalkylene polymer having a reactive silicon group, a specific (meth)acrylic copolymer having a reactive silicon group, and a curing catalyst. The polyoxyalkylene polymer has a predetermined high ratio of a silicon-containing group that may be produced by a hydrosilylation reaction between an allyl group and a hydrosilane compound and has a number average molecular weight of more than 3,000.

Description

curable composition

[0001] The present invention relates to a curable composition containing a polyoxyalkylene polymer, and a cured product of the curable composition.

[0002] Organic polymers having at least one hydrolyzable silyl group in the molecule can be crosslinked by forming siloxane bonds accompanied by hydrolysis of the silyl group due to moisture or the like, even at room temperature. Polyoxyalkylene polymers having hydrolyzable silyl groups are widely used as such organic polymers. Organic polymers having hydrolyzable silyl groups are known to have the property of giving rubber-like cured products through such crosslinking reactions.

[0003] An organic polymer having a hydrolyzable silyl group is produced, for example, by a hydrosilylation reaction between an organic polymer having an allyl group at its terminal and a hydrosilane compound that provides a hydrolyzable silyl group. In this method, a Karstedt catalyst (platinum divinyldisiloxane complex) is often used as a catalyst for the hydrosilylation reaction (see, for example, Synthesis Example 2-1 of Patent Document 1).

[0004] Also known is a curable composition that combines both a reactive silicon group-containing polyoxyalkylene polymer and a reactive silicon group-containing (meth)acrylic acid ester copolymer in order to improve the balance between the elongation and strength of the resulting cured product and the adhesiveness and weather resistance.

[0005] Japanese Patent Application Laid-Open No. 2021-75722

[0006] However, when a curable composition containing an organic polymer having a hydrolyzable silyl group is cured using a Karstedt catalyst, there is room for improvement in the curing speed.

[0007] Therefore, an object of the present invention is to provide a curable composition that exhibits good curability and a cured product of the curable composition.

[0008] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that, in a curable composition comprising a polyoxyalkylene polymer having a reactive silicon group, a specific (meth)acrylic copolymer having a reactive silicon group, and a curing catalyst, the above problems can be solved by using a polyoxyalkylene polymer having a predetermined high proportion of silicon-containing groups that can be generated by a hydrosilylation reaction between allyl groups and a hydrosilane compound and having a number-average molecular weight of more than 3,000, thereby completing the present invention.

[0009] That is, the present invention provides a composition comprising a polyoxyalkylene polymer (A) having a reactive silicon group, a (meth)acrylic copolymer (B) having a reactive silicon group, and a curing catalyst (C), wherein the polyoxyalkylene polymer (A) is a compound represented by the following formula (1): (1) (in formula (1), R is a substituted or unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, and a is 0, 1, or 2), the number average molecular weight of the polyoxyalkylene polymer (A) is more than 3,000, and the total number N of the reactive silicon groups, 1-propenyl groups, propyl groups, and allyl groups in the polyoxyalkylene polymer (A) is 0. ｔ The number N of silicon-containing groups (a1) relative to ａ１ Ratio N ａ１ / N ｔ is 0.85 or more and 1.00 or less, the molecular chain of the (meth)acrylic copolymer (B) contains units derived from two or more types of alkyl (meth)acrylate, and the reactive silicon group of the (meth)acrylic copolymer (B) is represented by the following formula (2): —SiR １ ａ X ３－ａ (2) (In formula (2), R １ , X, and a are R in formula (1). １ , X, and a are the same as those in the formula (1).

[0010] According to the present invention, it is possible to provide a curable composition that exhibits good curability and a cured product of the curable composition.

[0011] The present invention will be described in detail below.

[0012] <Curable Composition> The curable composition contains a polyoxyalkylene polymer (A) having a reactive silicon group, a (meth)acrylic copolymer (B) having a reactive silicon group, and a curing catalyst (C). In the specification and claims of the present application, "(meth)acrylic" encompasses both "acrylic" and "methacrylic."

[0013] Here, the reactive silicon group is a silicon atom-containing group that has a silanol group or can generate a silanol group by hydrolysis. When the reactive silicon group has a silanol group, the molecules of the polyoxyalkylene polymer are condensed by a condensation reaction between the silanol groups. When the reactive silicon group has a hydrolyzable group that can generate a silanol group by hydrolysis, after the reactive silicon group is hydrolyzed, the molecules of the polyoxyalkylene polymer are condensed by a condensation reaction between the silanol groups.

[0014] The polyoxyalkylene polymer (A) has a number average molecular weight of more than 3,000.

[0015] The polyoxyalkylene polymer (A) has a silicon-containing group (a1) represented by the following formula (1). (1) In formula (1), R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, and a is 0, 1, or 2.

[0016] In the polyoxyalkylene polymer (A), the total number N of reactive silicon groups, 1-propenyl groups, propyl groups, and allyl groups is ｔ The number N of silicon-containing groups (a1) relative to ａ１ Ratio N ａ１ / N ｔ is 0.85 or more and 1.00 or less.

[0017] The molecular chain of the (meth)acrylic copolymer (B) is composed of units derived from two or more types of alkyl (meth)acrylates.

[0018] The reactive silicon group contained in the (meth)acrylic copolymer (B) is a group represented by the following formula (2): —SiR １ ａ X ３－ａ (2) In formula (2), R １ , X, and a are R in formula (1). １ , X, and a.

[0019] The above curable composition exhibits good curability.

[0020] Essential and optional components that may be included in the curable composition are described below.

[0021] <Polyoxyalkylene Polymer (A)> The polyoxyalkylene polymer (A) has a reactive silicon group. As described above, the number average molecular weight of the polyoxyalkylene polymer (A) is greater than 3,000. Here, the number average molecular weight is a polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC).

[0022] The number average molecular weight of the polyoxyalkylene polymer (A) is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more. There is no particular upper limit to the number average molecular weight of the polyoxyalkylene polymer (A). The number average molecular weight of the polyoxyalkylene polymer (A) may be, for example, 100,000 or less, and preferably 50,000 or less. The number average molecular weight of the polyoxyalkylene polymer (A) is preferably 5,000 or more and 100,000 or less, more preferably 10,000 or more and 100,000 or less, even more preferably 10,000 or more and 50,000 or less, and particularly preferably 20,000 or more and 50,000 or less.

[0023] The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) of the polyoxyalkylene polymer (A) is not particularly limited. It is preferable that the molecular weight distribution is narrow. Specifically, the molecular weight distribution is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, still more preferably 1.4 or less, and most preferably 1.3 or less. The weight average molecular weight is also measured by GPC.

[0024] The polyoxyalkylene polymer (A) has a polyoxyalkylene skeleton, which is preferably a skeleton composed only of a plurality of oxyalkylene repeating units, or a skeleton composed only of a plurality of oxyalkylene repeating units and units derived from an initiator used in the polymerization.

[0025] The number of carbon atoms in the oxyalkylene repeating unit is preferably 2 or more and 6 or less, and more preferably 2 or more and 4 or less.

[0026] The molecular chain structure of the polyoxyalkylene polymer (A) may be either linear or branched.

[0027] The polyoxyalkylene polymer (A) may contain linear molecules and branched molecules.

[0028] Linear molecules are preferred because they provide good elongation of the cured product of the curable composition, as described below, whereas branched molecules are preferred because they provide good strength of the curable composition, as described below.

[0029] The linear molecular structure is formed by ring-opening polymerization of a cyclic ether compound using an initiator having one or two hydroxyl groups per molecule, while the branched molecular structure is formed by ring-opening polymerization of an alkylene oxide using an initiator having three or more hydroxyl groups per molecule.

[0030] The polyoxyalkylene polymer skeleton is not particularly limited. Specific examples of suitable polyoxyalkylene polymer skeletons include a polyoxyethylene skeleton, a polyoxypropylene skeleton, a polyoxybutylene skeleton, a polyoxytetramethylene skeleton, a polyoxyethylene-polyoxypropylene copolymer skeleton, and a polyoxypropylene-polyoxybutylene copolymer skeleton. Of these skeletons, a polyoxypropylene skeleton is preferred. The polyoxyalkylene polymer (A) may contain only molecules having one type of polyoxyalkylene skeleton, or may contain multiple types of molecules having different types of polyoxyalkylene skeletons.

[0031] When the curable composition is used as a sealant, adhesive, or the like, the ratio of the mass of oxypropylene repeating units to the mass of the polyoxyalkylene skeleton in the polyoxyalkylene polymer (A) is preferably 50 mass% or more, more preferably 80 mass% or more. In this case, the polyoxyalkylene polymer (A) is amorphous. Furthermore, the viscosity of the polyoxyalkylene polymer (A) tends to be low.

[0032] The polyoxyalkylene skeleton in the polyoxyalkylene polymer (A) can be formed by ring-opening polymerization of a cyclic ether compound using a polymerization catalyst in the presence of an initiator according to a conventionally known method. Such ring-opening polymerization produces a polyoxyalkylene polymer having a terminal hydroxyl group. The polyoxyalkylene polymer (A) having a terminal reactive silicon group can be obtained by the method described below using the polyoxyalkylene polymer having a terminal hydroxyl group as a raw material.

[0033] Examples of methods for producing polyoxyalkylene polymers include a polymerization method using an alkali catalyst such as KOH, a polymerization method using a transition metal compound-porphyrin complex catalyst such as the complex obtained by reacting an organoaluminum compound with porphyrin disclosed in JP-A-61-215623, a polymerization method using a composite metal cyanide complex catalyst disclosed in JP-B-46-27250, JP-B-59-15336, U.S. Pat. Nos. 3,278,457, 3,278,458, 3,278,459, 3,427,256, 3,427,334, and 3,427,335, a polymerization method using a catalyst made of a polyphosphazene salt exemplified in JP-A-10-273512, and a polymerization method using a catalyst made of a phosphazene compound exemplified in JP-A-11-060722. A method of ring-opening polymerization of a cyclic ether compound using a composite metal cyanide complex catalyst such as zinc hexacyanocobaltate glyme complex is preferred because it is easy to obtain a polyoxyalkylene polymer having a narrow molecular weight distribution (Mw / Mn).

[0034] Examples of the cyclic ether compound include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and tetrahydrofuran. As the cyclic ether compound, only one type may be used, or two or more types may be used in combination. Among the cyclic ether compounds, propylene oxide is particularly preferred because it is easy to obtain an amorphous, low-viscosity polyoxyalkylene polymer.

[0035] The initiator is not particularly limited. Specific preferred examples of the initiator include monools such as butanol and propylene glycol monoalkyl ether, glycols such as ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, and triethylene glycol, and polyols having three or more hydroxyl groups such as glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, and sorbitol.

[0036] Alternatively, a hydroxyl-terminated polyoxyalkylene polymer having a number average molecular weight of 300 to 4000 can be used as the initiator. Specific examples of the hydroxyl-terminated polyoxyalkylene polymer include polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene diol, and polyoxyethylene triol.

[0037] The polyoxyalkylene polymer (A) is represented by the following formula (1): (1) (in formula (1), R is a substituted or unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, and a is 0, 1, or 2).

[0038] The polyoxyalkylene polymer (A) usually has a plurality of silicon-containing groups (a1). The plurality of silicon-containing groups (a1) in the polyoxyalkylene polymer (A) may be the same group or two or more different groups. Furthermore, when a plurality of Rs are present in formula (1), the plurality of Rs may be the same group or two or more different groups. When a plurality of Xs are present in formula (1), the plurality of Xs may be the same group or two or more different groups.

[0039] The silicon-containing group (a1) is introduced into the polyoxyalkylene polymer (A) by a hydrosilylation reaction between a polyoxyalkylene polymer having an allyl group and a hydrosilane compound. The hydrosilane compound may be a compound represented by the following formula (1-1): HSiR １ ａ X ３－ａ The hydrosilane compound represented by formula (1-1) undergoes a hydrosilylation reaction with an allyl group in the polyoxyalkylene polymer to give the silicon-containing group (a1) represented by formula (1).

[0040] The polyoxyalkylene polymer (A) may have one or more of an allyl group, a 1-propenyl group, and a propyl group. The allyl group is an unreacted allyl group. The 1-propenyl group may be produced by an internal isomerization reaction of an allyl group as a side reaction. The propyl group may be produced by a hydrogenation reaction of an allyl group as a side reaction.

[0041] In the above formula (1), the oxygen atom bonded to the trimethylene group is bonded to any position in the polyoxyalkylene skeleton of the polyoxyalkylene polymer. The bonding position of the oxygen atom is not particularly limited. The oxygen atom may be bonded not only to the terminal of the polyoxyalkylene skeleton, but also to a position other than the terminal of the polyoxyalkylene skeleton. The bonding position of the oxygen atom is preferably only to the terminal of the polyoxyalkylene skeleton.

[0042] In formula (1), R １ R are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. １ The hydrocarbon group as R may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. １ The hydrocarbon group as R may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. １ The structure of the aliphatic hydrocarbon group constituting the hydrocarbon group as R may be linear, branched, cyclic, or a combination of these structures. １ The number of carbon atoms in the hydrocarbon group as is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, even more preferably 1 or more and 6 or less, even more preferably 1 or more and 3 or less, and particularly preferably 1 or 2.

[0043] R １When the hydrocarbon group has a substituent, the type of the substituent is not particularly limited as long as the desired effect is not impaired. Specific examples of the substituent include halogen atoms such as chlorine and bromine, alkoxy groups such as methoxy and ethoxy, and substituted or unsubstituted amino groups such as amino, N-methylamino, N-ethylamino, N,N-dimethylamino, and N,N-diethylamino.

[0044] R １ Specific examples of the substituted or unsubstituted hydrocarbon group as the substituent include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-hexyl group, a 2-ethylhexyl group, and an n-dodecyl group; cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group; substituted alkyl groups such as a chloromethyl group, a methoxymethyl group, and an N,N-diethylaminomethyl group; alkenyl groups such as a vinyl group, an isopropenyl group, and an allyl group; aryl groups such as a phenyl group, a toluyl group, a naphthalen-1-yl group, and a naphthalen-2-yl group; and aralkyl groups such as a benzyl group and a phenethyl group.

[0045] Of the above-mentioned substituted or unsubstituted hydrocarbon groups, alkyl groups and substituted alkyl groups are preferred, with methyl groups, ethyl groups, chloromethyl groups and methoxymethyl groups being more preferred, and methyl groups being particularly preferred.

[0046] X in formula (1) is a hydroxyl group or a hydrolyzable group. The hydrolyzable group is not particularly limited and may be a known hydrolyzable group. Specific examples of the hydrolyzable group include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, an alkoxy group, an acyloxy group, a ketoximate group, and an alkenyloxy group are preferred, and an alkoxy group such as a methoxy group and an ethoxy group is more preferred because of its mild hydrolysis and ease of handling.

[0047] In formula (1), a is 0, 1, or 2. In terms of curability, a is preferably 0 or 1.

[0048] In the group represented by formula (1), —SiR １ ａ X ３－ａ Preferred specific examples of the group represented by the formula (I) include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a (chloromethyl)dimethoxysilyl group, a (chloromethyl)diethoxysilyl group, a (methoxymethyl)dimethoxysilyl group, a (methoxymethyl)diethoxysilyl group, an (N,N-diethylaminomethyl)dimethoxysilyl group, and an (N,N-diethylaminomethyl)diethoxysilyl group.

[0049] Of these groups, trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, and (methoxymethyl)dimethoxysilyl are preferred in that they are likely to give a cured product with good mechanical properties. １ ａ X ３－ａ As the group represented by the formula (I), a trimethoxysilyl group, a (chloromethyl)dimethoxysilyl group, and a (methoxymethyl)dimethoxysilyl group are preferred, and a trimethoxysilyl group and a (methoxymethyl)dimethoxysilyl group are more preferred. １ ａ X ３－ａ As the group represented by the formula (I), a dimethoxymethylsilyl group and a triethoxysilyl group are more preferred, and a dimethoxymethylsilyl group is particularly preferred.

[0050] In the polyoxyalkylene polymer (A), the total number N of reactive silicon groups, 1-propenyl groups, propyl groups, and allyl groups is ｔ The number N of silicon-containing groups (a1) relative to ａ１ Ratio N ａ１ / N ｔ In the polyoxyalkylene polymer (A), N ａ１ / N ｔ is preferably 0.90 or more and 1.00 or less, and more preferably 0.95 or more and 1.00 or less.

[0051] The method for producing the polyoxyalkylene polymer (A) will be described in detail later, but the polyoxyalkylene polymer (A) is produced by a hydrosilylation reaction using a ruthenium complex as a catalyst, and therefore the polyoxyalkylene polymer (A) may contain the ruthenium complex (B) used as the catalyst.

[0052] The method for producing the polyoxyalkylene polymer (A) will be described below.

[0053] The polyoxyalkylene polymer (A) described above can be produced by a method comprising hydrosilylation of a polyoxyalkylene polymer having an allyl group with a hydrosilane compound in the presence of a ruthenium complex (D).

[0054] The polyoxyalkylene polymer having an allyl group is prepared using a polyoxyalkylene polymer having a hydroxyl group, which is obtained by ring-opening polymerization of a cyclic ether compound by the method described above.

[0055] In order to introduce allyl groups into the terminal hydroxyl groups of the polyoxyalkylene polymer, the terminal hydroxyl groups are reacted with an alkali metal compound to convert the terminal hydroxyl groups into alkali metal alcoholates. A composite metal cyanide complex catalyst can also be used instead of the alkali metal compound.

[0056] Specific examples of alkali metal compounds include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide; and alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, sodium tert-butoxide, and potassium tert-butoxide. Among these, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred, with sodium methoxide and sodium tert-butoxide being more preferred. In terms of availability, sodium methoxide is particularly preferred. In terms of reactivity, sodium tert-butoxide is particularly preferred. The alkali metal compound may be subjected to the reaction in the form of a solution.

[0057] The amount of the alkali metal compound used is not particularly limited as long as it can introduce a desired amount of allyl groups into the hydroxyl groups of the polyoxyalkylene polymer. The amount of the alkali metal compound used is preferably 0.5 mol or more, more preferably 0.6 mol or more, even more preferably 0.7 mol or more, and even more preferably 0.8 mol or more, per 1.0 mol of hydroxyl groups of the polyoxyalkylene polymer. The amount of the alkali metal compound used is preferably 1.2 mol or less, more preferably 1.1 mol or less, per 1.0 mol of hydroxyl groups of the polyoxyalkylene polymer. Therefore, the amount of the alkali metal compound used is preferably 0.5 mol or more to 1.2 mol or less, more preferably 0.6 mol or more to 1.2 mol or less, more preferably 0.7 mol or more to 1.1 mol or less, and particularly preferably 0.8 mol or more to 1.1 mol or less, per 1.0 mol of hydroxyl groups of the polyoxyalkylene polymer.

[0058] In order to ensure that the reaction between the hydroxyl groups of the polyoxyalkylene polymer and the alkali metal compound proceeds smoothly, it is preferable to remove water and alcohol other than the polyoxyalkylene polymer having hydroxyl groups from the reaction solution containing the polyoxyalkylene polymer and the alkali metal compound in advance. Various known methods can be used to remove water and alcohol. Specifically, a method selected from the group consisting of thermal evaporation, reduced pressure devolatilization, spray evaporation, thin film evaporation, and azeotropic devolatilization can be used.

[0059] The temperature at which the hydroxyl groups of the polyoxyalkylene polymer are reacted with the alkali metal compound is not particularly limited as long as the reaction proceeds smoothly. The reaction temperature is preferably 50° C. or higher and 150° C. or lower, more preferably 110° C. or higher and 145° C. or lower. The reaction time between the hydroxyl groups of the polyoxyalkylene polymer and the alkali metal compound is preferably 10 minutes or higher and 5 hours or lower, more preferably 30 minutes or higher and 3 hours or lower.

[0060] The polyoxyalkylene polymer in which the hydroxyl groups have been converted to alkali metal alcoholates as described above is reacted with an allyl halide to obtain a polyoxyalkylene polymer having allyl groups.

[0061] Specific examples of allyl halides include allyl chloride, allyl bromide, allyl iodide, etc. Among these, allyl chloride is preferred from the viewpoint of ease of handling.

[0062] The amount of allyl halide used is not particularly limited as long as a desired amount of allyl groups is introduced into the polyoxyalkylene polymer. The amount of allyl halide used is preferably 0.7 mol or more, more preferably 1.0 mol or more, per 1.0 mol of terminal hydroxyl groups of the polyoxyalkylene polymer used to prepare the polyoxyalkylene polymer whose hydroxyl groups have been alcoholated with an alkali metal. The amount of allyl halide used is preferably 5.0 mol or less, more preferably 2.0 mol or less, per 1.0 mol of terminal hydroxyl groups of the polyoxyalkylene polymer used to prepare the polyoxyalkylene polymer whose hydroxyl groups have been alcoholated with an alkali metal. Therefore, the amount of allyl halide used is preferably 0.7 mol or more and 5.0 mol or less, more preferably 1.0 mol or more and 2.0 mol or less, per 1.0 mol of terminal hydroxyl groups of the polyoxyalkylene polymer used to prepare the polyoxyalkylene polymer whose hydroxyl groups have been alcoholated with an alkali metal.

[0063] The reaction temperature between the polyoxyalkylene polymer whose hydroxyl groups have been alcoholated with an alkali metal and the allyl halide is preferably 50° C. or higher and 150° C. or lower, more preferably 110° C. or higher and 140° C. The reaction time between the polyoxyalkylene polymer whose hydroxyl groups have been alcoholated with an alkali metal and the allyl halide is preferably 10 minutes or higher and 5 hours or lower, more preferably 30 minutes or higher and 3 hours or lower.

[0064] The polyoxyalkylene polymer having an allyl group obtained as described above is subjected to hydrosilylation with a hydrosilane compound to produce a polyoxyalkylene polymer (A) having a reactive silicon group. ａ１ / N ｔ When the value of is 0.85 or more and 1.00 or less, the hydrosilylation is preferably carried out in the presence of a ruthenium complex (D).

[0065] The polyoxyalkylene polymer (A) has a silicon-containing group (a1) represented by the above formula (1).

[0066] Therefore, the hydrosilane compound is preferably a compound represented by the following formula (1-1): HSiR １ ａ X ３－ａ The hydrosilane compound represented by formula (1-1) undergoes a hydrosilylation reaction with an allyl group in the polyoxyalkylene polymer to give the silicon-containing group (a1) represented by formula (1).

[0067] Specific examples of the hydrosilane compound represented by formula (1-1) include trimethoxysilane, triethoxysilane, triphenoxysilane, tris(2-propenyloxy)silane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, (methoxymethyl)dimethoxysilane, (methoxymethyl)diethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, and diphenoxymethylsilane.

[0068] In terms of the curability of the polyoxyalkylene polymer (A) and the strength of the cured product, trimethoxysilane and dimethoxymethylsilane are particularly preferred as the hydrosilane compound.

[0069] The amount of the hydrosilane compound used is preferably 1.0 mol or more, more preferably 3.0 mol or more, and even more preferably 5.0 mol or more, per 1.0 mol of allyl groups in the polyoxyalkylene polymer. The amount of the hydrosilane compound used is preferably 20.0 mol or less, and more preferably 10.0 mol or less, per 1.0 mol of allyl groups in the polyoxyalkylene polymer. Therefore, the amount of the hydrosilane compound used is preferably 1.0 mol or more and 20.0 mol or less, more preferably 3.0 mol or more and 20.0 mol or less, and even more preferably 5.0 mol or more and 10.0 mol or less, per 1.0 mol of allyl groups in the polyoxyalkylene polymer. When the hydrosilane compound is used in an amount within the above range, a polyoxyalkylene polymer (A) that has a low viscosity and is easy to handle is easily obtained.

[0070] The ruthenium complex (D) is not particularly limited as long as it is a complex compound that contains a ruthenium atom and that effectively promotes the above-mentioned hydrosilylation reaction.

[0071] The ruthenium complex (D) is preferably a complex compound having a ligand (D1) derived from compound (E). Compound (E) has at least one carbon-carbon double bond and at least one electron-withdrawing group per molecule. Here, the carbon-carbon double bond possessed by compound (E) may be an ethylenic carbon-carbon double bond or an aromatic carbon-carbon double bond. Furthermore, in compound (E), at least one of the electron-withdrawing groups is bonded to a carbon atom constituting the carbon-carbon double bond.

[0072] The type of the ligand (D1) contained in the ruthenium complex (D) may be one type or two or more types.

[0073] Examples of the electron-withdrawing group contained in compound (E) include halogen atoms such as a fluoro group, a chloro group, a bromo group, and an iodo group, a cyano group, an aldehyde group, and a nitro group. When multiple electron-withdrawing groups are present in the same molecule, the multiple electron-withdrawing groups may be the same or different. Compound (E) has one or more, preferably two or more, more preferably two to four, and even more preferably two or three electron-withdrawing groups in one molecule.

[0074] The electron-withdrawing group is preferably a halogen atom, and more preferably one or more selected from the group consisting of a fluoro group, a bromo group, and an iodo group. The electron-withdrawing group is more preferably a bromo group or an iodo group, and even more preferably a bromo group. In particular, compound (E) preferably has one or more, more preferably two or more, electron-withdrawing groups selected from a fluoro group, a bromo group, and an iodo group per molecule. Compound (E) preferably has one or more electron-withdrawing groups selected from a bromo group and an iodo group per molecule. In this case, compound (E) may have a fluoro group in addition to a bromo group and / or an iodo group. These electron-withdrawing groups are directly bonded to the carbon atoms constituting the carbon-carbon double bond in compound (E).

[0075] Compound (E) typically includes compounds having a cyclic skeleton. The cyclic skeleton may be a monocyclic skeleton consisting of only one monocycle, such as a cyclooctadiene skeleton, a benzene ring skeleton, or a cyclooctadiene skeleton; a polycyclic skeleton in which two or more monocycles are fused or bonded via a single bond, such as a naphthalene ring skeleton or a biphenyl skeleton; or a bridged aliphatic cyclic skeleton, such as a norbornadiene ring. Substituents such as the electron-withdrawing groups described above may be bonded to these skeletons. For example, 1,4-dibromobenzene is a compound having a benzene ring skeleton bonded to a bromo group as a substituent. Compound (E) is preferably a compound having a norbornadiene skeleton, a cyclooctadiene skeleton, a benzene skeleton, or a benzoquinone skeleton. More specifically, compounds having a 2,5-norbornadiene skeleton, a 1,5-cyclooctadiene skeleton, a p-cymene skeleton, a mesitylene skeleton, a benzene skeleton, or a benzoquinone skeleton are preferred, and compounds having a benzene ring skeleton or a norbornadiene skeleton are more preferred. The benzene ring skeleton is a skeleton consisting of one benzene ring, and the norbornadiene skeleton is a skeleton consisting of one norbornadiene ring.

[0076] Specific preferred examples of compound (E) include 2-bromonorbornadiene, 2,3-dibromonorbornadiene, 1,4-dibromobenzene, structural isomers of 1,4-dibromobenzene, 1,3,5-tribromobenzene, structural isomers of 1,3,5-tribromobenzene, 1,2,4,5-tetrabromobenzene, structural isomers of 1,2,4,5-tetrabromobenzene, hexabromobenzene, 1-bromo-3,5- Difluorobenzene, structural isomers of 1-bromo-3,5-difluorobenzene, 1-bromo-3,5-dichlorobenzene, structural isomers of 1-bromo-3,5-dichlorobenzene, 1-bromo-3-chloro-5-fluorobenzene, structural isomers of 1-bromo-3-chloro-5-fluorobenzene, 1,4-diiodobenzene, structural isomers of 1,4-diiodobenzene, 1,3,5-triiodobenzene, 1,3, Structural isomers of 5-triiodobenzene, 1,2,4,5-tetraiodobenzene, structural isomers of 1,2,4,5-tetraiodobenzene, hexaiodobenzene, 1,3-difluoro-5-iodobenzene, structural isomers of 1,3-difluoro-5-iodobenzene, 1,3-dichloro-5-iodobenzene, structural isomers of 1,3-dichloro-5-iodobenzene, 1,3-dibromo-5-iodobenzene, structural isomers of 1,3-dibromo-5-iodobenzene, 1-chloro-3-fluoro-5-iodobenzene, structural isomers of 1-chloro-3-fluoro-5-iodobenzene, 1-bromo-3-chloro-5-iodobenzene, structural isomers of 1-bromo-3-chloro-5-iodobenzene, 1-bromo-3-fluoro-5-iodobenzene, and structural isomers of 1-bromo-3-fluoro-5-iodobenzene.

[0077] Among these compounds, one or more selected from the group consisting of 2,3-dibromonorbornadiene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene, and 1,3,5-tribromobenzene are preferred as compound (E) in terms of the efficiency of conversion of the allyl group to the silicon-containing group (a1).

[0078] Ruthenium complex (D) can be produced by a known production method. Examples of raw materials for ruthenium complex (D) include anhydrides and hydrates of compounds selected from ruthenium(III) chloride, ruthenium(III) bromide, and ruthenium(III) iodide. For example, ruthenium complex (D) can be produced specifically by the following production method. First, compound (E) is added to an ethanol solution of ruthenium(III) chloride hydrate, and the mixture is heated to reflux. Solids in the reaction solution are then recovered by filtration. The recovered solids are dried to obtain ruthenium complex (D). When ruthenium(III) chloride hydrate is used as a raw material, a reaction solution to which a basic compound such as sodium carbonate or sodium bicarbonate has been added may be heated to reflux in order to neutralize hydrogen chloride generated during heating to reflux. When ruthenium(III) chloride hydrate is reacted with compound (E), it is preferable to use at least 1 molar equivalent of compound (E) relative to the raw ruthenium compound in terms of reaction rate. The ruthenium complex (D) may be a nanoparticle catalyst. The particle size (cumulative median diameter) of the nanoparticles of the ruthenium complex (D) is not particularly limited as long as the hydrosilylation reaction proceeds to the desired extent. The particle size is preferably 0.3 nm or more and 200 nm or less. The lower limit of the particle size is preferably 0.5 nm or more, more preferably 1 nm or more. The upper limit of the particle size is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 10 nm or less. Therefore, the particle size of the nanoparticles of the ruthenium complex (D) is more preferably 0.5 nm or more and 100 nm or less, even more preferably 0.5 nm or more and 50 nm or less, and particularly preferably 1 nm or more and 10 nm or less. The cumulative median diameter can be measured using a transmission electron microscope (TEM).

[0079] The ruthenium complex (D) may contain, in addition to the ligand (D1) derived from the compound (E), a ligand (D1) derived from a compound (E') that does not fall under the category of the compound (E). The compound (E') is a compound that can coordinate to a ruthenium atom and does not fall under the category of the compound (E). Specific examples of the ligand (D1) derived from the compound (E') include a 2,5-norbornadiene ligand, a 1,5-cyclooctadiene ligand, a p-cymene ligand, a mesitylene ligand, a benzene ligand, a carbonyl ligand, an isocyanide ligand, and an arene ligand.

[0080] When the ruthenium complex (D) has both the ligand (D1) derived from the compound (E) and the ligand (D1) derived from the compound (E'), a higher proportion of the ligand (D1) derived from the compound (E) among all the ligands (D1) possessed by the ruthenium complex (D) is preferable because this allows for higher selectivity in converting an allyl group to a silicon-containing group (a1) in the hydrosilylation reaction. The ratio of the amount of the ligand (D1) derived from the compound (E) to the total amount of the ligands (D1) is preferably 1 mol % or more and 100 mol % or less, more preferably 50 mol % or more and 100 mol % or less, even more preferably 70 mol % or more and 100 mol % or less, and particularly preferably 90 mol % or more and 100 mol % or less.

[0081] In the hydrosilylation reaction, the ruthenium complex (D) may be produced by reacting the compound (E) with a ruthenium complex (D′) that does not have a ligand (D1) derived from the compound (E) in a reaction liquid.

[0082] The amount of the ruthenium complex (D) used in the hydrosilylation reaction is preferably 0.01 ppm by mass or more, more preferably 0.1 ppm by mass or more, and even more preferably 1 ppm by mass or more, relative to the mass of the polyoxyalkylene polymer having an allyl group. The amount of the ruthenium complex (D) used in the hydrosilylation reaction is preferably 10% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less, relative to the mass of the polyoxyalkylene polymer having an allyl group. The amount of ruthenium complex (D) used in the hydrosilylation reaction may be 0.01 to 10 ppm by mass, 0.1 to 10 ppm by mass, 1 to 10 ppm by mass, 0.01 to 1 ppm by mass, 0.1 to 1 ppm by mass, or 0.01 to 0.1 ppm by mass, relative to the mass of the polyoxyalkylene polymer having an allyl group. When the amount of ruthenium complex (D) used is within the above range, the allyl groups in the polyoxyalkylene polymer can be converted to silicon-containing groups (a1) with high efficiency.

[0083] The hydrosilylation reaction may be carried out in the presence or absence of a solvent. When a solvent is used, the type of solvent is not particularly limited. A compound with which the raw materials and catalyst do not react is used as the solvent. Specific examples of suitable solvents include hydrocarbon solvents such as hexane and hydrogen halide solvents such as dichloromethane. For the hydrosilylation reaction, it is preferable to use a solvent that is sufficiently dehydrated and deoxygenated.

[0084] The reaction temperature of the hydrosilylation reaction can be appropriately determined taking into consideration the reactivity (reaction rate), the heat resistance temperature of the reaction vessel, etc. The reaction temperature is preferably 0°C or higher, more preferably 20°C or higher, and even more preferably 40°C or higher. The reaction temperature is preferably 200°C or lower, more preferably 150°C or lower. In other words, the reaction temperature is preferably 0°C or higher and 200°C or lower, more preferably 20°C or higher and 200°C or lower, and even more preferably 40°C or higher and 150°C or lower. The higher the reaction temperature, the more likely it is that the reaction will be completed in a shorter time and side reactions will be suppressed.

[0085] The reaction time for the hydrosilylation reaction is not particularly limited as long as the reaction proceeds to the desired extent. The reaction temperature is preferably from 5 minutes to 12 hours, more preferably from 10 minutes to 5 hours.

[0086] The hydrosilylation reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon.

[0087] It is also preferred that the hydrosilylation be carried out in the presence of compound (E). That is, it is preferred that the hydrosilylation be carried out in the presence of ruthenium complex (D) and compound (E). In this case, allyl groups in the polyoxyalkylene polymer are easily converted to silicon-containing groups (a1) with high efficiency.

[0088] After the polyoxyalkylene polymer (A) is produced as described above, the polyoxyalkylene polymer is washed with water and, if necessary, volatile components are distilled off from the polyoxyalkylene polymer to obtain the polyoxyalkylene polymer (A).

[0089] <(Meth)acrylic copolymer (B)> The curable composition contains a (meth)acrylic copolymer having a reactive silicon group. The molecular chain of the (meth)acrylic copolymer (B) contains units derived from two or more types of alkyl (meth)acrylate. The reactive silicon group contained in the (meth)acrylic copolymer (B) is a group represented by the following formula (2): -SiR １ ａ X ３－ａ (2) In formula (2), R １ , X, and a are R in formula (1). １ , X, and a.

[0090] Specific examples of alkyl acrylates that provide units constituting the molecular chain of the (meth)acrylic copolymer include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-undecyl acrylate, lauryl acrylate, n-tridecyl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate, and behenyl acrylate.

[0091] Specific examples of alkyl methacrylates that provide units constituting the molecular chain of the (meth)acrylic copolymer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, n-undecyl methacrylate, lauryl methacrylate, n-tridecyl methacrylate, myristyl methacrylate, cetyl methacrylate, stearyl methacrylate, and behenyl methacrylate.

[0092] The molecular chain of the (meth)acrylic copolymer (B) contains two or more types of units derived from alkyl (meth)acrylate. The ratio of the mass of the units derived from alkyl (meth)acrylate to the mass of the molecular chain of the (meth)acrylic copolymer (B) is preferably 50 mass% or more, more preferably 70 mass% or more.

[0093] From the viewpoint of compatibility of the (meth)acrylic copolymer (B) with the polyoxyalkylene copolymer (A) and the like, and stability of the (meth)acrylic copolymer (B), it is preferable that the monomer for preparing the (meth)acrylic copolymer (B) contains two or more selected from alkyl acrylates (ai) having an alkyl group containing 1 to 8 carbon atoms and / or alkyl methacrylates (aii) having an alkyl group containing 1 to 8 carbon atoms, and alkyl acrylates (bi) having an alkyl group containing 10 or more carbon atoms and / or alkyl methacrylates (bii) having an alkyl group containing 10 or more carbon atoms.

[0094] The alkyl acrylate (ai) having an alkyl group with 1 to 8 carbon atoms and the alkyl methacrylate (aii) having an alkyl group with 1 to 8 carbon atoms are represented by the following formula (B1): CH ２ =CR ｂ１ COOR ｂ２ (B1) In formula (B1), R ｂ１ is a hydrogen atom or a methyl group. ｂ２ is an alkyl group having 1 to 8 carbon atoms.

[0095] In formula (B1), R ｂ２ Examples of R include alkyl groups having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a tert-butyl group, and a 2-ethylhexyl group. ｂ２ The number of carbon atoms in the alkyl group as the alkyl group is more preferably 1 or more and 4 or less, and further preferably 1 or 2.

[0096] The alkyl acrylate (bi) having an alkyl group with 10 or more carbon atoms and the alkyl methacrylate (bii) having an alkyl group with 10 or more carbon atoms are represented by the following formula (B2): CH ２ =CR ｂ３ COOR ｂ４ (B2) In formula (B2), R ｂ３ is a hydrogen atom or a methyl group. ｂ４ is an alkyl group having 10 or more carbon atoms.

[0097] In formula (2), R ｂ４ R is an alkyl group having 10 or more carbon atoms, such as a lauryl group, an n-tridecyl group, a cetyl group, and a stearyl group. ｂ４ The number of carbon atoms in the alkyl group is more preferably 10 or more and 30 or less, and even more preferably 10 or more and 20 or less.

[0098] In the (meth)acrylic copolymer (B), the ratio Wb1:Wb2 of the mass Wb1 of the units (b1) derived from an alkyl (meth)acrylate represented by formula (B1) to the mass Wb2 of the units (b2) derived from an alkyl (meth)acrylate represented by formula (B2) is preferably 95:5 to 40:60, more preferably 90:10 to 60:40.

[0099] The monomer for producing the (meth)acrylic copolymer (B) may contain a monomer other than alkyl (meth)acrylate. Examples of such other monomers include acrylic acid and methacrylic acid; (meth)acrylamides such as acrylamide, methacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide; epoxy group-containing (meth)acrylic acid ester diesters such as glycidyl acrylate and glycidyl methacrylate; amino group-containing unsaturated compounds such as 2-(N,N-diethylamino)ethyl methacrylate and 2-aminoethyl vinyl ether; acrylonitrile and methacrylonitrile; styrenes such as styrene and α-methylstyrene; alkyl vinyl ethers; vinyl chloride; and fatty acid vinyl esters such as vinyl acetate and vinyl propionate.

[0100] The molecular weight of the (meth)acrylic copolymer (B) is not particularly limited as long as the desired effect is not impaired. The molecular weight of the (meth)acrylic copolymer (B) is preferably 500 to 100,000, more preferably 1,000 to 10,000, in terms of polystyrene equivalent number average molecular weight measured by GPC.

[0101] The (meth)acrylic copolymer (B) can be produced by a conventional vinyl polymerization method. Examples of the vinyl polymerization method include a solution polymerization method using a radical reaction and a bulk polymerization method. The vinyl polymerization method is not limited to these methods. The above polymerization reaction is typically carried out at 50°C or higher and 150°C or lower in the presence of a monomer, a radical initiator, a chain transfer agent, a solvent, etc. The polymerization reaction conditions are not limited to the above conditions.

[0102] Specific examples of the radical initiator include azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and benzoyl peroxide. Specific examples of the chain transfer agent include mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and lauryl mercaptan, as well as halogen-containing compounds. As the solvent, for example, solvents inert to the polymerization reaction, such as ethers, hydrocarbons, and esters, can be preferably used.

[0103] As the method of introducing reactive silicon group into (meth)acrylic copolymer, various methods are known.Specific examples include: I) the method of copolymerizing the compound having ethylenically unsaturated double bond and reactive silicon group with the alkyl (meth)acrylate represented by formula (B1) and the monomer comprising alkyl (meth)acrylate represented by formula (B2); II) the method of copolymerizing the compound having ethylenically unsaturated double bond and reactive functional group (for example, acrylic acid) with the alkyl (meth)acrylate represented by formula (B1) and the monomer comprising alkyl (meth)acrylate represented by formula (B2), and reacting reactive silicon and the compound capable of reacting with the reactive group (for example, reactive silicon-containing isocyanate compound) with the reactive functional group in the copolymer obtained; III) the method of copolymerizing the alkyl (meth)acrylate represented by formula (B1) and the monomer comprising alkyl (meth)acrylate represented by formula (B2) in the presence of mercaptan having reactive silicon group as chain transfer agent; VI) a method in which an azobisnitrile compound having a reactive silicon group or a disulfide compound having a reactive silicon group is used as an initiator to copolymerize a monomer containing an alkyl (meth)acrylate represented by formula (B1) and an alkyl (meth)acrylate represented by formula (B2); and V) a method in which a reactive silicon group is introduced into the molecular chain terminal of a copolymer obtained by copolymerizing a monomer containing an alkyl (meth)acrylate represented by formula (B1) and an alkyl (meth)acrylate represented by formula (B2) by living radical polymerization. The method for introducing a reactive silicon group into a (meth)acrylic copolymer is not limited to the above methods.

[0104] The compound having an ethylenically unsaturated double bond and a reactive silicon group, which is used in the above method I), is preferably a compound represented by the following formula (B3): CH ２ =CR ｂ５ COOR ｂ６ -SiR １ ａ X ３－ａ (B3) In formula (B3), R １ , X, and a are R in formula (1). １ , X, and a. ｂ５ is a hydrogen atom or a methyl group. ｂ６ is an alkylene group having from 1 to 6 carbon atoms.

[0105] In formula (B3), R ｂ６ The alkylene group as the alkylene group is an alkylene group having from 1 to 6 carbon atoms, such as a methylene group, an ethane-1,2-diyl group (ethylene group), and a propane-1,3-diyl group (trimethylene group), and is preferably an alkylene group having from 1 to 4 carbon atoms.

[0106] Specific examples of the compound having an ethylenically unsaturated double bond and a reactive silicon group include γ-methacryloxypropylalkoxysilanes such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacryloxypropyltriethoxysilane; γ-acryloxypropylalkoxysilanes such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, and γ-acryloxypropyltriethoxysilane; and vinylalkoxysilanes such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and vinyltriethoxysilane.

[0107] Examples of reactive functional groups in the compound having an ethylenically unsaturated double bond and a reactive functional group used in the above method II) include amino groups, hydroxyl groups, and carboxy groups. Examples of groups that can react with these reactive functional groups include isocyanate groups. Other examples of reactive functional groups include allyl groups, as described in JP-A-54-36395, JP-A-01-272654, and JP-A-02-214759. Examples of groups that can react with allyl groups include silicon hydride groups (H—Si).

[0108] Examples of the mercaptan containing a reactive silicon group used as a chain transfer agent in the above method III) include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropyltriethoxysilane.

[0109] Examples of the azobisnitrile compound having a reactive silicon group and the disulfide compound used in the above method IV) include the azobisnitrile compound having an alkoxysilyl group and the disulfide compound having an alkoxysilyl group described in JP-A-60-23405 and JP-A-62-70405.

[0110] As the method V) above, there may be mentioned the method described in JP-A-09-272714.

[0111] Other methods include those described in JP-A Nos. 59-168014 and 60-228516, which use a mercaptan having a reactive silicon group in combination with a radical polymerization initiator having a reactive silicon group.

[0112] The number of reactive silicon groups contained in the (meth)acrylic copolymer (B) is not particularly limited, and the number of reactive silicon groups contained in the (meth)acrylic copolymer (B) is preferably 0.1 or more and 2.0 or less, and more preferably 0.5 or more and 1.5 or less, on average per molecule.

[0113] The amount of the (meth)acrylic copolymer (B) used in the curable composition is not particularly limited as long as the desired effect is not impaired. The amount of the (meth)acrylic copolymer (B) used in the curable composition is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 20 parts by mass or more and 160 parts by mass or less, relative to 100 parts by mass of the polyoxyalkylene polymer (A).

[0114] It is common knowledge among those skilled in the art that the monomer composition of the (meth)acrylic acid ester polymer (B) is selected depending on the application and purpose of the curable composition. When the curable composition is used for applications requiring strength, such as adhesives, it is preferable that the (meth)acrylic acid ester polymer (B) has a relatively high glass transition temperature (Tg). Specifically, the Tg of the (meth)acrylic acid ester polymer (B) is preferably 0°C or higher and 200°C or lower, and more preferably 20°C or higher and 100°C or lower. Tg can be calculated using the Fox formula below.

[0115] Fox's formula: 1 / (Tg(K))=Σ(Mi / Tgi) (where Mi is the weight fraction of monomer i constituting the polymer, and Tgi is the glass transition temperature (K) of a homopolymer of monomer i.)

[0116] For example, polymethyl methacrylate is known as a (meth)acrylic acid ester polymer having a relatively high glass transition temperature (Tg). Therefore, in the monomers used to produce the (meth)acrylic copolymer (B), the greater the mass ratio of methyl methacrylate to the mass of the monomer, the higher the glass transition temperature (Tg) of the (meth)acrylic copolymer (B) tends to be. Conversely, the smaller the mass ratio of methyl methacrylate to the mass of the monomer, the lower the glass transition temperature (Tg) of the (meth)acrylic copolymer (B) tends to be. When the curable composition is used as an adhesive, it is preferable that the mass ratio of methyl methacrylate to the mass of the monomer used to produce the (meth)acrylic copolymer (B) is 50% or more, as this facilitates the formation of a high-strength cured product. When the curable composition is used as a sealant, it is preferable that the mass ratio of methyl methacrylate to the mass of the monomer used to produce the (meth)acrylic copolymer (B) is less than 50%, as this results in a low viscosity and good workability of the curable composition.

[0117] <Curing Catalyst (C)> The curable composition contains a curing catalyst (C) for the purpose of promoting the reaction of hydrolysis and condensation of reactive silicon groups, i.e., the curing reaction.

[0118] As the curing catalyst (C), a conventionally known catalyst can be used, specifically, an organotin compound, a metal carboxylate, an amine compound, a carboxylic acid, an alkoxy metal, an inorganic acid, a mixture thereof, or the like can be used as the curing catalyst (C).

[0119] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), a reaction product of dibutyltin oxide with a silicate compound, a reaction product of dibutyltin oxide with a phthalate ester, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate), dioctyltin distearate, dioctyltin oxide, and a reaction product of dioctyltin oxide with a silicate compound. Among these, dioctyltin compounds are preferred due to the growing concern about the environment in recent years.

[0120] Specific examples of the metal carboxylate include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, calcium carboxylate, etc. The metal carboxylate can be a combination of the following carboxylic acids and various metals.

[0121] Specific examples of the amine compound include amines such as octylamine, 2-ethylhexylamine, laurylamine, stearylamine, piperidine, 4-methylpiperidine, and hexamethyleneimine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), and 1,5-diazabicyclo[4.3.0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; and ketimine compounds.

[0122] Specific examples of carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

[0123] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis(acetylacetonate), titanium ethylacetoacetate, and diisopropoxytitanium bis(ethylacetoacetate); aluminum compounds such as aluminum tris(acetylacetonate) and diisopropoxyaluminum ethylacetoacetate; and zirconium compounds such as zirconium tetrakis(acetylacetonate).

[0124] Other curing catalysts (C) that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0125] Two or more different catalysts may be used in combination as the curing catalyst (C). For example, the reactivity of the curing reaction can be improved by using the above-mentioned amine compound in combination with a carboxylic acid or by using the above-mentioned amine compound in combination with an alkoxy metal.

[0126] The amount of the curing catalyst (C) used is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 15 parts by mass, and particularly preferably 0.01 to 10 parts by mass, per 100 parts by mass of the polyoxyalkylene polymer (A). Depending on the type of curing catalyst (C), after the curable composition has cured, the curing catalyst (C) may seep out onto the surface of the cured product, or the surface of the cured product may be contaminated with the curing catalyst (C). In such cases, the amount of the curing catalyst (C) used is preferably 0.01 to 3.0 parts by mass per 100 parts by mass of the polyoxyalkylene polymer (A). In this case, the surface condition of the cured product can be maintained good while ensuring curability.

[0127] <Other Additives> The curable composition may contain additives other than the above components. Examples of such additives include silicon compounds, adhesion promoters, plasticizers, solvents, diluents, silicates, fillers, anti-sagging agents, antioxidants, light stabilizers, UV absorbers, physical property adjusters, tackifier resins, epoxy group-containing compounds, photocurable substances, oxygen-curable substances, surface property improvers, epoxy resins, other resins, flame retardants, and foaming agents. Various additives may also be added to the curable composition as needed to adjust the physical properties of the curable composition or the cured product. Examples of such additives include curability adjusters, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, and mildew inhibitors.

[0128] (Filler) The curable composition can contain various fillers, such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, silicic acid anhydride, hydrated silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc white, PVC powder, PMMA powder, glass fiber, and filament.

[0129] The amount of the filler used is preferably 1 part by mass or more and 300 parts by mass or less, and more preferably 10 parts by mass or more and 250 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer (A).

[0130] To reduce the weight (specific gravity) of the cured product, organic balloons and / or inorganic balloons may be added to the curable composition. Balloons are hollow spherical fillers. Examples of balloon materials include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran.

[0131] The amount of balloons used is preferably 0.1 parts by mass or more and 100 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer (A).

[0132] (Adhesion Imparting Agent) An adhesion imparting agent can be added to the curable composition. Examples of the adhesion imparting agent include silane coupling agents and reaction products of silane coupling agents.

[0133] Specific examples of the silane coupling agent include amino group-containing silanes such as γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-isocyanatepropyltriethoxysilane; Examples of suitable adhesion promoters include isocyanate group-containing silanes such as anthracene propylmethyldimethoxysilane, α-isocyanatomethyltrimethoxysilane, and α-isocyanatomethyldimethoxymethylsilane; 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. Condensates of various silane coupling agents, such as condensates of amino group-containing silanes and condensates of amino group-containing silanes with other alkoxysilanes; and reaction products of various silane coupling agents, such as reaction products of amino group-containing silanes and epoxy group-containing silanes and reaction products of amino group-containing silanes and (meth)acrylic group-containing silanes. The adhesion promoters may be used alone or in combination of two or more.

[0134] The amount of the silane coupling agent used is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 0.5 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer (A).

[0135] (Plasticizer) A plasticizer can be added to the curable composition. Specific examples of plasticizers include phthalate ester compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl)phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate ester compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; non-phthalate ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; aliphatic polycarboxylic acid ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and acetyl tributyl citrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkylsulfonic acid phenyl esters; phosphate ester compounds; trimellitic acid ester compounds; chlorinated paraffins; hydrocarbon oils such as alkyl diphenyls and partially hydrogenated terphenyls; process oils; epoxidized soybean oil, and epoxy plasticizers such as epoxy benzyl stearate.

[0136] Furthermore, a polymer plasticizer can be used. Specific examples of the polymer plasticizer include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more, and polyethers such as derivatives in which the hydroxy groups of these polyether polyols are converted into ester groups, ether groups, etc.; polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, and polychloroprene. Only one type of plasticizer may be used, or two or more types may be mixed and used.

[0137] The polymeric plasticizer may or may not have a reactive silicon group. When the polymeric plasticizer has a reactive silicon group, it acts as a reactive plasticizer and can prevent the plasticizer from migrating from the cured product. When the polymeric plasticizer has a reactive silicon group, the average number of reactive silicon groups per molecule is preferably 1 or less, more preferably 0.8 or less. When a plasticizer having a reactive silicon group, particularly a polyoxyalkylene polymer having a reactive silicon group, is used as the plasticizer, the number average molecular weight of the polyoxyalkylene polymer as the plasticizer is preferably lower than the number average molecular weight of the polyoxyalkylene polymer (A).

[0138] The amount of the plasticizer used is preferably 5 parts by mass or more and 150 parts by mass or less, more preferably 10 parts by mass or more and 120 parts by mass or less, and even more preferably 20 parts by mass or more and 100 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer (A).

[0139] (Solvent, Diluent) A solvent or diluent may be added to the curable composition. The solvent or diluent is not particularly limited as long as the desired effect is not impaired. As the solvent or diluent, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, and the like can be used. When a solvent or diluent is used, in view of the problem of air pollution when the curable composition is used indoors, the boiling point of the solvent is preferably 150°C or higher, more preferably 200°C or higher, and particularly preferably 250°C or higher. Only one type of solvent or diluent may be used, or two or more types may be mixed and used.

[0140] (Anti-sagging agent) If necessary, an anti-sagging agent may be added to the curable composition to prevent sagging and improve workability. The anti-sagging agent is not particularly limited. Examples of the anti-sagging agent include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Only one type of anti-sagging agent may be used, or two or more types may be used in combination.

[0141] The amount of the anti-sagging agent used is preferably 0.1 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the polyoxyalkylene polymer (A).

[0142] (Antioxidant) An antioxidant (antiaging agent) may be added to the curable composition. The use of an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenol compounds, monophenol compounds, bisphenol compounds, and polyphenol compounds. For example, Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330, and Irganox 1520 (all manufactured by BASF); SONGNOX 1076 (manufactured by SONGWON), and BHT are examples of suitable antioxidants. Similarly, hindered amine light stabilizers such as TINUVIN 622LD, TINUVIN 144, TINUVIN 292, CHIMASSORB 944LD, and CHIMASSORB 119FL (all manufactured by BASF); Adeka STAB LA-57, Adeka STAB LA-62, Adeka STAB LA-67, Adeka STAB LA-63, and Adeka STAB LA-68 (all manufactured by ADEKA Corporation); Sanol LS-2626, Sanol LS-1114, and Sanol LS-744 (all manufactured by Sankyo Lifetech Co., Ltd.); and Nocrac CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) can also be used. Other antioxidants that can be used include SONGNOX 4120, Nauguard 445, and OKABEST CLX050. Specific examples of antioxidants are also described in Japanese Patent Application Laid-Open Nos. 4-283259 and 9-194731.

[0143] The amount of the antioxidant used is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer (A).

[0144] (Light stabilizer) A light stabilizer may be added to the curable composition. The use of a light stabilizer can prevent photooxidative deterioration of the cured product. Examples of light stabilizers include benzotriazole-based compounds, hindered amine-based compounds, and benzoate-based compounds. Hindered amine-based compounds are particularly preferred.

[0145] The amount of the light stabilizer used is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer (A).

[0146] (Ultraviolet Absorber) An ultraviolet absorber may be added to the curable composition. Use of an ultraviolet absorber can improve the surface weather resistance of the cured product. Examples of ultraviolet absorbers include benzophenone-based compounds, benzotriazole-based compounds, salicylate-based compounds, substituted acrylonitrile-based compounds, and metal chelate-based compounds. Benzotriazole-based compounds are particularly preferred. Suitable specific examples of ultraviolet absorbers include Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571, Tinuvin 1600, and Tinuvin B75 (all manufactured by BASF).

[0147] The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the polyoxyalkylene polymer (A).

[0148] (Physical Property Modifier) ​​A physical property modifier may be added to the curable composition as needed for the purpose of adjusting the tensile properties of the resulting cured product. The physical property modifier is not particularly limited. Suitable specific examples of the physical property modifier include alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as tris(trimethylsilyl)borate and tris(triethylsilyl)borate; silicone varnish; polysiloxane, and the like. The use of a physical property modifier can increase the hardness of the cured product, or conversely, decrease the hardness and improve the elongation at break of the cured product. The physical property adjusting agent may be used alone or in combination of two or more.

[0149] In particular, compounds that produce a compound having a monovalent silanol group in the molecule upon hydrolysis have the effect of reducing the modulus of the cured product without increasing the stickiness of the surface of the cured product. Compounds that produce trimethylsilanol are particularly preferred as such compounds. Examples of compounds that produce a compound having a monovalent silanol group in the molecule upon hydrolysis include silicon compounds that are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, and that produce silane monool upon hydrolysis. Specific examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.

[0150] The amount of the physical property adjuster used is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.5 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer (A).

[0151] (Tackifying Resin) A tackifying resin may be added to the curable composition for the purpose of improving adhesion or adhesion to a substrate, or for other reasons. The tackifying resin is not particularly limited.

[0152] Specific examples of tackifying resins include terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers, hydrogenated styrene block copolymers, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, and DCPD resins. Only one type of tackifying resin may be used, or two or more types may be mixed and used.

[0153] The amount of the tackifier resin used is preferably 2 parts by mass or more and 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, and even more preferably 5 parts by mass or more and 30 parts by mass or less, per 100 parts by mass of the polyoxyalkylene polymer (A).

[0154] (Epoxy Group-Containing Compound) An epoxy group-containing compound may be added to the curable composition. The use of an epoxy group-containing compound can improve the recovery of the cured product. Examples of epoxy group-containing compounds include epoxy compounds such as epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, and epichlorohydrin derivatives, as well as mixtures thereof. Specific examples of epoxy group-containing compounds include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, and epoxy butyl stearate. The epoxy group-containing compound is preferably used in an amount of 0.5 to 50 parts by mass per 100 parts by mass of the polyoxyalkylene polymer (A).

[0155] (Photocurable Substance) A photocurable substance may be added to the curable composition. 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. Many photocurable substances are known, such as organic monomers, oligomers, resins, and compositions containing these. Representative photocurable substances include unsaturated acrylic compounds, such as monomers and oligomers having one or more acrylic unsaturated groups or one or more methacrylic unsaturated groups, and mixtures thereof; polyvinyl cinnamates; and azido resins.

[0156] The amount of the photocurable substance used is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the polyoxyalkylene polymer (A).

[0157] (Oxygen-Curable Substance) An oxygen-curable substance may be added to the curable composition. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air. The oxygen-curable substance reacts with oxygen in the air to form a cured film near the surface of the cured product, preventing surface stickiness and preventing dirt and dust from adhering to the surface of the cured product. Specific examples of oxygen-curable substances include drying oils such as tung oil and linseed oil; various alkyd resins obtained by modifying drying oils; acrylic polymers, epoxy resins, or silicone resins modified with drying oils; and liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, and polymers of C5 to C8 dienes obtained by homopolymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene. Only one type of oxygen-curable substance may be used, or two or more types may be mixed and used.

[0158] The amount of the oxygen-curable substance used is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the polyoxyalkylene polymer (A). As described in JP-A-3-160053, the oxygen-curable substance is preferably used in combination with a photo-curable substance.

[0159] (Epoxy Resin) The curable composition may contain an epoxy resin. The curable composition containing an epoxy resin is preferably used as an adhesive, and particularly preferably as an adhesive for exterior wall tiles. Examples of the epoxy resin include bisphenol A epoxy resin and novolac epoxy resin.

[0160] The ratio of the epoxy resin to the polyoxyalkylene polymer (A) used is preferably within the range of 100 / 1 to 1 / 100 in terms of the mass ratio of polyoxyalkylene polymer (A) / epoxy resin.

[0161] When an epoxy resin is added to the curable composition, a curing agent for curing the epoxy resin may be added to the curable composition together with the epoxy resin. The epoxy resin curing agent is not particularly limited, and any commonly used epoxy resin curing agent can be used.

[0162] When a curing agent for epoxy resin is used, the amount of the curing agent used is preferably in the range of 0.1 parts by mass to 300 parts by mass per 100 parts by mass of the epoxy resin.

[0163] The curable composition described above is cured by a method appropriate for the intended use of the curable composition to form a cured product.

[0164] <<Preparation of Curable Composition>> The curable composition can be prepared as a one-component type in which all ingredients are mixed in advance and stored in a sealed container, and then cured by moisture in the air after application. Alternatively, it can be prepared as a two-component type in which ingredients such as a curing catalyst, a filler, a plasticizer, and water are separately mixed as a curing agent, and the ingredients are mixed with a polymer composition containing a polyoxyalkylene polymer (A) before use. From the viewpoint of workability, the one-component type is preferred.

[0165] When the curable composition is a one-component type, all of the components are blended in advance. For this reason, it is preferable that the components containing water are dehydrated and dried before use, or that they are dehydrated under reduced pressure or the like during blending and kneading. In addition to the dehydration and drying method, the storage stability of the curable composition can be further improved by adding an alkoxysilane compound such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, or γ-glycidoxypropyltrimethoxysilane to the curable composition.

[0166] <<Uses of Curable Compositions>> The curable compositions can be used as architectural sealants, industrial adhesives, waterproof coating compositions, adhesive raw materials, and the like. They can also be used as sealants for buildings, ships, automobiles, roads, and the like. Furthermore, the curable compositions can adhere to a wide range of substrates, such as glass, porcelain, wood, metal, and resin moldings, either alone or with the aid of a primer. Therefore, the curable compositions can also be used as various types of sealing and adhesive compositions. In addition to conventional adhesives, the curable compositions can also be used as contact adhesives. Furthermore, the curable compositions are useful as food packaging materials, cast rubber materials, molding materials, and paints. The cured products of the above curable compositions exhibit low water absorption. Therefore, the above curable compositions and their cured products are particularly suitable for waterproof materials, such as sealants, waterproof adhesives, and waterproof coatings.

[0167] The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0168] That is, the present invention includes the following.

[0169] <1> A composition comprising a polyoxyalkylene polymer (A) having a reactive silicon group, a (meth)acrylic copolymer (B) having a reactive silicon group, and a curing catalyst (C), wherein the polyoxyalkylene polymer (A) is a compound represented by the following formula (1): (1) (in formula (1), R is a substituted or unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, and a is 0, 1, or 2), the number average molecular weight of the polyoxyalkylene polymer (A) is more than 3,000, and the total number N of the reactive silicon groups, 1-propenyl groups, propyl groups, and allyl groups in the polyoxyalkylene polymer (A) is 0. ｔ The number N of silicon-containing groups (a1) relative to ａ１ Ratio N ａ１ / N ｔ is 0.85 or more and 1.00 or less, the molecular chain of the (meth)acrylic copolymer (B) contains units derived from two or more types of alkyl (meth)acrylate, and the reactive silicon group of the (meth)acrylic copolymer (B) is represented by the following formula (2): —SiR １ ａ X ３－ａ (2) (In formula (2), R １ , X, and a are R in formula (1). １ , X, and a are the same as those of the curable composition. ａ１ / N ｔThe curable composition according to claim <1>, wherein the number-average molecular weight of the polyoxyalkylene polymer (A) is 10,000 or more. <4> The curable composition according to <3>, wherein the number-average molecular weight of the polyoxyalkylene polymer (A) is 20,000 or more. <5> The curable composition according to any one of <1> to <4>, wherein the (meth)acrylic copolymer (B) is a polymer of a monomer containing methyl methacrylate, wherein the ratio of the mass of the methyl methacrylate to the mass of the monomer is 50 mass% or more, and the curable composition is used as an adhesive. <6> The curable composition according to any one of <1> to <4>, wherein the (meth)acrylic copolymer (B) is a polymer of a monomer containing methyl methacrylate, wherein the ratio of the mass of the methyl methacrylate to the mass of the monomer is less than 50 mass%, and the curable composition is used as a sealant. <7> The curable composition according to any one of <1> to <6>, which contains a ruthenium complex (D). <8> The curable composition according to <7>, in which the ruthenium complex (D) has a ligand (D1) derived from a compound (E), the compound (E) has at least one carbon-carbon double bond and at least one electron-withdrawing group in one molecule, and at least one of the electron-withdrawing groups is bonded to a carbon atom constituting the carbon-carbon double bond. <9> The curable composition according to <8>, in which the compound (E) has a benzene ring skeleton or a norbornadiene skeleton. <10> The curable composition according to <8> or <9>, in which the compound (E) has, as the electron-withdrawing group, at least one selected from the group consisting of a fluoro group, a bromo group, and an iodo group. <11> A cured product of the curable composition according to any one of <1> to <10>.

[0170] The number average molecular weight in the examples is a GPC molecular weight measured under the following conditions: Solution delivery system: HLC-8420GPC manufactured by Tosoh Corporation Column: TSKgel Super H series manufactured by Tosoh Corporation Solvent: THF (tetrahydrofuran) Molecular weight: polystyrene equivalent Measurement temperature: 40°C

[0171] The proportion of silyl groups, 1-propenyl groups, propyl groups, or allyl groups was calculated using the following nuclear magnetic resonance (NMR) spectrometer: １ H NMR measurement was performed. Apparatus: AVANCE III HD500 digital instrument (manufactured by BRUKER)

[0172] Synthesis Example 1 Using polyoxypropylene glycol having a number-average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized in the presence of a zinc hexacyanocobaltate glyme complex catalyst to obtain a linear hydroxyl group-containing polyoxyalkylene polymer (H-1) having a number-average molecular weight of 27,600 and hydroxyl groups at both ends. To the polymer (F-1), 1.1 mol equivalent of sodium methoxide relative to the hydroxyl groups of the polymer (H-1) was added as a 28% methanol solution. After removing the methanol from the resulting mixture by distillation under reduced pressure, 1.3 mol equivalent of allyl chloride relative to the hydroxyl groups of the polymer (H-1) was added and the reaction was carried out at 130°C for 1 hour. Thereafter, unreacted allyl chloride was removed by distillation under reduced pressure from the reaction solution. The resulting unpurified allyl group-containing polyoxyalkylene polymer was mixed and stirred with n-hexane and water, after which the water was removed by centrifugation. The hexane was then removed from the resulting hexane solution by distillation under reduced pressure to remove metal salts from the polymer. As a result of the above, a linear allyl group-containing polyoxyalkylene polymer (A-1) was obtained.

[0173] Synthesis Example 2 An allyl group-containing polyoxyalkylene polymer (A-1) was treated with 48 ppm by mass of [RuCl ２ (nbd)] ｎand 120 ppm by mass of 2,3-dibromonorbornadiene relative to the mass of polymer (A-1). nbd is a 2,5-norbornadiene ligand. 2,5-norbornadiene ligands do not have an electron-withdrawing group. On the other hand, 2,3-dibromonorbornadiene is a compound that has an electron-withdrawing group and can coordinate to ruthenium. The resulting mixture was stirred at 90°C for 10 minutes. Next, 5.0 mol equivalents of dimethoxymethylsilane relative to the allyl groups in polymer (A-1) were added to the mixture, and a hydrosilylation reaction between the allyl groups in polymer (A-1) and dimethoxymethylsilane was carried out at 90°C. The reaction was continued for 1 hour from the start of the reaction. １ H NMR measurement confirmed that the allyl groups in the polymer (A-1) had completely disappeared within 2 hours from the start of the reaction. Thereafter, volatile components were distilled off from the mixture under reduced pressure to obtain a polyoxyalkylene polymer (A1) having a reactive silicon group. １ H NMR measurement was carried out to determine the total number N of reactive silicon groups (silicon-containing groups (a1)), 1-propenyl groups, propyl groups, and allyl groups. ｔ The ratio of the number of each group to N was calculated. ｔ The number N of silicon-containing groups (a1) relative to ａ１ The ratio of N was 99%. ｔ The ratio of the number of 1-propenyl groups to the number of N ｔ The ratio of the number of propyl groups to the number of N ｔ The ratio of the number of allyl groups to the total number of allyl groups was 0%.

[0174] (Synthesis Example 3) To the polymer (A-1) obtained in Synthesis Example 1, 50 ppm by mass of a commercially available Karstedt catalyst relative to the mass of the polymer (A-1) and 5.0 mol equivalents of dimethoxymethylsilane relative to the allyl groups of the polymer (A-1) were added, and a hydrosilylation reaction between the allyl groups of the polymer (A-1) and dimethoxymethylsilane was carried out at 90°C. One hour after the start of the reaction, １H NMR measurement was carried out, and it was confirmed that the allyl groups in the polymer (A-1) had completely disappeared one hour after the start of the reaction. Thereafter, volatile components were distilled off from the mixture under reduced pressure to obtain a polyoxyalkylene polymer (A'1) having a reactive silicon group. １ H NMR measurement was carried out to determine the total number N of reactive silicon groups (silicon-containing groups (a1)), 1-propenyl groups, propyl groups, and allyl groups. ｔ The ratio of the number of each group to N was calculated. ｔ The number N of silicon-containing groups (a1) relative to ａ１ The ratio of N was 79%. ｔ The ratio of the number of 1-propenyl groups to the number of N ｔ The ratio of the number of propyl groups to the number of N ｔ The ratio of the number of allyl groups to the total number of allyl groups was 0%.

[0175] Synthesis Example 4 To the polymer (H-1) obtained in Synthesis Example 1, 0.9 mol equivalents of sodium methoxide relative to the hydroxyl groups of the polymer (H-1) were added as a 28% methanol solution. Methanol was then removed from the resulting mixture by distillation under reduced pressure, and 1.2 mol equivalents of 3-chloro-2-methyl-1-propene (methallyl chloride) relative to the hydroxyl groups of the polymer (H-1) were added, followed by a reaction at 130°C for 1 hour. Thereafter, unreacted 3-chloro-2-methyl-1-propene was removed by distillation under reduced pressure from the reaction solution. Thereafter, 0.6 mol equivalents of sodium methoxide relative to the hydroxyl groups of the polymer (H-1) were added as a 28% methanol solution to the above mixture. Methanol was then removed by distillation under reduced pressure, and 0.7 mol equivalents of 3-chloro-2-methyl-1-propene relative to the hydroxyl groups of the polymer (H-1) were added, followed by a reaction at 130°C for 1 hour, thereby converting the remaining terminal hydroxyl groups to methallyl groups. Next, unreacted 3-chloro-2-methyl-1-propene was distilled off under reduced pressure from the mixture. The obtained unpurified methallyl group-containing polyoxyalkylene polymer was mixed and stirred with n-hexane and water, and then the water was removed by centrifugation. The hexane was then distilled off under reduced pressure from the obtained hexane solution to remove metal salts from the polymer. In this manner, a linear methallyl group-containing polyoxyalkylene polymer (M-1) was obtained. To the polymer (M-1), 100 ppm by mass of a Karstedt catalyst relative to the mass of the polymer (M-1) and 1,000 ppm by mass of 2,5-di-t-butyl-1,4-benzoquinone relative to the mass of the polymer (M-1) were added. To the obtained mixture, 1.5 mol equivalents of dimethoxymethylsilane relative to the methallyl groups in the polymer (M-1) were added, and a hydrosilylation reaction between the methallyl groups in the polymer (M-1) and the dimethoxymethylsilane was carried out at 100°C. The reaction was continued for 1 hour from the start of the reaction. １ H NMR measurement was carried out, and it was confirmed that the methallyl groups in the polymer (M-1) had completely disappeared 6 hours after the start of the reaction. Thereafter, volatile components were distilled off from the mixture under reduced pressure to obtain a linear polyoxyalkylene polymer (A'2) having a reactive silicon group. １H NMR measurement was performed to determine the total number N of reactive silicon groups, 1-propenyl groups, propyl groups, and allyl groups. ｔ The ratio of the number of reactive silicon groups to the number of silicon-containing groups (a1) N was calculated. ａ１ and the number N of silicon-containing groups (a2) formed by hydrosilylation of the methallyl group with dimethoxymethylsilane. ａ２ As a result, the silicon-containing group contained in the polymer (A'2) is mainly the silicon-containing group (a2), and N ｔ The number N of silicon-containing groups (a1) relative to ａ１ The ratio of Na １ / N ｔ was less than 85%. １ / N ｔ and Na ２ / N ｔ The sum was 97%.

[0176] Synthesis Example 5: 537 parts by mass of isobutyl alcohol was added to a four-neck flask equipped with a stirrer. The isobutyl alcohol was heated to 90°C, and the atmosphere in the flask was replaced with a nitrogen atmosphere. Then, while stirring the isobutyl alcohol, a mixed solution containing 150 parts by mass of methyl methacrylate, 704 parts by mass of n-butyl acrylate, 154 parts by mass of stearyl methacrylate, 25 parts by mass of γ-methacryloxypropyldimethoxymethylsilane, and 3 parts by mass of 2,2'-azobis(2-methylbutyronitrile) dissolved in 128 parts by mass of isobutyl alcohol was added dropwise to the flask over 7 hours. Polymerization was then carried out at 90°C for 2 hours to obtain a (meth)acrylic copolymer (B1) having a number-average molecular weight of 17,000 and a weight-average molecular weight of 48,000 as a resin solution with a solids concentration of 60% by mass. The (meth)acrylic copolymer (B1) has an average of 1.8 dimethoxymethylsilyl groups per molecule.

[0177] The resin solution obtained in Synthesis Example 5, which contained 30 parts by mass of the (meth)acrylic copolymer (B1), was uniformly mixed with 70 parts by mass of a polyoxyalkylene polymer (A1) having a reactive silicon group. Isobutyl alcohol was removed from the resulting solution using a rotary evaporator to obtain a polymer mixture (M1) containing the (meth)acrylic copolymer (B1) and the polyoxyalkylene polymer (A1).

[0178] Comparative Example 1 The resin solution obtained in Synthesis Example 5 containing 30 parts by mass of the (meth)acrylic copolymer (B1) was uniformly mixed with 70 parts by mass of a polyoxyalkylene polymer (A'1) having a reactive silicon group. Isobutyl alcohol was removed from the resulting solution using a rotary evaporator to obtain a polymer mixture (M2) containing the (meth)acrylic copolymer (B1) and the polyoxyalkylene polymer (A'1).

[0179] Comparative Example 2 The resin solution obtained in Synthesis Example 5 containing 30 parts by mass of the (meth)acrylic copolymer (B1) was uniformly mixed with 70 parts by mass of a polyoxyalkylene polymer (A'2) having a reactive silicon group. Isobutyl alcohol was removed from the resulting solution using a rotary evaporator to obtain a polymer mixture (M3) containing the (meth)acrylic copolymer (B1) and the polyoxyalkylene polymer (A'2).

[0180] (Example 2, Comparative Example 3, and Comparative Example 4) Using a 5 L planetary mixer (manufactured by Dalton Co., Ltd.), one-component curable compositions for sealant use were prepared according to the formulations shown in Table 1. First, 160 parts by mass of Hakuenka CCR (manufactured by Shiraishi Calcium Co., Ltd.: precipitated calcium carbonate), 54 parts by mass of Whiten SB (manufactured by Shiraishi Calcium Co., Ltd.: heavy calcium carbonate), and 5 parts by mass of Typen R820 (manufactured by Ishihara Sangyo Kaisha, Ltd.: titanium oxide) were dried under reduced pressure at 120°C for 2 hours. Next, 100 parts by mass of the polymer mixture obtained in Example 1, Comparative Example 1, or Comparative Example 2, 90 parts by mass of DINP (diisononyl phthalate, manufactured by J-Plus Corporation), 2 parts by mass of Disparlon 6500 (fatty acid amide wax, manufactured by Kusumoto Chemical Co., Ltd.), 1 part by mass of Tinuvin 326 (2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, manufactured by BASF), and 1 part by mass of Tinuvin 770 (light stabilizer, manufactured by BASF) were each charged into a mixer and kneaded for 10 minutes. The resulting mixture was removed and passed through a three-roll mill once to uniformly disperse the mixture, and then charged back into the mixer and dehydrated under reduced pressure for 2 hours. After dehydration under reduced pressure, the mixture was cooled to 50°C or below, and then 3 parts by mass of A-171 (vinyltrimethoxysilane, manufactured by Momentive), 3 parts by mass of A-1120 (N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, manufactured by Momentive), and 2 parts by mass of Neostan U-220H (dibutyltin bis(acetylacetonate), manufactured by Nitto Kasei Co., Ltd.) were added and kneaded for 3 minutes. After degassing under reduced pressure for 2 minutes, the resulting mixture was immediately filled into a moisture-proof aluminum cartridge and sealed to obtain a curable composition. The resulting curable composition was used to evaluate the skinning time, dumbbell tensile properties, tear strength, and tensile shear strength. The results are shown in Table 1.

[0181] <Skinning Time> The obtained curable composition was filled into a mold approximately 5 mm thick using a spatula in an atmosphere of 23°C and 50% relative humidity. The time when the surface of the filled curable composition was smoothed to a flat surface was defined as the curing initiation time. The surface was touched with a spatula, and the time when the composition to be evaluated no longer adhered to the spatula was defined as the skinning time. The results are shown in Table 1.

[0182] <Dumbbell Tensile Properties> The resulting curable composition was filled into a mold and aged for 3 days at 23°C and 50% relative humidity, followed by 4 days at 50°C to produce a sheet-like cured product approximately 3 mm thick. The sheet-like cured product was punched into a No. 3 dumbbell shape and subjected to a tensile strength test at 23°C and 50% relative humidity to measure the modulus at 50% and 100% elongation (M50 and M100). The strength at break (TB) and elongation (EB) were also measured. Measurements were performed using an autograph (AGS-J) manufactured by Shimadzu Corporation at a tensile speed of 200 mm / min. The results are shown in Table 1.

[0183] <Tear Strength> The obtained curable composition was filled into a 3 mm thick sheet mold at 23°C and 50% relative humidity. The curable composition was cured for 3 days at 23°C and 50% relative humidity, and then aged in a 50°C dryer for 4 days to obtain a sheet-like cured product. The obtained cured product was punched into a dumbbell shape (JIS Type A) for tear testing to obtain a test specimen. Using the obtained test specimen, a tear test (tensile speed 200 mm / min) was performed using an autograph at 23°C and 50% relative humidity to measure the stress at break (TB). The results are shown in Table 1.

[0184] <Tensile Shear Strength> An aluminum plate was used as an adherend. At 23°C and 50% relative humidity, the curable composition was applied to a 25 mm x 25 mm adhesive surface of the aluminum plate to a thickness of 50 μm. Two minutes after application, an aluminum plate not coated with the curable composition was pressed against the coated surface of the aluminum plate to bond the two adherends. The resulting test specimen was placed under constant temperature and humidity conditions of 23°C and 50% relative humidity. Tensile shear tests (tensile speed 50 mm / min) were performed using an autograph to measure the stress at break (TB) after 1 hour, 3 hours, and 24 hours from the time of placement under constant temperature and humidity conditions. Furthermore, the resulting test specimen was aged for 3 days at 23°C and 50% relative humidity, and then for 4 days at 50°C, after which a tensile shear test was performed using an autograph to measure the stress at break (TB). The strength development rate at each time point was calculated as follows: Strength development rate (%) = (shear strength at each time) ÷ (shear strength after aging at 23°C and 50% relative humidity for 3 days and then at 50°C for 4 days) × 100 The results are shown in Table 1.

[0185]

[0186] Table 1 shows that the curable composition of Example 2, which contains a combination of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B), has excellent curability. On the other hand, Table 1 shows that the curable compositions of Comparative Examples 3 and 4, which contain a combination of a polyoxyalkylene polymer other than the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B), require a long time to cure. Furthermore, as can be seen from the tensile shear strength measurement results, the curable composition of Example 2 exhibited a higher tensile shear strength than the curable compositions of Comparative Examples 3 and 4 in the early stage of curing.

[0187] Synthesis Example 6 412 parts by mass of isobutyl alcohol was added to a four-neck flask equipped with a stirrer. The isobutyl alcohol was heated to 105°C, and the atmosphere in the flask was replaced with a nitrogen atmosphere. Thereafter, while stirring the isobutyl alcohol, a solution consisting of 670 parts by mass of methyl methacrylate, 60 parts by mass of n-butyl acrylate, 134 parts by mass of stearyl methacrylate, 55 parts by mass of γ-methacryloxypropyldimethoxymethylsilane, 73 parts by mass of γ-mercaptopropyldimethoxymethylsilane, 223 parts by mass of isobutyl alcohol, and 24.8 parts by mass of azobis-2-methylbutyronitrile was added dropwise into the flask over 5 hours. Thereafter, a solution obtained by dissolving 2.8 parts by mass of azobis-2-methylbutyronitrile in 45 parts by mass of isobutyl alcohol was added dropwise into the flask over 1 hour. Subsequently, post-polymerization was carried out for 2 hours at 105°C to obtain a (meth)acrylic copolymer (B2) having a number average molecular weight of 2,100 and a weight average molecular weight of 3,700 as a resin solution with a solid content of 60% by mass. The (meth)acrylic copolymer (B2) has an average of 1.3 dimethoxymethylsilyl groups per molecule.

[0188] The resin solution obtained in Synthesis Example 6, which contained 30 parts by mass of the (meth)acrylic acid copolymer (B2), was uniformly mixed with 70 parts by mass of the polyoxyalkylene polymer (A1) having a reactive silicon group. From the resulting solution, isobutyl alcohol was distilled off using a rotary evaporator to obtain a polymer mixture (M4).

[0189] The resin solution obtained in Synthesis Example 6 containing 30 parts by mass of the (meth)acrylic acid copolymer (B2) was uniformly mixed with 70 parts by mass of the polyoxyalkylene polymer (A'1) having a reactive silicon group. The isobutyl alcohol was distilled off from the resulting solution using a rotary evaporator to obtain a polymer mixture (M5).

[0190] The resin solution obtained in Synthesis Example 6, containing 30 parts by mass of the (meth)acrylic acid copolymer (B2), was uniformly mixed with 70 parts by mass of the polyoxyalkylene polymer (A'2) having a reactive silicon group. Isobutyl alcohol was distilled off from the resulting solution using a rotary evaporator to obtain a polymer mixture (M6).

[0191] (Example 4, Comparative Example 7, and Comparative Example 8) Using a 5L planetary mixer (manufactured by Dalton Corporation), one-component curable compositions for adhesive use were prepared according to the formulations shown in Table 2. First, 100 parts by mass of the polymer mixture obtained in Example 3, Comparative Example 5, or Comparative Example 6, 15 parts by mass of Sylophobic 200 (manufactured by Fuji Silysia Chemical Ltd.: silica), and 3 parts by mass of Aerosil R812S (manufactured by Nippon Aerosil Co., Ltd.: silica) were kneaded for 10 minutes. The resulting mixture was removed and passed through a three-roll mill once to uniformly disperse the mixture. The mixture was then recharged into the mixer, and 1 part by mass of A-171 (manufactured by Momentive: vinyltrimethoxysilane) was added. The mixture was then dehydrated under reduced pressure at 70°C for 1 hour. After dehydration under reduced pressure, the mixture was cooled to 50°C or below, and then 5 parts by mass of A-171 (manufactured by Momentive: vinyltrimethoxysilane), 4 parts by mass of A-1120 (manufactured by Momentive: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane), 1 part by mass of A-187 (manufactured by Momentive: 3-glycidoxypropyltrimethoxysilane), and 2 parts by mass of Neostan U-220H (manufactured by Nitto Kasei Co., Ltd., dibutyltin bis(acetylacetonate)) were added and kneaded for 3 minutes. After degassing under reduced pressure for 2 minutes, the resulting mixture was immediately filled into a moisture-proof aluminum cartridge and sealed to obtain a curable composition. Using the resulting curable composition, the skinning time, dumbbell tensile properties, tear strength, and tensile shear strength were evaluated in the same manner as in Example 2. The results are shown in Table 2.

[0192]

[0193] Table 2 shows that the curable composition of Example 4, which contains a combination of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B), has excellent curability. On the other hand, Table 2 shows that the curable compositions of Comparative Examples 7 and 8, which contain a combination of a polyoxyalkylene polymer other than the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B), require a long time to cure. Furthermore, as can be seen from the measurement results of the tensile shear strength, the curable composition of Example 4 exhibited a higher tensile shear strength than the curable compositions of Comparative Examples 7 and 8 at the initial stage of curing.

[0194] Synthesis Example 7 To an allyl group-containing polyoxyalkylene polymer (A-1), 0.1 mol equivalent of crotonic acid relative to the allyl groups contained in the polymer (A-1) was added. Then, 10 ppm by mass of hexachloroplatinic (IV) acid hexahydrate relative to the mass of the polymer (A-1) and 7 ppm by mass of phenylpropiolic acid relative to the mass of the polymer (A-1) were mixed with the polymer (A-1). The ratio of the platinum catalyst to the phenylpropiolic acid was 1:25 in terms of platinum catalyst:phenylpropiolic acid (molar ratio). Furthermore, an acetonitrile solution of triethylsilane containing an equimolar amount of triethylsilane to the phenylpropiolic acid was added to the polymer (A-1). Next, 2.0 mol equivalent of dimethoxymethylsilane relative to the allyl groups contained in the polymer (A-1) was added to the mixture. Thereafter, a hydrosilylation reaction between the allyl groups of the polymer (A-1) and dimethoxymethylsilane was carried out at 90° C. １ H NMR measurement confirmed that the allyl groups in the polymer (A-1) had completely disappeared within 2 hours from the start of the reaction. Thereafter, volatile components were distilled off from the mixture under reduced pressure to obtain a polyoxyalkylene polymer (A2) having a reactive silicon group. １ H NMR measurement was carried out to determine the total number N of reactive silicon groups (silicon-containing groups (a1)), 1-propenyl groups, propyl groups, and allyl groups. ｔ The ratio of the number of each group to N was calculated.ｔ The number N of silicon-containing groups (a1) relative to ａ１ The ratio of N was 86%. ｔ The ratio of the number of 1-propenyl groups to the number of N was 11%. ｔ The ratio of the number of propyl groups to the number of N ｔ The ratio of the number of allyl groups to the total number of allyl groups was 0%.

[0195] Synthesis Example 8: 550 parts by mass of isobutyl alcohol was added to a four-neck flask equipped with a stirrer. The isobutyl alcohol was heated to 105°C, and the atmosphere in the flask was replaced with a nitrogen atmosphere. Then, while stirring the isobutyl alcohol, a mixed solution containing 100 parts by mass of methyl methacrylate, 715 parts by mass of n-butyl acrylate, 150 parts by mass of stearyl methacrylate, 35 parts by mass of γ-methacryloxypropyldimethoxymethylsilane, and 6 parts by mass of 2,2'-azobis(2-methylbutyronitrile) dissolved in 120 parts by mass of isobutyl alcohol was added dropwise to the flask over 5 hours. Polymerization was then carried out at 105°C for 1 hour, yielding a (meth)acrylic copolymer (B3) having a number-average molecular weight of 10,500 and a weight-average molecular weight of 26,500 as a resin solution with a solids concentration of 60% by mass. The (meth)acrylic copolymer (B3) has an average of 1.6 dimethoxymethylsilyl groups per molecule.

[0196] The resin solution obtained in Synthesis Example 8, which contained 30 parts by mass of the (meth)acrylic copolymer (B3), was uniformly mixed with 70 parts by mass of the polyoxyalkylene polymer (A2) having a reactive silicon group. Isobutyl alcohol was removed from the resulting solution using a rotary evaporator to obtain a polymer mixture (M7) containing the (meth)acrylic copolymer (B3) and the polyoxyalkylene polymer (A2).

[0197] Comparative Example 9 The resin solution obtained in Synthesis Example 8 containing 30 parts by mass of the (meth)acrylic copolymer (B3) was uniformly mixed with 70 parts by mass of a polyoxyalkylene polymer (A'1) having a reactive silicon group. Isobutyl alcohol was removed from the resulting solution using a rotary evaporator to obtain a polymer mixture (M8) containing the (meth)acrylic copolymer (B3) and the polyoxyalkylene polymer (A'1).

[0198] (Example 6 and Comparative Example 10) Masterbatch compositions were prepared using a 5L planetary mixer (manufactured by Dalton Co., Ltd.). First, 160 parts by weight of Hakuenka CCR (Shiraishi Calcium Co., Ltd.: colloidal calcium carbonate), 54 parts by weight of Whiten SB (Shiraishi Calcium Co., Ltd.: surface-untreated heavy calcium carbonate), and 5 parts by weight of Typek R820 (Ishihara Sangyo Kaisha: titanium oxide) were dried under reduced pressure at 120°C for 2 hours. Next, 90 parts by weight of DINP (J-Plus Corporation: diisononyl phthalate), 2 parts by weight of Disparlon 6500 (Kusumoto Chemicals Co., Ltd.: fatty acid amide wax), 1 part by weight of Tinuvin 328 (BASF: ultraviolet absorber), and 1 part by weight of Tinuvin 770 (BASF: light stabilizer) were each added to the mixer and kneaded for 10 minutes. The resulting mixture was removed and passed through a three-roll mill once to uniformly disperse the mixture, after which the mixture was again charged into the mixer and dehydrated under reduced pressure at 120 ° C. for 2 hours. After cooling the mixture to 50 ° C or below, 2 parts by weight of A-171 (manufactured by Momentive: vinyltrimethoxysilane) was added to the mixture, and the mixture was kneaded in a state substantially free of moisture. The thoroughly kneaded mixture was degassed under reduced pressure, and then the mixture was sealed in a moisture-proof cartridge container to obtain a masterbatch composition. Thereafter, 100 parts by weight of the polymer mixture (M7 or M8) shown in Table 3, 3 parts by weight of A-1120 (manufactured by Momentive: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane), and 2 parts by weight of Neostan U-220H (manufactured by Nitto Kasei Co., Ltd., dibutyltin bis(acetylacetonate)) were added to 315 parts by weight of the masterbatch composition and thoroughly mixed, followed by uniform kneading and degassing using a planetary centrifugal mixer, to prepare each curable composition. The obtained curable composition was used to evaluate the skinning time, dumbbell tensile properties, and tensile shear strength in the same manner as in Example 2. The results are shown in Table 3.

[0199]

[0200] Table 3 shows that the curable composition of Example 6, which contains a combination of the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B), has excellent curability. On the other hand, Table 3 shows that the curable composition of Comparative Example 10, which contains a combination of a polyoxyalkylene polymer other than the polyoxyalkylene polymer (A) and the (meth)acrylic polymer (B), takes a long time to cure. Furthermore, as can be seen from the tensile shear strength measurement results, the curable composition of Example 6 exhibited a higher tensile shear strength than the curable composition of Comparative Example 10 in the early stage of curing.

Claims

1. A composition comprising a polyoxyalkylene polymer (A) having a reactive silicon group, a (meth)acrylic copolymer (B) having a reactive silicon group, and a curing catalyst (C), wherein the polyoxyalkylene polymer (A) is represented by the following formula (1): (1) A polyoxyalkylene polymer (A) having a silicon-containing group (a1) represented by the following formula (1): (in formula (1), R is a substituted or unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, and a is 0, 1, or 2), the number average molecular weight of the polyoxyalkylene polymer (A) is more than 3,000, and the total number N of the reactive silicon groups, 1-propenyl groups, propyl groups, and allyl groups in the polyoxyalkylene polymer (A) is greater than 3,000. ｔ The number N of the silicon-containing groups (a1) relative to ａ１ Ratio N ａ１ / N ｔ is 0.85 or more and 1.00 or less, the molecular chain of the (meth)acrylic copolymer (B) contains units derived from two or more types of alkyl (meth)acrylate, and the reactive silicon group of the (meth)acrylic copolymer (B) is represented by the following formula (2): １ ａ X ３－ａ (2) (In formula (2), R １ , X, and a are R in formula (1). １ , X, and a are the same as those in the above-mentioned formula (1).

2. In the polyoxyalkylene polymer (A), ａ１ / N ｔ The curable composition according to claim 1 , wherein the σ is 0.90 or more and 1.00 or less.

3. The curable composition according to claim 1 or 2, wherein the polyoxyalkylene polymer (A) has a number average molecular weight of 10,000 or more.

4. The curable composition according to claim 3, wherein the polyoxyalkylene polymer (A) has a number average molecular weight of 20,000 or more.

5. The curable composition according to claim 1 or 2, wherein the (meth)acrylic copolymer (B) is a polymer of a monomer containing methyl methacrylate, the ratio of the mass of the methyl methacrylate to the mass of the monomer is 50 mass% or more, and the curable composition is used as an adhesive.

6. The curable composition according to claim 1 or 2, wherein the (meth)acrylic copolymer (B) is a polymer of a monomer containing methyl methacrylate, and the ratio of the mass of the methyl methacrylate to the mass of the monomer is less than 50 mass%, and the composition is used as a sealant.

7. The curable composition according to claim 1 or 2, comprising a ruthenium complex (D).

8. The curable composition according to claim 7, wherein the ruthenium complex (D) has a ligand (D1) derived from a compound (E), the compound (E) has at least one carbon-carbon double bond and at least one electron-withdrawing group in one molecule, and at least one of the electron-withdrawing groups is bonded to a carbon atom that constitutes the carbon-carbon double bond.

9. The curable composition according to claim 8, wherein the compound (E) has a benzene ring skeleton or a norbornadiene skeleton.

10. The curable composition according to claim 8, wherein the compound (E) has, as the electron-withdrawing group, at least one selected from the group consisting of a fluoro group, a bromo group, and an iodo group.

11. A cured product of the curable composition according to claim 1 or 2.

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