Curable composition

Abstract

The present invention provides a curable composition exhibiting good curability, and a cured product of the curable composition. A curable composition containing a polyoxyalkylene polymer having a reactive silicon group, a specific (meth) acrylic copolymer having a reactive silicon group, and a curing catalyst, a polyoxyalkylene-based polymer having a number average molecular weight of more than 3000 and a silicon-containing group that can be generated by a hydrosilylation reaction of an allyl group and a hydrosilane compound at a given high ratio is used.

Description

Technical Field

[0001] This invention relates to curable compositions comprising polyoxyethylene polymers and cured products of the above-mentioned curable compositions. Background Technology

[0002] Organic polymers having at least one hydrolyzable silyl group in their molecule can crosslink even at room temperature through the formation of siloxane bonds, such as those resulting from the hydrolysis of the silyl group due to moisture absorption. Polyoxyalkylene polymers having hydrolyzable silyl groups are widely used as such organic polymers. Organic polymers having hydrolyzable silyl groups are known to form rubber-like cured products through the aforementioned crosslinking reactions.

[0003] Organic polymers having hydrolyzable silyl groups are manufactured, for example, by a hydrosilylation reaction of an organic polymer having an allyl group at the end with a hydrosilane compound that forms a hydrolyzable silyl group.

[0004] In this method, Karstedt catalyst (platinum divinyldisilazane complex) is often used as the catalyst for the hydrosilylation reaction (see Synthesis Example 2-1 in Patent Document 1, etc.).

[0005] In addition, curable compositions containing both a polyoxyethylene polymer containing reactive silicon groups and a (meth)acrylate copolymer containing reactive silicon groups are known to improve the balance of elongation, strength, adhesion and weather resistance of the obtained cured product.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2021-75722 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] However, when using a Karstedt catalyst to cure a curable composition containing an organic polymer with hydrolyzable silyl groups, there is room for improvement in the curing speed.

[0011] Therefore, the object of the present invention is to provide a curable composition exhibiting good curability, and a cured product of the above-described curable composition.

[0012] Problem Solving Methods

[0013] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that by using a polyoxyethylene polymer having silicon-containing groups that can be generated by the hydrosilylation reaction of allyl groups with hydrosilane compounds and a number average molecular weight of more than 3000 in a given high ratio in a curable composition comprising a polyoxyethylene polymer having reactive silicon groups, a specific (meth)acrylic acid copolymer having reactive silicon groups, and a curing catalyst, the above-mentioned problems can be solved, thereby completing the present invention.

[0014] That is, the present invention relates to a curable composition comprising: a polyoxyethylene polymer (A) having reactive silicon groups, a (meth)acrylic copolymer (B) having reactive silicon groups, and a curing catalyst (C).

[0015] Polyoxyolefin polymer (A) has a silicon-containing group (a1) represented by the following formula (1).

[0016] [Chemical Formula 1]

[0017]

[0018] In formula (1), R is a hydrocarbon group with 1 or more but less than 20 carbon atoms, either substituted or unsubstituted; X is a hydroxyl group or a hydrolyzable group; and a is 0, 1, or 2.

[0019] Polyoxyolefin polymers (A) have a number average molecular weight exceeding 3000.

[0020] In polyoxyethylene polymers (A), the number N of silicon groups (a1) is... a1 The total N relative to the number of reactive silicon groups, the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups. t The ratio N a1 / N t Values ​​between 0.85 and 1.00

[0021] The molecular chain of the above-mentioned (meth)acrylic copolymer (B) contains two or more units derived from alkyl (meth)acrylic esters.

[0022] The reactive silicon group in (meth)acrylic acid copolymer (B) is represented by the group in formula (2) below.

[0023] -SiR 1 a X 3-a (2)

[0024] In equation (2), R 1 X and a are related to R in equation (1) 1 The same applies to X and a.

[0025] The effects of the invention

[0026] According to the present invention, it is possible to provide a curable composition exhibiting good curability, and a cured product of the above-described curable composition. Detailed Implementation

[0027] The present invention will now be described in detail.

[0028] Curing Compositions

[0029] The curable composition comprises: a polyoxyethylene polymer having reactive silicon groups (A), a (meth)acrylic copolymer having reactive silicon groups (B), and a curing catalyst (C).

[0030] In the specification and claims of this application, "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid".

[0031] Here, reactive silicon groups refer to silicon-containing groups that have silanol groups or can be hydrolyzed to generate silanol groups.

[0032] In the case of reactive silicon groups having silanol groups, the molecules of polyoxyalkylene polymers condense with each other through a condensation reaction of the silanol groups.

[0033] When the reactive silicon group has hydrolyzable groups that can be hydrolyzed to generate silanol groups, after the reactive silicon group is hydrolyzed, the molecules of the polyoxyethylene polymer condense with each other through the condensation reaction of the silanol groups.

[0034] The number average molecular weight of polyoxyethylene polymers (A) exceeds 3000.

[0035] Polyoxyolefin polymer (A) has a silicon-containing group (a1) represented by the following formula (1).

[0036] [Chemical Formula 2]

[0037]

[0038] In formula (1), R is a hydrocarbon group with 1 or more but less than 20 carbon atoms, either substituted or unsubstituted. X is a hydroxyl group or a hydrolyzable group. a is 0, 1 or 2.

[0039] In polyoxyolefin polymers (A), the number N of silicon-containing groups (a1) is... a1 The total N relative to the number of reactive silicon groups, the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups. t The ratio N a1 / N t It is above 0.85 and below 1.00.

[0040] The molecular chain of (meth)acrylic copolymer (B) contains two or more units derived from alkyl (meth)acrylic esters.

[0041] The reactive silicon group in (meth)acrylic acid copolymer (B) is represented by the group in formula (2) below.

[0042] -SiR 1 a X 3-a (2)

[0043] In equation (2), R 1 X and a are related to R in equation (1) 1 The same applies to X and a.

[0044] The above-described curable composition exhibits good curability.

[0045] The following describes the essential or optional components that may be included in a curable composition.

[0046] <Polyoxyolefin polymers (A)>

[0047] Polyoxyolefin polymer (A) has reactive silicon groups. Furthermore, as mentioned above, the number-average molecular weight of polyoxyolefin polymer (A) exceeds 3000. Here, the number-average molecular weight is the equivalent molecular weight of polystyrene determined by gel permeation chromatography (GPC).

[0048] The number average molecular weight of the polyoxyethylene polymer (A) is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more.

[0049] There is no particular upper limit to the number average molecular weight of the polyoxyethylene polymer (A). The number average molecular weight of the polyoxyethylene polymer (A) can be, for example, 100,000 or less, preferably 50,000 or less.

[0050] The number average molecular weight of the polyoxyethylene 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.

[0051] The molecular weight distribution (weight-average molecular weight Mw / number-average molecular weight Mn) of the polyoxyethylene polymer (A) is not particularly limited. A narrow molecular weight distribution is preferred.

[0052] Specifically, the molecular weight distribution is preferably less than 2.0, more preferably less than 1.6, even more preferably less than 1.5, even more preferably less than 1.4, and most preferably less than 1.3.

[0053] It should be noted that the weight-average molecular weight can also be determined by GPC.

[0054] Polyoxyethylene polymers (A) have a polyoxyethylene backbone.

[0055] The polyoxyethylene skeleton is preferably a skeleton consisting only of multiple repeating oxyethylene units, or a skeleton consisting only of multiple repeating oxyethylene units and units from the initiator used during polymerization.

[0056] The number of carbon atoms in the repeating unit of the olefin oxide is preferably 2 or more and 6 or less, more preferably 2 or more and 4 or less.

[0057] The molecular chain structure of polyoxyethylene polymers (A) can be linear or branched.

[0058] Polyoxyolefin polymers (A) can contain linear molecules and branched molecules.

[0059] From the perspective of good elongation of the cured product of the curable composition described later, linear molecules are preferred.

[0060] From the perspective of good strength of the curable composition described later, branched molecules are preferred.

[0061] The linear molecular structure is formed by ring-opening polymerization of cyclic ether compounds using an initiator having one or two hydroxyl groups in one molecule.

[0062] The branched molecular structure is formed by ring-opening polymerization of oxidized olefins using an initiator having more than three hydroxyl groups in one molecule.

[0063] The polymer backbone of polyoxyethylene is not particularly limited. Preferred specific examples of the polymer backbone of polyoxyethylene include: polyoxyethylene backbone, polyoxypropylene backbone, polyoxybutene backbone, polyoxytetramethylene backbone, polyoxyethylene-polyoxypropylene copolymer backbone, and polyoxypropylene-polyoxybutene copolymer backbone.

[0064] Among these skeletons, polyoxypropylene skeletons are preferred.

[0065] Polyoxyethylene polymers (A) may contain only molecules with one type of polyoxyethylene backbone, or they may contain multiple molecules with different types of polyoxyethylene backbones.

[0066] When the curable composition is used as a sealant, adhesive, etc., the mass ratio of the oxypropylene repeating unit in the polyoxypropylene backbone of the polyoxypropylene polymer (A) is preferably 50% by mass or more, more preferably 80% by mass or more.

[0067] In this case, the polyoxyethylene polymer (A) is amorphous. Furthermore, the polyoxyethylene polymer (A) tends to have low viscosity.

[0068] The polyoxyethylene backbone in the polyoxyethylene polymer (A) can be formed by ring-opening polymerization of cyclic ether compounds in the presence of an initiator using a polymerization catalyst via existing known methods.

[0069] Through such ring-opening polymerization, a polyoxyethylene polymer with hydroxyl groups at the ends can be obtained. Using the polyoxyethylene polymer with hydroxyl groups at the ends as a raw material, the above-mentioned polyoxyethylene polymer (A) with reactive silicon groups at the ends can be obtained by the method described later.

[0070] Examples of methods for manufacturing polyoxyethylene polymers include: polymerization methods based on alkaline catalysts such as KOH; polymerization methods based on transition metal compound-porphyrin complex catalysts such as the complex obtained by reacting an organoaluminum compound with porphyrin as shown in Japanese Patent Application Publication No. 61-215623; polymerization methods based on composite metal cyanide complex catalysts shown in Japanese Patent Publication Nos. 46-27250, 59-15336, US Patent Nos. 3278457, 3278458, 3278459, 3427256, 3427334, and 3427335; polymerization methods using catalysts containing polyphosphazene salts as exemplified in Japanese Patent Application Publication No. 10-273512; and polymerization methods using catalysts containing phosphazene compounds as exemplified in Japanese Patent Application Publication No. 11-060722.

[0071] From the perspective of easily obtaining polyoxyethylene polymers with small molecular weight distribution (Mw / Mn), it is preferable to use a method of ring-opening polymerization of cyclic ether compounds using a complex metal cyanide complex catalyst such as zinc hexacyanocobaltate glycol dimethyl ether complex.

[0072] Examples of cyclic ether compounds include ethylene oxide, propylene oxide, butane oxide, tetramethylene oxide, and tetrahydrofuran.

[0073] As cyclic ether compounds, only one type can be used, or two or more types can be used in combination.

[0074] Among cyclic ether compounds, propylene oxide is particularly preferred because it readily yields amorphous and low-viscosity polyoxyolefin polymers.

[0075] The initiator is not particularly limited. Preferred specific examples of initiators include: monohydric alcohols such as butanol and propylene glycol monoalkyl ethers; dihydric alcohols such as ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, and triethylene glycol; and polyhydric alcohols having three or more hydroxyl groups such as glycerol, trimethylolpropane, pentaerythritol, and sorbitol.

[0076] Alternatively, hydroxyl-terminated polyoxyethylene polymers with a number-average molecular weight of 300-4000 can be used as initiators.

[0077] Specific examples of hydroxyl-terminated polyoxyethylene polymers include: polyoxypropylene glycol, polyoxypropylene triol, polyoxyethylene glycol, and polyoxyethylene triol.

[0078] Polyoxyolefin polymer (A) has a silicon-containing group (a1) represented by the following formula (1).

[0079] [Chemical Formula 3]

[0080]

[0081] (In formula (1), R is a hydrocarbon group with 1 or more but less than 20 carbon atoms, either substituted or unsubstituted; X is a hydroxyl group or a hydrolyzable group; and a is 0, 1 or 2.)

[0082] Polyoxyolefin polymers (A) typically have multiple silicon-containing groups (a1). The multiple silicon-containing groups (a1) in polyoxyolefin polymers (A) can be the same group or two or more different groups.

[0083] In addition, in equation (1), when there are multiple Rs, the multiple Rs can be the same group or two or more different groups.

[0084] In equation (1), when there are multiple Xs, the multiple Xs can be the same group or two or more different groups.

[0085] Silicon-containing groups (a1) are introduced into polyoxyethylene polymers (A) through a hydrosilylation reaction of allyl-containing polyoxyethylene polymers with hydrosilane compounds.

[0086] As a hydrosilane compound, the compound represented by the following formula (1-1) is used.

[0087] HSiR 1 a X 3-a (1-1)

[0088] The hydrosilane compound represented by formula (1-1) forms the silicon-containing group (a1) represented by formula (1) by hydrosilylation reaction with the allyl group of the polyoxyolefin polymer.

[0089] In addition, the polyoxyolefin polymer (A) may have one or more of allyl, 1-propenyl and propyl groups.

[0090] The allyl group is the unreacted allyl group. The 1-propenyl group can be formed through an internal isomerization reaction of the allyl group as a side reaction. The propyl group can be formed through the hydrogenation reaction of the allyl group as a side reaction.

[0091] In the above formula (1), the oxygen atom bonded to the trimethylene group is bonded to any position in the polyoxyethylene backbone of the polyoxyethylene polymer.

[0092] The bonding positions of the oxygen atoms mentioned above are not particularly limited. The oxygen atoms can be bonded not only to the ends of the polyoxyethylene skeleton, but also to positions other than the ends of the polyoxyethylene skeleton.

[0093] Preferably, the bonding positions of the oxygen atoms mentioned above are only at the ends of the polyoxyethylene skeleton.

[0094] In equation (1), R 1 Each is an independent hydrocarbon group consisting of 1 or more but less than 20 substituted or unsubstituted carbon atoms.

[0095] As R 1 The hydrocarbon group can be either a saturated hydrocarbon group or an unsaturated hydrocarbon group.

[0096] As R 1 The hydrocarbon group can be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of aliphatic and aromatic hydrocarbon groups.

[0097] Composition as R 1 The structure of the aliphatic hydrocarbon group can be straight-chain, branched, cyclic, or a combination of these structures.

[0098] As R 1 The number of carbon atoms in the hydrocarbon group 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.

[0099] As R 1 When the hydrocarbon group has substituents, the type of substituent is not particularly limited as long as it does not impair the desired effect.

[0100] Specific examples of substituents include: halogen atoms such as chloro and bromo; 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.

[0101] As R 1 Specific examples of substituents or unsubstituted hydrocarbon groups include: alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, 2-ethylhexyl, and n-dodecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; substituted alkyl groups such as chloromethyl, methoxymethyl, and N,N-diethylaminomethyl; alkenyl groups such as vinyl, isopropenyl, and allyl; aryl groups such as phenyl, tolyl, naphth-1-yl, and naphth-2-yl; and aralkyl groups such as benzyl and phenethyl.

[0102] Among the substituted or unsubstituted hydrocarbon groups mentioned above, alkyl and substituted alkyl groups are preferred, more preferably methyl, ethyl, chloromethyl and methoxymethyl, and particularly preferably methyl.

[0103] In formula (1), X is a hydroxyl group or a hydrolyzable group. There is no particular limitation on the hydrolyzable group; any known hydrolyzable group may be used. Specific examples of hydrolyzable groups include: hydrogen atoms, halogen atoms, alkoxy groups, acyloxy groups, ketoxime groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenoxy groups. Among these, alkoxy groups, acyloxy groups, ketoxime groups, and alkenoxy groups are preferred. From the perspective of hydrolytic stability and ease of handling, alkoxy groups such as methoxy and ethoxy groups are more preferred.

[0104] In equation (1), a is 0, 1, or 2. From the perspective of curing properties, a is preferably 0 or 1.

[0105] -SiR, as represented by formula (1) 1 a X 3-a Preferred examples of the indicated group include: trimethoxysilyl, triethoxysilyl, tri(2-propenoxy)silyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethoxyethylsilyl, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N-diethylaminomethyl)dimethoxysilyl, and (N,N-diethylaminomethyl)diethoxysilyl, etc.

[0106] From the viewpoint of easily obtaining cured products with good mechanical properties, these groups are preferably trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, and (methoxymethyl)dimethoxysilyl.

[0107] Considering the activity of silicon-containing groups (a1), as -SiR 1 a X 3-a The indicated group is preferably trimethoxysilyl, (chloromethyl)dimethoxysilyl, and (methoxymethyl)dimethoxysilyl, more preferably trimethoxysilyl and (methoxymethyl)dimethoxysilyl.

[0108] From a stability perspective, as -SiR 1 a X 3-a The indicated group is more preferably dimethoxymethylsilyl or triethoxysilyl, and particularly preferably dimethoxymethylsilyl.

[0109] In polyoxyolefin polymers (A), the number N of silicon-containing groups (a1) is... a1 The total N relative to the number of reactive silicon groups, the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups. t The ratio N a1 / N t It is above 0.85 and below 1.00.

[0110] In polyoxyolefin polymers (A), N a1 / N t Preferably, the value is 0.90 or higher and 1.00 or lower, more preferably 0.95 or higher and 1.00 or lower.

[0111] The manufacturing method of the polyoxyethylene polymer (A) will be described in detail later. The polyoxyethylene polymer (A) described above is manufactured by a hydrosilylation reaction using a ruthenium complex as a catalyst. Therefore, the polyoxyethylene polymer (A) may contain a ruthenium complex (B) used as a catalyst.

[0112] The manufacturing method of polyoxyethylene polymer (A) will be described below.

[0113] The polyoxyethylene polymer (A) described above can be manufactured by a method involving the hydrosilylation of an allyl polyoxyethylene polymer with a hydrosilane compound in the presence of a ruthenium complex (D).

[0114] Allyl polyoxyethylene polymers are prepared using hydroxyl polyoxyethylene polymers obtained by ring-opening polymerization of cyclic ether compounds through the method described above.

[0115] To introduce allyl groups into the terminal hydroxyl groups of polyoxyethylene polymers, alkali metal compounds are used to act on the terminal hydroxyl groups, converting them into alkali metal alkoxides. Alternatively, complex metal cyanide catalysts can be used instead of alkali metal compounds.

[0116] 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.

[0117] Among these, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide and potassium tert-butoxide are preferred, and sodium methoxide and sodium tert-butoxide are more preferred.

[0118] From an availability perspective, sodium methoxide is particularly preferred. From a reactivity perspective, sodium tert-butoxide is particularly preferred.

[0119] Alkali metal compounds can be supplied to the reaction in solution form.

[0120] The amount of alkali metal compound used is only required to introduce the desired amount of allyl groups into the hydroxyl groups of the polyoxyethylene polymer; there is no particular limitation.

[0121] The amount of alkali metal compound used is preferably 0.5 moles or more, more preferably 0.6 moles or more, further preferably 0.7 moles or more, and even more preferably 0.8 moles or more, relative to 1.0 mole of hydroxyl groups in the polyoxyethylene polymer.

[0122] The amount of alkali metal compound used is preferably 1.2 moles or less, more preferably 1.1 moles or less, relative to 1.0 mole of hydroxyl groups in the polyoxyethylene polymer.

[0123] Therefore, relative to 1.0 mole of hydroxyl groups in the polyoxyethylene polymer, the amount of alkali metal compound used is preferably 0.5 moles or more and 1.2 moles or less, more preferably 0.6 moles or more and 1.2 moles or less, further preferably 0.7 moles or more and 1.1 moles or less, and particularly preferably 0.8 moles or more and 1.1 moles or less.

[0124] From the viewpoint of ensuring that the reaction of the hydroxyl groups of the polyoxyethylene polymer with the alkali metal compound proceeds well, it is preferable to remove water and alcohols other than the polyoxyethylene polymer having hydroxyl groups from the reaction solution containing the polyoxyethylene polymer and the alkali metal compound beforehand.

[0125] Various known methods can be used to remove water and alcohol. Specifically, methods selected from heating evaporation, vacuum devolatilization, spray vaporization, thin-film evaporation, and azeotropic devolatilization can be employed.

[0126] There is no particular temperature limit for the reaction of the hydroxyl groups in polyoxyethylene polymers with alkali metal compounds, as long as the reaction proceeds well.

[0127] 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.

[0128] The reaction time between the hydroxyl groups of the polyoxyethylene polymer and the alkali metal compound is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.

[0129] By reacting the polyoxyolefin polymer obtained by alkali metal alkali saltation of hydroxyl groups as described above with a haloallyl group, a polyoxyolefin polymer having an allyl group is obtained.

[0130] Specific examples of halogenated allyl groups include allyl chloride, allyl bromide, and allyl iodide. Among these, allyl chloride is preferred due to ease of handling.

[0131] The amount of haloallyl used is only required to introduce the desired amount of allyl into the polyoxyethylene polymer; there is no particular limitation.

[0132] The amount of allyl halide is preferably 0.7 moles or more, more preferably 1.0 moles or more, relative to 1.0 moles of terminal hydroxyl groups in the polyoxyethylene polymer used to prepare the polyoxyethylene polymer obtained by alkali metal alkoxideation of hydroxyl groups.

[0133] Furthermore, relative to 1.0 mole of terminal hydroxyl groups in the polyoxyethylene polymer used to prepare the polyoxyethylene polymer obtained by alkali metal alkoxideation of hydroxyl groups, the amount of haloallyl groups is preferably 5.0 moles or less, more preferably 2.0 moles or less.

[0134] Therefore, relative to 1.0 mole of the terminal hydroxyl group of the polyoxyethylene polymer used to prepare the polyoxyethylene polymer obtained by alkali metal alkoxideation of hydroxyl groups, the amount of haloallyl group is preferably 0.7 moles or more and 5.0 moles or less, more preferably 1.0 moles or more and 2.0 moles or less.

[0135] The reaction temperature of the polyoxyolefin polymer obtained by alkali metal alkali saltation with the haloallyl group is preferably 50°C or higher and 150°C or lower, more preferably 110°C or higher and 140°C or lower.

[0136] The reaction time of the polyoxyolefin polymer obtained by alkali metal alkoxideation with the haloallyl group is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.

[0137] By hydrosilylating the allyl-containing polyoxyalkylene polymer obtained as described above with a hydrosilane compound, a reactive silicon-containing polyoxyalkylene polymer (A) is generated.

[0138] In the above N a1 / N t When the value is set to 0.85 or higher and 1.00 or lower, hydrosilylation is preferably carried out in the presence of a ruthenium complex (D).

[0139] The polyoxyolefin polymer (A) has the silicon-containing group (a1) represented by the above formula (1).

[0140] Therefore, as a hydrosilane compound, the compound represented by the following formula (1-1) is used.

[0141] HSiR 1 a X 3-a (1-1)

[0142] The hydrosilane compound represented by formula (1-1) forms the silicon-containing group (a1) represented by formula (1) by hydrosilylation reaction with the allyl group of the polyoxyolefin polymer.

[0143] Specific examples of hydrosilane compounds represented by formula (1-1) include: trimethoxysilane, triethoxysilane, triphenoxysilane, tri(2-propenoxy)silane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, (methoxymethyl)dimethoxysilane, (methoxymethyl)diethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, and diphenoxymethylsilane, etc.

[0144] From the perspective of the curability of the polyoxyethylene polymer (A) and the strength of the cured product, trimethoxysilane and dimethoxymethylsilane are particularly preferred as hydrosilane compounds.

[0145] The amount of hydrosilane compound used is preferably 1.0 mole or more, more preferably 3.0 mole or more, and even more preferably 5.0 mole or more, relative to the 1.0 mole of allyl groups in the polyoxyethylene polymer.

[0146] The amount of hydrosilane compound used is preferably 20.0 moles or less, more preferably 10.0 moles or less, relative to 1.0 mole of allyl groups in the polyoxyethylene polymer.

[0147] Therefore, relative to 1.0 mole of allyl groups in the polyoxyethylene polymer, the amount of hydrosilane compound is preferably 1.0 mole or more and 20.0 moles or less, more preferably 3.0 moles or more and 20.0 moles or less, and even more preferably 5.0 moles or more and 10.0 moles or less.

[0148] If the amount of hydrosilane compound within the above range is used, it is easy to obtain a low-viscosity and easy-to-handle polyoxyalkylene polymer (A).

[0149] As a ruthenium complex (D), any complex compound containing ruthenium atoms that can effectively promote the above-mentioned hydrosilylation reaction is acceptable, without any particular limitation.

[0150] As a ruthenium complex (D), a complex compound having a ligand (D1) from compound (E) is preferred.

[0151] Compound (E) has at least one carbon-carbon double bond and at least one electron-withdrawing group in one molecule. Here, the carbon-carbon double bond in compound (E) can be an alkene carbon-carbon double bond or an aromatic carbon-carbon double bond.

[0152] In addition, in compound (E), at least one electron-withdrawing group is bonded to a carbon atom that forms a carbon-carbon double bond.

[0153] The ruthenium complex (D) may have one or more ligands (D1).

[0154] Examples of electron-withdrawing groups in compound (E) include halogen atoms such as fluorine, chlorine, bromine, and iodine, as well as cyano, aldehyde, and nitro groups. When multiple electron-withdrawing groups exist within the same molecule, these groups may be identical or different.

[0155] The compound (E) has one or more electron-withdrawing groups in one molecule, preferably two or more, more preferably two to four, and even more preferably two or three.

[0156] As an electron-withdrawing group, a halogen atom is preferred, and more preferably one or more selected from fluorine, bromine, and iodine groups. As an electron-withdrawing group, bromine and iodine groups are more preferred, and bromine groups are even more preferred.

[0157] In particular, the compound (E) preferably has one or more, more preferably two or more, electron-withdrawing groups selected from fluorine, bromine and iodine groups in one molecule.

[0158] The compound (E) preferably has one or more electron-withdrawing groups selected from bromine and iodine groups in one molecule.

[0159] In this case, compound (E) may have fluorine groups in addition to bromine and / or iodine groups. These electron-withdrawing groups are directly bonded to the carbon atoms in compound (E) that form carbon-carbon double bonds.

[0160] As compounds (E), typically, compounds with cyclic skeletons can be cited. Cyclic skeletons can be monocyclic skeletons formed by only one single ring, such as cyclooctadiene skeletons, benzene skeletons, and cyclooctadiene skeletons; they can also be polycyclic skeletons formed by the condensation of two or more single rings or by single bond, such as naphthalene skeletons and biphenyl skeletons; and they can also be aliphatic cyclic skeletons with cross-linked structures, such as norbornene rings.

[0161] It should be noted that these skeletons may contain substituents such as the electron-withdrawing groups mentioned above. For example, 1,4-dibromobenzene is a compound having a benzene ring skeleton with bromine groups as substituents.

[0162] As compound (E), compounds having a norbornene skeleton, a cyclooctadiene skeleton, a benzene skeleton, or a benzoquinone skeleton are preferred. More specifically, compounds having a 2,5-norbornene 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 norbornene skeleton are more preferred. It should be noted that the benzene ring skeleton is a skeleton formed by a single benzene ring. The norbornene skeleton is a skeleton formed by a single norbornene ring.

[0163] Preferred specific examples of compound (E) include: 2-bromonorbornene, 2,3-dibromonorbornene, 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 1,4-diiodobenzene, structural isomers of 1,3,5-dichlorobenzene, and 1,3,5-dibromobenzene. - Triiodobenzene, structural isomers of 1,3,5-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-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, structural isomers of 1-bromo-3-chloro-5-iodobenzene, structural isomers of 1-bromo-3-fluoro-5-iodobenzene and 1-bromo-3-fluoro-5-iodobenzene.

[0164] From the viewpoint of improving the efficiency of conversion from allyl to silicon-containing group (a1), among these compounds, one or more selected from 2,3-dibromonorbornene, 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene and 1,3,5-tribromobenzene are preferred as compounds (E).

[0165] Ruthenium complex (D) can be manufactured by known manufacturing methods. Examples of raw materials for ruthenium complex (D) include, for example, anhydrous and hydrated compounds selected from ruthenium(III) chloride, ruthenium(III) bromide and ruthenium(III) iodide.

[0166] For example, the ruthenium complex (D) can be manufactured by the following method: First, compound (E) is added to an ethanol solution of ruthenium(III) chloride hydrate, and the mixture is heated under reflux. Then, the solid matter in the reaction solution is recovered by filtration. By drying the recovered solid matter, the ruthenium complex (D) is obtained.

[0167] When using ruthenium(III) chloride hydrate as a raw material, the reaction solution containing alkaline compounds such as sodium carbonate and sodium bicarbonate can be heated and refluxed to neutralize the hydrogen chloride generated during heating and reflux.

[0168] When reacting ruthenium(III) chloride hydrate with compound (E), from the viewpoint of reaction rate, it is preferable to use 1 molar equivalent or more of compound (E) relative to the ruthenium compound of the starting material.

[0169] The ruthenium complex (D) can be used as a nanoparticle catalyst. The particle size (cumulative median diameter) of the ruthenium complex (D) nanoparticles 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 more preferably 10 nm or less.

[0170] Therefore, the particle size of the ruthenium complex (D) nanoparticles is more preferably 0.5 nm or more and 100 nm or less, further preferably 0.5 nm or more and 50 nm or less, and particularly preferably 1 nm or more and 10 nm or less.

[0171] It should be noted that the cumulative median diameter can be determined using a transmission electron microscope (TEM).

[0172] The ruthenium complex (D) may contain a ligand (D1) from compound (E) as well as a ligand (D1) from a compound (E') that is not a compound (E).

[0173] Compound (E') is a compound that can coordinate with a ruthenium atom and does not belong to compound (E).

[0174] Specific examples of ligands (D1) derived from compound (E') include: 2,5-norbornadiene ligand, 1,5-cyclooctadiene ligand, p-cymene ligand, mesitylene ligand, benzene ligand, carbonyl ligand, isocyanate ligand, and aromatic ligand.

[0175] When the ruthenium complex (D) has both ligands (D1) from compound (E) and ligands (D1) from compound (E'), the higher the proportion of ligands (D1) from compound (E) among all the ligands (D1) in the ruthenium complex (D), the more selectively the allyl group can be converted into a silicon-containing group (a1) in the hydrosilylation reaction, which is therefore preferred.

[0176] The ratio of the amount of ligand (D1) from compound (E) to the total amount of ligand (D1) is preferably 1 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 100 mol% or less, further preferably 70 mol% or more and 100 mol% or less, and particularly preferably 90 mol% or more and 100 mol% or less.

[0177] In the above-described hydrosilylation reaction, compound (E) can be reacted with a ruthenium complex (D') that does not have a ligand (D1) from compound (E) in the reaction solution to generate a ruthenium complex (D).

[0178] The amount of 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 allyl polyoxyethylene polymer.

[0179] The amount of 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 allyl polyoxyethylene polymer.

[0180] The amount of ruthenium complex (D) used in the hydrosilylation reaction can be 0.01 ppm or more and 10 ppm or less, 0.1 ppm or more and 10 ppm or less, 1 ppm or more and 10 ppm or less, 0.01 ppm or more and 1 ppm or less, 0.1 ppm or more and 1% or less, or 0.01 ppm or more and 0.1 ppm or less, relative to the mass of the allyl polyoxyethylene polymer.

[0181] If the amount of ruthenium complex (D) is within the above range, the allyl group of the polyoxyethylene polymer can be converted into silicon-containing groups (a1) with high efficiency.

[0182] The hydrosilylation reaction can be carried out in the presence of a solvent or in the absence of a solvent.

[0183] When using a solvent, the type of solvent is not particularly limited. The solvent should be a compound that does not react with the raw materials or catalyst. Preferred examples of solvents include hydrocarbon solvents such as hexane and hydrogen halide solvents such as dichloromethane.

[0184] In the hydrosilylation reaction, it is preferable to use a solvent that has been fully dehydrated and fully deoxidized.

[0185] The reaction temperature for the hydrosilylation reaction can be appropriately determined by taking into account factors such as reactivity (reaction rate) and the heat resistance temperature of the reaction vessel. The reaction temperature is preferably 0°C or higher, more preferably 20°C or higher, and even more preferably 40°C or higher.

[0186] In addition, the reaction temperature is preferably below 200°C, and more preferably below 150°C.

[0187] That is, the reaction temperature is preferably above 0°C and below 200°C, more preferably above 20°C and below 200°C, and even more preferably above 40°C and below 150°C.

[0188] The higher the reaction temperature, the shorter the reaction time, and sometimes it can suppress side reactions.

[0189] The reaction time for the hydrosilylation reaction is not particularly limited, as long as the desired degree of reaction can be achieved. The reaction temperature is preferably 5 minutes or more and 12 hours or less, more preferably 10 minutes or more and 5 hours or less.

[0190] The hydrosilylation reaction is preferably carried out in an atmosphere of inert gases such as nitrogen or argon.

[0191] Hydrosilylation is also preferably carried out in the presence of compound (E).

[0192] In other words, hydrosilylation is preferably carried out in the presence of a ruthenium complex (D) and a compound (E). Under these conditions, the allyl groups in the polyoxyalkylene polymer can be readily and efficiently converted into silicon-containing groups (a1).

[0193] After generating the polyoxyethylene polymer (A) as described above, the polyoxyethylene polymer is washed with water, or the volatiles are removed from the polyoxyethylene polymer by distillation as needed, to obtain the polyoxyethylene polymer (A).

[0194] <(Meth)acrylic acid copolymer (B)>

[0195] The curable composition comprises a (meth)acrylic copolymer having a reactive silicone group.

[0196] The molecular chain of (meth)acrylic copolymer (B) contains two or more units derived from alkyl (meth)acrylic esters.

[0197] The reactive silicon group in (meth)acrylic acid copolymer (B) is represented by the group in formula (2) below.

[0198] -SiR 1 a X 3-a (2)

[0199] In equation (2), R 1 X and a are related to R in equation (1) 1 The same applies to X and a.

[0200] Specific examples of alkyl acrylates that form the molecular chains constituting (meth)acrylic acid copolymers 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 methacrylate. Esters, etc.

[0201] Specific examples of alkyl methacrylates that form the molecular chains constituting (meth)acrylic acid copolymers 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 methyl methacrylate. Esters, etc.

[0202] The molecular chain of (meth)acrylic copolymer (B) contains two or more units derived from alkyl (meth)acrylic esters.

[0203] The ratio of the mass of the unit derived from the alkyl methacrylate to the mass of the molecular chain of the (meth)acrylate copolymer (B) is preferably 50% by mass or more, more preferably 70% by mass or more.

[0204] From the perspective of the compatibility of (meth)acrylic copolymer (B) with polyoxyethylene copolymer (A) and the stability of (meth)acrylic copolymer (B), the monomer used to prepare (meth)acrylic copolymer (B) preferably includes two or more selected from alkyl acrylate (ai) having 1 or more and 8 or less carbon atoms, and / or alkyl methacrylate (aii) having 1 or more and 8 or less carbon atoms, alkyl acrylate (bi) having 10 or more carbon atoms, and / or alkyl methacrylate (bii) having 10 or more carbon atoms.

[0205] Alkyl acrylate (ai) having 1 or more and 8 or fewer carbon atoms and alkyl methacrylate (aii) having 1 or more and 8 or fewer carbon atoms are represented by the following formula (B1).

[0206] CH2=CR b1 COOR b2 (B1)

[0207] In equation (B1), R b1 It can be a hydrogen atom or a methyl group. R b2 It is an alkyl group with 1 or more but less than 8 carbon atoms.

[0208] As R in equation (B1) b2 Examples include alkyl groups with 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, tert-butyl, and 2-ethylhexyl.

[0209] As R b2 The alkyl group preferably has 1 or more and 4 or less carbon atoms, and more preferably 1 or 2.

[0210] Alkyl acrylate (bi) having 10 or more carbon atoms and alkyl methacrylate (bii) having 10 or more carbon atoms are represented by the following formula (B2).

[0211] CH2=CR b3 COOR b4 (B2)

[0212] In equation (B2), R b3It can be a hydrogen atom or a methyl group. R b4 It is an alkyl group with 10 or more carbon atoms.

[0213] As R in equation (2) b4 Examples include alkyl groups with 10 or more carbon atoms, such as lauryl, n-tridecyl, cetyl, and stearyl.

[0214] As R b4 The alkyl group has a more preferred number of carbon atoms of 10 or more and 30 or less, and even more preferably 10 or more and 20 or less.

[0215] The ratio Wb1:Wb2 of the mass Wb1 of the unit (b1) of the alkyl methacrylate represented by formula (B1) and the mass Wb2 of the unit (b2) of the alkyl methacrylate represented by formula (B2) in the (meth)acrylate copolymer (B) is preferably 95:5 to 40:60, more preferably 90:10 to 60:40.

[0216] The monomers used to manufacture (meth)acrylic copolymers (B) may also contain monomers other than alkyl (meth)acrylic esters.

[0217] Other monomers include: acrylic acid and methacrylic acid; (meth)acrylamides such as acrylamide, methacrylamide, N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide; (meth)acrylates containing epoxy groups such as glycidyl acrylate and glycidyl methacrylate; amino-unsaturated compounds such as 2-(N,N-diethylamino)ethyl methacrylate and 2-aminoethyl vinyl ether; acrylonitrile and methacrylonitrile; styrene and α-methylstyrene; alkyl vinyl ethers; vinyl chloride; and vinyl acetate and vinyl propionate, etc.

[0218] The molecular weight of the (meth)acrylic acid copolymer (B) is not particularly limited as long as it does not impair the desired effect. The molecular weight of the (meth)acrylic acid copolymer (B), calculated as the number average molecular weight of polystyrene as determined by GPC, is preferably 500 or more and 100,000 or less, more preferably 1,000 or more and 10,000 or less.

[0219] (Meth)acrylic acid copolymers (B) can be manufactured by conventional vinyl polymerization. Examples of vinyl polymerization methods include, for example, solution polymerization based on free radical reactions and bulk polymerization. Vinyl polymerization is not limited to these methods.

[0220] Typically, the polymerization reaction described above is carried out at a temperature above 50°C and below 150°C in the presence of monomers, free radical initiators, chain transfer agents, and solvents.

[0221] The conditions for polymerization reactions are not limited to those described above.

[0222] Specific examples of free radical initiators include: azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and benzoyl peroxide.

[0223] Specific examples of chain transfer agents include thiols such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and lauryl mercaptan, as well as halogenated compounds.

[0224] As a solvent, solvents that are inactive in the polymerization reaction, such as ethers, hydrocarbons and esters, are preferred.

[0225] Various methods are known as ways to introduce reactive silicon groups into (meth)acrylic acid copolymers.

[0226] As a specific example, the following can be cited:

[0227] I) A method for copolymerizing a compound having an olefinic unsaturated double bond and a reactive silicon group with a monomer comprising an alkyl methacrylate represented by formula (B1) and an alkyl methacrylate represented by formula (B2);

[0228] II) A method for reacting reactive silicon and a compound capable of reacting with the reactive functional group (e.g., acrylic acid) with a monomer containing an alkyl methacrylate represented by formula (B1) and an alkyl methacrylate represented by formula (B2) to obtain a copolymer;

[0229] III) A method for copolymerizing monomers comprising alkyl methacrylates represented by formula (B1) and alkyl methacrylates represented by formula (B2) in the presence of a reactive silyl thiol as a chain transfer agent.

[0230] VI) A method for copolymerizing monomers comprising alkyl methacrylates represented by formula (B1) and alkyl methacrylates represented by formula (B2) using a reactive silicon-based azodicarbonyl compound or a reactive silicon-based disulfide compound as initiators; and

[0231] V) A method for introducing reactive silicon groups into the ends of molecular chains of copolymers obtained by copolymerizing monomers containing alkyl methacrylates represented by formula (B1) and alkyl methacrylates represented by formula (B2) via living radical polymerization.

[0232] The method of introducing reactive silicon groups into (meth)acrylic copolymers is not limited to the methods described above.

[0233] As the compound having an olefinic unsaturated double bond and a reactive silicon group used in the method described in I), the compound represented by the following formula (B3) is preferred.

[0234] CH2=CR b5 COOR b6 -SiR 1 a X 3-a (B3)

[0235] In formula (B3), R 1 X and a are related to R in equation (1) 1 The same applies to X and a. R b5 It can be a hydrogen atom or a methyl group. R b6 It is an alkylene group having 1 or more but less than 6 carbon atoms.

[0236] In equation (B3), R is used as b6 The alkylene group is a alkylene group with 1 or more carbon atoms and 6 or less, such as methylene, ethane-1,2-diyl (ethylene), and propane-1,3-diyl (trimethylene), and is preferably a alkylene group with 1 or more carbon atoms and 4 or less.

[0237] Specific examples of compounds having olefinic unsaturated double bonds and reactive silicon groups include: γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacryloxypropyltriethoxysilane, etc.; γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacryloxypropyltriethoxysilane, etc.; vinylalkoxysilane, vinylmethyldimethoxysilane, and vinyltriethoxysilane, etc.

[0238] Examples of reactive functional groups in compounds having olefinic unsaturated double bonds and reactive functional groups used in method II) above include amino, hydroxyl, and carboxyl groups. Examples of groups capable of reacting with these reactive functional groups include isocyanate groups.

[0239] In addition, as other examples, allyl groups, which are reactive functional groups, can be cited as described in Japanese Patent Application Publication Nos. 54-36395, 01-272654, and 02-214759. Hydrogenated silicon (H-Si) groups can be cited as examples of groups capable of reacting with allyl groups.

[0240] Examples of reactive silyl thiols used as chain transfer agents in the method described in III) above include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropyltriethoxysilane.

[0241] Examples of reactive silicon-based azodiacetic compounds and disulfide compounds used in the method described in the above IV) include azodiacetic compounds and disulfide compounds containing alkoxysilyl groups as disclosed in Japanese Patent Application Publication No. 60-23405 and Japanese Patent Application Publication No. 62-70405.

[0242] As an example of the method described in the above-mentioned V), the method described in Japanese Patent Application Publication No. 09-272714, etc.

[0243] Other methods include those described in Japanese Patent Application Publication Nos. 59-168014 and 60-228516, which combine a reactive silicon-based thiol with a reactive silicon-based free radical polymerization initiator.

[0244] The number of reactive silicon groups in the (meth)acrylic acid copolymer (B) is not particularly limited. The number of reactive silicon groups in the (meth)acrylic acid copolymer (B) is preferably 0.1 or more and 2.0 or less on average per molecule, more preferably 0.5 or more and 1.5 or less.

[0245] The amount of (meth)acrylic copolymer (B) in the curable composition is not particularly limited as long as it does not impair the desired effect. The amount of (meth)acrylic copolymer (B) in the curable composition is preferably 10 parts by weight or more and 200 parts by weight or less, more preferably 20 parts by weight or more and 160 parts by weight or less, relative to 100 parts by weight of polyoxyethylene polymer (A).

[0246] Among those skilled in the art, the monomer composition of (meth)acrylate polymers (B) is typically selected based on the intended use and purpose of the curable composition.

[0247] When the curable composition is used in applications requiring strength, such as adhesives, a relatively high glass transition temperature (Tg) is preferred for the (meth)acrylate polymer (B). Specifically, the Tg of the (meth)acrylate polymer (B) is preferably 0°C or higher and 200°C or lower, more preferably 20°C or higher and 100°C or lower. It should be noted that Tg is determined using the following Fox formula.

[0248] Fox-style:

[0249] 1 / (Tg(K))=Σ(Mi / Tgi)

[0250] (Where, Mi is the weight fraction of monomer i constituting the polymer, and Tgi is the glass transition temperature (K) of the homopolymer of monomer i.)

[0251] For example, polymethyl methacrylate (PMMA) is known as a (meth)acrylate polymer with a relatively high glass transition temperature (Tg). Therefore, there is a tendency that the higher the mass ratio of PMMA to monomer in the monomers used to manufacture the (meth)acrylate copolymer (B), the higher the glass transition temperature (Tg) of the (meth)acrylate copolymer (B). Conversely, there is a tendency that the lower the mass ratio of PMMA to monomer, the lower the glass transition temperature (Tg) of the (meth)acrylate copolymer (B).

[0252] When using a curable composition as an adhesive, from the viewpoint of easily forming a high-strength cured product, it is preferable that the mass ratio of methyl methacrylate used in the manufacture of (meth)acrylic copolymer (B) is 50% or more relative to the mass ratio of the monomer used in the manufacture of (meth)acrylic copolymer (B).

[0253] When using a curable composition as a sealing material, considering the low viscosity and good workability of the curable composition, it is preferable that the mass ratio of methyl methacrylate to the mass ratio of the monomer used in the manufacture of the (meth)acrylic copolymer (B) is less than 50%.

[0254] <Cure Catalyst (C)>

[0255] The curable composition contains a curing catalyst (C) for the purpose of enabling the reactive silicon group to undergo a hydrolysis / condensation reaction, i.e., promoting the curing reaction.

[0256] As the curing catalyst (C), existing known catalysts can be used. Specifically, organotin compounds, metal salts of carboxylic acids, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, and mixtures thereof can be used as curing catalysts (C).

[0257] Specific examples of organotin compounds include: dibutyltin dilaurate, dibutyltin dioctanoate, bis(butylmaleic acid) dibutyltin, dibutyltin diacetate, dibutyltin oxide, bis(acetylacetonyl) dibutyltin, reactants of dibutyltin oxide with silicate compounds, reactants of dibutyltin oxide with phthalates, dioctyltin diacetate, dioctyltin dilaurate, bis(ethylmaleic acid) dioctyltin, bis(octylmaleic acid) dioctyltin, bis(acetylacetonyl) dioctyltin, dioctyltin distearate, dioctyltin oxide, and reactants of dioctyltin oxide with silicate compounds. Among these, dioctyltin compounds are preferred due to increased environmental concerns in recent years.

[0258] Specific examples of metal salts of carboxylic acids include: tin carboxylic acid, bismuth carboxylic acid, titanium carboxylic acid, zirconium carboxylic acid, iron carboxylic acid, potassium carboxylic acid, and calcium carboxylic acid. As metal salts of carboxylic acids, the following carboxylic acids can be combined with various metals.

[0259] Specific examples of amine compounds 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.

[0260] 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 tertiary carbonic acid.

[0261] Specific examples of alkoxy metals include: titanium compounds such as tetrabutyl titanate, tetra(acetylacetonyl)titanium, ethyl acetoacetate titanium, and bis(ethyl acetoacetate)diisopropoxytitanium; aluminum compounds such as tri(acetylacetonyl)aluminum and ethyl acetoacetatediisopropoxyaluminum; and zirconium compounds such as tetra(acetylacetonyl)zirconium.

[0262] Other curing catalysts (C) can include fluorinated anionic compounds, photoacid generators, and photoalkali generators.

[0263] As a curing catalyst (C), two or more different catalysts can be used in combination. For example, by combining the above-mentioned amine compound with a carboxylic acid, or by combining an amine compound with an alkoxy metal, the reactivity of the curing reaction can be improved.

[0264] The amount of curing catalyst (C) relative to 100 parts by mass of polyoxyethylene polymer (A) is preferably 0.001 parts by mass or more and 20 parts by mass or less, more preferably 0.01 parts by mass or more and 15 parts by mass or less, and particularly preferably 0.01 parts by mass or more and 10 parts by mass or less.

[0265] Depending on the type of curing catalyst (C), sometimes after the curing composition has cured, the curing catalyst (C) may seep to the surface of the cured material, or the surface of the cured material may become contaminated with the curing catalyst (C). In such cases, it is preferable to use 0.01 parts by weight or more and 3.0 parts by weight or less of the curing catalyst (C) relative to 100 parts by weight of the polyoxyethylene polymer (A). In this case, the surface condition of the cured material is well maintained while ensuring curability.

[0266] <Other Additives>

[0267] Other additives besides those mentioned above can be incorporated into the curable composition. These other additives may include silicone compounds, adhesive agents, plasticizers, solvents, diluents, silicates, fillers, anti-sagging agents, antioxidants, light stabilizers, UV absorbers, property modifiers, tackifying resins, epoxy-containing compounds, photocurable substances, oxygen-curable substances, surface modifiers, epoxy resins, other resins, flame retardants, and foaming agents.

[0268] Furthermore, various additives may be added to the curing composition as needed to adjust the various physical properties of the curing composition or cured product. Examples of such additives include: curing modifiers, polymerization inhibitors, metal passivators, ozone deterioration inhibitors, phosphorus peroxide decomposers, lubricants, pigments, and fungicides.

[0269] (filler)

[0270] Various fillers can be incorporated into the curing composition. Examples of fillers include: heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium dioxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silica, hydrated silica, carbon black, iron oxide, aluminum micropowder, zinc oxide, active zinc oxide, PVC powder, PMMA powder, glass fiber and filaments, etc.

[0271] The amount of filler used is preferably 1 part or more and 300 parts or less, more preferably 10 parts or more and 250 parts or less, relative to 100 parts by mass of the polyoxyethylene polymer (A).

[0272] For the purpose of reducing the weight (specific gravity) of the cured product, organic hollow spheres and / or inorganic hollow spheres can be added to the curable composition. Hollow spheres are spherical fillers with a hollow interior. Examples of materials that can be used for hollow spheres include inorganic materials such as glass, white sand, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and styrene.

[0273] The amount of hollow spheres used is preferably 0.1 parts by mass or more and 100 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the polyoxyethylene polymer (A).

[0274] (Adhesive-enhancing agent)

[0275] Adhesive-enhancing agents can be added to curable compositions. Examples of adhesive-enhancing agents include silane coupling agents and reactants of silane coupling agents.

[0276] Specific examples of silane coupling agents include: γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane, etc., which contain amino silanes; γ-isocyanate propyltrimethoxysilane, γ-isocyanate propyltrimethoxysilane, etc. Ethoxysilane, γ-isocyanate propylmethyl dimethoxysilane, α-isocyanate methyl trimethoxysilane and α-isocyanate methyl dimethoxymethylsilane, etc., containing isocyanate groups; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane and γ-mercaptopropylmethyl dimethoxysilane, etc., containing mercaptosilanes; γ-epoxypropoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc., containing epoxy groups, etc.

[0277] In addition, condensates of various silane coupling agents, such as aminosilane condensates, condensates of aminosilane and other alkoxysilanes, and reactants of various silane coupling agents, such as aminosilane and epoxysilane reactants, and reactants of aminosilane and (meth)acrylate silane reactants, can also be used as adhesive imparting agents.

[0278] The adhesive agent mentioned above can be used alone or in combination of two or more.

[0279] The amount of silane coupling agent used is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the polyoxyethylene polymer (A).

[0280] (Plasticizer)

[0281] Plasticizers can be added to the curing composition. Specific examples of plasticizers include: phthalate compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate compounds such as bis(2-ethylhexyl)-1,4-benzenediacarboxylate; and non-phthalate compounds such as diisononyl 1,2-cyclohexanedicarboxylate. Compounds; aliphatic polycarboxylic acid esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and acetyl tributyl citrate; unsaturated fatty acid esters such as butyl oleate and acetyl methyl castor oil; alkyl sulfonates; phosphate esters; trimellitic acid esters; chlorinated paraffins; hydrocarbon oils such as alkyl biphenyls and partially hydrogenated terphenyls; processing oils; epoxidized soybean oil and epoxy plasticizers such as benzyl epoxidized stearate, etc.

[0282] Alternatively, polymeric plasticizers can be used. Specific examples of polymeric plasticizers include: vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol with a number average molecular weight of 500 or higher, and derivatives obtained by converting the hydroxyl groups of these polyether polyols into ester groups, ether groups, etc.; polystyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, and polychloroprene, etc.

[0283] Plasticizers can be used in combination, either one type or two or more.

[0284] Polymer plasticizers may or may not have reactive silicon groups. When a polymer plasticizer has reactive silicon groups, it functions as a reactive plasticizer, preventing the transfer of the plasticizer from the cured product. When a polymer plasticizer has reactive silicon groups, the average number of reactive silicon groups per molecule is preferably 1 or less, more preferably 0.8 or less.

[0285] When using a plasticizer with reactive silicon groups, especially a polyoxyethylene polymer with reactive silicon groups, it is preferable that the number average molecular weight of the polyoxyethylene polymer used as the plasticizer is lower than that of the polyoxyethylene polymer (A).

[0286] The amount of plasticizer used is preferably 5 parts or more and 150 parts or less, more preferably 10 parts or more and 120 parts or less, and even more preferably 20 parts or more and 100 parts or less, relative to 100 parts by mass of the polyoxyethylene polymer (A).

[0287] (Solvent, diluent)

[0288] Solvents or diluents may be added to the curable composition. There are no particular limitations on the choice of solvent or diluent, as long as it does not impair the desired effect. Aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, and ethers may be used as solvents or diluents.

[0289] When using solvents or diluents, to address the issue of air pollution when using curing compositions 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.

[0290] Solvents or diluents can be used alone or in combination of two or more.

[0291] (Anti-sagging agent)

[0292] To prevent sagging and improve workability, an anti-sagging agent may be added to the curing composition as needed. There are no particular limitations on the anti-sagging agent. Examples of anti-sagging agents include: polyamide waxes; hydrogenated castor oil derivatives; and metallic soaps such as calcium stearate, aluminum stearate, and barium stearate.

[0293] Anti-sagging agents can be used in single-agent or in combination of two or more types.

[0294] The amount of anti-sagging agent is preferably 0.1 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the polyoxyethylene polymer (A).

[0295] (Antioxidant)

[0296] Antioxidants (anti-aging agents) can be added to the curing composition. Using antioxidants can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenolic compounds, monophenolic compounds, bisphenolic compounds, and polyphenolic compounds.

[0297] Examples of suitable antioxidants include Irganox 245, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 1330, and Irganox 1520 (all manufactured by BASF); SONGNOX 1076 (manufactured by SONGWON) and BHT.

[0298] Similarly, hindered amine light stabilizers such as Tinuvin 622LD, Tinuvin 144, Tinuvin 292, ChimassorB944LD, and ChimassorB119FL (all manufactured by BASF); Adekastab LA-57, Adekastab LA-62, Adekastab LA-67, Adekastab LA-63, and Adekastab LA-68 (all manufactured by ADEKA Corporation); Sanol LS-2626, Sanol LS-1114, and Sanol LS-744 (all manufactured by Sankyo Life Sciences Co., Ltd.); and NocRac CD (manufactured by Ouchi Shinsei Chemical Co., Ltd.) can also be used.

[0299] In addition, antioxidants such as SONGNOX4120, Naugard 445, and OKABEST CLX050 can also be used. Specific examples of antioxidants are also described in Japanese Patent Application Publication Nos. 4-283259 and 9-194731.

[0300] The amount of antioxidant used is preferably 0.1 parts by mass and 10 parts by mass and less than 10 parts by mass relative to 100 parts by mass of polyoxyethylene polymer (A), more preferably 0.2 parts by mass and 5 parts by mass and less.

[0301] (Light stabilizer)

[0302] A light stabilizer can be added to the curable composition. Using a light stabilizer prevents photo-oxidative degradation of the cured product. Examples of light stabilizers include benzotriazole compounds, hindered amine compounds, and benzoate esters. Hindered amine compounds are particularly preferred.

[0303] The amount of light stabilizer used is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.2 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the polyoxyethylene polymer (A).

[0304] (UV absorber)

[0305] UV absorbers can be added to the curing composition. Using UV absorbers can improve the surface weather resistance of the cured product.

[0306] Examples of UV absorbers include benzophenone compounds, benzotriazole compounds, salicylates, substituted acrylonitrile compounds, and metal chelate compounds. Benzotriazole compounds are particularly preferred.

[0307] Preferred 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).

[0308] The amount of ultraviolet absorber is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.2 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the polyoxyethylene polymer (A).

[0309] (Modifier)

[0310] For the purpose of adjusting the tensile properties of the cured product, a property modifier may be added to the curing composition as needed. There are no particular limitations on the property modifier.

[0311] Preferred specific examples of property modifiers include: alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltrimethoxysilane; alkylisopropoxysilanes such as dimethyldiisopropoxysilane, methyltriisopropoxysilane, and γ-glycidoxypropylmethyldiisopropoxysilane; trialkylsilyl borates such as tri(trimethylsilyl)borate and tri(triethylsilyl)borate; organosilicon varnishes; polysiloxanes, etc.

[0312] By using property modifiers, the hardness of the cured material can be increased, or conversely, the hardness can be decreased to increase the elongation at break of the cured material.

[0313] One type of property modifier can be used, or two or more types can be used in combination.

[0314] In particular, compounds that are hydrolyzed to form compounds with monovalent silanol groups within the molecule do not worsen the stickiness of the cured surface, but instead reduce the modulus of the cured material.

[0315] As such compounds, compounds that generate trimethylsilanol are particularly preferred. Examples of compounds that generate monovalent silanol groups within the molecule through hydrolysis include derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerol, pentaerythritol, and sorbitol, i.e., silicon compounds that generate monosilane alcohols through hydrolysis.

[0316] Specific examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.

[0317] The amount of property modifier used is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of polyoxyethylene polymer (A).

[0318] (Tackifying resin)

[0319] Tackifying resins may be added to the curable composition to improve adhesion and bonding with the substrate, or as needed for other purposes. There are no particular limitations on the tackifying resins used.

[0320] Specific examples of tackifying resins include: terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenolic resins, phenolic resins, modified phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers, hydrogenated styrene block copolymers, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymers, etc.), hydrogenated petroleum resins, and DCPD resins, etc.

[0321] Tackifying resins can be used in combination with one type or two or more types.

[0322] The amount of tackifying resin used is preferably 2 parts or more and 100 parts or less, more preferably 5 parts or more and 50 parts or less, and even more preferably 5 parts or more and 30 parts or less, relative to 100 parts by weight of the polyoxyethylene polymer (A).

[0323] (Compounds containing epoxy groups)

[0324] Compounds containing epoxy groups can be added to curable compositions. Using compounds with epoxy groups improves the resilience of the cured product. Examples of compounds with epoxy groups include: epoxidized unsaturated oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof.

[0325] Specific examples include epoxidized soybean oil, epoxidized flaxseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylic acid ester (E-PS), epoxyoctyl stearate, and epoxybutyl stearate, which are compounds containing epoxy groups.

[0326] Relative to 100 parts by weight of the polyoxyethylene polymer (A), it is preferable to use a compound containing an epoxy group at a rate of 0.5 parts by weight or more and 50 parts by weight or less.

[0327] (Photocurable substances)

[0328] A photocurable substance can be added to the curing composition. Using a photocurable substance allows a film to form on the surface of the cured material, improving its stickiness and weather resistance. Known photocurable substances include organic monomers, oligomers, resins, or compositions containing these substances. Representative photocurable substances include monomers, oligomers, and mixtures thereof having one or more acrylic unsaturated groups or methacrylic unsaturated groups (i.e., unsaturated acrylic compounds); polyvinyl cinnamates; and azide resins.

[0329] The amount of photocurable substance used is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the polyoxyethylene polymer (A).

[0330] (Oxygen-curing substances)

[0331] Oxygen-curing substances can be added to the curing composition. Examples of oxygen-curing substances include unsaturated compounds that can react with oxygen in the air. When the oxygen-curing substance reacts with oxygen in the air, a cured film is formed near the surface of the cured material, exhibiting the effect of preventing surface stickiness, and preventing the adhesion of debris and dust to the surface of the cured material.

[0332] 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 obtained by modifying drying oils; and liquid polymers such as polymers of 1,2-polybutadiene, 1,4-polybutadiene, and C5-C8 dienes obtained by homopolymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene.

[0333] Oxygen-curing substances can be used in single-use or mixed combinations of two or more.

[0334] The amount of oxygen-curing substance used is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the polyoxyethylene polymer (A). As described in Japanese Patent Application Publication No. 3-160053, the oxygen-curing substance is preferably used in combination with a photocurable substance.

[0335] (Epoxy resin)

[0336] Epoxy resin can be added to the curing composition. The curing composition containing epoxy resin is preferably used as an adhesive, and particularly preferably as an adhesive for exterior wall tiles. Examples of epoxy resins include bisphenol A type epoxy resin and phenolic varnish type epoxy resin.

[0337] The ratio of epoxy resin to polyoxyethylene polymer (A) by mass is preferably in the range of 100 / 1 to 1 / 100.

[0338] When epoxy resin is added to a curing composition, a curing agent that cures the epoxy resin can be added to the curing composition together with the epoxy resin.

[0339] There are no special restrictions on the use of epoxy resin curing agents; any commonly used epoxy resin curing agents can be used.

[0340] When using a curing agent for epoxy resin, the amount of curing agent used is preferably in the range of 0.1 parts by weight or more and 300 parts by weight or less per 100 parts by weight of epoxy resin.

[0341] The curable composition described above can be cured by a method appropriate to the intended use of the curable composition, thereby forming a cured product.

[0342] Preparation of Curable Compositions

[0343] Curing compositions can be prepared in a single-component form in which all components are pre-mixed and sealed, and cured by the action of moisture in the air after application.

[0344] Alternatively, it can be prepared in a two-component form, in which a curing catalyst, filler, plasticizer, water, and other components are separately formulated as a curing agent before use, and this formulated material is mixed with a polymer composition containing a polyoxyethylene polymer (A) before use. From an operability perspective, a single-component form is preferred.

[0345] When the curable composition is a single-component form, all compounding components are pre-formulated. Therefore, it is preferable to pre-dehydrate and dry the compounding components containing moisture before use, or to dehydrate them during compounding by means of reduced pressure or the like.

[0346] In addition to the dehydration and drying method, the storage stability of the curable composition is further improved by adding alkoxysilane compounds such as methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-epoxypropoxypropyltrimethoxysilane to the curable composition.

[0347] Uses of Curing Compositions

[0348] The curable compositions can be used as sealing materials for construction, adhesives for industrial applications, compositions for forming waterproof coatings, and raw materials for adhesives. Furthermore, they can be used as sealants for buildings, ships, automobiles, and roads. In addition, the curable compositions can bond well to a wide range of substrates, including glass, porcelain, wood, metal, and resin molded products, 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. Besides being conventional adhesives, the curable compositions can also be used as contact adhesives. Furthermore, the curable compositions are useful as food packaging materials, injection molding rubber materials, release agents, and coatings. The cured products of the aforementioned curable compositions exhibit low water absorption. Therefore, the aforementioned curable compositions and their cured products are particularly suitable for use as sealing materials, waterproof adhesives, waterproof coatings, and other waterproofing materials.

[0349] This invention is not limited to the embodiments described above, and various modifications can be made within the scope shown in the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included within the technical scope of this invention.

[0350] That is, the present invention includes the following methods.

[0351] <1> A curable composition comprising: a polyoxyethylene polymer having reactive silicon groups (A), a (meth)acrylic acid copolymer having reactive silicon groups (B), and a curing catalyst (C).

[0352] Polyoxyolefin polymer (A) has a silicon-containing group (a1) represented by the following formula (1).

[0353] [Chemical Formula 4]

[0354]

[0355] In formula (1), R is a hydrocarbon group with 1 or more but less than 20 carbon atoms, either substituted or unsubstituted; X is a hydroxyl group or a hydrolyzable group; and a is 0, 1, or 2.

[0356] Polyoxyolefin polymers (A) have a number average molecular weight exceeding 3000.

[0357] In polyoxyethylene polymers (A), the number N of silicon groups (a1) is... a1 The total N relative to the number of reactive silicon groups, the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups. t The ratio N a1 / N tValues ​​between 0.85 and 1.00

[0358] The molecular chain of (meth)acrylic copolymer (B) contains two or more units derived from alkyl (meth)acrylic esters.

[0359] The reactive silicon group in (meth)acrylic acid copolymer (B) is represented by the group in formula (2) below.

[0360] -SiR 1 a X 3-a (2)

[0361] (In equation (2), R) 1 X and a are related to R in equation (1) 1 (The same applies to X and a.)

[0362] <2> according to <1> The curable composition, wherein,

[0363] In the polyoxyolefin polymer (A), the above-mentioned N a1 / N t It is above 0.90 and below 1.00.

[0364] <3> according to <1> or <2> The curable composition, wherein,

[0365] The number average molecular weight of polyoxyethylene polymers (A) is above 10,000.

[0366] <4> according to <3> The curable composition, wherein,

[0367] The number average molecular weight of polyoxyethylene polymers (A) is above 20,000.

[0368] <5> according to <1> ~ <4> The curable composition described in any one of the following statements, wherein,

[0369] (Meth)acrylic copolymer (B) is a polymer containing monomers of methyl methacrylate.

[0370] The mass ratio of methyl methacrylate to the monomer is 50% or more by mass.

[0371] The above-mentioned curable composition is used as an adhesive.

[0372] <6> according to <1> ~ <4> The curable composition described in any one of the following statements, wherein,

[0373] (Meth)acrylic copolymer (B) is a polymer containing monomers of methyl methacrylate.

[0374] The mass ratio of the above-mentioned methyl methacrylate to the monomer is less than 50% by mass.

[0375] The above-mentioned curable composition is used as a sealing material.

[0376] <7> A sort of <1> ~ <6> The curable composition described in any one of the following statements comprises a ruthenium complex (D).

[0377] <8> according to <7> The curable composition, wherein,

[0378] The ruthenium complex (D) has a ligand (D1) derived from compound (E).

[0379] Compound (E) has at least one carbon-carbon double bond and at least one electron-withdrawing group in one molecule.

[0380] At least one of the electron-withdrawing groups is bonded to a carbon atom that forms a carbon-carbon double bond.

[0381] <9> according to <8> The curable composition, wherein,

[0382] Compound (E) has a benzene ring skeleton or a norbornene skeleton.

[0383] <10> according to <8> or <9> The curable composition, wherein,

[0384] The compound (E) has at least one electron-withdrawing group selected from fluorine, bromine and iodine.

[0385] <11> A solidified substance, which is <1> ~ <10> The cured product of any one of the curable compositions.

[0386] Example

[0387] The number-average molecular weights in the examples are GPC molecular weights determined under the following conditions.

[0388] Liquid delivery system: Tosoh HLC-8420GPC

[0389] Column: Tosoh TSKgel SuperH series

[0390] Solvent: THF (tetrahydrofuran)

[0391] Molecular weight: Polystyrene conversion

[0392] Measurement temperature: 40℃

[0393] The proportions of silyl, 1-propenyl, propyl, or allyl were calculated using nuclear magnetic resonance (NMR) with the following instruments. 1 H NMR determination.

[0394] Device: AVANCE III HD500 digital device (manufactured by BRUKER)

[0395] (Synthesis example 1)

[0396] Polyoxypropylene glycol with a number average molecular weight of approximately 4500 was used as an initiator to polymerize propylene oxide using zinc hexacyanocobalt glycol dimethyl ether complex catalyst, resulting in a linear hydroxyl-containing polyoxyethylene polymer (H-1) with hydroxyl groups at both ends and a number average molecular weight of 27600.

[0397] For polymer (F-1), sodium methoxide with a content of 1.1 mol equivalent relative to the hydroxyl groups of polymer (H-1) was added in the form of a 28% methanol solution. After removing methanol from the resulting mixture by vacuum distillation, 1.3 mol equivalent of allyl chloride was added relative to the hydroxyl groups of polymer (H-1), and the reaction was carried out at 130 °C for 1 hour. Then, the unreacted allyl chloride was removed from the reaction solution by vacuum distillation. The resulting unpurified allyl-containing polyoxyethylene polymer was mixed with n-hexane and water, and the water was removed by centrifugation. The hexane was removed from the resulting hexane solution by vacuum distillation, thereby removing the metal salt from the polymer. Through the above operations, a linear allyl-containing polyoxyethylene polymer (A-1) was obtained.

[0398] (Synthesis example 2)

[0399] Adding 48 ppm [RuCl2(nbd)] relative to the mass of polymer (A-1) to the allyl polyoxyethylene polymer (A-1) n 2,3-Dibromonorbornadiene, at a mass of 120 ppm relative to polymer (A-1), and nbd is a 2,5-norbornadiene ligand. The 2,5-norbornadiene ligand does not possess electron-withdrawing groups. On the other hand, 2,3-dibromonorbornadiene is a compound possessing electron-withdrawing groups and capable of coordinating with ruthenium.

[0400] The resulting mixture was stirred at 90°C for 10 minutes. Next, 5.0 mol equivalents of dimethoxymethylsilane were added to the mixture relative to the allyl groups present in polymer (A-1), and the hydrosilylation reaction of the allyl groups in polymer (A-1) with dimethoxymethylsilane was carried out at 90°C. This was repeated every hour from the start of the reaction. 1 ¹H NMR analysis confirmed the complete disappearance of allyl groups in polymer (A-1) two hours after the start of the reaction. Volatile components were then removed from the mixture by vacuum distillation, yielding a polyoxyalkylene polymer (A1) with reactive silica groups.

[0401] The obtained polymer (A1) was subjected to 1 ¹H NMR determination was performed to calculate the total N value of each group relative to the number of reactive silicon groups (containing silicon groups (a1)), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups. t The proportion.

[0402] The result is that the number N of silicon-containing groups (a1) a1 Relative to N t The ratio is 99%. The number of 1-propenyl groups relative to N t The ratio is 0%. The amount of propyl groups relative to N... t The ratio is 1%. The number of allyl groups relative to N t The ratio is 0%.

[0403] (Synthesis example 3)

[0404] The polymer (A-1) obtained in Synthesis Example 1 was added with 50 ppm of commercially available Karstedt catalyst relative to the mass of polymer (A-1) and 5.0 mol equivalents of dimethoxymethylsilane relative to the allyl group of polymer (A-1). The hydrosilylation reaction of the allyl group of polymer (A-1) with dimethoxymethylsilane was carried out at 90 °C. The reaction was initiated 1 hour after the start of reaction. 1 ¹H NMR analysis confirmed the complete disappearance of allyl groups in polymer (A-1) one hour after the start of the reaction. Volatile components were then removed from the mixture by vacuum distillation, yielding a polyoxyalkylene polymer (A'1) with reactive silica groups.

[0405] The obtained polymer (A'1) was subjected to 1 ¹H NMR determination was performed to calculate the total N value of each group relative to the number of reactive silicon groups (containing silicon groups (a1)), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups. t The proportion.

[0406] The result is that the number N of silicon-containing groups (a1) a1 Relative to N t The ratio is 79%. The number of 1-propenyl groups relative to N t The ratio is 20%. The amount of propyl groups relative to N... t The ratio is 1%. The number of allyl groups relative to N t The ratio is 0%.

[0407] (Synthesis Example 4)

[0408] The polymer (H-1) obtained in Synthesis Example 1 was added to a 28% methanol solution with a sodium methoxide concentration of 0.9 mol equivalent relative to the hydroxyl groups of polymer (H-1). After removing the methanol from the resulting mixture by vacuum distillation, 1.2 mol equivalent relative to the hydroxyl groups of polymer (H-1) of 3-chloro-2-methyl-1-propene (methylallyl chloride) was added, and the reaction was carried out at 130°C for 1 hour. Unreacted 3-chloro-2-methyl-1-propene was then removed from the reaction solution by vacuum distillation.

[0409] Then, sodium methoxide with a hydroxyl group of 0.6 mol equivalent relative to the hydroxyl group of polymer (H-1) was added to the above mixture in the form of a 28% methanol solution. After removing the methanol by vacuum distillation, 3-chloro-2-methyl-1-propene with a hydroxyl group of 0.7 mol equivalent relative to the hydroxyl group of polymer (H-1) was added, and the reaction was carried out at 130°C for 1 hour, thereby converting the remaining terminal hydroxyl groups into methylpropene groups.

[0410] Next, the unreacted 3-chloro-2-methyl-1-propene was removed from the mixture by vacuum distillation. The resulting unpurified methpropylene-containing polyoxyethylene polymer was mixed with hexane and water, and the water was removed by centrifugation. The hexane was then removed from the resulting hexane solution by vacuum distillation, thereby removing the metal salt from the polymer. Through these operations, a linear methpropylene-containing polyoxyethylene polymer (M-1) was obtained.

[0411] A Karstedt catalyst at a mass ratio of 100 ppm relative to polymer (M-1) and 2,5-di-tert-butyl-1,4-benzoquinone at a mass ratio of 1000 ppm relative to polymer (M-1) were added to polymer (M-1). A dimethoxymethylsilane equivalent of 1.5 mol relative to the methacrylyl groups present in polymer (M-1) was added to the resulting mixture, and a hydrosilylation reaction of the methacrylyl groups in polymer (M-1) with the dimethoxymethylsilane was carried out at 100 °C. The reaction was carried out every 1 hour from the start of the reaction. 1 ¹H NMR analysis confirmed the complete disappearance of the methpropylene groups in polymer (M-1) 6 hours after the start of the reaction. The volatile components were then removed from the mixture by vacuum distillation, yielding a linear polyoxyethylene polymer (A'2) with reactive silica groups.

[0412] The obtained polymer (A'2) was subjected to 1 ¹H NMR determination was performed to calculate the total N0 of each group relative to the number of reactive silicon groups, 1-propenyl groups, propyl groups, and allyl groups. t The ratio. It should be noted that the number of reactive silicon groups is the same as the number of silicon-containing groups (a1), N.a1 The number N of silicon-containing groups (a2) generated by the hydrosilylation of methpropenyl group with dimethoxymethylsilane. a2 The total.

[0413] As a result, the polymer (A'2) contains mainly silicon-containing groups (a2), with the number of silicon-containing groups (a1) being N. a1 Relative to N t The ratio Na1 / N t Less than 85%. Na1 / N t With Na2 / N t The sum is 97%.

[0414] (Synthesis Example 5)

[0415] In a four-necked flask equipped with a stirrer, 537 parts by mass of isobutanol were added. The isobutanol was heated to 90°C, and the atmosphere inside the flask was replaced with a nitrogen atmosphere. Then, while stirring the isobutanol, a mixed solution obtained by dissolving 150 parts by mass of methyl methacrylate, 704 parts by mass of n-butyl acrylate, 154 parts by mass of stearate methacrylate, 25 parts by mass of γ-methacryloyloxypropyl dimethoxymethylsilane, and 3 parts by mass of 2,2'-azobis(2-methylbutyronitrile) in 128 parts by mass of isobutanol was added dropwise to the flask over 7 hours. Polymerization was then carried out at 90°C for 2 hours, yielding a (meth)acrylic acid copolymer (B1) with a number average molecular weight of 17,000 and a weight average molecular weight of 48,000 as a resin solution with a solid content of 60% by mass. The (meth)acrylic acid copolymer (B1) has an average of 1.8 dimethoxymethylsilane groups per molecule.

[0416] (Example 1)

[0417] The resin solution obtained in Synthesis Example 5, containing 30 parts by mass of a (meth)acrylic acid copolymer (B1), was uniformly mixed with 70 parts by mass of a polyoxyethylene polymer (A1) having reactive silicon groups. Isobutanol was removed from the resulting solution by distillation using a rotary evaporator to obtain a polymer mixture (M1) containing the (meth)acrylic acid copolymer (B1) and the polyoxyethylene polymer (A1).

[0418] (Comparative Example 1)

[0419] The resin solution obtained in Synthesis Example 5, containing 30 parts by mass of a (meth)acrylic acid copolymer (B1), was uniformly mixed with 70 parts by mass of a polyoxyethylene polymer (A'1) having reactive silicon groups. Isobutanol was removed from the resulting solution by distillation using a rotary evaporator to obtain a polymer mixture (M2) containing the (meth)acrylic acid copolymer (B1) and the polyoxyethylene polymer (A'1).

[0420] (Comparative Example 2)

[0421] The resin solution obtained in Synthesis Example 5, containing 30 parts by mass of a (meth)acrylic acid copolymer (B1), was uniformly mixed with 70 parts by mass of a polyoxyethylene polymer (A'2) having reactive silicon groups. Isobutanol was removed from the resulting solution by distillation using a rotary evaporator to obtain a polymer mixture (M3) containing the (meth)acrylic acid copolymer (B1) and the polyoxyethylene polymer (A'2).

[0422] (Example 2, Comparative Example 3 and Comparative Example 4)

[0423] A single-component curable composition for sealing materials was prepared using a 5L planetary mixer (manufactured by DALTON Corporation) according to the composition shown in Table 1. First, 160 parts by weight of Baiyanhua CCR (manufactured by Baishigai Co., Ltd.: precipitated calcium carbonate), 54 parts by weight of Whiton SB (manufactured by Baishigai Co., Ltd.: heavy calcium carbonate), and 5 parts by weight of TIPAQUE R820 (manufactured by Ishihara Sangyo Co., Ltd.: titanium dioxide) were dried under reduced pressure at 120°C for 2 hours. Next, 100 parts by weight of the polymer mixture obtained in Example 1, Comparative Example 1, or Comparative Example 2, 90 parts by weight of DINP (manufactured by J-Plus Co., Ltd.: diisononyl phthalate), 2 parts by weight of Disparlon 6500 (manufactured by Kusunoki Chemical Co., Ltd.: fatty acid amide wax), 1 part by weight of Tinuvin 326 (manufactured by BASF: 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole), and 1 part by weight of Tinuvin 770 (manufactured by BASF: light stabilizer) were added to a mixer and mixed for 10 minutes. The resulting mixture was removed and passed through a three-roll mill once to achieve uniform dispersion. The mixture was then added back to the mixer and subjected to vacuum dehydration for 2 hours. After dehydration under reduced pressure, the mixture was cooled to below 50°C, and then 3 parts by weight of A-171 (manufactured by Momentive: vinyltrimethoxysilane), 3 parts by weight of A-1120 (manufactured by Momentive: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane), and 2 parts by weight of NEOSTANNU U-220H (manufactured by Nitto Chemical Co., Ltd.: bis(acetylacetonyl)dibutyltin) were added and mixed for 3 minutes. Following this, degassing under reduced pressure was performed for 2 minutes, and the resulting mixture was immediately filled into a moisture-proof aluminum cylinder and sealed, thus obtaining a cured composition.

[0424] The peeling time, dumbbell tensile properties, tear strength, and tensile shear strength were evaluated using the obtained cured composition. The results are shown in Table 1.

[0425] <Peeling Time>

[0426] In an atmosphere of 23°C and 50% relative humidity, the obtained curable composition was filled into a mold frame with a thickness of approximately 5 mm using a spatula. The time it took for the surface of the filled curable composition to become flat was defined as the curing start time. The time it took for the composition of the evaluation object to no longer adhere to the spatula after contacting the surface with the spatula was defined as the peeling time. The results are shown in Table 1.

[0427] <Dumbbell Stretching Properties>

[0428] The obtained curable composition was filled into a mold frame and cured at 23°C and 50% relative humidity for 3 days, followed by curing at 50°C for 4 days to produce a sheet-like cured material with a thickness of approximately 3 mm. The sheet-like cured material was punched into a No. 3 dumbbell shape and tensile strength tests were conducted in an atmosphere of 23°C and 50% relative humidity. The modulus (M50 and M100) at 50% and 100% extension was measured. In addition, the strength at break (TB) and elongation at break (EB) were measured. The tests were conducted using an Autogragh (AGS-J) manufactured by Shimadzu Corporation at a tensile speed of 200 mm / min. The results are shown in Table 1.

[0429] <Tear strength>

[0430] The obtained curable composition was filled into a 3 mm thick sheet mold frame at 23°C and 50% relative humidity. After curing the composition for 3 days at 23°C and 50% relative humidity, it was further cured in a 50°C dryer for 4 days to obtain a sheet-like cured product. The cured product was punched into dumbbell shapes (JIS Type A) for tear testing to obtain test pieces. Using the obtained test pieces, tear tests were performed using Autogragh at 23°C and 50% relative humidity (tensile speed 200 mm / min), and the stress at break (TB) was measured. The results are shown in Table 1.

[0431] Tensile shear strength

[0432] Aluminum plates were used as the substrates. The curable composition was applied to a 25mm x 25mm bonding surface of the aluminum plate with a thickness of 50μm at 23°C and 50% relative humidity. Two minutes after application, the aluminum plate without the curable composition was pressed onto the side of the aluminum plate coated with the curable composition, thus bonding the aluminum plates together. The resulting test specimens were then placed under constant temperature and humidity conditions of 23°C and 50%. Tensile shear tests (tensile speed 50mm / min) were performed using Autogragh after 1 hour, 3 hours, and 24 hours of constant temperature and humidity conditions, and the stress at fracture (TB) was measured.

[0433] In addition, the obtained test specimens were cured at 23°C and 50% relative humidity for 3 days, and then cured at 50°C for 4 days. Tensile shear tests were then performed using Autogragh to determine the stress (TB) at fracture. The strength yield at each time point was calculated as described below.

[0434] Strength performance rate (%) = (shear strength at various times) ÷ (shear strength after curing at 23℃ and 50% relative humidity for 3 days, and then at 50℃ for 4 days) × 100

[0435] The results are shown in Table 1.

[0436] [Table 1]

[0437]

[0438] As shown in Table 1, the curable composition of Example 2, which includes the above-mentioned polyoxyethylene polymer (A) and the above-mentioned (meth)acrylic polymer (B), exhibits excellent curability.

[0439] On the other hand, as shown in Table 1, the curing time required for the curable compositions of Comparative Examples 3 and 4, which combine other polyoxyethylene polymers that do not belong to polyoxyethylene polymers (A) and the above-mentioned (meth)acrylic polymers (B), is as follows.

[0440] Furthermore, according to the results of the tensile shear strength test, the curable composition of Example 2 showed a higher tensile shear strength than the curable compositions of Comparative Example 3 and Comparative Example 4 in the initial stage of curing.

[0441] (Synthesis Example 6)

[0442] Add 412 parts by mass of isobutanol to a four-necked flask equipped with a stirrer. Heat the isobutanol to 105°C, then replace the atmosphere in the flask with nitrogen. Then, while stirring the isobutanol, add dropwise over 5 hours a solution prepared from 670 parts by mass of methyl methacrylate, 60 parts by mass of n-butyl acrylate, 134 parts by mass of stearate methacrylate, 55 parts by mass of γ-methacryloyloxypropyl dimethoxymethylsilane, 73 parts by mass of γ-mercaptopropyl dimethoxymethylsilane, 223 parts by mass of isobutanol, and 24.8 parts by mass of azobis-2-methylbutyronitrile. Then, for another hour, add dropwise a solution obtained by dissolving 2.8 parts by mass of azobis-2-methylbutyronitrile in 45 parts by mass of isobutanol. Next, post-polymerization was carried out at 105°C for 2 hours to obtain a (meth)acrylic acid copolymer (B2) with a number average molecular weight of 2100 and a weight average molecular weight of 3700 in the form of a resin solution with a solid content concentration of 60% by mass. The (meth)acrylic acid copolymer (B2) has an average of 1.3 dimethoxymethylsilyl groups per molecule.

[0443] (Example 3)

[0444] The resin solution obtained in Synthesis Example 6, containing 30 parts by mass of a (meth)acrylic acid copolymer (B2), was uniformly mixed with 70 parts by mass of a polyoxyethylene polymer (A1) having a reactive silicon group. Isobutanol was removed from the resulting solution by distillation using a rotary evaporator to obtain a polymer mixture (M4).

[0445] (Comparative Example 5)

[0446] The resin solution obtained in Synthesis Example 6, containing 30 parts by mass of a (meth)acrylic acid copolymer (B2), was uniformly mixed with 70 parts by mass of a polyoxyethylene polymer (A'1) having reactive silicone groups. Isobutanol was removed from the resulting solution by distillation using a rotary evaporator to obtain a polymer mixture (M5).

[0447] (Comparative Example 6)

[0448] The resin solution obtained in Synthesis Example 6, containing 30 parts by mass of a (meth)acrylic acid copolymer (B2), was uniformly mixed with 70 parts by mass of a polyoxyethylene polymer (A'2) having reactive silicone groups. Isobutanol was removed from the resulting solution by distillation using a rotary evaporator to obtain a polymer mixture (M6).

[0449] (Example 4, Comparative Example 7 and Comparative Example 8)

[0450] A single-component curable composition for adhesive applications was prepared using a 5L planetary mixer (manufactured by DALTON Co., Ltd.) according to the composition shown in Table 2. First, 100 parts by weight of the polymer mixture obtained in Example 3, Comparative Example 5, or Comparative Example 6, 15 parts by weight of Sylophobic 200 (manufactured by Fuji-Silysia Co., Ltd.: silica), and 3 parts by weight of Aerosil R812S (manufactured by Nippon Aerosil Co., Ltd.: silica) were mixed for 10 minutes. The resulting mixture was removed, passed through a three-roll mill once to ensure uniform dispersion, and then added back into the mixer. One part by weight of A-171 (manufactured by Momentive: vinyltrimethoxysilane) was added, and the mixture was dehydrated under reduced pressure at 70°C for 1 hour. After dehydration under reduced pressure, the mixture was cooled to below 50°C, and then 5 parts by weight of A-171 (manufactured by Momentive: vinyltrimethoxysilane), 4 parts by weight of A-1120 (manufactured by Momentive: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane), 1 part by weight of A-187 (manufactured by Momentive: 3-epoxypropoxypropyltrimethoxysilane), and 2 parts by weight of NEOSTANNU U-220H (manufactured by Nitto Chemical Co., Ltd.: bis(acetylacetonyl)dibutyltin) were added, and the mixture was mixed for 3 minutes. After degassing under reduced pressure for 2 minutes, the resulting mixture was immediately filled into a moisture-proof aluminum cylinder and sealed, thus obtaining a cured composition.

[0451] Using the obtained cured composition, the peeling 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.

[0452] [Table 2]

[0453]

[0454] As shown in Table 2, the curable composition of Example 4, which includes the above-mentioned polyoxyethylene polymer (A) and the above-mentioned (meth)acrylic polymer (B), exhibits excellent curability.

[0455] On the other hand, as shown in Table 2, the curing time required for the curable compositions of Comparative Examples 7 and 8, which combine other polyoxyethylene polymers that are not polyoxyethylene polymers (A) and the above-mentioned (meth)acrylic polymers (B), is as follows.

[0456] Furthermore, according to the results of the tensile shear strength test, the curable composition of Example 4 showed a higher tensile shear strength than the curable compositions of Comparative Example 7 and Comparative Example 8 in the initial stage of curing.

[0457] (Synthesis Example 7)

[0458] Crotonic acid, in an amount of 0.1 mol equivalent relative to the allyl groups present in polymer (A-1), was added to an allyl-containing polyoxyethylene polymer (A-1). Then, hexachloroplatinic acid hexahydrate (10 ppm by mass relative to polymer (A-1)) and phenylpropynic acid (7 ppm by mass relative to polymer (A-1)) were mixed with polymer (A-1). The ratio of platinum catalyst to phenylpropynic acid was 1:25 (molar ratio). Further, an acetonitrile solution of triethylsilane containing an equimolar amount of triethylsilane as phenylpropynic acid was added to polymer (A-1).

[0459] Next, a 2.0 mol equivalent of dimethoxymethylsilane relative to the allyl group of polymer (A-1) was added to the mixture. Then, a hydrosilylation reaction of the allyl group of polymer (A-1) with the dimethoxymethylsilane was carried out at 90°C. This was performed every hour from the start of the reaction. 1 ¹H NMR analysis confirmed the complete disappearance of allyl groups in polymer (A-1) two hours after the start of the reaction. Volatile components were then removed from the mixture by vacuum distillation, yielding a polyoxyalkylene polymer (A2) with reactive silica groups.

[0460] The obtained polymer (A2) was subjected to 1 ¹H NMR determination was performed to calculate the total N value of each group relative to the number of reactive silicon groups (containing silicon groups (a1)), the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups. t The proportion.

[0461] The result is that the number N of silicon-containing groups (a1) a1 Relative to N t The ratio is 86%. The number of 1-propenyl groups relative to N t The ratio is 11%. The amount of propyl groups relative to N... t The ratio is 3%. The number of allyl groups relative to N t The ratio is 0%.

[0462] (Synthesis Example 8)

[0463] In a four-necked flask equipped with a stirrer, 550 parts by weight of isobutanol were added. The isobutanol was heated to 105°C, and the atmosphere inside the flask was replaced with a nitrogen atmosphere. Then, while stirring the isobutanol, a mixed solution obtained by dissolving 100 parts by weight of methyl methacrylate, 715 parts by weight of n-butyl acrylate, 150 parts by weight of stearate methacrylate, 35 parts by weight of γ-methacryloyloxypropyl dimethoxymethylsilane, and 6 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 120 parts by weight of isobutanol was added dropwise to the flask over 5 hours. Polymerization was then carried out at 105°C for 1 hour, yielding a (meth)acrylic acid copolymer (B3) with a number average molecular weight of 10,500 and a weight average molecular weight of 26,500 as a resin solution with a solids content of 60% by weight. The (meth)acrylic acid copolymer (B3) has an average of 1.6 dimethoxymethylsilane groups per molecule.

[0464] (Example 5)

[0465] The resin solution obtained in Synthesis Example 8, containing 30 parts by mass of a (meth)acrylic acid copolymer (B3), was uniformly mixed with 70 parts by mass of a polyoxyethylene polymer (A2) having reactive silicon groups. Isobutanol was removed from the resulting solution by distillation using a rotary evaporator to obtain a polymer mixture (M7) containing the (meth)acrylic acid copolymer (B3) and the polyoxyethylene polymer (A2).

[0466] (Comparative Example 9)

[0467] The resin solution obtained in Synthesis Example 8, containing 30 parts by mass of a (meth)acrylic acid copolymer (B3), was uniformly mixed with 70 parts by mass of a polyoxyethylene polymer (A'1) having reactive silicon groups. Isobutanol was removed from the resulting solution by distillation using a rotary evaporator to obtain a polymer mixture (M8) containing the (meth)acrylic acid copolymer (B3) and the polyoxyethylene polymer (A'1).

[0468] (Example 6 and Comparative Example 10)

[0469] A masterbatch composition was prepared using a 5L planetary mixer (manufactured by DALTON Corporation). First, 160 parts by weight of Baiyanhua CCR (manufactured by Baishi Calcium Co., Ltd.: colloidal calcium carbonate), 54 parts by weight of Whiton SB (manufactured by Baishi Calcium Co., Ltd.: untreated heavy calcium carbonate), and 5 parts by weight of TIPAQUE R820 (manufactured by Ishihara Sangyo: titanium dioxide) were dried under reduced pressure at 120°C for 2 hours. Next, 90 parts by weight of DINP (manufactured by J-Plus Corporation: diisononyl phthalate), 2 parts by weight of Disparlon 6500 (manufactured by Kusunoki Chemicals: fatty acid amide wax), 1 part by weight of Tinuvin 328 (manufactured by BASF: ultraviolet absorber), and 1 part by weight of Tinuvin 770 (manufactured by BASF: light stabilizer) were added to the mixer and mixed for 10 minutes. The resulting mixture was removed and passed through a three-roll mill once to ensure uniform dispersion. It was then fed back into a mixer and dehydrated under reduced pressure at 120°C for 2 hours. After cooling the mixture to below 50°C, 2 parts by weight of A-171 (Momentive: vinyltrimethoxysilane) were added, and the mixture was kneaded in a substantially moisture-free state. The thoroughly kneaded mixture was then degassed under reduced pressure and sealed in a moisture-proof container to obtain the masterbatch composition.

[0470] Then, 100 parts by weight of the polymer mixture (M7 or M8) listed in Table 3, 3 parts by weight of A-1120 (made by Momentive: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane), and 2 parts by weight of NEOSTANNU U-220H (made by Nitto Chemical Co., Ltd., bis(acetylacetonyl)dibutyltin) were added to 315 parts by weight of the masterbatch composition and mixed thoroughly. The mixture was then uniformly kneaded and degassed using a rotary mixer to prepare various curable compositions.

[0471] Using the obtained cured composition, the peeling time, dumbbell tensile properties, and tensile shear strength were evaluated in the same manner as in Example 2. The results are shown in Table 3.

[0472] [Table 3]

[0473]

[0474] As shown in Table 3, the curable composition of Example 6, which includes the above-mentioned polyoxyethylene polymer (A) and the above-mentioned (meth)acrylic polymer (B), exhibits excellent curability.

[0475] On the other hand, as shown in Table 3, the curing time required for the curable composition of Comparative Example 10, which includes other polyoxyethylene polymers that are not polyoxyethylene polymers (A) and the above-mentioned (meth)acrylic polymer (B), is as follows.

[0476] Furthermore, according to the results of the tensile shear strength test, the curable composition of Example 6 showed a higher tensile shear strength than the curable composition of Comparative Example 10 in the initial stage of curing.

Claims

1. A curable composition comprising: a polyoxyethylene polymer having reactive silicone groups (A), a (meth)acrylic copolymer having reactive silicone groups (B), and a curing catalyst (C), The polyoxyolefin polymer (A) has a silicon-containing group (a1) represented by the following formula (1). [Chemical Formula 1] ， In formula (1), R is a hydrocarbon group with 1 or more but less than 20 carbon atoms, either substituted or unsubstituted; X is a hydroxyl group or a hydrolyzable group; and a is 0, 1, or 2. The number-average molecular weight of the polyoxyethylene polymer (A) exceeds 3000. In the polyoxyolefin polymer (A), the number N of the silicon-containing groups (a1) is... a1 The total N relative to the number of reactive silicon groups, the number of 1-propenyl groups, the number of propyl groups, and the number of allyl groups. t The ratio N a1 / N t Values ​​between 0.85 and 1.00 The molecular chain of the (meth)acrylic copolymer (B) contains two or more units derived from alkyl (meth)acrylic esters. The reactive silicon group in the (meth)acrylic acid copolymer (B) is a group represented by the following formula (2). -SiR 1 a X 3-a (2) In equation (2), R 1 X and a are related to R in equation (1) 1 The same applies to X and a.

2. The curable composition according to claim 1, wherein, In the polyoxyolefin polymer (A), the N a1 / N t It is above 0.90 and below 1.

00.

3. The curable composition according to claim 1 or 2, wherein, The number-average molecular weight of the polyoxyethylene polymer (A) is above 10,000.

4. The curable composition according to claim 3, wherein, The number-average molecular weight of the polyoxyethylene polymer (A) is above 20,000.

5. The curable composition according to claim 1 or 2, wherein, The (meth)acrylic copolymer (B) is a polymer containing methyl methacrylate monomers. The mass ratio of the methyl methacrylate to the monomer is 50% or more by mass. 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 containing methyl methacrylate monomers. The mass ratio of the methyl methacrylate to the monomer is less than 50% by mass. The curable composition is used as a sealing material.

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 compound (E). The compound (E) has at least one carbon-carbon double bond and at least one electron-withdrawing group in one molecule. 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 claim 8, wherein, The compound (E) has a benzene ring skeleton or a norbornene skeleton.

10. The curable composition according to claim 8, wherein, The compound (E) has at least one electron-withdrawing group selected from fluorine, bromine and iodine.

11. A cured product, which is a cured product of the curable composition according to claim 1 or 2.

Images