Heat-curable curable composition and cured product thereof

Abstract

A heat-curable curable composition comprising: (A) a polyoxyalkylene polymer having a hydrolyzable silyl group represented by the general formula (1), ‑Si(R 1 ) 3‑a (X) a (1)(where R 1 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, which may optionally contain a heteroatom-containing group. Each X independently represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. ); (B) a metal compound comprising at least one metal element selected from aluminum and zinc and a chelate compound as a ligand; and (C) a chelate compound.

Description

Technical Field

[0001] The present invention relates to a heat-curable curable composition containing a hydrolyzable silyl group-containing polymer, and a cured product thereof. Background Art

[0002] Hydrolyzable silyl group-containing polymers are known as wet-process reactive polymers and are included in a large number of industrial products such as adhesives, sealants, coatings, paints, and pressure-sensitive adhesives, and are used in a wide range of fields.

[0003] As such hydrolyzable silyl group-containing polymers, various polymers having a main chain skeleton such as polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylate copolymers are known. Among them, polyoxyalkylene polymers as described in Patent Document 1 have a wide range of applications due to their relatively low viscosity at room temperature, ease of handling, and excellent elasticity of the cured products obtained after the reaction.

[0004] When a curable composition containing such a hydrolyzable silyl group-containing polyoxyalkylene polymer is used for construction applications, for example, the composition is generally applied to the intended use area and then cured at room temperature for a long period of time to allow the curing reaction to proceed.

[0005] However, when used for industrial purposes, it is sometimes required to heat and cure in a short time after coating.

[0006] Patent Documents 2 and 3 describe heat-curable curable compositions containing a hydrolyzable silyl group-containing polyoxyalkylene polymer.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 52-73998

[0010] Patent Document 2: International Publication No. 2017 / 111121

[0011] Patent Document 3: International Publication No. 2017 / 188185 Summary of the Invention

[0012] Problems to be solved by the invention

[0013] Generally, it is known to mix an alkoxysilane-based dehydrating agent such as vinylsilane into a curable composition containing a hydrolyzable silyl group-containing polyoxyalkylene polymer in order to ensure stability during storage.

[0014] However, during storage, curable compositions containing alkoxysilane-based dehydrating agents react with water in the system. Consequently, heat curing, which requires a shorter curing time than room temperature curing, results in insufficient water contributing to the curing reaction, resulting in reduced curability and the formation of bubbles in the cured product.

[0015] Therefore, when the curable composition is used as a heat-curable composition, there is room for improvement in the balance between storage stability and curability during heating.

[0016] In view of the above-mentioned current situation, an object of the present invention is to obtain a heat-curable curable composition comprising a hydrolyzable silyl group-containing polyoxyalkylene polymer, having good storage stability under sealing and good curability when heated.

[0017] Solutions to the problem

[0018] The present inventors have conducted research to solve the above-mentioned problems and have found that by using (B) a metal compound containing at least one metal element selected from aluminum and zinc and a chelate compound as a ligand as a catalyst, and (C) a chelate compound, both storage stability under sealing and curing properties upon heating can be achieved.

[0019] That is, the present invention relates to a heat-curable curable composition comprising:

[0020] (A) a polyoxyalkylene polymer having a hydrolyzable silyl group represented by the general formula (1),

[0021] -Si(R 1 ) 3-a (X) a (1)

[0022] Where R 1 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group optionally having a heteroatom-containing group, each X independently represents a hydroxyl group or a hydrolyzable group, and a is 1, 2 or 3;

[0023] (B) a metal compound comprising at least one metal element selected from aluminum and zinc and a chelate compound as a ligand; and

[0024] (C) Chelating compounds.

[0025] The heat-curable curable composition may further contain (D) an epoxy compound containing at least two epoxy groups in one molecule.

[0026] The heat-curable curable composition may further contain (T) a zeolite-based adsorbent.

[0027] The water content of the heat-curable curable composition is preferably 100 to 500 ppm.

[0028] The chelate compound (C) is preferably a β-dicarbonyl compound, and more preferably at least one selected from the group consisting of β-diketone and β-ketoester.

[0029] It is preferred that a in the general formula (1) is 3.

[0030] The epoxy compound (D) is preferably an alicyclic epoxy compound.

[0031] Preferably, the content of the metal compound (B) is 0.1 to 10 parts by weight, and the content of the chelate compound (C) is 0.1 to 10 parts by weight, based on 100 parts by weight of the polymer (A).

[0032] It is preferred that the ratio of the total number of moles of the chelate compound and the chelate compound (C) in the metal compound (B) to the number of moles of the metal element in the metal compound (B) exceeds 3.

[0033] The present invention also relates to a method for producing the above-mentioned heat-curable curable composition, the method comprising:

[0034] A step of mixing the polymer (A), the metal compound (B) and the chelate compound (C).

[0035] The present invention also relates to a cured product obtained by curing the above-mentioned heat-curable curable composition.

[0036] Furthermore, the present invention relates to a method for producing a solidified material, the method comprising:

[0037] A step of heat-curing the heat-curable curable composition.

[0038] Preferably, the production method further comprises, before the step of heat-curing, storing the heat-curable curable composition in a sealed state at 23° C. to 50° C. for 1 day to 4 weeks.

[0039] The temperature of the heat curing step is preferably 40 to 220°C.

[0040] Effects of the Invention

[0041] According to the present invention, a heat-curable curable composition containing a polyoxyalkylene polymer having a hydrolyzable silyl group and having excellent storage stability under sealing and excellent curability when heated can be provided. DETAILED DESCRIPTION

[0042] Hereinafter, embodiments of the present invention will be described in detail.

[0043] This embodiment relates to a heat-curable curable composition comprising:

[0044] (A) a polyoxyalkylene polymer having a hydrolyzable silyl group represented by the general formula (1),

[0045] -Si(R 1 ) 3-a (X) a (1)

[0046] Where R 1 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, which may optionally contain a heteroatom-containing group. Each X independently represents a hydroxyl group or a hydrolyzable group, and a is 1, 2, or 3;

[0047] (B) a metal compound comprising at least one metal element selected from aluminum and zinc and a chelate compound as a ligand; and

[0048] (C) Chelating compounds.

[0049] <<(A) Polyoxyalkylene polymer having a hydrolyzable silyl group represented by general formula (1)>>

[0050] The heat-curable curable composition of the present embodiment contains (A) a polyoxyalkylene polymer having a hydrolyzable silyl group represented by the general formula (1) (hereinafter also referred to as polymer (A)) as a curable resin.

[0051] -Si(R 1 ) 3-a (X) a (1)

[0052] Where R 1 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the above hydrocarbon group may have a heteroatom-containing group; each X independently represents a hydroxyl group or a hydrolyzable group; and a is 1, 2 or 3.

[0053] Polymer (A) has a polymer backbone composed of a plurality of repeating units and an end structure bonded to the end of the polymer backbone. The polymer backbone refers to a polymer main chain composed of a plurality of repeating units. The polymer backbone of polymer (A) may be linear or branched. A linear polymer backbone may be formed by using an initiator having two hydroxyl groups in one molecule in the polymerization method for forming the polymer backbone, while a branched polymer backbone may be formed by using an initiator having three or more hydroxyl groups in one molecule.

[0054] The polymer backbone is preferably composed solely of a plurality of mutually linked repeating units, or may further include, in addition to the plurality of repeating units, a structure derived from an initiator used during polymerization and composed solely of these structures. The repeating units are oxyalkylene units, for example, oxyalkylene units having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

[0055] The terminal structure refers to a site that does not contain a repeating unit constituting the polymer backbone and is bonded to a terminal of the polymer backbone. The terminal structure is preferably bonded to an oxyalkylene unit located at a terminal of the polymer backbone via an oxygen atom. Furthermore, the hydrolyzable silyl group possessed by polymer (A) is preferably contained within the terminal structure. In this case, each terminal structure may contain a hydrolyzable silyl group, and terminal structures containing a hydrolyzable silyl group and terminal structures not containing a hydrolyzable silyl group may coexist.

[0056] The polymer (A) preferably has hydrolyzable silyl groups at two or more ends of the polymer backbone. When the polymer backbone of the polymer (A) is linear, the polymer (A) may have hydrolyzable silyl groups at both ends of the polymer backbone. In this case, the polymer (A) is preferably a polymer component composed of polymer molecules having hydrolyzable silyl groups at two or more ends of the polymer backbone. However, the polymer (A) as a whole may also include, in addition to the above-mentioned polymer molecules, polymer molecules having a hydrolyzable silyl group at only one end of the polymer backbone, and / or polymer molecules having no hydrolyzable silyl group.

[0057] The average number of hydrolyzable silyl groups per molecule of polymer (A) is preferably more than 1, more preferably 1.1 or more, and even more preferably 1.3 or more. The upper limit is preferably 5 or less, and more preferably 4 or less.

[0058] In addition, the average ratio of the number of hydrolyzable silyl groups in one molecule of polymer (A) to the number of terminals of the polymer backbone is not particularly limited and may be 1.0 or less or more than 1.0. When low modulus and high elongation are required, the above average ratio is preferably 1.0 or less, more preferably 0.8 or less. The lower limit of the above average ratio is preferably 0.3 or more, more preferably 0.5 or more. In addition, in order to be able to exert high strength, the above average ratio is preferably more than 1.0, more preferably 1.1 or more, further preferably 1.3 or more, and particularly preferably 1.5 or more. The upper limit of the above average ratio is preferably 5 or less, more preferably 3 or less. The numerical value of the average ratio can be determined by the method described in the examples. In addition, in addition to the method described in the examples, the numerical value of the above average ratio can also be calculated based on the results of GPC measurement and NMR measurement of polymer (A).

[0059] In this specification, the average ratio of the number of hydrolyzable silyl groups to the number of polymer backbone terminals refers to the average number of hydrolyzable silyl groups contained in the terminal structures of each polymer backbone, expressed as the average number of hydrolyzable silyl groups per polymer molecule divided by the number of polymer backbone terminals per polymer molecule. The number of polymer backbone terminals per polymer molecule is 2 when the polymer backbone is entirely linear, and 3 or more when the polymer backbone is entirely branched. Furthermore, the ratio may be between 2 and 3 when the polymer backbone is a mixture of linear and branched structures.

[0060] <Hydrolyzable silyl group>

[0061] The hydrolyzable silyl group contained in the polymer (A) is represented by the general formula (1):

[0062] -Si(R 1 ) 3-a (X) a (1)

[0063] Where R 1 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, which may optionally contain a heteroatom-containing group. Each X independently represents a hydroxyl group or a hydrolyzable group. a is 1, 2 or 3.

[0064] R 1 is a hydrocarbon group having 1 to 20 carbon atoms. 1 The number of carbon atoms in the hydrocarbon group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 4. The hydrocarbon group may be unsubstituted or may have a substituent.

[0065] As R 1 The heteroatom-containing group that the hydrocarbon group may optionally have as a substituent is a group containing a heteroatom. Here, atoms other than carbon atoms and hydrogen atoms are referred to as heteroatoms.

[0066] Preferred examples of heteroatoms include N, O, S, P, Si, and halogen atoms. In heteroatom-containing groups, the total number of carbon atoms and heteroatoms is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

[0067] Preferred examples of heteroatom-containing groups include: hydroxyl groups; mercapto groups; halogen atoms such as Cl, Br, I and F; nitro groups; cyano groups; alkoxy groups such as methoxy, ethoxy, n-propyloxy and isopropyloxy; alkylthio groups such as methylthio, ethylthio, n-propylthio and isopropylthio; acyl groups such as acetyl, propionyl and butyryl; acyloxy groups such as acetoxy, propionyloxy and butyryl; substituted or unsubstituted amino groups such as amino, methylamino, ethylamino, dimethylamino and diethylamino; substituted or unsubstituted aminocarbonyl groups such as aminocarbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl and diethylaminocarbonyl; cyano groups, etc.

[0068] In R 1 In the case of a hydrocarbon group having a heteroatom group, R 1 The total number of carbon atoms and heteroatoms in is preferably 2-30, more preferably 2-18, further preferably 2-10, and particularly preferably 2-6.

[0069] As R 1 Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include: alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-n-hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl, and n-eicosyl; alkenyl groups such as vinyl, 2-propenyl, 3-butenyl, and 4-pentenyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; aryl groups such as phenyl, naphthyl-1-yl, naphthyl-2-yl, o-phenylphenyl, m-phenylphenyl, and p-phenylphenyl; and aralkyl groups such as benzyl, phenethyl, naphthyl-1-ylmethyl, and naphthyl-2-ylmethyl.

[0070] The groups after these hydrocarbon groups are substituted by the above-mentioned heteroatom-containing groups are also referred to as R 1 And preferred.

[0071] As R 1 Preferred examples include: alkyl groups such as methyl and ethyl; alkyl groups containing heteroatoms such as chloromethyl and methoxymethyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl; aralkyl groups such as benzyl; and the like. 1 , preferably methyl, methoxymethyl and chloromethyl, more preferably methyl and methoxymethyl, further preferably methyl.

[0072] Examples of X include hydroxyl, hydrogen, halogen, alkoxy, acyloxy, ketoximate, amino, amide, acid amide, aminooxy, mercapto, and alkenyloxy groups. Of these, alkoxy groups such as methoxy and ethoxy are more preferred, and methoxy and ethoxy are particularly preferred, due to their stable hydrolysis and ease of handling.

[0073] a is 1, 2 or 3. a is preferably 2 or 3, more preferably 3.

[0074] Specific examples of the hydrolyzable silyl group include, but are not limited to, trimethoxysilyl, triethoxysilyl, tri(2-propyleneoxy)silyl, triacetoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethoxyethylsilyl, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N-diethylaminomethyl)dimethoxysilyl, and (N,N-diethylaminomethyl)diethoxysilyl. Among these, dimethoxymethylsilyl, trimethoxysilyl, triethoxysilyl, and (methoxymethyl)dimethoxysilyl are preferred because they can provide a cured product having excellent mechanical properties. From the viewpoint of activity, methoxysilyl, (chloromethyl)dimethoxysilyl, and (methoxymethyl)dimethoxysilyl are more preferred, and trimethoxysilyl and (methoxymethyl)dimethoxysilyl are particularly preferred. From the viewpoint of stability, dimethoxymethylsilyl and triethoxysilyl are preferred, and dimethoxymethylsilyl is particularly preferred.

[0075] In the polymer (A), the terminal structure having a hydrolyzable silyl group is not particularly limited, but typical terminal structures include terminal structures represented by any of the following general formulae (2) to (6).

[0076] -OR 2 -CH(R 3 )-CH2-Si(R 1 ) 3-a (X) a (2)

[0077] In formula (2), R 2 represents a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms, R 3 represents hydrogen or an alkyl group having 1 to 6 carbon atoms. The oxygen at the left end represents an oxygen in a repeating unit located at the terminal of a polymer backbone formed by linking multiple repeating units, or an oxygen bonded to a repeating unit located at the terminal of the polymer backbone. 1 , X and a have the same meanings as described above for formula (1).

[0078] As R 2, preferably a divalent hydrocarbon group having 1 to 3 carbon atoms, more preferably a divalent hydrocarbon group having 1 to 2 carbon atoms. The hydrocarbon group is preferably an alkylene group, and methylene, ethylene, propylene, and butylene groups can be used. Methylene is particularly preferred.

[0079] As R 3 , preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, more preferably hydrogen or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, and butyl. 3 , preferably hydrogen, methyl, ethyl, more preferably hydrogen, methyl.

[0080] [Chemical Formula 1]

[0081]

[0082] In formula (3), R 4 It is a direct bond or a divalent bond group having 1 to 6 carbon atoms. 5 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. n is an integer from 1 to 10. The oxygen at the left end represents an oxygen in a repeating unit at the terminal of a polymer backbone formed by linking multiple repeating units, or an oxygen bonded to a repeating unit at the terminal of the above polymer backbone. 1 、R 2 、R 3 , X and a are the same as those described above for formulas (1) and (2).

[0083] R 4 It may be a divalent organic group having 1 to 6 carbon atoms. The organic group is preferably a hydrocarbon group or a hydrocarbon group containing an oxygen atom. The number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2. It is preferably -CH2OCH2-, -CH2O-, or -CH2-, and more preferably -CH2OCH2-.

[0084] As R 5 , preferably hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, more preferably hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, further preferably hydrogen or a hydrocarbon group having 1 to 2 carbon atoms. A hydrogen atom or a methyl group is particularly preferred, and a hydrogen atom is most preferred.

[0085] The terminal structure represented by general formula (3) represents a terminal structure bonded to one terminal of the polymer backbone. Formula (3) shows the presence of two or more reactive silicon groups, but formula (3) represents the presence of two or more reactive silicon groups in one terminal structure, not at two or more terminals. Furthermore, in formula (3), excluding the oxygen at the left end, the polymer backbone does not include repeating units that are oxyalkylene units. In other words, in formula (3), there are n structures within parentheses that are not repeating units in the polymer backbone.

[0086] [Chemical Formula 2]

[0087]

[0088] [Chemical Formula 3]

[0089]

[0090] [Chemical Formula 4]

[0091]

[0092] In formulas (4) to (6), R 6 and R 7 Each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a silyl group. The oxygen at the left end represents an oxygen in a repeating unit at the terminal of a polymer backbone formed by linking multiple repeating units, or an oxygen bonded to a repeating unit at the terminal of the polymer backbone. 1 , X and a have the same meanings as described above for formula (1).

[0093] R 6 and R 7 Each independently represents any of hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a silyl group. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms. The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aralkyl group preferably has 7 to 12 carbon atoms.

[0094] As R 6 and R 7 Specific examples include hydrogen; alkyl groups such as methyl, ethyl, and cyclohexyl; aryl groups such as phenyl and tolyl; aralkyl groups such as benzyl and phenethyl; and silyl groups such as trimethylsilyl. Among these, hydrogen, methyl, and trimethylsilyl are preferred, hydrogen and methyl are more preferred, and hydrogen is even more preferred.

[0095] Main Chain Structure

[0096] The main chain structure of the polymer (A) may be linear or branched.

[0097] As the main chain skeleton of polymer (A), for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polytetrahydrofuran, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer can be mentioned. The above polymers can be mixed in a block shape, a graft shape, etc. Among these, polyoxypropylene is particularly preferred.

[0098] Polymer (A) can be a polymer having any one of the various main chain skeletons mentioned above, or a mixture of polymers having different main chain skeletons. In addition, about the mixture, it can be a mixture of polymers manufactured individually, or a mixture manufactured simultaneously in a manner to achieve any mixed composition.

[0099] The number average molecular weight of the polymer (A) is not particularly limited, but is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000, as measured by polystyrene conversion in GPC. When the number average molecular weight is within the above range, the amount of hydrolyzable silyl group introduced is appropriate, making it easy to obtain a polymer (A) having a viscosity that is easy to handle and excellent in handleability while keeping production costs within an appropriate range.

[0100] The molecular weight of polymer (A) can also be expressed as an end-group-converted molecular weight, which is determined by directly measuring the end-group concentration of a polymer precursor before the introduction of a hydrolyzable silyl group by titration analysis based on the principles of the hydroxyl value determination method specified in JIS K 1557 and the iodine value determination method specified in JIS K 0070, taking into account the polymer structure (the degree of branching determined by the polymerization initiator used). The end-group-converted molecular weight of polymer (A) can also be determined by preparing a calibration curve based on the number average molecular weight determined by conventional GPC measurement of the polymer precursor and the end-group-converted molecular weight, and converting the number average molecular weight determined by GPC of polymer (A) into an end-group-converted molecular weight.

[0101] The molecular weight distribution (Mw / Mn) of polymer (A) is not particularly limited, but preferably has a narrow molecular weight distribution. Specifically, it is preferably 1.6 or less, more preferably 1.4 or less, further preferably 1.3 or less, and particularly preferably 1.2 or less. The molecular weight distribution of polymer (A) can be determined based on the number average molecular weight and weight average molecular weight obtained by GPC measurement.

[0102] <(A) Method for producing a polyoxyalkylene polymer having a hydrolyzable silyl group represented by the general formula (1)>

[0103] Next, the method for producing polymer (A) will be described. Polymer (A) can be produced by introducing hydrolyzable silyl groups into a precursor polymer capable of introducing hydrolyzable silyl groups. Specifically, olefin groups are introduced into a polyoxyalkylene polymer (E) having terminal hydroxyl groups by utilizing the reactivity of hydroxyl groups to obtain a precursor polymer having olefin groups. This precursor polymer is then reacted with a hydrolyzable silyl-containing compound reactive with the olefin groups to introduce hydrolyzable silyl groups, thereby producing polymer (A).

[0104] (polymerization)

[0105] The polymer backbone of the polyoxyalkylene polymer can be formed by polymerizing an epoxy compound under the action of an initiator having a hydroxyl group by a conventionally known method, thereby obtaining a polyoxyalkylene polymer (E) having a hydroxyl group at a terminal. The specific polymerization method is not particularly limited, but a polymerization method using a composite metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex is preferred because it can produce a hydroxyl-terminated polymer with a small molecular weight distribution (Mw / Mn).

[0106] The initiator having a hydroxyl group is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, low molecular weight polyoxypropylene triol, butanol, allyl alcohol, low molecular weight polyoxypropylene monoallyl ether, and low molecular weight polyoxypropylene monoalkyl ether.

[0107] The epoxy compound is not particularly limited, and examples thereof include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and butyl glycidyl ether. Propylene oxide is preferred.

[0108] (Reaction with alkali metal salt)

[0109] When introducing an olefin group into a polyoxyalkylene polymer (E) having a hydroxyl group at the terminal, it is preferred to first react the polyoxyalkylene polymer (E) with an alkali metal salt to convert the terminal hydroxyl group into a metalloxyl group. Alternatively, a composite metal cyanide complex catalyst may be used instead of the alkali metal salt. In this manner, a metalloxyl-terminated polyoxyalkylene polymer (F) is formed.

[0110] The alkali metal salt is not particularly limited, and examples thereof include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. From the perspective of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred, with sodium methoxide and sodium tert-butoxide being more preferred. From the perspective of availability, sodium methoxide is preferred. The alkali metal salt can be provided to the reaction while dissolved in a solvent.

[0111] (Reaction with electrophile (G))

[0112] By reacting the metaloxy group-terminated polyoxyalkylene polymer (F) obtained above with an electrophilic reagent (G) having an olefin group, the metaloxy group can be converted into a structure containing an olefin group, thereby forming a polyoxyalkylene polymer (H) having an olefin group in its terminal structure.

[0113] The electrophilic reagent (G) having an olefin group is not particularly limited as long as it is a compound that can react with the above-mentioned metal oxygen group possessed by the polyoxyalkylene polymer (F) to introduce an olefin group into the polyoxyalkylene polymer. Examples thereof include organic halides (G1) having an olefin group and epoxy compounds (G2) having an olefin group.

[0114] The organic halide (G1) having an olefin group as one embodiment of the electrophilic reagent (G) can react with the metal oxygen group to form an ether bond through a halogen substitution reaction, thereby introducing an olefin group-containing structure as a terminal structure of the polyoxyalkylene polymer.

[0115] Specific examples of the organic halide (G1) having an olefin group are not particularly limited, and include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. From the perspective of ease of handling, allyl chloride and methallyl chloride are preferred. In addition, methallyl chloride, methallyl bromide, and methallyl iodide are preferred because they increase the average ratio of the number of hydrolyzable silyl groups to the number of terminals in the polymer backbone.

[0116] Alternatively, a halogenated hydrocarbon compound having a carbon-carbon triple bond may be used as the organic halide compound (G1) having an olefin group. The polyoxyalkylene polymer (J) obtained by reacting this compound has a carbon-carbon triple bond at the terminal end of the polymer backbone. When a hydrolyzable silyl group is introduced into such a polymer (J), the atom adjacent to the hydrolyzable silyl group has a carbon-carbon double bond, thereby forming a terminal structure represented by any of the general formulas (4) to (6) above.

[0117] Examples of the halogenated hydrocarbon compound having a carbon-carbon triple bond include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne, 1-chloro-2-pentyne, 1,4-dichloro-2-butyne, 5-chloro-1-pentyne, 6-chloro-1-hexyne, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, 1-bromo-2-octyne, 1-bromo-2-pentyne, 1,4-dibromo-2-butyne, 5-bromo-1-pentyne, 6-bromo-1-hexyne, propargyl iodide, 1-iodo-2-butyne, 4-iodo-1-butyne, 1-iodo-2-octyne, 1-iodo-2-pentyne, 1,4-diiodo-2-butyne, 5-iodo-1-pentyne, and 6-iodo-1-hexyne. Among these, propargyl chloride, propargyl bromide, and propargyl iodide are more preferred. In addition, a halogenated hydrocarbon compound having a carbon-carbon triple bond may be used together with a halogenated hydrocarbon compound having a carbon-carbon double bond.

[0118] As another embodiment of the electrophilic reagent (G), an epoxy compound (G2) having an olefin group can react with the aforementioned metal oxy group via a ring-opening addition reaction of the epoxy group to form an ether bond, thereby introducing a structure containing an olefin group and a hydroxyl group as a terminal structure of the polyoxyalkylene polymer. In this ring-opening addition reaction, by adjusting the amount of the epoxy compound (G2) relative to the aforementioned metal oxy group and the reaction conditions, a single or multiple epoxy compounds (G2) can be added to a single metal oxy group.

[0119] The epoxy compound (G2) having an olefin group is not limited and can be represented by the following general formula (7):

[0120] [Chemical Formula 5]

[0121]

[0122] In formula (7), R 8 and R 9 are respectively the same as R described above for general formula (3) 4 and R 5 Same group.

[0123] Specific examples of the epoxy compound (G2) having an olefin group are not particularly limited, but from the viewpoint of reactivity, allyl glycidyl ether, methacryloyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and butadiene monoxide are preferred, and allyl glycidyl ether is particularly preferred.

[0124] If the epoxy compound (G2) having an olefin group is acted on the metal oxy-terminated polyoxyalkylene polymer (F) as described above, a metal oxy group will be newly generated by the ring opening of the epoxy group. Therefore, after the epoxy compound (G2) is brought into play, the above-mentioned organic halide (G1) having an olefin group can be continuously brought into play. As the organic halide (G1) having an olefin group used in this embodiment, the same compound as above can be used, and its dosage and reaction temperature are also the same as above. This method is preferred because it can further increase the amount of olefin group introduced into the polymer and the amount of hydrolyzable silyl group introduced. If the polyoxyalkylene polymer (H) having an olefin group in the terminal structure obtained by the method of combining the epoxy compound (G2) with the organic halide (G1) is subjected to the introduction of the hydrolyzable silyl group described below, the terminal structure represented by the above-mentioned general formula (3) can be formed.

[0125] (Introduction of Hydrolyzable Silyl Group)

[0126] By subjecting the polyoxyalkylene polymer (H) having an olefin group in its terminal structure or the polyoxyalkylene polymer (J) having a carbon-carbon triple bond in its terminal structure (precursor polymer) obtained by the above method to a hydrosilylation reaction with a hydrosilane compound (K) having a hydrolyzable silyl group, hydrolyzable silyl groups can be introduced into the polymer. This produces a polyoxyalkylene polymer (A) containing a hydrolyzable silyl group. The hydrosilylation reaction has the following advantages: in addition to being simple to carry out, the amount of hydrolyzable silyl groups introduced can be easily adjusted, and the resulting polymer has stable physical properties.

[0127] Specific examples of the hydrolyzable silyl group-containing hydrosilane compound (K) include: halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, and bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, Dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, bis(chloromethyl)methoxysilane, (methoxymethyl)methylmethoxysilane, (methoxymethyl)dimethoxysilane, bis(methoxymethyl)methoxysilane, (methoxymethyl)diethoxysilane, (ethoxymethyl)diethoxysilane, (3,3,3-trimethoxysilane fluoropropyl)dimethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, [(chloromethyl)dimethoxysilyloxy]dimethylsilane, [(chloromethyl)diethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(methoxymethyl)diethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilyloxy]dimethylsilane Alkoxysilanes such as methylsilane and [(3,3,3-trifluoropropyl)dimethoxysiloxy]dimethylsilane; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; ketoximate silanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane; isopropenoxysilanes (deacetonide type) such as triisopropenoxysilane, (chloromethyl)diisopropenoxysilane and (methoxymethyl)diisopropenoxysilane, etc.

[0128] In order to promote the reaction, the hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst. As hydrosilylation catalysts, metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium, and their complexes are known, and these substances can be used. Specifically, they include: catalysts in which platinum is supported on a carrier such as alumina, silica, or carbon black; chloroplatinic acid; chloroplatinic acid complexes containing chloroplatinic acid and alcohols, aldehydes, ketones, etc.; platinum-olefin complexes [such as Pt(CH2=CH2)2(PPh3), Pt(CH2=CH2)2Cl2]; platinum-vinylsiloxane complexes [such as Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4]; platinum-phosphine complexes [such as Ph(PPh3)4, Pt(PBu3)4]; platinum-phosphite complexes [such as Pt{P(OPh)3}4], etc. From the viewpoint of reaction efficiency, platinum catalysts such as chloroplatinic acid and platinum vinylsiloxane complexes are preferred.

[0129] As another method for producing polymer (A), a method in which a compound (L) having a hydrolyzable silyl group and an isocyanate group in one molecule is allowed to act on a polyoxyalkylene polymer (E) (precursor polymer) having a hydroxyl group at a terminal to form a urethane bond and introduce a hydrolyzable silyl group can also be applied. Polymer (A) can also be produced by this method.

[0130] The compound (L) having a hydrolyzable silyl group and an isocyanate group in one molecule is not particularly limited as long as it has both an isocyanate group capable of undergoing a urethanization reaction with the hydroxyl group of the polyoxyalkylene polymer (E) and a hydrolyzable silyl group in one molecule. Specific examples include (3-isocyanatepropyl)trimethoxysilane, (3-isocyanatepropyl)dimethoxymethylsilane, (3-isocyanatepropyl)triethoxysilane, (3-isocyanatepropyl)diethoxymethylsilane, (isocyanatemethyl)trimethoxysilane, (isocyanatemethyl)triethoxysilane, (isocyanatemethyl)dimethoxymethylsilane, and (isocyanatemethyl)diethoxymethylsilane.

[0131] The urethanization reaction can be carried out without using a urethanization catalyst, but it can also be carried out in the presence of a urethanization catalyst to increase the reaction rate and reaction rate. Examples of such urethanization catalysts include those listed in "Polyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963," and other conventionally known urethanization catalysts. Specific examples include, but are not limited to, base catalysts such as organotin compounds, bismuth compounds, and organic amines.

[0132] As another method for producing the polymer (A), the following method can be applied: after reacting an excess of a polyisocyanate compound (M) with a polyoxyalkylene polymer (E) having a hydroxyl group at a terminal to produce a polymer having an isocyanate group at a terminal (precursor polymer), a compound (N) having a group reactive with an isocyanate group (e.g., an amino group) and a hydrolyzable silyl group is reacted with the precursor polymer. This method can also produce a polyoxyalkylene polymer (A) having a hydrolyzable silyl group at a terminal of the polymer backbone.

[0133] Examples of the polyisocyanate compound (M) include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylenediisocyanate; and aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate.

[0134] Examples of the compound (N) having a group reactive with an isocyanate group and a hydrolyzable silyl group include γ-aminopropyltrimethoxysilane, γ-aminopropyldimethoxymethylsilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyldimethoxymethylsilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, γ-(N-phenyl)aminopropyltrimethoxysilane, and γ-(N-phenyl)aminopropyltrimethoxysilane. Aminosilanes such as γ-(N-phenyl)aminopropyldimethoxymethylsilane, N-ethylaminoisobutyltrimethoxysilane, N-ethylaminoisobutyldimethoxymethylsilane, N-cyclohexylaminomethyltrimethoxysilane, N-cyclohexylaminomethyldimethoxymethylsilane; Hydroxysilanes such as γ-hydroxypropyltrimethoxysilane, γ-hydroxypropyldimethoxymethylsilane; Mercaptosilanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyldimethoxymethylsilane; and the like.

[0135] As another method for producing polymer (A), the following method can be applied: a compound (P) having a hydrolyzable silyl group and a thiol group in one molecule is allowed to react with a polyoxyalkylene polymer (H) having an olefin group in its terminal structure (precursor polymer), thereby forming a sulfide bond through addition of the thiol group to the olefin group, thereby introducing a hydrolyzable silyl group. This method can also produce a polyoxyalkylene polymer (A) having a hydrolyzable silyl group at the terminal of the polymer backbone.

[0136] The compound (P) having a hydrolyzable silyl group and a thiol group in one molecule is not particularly limited as long as it has both a thiol group capable of undergoing an addition reaction with an olefin group of the polyoxyalkylene polymer (H) and a hydrolyzable silyl group in one molecule. Specific examples include (3-mercaptopropyl)methyldimethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)methyldiethoxysilane, (3-mercaptopropyl)triethoxysilane, (mercaptomethyl)methyldimethoxysilane, (mercaptomethyl)trimethoxysilane, (mercaptomethyl)methyldiethoxysilane, and (mercaptomethyl)triethoxysilane.

[0137] The addition reaction of a thiol group to an olefin group can be carried out without using a free radical initiator, but it can be carried out in the presence of a free radical initiator to increase the reaction rate and reaction rate. As such a free radical initiator, any conventionally known free radical initiator can be used. Specific examples include, but are not limited to, azo initiators and peroxide initiators.

[0138] Among known free radical initiators, catalysts with low activity toward hydrolyzable silyl groups are preferred. From this viewpoint, azo initiators such as 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile) (V-59), and 2,2'-azobis(1-methylcyclohexanecarbonitrile) (V-40) are particularly preferred.

[0139] <<(B) Metal compound comprising at least one metal element selected from aluminum and zinc and a chelate compound as a ligand>>

[0140] The heat-curable curable composition of this embodiment contains (B) a metal compound containing at least one metal element selected from aluminum and zinc and a chelate compound as a ligand (hereinafter also referred to as metal compound (B)) as a curing catalyst for the polymer (A).

[0141] The metal element contained in the metal compound (B) is at least one selected from aluminum and zinc, and aluminum is more preferred from the viewpoint of good stability in air.

[0142] The metal compound (B) contains a ligand of the above-mentioned metal element as a chelate compound.

[0143] As the chelate compound, well-known chelate compounds can be used. Specific examples include: nitrogen-containing compounds such as 1,2-diaminoethane, N,N'-di-tert-butylethylenediamine, 1,2-cyclohexanediamine, 2,2'-bipyridine, 2,2'-(methylimino)bis(N,N-di-n-octylacetamide), tris(2-aminoethyl)amine, and 3,3'-iminobis(N,N-dimethylpropylamine); β-diketones such as acetylacetone, trifluoroacetylacetone, 3-phenylacetylacetone, 1-phenyl-1,3-butanedione, 2,4-hexanedione, 2,4-heptanedione, dibenzoylmethane, and 1,3-cyclohexanedione; and methyl acetoacetate, ethyl acetonate, and the like. β-ketoesters such as ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, methyl pivaloyl acetate, methyl isobutyryl acetate, methyl hexanoyl acetate, and methyl lauroyl acetate, and other oxygen-containing compounds; β-ketoamides such as N-methyl-3-oxo-N-phenylbutyramide, and other oxygen / nitrogen-containing compounds; 1,2-bis(diphenylphosphino)ethane, 1,2-bis(diphenylphosphino)propane, 1,2-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, 2,2'-bis(diphenylphosphino)-1,1'-naphthyl, 4,5-bisdiphenylphosphino-9,9-dimethylxanthene (Xantphos), and other phosphorus-containing compounds.

[0144] Among them, β-dicarbonyl compounds such as β-diketone, β-ketoester, and β-ketoamide are preferred, β-diketone or β-ketoester is more preferred, β-diketone is further preferred, and acetylacetone is most preferred.

[0145] Specific examples of the metal compound (B) include aluminum triacetylacetonate, aluminum triethylacetoacetate, zinc bisacetylacetonate, etc. Among them, aluminum triacetylacetonate and zinc bisacetylacetonate are preferred, and aluminum triacetylacetonate is more preferred from the perspective of good stability in air and low solubility in the heat-curable curable composition of this embodiment.

[0146] The content of the metal compound (B) is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polymer (A).

[0147] <<(C) Chelated compounds>>

[0148] The heat-curable curable composition of the present embodiment contains (C) a chelate compound (hereinafter also referred to as chelate compound (C)) in addition to the polymer (A) and the metal compound (B).

[0149] By adding the chelate compound (C), the activity of the metal compound (B) as a curing catalyst can be reduced, and therefore, long-term storage stability can be maintained. In addition, during heat curing, the chelate compound is gasified, and thus, the activity of the metal compound (B) is improved, which can promote curing.

[0150] As the chelate compound (C), the chelate compounds described for the metal compound (B) can be used, preferably a β-dicarbonyl compound, more preferably a β-diketone or a β-ketoester, further preferably a β-diketone, and most preferably acetylacetone from the perspective of easy availability and having a moderate boiling point.

[0151] Furthermore, the chelate compound (C) is preferably the same compound as the chelate compound contained in the metal compound (B).

[0152] The content of the chelate compound (C) is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, and even more preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the polymer (A).

[0153] Furthermore, the ratio of the total number of moles of the chelate compound and the chelate compound (C) in the metal compound (B) to the number of moles of the metal element in the metal compound (B) is preferably greater than 3, more preferably 4 or greater, and even more preferably 5 or greater. By setting the ratio within the above range, it is easier to maintain the long-term storage stability of the curable composition.

[0154] <<(D) Epoxy compounds containing at least two epoxy groups in one molecule>>

[0155] The heat-curable curable composition of the present embodiment may further contain (D) an epoxy compound containing at least two epoxy groups in one molecule (hereinafter also referred to as epoxy compound (D)) in addition to the polymer (A), the metal compound (B) and the chelate compound (C). By adding (D) an epoxy compound containing at least two epoxy groups in one molecule, an effect of improved adhesion can be obtained. In addition, an effect of improved curability can be obtained after the curable composition is stored in a sealed state.

[0156] Specific examples of the epoxy compound (D) include 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: Celloxide 2021P), ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: Celloxide 2081), and (3,3',4,4'-diepoxy)bicyclohexane.

[0157] The epoxy compound (D) does not include epoxy group-containing silanes which are silane coupling agents described below.

[0158] As the epoxy compound (D), an epoxy resin containing at least two epoxy groups per molecule may also be used. Specific examples of such epoxy resins include flame-retardant epoxy resins such as epichlorohydrin-bisphenol A epoxy resins, epichlorohydrin-bisphenol F epoxy resins, glycidyl ethers of tetrabromobisphenol A, novolac epoxy resins, hydrogenated bisphenol A epoxy resins, glycidyl ethers of bisphenol A propylene oxide adducts, glycidyl p-hydroxybenzoate epoxy resins, m-aminophenol epoxy resins, diaminodiphenylmethane epoxy resins, urethane-modified epoxy resins, various alicyclic epoxy resins, N,N-diglycidyl aniline, N,N-diglycidyl o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ethers, glycidyl ethers of polyols such as glycerol, hydantoin epoxy resins, and epoxides of unsaturated polymers such as petroleum resins.

[0159] Among them, alicyclic epoxy compounds are preferred, more preferred are 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: Celloxide 2021P), ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: Celloxide 2081), and (3,3',4,4'-diepoxy)bicyclohexane, and particularly preferred is 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate.

[0160] The number of epoxy groups in the epoxy compound (D) is preferably 2 or more, more preferably 2, per molecule.

[0161] The content of the epoxy compound (D) is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, and even more preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the polymer (A).

[0162] <(T) Zeolite-based adsorbent>

[0163] In order to suppress the viscosity increase of the curable composition during storage, the heat-curable curable composition of the present embodiment preferably further contains (T) a zeolite-based adsorbent (hereinafter also referred to as zeolite-based adsorbent (T)) as a dehydrating agent.

[0164] The use of a zeolite-based adsorbent (T) in the heat-curable curable composition of this embodiment achieves moderate water absorption during storage and promotes moisture curing by releasing water during heating. This is particularly effective when the curable composition has a high moisture content. The zeolite-based adsorbent (T) is preferably added when the moisture content of the curable composition after preparation is 400 ppm or higher, and more preferably when it is 500 ppm or higher. The upper limit of this moisture content is preferably 2000 ppm or lower, more preferably 1500 ppm or lower, even more preferably 1200 ppm or lower, and even more preferably 1000 ppm or lower.

[0165] Specific examples of the zeolite-based adsorbent (T) include molecular sieves such as molecular sieve 3A, molecular sieve 4A, molecular sieve 5A, molecular sieve 3A-B, and molecular sieve 13X.

[0166] The content of the zeolite-based adsorbent (T) is not particularly limited, but is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, and even more preferably 1 to 15 parts by weight, relative to 100 parts by weight of the polymer (A).

[0167] <<Curable composition>>

[0168] The heat-curable curable composition of the present embodiment may contain various additives as needed, in addition to the polymer (A), the metal compound (B), the chelate compound (C), and the epoxy compound (D).

[0169] Examples of the additive include silanol condensation catalysts other than the metal compound (B), fillers, tackifiers, plasticizers, anti-sagging agents, antioxidants, light stabilizers, ultraviolet absorbers, physical property adjusters, photocurable substances, oxygen-curable substances, and resins other than the polymer (A).

[0170] In addition, the heat-curable curable composition of this embodiment may further contain other additives other than those listed above, as needed, for the purpose of adjusting various physical properties of the curable composition or cured product. Examples of such other additives include tackifying resins, solvents, diluents, surface modifiers, foaming agents, curability modifiers, flame retardants, silicates, free radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, and mildew inhibitors.

[0171] Hereinafter, representative additives will be described respectively.

[0172] <Silanol condensation catalyst>

[0173] The curable composition may contain a silanol condensation catalyst other than the metal compound (B) within a range not inhibiting the effect of the metal compound (B).

[0174] Examples of the silanol condensation catalyst other than the metal compound (B) include organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, and metal alkoxides.

[0175] Specific examples of the organotin compound include dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin bis(butylmaleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dioctyltin bis(acetylacetonate), a reaction product of dibutyltin oxide with a silicate compound, a reaction product of dioctyltin oxide such as dioctyltin bis(triethoxysilicate) with a silicate compound, and a reaction product of dibutyltin oxide with a phthalate.

[0176] Specific examples of the carboxylate metal salt include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, and iron carboxylate, etc. As the carboxylate metal salt, salts of combinations of the following carboxylic acids and various metals can be used.

[0177] Specific examples of the amine compound include octylamine, 2-ethylhexylamine, laurylamine, stearylamine, pyridine, an amino group-containing silane coupling agent, and a ketimine compound.

[0178] Specific examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

[0179] Specific examples of the metal alkoxide include titanium compounds such as tetrabutyl titanate, titanium tetrakis(acetylacetonate), and diisopropoxytitanium bis(ethyl acetylacetonate); and zirconium compounds such as zirconium tetrakis(acetylacetonate).

[0180] As other silanol condensation catalysts, compounds containing fluorine anions, photoacid generators, and photobase generators may also be used.

[0181] A silanol condensation catalyst other than the metal compound (B) may not be used. However, when used, the amount thereof is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the polymer (A).

[0182] Fillers

[0183] Various fillers can be incorporated into the curable composition. Examples of fillers include ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, kaolin, silica (sillitin), calcined silica, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, silicic anhydride, hydrous silicic acid, carbon black, iron oxide, aluminum powder, zinc oxide, activated zinc flower, PVC powder, PMMA powder, glass fibers and filaments, and the like.

[0184] The amount of the filler used is preferably 1 to 400 parts by weight, particularly preferably 10 to 300 parts by weight, based on 100 parts by weight of the polymer (A).

[0185] For the purpose of reducing the weight (lowering the specific gravity) of the cured product formed using the curable composition, hollow balls (hollow fillers) such as organic hollow balls and inorganic hollow balls can be added. Hollow balls are spherical fillers, and the interior of the hollow balls is hollow. Examples of the material of the hollow balls include inorganic materials such as glass, white sand, and silica, and organic materials such as phenolic resin, urea-formaldehyde resin, polystyrene, and saran.

[0186] The amount of the hollow spheres used is preferably 0.1 to 100 parts by weight, particularly preferably 1 to 20 parts by weight, based on 100 parts by weight of the polymer (A).

[0187] Thickener

[0188] A tackifier may be added to the curable composition. As the tackifier, a silane coupling agent or a reaction product of a silane coupling agent may be added.

[0189] Specific examples of the silane coupling agent include amino group-containing silanes such as γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, α-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltrieth ... Isocyanate group-containing silanes such as methyltrimethoxysilane and α-isocyanatemethyldimethoxymethylsilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; epoxy group-containing silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. In addition, when using amino group-containing silanes, it is preferred because it improves curability.

[0190] The above-mentioned thickeners may be used alone or in combination of two or more. In addition, reaction products of various silane coupling agents may also be used as thickeners.

[0191] The amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer (A).

[0192] Plasticizers

[0193] A plasticizer may be added to the curable composition. Specific examples of the plasticizer include phthalate compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butylbenzyl phthalate; terephthalate compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; non-phthalate compounds such as diisononyl 1,2-cyclohexanedicarboxylate; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and diisodecyl succinate. , and aliphatic polycarboxylic acid ester compounds such as acetyl tributyl citrate; unsaturated fatty acid ester compounds such as butyl oleate and acetyl ricinoleic acid methyl ester; alkyl phenyl sulfonate; phosphate compounds; trimellitate compounds; chlorinated paraffin; hydrocarbon oils such as alkyl biphenyl and partially hydrogenated terphenyl; process oil; epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy stearate octyl, epoxy stearate butyl and epoxy stearate benzyl, etc.

[0194] In addition, a polymer plasticizer may be used. Specific examples of polymer plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more, and polyether derivatives such as those obtained by converting the hydroxyl groups of these polyether polyols into ester groups, ether groups, etc.; polystyrenes; polybutadiene, polybutylene, polyisobutylene, butadiene-acrylonitrile, and polychloroprene.

[0195] The amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and particularly preferably 20 to 100 parts by weight, per 100 parts by weight of polymer (A). When the plasticizer is used within this range, the desired effects as a plasticizer can be achieved, and a curable composition capable of forming a cured product having excellent mechanical strength can be readily obtained. The plasticizer may be used alone or in combination of two or more.

[0196] <Anti-sagging agent>

[0197] To prevent dripping and improve workability, an anti-drip agent may be added to the curable composition as needed. The anti-drip agent is not particularly limited. Examples of anti-drip agents include polyamide waxes, hydrogenated castor oil derivatives, and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-drip agents may be used alone or in combination of two or more.

[0198] The amount of the anti-sagging agent used is preferably 0.1 to 20 parts by weight relative to 100 parts by weight of the polymer (A).

[0199] <Antioxidants>

[0200] An antioxidant (anti-aging agent) may be used in the curable composition. The use of an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenols, monophenols, bisphenols, diarylamines, and polyphenols. Specific examples of antioxidants are described in, for example, Japanese Patent Application Publication No. 4-283259 and Japanese Patent Application Publication No. 9-194731.

[0201] The amount of the antioxidant used is preferably 0.1 to 15 parts by weight, particularly preferably 1.0 to 10 parts by weight, based on 100 parts by weight of the polymer (A).

[0202] Light stabilizer

[0203] A light stabilizer may be used in the curable composition. The use of a light stabilizer can prevent photooxidative degradation of the cured product. Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds. Hindered amine-based light stabilizers are particularly preferred.

[0204] The amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polymer (A).

[0205] UV absorbers

[0206] A UV absorber may be used in the curable composition. The use of a UV absorber can improve the surface weather resistance of the cured product. Examples of UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds. Benzotriazole-based UV absorbers are particularly preferred. Preferred specific examples of benzotriazole-based UV absorbers include Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (all manufactured by BASF).

[0207] The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polymer (A).

[0208] <Physical property adjusters>

[0209] If necessary, a physical property adjuster that adjusts the tensile properties of the generated cured product can be added to the curable composition. There is no particular limitation on the physical property adjuster. Examples of the physical property adjuster include: alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as tris(trimethylsilyl)borate and tris(triethylsilyl)borate; silicone varnishes; polysiloxanes, etc. By using a physical property adjuster, the hardness of the cured product of the curable composition can be increased, or conversely, the hardness can be reduced and the elongation at break can be increased. The physical property adjuster can be used alone or in combination of two or more.

[0210] In particular, compounds that generate compounds having a monovalent silanol group in the molecule by hydrolysis have the effect of not causing the viscosity of the surface of the cured product to deteriorate and reducing the modulus of the cured product. Particularly preferred are compounds that generate trimethylsilanol. As compounds that generate compounds having a monovalent silanol group in the molecule by hydrolysis, hexanol, octanol, phenol, trimethylolpropane, glycerol, pentaerythritol, and sorbitol, which are derivatives of alcohols and can generate silicon compounds of silane monools by hydrolysis, can be mentioned. Specifically, phenoxytrimethylsilane, tris((trimethylsiloxy)methyl)propane, etc. can be mentioned.

[0211] The amount of the property modifier used is preferably 0.1 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the polymer (A).

[0212] <Photocurable substances>

[0213] A photocurable substance can be used in a curable composition. If a photocurable substance is used, a film of the photocurable substance can be formed on the surface of the cured product, which can improve the stickiness and weather resistance of the cured product. As such substances, many substances are known, such as organic monomers, oligomers, resins, or compositions containing the above substances. As representative substances, monomers having one or more acrylic or methacrylic unsaturated groups, unsaturated acrylic compounds as oligomers or mixtures thereof, polyvinyl cinnamates, or azidated resins can be used.

[0214] The amount of the photocurable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the polymer (A). If the photocurable substance is used within the above range, a curable composition that can form a cured product that is excellent in weather resistance, flexible, and resistant to cracking can be easily obtained.

[0215] <Oxygen-curable substances>

[0216] Oxygen-curing substances can be used in curable compositions. Examples of oxygen-curing substances include unsaturated compounds that react with oxygen in the air. Oxygen-curing substances react with oxygen in the air to form a cured film near the surface of the cured product, thereby preventing surface stickiness and preventing the adhesion of dirt and dust to the surface of the cured product.

[0217] Specific examples of oxygen-curable substances include drying oils such as tung oil and linseed oil, various alkyd resins modified from these compounds, modified resins such as acrylic polymers, epoxy resins, and silicone resins using drying oils, and liquid polymers such as 1,2-polybutadiene and 1,4-polybutadiene obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene, as well as polymers of dienes having 5 to 8 carbon atoms. These can be used alone or in combination of two or more.

[0218] The amount of the oxygen-curable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of polymer (A). When the amount of the oxygen-curable substance used is within the above range, a sufficient stain-reducing effect is easily achieved, and the tensile properties of the cured product are less likely to be impaired. As described in Japanese Patent Application Laid-Open No. 3-160053, the oxygen-curable substance is preferably used in combination with a photocurable substance.

[0219] <<Preparation of curable composition>>

[0220] The curable composition of the present embodiment can be prepared as a one-component type in which all the ingredients are mixed and stored in a sealed container, and the composition is cured by moisture in the air after application.

[0221] In the case of a one-component curable composition, since all components are pre-blended, components containing water are preferably dehydrated and dried before use, or dehydrated by reduced pressure or the like during blending and kneading.

[0222] The curable composition containing (D) an epoxy compound having at least two epoxy groups per molecule is preferably stored in a sealed container at 23°C to 50°C for 1 day to 4 weeks before application (coating on a substrate, etc.). This improves the surface curability after application.

[0223] The water content of the curable composition of the present heat-curable type is preferably 100 ppm or more, preferably 120 ppm or more, preferably 140 ppm or more, preferably 160 ppm or more. In addition, the water content of the curable composition of the present heat-curable type is preferably 500 ppm or less, preferably 480 ppm or less, preferably 450 ppm or less, preferably 400 ppm or less. More specifically, the water content of the curable composition of the present heat-curable type is preferably 100 to 500 ppm, preferably 120 to 480 ppm or less, preferably 140 to 450 ppm or less, preferably 160 to 400 ppm or less. When the water content is within the above range, even if the curable composition of the present embodiment does not contain a dehydrating agent, it can be used without curing for a long time by storing it in a sealed container, and it is also possible to take into account the heat curing properties when heated after construction.

[0224] Even if the water content of the compound during preparation exceeds the above range, the same effect can be achieved by adjusting the water content to within the above range by adding a dehydrating agent, etc. The water content of the compound during preparation (before adding a dehydrating agent, if any) is preferably 100 to 2000 ppm, more preferably 100 to 1500 ppm, and even more preferably 100 to 1000 ppm.

[0225] <<Method for producing cured product>>

[0226] The curable composition of this embodiment can be adjusted to a desired shape before curing by coating, injection molding, or filling. The curable composition after coating, injection molding, or filling and adjusting the shape is preferably cured under heating.

[0227] The curable composition of this embodiment is a heat-curable curable composition. A heat-curable curable composition is one that cures in a short time (e.g., within 1 hour) when heated, but cures very slowly at room temperature and requires a long time.

[0228] The conditions for heat-curing the curable composition of this embodiment are not particularly limited. The heating temperature is preferably 40°C or higher, more preferably 60°C or higher, and even more preferably 100°C or higher. In addition, the heating temperature is preferably 220°C or lower, more preferably 210°C or lower, and even more preferably 200°C or lower. More specifically, the heating temperature is preferably 40 to 220°C, more preferably 60 to 210°C, even more preferably 100 to 200°C, and even more preferably 120 to 200°C. The heating time is preferably 1 to 120 minutes, more preferably 5 to 60 minutes. There is no particular limitation on the method for heating the curable composition, and hot air or infrared rays can be used as appropriate. The method using hot air is particularly preferred.

[0229] The curable composition of the present embodiment undergoes a rapid and sufficient curing reaction under curing conditions under heating, and a cured product containing no bubbles inside can be obtained. Therefore, the curable composition of the present embodiment can be suitably used for applications where a short curing reaction is desired, such as applications within a factory.

[0230] <<Application>>

[0231] The curable composition of the present embodiment can be used for sealing materials, die-stamping agents, adhesives, coatings, and propellants for sealing material construction in adhesives, buildings / ships / cars / buses / roads / home appliances, etc. In addition, the cured product obtained by curing the curable composition of the present embodiment can be suitably used as waterproof materials, coating waterproof materials, shockproof materials, shock-absorbing materials, sound-insulating materials, and foaming materials, etc. The softness and adhesiveness of the cured product obtained are excellent, and therefore, the curable composition of the present embodiment is more preferably used as sealing materials or adhesives in the above-mentioned purposes.

[0232] Example

[0233] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0234] The number average molecular weight in the examples is a GPC molecular weight measured under the following conditions.

[0235] Liquid delivery system: Tosoh HLC-8220GPC

[0236] Chromatographic column: Tosoh TSKgel SuperH series

[0237] Solvent: THF

[0238] Molecular weight: polystyrene conversion

[0239] Measurement temperature: 40°C

[0240] The terminal group-equivalent molecular weight in the examples is determined by measuring the hydroxyl value according to JIS K 1557 and the iodine value according to JIS K 0070, taking into account the structure of the organic polymer (branching degree determined by the polymerization initiator used).

[0241] The average number of silyl groups per terminal or per molecule of the polymers shown in the Examples was calculated by NMR measurement.

[0242] (Synthesis Example 1) A-1

[0243] Using polyoxypropylene triol with a number average molecular weight of approximately 4500 as an initiator and zinc hexacyanocobaltate glyme complex as a catalyst, propylene oxide polymerization was carried out to obtain polyoxypropylene (P-1) with a number average molecular weight of 24600 (terminal group converted molecular weight of 17400) and a molecular weight distribution Mw / Mn = 1.31, having hydroxyl groups at the ends.

[0244] Relative to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (P-1) obtained, 1.2 molar equivalents of sodium methoxide are made into a 28% methanol solution and added. After the methanol is distilled off by vacuum devolatilization, 1.5 molar equivalents of allyl chloride are further added relative to the hydroxyl group of the polymer (P-1) to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride is removed by vacuum devolatilization. After mixing and stirring the obtained unpurified polyoxypropylene with n-hexane and water, the water is removed by centrifugal separation, and the hexane is decompressed and devolatilized from the obtained hexane solution to remove the metal salt in the polymer. Through the above operation, polyoxypropylene (Q-1) having an allyl group at the end is obtained.

[0245] To 500 g of the resulting polymer (Q-1), 50 μL of a divinyldisiloxane platinum complex solution (3% by weight platinum in isopropanol) was added, and 8.5 g of trimethoxysilane was slowly added dropwise while stirring. After reacting at 100° C. for 2 hours, the unreacted trimethoxysilane was distilled off under reduced pressure to obtain polyoxypropylene (A-1) having a number average molecular weight of 26,200 and a trimethoxysilyl group at the terminal. It was found that polymer (A-1) had an average of 0.7 trimethoxysilyl groups at one terminal and an average of 2.1 trimethoxysilyl groups per molecule.

[0246] (Synthesis Example 2) A-2

[0247] Using polyoxypropylene glycol with a number average molecular weight of approximately 3,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst, propylene oxide polymerization was carried out to obtain polyoxypropylene (P-2) with a number average molecular weight of 27,900 (terminal group equivalent molecular weight of 17,700) and a molecular weight distribution Mw / Mn = 1.21, having hydroxyl groups at both ends.

[0248] Relative to the hydroxyl groups of the obtained polymer (P-2), 1.0 molar equivalent of sodium methoxide was prepared into a 28% methanol solution and added. After distilling off the methanol by vacuum devolatilization, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl groups of the polymer (P-2), and the reaction was carried out at 130°C for 2 hours. Then, 0.3 molar equivalent of a methanol solution of sodium methoxide was added to remove the methanol, and 1.8 molar equivalents of allyl chloride were further added to convert the terminal hydroxyl groups into allyl groups. After mixing and stirring the obtained unpurified polyoxypropylene with n-hexane and water, the water was removed by centrifugal separation, and the hexane was decompressed and devolatilized from the obtained hexane solution to remove the metal salts in the polymer. Through the above operations, polyoxypropylene (Q-2) having multiple carbon-carbon unsaturated bonds at the end was obtained.

[0249] To 500 g of the resulting polymer (Q-2), 50 μL of a divinyldisiloxane platinum complex solution (3% by weight platinum in isopropanol) was added, and 9.6 g of trimethoxysilane was slowly added dropwise while stirring. The mixed solution was reacted at 90°C for 2 hours, and then the unreacted trimethoxysilane was distilled off under reduced pressure to obtain polyoxypropylene (A-2) with a number average molecular weight of 28,000 and multiple trimethoxysilyl groups at the terminals. It was found that polymer (A-2) had an average of 1.7 trimethoxysilyl groups at each terminal and an average of 3.4 trimethoxysilyl groups per molecule.

[0250] (Synthesis Example 3) A-3

[0251] To 500 g of the polymer (Q-1) obtained in Synthesis Example 1, 50 μl of a divinyldisiloxane platinum complex solution (3% by weight platinum solution in isopropanol) was added, and 6.4 g of dimethoxymethylsilane was slowly added dropwise while stirring. After reacting at 100°C for 2 hours, the unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (A-3) having a number average molecular weight of 26,200 and terminal dimethoxymethylsilyl groups. It was found that the polymer (A-3) had an average of 0.7 dimethoxymethylsilyl groups at each terminal and an average of 2.2 dimethoxymethylsilyl groups per molecule.

[0252] (Synthesis Example 4) A-4

[0253] Using polyoxypropylene glycol with a number-average molecular weight of approximately 4500 as an initiator, propylene oxide was polymerized using a zinc hexacyanocobaltate glyme complex catalyst to produce polyoxypropylene (P-3) with a number-average molecular weight of 27900 and terminal hydroxyl groups. A mercaptotin catalyst (U-360 manufactured by Tiandong Chemical) was added at a concentration of 50 ppmd per 100 parts by weight of polymer (P-3) along with 0.95 molar equivalents of 3-isocyanatepropyltrimethoxysilane relative to the hydroxyl groups in the polymer to form a carbamate in the hydroxyl groups in the polymer, yielding silyl-containing polyoxypropylene (A-4).

[0254] (Production Example 1)

[0255] To 100 parts by weight of the polymer (A-1) obtained in Synthesis Example 1, 5 parts by weight of an antioxidant (trade name: Irganox 245, manufactured by BASF Japan Co., Ltd.), 160 parts by weight of surface-treated colloidal calcium carbonate (trade name: NEOLIGHT SP, manufactured by Takehara Chemical Industry Co., Ltd.), 54 parts by weight of heavy calcium carbonate (trade name: LM2200, manufactured by Maruo Calcium Co., Ltd.), 20 parts by weight of carbon black (trade name: HIBLACK 10, manufactured by Orion Engineered Carbons), 10 parts by weight of polypropylene glycol (trade name: ACTCOL P-23, number average molecular weight: 3000, manufactured by Mitsui Chemicals SKC Polyurethanes Co., Ltd.) as a plasticizer, and 40 parts by weight of SANSO CIZER E-PS (di-2-ethylhexyl 4,5-epoxycyclohexane-1,2-dicarboxylate, manufactured by Shin Nippon Rika Co., Ltd.) were added, mixed with a spatula, and dispersed by passing through a triple roll mill three times. Then, using a planetary mixer, reduced pressure drying was carried out at 120°C for 2 hours, and the water content of the obtained complex was measured. After cooling to below 50°C, 2 parts by weight of 3-glycidoxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-402) as an epoxy silane coupling agent and 1 part by weight of acetylacetone (manufactured by Tokyo Chemical Industry Co., Ltd.) as a β-dicarbonyl compound were added and mixed. 2 parts by weight of aluminum triacetylacetonate (manufactured by KISHIDA Chemical Co., Ltd.) as a curing catalyst were further added and mixed to obtain a curable composition. The obtained curable composition was filled in a moisture-proof cartridge and sealed to obtain a one-component heat-curing curable composition (compound 1).

[0256] (Production Example 2)

[0257] A one-component heat-curable curable composition (compound 2) was obtained in the same manner as in Production Example 1 except that 2 parts by weight of 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: Celloxide 2021P) was further added as an epoxy compound.

[0258] (Production Example 3)

[0259] A one-component heat-curable curable composition (compound 3) was obtained in the same manner as in Production Example 2, except that reduced-pressure drying was carried out at 120°C for 3.5 hours instead of 2 hours at 120°C using a planetary mixer and the moisture content of the obtained compound was measured.

[0260] (Production Example 4)

[0261] A one-component heat-curable curable composition (complex 4) was obtained in the same manner as in the preparation of complex 1, except that 2 parts by weight of 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: Celloxide 2021P) was further added as an epoxy compound, and 2 parts by weight of zinc diacetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 2 parts by weight of aluminum triacetylacetonate.

[0262] (Production Example 5)

[0263] A one-component heat-curable curable composition (compound 5) was obtained in the same manner as in Production Example 1 except that acetylacetone was not used.

[0264] (Production Example 6)

[0265] A one-component heat-curable curable composition (compound 6) was obtained in the same manner as in Production Example 1, except that 0.1 parts by weight of dibutyltin bis(acetylacetonate) (manufactured by Amado Chemical Industry Co., Ltd., trade name: Neostan U-220H) was used instead of 2 parts by weight of aluminum triacetylacetonate, and 2 parts by weight of 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: Celloxide 2021P) was used as an epoxy compound.

[0266] (Examples 1 to 4, Comparative Examples 1 and 2)

[0267] The formulations listed in Table 1 were applied to steel plates in the form of 20 mm x 5 mm beads and then cured at 160°C for 30 minutes. After returning to room temperature (23°C), the cured product was cut with a cutter, and the cured state and the presence of bubbles on the cut surface were visually inspected. The results are shown in Table 1.

[0268] The mixture in the cylinder was then stored at 23°C, 50% RH for one day. Under the same conditions, the mixture was placed in a 100cc disposable cup to prevent air bubbles from entering. The viscosity was measured at 2 rpm (the value after 3 revolutions) using a BS viscometer (manufactured by Tokyo Keiki) and a No. 7 rotor. This was used as the initial viscosity. Separately, the mixture in the cylinder was stored at 40°C for 14 days. The viscosity after storage at 23°C, 50% RH for one day was then measured. This was used as the post-storage viscosity. The viscosity increase was calculated by dividing the post-storage viscosity by the initial viscosity × 100%.

[0269] The water content of the complex was measured using a Karl Fischer titrator (EBU-610, manufactured by Kyoto Electronics Co., Ltd.) using Aquamicron Titrant SS 3 mg (titer 2.5-3.5 mgH₂O / mL, manufactured by Mitsubishi Chemical Corporation) and Aquamicron Dehydrating Agent CM (water content 0.3 mgH₂O / mL or less, manufactured by Mitsubishi Chemical Corporation). The results are shown in Table 1.

[0270]

[0271] As is clear from Table 1, in Examples 1 to 4 in which the metal compound (B) and the chelate compound (C) are combined, the viscosity increase rate is low even after storage at 40°C for 14 days, indicating good heat-resistant storage stability, and good heat curing properties are exhibited at a heating temperature of 160°C.

[0272] On the other hand, Comparative Example 1 did not contain a chelate compound (C) as a curing catalyst, and Comparative Example 2 used a tin catalyst instead of the metal compound (B). Both solidified in the drum during storage at 40°C. In these Comparative Examples, the catalyst activity could not be sufficiently suppressed under the above-mentioned heated storage conditions, resulting in poor heat-resistant storage stability.

[0273] (Examples 5-6)

[0274] The mixture listed in Table 2 was placed in a cylinder and allowed to stand at 23°C, 50% RH for one day. The mixture was then applied to a polyethylene sheet and stretched to a thickness of 3 mm. The curing start time was defined as the time when the surface became smooth. The curing time was measured by touching the surface with a spatula until the curable composition no longer adhered to the spatula. Furthermore, the mixture in the cylinder was stored at 40°C for 14 days and then placed at 23°C, 50% RH for one day. The curing time was then measured as the skinning time. The results are shown in Table 2.

[0275] [Table 2]

[0276]

[0277] As is clear from Table 2, in Examples 5 and 6, when the coating was applied without storage at 40°C, skinning took 18 hours at room temperature. In Example 5, even when the coating was applied after storage at 40°C for 14 days, it still took 18 hours. However, in Example 6, which incorporated the epoxy compound (D), the skinning time was shortened to 6 hours, indicating better curability.

[0278] (Examples 7-8)

[0279] The surfaces of anodized aluminum plates, electrolytically colored aluminum plates, cold-rolled stainless steel plates, cold-rolled steel plates, or galvanized steel plates were cleaned with gauze soaked in ethanol. The compounds listed in Table 3 were extruded onto the surfaces in the form of beads, gently pressed with a micro spatula to achieve a close fit, and then cured by heating at 180°C for 30 minutes.

[0280] After removing the cured product and returning it to room temperature (23°C), the interface between the cured product and the substrate was cut with a spatula. The cured product was then pulled at 90 degrees relative to the substrate with a finger to confirm manual peel adhesion. Manual peel adhesion was determined by visually inspecting the fracture surface after the tensile test to determine whether it was cohesive failure (CF) or interfacial failure (AF). The results are shown in Table 3.

[0281] [Table 3]

[0282]

[0283] It can be clearly seen from Table 3 that in Example 7, good adhesion is shown to electrolytically colored aluminum plates, cold-rolled stainless steel plates, cold-rolled steel plates, or galvanized steel plates under heating conditions, and in Example 8, in addition to the above plates, good adhesion is also shown to anodized aluminum plates.

[0284] (Production Example 7)

[0285] Using a planetary mixer, reduced pressure drying was carried out at 120°C for 1 hour instead of 2 hours at 120°C, and the moisture content of the resulting complex was measured. Then, 4 parts by weight of molecular sieve 4A (manufactured by Union Showa Co., Ltd.) was further added as a zeolite-based adsorbent. Except for this, a one-component heat-curable curable composition (complex 7) was obtained in the same manner as in Production Example 2 to obtain the composition.

[0286] (Production Example 8)

[0287] Using a planetary mixer, reduced pressure drying was carried out at 120°C for 1.5 hours instead of 2 hours at 120°C, and the moisture content of the resulting complex was measured. Then, 4 parts by weight of molecular sieve 3A (manufactured by Union Showa Co., Ltd.) was further added as a zeolite-based adsorbent. Except for this, a one-component heat-curable curable composition (complex 8) was obtained in the same manner as in Production Example 2 to obtain the composition.

[0288] (Production Example 9)

[0289] Using a planetary mixer, reduced pressure drying was carried out at 120°C for 1.5 hours instead of 2 hours at 120°C, and the moisture content of the resulting complex was measured. Then, 4 parts by weight of molecular sieve 3A-B (manufactured by Union Showa Co., Ltd.) was further added as a zeolite-based adsorbent. Except for this, a one-component heat-curable curable composition (complex 9) was obtained in the same manner as in Production Example 2.

[0290] (Production Example 10)

[0291] Using a planetary mixer, reduced pressure drying was carried out at 120°C for 1.5 hours instead of 2 hours at 120°C, and the moisture content of the resulting complex was measured. Then, 10 parts by weight of molecular sieve 3A (manufactured by Union Showa Co., Ltd.) was further added as a zeolite-based adsorbent. Except for this, a one-component heat-curable curable composition (complex 10) was obtained in the same manner as in Production Example 2.

[0292] (Examples 9 to 12)

[0293] The formulations listed in Table 4 were applied to steel plates in the form of 20 mm x 5 mm beads and then cured at 160°C for 30 minutes. After returning to room temperature (23°C), the cured product was cut with a cutter, and the cured state and the presence of bubbles were visually inspected on the cut surface. The results are shown in Table 4.

[0294] The mixture in the cylinder was then stored at 23°C, 50% RH for one day. Under the same conditions, the mixture was placed in a 100cc disposable cup to prevent air bubbles from entering. The viscosity was measured at 2 rpm (the value after 3 revolutions) using a BS viscometer (manufactured by Tokyo Keiki) and a No. 7 rotor. This was used as the initial viscosity. Separately, the mixture in the cylinder was stored at 40°C or 50°C for 14 days. The viscosity after storage at 23°C, 50% RH for one day was then measured. This was used as the viscosity after storage. The viscosity increase was calculated by dividing the viscosity after storage by the initial viscosity × 100%.

[0295] The water content of the complex was measured using a Karl Fischer titrator (EBU-610, manufactured by Kyoto Electronics Co., Ltd.) using Aquamicron Titrant SS 3 mg (titer 2.5-3.5 mgH₂O / mL, manufactured by Mitsubishi Chemical Corporation) and Aquamicron Dehydrating Agent CM (water content 0.3 mgH₂O / mL or less, manufactured by Mitsubishi Chemical Corporation). The results are shown in Table 4.

[0296] [Table 4]

[0297]

[0298] As is clear from Table 4, although Examples 9 to 12 had relatively high water contents in the complexes, they exhibited good heat-resistant storage stability due to the addition of the zeolite-based adsorbent (T).

[0299] (Production Example 11)

[0300] A one-component heat-curable curable composition (compound 11) was obtained in the same manner as in Preparation Example 10 except that NOCRAC CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) was used as an antioxidant instead of Irganox 245 and ACTCOL P-23 was not used as a plasticizer.

[0301] (Production Example 12)

[0302] A one-component heat-curable curable composition (compound 12) was obtained in the same manner as in Production Example 11 except that the blending amount of aluminum triacetylacetonate was changed to 0.5 parts by weight.

[0303] (Production Example 13)

[0304] A one-component heat-curable curable composition (compound 13) was obtained in the same manner as in Production Example 12 except that the polymer (A-2) obtained in Synthesis Example 2 was used instead of the polymer (A-1).

[0305] (Production Example 14)

[0306] A one-component heat-curable curable composition (compound 14) was obtained in the same manner as in Production Example 11 except that the polymer (A-3) obtained in Synthesis Example 3 was used instead of the polymer (A-1).

[0307] (Production Example 15)

[0308] A one-component heat-curable curable composition (compound 15) was obtained in the same manner as in Production Example 11 except that the polymer (A-4) obtained in Synthesis Example 4 was used instead of the polymer (A-1).

[0309] (Examples 13 to 17)

[0310] The compounds listed in Table 5 were used to visually confirm the curing state and the presence of bubbles when the compounds were cured using the same evaluation method as in Examples 9 to 12. The viscosity increase and the water content of the compounds after further storage at 50°C for 14 days were measured.

[0311] [Table 5]

[0312]

[0313] As is clear from Table 5, Examples 13 to 17 using polymers (A-1) to (A-4) exhibited good heat curability and heat-resistant storage stability.

[0314] (Production Example 16)

[0315] A one-component heat-curable curable composition (compound 16) was obtained in the same manner as in Production Example 11, except that the amount of carbon black (manufactured by Orion Engineered Carbons, trade name: HIBLACK 10) was changed to 30 parts by weight, the amount of aluminum triacetylacetonate was changed to 0.5 parts by weight, and the amount of acetylacetone was changed to 1.5 parts by weight.

[0316] (Production Example 17)

[0317] A one-component heat-curable curable composition (compound 17) was obtained in the same manner as in Production Example 16 except that 2 parts by weight of 3-glycidoxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-402) was used instead of KBM-402 as the epoxy silane coupling agent.

[0318] (Examples 18-19)

[0319] The compounds listed in Table 6 were heated at 140°C for 30 minutes, 160°C for 30 minutes, 180°C for 30 minutes, and 200°C for 30 minutes, and the curing state and the presence of bubbles of the compounds were visually confirmed using the same evaluation method as in Examples 9 to 12. The water content of the compounds was further measured.

[0320] [Table 6]

[0321]

[0322] As is clear from Table 6, Examples 18 and 19 exhibited good curability at heating temperatures of 160 to 200° C. In Example 19, which used 3-glycidoxypropylmethyldiethoxysilane as the epoxysilane coupling agent, good curability was also exhibited even at a heating temperature of 140° C.

Claims

1. A heat-curable curable composition comprising: (A) a polyoxyalkylene polymer having a hydrolyzable silyl group represented by the general formula (1), -Si(R 1 ) 3-a (X) a (1) Where R 1 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group optionally having a heteroatom-containing group, each X independently represents a hydroxyl group or a hydrolyzable group, and a is 1, 2 or 3; (B) a metal compound comprising at least one metal element selected from aluminum and zinc and a chelate compound as a ligand; and (C) a chelate compound which is the same chelate compound as that contained in the metal compound (B), The ratio of the total number of moles of the chelate compound and the chelate compound (C) in the metal compound (B) to the number of moles of the metal element in the metal compound (B) is 4 or more. 2 . The heat-curable curable composition according to claim 1 , further comprising (D) an epoxy compound having at least two epoxy groups in one molecule. 3 . The heat-curable curable composition according to claim 1 , further comprising (T) a zeolite-based adsorbent.

4. The heat-curable curable composition according to claim 1 or 2, wherein The heat-curable curable composition has a water content of 100 to 500 ppm.

5. The heat-curable curable composition according to claim 1 or 2, wherein The chelate compound (C) is a β-dicarbonyl compound.

6. The heat-curable curable composition according to claim 5, wherein The β-dicarbonyl compound is at least one selected from the group consisting of β-diketone and β-ketoester.

7. The heat-curable curable composition according to claim 1 or 2, wherein a in the general formula (1) is 3.

8. The heat-curable curable composition according to claim 2, wherein The epoxy compound (D) is an alicyclic epoxy compound.

9. The heat-curable curable composition according to claim 1 or 2, wherein The content of the metal compound (B) is 0.1 to 10 parts by weight, and the content of the chelate compound (C) is 0.1 to 10 parts by weight, based on 100 parts by weight of the polymer (A).

10. A method for producing a heat-curable curable composition, the method comprising: A step of mixing the following (A), (B) and (C), (A) a polyoxyalkylene polymer having a hydrolyzable silyl group represented by the general formula (1), -Si(R 1 ) 3-a (X) a (1) Where R 1 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group optionally having a heteroatom-containing group, each X independently represents a hydroxyl group or a hydrolyzable group, and a is 1, 2 or 3; (B) a metal compound comprising at least one metal element selected from aluminum and zinc and a chelate compound as a ligand; as well as (C) a chelate compound which is the same chelate compound as that contained in the metal compound (B), The ratio of the total number of moles of the chelate compound and the chelate compound (C) in the metal compound (B) to the number of moles of the metal element in the metal compound (B) is 4 or more.

11. A method for producing a solidified product, the method comprising: A step of heat-curing the heat-curable curable composition according to any one of claims 1 to 9, wherein: Prior to the heat curing step, the method further includes storing the heat-curable curable composition in a sealed state at 23° C. to 50° C. for 1 day to 4 weeks.

12. The method for producing a cured product according to claim 11, wherein The temperature of the heat curing step is 40 to 220°C.

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