Moisture-curing resin composition and cured product

Abstract

To provide a moisture-curing resin composition that is excellent in workability, storage stability, and heat resistance. [Solution] The moisture-curable resin composition according to the present disclosure comprises (A) at least one of a polyoxyalkylene polymer having a hydrolyzable silyl group and a (meth)acrylic acid ester polymer, (B) a thermally conductive filler, (C) a specific heat-resistant plasticizer, (D) a specific metal carboxylic acid compound, and (E) a specific cyclic secondary amine compound, wherein (B) is present in an amount of 500 to 1000 parts by weight per 100 parts by weight of the total of (A) and (C).

Description

[Technical Field]

[0001] This invention relates to moisture-curing resin compositions and cured products. [Background technology]

[0002] Conventionally, curable resin compositions containing thermally conductive fillers for heat dissipation have been used as cooling technologies in electronic devices such as mobile phones and personal computers. Since such curable resin compositions contain a large amount of thermally conductive filler, they generally also contain plasticizers to ensure coatability (for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2014-24958 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] However, the conventional technologies described above had room for improvement in terms of workability, storage stability, and heat resistance. One aspect of the present invention aims to realize a moisture-curable resin composition that is excellent in workability, storage stability, and heat resistance. [Means for solving the problem]

[0005] To solve the above problems, a moisture-curing resin composition according to one aspect of the present invention is described below. (A) Components: (A-1) A polyoxyalkylene polymer having a crosslinkable hydrolyzable silyl group, and (A-2) At least one of a (meth)acrylic acid ester polymer having a crosslinkable hydrolyzable silyl group. (B) Component: Thermally conductive filler, (C) Components: A heat-resistant plasticizer which is at least one of pyromellitic acid ester and trimellitic acid ester. (D) Component: Carboxylic acid metal compound, (E) component: contains a cyclic secondary amine compound, The aforementioned component (D) includes divalent tin, or one or more metals selected from the group consisting of titanium, bismuth, zirconium, and zinc. The aforementioned component (E) has one or more skeletons selected from the group consisting of a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, and an azepane skeleton. The total of 100 parts by weight of component (A) and component (C) contains 500 to 1000 parts by weight of component (B). [Effects of the Invention]

[0006] According to one aspect of the present invention, a moisture-curable resin composition with excellent workability, storage stability, and heat resistance can be provided. [Modes for carrying out the invention]

[0007] The following describes in detail some examples of embodiments of the present invention, but the present invention is not limited to these. Unless otherwise specified herein, "A to B" representing a numerical range means "greater than or equal to A and less than or equal to B". Also, (meth)acrylic means acrylic and / or methacrylic.

[0008] [1. Moisture-curing resin composition] A moisture-curing resin composition according to one embodiment of the present invention, (A) Components: (A-1) A polyoxyalkylene polymer having a crosslinkable hydrolyzable silyl group, and (A-2) At least one of a (meth)acrylic acid ester polymer having a crosslinkable hydrolyzable silyl group. (B) Component: Thermally conductive filler, (C) Components: A heat-resistant plasticizer which is at least one of pyromellitic acid ester and trimellitic acid ester. (D) Component: Carboxylic acid metal compound, (E) component: contains a cyclic secondary amine compound, The aforementioned component (D) includes divalent tin, or one or more metals selected from the group consisting of titanium, bismuth, zirconium, and zinc. The aforementioned component (E) has one or more skeletons selected from the group consisting of a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, and an azepane skeleton. The total of 100 parts by weight of component (A) and component (C) contains 500 to 1000 parts by weight of component (B).

[0009] Moisture-curing resin compositions are widely used in flame-retardant adhesives and heat-dissipating adhesives, etc. Hereinafter, moisture-curing resin compositions will also be simply referred to as "curable compositions." Thermally conductive fillers are used to impart heat dissipation to curable compositions, but adding a large amount of thermally conductive filler to achieve this heat dissipation significantly increases the viscosity of the curable composition. Therefore, plasticizers are also used to ensure applicability. However, commonly used plasticizers volatilize at high temperatures, which may reduce the adhesive performance after heat resistance. On the other hand, high heat-resistant plasticizers are also known, but they may interact with catalysts contained in curable compositions and reduce storage stability. Furthermore, it has been found that depending on the type of co-catalyst, it may take time for the curable composition to harden, which may result in poor workability. As a result of diligent research into these issues, the inventors have developed a curable composition with excellent workability, storage stability, and heat resistance by combining a specific plasticizer (component (C)), a specific catalyst (component (D)), and a specific co-catalyst (component (E)).

[0010] <1-1. (A) Component> Component (A) is at least one of (A-1) a polyoxyalkylene polymer having a crosslinkable hydrolyzable silyl group, and (A-2) a (meth)acrylic acid ester polymer having a crosslinkable hydrolyzable silyl group. That is, the curable composition may contain only component (A-1), only component (A-2), or both. Component (A) has high moisture permeability, excellent deep curing properties when used in a one-component curable composition, and also excellent adhesive properties.

[0011] (Component (A-1)) has a polyoxyalkylene polymer as the main chain. The polyoxyalkylene polymer is a polymer having a repeating unit represented by the following general formula (1): -R-O- (1) In the general formula (1), R is a linear or branched alkylene group having 1 to 14 carbon atoms. More preferably, R is a linear or branched alkylene group having 2 to 4 carbon atoms. Examples of the repeating unit represented by the general formula (1) include -CH2O-, -CH2CH2O-, -CH2CH(CH3)O-, -CH2CH(C2H5)O-, -CH2C(CH3)2O-, -CH2CH2CH2CH2O- and the like. The polyoxyalkylene polymer may consist of only one type of repeating unit, or may consist of two or more types of repeating units.

[0012] The structure represented by the general formula (1) preferably occupies 50% by weight or more of the total weight of the main chain in the component (A-1), more preferably 70% by weight or more, and even more preferably 90% by weight or more.

[0013] Specific examples of the polyoxyalkylene polymer include polyacetal, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer and the like. Among them, it is preferable that the main chain of the component (A) is at least one selected from the group consisting of polyacetal, polyoxyethylene and polyoxypropylene, and more preferably polyoxypropylene.

[0014] The polymerization method of the polyoxyalkylene polymer is not particularly limited. For example, a polymerization method using an alkali catalyst such as KOH, a polymerization method using a transition metal compound - porphyrin complex catalyst such as a complex obtained by reacting an organoaluminum compound and porphyrin shown in JP-A-61-215623, a polymerization method using a double metal cyanide complex catalyst shown in each of JP-B-46-27250, JP-B-59-15336, US Patent No. 3278457, US Patent No. 3278458, US Patent No. 3278459, US Patent No. 3427256, US Patent No. 3427334, US Patent No. 3427335, etc., a polymerization method using a catalyst composed of a polyphosphazene salt shown in JP-A-10-273512, a polymerization method using a catalyst composed of a phosphazene compound shown in JP-A-11-060722, etc. can be mentioned.

[0015] (Component (A-1)) may be a polyoxyalkylene polymer containing a urethane bond or a urea bond in the structure of the main chain. Specific examples of such a polymer include polyurethane prepolymers.

[0016] The polyurethane prepolymer can be obtained by a known method. For example, it can be obtained by reacting a polyol compound and a polyisocyanate compound. Specific examples of the polyol compound include polyether polyol, polyester polyol, polycarbonate polyol, polyether polyester polyol, etc. Specific examples of the polyisocyanate compound include diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, methylene-bis(cyclohexyl isocyanate), isophorone diisocyanate, hexamethylene diisocyanate, etc. Note that the polyurethane prepolymer may have a hydroxyl group or an isocyanate group at the terminal.

[0017] Component (A-2) has a (meth)acrylic acid ester polymer as its main chain. (Meth)acrylic acid ester monomers that form the building blocks of (meth)acrylic acid ester polymers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, and isopropanopropyl (meth)acrylate. Examples include hydroxyethyl, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, γ-(methacryloyloxypropyl)trimethoxysilane, ethylene oxide adducts of (meth)acrylic acid, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, perfluoromethyl perfluoroethylmethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate. Only one of these may be used, or two or more may be used.

[0018] The constituent units derived from (meth)acrylic acid ester monomers preferably account for 50% or more by weight of the total weight of the main chain in component (A-2), more preferably 70% or more by weight, and even more preferably 90% or more by weight.

[0019] The polymerization method for (meth)acrylic acid ester polymers is not particularly limited, but radical polymerization is preferred in terms of monomer versatility and ease of control, and among radical polymerization methods, controlled radical polymerization is more preferred. This controlled radical polymerization method can be classified into "chain transfer agent method" and "living radical polymerization method". Living radical polymerization is even more preferred because it allows for easy control of the molecular weight and molecular weight distribution of the resulting (meth)acrylic acid ester polymer, and atom transfer radical polymerization is particularly preferred due to the availability of raw materials and the ease of introducing functional groups to the polymer ends. For each of these polymerization methods, refer to, for example, the descriptions in Japanese Patent Publication No. 2005-232419 and Japanese Patent Publication No. 2006-291073.

[0020] Component (A) has a crosslinkable hydrolyzable silyl group, and therefore reacts intermolecularly with moisture to form siloxane bonds and create a crosslinked product. The crosslinkable hydrolyzable silyl group is represented by the following general formula (2): -Si(R 1 ) 3-a (X) a (2) In general formula (2), R 1 Each of these independently consists of a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or -OSi(R 0 This is a triorganosiloxy group represented by 3. 0 Each of these is independently a hydrocarbon group having 1 to 20 carbon atoms. Each of these is independently a hydroxyl group or a hydrolyzable group. a is an integer from 1 to 3.

[0021] R 1 The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. 1Specific examples thereof include an alkyl group such as a methyl group or an ethyl group; an alkyl group having a heteroatom-containing group such as a chloromethyl group, a methoxymethyl group, a 3,3,3-trifluoropropyl group, or a N,N-diethylaminomethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; R 0 where R is a methyl group or a phenyl group, etc., and a triorganosiloxy group represented by -OSi(R 0 )3, etc. R 1 is preferably a methyl group, an ethyl group, a chloromethyl group, or a methoxymethyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0022] The hydrolyzable group is not particularly limited, and examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group, etc. Among these, an alkoxy group, an acyloxy group, a ketoximate group, and an alkenyloxy group are preferable, and an alkoxy group is more preferable because of its mild hydrolyzability and ease of handling. A methoxy group and an ethoxy group are even more preferable, and a methoxy group is particularly preferable.

[0023] a is preferably 2 or 3. From the viewpoint of better curability, a is more preferably 3.

[0024] Examples of hydrolyzable silyl groups include, but are not limited to, trimethoxysilyl, triethoxysilyl, tris(2-propenyloxy)silyl, triacetoxysilyl, methyldimethoxysilyl, methyldiethoxysilyl, ethyldimethoxysilyl, phenyldimethoxysilyl, (chloromethyl)dimethoxysilyl, (chloromethyl)diethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N-diethylaminomethyl)dimethoxysilyl, and (N,N-diethylaminomethyl)diethoxysilyl. Among these, methyldimethoxysilyl and trimethoxysilyl are preferred because they are easy to synthesize. Trimethoxysilyl and (methoxymethyl)dimethoxysilyl are preferred because they provide high curability. Trimethoxysilyl and triethoxysilyl are preferred because they yield cured products with high recovery rate and low water absorption.

[0025] (A) As a method for introducing hydrolyzable silyl groups into component (A), known methods can be used. For example, the method described in paragraphs

[0083] to

[0117] of Japanese Patent Publication No. 2007-302749 can be cited. Methods for producing vinyl polymers having hydrolyzable silyl groups at the molecular chain ends, particularly (meth)acrylic polymers, are disclosed in Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, Japanese Patent Publication No. 6-211922, etc. In addition, methods for introducing alkoxysilyl groups into oxyalkylene polymers obtained using a complex metal cyanide catalyst as shown in Japanese Patent Publication No. 3-72527, and methods for introducing alkoxysilyl groups into oxyalkylene polymers obtained using a polyphosphazene salt and active hydrogen as catalysts as shown in Japanese Patent Publication No. 11-60723 can also be referenced.

[0026] Another method for introducing hydrolyzable silyl groups into component (A-2) is copolymerization of a compound having polymerizable unsaturated groups and hydrolyzable silyl groups with the (meth)acrylic acid ester monomers mentioned above. When this method is used, the hydrolyzable silyl groups tend to be introduced randomly into the main chain of component (A-2).

[0027] Examples of compounds having polymerizable unsaturated groups and hydrolyzable silyl groups include (meth)acrylate 3-(trimethoxysilyl)propyl, (meth)acrylate 3-(triethoxysilyl)propyl, (meth)acrylate 3-(methyldimethoxysilyl)propyl, (meth)acrylate 2-(trimethoxysilyl)ethyl, (meth)acrylate 2-(methyldimethoxysilyl)ethyl, (meth)acrylate (trimethoxysilyl)methyl, (meth)acrylate (triethoxysilyl)methyl, (meth)acrylate (methyldimethoxysilyl)methyl, and (meth)acrylate 3-((methoxymethyl)dimethoxysilyl)propyl. From the viewpoint of availability, (meth)acrylate 3-(methyldimethoxysilyl)propyl and (meth)acrylate 3-(trimethoxysilyl)propyl are particularly preferred.

[0028] In the method for introducing a hydrolyzable silyl group into component (A-2), a compound having a hydrolyzable silyl group and a mercapto group may be used as a chain transfer agent. Examples of compounds having a hydrolyzable silyl group and a mercapto group include 3-mercaptopropyltrimethoxysilane.

[0029] The molecular weight distribution (weight-average molecular weight Mw / number-average molecular weight Mn) of component (A-1) is not particularly limited, but is preferably 1.6 or less, more preferably 1.5 or less, and even more preferably 1.4 or less. Furthermore, from the viewpoint of improving various mechanical properties such as the durability and elongation of the cured product, the molecular weight distribution of component (A-1) is particularly preferably 1.2 or less. In this specification, the weight-average molecular weight and number-average molecular weight of component (A-1) refer to the values ​​measured as polystyrene-equivalent molecular weight in gel permeation chromatography (GPC).

[0030] The (A-1) component may include at least one component whose number average molecular weight is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 8,000 to 30,000. When the (A-1) component includes a component with a number average molecular weight within these ranges, the cured product exhibits excellent mechanical properties. Furthermore, when the (A-1) component includes a component with a number average molecular weight within these ranges, the amount of hydrolyzable silyl group introduced is appropriate, allowing for the production cost to be kept within a reasonable range while obtaining an (A-1) component that exhibits good curability, has an easy-to-handle viscosity, and has excellent workability.

[0031] The molecular weight of component (A-1) can also be expressed as the end-group-reduced molecular weight, which is determined by directly measuring the end-group concentration of the polymer precursor before the introduction of hydrolyzable silyl groups by titration analysis based on the principles of the hydroxyl value measurement method specified in JIS K 1557 and the iodine value measurement method specified in JIS K 0070, and taking into account the structure of the organic polymer (degree of branching determined by the polymerization initiator used). The end-group-reduced molecular weight of component (A-1) can also be determined by creating a calibration curve between the number-average molecular weight obtained by general GPC measurement of the polymer precursor and the above-mentioned end-group-reduced molecular weight, and then converting the number-average molecular weight obtained by GPC of component (A-1) to the end-group-reduced molecular weight.

[0032] To obtain a good rubber-like cured product, it is preferable that the hydrolyzable silyl groups of component (A-1) are located at the polymer chain ends. Because this exhibits good curability and facilitates the development of rubber elasticity, the number of hydrolyzable silyl groups is preferably 0.5 or more on average per polymer chain end of component (A-1), more preferably 0.6 or more, even more preferably 0.7 or more, and particularly preferably 0.8 or more. Furthermore, the number of hydrolyzable silyl groups may be 2.0 or less on average per polymer chain end of component (A-1), or 1.8 or less.

[0033] (A-1) The number of polymer chain ends per molecule is preferably 2 to 8, more preferably 2 to 4, and even more preferably 2 or 3. The number of hydrolyzable silyl groups in one molecule of (A-1) is preferably 1 to 7 on average, more preferably 1 to 3.4, and particularly preferably 1 to 2.6.

[0034] The (A-2) component is not particularly limited, but may include at least one component having a number-average molecular weight preferably between 500 and 100,000, more preferably between 800 and 70,000, and even more preferably between 1,000 and 50,000. When the (A-2) component includes a component with a number-average molecular weight within these ranges, the cured product exhibits excellent mechanical properties. Furthermore, when the (A-2) component includes a component with a number-average molecular weight within these ranges, the amount of hydrolyzable silyl group introduced is appropriate, allowing for a (A-2) component that exhibits good curability, has an easy-to-handle viscosity, and has excellent workability, while keeping manufacturing costs within a reasonable range.

[0035] The hydrolyzable silyl groups of component (A-2) may be present at the ends of the polymer chain or in regions other than the ends of the main chain. Component (A-2) may have polymer side chains, and the hydrolyzable silyl groups may be present in the polymer side chains. When present at the ends of the polymer chain, the number of hydrolyzable silyl groups is preferably 0.3 or more on average per polymer chain end, more preferably 0.5 or more, and even more preferably 0.8 or more, as they exhibit good curability and easily exhibit rubber elastic behavior. When present in the polymer side chains, the number of hydrolyzable silyl groups is preferably 0.3 or more on average per polymer side chain, more preferably 0.7 or more, and even more preferably 1.0 or more, as they exhibit good curability and easily exhibit rubber elastic behavior.

[0036] The weight ratio of component (A-1) to component (A-2) in the curable composition may be 100:0 to 0:100, 90:10 to 10:90, 80:20 to 20:80, 70:30 to 30:70, or 60:40 to 40:60. For example, the curable composition may contain at least component (A-1), and the weight ratio of component (A-1) to component (A-2) may be 100:0 to 60:40. Alternatively, the curable composition may contain at least component (A-2), and the weight ratio of component (A-1) to component (A-2) may be 0:100 to 40:60.

[0037] <1-2.(B) Component> Component (B) is a thermally conductive filler. In this specification, a thermally conductive filler means a filler exhibiting a thermal conductivity of 0.1 W / mK or higher. Component (B) may be used alone or two or more types.

[0038] Component (B) is preferably one or more selected from the group consisting of metals, graphite, metal oxides, metal hydroxides, metal nitrides, and metal carbides, and more preferably one or more selected from the group consisting of metal oxides, metal hydroxides, and metal nitrides. Nonmetallic oxides, nitrides, carbides, etc. can also be used as component (B). Examples of metals include aluminum, copper, nickel, and silver. Examples of graphite include graphite and graphite. Examples of oxides include aluminum oxide, zinc oxide, magnesium oxide, titanium oxide, silicon oxide, and beryllium oxide. Examples of hydroxides include aluminum hydroxide and magnesium hydroxide. Examples of nitrides include aluminum nitride, silicon nitride, and boron nitride. Examples of carbides include boron carbide, titanium carbide, and silicon carbide.

[0039] The curable composition contains 500 to 1000 parts by weight of component (B) per 100 parts by weight of the total of components (A) and (C), preferably 500 to 900 parts by weight, more preferably 500 to 800 parts by weight, and even more preferably 500 to 700 parts by weight. A content of 500 parts by weight or more of component (B) is preferable from the viewpoint of heat dissipation. A content of 1000 parts by weight or less of component (B) is preferable from the viewpoint of coatability.

[0040] <1-3.(C) component> Component (C) is a heat-resistant plasticizer, and is at least one of pyromellitic acid ester and trimellitic acid ester. That is, the curable composition may contain only pyromellitic acid ester, only trimellitic acid ester, or both as component (C). Component (C) is preferred because it has particularly high heat resistance and is not easily volatile among plasticizers.

[0041] Pyromellitic acid esters may be, for example, alkyl pyromellitic acid esters. Trimmellitic acid esters may be, for example, alkyl trimellitic acid esters. The alkyl group in these alkyl pyromellitic acid esters and alkyl trimellitic acid esters may be linear or branched, and may have, for example, 8 to 10 carbon atoms.

[0042] Examples of commercially available pyromellitic acid esters include ADEKA Corporation's Adekasizer UL-80 and Adekasizer UL-100, while examples of commercially available trimellitic acid esters include ADEKA Corporation's Adekasizer C-8, Adekasizer C-880, and Adekasizer C-9N, as well as Kao Corporation's Trimex N-08 and Trimex T-08.

[0043] The curable composition preferably contains 100 to 300 parts by weight of component (C) per 100 parts by weight of component (A), and more preferably 150 to 250 parts by weight of component (C). A content of 100 parts by weight or more of component (C) is preferable from the viewpoint of the coatability of the curable composition. Furthermore, a content of 300 parts by weight or less of component (C) is preferable from the viewpoint of the mechanical properties of the curable composition. The content of component (C) may be more than 200 parts by weight and 300 parts by weight or less per 100 parts by weight of component (A).

[0044] <1-4.(D) component> Component (D) is a carboxylate metal compound and contains divalent tin, or one or more metals selected from the group consisting of titanium, bismuth, zirconium, and zinc. Specifically, examples of component (D) include tin carboxylate, titanium carboxylate, bismuth carboxylate, zirconium carboxylate, and zinc carboxylate. Component (D) acts as a curing catalyst. By using a specific compound as component (D), the storage stability of the curable composition is improved. From the viewpoint of adhesion when the curable composition is used as an adhesive, it is preferable that component (D) contains divalent tin as the metal. Only one type of component (D) may be used, or two or more types may be used.

[0045] Examples of tin carboxylates containing divalent tin include bis(octylate)tin(II), bis(neodecanate)tin(II), bis(2-ethylhexanoate)tin(II), bis(stearate)tin(II), bis(naphthenate)tin(II), bis(versaticate)tin(II), and bis(pivalate)tin(II). Examples of titanium carboxylates include titanium acylate. Examples of bismuth carboxylates include bismuth neodecanoate and bismuth versaticate. Examples of zirconium carboxylates include zirconium versaticate.

[0046] The curable composition preferably contains 0.1 to 30 parts by weight of component (D) per 100 parts by weight of component (A). If the content of component (D) is 0.1 parts by weight or more, the curing reaction can be sufficiently promoted. Furthermore, if the content of component (D) is 30 parts by weight or less, it is preferable from the viewpoint of workability.

[0047] <1-5.(E) component> Component (E) is a cyclic secondary amine compound having one or more skeletons selected from the group consisting of a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, and an azepane skeleton. Component (E) acts as a co-catalyst. By using a specific compound as component (E), the curable composition hardens quickly and has excellent workability. Furthermore, by using a specific compound as component (E), the curable composition also has excellent storage stability. Component (E) may be used alone or two or more types.

[0048] Cyclic secondary amine compounds refer to heterocyclic amine compounds having an NH group. Examples of heterocyclic amine compounds having an NH group include non-aromatic heterocyclic amine compounds such as pyrrolidine, piperidine, piperazine, and azepane (hexamethyleneimine); ester compounds of piperidine carboxylic acids such as 4-piperidinecarboxylic acid, 2-piperidinecarboxylic acid, and 3-piperidinecarboxylic acid; ester compounds of pyrrolidine carboxylic acids such as 2-pyrrolidinecarboxylic acid; hydroxypiperidine such as 4-hydroxypiperidine and 3-hydroxypiperidine; piperidine methanol such as 3-piperidinemethanol; piperidineethanol; methylpiperidine such as 4-methylpiperidine; dimethylpiperidine such as 3,5-dimethylpiperidine; and N-substituted piperazines such as N-methylpiperazine. Specific examples of the above ester compounds include alkyl esters such as methyl esters, ethyl esters, and propyl esters, with ethyl esters being preferred from the viewpoint of curability. In this specification, component (E), N-substituted piperazine, refers to a compound in which one of the two nitrogen atoms in the piperazine skeleton has a substituent and the other exists as an NH group.

[0049] Among these, cyclic secondary amine compounds having a piperidine skeleton, such as piperidine, ester compounds of piperidine carboxylic acid, hydroxypiperidine, piperidine methanol, piperidine ethanol, methylpiperidine, and dimethylpiperidine, are preferred as component (E). Cyclic secondary amine compounds having a piperidine skeleton are preferred from the viewpoint of workability.

[0050] The curable composition preferably contains 5 to 100 parts by weight of component (E) per 100 parts by weight of component (D). From the viewpoint of curability and storage stability, the content of component (E) is preferably 10 to 80 parts by weight, and more preferably 20 to 50 parts by weight.

[0051] <1-6. Other Ingredients> The curable composition may optionally contain components other than components (A) to (E). In this specification, components other than components (A) to (E) are also referred to as other components. Examples of other components include antioxidants, dehydrating agents, adhesion modifiers, thixotropic agents, light stabilizers, compatibilizers, property modifiers, photocurable substances, air oxidation curable substances, flame retardants, curing modifiers, metal deactivators, ozone degradation inhibitors, lubricants, pigments, foaming agents, tackifying resins, dispersants, etc. Only one type of other component may be used, or two or more types may be used.

[0052] Examples of antioxidants include hindered phenol antioxidants, thioether antioxidants, and phosphorus antioxidants, with hindered phenol antioxidants being particularly preferred. Examples of hindered phenol compounds include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono(or di or tri)(α-methylbenzyl)phenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), and 4,4'-thiobis(3-methyl-6- tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, triethylene glycol-bis-[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine Pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate Tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, bis(3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl)calcium, tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 2,4-bis[(octylthio)methyl]o-cresol, N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine, tris(2,4-di-t-butylphenyl) phosphite, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole Examples include 2-(2'-hydroxy-5'-t-octylphenyl)-benzotriazole, a condensate of methyl-3-[3-t-butyl-5-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate and polyethylene glycol (molecular weight approximately 300), hydroxyphenylbenzotriazole derivatives, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl), 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, etc.

[0053] The curable composition preferably contains 0.1 to 10 parts by weight of antioxidant per 100 parts by weight of component (A). If the antioxidant content is 0.1 parts by weight or more, the antioxidant effect can be fully exerted. Furthermore, if the antioxidant content is 10 parts by weight or less, it is preferable from a cost viewpoint.

[0054] Examples of dehydrating agents include hydrolyzable silane compounds; inorganic solids such as phosphorus pentoxide, sodium bicarbonate, sodium sulfate (anhydrous sodium sulfate), and molecular sieves; and hydrolyzable ester compounds such as trialkyl orthoformates (e.g., trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate) and trialkyl orthoacetates (e.g., trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate, tributyl orthoacetate). Among these, hydrolyzable silane compounds are preferred from the viewpoint of workability and storage stability.

[0055] Examples of hydrolyzable silane compounds that are suitably used as dehydrating agents include vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, methyltriacetoxysilane, tetramethyl orthosilicate (tetramethoxysilane or methyl silicate), tetraethyl orthosilicate (tetraethoxysilane or ethyl silicate), tetrapropyl orthosilicate, tetrabutyl orthosilicate, or partially hydrolyzed condensates thereof.

[0056] The curable composition preferably contains 0.1 to 30 parts by weight of a dehydrating agent, more preferably 0.3 to 20 parts by weight, and even more preferably 0.5 to 10 parts by weight, per 100 parts by weight of component (A). If the dehydrating agent content is 0.1 parts by weight or more, the dehydrating agent's effect can be fully exerted. Furthermore, if the dehydrating agent content is 30 parts by weight or less, it is preferable from a cost viewpoint.

[0057] Examples of adhesion-imparting agents include silane coupling agents; epoxy resins; phenolic resins; linear or branched block copolymers such as polystyrene-polybutadiene-polystyrene, polystyrene-polyisoprene-polystyrene, polystyrene-polyisoprene / butadiene copolymer-polystyrene, polystyrene-polyethylene / propylene copolymer-polystyrene, polystyrene-polyethylene / butylene copolymer-polystyrene, and polystyrene-polyisobutene-polystyrene; alkylsulfonic acid esters; sulfur; alkyl titanates; and aromatic polyisocyanates. Among these, silane coupling agents are preferred from the viewpoint of adhesion.

[0058] Suitable silane coupling agents for use as adhesion imparters include, for example, isocyanate group-containing silanes such as γ-isocyanatetopropyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane, γ-isocyanatetopropylmethyldiethoxysilane, and γ-isocyanatetopropylmethyldimethoxysilane; and γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyldiethoxysilane. N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyl amino group-containing silanes such as triethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltri Silanes containing epoxy groups such as ethoxysilane; carboxysilanes such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis(2-methoxyethoxy)silane, and N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane; silanes containing (meth)acryloyloxy groups such as γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-acryloyloxypropyltriethoxysilane;Examples of silane coupling agents include halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris(trimethoxysilyl)isocyanurate; and polysulfans such as bis(3-triethoxysilylpropyl)tetrasulfan. Reaction products of the above amino group-containing silanes with epoxy group-containing silanes, reaction products of amino group-containing silanes with (meth)acryloyloxy group-containing silanes, and reaction products of amino group-containing silanes with isocyanate group-containing silanes can also be used. Furthermore, modified derivatives of these, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkyl silanes, aminosilylated silicones, blocked isocyanate silanes, and silylated polyesters, can also be used as silane coupling agents. Additionally, ketimine compounds obtained by the reaction of the above amino group-containing silanes with ketone compounds such as methyl isobutyl ketone can also be used as silane coupling agents.

[0059] The curable composition preferably contains 0.1 to 20 parts by weight of an adhesion promoter per 100 parts by weight of component (A), and more preferably 0.5 to 10 parts by weight. If the adhesion promoter content is 0.1 parts by weight or more, the effect of the adhesion promoter can be fully exerted. Furthermore, if the adhesion promoter content is 20 parts by weight or less, it is preferable from a cost viewpoint.

[0060] Thixotropic agents are also called anti-sagging agents. Thixotropic agents impart the property of being fluid when strong force is applied, such as during the application of a curable composition, but not flowing until it hardens after application.

[0061] Examples of thixotropic agents include amide waxes, hydrogenated castor oil, hydrogenated castor oil derivatives; fatty acid derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate; organic compounds such as 1,3,5-tris(trialkoxysilylalkyl) isocyanurate; and inorganic compounds such as calcium carbonate surface-treated with fatty acids or resin acids, fine silica powder, and carbon black.

[0062] Fine silica powder refers to natural or artificial inorganic fillers whose main component is silicon dioxide. Specific examples of fine silica powder include kaolin, clay, activated clay, silica sand, silica, diatomaceous earth, anhydrous aluminum silicate, hydrated magnesium silicate, talc, perlite, white carbon, mica powder, bentonite, and organic bentonite.

[0063] [2. Uses of curable compositions] The curable compositions described above can be suitably used, for example, as adhesives, gap fillers, or as materials for the cured products described below. One embodiment of the present invention also includes cured products obtained by curing the above-described curable compositions.

[0064] The cured material can be used, for example, as a thermal interface to transfer heat between a heat-generating material and a heat spreader, or between a heat spreader and a cooling element. The cured material can also be used as the heat spreader itself. Examples of heat-generating materials are not limited to heaters, temperature sensors, computing elements, transistors, light-emitting elements, and other electronic components. Examples of cooling elements are not limited to heat-dissipating materials, but include heat sinks such as heat sink fins, graphite sheets (graphite films), liquid ceramics, and Peltier elements. The cured material is suitably used as a thermally conductive material to dissipate heat from these heat-generating materials to the cooling element. Alternatively, the cured material may be used as the heat-dissipating material itself. Furthermore, the curable composition can also be used as a sealing material on thin substrate chips in mobile phones, or as a heat-dissipating material filled into shielded cans.

[0065] While not limited to applications that take advantage of the thermal conductivity of the curable composition, it is particularly suitable for small electronic devices such as mobile phones or personal computers. Furthermore, the curable composition can be used in a variety of applications, including materials for electrical and electronic components in automobiles or home appliances; electrical insulating materials such as insulating coatings for wires or cables; and potting agents for electrical and electronic components.

[0066] The present invention is not limited to the embodiments described above, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0067] One embodiment of the present invention may include the following configuration: <1> (A) Components: (A-1) A polyoxyalkylene polymer having a crosslinkable hydrolyzable silyl group, and (A-2) At least one of a (meth)acrylic acid ester polymer having a crosslinkable hydrolyzable silyl group. (B) Component: Thermally conductive filler, (C) Components: A heat-resistant plasticizer which is at least one of pyromellitic acid ester and trimellitic acid ester. (D) Component: Carboxylic acid metal compound, (E) component: contains a cyclic secondary amine compound, The aforementioned component (D) includes divalent tin, or one or more metals selected from the group consisting of titanium, bismuth, zirconium, and zinc. The aforementioned component (E) has one or more skeletons selected from the group consisting of a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, and an azepane skeleton. A moisture-curing resin composition comprising 500 to 1000 parts by weight of component (B) per 100 parts by weight of the total of component (A) and component (C). <2> The aforementioned component (D) is a carboxylic acid metal compound containing divalent tin. <1> The moisture-curing resin composition described above. <3> The mixture contains 100 to 300 parts by weight of component (C) relative to 100 parts by weight of component (A). <1> or <2> The moisture-curing resin composition described above. <4> The aforementioned component (E) is a cyclic secondary amine compound having a piperidine skeleton. <1> ~ <3> A moisture-curing resin composition as described in any one of the following. <5> <1> ~ <4> A cured product obtained by curing any one of the moisture-curing resin compositions described in the following. [Examples]

[0068] The present invention will be described in more detail below with reference to specific examples, but the present invention is not limited to the following examples.

[0069] [Measurement and evaluation methods] Measurements and evaluations in the examples and comparative examples were performed using the following methods.

[0070] <Number-average molecular weight and weight-average molecular weight> The number-average molecular weight and weight-average molecular weight in each synthesis example are GPC molecular weights measured under the following conditions. • Fluid transfer system: Tosoh HLC-8120GPC • Column: Tosoh TSKgel SuperH series • Solvent: THF • Molecular weight: Polystyrene equivalent ·Measurement temperature: 40℃.

[0071] <Average number of hydrolyzable silyl groups> (A) The average number of hydrolyzable silyl groups per terminal or per molecule of component was calculated by 1H-NMR. Specifically, the 1H-NMR measurement was performed in CDCl3 solvent using a Bruker AVANCE III HD-500.

[0072] <Viscosity> A one-component curable composition, filled in a cartridge described below, was stored for 7 days under constant temperature and humidity conditions of 23°C and 50% relative humidity. The viscosity of this one-component curable composition was measured at 23°C and a shear rate of 10 (1 / sec) using a TA Instruments DISCOVERY-HR2 rheometer, with a 20 mm diameter parallel disc plate as the jig and a gap set to 0.5 mm. This viscosity was taken as the initial measurement value.

[0073] After storing the cartridges in a 40°C oven for 4 weeks, they were left to stand overnight under constant temperature and humidity conditions of 23°C and 50% relative humidity, and the viscosity was measured again, similar to the initial measurement. The rate of change in viscosity was calculated using the following formula. Viscosity change rate = (measured value after 4 weeks at 40°C) / (initial measurement value) × 100.

[0074] <Skinning time (hardening)> The one-component curable composition, filled in the cartridge described below, was stored for 7 days under constant temperature and humidity conditions of 23°C and 50% relative humidity. This one-component curable composition was filled into a mold approximately 5 mm thick using a spatula, and curing was defined as starting when the surface was leveled. The time from the start of curing until the one-component curable composition no longer adhered to the spatula when the surface was touched was measured. The obtained result was defined as the "skinning time." This skinning time was used as the initial measurement value.

[0075] After storing the cartridges in a 40°C oven for 4 weeks, they were left to stand overnight under constant temperature and humidity conditions of 23°C and 50% relative humidity, and the skinning time was measured in the same way as the initial measurements. The rate of change in skinning time was calculated using the following formula. The rate of change in leather stretching time = (measured value after 4 weeks at 40°C) / (initial measurement value) × 100.

[0076] <Mechanical properties> Under constant temperature and humidity conditions of 23°C and 50% relative humidity, a one-component curable composition was filled into a 3mm thick sheet-like mold. After curing at 23°C and 50% relative humidity for 3 days, it was cured in a 50°C dryer for 4 days to obtain a sheet-like cured material. The obtained sheet-like cured material was punched out into a No. 7 dumbbell shape according to JIS K 6251. A tensile test (tensile speed 200 mm / min) was performed on the sheet-like cured material punched into the No. 7 dumbbell shape using an Autograph machine manufactured by Shimadzu Corporation, and the stress at 30% extension, stress at fracture, and elongation at fracture were measured. Furthermore, the sheet-like cured material punched into the No. 7 dumbbell shape was stored in a 120°C oven for 1 week, then removed and left to stand overnight under constant temperature and humidity conditions of 23°C and 50% relative humidity, after which a tensile test was performed in the same manner. The retention rate for each test item was calculated using the following formula. Maintenance rate = (Measurement value after storage at 120°C for 1 week) / (Measurement value after curing) × 100.

[0077] <Weight maintenance rate> As described above, the sheet-like cured material obtained from the curable composition was cut into approximately 1 cm squares and weighed using a precision balance. This weighing result was taken as the measured value after curing. The weighed sheet-like cured material was stored in a 120°C oven for one week, then removed and left to stand overnight under constant temperature and humidity conditions of 23°C and 50% relative humidity, and weighed again. The weight retention rate was calculated using the following formula. Weight retention rate = (Measurement value after storage at 120°C for 1 week) / (Measurement value after curing) × 100.

[0078] [Synthesis of polyoxyalkylene polymer (A-1)] <Synthesis example 1 (A-1a)> Using polyoxypropylene glycol with a number-average molecular weight of approximately 3,000 as an initiator, propylene oxide was polymerized using a zinc hexacyanocobaltate grime complex catalyst to obtain polyoxypropylene (P-1a) with a number-average molecular weight of 27,900 (end-group equivalent molecular weight of 17,700) and a molecular weight distribution Mw / Mn = 1.21, with hydroxyl groups at both ends.

[0079] To the hydroxyl groups of the obtained polyoxypropylene (P-1a), 1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution. After removing methanol by vacuum defoliation, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl groups of polyoxypropylene (P-1a) and the reaction was carried out at 130°C for 2 hours. Subsequently, methanol was removed by adding 0.3 molar equivalents of a methanol solution of sodium methoxide, and then 1.8 molar equivalents of allyl chloride were added. This converted the terminal hydroxyl groups of polyoxypropylene (P-1a) to allyl groups. The obtained unpurified polyoxypropylene was mixed with n-hexane and water and stirred, then the water was removed by centrifugation, and the metal salts in the polymer were removed by vacuum defoliation of the hexane from the resulting hexane solution. Thus, polyoxypropylene (Q-1a) having multiple carbon-carbon unsaturated bonds at the terminals was obtained.

[0080] To 500 g of the obtained polyoxypropylene (Q-1a), 50 μL of platinum divinyldisiloxane complex solution (3% by weight isopropanol solution in terms of platinum) was added, and 9.6 g of trimethoxysilane was slowly added dropwise while stirring. The resulting mixed solution was reacted at 90°C for 2 hours, and then the unreacted trimethoxysilane was removed under reduced pressure to obtain polyoxypropylene (A-1a) with a number-average molecular weight of 28,000 and multiple trimethoxysilyl groups at the ends. It was found that polyoxypropylene (A-1a) has an average of 1.7 trimethoxysilyl groups at each end and an average of 3.4 trimethoxysilyl groups per molecule.

[0081] <Synthesis example 2 (A-1b)> Using polyoxypropylene glycol with a number-average molecular weight of approximately 2,000 as an initiator, propylene oxide was polymerized using a zinc hexacyanocobaltate grime complex catalyst to obtain polyoxypropylene (P-1b) with a number-average molecular weight of 27,900 (end-group equivalent molecular weight of 17,700) and a molecular weight distribution Mw / Mn = 1.21, with hydroxyl groups at both ends.

[0082] To the hydroxyl groups of the obtained polyoxypropylene (P-1b), 1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution. After removing the methanol by vacuum defoliation, 1.79 molar equivalents of allyl chloride were added to the hydroxyl groups of polyoxypropylene (P-1b). This converted the terminal hydroxyl groups of polyoxypropylene (P-1b) to allyl groups. The obtained unpurified polyoxypropylene was mixed with n-hexane and water and stirred. After removing the water by centrifugation, the metal salts in the polymer were removed by vacuum defoliation of the hexane from the resulting hexane solution. Thus, polyoxypropylene (Q-1b) having allyl groups at the terminals was obtained.

[0083] To 500 g of the obtained polyoxypropylene (Q-1b), 50 μL of platinum divinyldisiloxane complex solution (3% by weight isopropanol solution in terms of platinum) was added, and 7.5 g of trimethoxysilane was slowly added dropwise while stirring. The resulting mixed solution was reacted at 90°C for 2 hours, and then the unreacted trimethoxysilane was removed under reduced pressure to obtain polyoxypropylene (A-1b) with a number average molecular weight of 28,500 and containing trimethoxysilyl groups. It was found that polyoxypropylene (A-1b) has an average of 0.8 trimethoxysilyl groups at each end and an average of 1.6 trimethoxysilyl groups per molecule.

[0084] <Synthesis example 3 (A-1c)> Using polyoxypropylene glycol with a number-average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized using a zinc hexacyanocobaltate grime complex catalyst to obtain polyoxypropylene (P-1c) with a number-average molecular weight of 14,300 (end-group equivalent molecular weight of 9,100) and a molecular weight distribution Mw / Mn = 1.21, with hydroxyl groups at both ends.

[0085] To the hydroxyl groups of the obtained polyoxypropylene (P-1c), 1.2 molar equivalents of sodium methoxide were added as a 28% methanol solution. After removing the methanol by vacuum defoliation, a further 1.5 molar equivalents of allyl chloride were added to the hydroxyl groups of the polyoxypropylene (P-1c). This converted the terminal hydroxyl groups of polyoxypropylene (P-1c) to allyl groups. Unreacted allyl chloride was removed by vacuum defoliation. The obtained unpurified polyoxypropylene was mixed with n-hexane and water and stirred. After removing the water by centrifugation, the metal salts in the polymer were removed by vacuum defoliation of the hexane from the resulting hexane solution. Thus, polyoxypropylene (Q-1c) having allyl groups at the terminals was obtained.

[0086] To 500 g of the obtained polyoxypropylene (Q-1c), 50 μL of platinum divinyldisiloxane complex solution (3% by weight isopropanol solution in terms of platinum) was added, and 8.4 g of trimethoxysilane was slowly added dropwise while stirring. The resulting mixed solution was reacted at 100°C for 2 hours, and the unreacted trimethoxysilane was removed under reduced pressure to obtain polyoxypropylene (A-1c) with a number-average molecular weight of 14,600 and trimethoxysilyl groups at the ends. It was found that polyoxypropylene (A-1c) has an average of 0.8 trimethoxysilyl groups at each end and an average of 1.5 trimethoxysilyl groups per molecule.

[0087] [Synthesis of (meth)acrylic acid ester polymer (A-2)] <Synthesis example 4 (A-2a)> 48.6 parts by weight of 2-butanol were placed in a four-necked flask equipped with a stirrer, and the temperature was raised to 105°C under a nitrogen atmosphere. The following monomer mixture was then added dropwise over 5 hours, followed by "post-polymerization" for 1 hour to obtain (meth)acrylic acid ester copolymer (A-2a).

[0088] Composition of monomer mixture: Methyl methacrylate (65 parts by weight), 2-ethylhexyl acrylate (25 parts by weight), 3-(trimethoxysilyl)propyl methacrylate (10 parts by weight), 3-mercaptopropyltrimethoxysilane (7 parts by weight), 2,2'-azobis(2-methylbutyronitrile) (1.8 parts by weight), 2-butanol (22.7 parts by weight).

[0089] <Synthesis example 5 (A-2b)> Using diethyl 2,5-dibromoadipate (3.5 parts by weight) as an initiator, cuprous bromide (0.84 parts by weight) as a catalyst, and pentamethyldiethylenetriamine as a catalytic ligand, butyl acrylate (100 parts by weight) was polymerized in acetonitrile solvent at approximately 80-90°C to obtain polyacrylic acid ester (P-2b) having bromine groups at both ends. The polymerization reaction rate was adjusted as appropriate by changing the amount of pentamethyldiethylenetriamine.

[0090] Next, using a pentamethyldiethylenetriamine complex of cuprous bromide as a catalyst, the terminal bromine groups of the polyacrylic acid ester (P-2b) were reacted with 1,7-octadiene in acetonitrile solvent to obtain polyacrylic acid ester (Q-2b). 20 molar equivalents of 1,7-octadiene were used relative to the initiator. After the reaction, unreacted 1,7-octadiene was recovered by defoliation. The resulting polymer was purified using an adsorbent, heated to approximately 190°C for debromination, and then purified again using an adsorbent. This yielded polyacrylic acid ester (R-2b) having alkenyl groups at both ends.

[0091] The obtained polyacrylic acid ester (R-2b) having alkenyl groups at both ends was subjected to a hydrosilylation reaction with 3 parts by weight of methyldimethoxysilane relative to the alkenyl groups of polyacrylic acid ester (R-2b) using a 300 ppm isopropanol solution of a platinum vinylsiloxane complex with a platinum content of 3% by weight as a catalyst. The reaction was carried out at 100°C for 1 hour. The reaction was carried out in the presence of methyl orthoformate, and 3 molar equivalents of methyldimethoxysilane were used relative to the alkenyl groups. After the reaction, unreacted methyldimethoxysilane and methyl orthoformate were removed by defoliation to obtain methyldimethoxysilyl-terminated polyacrylic acid ester (A-2b). The obtained polyacrylic acid ester (A-2b) had a number-average molecular weight of 14,000, a molecular weight distribution of 1.3, and 2 silyl groups introduced per molecule.

[0092] [Raw materials for curable compositions] The following raw materials were used in the preparation of the curable composition.

[0093] <(A-1) Polyoxyalkylene polymer having crosslinkable hydrolyzable silyl groups> Polyoxypropylene (A-1a)~(A-1c) <(A-2) (meth)acrylic acid ester polymer having a crosslinkable hydrolyzable silyl group> • (meth)acrylic acid ester copolymer (A-2a), polyacrylic acid ester (A-2b) <(B) Thermally conductive filler> • Denka Spherical Alumina DAW-70: Manufactured by Denka Co., Ltd. • Denka Spherical Alumina DAW-45: Manufactured by Denka Co., Ltd. • Denka Spherical Alumina DAW-05: Manufactured by Denka Co., Ltd. • Denka Spherical Alumina ASFP-20: Manufactured by Denka Co., Ltd. • Low-soda aluminum hydroxide BE-033: Manufactured by Nippon Light Metal Co., Ltd. • Fine-grained aluminum hydroxide B303: Manufactured by Nippon Light Metal Co., Ltd. <(C) Heat-resistant plasticizer> • Trimex T-08A: Trimellitate ester, manufactured by Kao Corporation • ADEKA Sizer UL-100: Pyromellitic acid ester, manufactured by ADEKA Corporation <(C) Plasticizers not applicable> • Hexamoll® DINCH®: Manufactured by BASF. <(D) Carboxylic acid metal compounds> • U-28: Bis(neodecanoate)tin(II), manufactured by Nitto Kasei Co., Ltd. • U-50: Tin(II) bis(octylate), manufactured by Nitto Chemical Co., Ltd. <Carboxylic acid metal compounds that do not fall under (D)> U-810: Dioctyl tin dilaurate, manufactured by Nitto Kasei Co., Ltd. U-820: Dioctyl tin diacetate, manufactured by Nitto Kasei Co., Ltd. • SCAT-27: Tetravalent organotin compound, manufactured by Nitto Chemical Co., Ltd. <(E) Cyclic secondary amine compounds> • 4-Ethyl piperidinecarboxylate: Manufactured by Tokyo Chemical Industry Co., Ltd. • 4-Methylpiperidine: Manufactured by Tokyo Chemical Industry Co., Ltd. <Amine compounds that do not fall under (E)> • Laurylamine: Manufactured by Tokyo Chemical Industry Co., Ltd. <(E) non-applicable co-catalysts> Versatic 10: Neodecanoic acid, manufactured by HEXION. <Thixotropic agent> • Aerosil® R974: Fumed silica, manufactured by Aerosil Japan Co., Ltd. <Antioxidant> • ADEKA Stub AO-60: Manufactured by ADEKA Corporation • Nocrack CD: Manufactured by Ouchi Shinko Chemical Industry Co., Ltd. <Dehydrating agent> A-171: Vinyltrimethoxysilane, manufactured by Momentive Performance Materials. <Adhesion-enhancing agent> A-1120: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, manufactured by Momentive Performance Materials.

[0094] [Preparation of curable compositions] <Example 1> Component (B) shown in Example 1 of Table 1 was stirred under reduced pressure at 120°C for 1 hour in a 5L universal mixing and stirring machine (Dalton 5DMV-r type). Component (A), component (C), antioxidant, and R974 were added in the amounts listed in Table 1, and the mixture was stirred again under reduced pressure at 120°C for 1 hour. After cooling to room temperature, A-171, A-1120, component (D), and component (E) were added in order to the main component in the amounts listed in Table 1, and the mixture was stirred.

[0095] A one-component curable composition was obtained by filling the resulting curable composition into a moisture-proof container, which is a cartridge, and sealing it.

[0096] <Examples 2-4, Comparative Examples 1-5> The curable compositions were prepared and evaluated in the same manner as in Example 1, except that the raw materials for the curable composition were changed as shown in Table 1 or 2. In Comparative Examples 1 to 3, a curing catalyst that does not correspond to component (D) was added instead of component (D). In Comparative Examples 4 and 5, an amine compound or co-catalyst that does not correspond to component (E) was added instead of component (E).

[0097] <Evaluation Results> The compositions and evaluation results of Examples 1-4 and Comparative Examples 1-6 are shown in Tables 1 and 2.

[0098] [Table 1]

[0099] [Table 2]

[0100] The curable compositions of Examples 1-4, which contain a carboxylic acid metal compound with divalent tin and a cyclic secondary amine compound, exhibited excellent workability due to a good pre-skinning time and good storage stability due to little change in skinning time after 4 weeks of storage at 40°C. On the other hand, Comparative Examples 1-3, which contain a tetravalent tin compound, showed a large rate of change in skinning time after 4 weeks of storage at 40°C and had poor storage stability. Comparative Example 4, which contains a primary amine compound instead of a cyclic secondary amine compound, had poor workability due to a long pre-skinning time. Comparative Example 5, which contains a carboxylic acid instead of a cyclic secondary amine compound, showed excellent workability due to a good pre-skinning time, but had poor storage stability due to a large rate of change in skinning time after 4 weeks of storage at 40°C.

[0101] <Examples 5-11> The curable compositions were prepared and evaluated in the same manner as in Example 1, except that the raw materials for the curable composition were changed as shown in Table 3 or 4.

[0102] <Evaluation Results> The compositions and evaluation results of Examples 3, 5-11 are shown in Tables 3 and 4.

[0103] [Table 3]

[0104] [Table 4]

[0105] Examples 5 to 11, which differed in the types and ratios of components (A-1) and (A-2), all showed good heat resistance, as evidenced by the high retention rates of mechanical properties and weight after the heat resistance test. In particular, Examples 3, 6 to 9 and 11, which contained both components (A-1) and (A-2), showed especially good heat resistance.

[0106] <Example 12, Comparative Example 6> The curable compositions were prepared and evaluated in the same manner as in Example 1, except that the raw materials for the curable composition were changed as shown in Table 5. In Comparative Example 6, a plasticizer that does not correspond to component (C) was added instead of component (C).

[0107] <Evaluation Results> Table 5 shows the compositions and evaluation results for Examples 3 and 12, and Comparative Example 6.

[0108] [Table 5]

[0109] Example 12, which contains pyromellitic acid ester as the heat-resistant plasticizer (C), showed good heat resistance, as evidenced by the high retention rate of mechanical properties and weight after the heat resistance test, similar to Example 3, which contains trimellitic acid ester. On the other hand, Comparative Example 6, which contains DINCH instead of the heat-resistant plasticizer (C), showed poor heat resistance, as evidenced by the low retention rate of mechanical properties and weight after the heat resistance test.

[0110] <Example 13> The curable compositions were prepared and evaluated using the same method as in Example 1, except that the raw materials for the curable composition were changed as shown in Table 6.

[0111] <Evaluation Results> The composition and evaluation results of Example 13 are shown in Table 6.

[0112] [Table 6]

[0113] Example 13 demonstrated good heat resistance, as evidenced by its high retention rate of mechanical properties and weight after the heat resistance test. [Industrial applicability]

[0114] One aspect of the present invention can be used, for example, in curable compositions where heat dissipation is required.

Claims

1. (A) Components: (A-1) A polyoxyalkylene polymer having a crosslinkable hydrolyzable silyl group, and (A-2) At least one of a (meth)acrylic acid ester polymer having a crosslinkable hydrolyzable silyl group. (B) Component: Thermally conductive filler, (C) Component: A heat-resistant plasticizer which is at least one of pyromellitic acid ester and trimellitic acid ester. (D) Component: Metal carboxylate compound, and (E) Component: Contains a cyclic secondary amine compound, The aforementioned component (D) includes divalent tin, or one or more metals selected from the group consisting of titanium, bismuth, zirconium, and zinc. The aforementioned component (E) has one or more skeletons selected from the group consisting of a pyrrolidine skeleton, a piperidine skeleton, a piperazine skeleton, and an azepane skeleton. A moisture-curable resin composition comprising 500 to 1000 parts by weight of component (B) per 100 parts by weight of the total of component (A) and component (C).

2. The moisture-curable resin composition according to claim 1, wherein component (D) is a carboxylate metal compound containing divalent tin.

3. The moisture-curable resin composition according to claim 1, comprising 100 to 300 parts by weight of component (C) per 100 parts by weight of component (A).

4. The moisture-curable resin composition according to claim 1, wherein component (E) is a cyclic secondary amine compound having a piperidine skeleton.

5. A cured product obtained by curing a moisture-curing resin composition according to any one of claims 1 to 4.

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