Curable resin composition and cured product thereof

Abstract

To provide a curable resin composition which has good curability and can give a cured product showing high strength.SOLUTION: A curable resin composition contains a polyoxyalkylene-based polymer (A) having a reactive silyl group of formula (1), a polysilsesquioxane-based polymer (B) that has an alkoxysilyl group and / or a silanol group and further has an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms on a silicon atom, and at least one curing catalyst (C) selected from the group consisting of a tin compound having such a structure that a carbonyloxy group is bonded to a tin atom, a carboxylic acid and a compound having an amidine skeleton, where a content ratio of the (A) in the curable resin composition is 10-90 wt.%. Formula (1): -Si(R1)(X)2. In the formula (1), R1 represents a hydrocarbon group that may have a hetero-containing group and has 1 to 20 carbon atom; and X represents a hydroxyl group or a hydrolyzable group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a curable resin composition containing a polymer having a reactive silyl group, and a cured product thereof. [Background technology]

[0002] Organic polymers having a silicon-containing group (hereinafter referred to as "reactive silyl group") that has a hydroxyl group or a hydrolyzable group on a silicon atom and can form a siloxane bond are known as moisture-reactive polymers, and are included in many industrial products such as adhesives, sealing materials, coating materials, paints, and pressure sensitive adhesives, and are used in a wide range of fields. As such reactive silyl group-containing polymers, those whose main chain skeleton is a polyoxyalkylene polymer are widely used.

[0003] As a method for improving the mechanical properties exhibited after curing such an organic polymer having a reactive silyl group, a technique of blending a polysilsesquioxane-based polymer with the organic polymer is known. A polysilsesquioxane-based polymer is a siloxane-based polymer formed by the hydrolysis and dehydration condensation reaction of an organotrialkoxysilane, and has the composition formula: (RSiO 1.5 ) n In the above formula, R represents a monovalent organic group such as a methyl group.

[0004] For example, Patent Document 1 discloses a crosslinked composition containing a polymer having a reactive silyl group and a silicone resin containing a silsesquioxane unit. Patent Document 2 discloses a composition containing a silsesquioxane containing a phenyl group and an alkoxy group, a silylated polymer containing an alkoxysilane group, and a carbonate filler. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2014-521819 [Patent Document 2] Special Publication No. 2020-521034 Summary of the Invention [Problem to be solved by the invention]

[0006] The present inventors have found that in a system in which a polysilsesquioxane-based polymer is blended with an organic polymer having a specific reactive silyl group, i.e., a reactive silyl group having two bonded hydroxyl groups or two hydrolyzable groups, and a curing catalyst is further blended to improve curability, the strength after curing may be significantly reduced in some cases.

[0007] In view of the above-mentioned current situation, an object of the present invention is to provide a curable resin composition which contains an organic polymer having a reactive silyl group and a polysilsesquioxane-based polymer, and which has good curability and can give a cured product exhibiting high strength. [Means for solving the problem]

[0008] Means for Solving the Problems The present inventors have conducted intensive research to solve the above problems, and have found that the above problems can be solved by using a specific curing catalyst in a system containing a polyoxyalkylene polymer having a specific reactive silyl group and a polysilsesquioxane polymer having a specific substituent on a silicon atom, thereby completing the present invention.

[0009] That is, the present invention relates to a curable resin composition comprising: a polyoxyalkylene polymer (A) having a reactive silyl group represented by the following general formula (1); a polysilsesquioxane polymer (B) having an alkoxysilyl group and / or a silanol group, and further having an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms on a silicon atom; and at least one curing catalyst (C) selected from the group consisting of tin compounds having a structure in which a carbonyloxy group is bonded to a tin atom, carboxylic acids, and compounds having an amidine skeleton, wherein the content of the polyoxyalkylene polymer (A) in the curable resin composition is 10 to 90% by weight. -Si(R 1 )(X)2(1) (In the formula, R 1 represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group. Each X independently represents a hydroxyl group or a hydrolyzable group. Preferably, the content of the polyoxyalkylene polymer (H) having a reactive silyl group represented by the following general formula (1') is 0% by weight or more and less than 10% by weight. -Si(X')3(1') (In the formula, each X' independently represents a hydroxyl group or a hydrolyzable group.) Preferably, the proportion of the polysilsesquioxane polymer (B) in the total of the polyoxyalkylene polymer (A) and the polysilsesquioxane polymer (B) is 1 to 60% by weight. Preferably, the content of the curing catalyst (C) is 0.1 to 10 parts by weight based on 100 parts by weight in total of the polyoxyalkylene polymer (A) and the polysilsesquioxane polymer (B). Preferably, the molar ratio of the alkyl group to the aryl group (alkyl group:aryl group) in the polysilsesquioxane polymer (B) is 10:90 to 90:10. Preferably, the tin compound containing a structure in which a carbonyloxy group is bonded to a tin atom is represented by the following general formula (8) or (9). Sn(OCOR 3 )2(8) (R 4 )2Sn(OCOR 3 )2(9) (In the formula, R 3 R is the same or different, and represents a substituted or unsubstituted, saturated or unsaturated hydrocarbon group. 4 are the same or different, and each represents a substituted or unsubstituted, saturated or unsaturated hydrocarbon group. The present invention also relates to a sealant or adhesive containing the curable composition, or a cured product obtained by curing the curable resin composition. Effect of the Invention

[0010] According to the present invention, it is possible to provide a curable resin composition which contains an organic polymer having a reactive silyl group and a polysilsesquioxane-based polymer, has good curability, and is capable of giving a cured product exhibiting high strength. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The embodiments of the present invention will be described in detail below. The curable resin composition according to the present disclosure contains at least a polyoxyalkylene polymer (A) having a reactive silyl group, and a polysilsesquioxane polymer (B).

[0012] <<Reactive silyl group-containing polyoxyalkylene polymer (A)>> The reactive silyl group-containing polyoxyalkylene polymer (A) has a polymer backbone composed of a plurality of repeating units and a terminal structure bonded to the end of the polymer backbone. The polymer backbone means a polymer main chain composed of a plurality of repeating units. The polymer backbone of the polymer (A) may be either a straight chain or a branched chain.

[0013] The polymer skeleton is preferably a polymer skeleton composed only of a plurality of repeating units linked together, or a polymer skeleton composed only of the plurality of repeating units and a structure derived from an initiator used during polymerization. The repeating unit refers to an oxyalkylene unit, for example, an oxyalkylene unit having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

[0014] The terminal structure refers to a portion that does not contain a repeating unit constituting the polymer skeleton and is bonded to the end of the polymer skeleton. The terminal structure is preferably bonded to an oxyalkylene unit located at the end of the polymer skeleton via an oxygen atom. The reactive silyl group of the polymer (A) is preferably contained in the terminal structure. In this case, each terminal structure may contain a reactive silyl group, or a terminal structure containing a reactive silyl group and a terminal structure not containing a reactive silyl group may coexist.

[0015] <Reactive silyl group> The polyoxyalkylene polymer (A) has a reactive silyl group. The reactive silyl group refers to a silicon-containing group that has a hydroxyl group or a hydrolyzable group on a silicon atom and can form a siloxane bond by hydrolysis-dehydration condensation reaction. The polyoxyalkylene polymer (A) according to this embodiment has a reactive silyl group in which two hydroxyl groups or two hydrolyzable groups are bonded to one silicon atom. The reactive silyl group is represented by the following general formula (1). -Si(R 1 )(X)2(1) In formula (1), R 1 represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group. Each X independently represents a hydroxyl group or a hydrolyzable group.

[0016] R 1 is a hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 4. The hydrocarbon group may be an unsubstituted hydrocarbon group, or a hydrocarbon group having a substituent.

[0017] R 1 The hetero-containing group which the hydrocarbon group may have as a substituent is a group containing a hetero atom, where an atom other than carbon and hydrogen atoms is defined as a hetero atom.

[0018] Suitable examples of the heteroatom include N, O, S, P, Si, and halogen atoms. In the hetero-containing group, the total number of carbon atoms and heteroatoms is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4.

[0019] Suitable examples of the hetero-containing group include a hydroxyl group; a mercapto group; halogen atoms such as Cl, Br, I, and F; a nitro group; a cyano group; alkoxy groups such as a methoxy group, an ethoxy group, an n-propyloxy group, and an isopropyloxy group; alkylthio groups such as a methylthio group, an ethylthio group, an n-propylthio group, and an isopropylthio group; acyl groups such as an acetyl group, a propionyl group, and a butanoyl group; acyloxy groups such as an acetyloxy group, a propionyloxy group, and a butanoyloxy group; substituted or unsubstituted amino groups such as an amino group, a methylamino group, an ethylamino group, a dimethylamino group, and a diethylamino group; substituted or unsubstituted aminocarbonyl groups such as an aminocarbonyl group, a methylaminocarbonyl group, an ethylaminocarbonyl group, a dimethylaminocarbonyl group, and a diethylaminocarbonyl group; and a cyano group.

[0020] R 1 Specific examples of the hydrocarbon group having 1 to 20 carbon atoms as the substituent include alkyl groups such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a 2-ethyl-n-hexyl group, a n-nonyl group, a n-decyl group, a n-undecyl group, a n-dodecyl group, a n-tridecyl group, a n-tetradecyl group, a n-pentadecyl group, a n-hexadecyl group, a n-octadecyl group, a n-nonadecyl group, and a n-icosyl group; Examples of such groups include 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, naphthalene-1-yl, naphthalene-2-yl, o-phenylphenyl, m-phenylphenyl, and p-phenylphenyl; and aralkyl groups such as benzyl, phenethyl, naphthalene-1-ylmethyl, and naphthalene-2-ylmethyl. Groups in which these hydrocarbon groups are substituted with the aforementioned hetero-containing groups are also included in R. 1 As preferred.

[0021] R 1Suitable examples of R include alkyl groups such as methyl and ethyl groups; alkyl groups having a hetero-containing group such as chloromethyl and methoxymethyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl groups; and aralkyl groups such as benzyl groups. 1 As the alkyl group, a methyl group, a methoxymethyl group, and a chloromethyl group are preferable, a methyl group and a methoxymethyl group are more preferable, and a methyl group is further preferable.

[0022] Examples of X include a hydroxyl group, hydrogen, halogen, 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 is preferred because it is mildly hydrolyzable and easy to handle, and a methoxy group and an ethoxy group are more preferred.

[0023] Specific examples of the reactive silyl group include, but are not limited to, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group, etc. Among these, dimethoxymethylsilyl group is preferred from the viewpoint of stability.

[0024] The average number of reactive silyl groups per molecule of the polyoxyalkylene polymer (A) is preferably more than 1.0, more preferably 1.3 or more, and even more preferably 1.6 or more. The upper limit of the average number is not particularly limited, but is preferably 6 or less, more preferably 5 or less. The average number of reactive silyl groups per molecule of the polymer (A) can be calculated from the results of NMR measurement.

[0025] In the polyoxyalkylene polymer (A), the terminal structure having a reactive silyl group is not particularly limited, but a representative example is the terminal structure represented by the following general formula (2).

[0026] -OR 6 -CH(R 7 )-CH2-Si(R 1 )(X)2(2) In formula (2), R 6 represents a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms; R 7 represents hydrogen or an alkyl group having 1 to 6 carbon atoms. The oxygen atom at the left end represents an oxygen atom in the repeating unit located at the end of the polymer skeleton, or an oxygen atom bonded to the repeating unit located at the end of the polymer skeleton. R 1 and X are the same as described above for formula (1).

[0027] R 6 is preferably a divalent hydrocarbon group having 1 to 3 carbon atoms, more preferably a divalent hydrocarbon group having 1 to 2 carbon atoms. As the hydrocarbon group, an alkylene group is preferred, and a methylene group, ethylene group, propylene group, or butylene group can be used. A methylene group is particularly preferred.

[0028] R 7 R is 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 a methyl group, an ethyl group, a propyl group, and a butyl group. 7 As the alkyl group, hydrogen, a methyl group, and an ethyl group are preferable, and hydrogen and a methyl group are more preferable.

[0029] <Polymer backbone> Examples of the polymer skeleton of the polyoxyalkylene polymer (A) include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Each polymer may be mixed in a block form, a graft form, etc. Among these, polyoxypropylene is particularly preferred. The polyoxyalkylene polymer (A) preferably contains 50% by weight or more, more preferably 70% by weight or more of the polyoxyalkylene repeating unit in the polymer skeleton.

[0030] The polyoxyalkylene polymer (A) may be a polymer having any one kind of polymer backbone, or a mixture of two or more kinds of polymers having different polymer backbones. The mixture may be a mixture of polymers produced separately, or may be a mixture produced simultaneously to have any mixture composition.

[0031] The number average molecular weight of the polyoxyalkylene 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 calculated as polystyrene by GPC. When the number average molecular weight is within the above range, the amount of reactive silyl groups introduced is appropriate, and therefore, the polyoxyalkylene polymer (A) having an easy-to-handle viscosity and excellent workability can be relatively easily produced while keeping production costs within an appropriate range.

[0032] The molecular weight of the polyoxyalkylene polymer (A) can also be expressed as an end-group-converted molecular weight obtained by directly measuring the end-group concentration of a polymer precursor before the introduction of reactive silyl groups by titration analysis based on the principles of the hydroxyl value measurement method of JIS K 1557 and the iodine value measurement method specified in JIS K 0070, and taking into consideration the structure of the polymer (the degree of branching determined by the polymerization initiator used). The end-group-converted molecular weight of the polyoxyalkylene polymer (A) can also be obtained by preparing a calibration curve of the number average molecular weight obtained by general GPC measurement of the polymer precursor and the end-group-converted molecular weight, and converting the number average molecular weight obtained by GPC of the polyoxyalkylene polymer (A) into the end-group-converted molecular weight.

[0033] The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer (A) is not particularly limited, but is preferably narrow. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, particularly preferably 1.4 or less, even more particularly preferably 1.3 or less, and most particularly preferably 1.2 or less. The molecular weight distribution of the polyoxyalkylene polymer (A) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.

[0034] <Method for producing reactive silyl group-containing polyoxyalkylene polymer (A)> Next, a method for producing the reactive silyl group-containing polyoxyalkylene polymer (A) will be described. The reactive silyl group-containing polyoxyalkylene polymer (A) can be produced by introducing a reactive silyl group into a precursor polymer to which a reactive silyl group can be introduced. Specifically, the polyoxyalkylene polymer (A) can be produced by introducing a carbon-carbon unsaturated bond into a polyoxyalkylene polymer (P) having a hydroxyl group at its terminal by utilizing the reactivity of the hydroxyl group to obtain a precursor polymer having a carbon-carbon unsaturated bond, and then reacting the precursor polymer with a reactive silyl group-containing compound having reactivity with the carbon-carbon unsaturated bond to introduce the reactive silyl group.

[0035] (polymerization) The polymer backbone of the polyoxyalkylene polymer can be formed by polymerizing an epoxy compound with an initiator having a hydroxyl group by a conventionally known method, thereby obtaining a polyoxyalkylene polymer (P) having a hydroxyl group at its terminal. Although the specific polymerization method is not particularly limited, a polymerization method using a composite metal cyanide complex catalyst such as zinc hexacyanocobaltate glyme complex is preferred because it can obtain a hydroxyl-terminated polymer with a small molecular weight distribution (Mw / Mn).

[0036] The initiator having a hydroxyl group is not particularly limited, but 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.

[0037] The epoxy compound is not particularly limited, but examples thereof include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and butyl glycidyl ether, etc. Propylene oxide is preferred.

[0038] (Reaction with alkali metal salts) When introducing a carbon-carbon unsaturated bond into a polyoxyalkylene polymer (P) having a terminal hydroxyl group, it is preferable to first react an alkali metal salt with the polyoxyalkylene polymer (P) to convert the terminal hydroxyl group into a metaloxy group. Also, a composite metal cyanide complex catalyst can be used instead of the alkali metal salt. In this manner, a metaloxy group-terminated polyoxyalkylene polymer (D) is formed.

[0039] 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, cesium alkoxide, etc. The alkali metal salt may be subjected to the reaction in a state of being dissolved in a solvent.

[0040] (Reaction with electrophiles (E)) Next, the metaloxy group-terminated polyoxyalkylene polymer (D) is reacted with an electrophilic agent (E) having a carbon-carbon unsaturated bond to convert the metaloxy group into a structure containing a carbon-carbon unsaturated bond, thereby forming a polyoxyalkylene polymer (F) having a carbon-carbon unsaturated bond in the terminal structure.

[0041] The electrophile (E) having a carbon-carbon unsaturated bond is not particularly limited as long as it is a compound that can react with the metaloxy group in the polyoxyalkylene polymer (D) and introduce a carbon-carbon unsaturated bond into the polyoxyalkylene polymer. Examples of the electrophile (E) having a carbon-carbon unsaturated bond include an organic halide (E1) having a carbon-carbon unsaturated bond and an epoxy compound (E2) having a carbon-carbon unsaturated bond.

[0042] The organic halide (E1) having a carbon-carbon unsaturated bond reacts with the metaloxy group through a halogen substitution reaction to form an ether bond, thereby introducing a structure containing a carbon-carbon unsaturated bond as a terminal structure of the polyoxyalkylene polymer.

[0043] The organic halide (E1) having a carbon-carbon unsaturated bond is preferably a halogenated hydrocarbon compound having a carbon-carbon double bond. The polyoxyalkylene polymer (G) obtained by reacting the compound has a carbon-carbon double bond at the end of the polymer skeleton. The halogenated hydrocarbon compound having a carbon-carbon double bond can be represented by the following general formula (7), but is not limited thereto. ZR 6 -C(R 7 )=CH2(7)

[0044] In formula (7), R 6 and R 7 are the same as those described above for general formula (2), 6 and R 7 Z represents a halogen atom. When a reactive silyl group, which will be described later, is introduced into the polyoxyalkylene polymer (F) having a carbon-carbon unsaturated bond in the terminal structure obtained by reacting the organic halide (E1), the terminal structure represented by the general formula (2) can be formed.

[0045] Specific examples of the halogenated hydrocarbon compound having a carbon-carbon double bond include, but are not limited to, vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, methallyl iodide, etc. Allyl chloride and methallyl chloride are preferred from the viewpoint of ease of handling. Furthermore, methallyl chloride, methallyl bromide, and methallyl iodide are preferred from the viewpoint of improving the average ratio of the number of reactive silyl groups to the number of terminals of the polymer skeleton.

[0046] The epoxy compound (E2) having a carbon-carbon unsaturated bond reacts with the metaloxy group through a ring-opening addition reaction of the epoxy group to form an ether bond, and can introduce a structure containing a carbon-carbon unsaturated bond and a hydroxyl group as a terminal structure of the polyoxyalkylene polymer. In the ring-opening addition reaction, one or more epoxy compounds (E2) can be added to one metaloxy group by adjusting the amount of the epoxy compound (E2) used relative to the metaloxy group and the reaction conditions.

[0047] The epoxy compound (E2) having a carbon-carbon unsaturated bond is not limited, but is preferably an epoxy compound having a carbon-carbon double bond. Specifically, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and butadiene monoxide are preferred in terms of reaction activity, and allyl glycidyl ether is particularly preferred.

[0048] As described above, when the epoxy compound (E2) having a carbon-carbon unsaturated bond is reacted with the metaloxy group-terminated polyoxyalkylene polymer (D), a new metaloxy group is generated by ring-opening of the epoxy group. Therefore, after the reaction with the epoxy compound (E2), it is also possible to continuously react with the organic halide (E1) having a carbon-carbon unsaturated bond. This method is preferable because it can further increase the amount of carbon-carbon unsaturated bonds and the amount of reactive silyl groups introduced into the polymer.

[0049] (Introduction of reactive silyl groups) The polyoxyalkylene polymer (F) (precursor polymer) having a carbon-carbon unsaturated bond in the terminal structure obtained as above is subjected to a hydrosilylation reaction with a hydrosilane compound (G) having a reactive silyl group, whereby a reactive silyl group can be introduced into the polymer. This allows the production of a polyoxyalkylene polymer (A) containing a reactive silyl group. The hydrosilylation reaction has the advantages that it can be easily carried out, the amount of reactive silyl group introduced can be easily adjusted, and the physical properties of the resulting polymer are stable.

[0050] Specific examples of the hydrosilane compound (G) having a reactive silyl group include halosilanes such as dichloromethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, (methoxymethyl)dichlorosilane, and (dimethoxymethyl)dichlorosilane; dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, ethyldimethoxysilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, (methoxymethyl)dimethoxysilane, (methoxymethyl)diethoxysilane, and (ethoxymethyl)diethoxysilane. Examples of suitable silanes include alkoxysilanes such as silane, (3,3,3-trifluoropropyl)dimethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, and (N,N-diethylaminomethyl)diethoxysilane; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; ketoximate silanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane; and isopropenyloxysilanes (deacetone type) such as (chloromethyl)diisopropenyloxysilane and (methoxymethyl)diisopropenyloxysilane.

[0051] The hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst in order to promote the reaction. Known examples of the hydrosilylation catalyst include metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium, and complexes thereof. Specifically, platinum is supported on a support such as alumina, silica, or carbon black; chloroplatinic acid; chloroplatinic acid complexes consisting of chloroplatinic acid and alcohols, aldehydes, or ketones; platinum-olefin complexes [e.g., Pt(CH2=CH2)2(PPh3), Pt(CH2=CH2)2Cl2]; platinum-vinylsiloxane complexes [e.g., Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4]; platinum-phosphine complexes [e.g., Ph(PPh3)4, Pt(PBu3)4]; platinum-phosphite complexes [e.g., Pt{P(OPh)3}4], etc. From the viewpoint of reaction efficiency, platinum catalysts such as chloroplatinic acid and platinum-vinylsiloxane complexes are preferred.

[0052] The content of the polyoxyalkylene polymer (A) in the curable resin composition according to the present disclosure is 10 to 90% by weight. By including the polyoxyalkylene polymer (A) in such a ratio, it is possible to form a cured product that has good curability and high strength. The content is preferably 15 to 80% by weight, more preferably 20 to 70% by weight, and further preferably 25 to 60% by weight.

[0053] The curable resin composition according to the present disclosure may contain, in addition to the polyoxyalkylene polymer (A), a polyoxyalkylene polymer (H) having a reactive silyl group represented by the following general formula (1'). -Si(X')3(1') In formula (1'), X' each independently represents a hydroxyl group or a hydrolyzable group. Specific examples of X' include the same groups as the specific examples of X described above. In the reactive silyl group represented by formula (1'), three hydroxyl groups or hydrolyzable groups are bonded to one silicon atom.

[0054] However, since such a polyoxyalkylene polymer (H) having a reactive silyl group may impair the effects of the present invention, its content is preferably small. Specifically, the content of the polyoxyalkylene polymer (H) in the curable resin composition according to the present disclosure is preferably 0% by weight or more and less than 10% by weight, more preferably 0 to 5% by weight, and even more preferably 0 to 1% by weight. The curable resin composition according to the present disclosure may not contain the polyoxyalkylene polymer (H).

[0055] <<Polysilsesquioxane polymer (B)>> Polysilsesquioxane polymers are polymers with the composition formula (RSiO 1.5 ) n and is a hydrolysis condensation product of an alkoxysilane component containing at least an organotrialkoxysilane. The polysilsesquioxane polymer (B) in the present disclosure has both an alkyl group having 1 to 10 carbon atoms bonded to a silicon atom and an aryl group having 6 to 12 carbon atoms bonded to a silicon atom. This improves the compatibility of the polyoxyalkylene polymer (A) and the polysilsesquioxane polymer (B), and also improves the co-condensation property by bringing the curing rates of both polymers closer to each other, making it possible to form a cured product exhibiting high strength.

[0056] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group. The number of carbon atoms in the alkyl group is preferably 1 to 4, more preferably 1 to 3, further preferably 1 to 2, and particularly preferably 1. The alkyl group may have no substituent or may have a hetero-containing group such as a halogen atom, an alkoxy group, or an acyl group as a substituent. The alkyl group may be of one type, or may be of two or more types in combination.

[0057] Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. The number of carbon atoms in the aryl group is preferably 6 to 10, more preferably 6 to 8, further preferably 6 to 7, and particularly preferably 6. The aryl group may have no substituent, or may have a hetero-containing group such as a halogen atom, an alkoxy group, or an acyl group as a substituent. The aryl group may be of one type, or may be of two or more types in combination.

[0058] The molar ratio of the alkyl group and the aryl group (alkyl group:aryl group) contained on a silicon atom in the polysilsesquioxane polymer (B) is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 30:70 to 70:30, from the viewpoint of strength of a cured product obtained by curing the curable resin composition.

[0059] The polysilsesquioxane polymer (B) further contains an alkoxysilyl group and / or a silanol group. By containing the alkoxysilyl group and / or the silanol group, the polysilsesquioxane polymer (B) can exhibit curability by hydrolysis and dehydration condensation reaction together with the polyoxyalkylene polymer (A).

[0060] The alkoxysilyl group that the polysilsesquioxane polymer (B) may have is a part of the alkoxy groups contained in the organotrialkoxysilane raw material that remains unreacted during the production of the polysilsesquioxane polymer (B). The alkoxysilyl group may be, for example, an alkoxysilyl group having 1 to 3 carbon atoms. Specific examples include a methoxysilyl group, an ethoxysilyl group, and a propoxysilyl group, with a methoxysilyl group and an ethoxysilyl group being preferred, and a methoxysilyl group being more preferred. The alkoxysilyl group may be of one type only, or may be of two or more types mixed together.

[0061] The silanol groups (—SiOH) that the polysilsesquioxane polymer may have are those that are generated when some of the alkoxy groups contained in the organotrialkoxysilane raw material are subjected to a hydrolysis reaction during the production of the polysilsesquioxane polymer (B) and then do not undergo a dehydration condensation reaction, i.e., do not form a siloxane bond and remain.

[0062] The organotrialkoxysilane used as a raw material for the polysilsesquioxane polymer (B) refers to a silane compound having one organic group bonded to a silicon atom and three alkoxy groups bonded to the silicon atom, and is represented by the formula: RSi(OR')3. In the formula, R represents the organic group, and OR' represents an alkoxy group. The organic group refers to an organic group other than an alkoxy group, and includes at least both the alkyl group having 1 to 10 carbon atoms described above and the aryl group having 6 to 12 carbon atoms described above.

[0063] The alkoxy group OR' bonded to a silicon atom is the same as the alkoxy group in the alkoxysilyl group that the polysilsesquioxane polymer (B) may have, and specifically may be an alkoxy group having 1 to 3 carbon atoms. Specific examples include a methoxy group, an ethoxy group, and a propoxy group, with a methoxy group and an ethoxy group being preferred, and a methoxy group being more preferred. The alkoxy group may be of one type only, or may be of two or more types mixed together.

[0064] As the organotrialkoxysilane, at least both an organotrialkoxysilane in which the organic group is an alkyl group and an organotrialkoxysilane in which the organic group is an aryl group are used.

[0065] Specific examples of the organotrialkoxysilane in which the organic group is an alkyl group are not particularly limited, but include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltriisopropoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, pentyltriisopropoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, etc. Among them, methyltrialkoxysilane is preferred, and methyltrimethoxysilane is particularly preferred.

[0066] Specific examples of organotrialkoxysilanes in which the organic group is an aryl group are not particularly limited, and include, for example, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrippropoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, tolyltrippropoxysilane, xylyltrimethoxysilane, xylyltriethoxysilane, xylyltrippropoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltrippropoxysilane, etc. Among these, phenyltrialkoxysilane is preferred, and phenyltrimethoxysilane is particularly preferred.

[0067] In the alkoxysilane component, the molar ratio (alkyl group:aryl group) of the organotrialkoxysilane in which the organic group is an alkyl group to the organotrialkoxysilane in which the organic group is an aryl group is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 30:70 to 70:30, from the viewpoint of the strength of the cured product obtained by curing the curable resin composition.

[0068] In the alkoxysilane component, the total ratio of organotrialkoxysilanes whose organic group is an alkyl group and organotrialkoxysilanes whose organic group is an aryl group is preferably 80 to 100 mol %, more preferably 90 to 100 mol %, further preferably 95 to 100 mol %, and particularly preferably 99 to 100 mol %, from the viewpoint of the physical properties exhibited by the polysilsesquioxane polymer (B). Examples of alkoxysilanes other than organotrialkoxysilanes whose organic group is an alkyl group and organotrialkoxysilanes whose organic group is an aryl group include organotrialkoxysilanes whose organic group does not fall into either of the alkyl group and aryl group, diorganodialkoxysilanes, triorganomonoalkoxysilanes, and tetraalkoxysilanes.

[0069] The number average molecular weight of the polysilsesquioxane polymer (B) is preferably from 400 to 10,000, and more preferably from 500 to 5000. The number average molecular weight of the polysilsesquioxane polymer (B) can be measured by GPC.

[0070] The polysilsesquioxane polymer (B) can be produced by subjecting an alkoxysilane component containing the organotrialkoxysilane to hydrolysis and dehydration condensation reaction in the presence of water and, if necessary, a condensation catalyst. During the reaction, some of the alkoxy groups contained in the alkoxysilane component remain unreacted and / or the alkoxy groups undergo hydrolysis and then remain without undergoing a dehydration condensation reaction, so that the produced polysilsesquioxane polymer has alkoxysilyl groups and / or silanol groups.

[0071] The hydrolysis and dehydration condensation reactions are preferably carried out by adding water. At this time, the amount of alkoxysilyl groups and / or silanol groups in the resulting polysilsesquioxane polymer and the molecular weight of the polysilsesquioxane polymer can be controlled by adjusting the amount of water used. From this viewpoint, the amount of water used is preferably 30 mol% to 50 mol%, more preferably 32 mol% to 49 mol%, and even more preferably 35 mol% to 45 mol%, based on the total number of moles of alkoxy groups on silicon atoms contained in the alkoxysilane component (100%).

[0072] The hydrolysis and dehydration condensation reaction is preferably carried out in the presence of a condensation catalyst in order to promote the reaction. A known condensation catalyst can be used. Specific examples include basic catalysts, acidic catalysts, and neutral salts. In order to improve the storage stability of the resulting polysilsesquioxane polymer, the condensation catalyst is preferably an acidic catalyst or a neutral salt, and more preferably a neutral salt.

[0073] As the acid catalyst, from the viewpoint of compatibility with the alkoxysilane component, an organic acid is preferable, and a phosphoric acid ester or a carboxylic acid is more preferable. Specific examples of the organic acid include ethyl acid phosphate, butyl acid phosphate, dibutyl pyrophosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, isotridecyl acid phosphate, dibutyl phosphate, bis(2-ethylhexyl)phosphate, formic acid, acetic acid, butyric acid, and isobutyric acid.

[0074] Examples of the basic catalyst include amine compounds such as N-ethylmorpholine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, Nt-butyldiethanolamine, triethylamine, n-butylamine, hexylamine, triethanolamine, diazabicycloundecene, and ammonia; and metal hydroxides such as sodium hydroxide and potassium hydroxide.

[0075] A neutral salt is a positive salt consisting of a strong acid and a strong base, and is, for example, a salt consisting of a combination of a cation selected from the group consisting of a Group 1 element ion, a Group 2 element ion, a tetraalkylammonium ion, and a guanidinium ion, and an anion selected from the group consisting of a Group 17 element ion excluding fluoride ion, a sulfate ion, a nitrate ion, and a perchlorate ion. In particular, as an anion, a Group 17 element ion is preferred because of its high nucleophilicity, and as a cation, a Group 1 element ion or a Group 2 element ion is preferred because it is not bulky so as not to inhibit the nucleophilic action.

[0076] The specific compound of the neutral salt is not particularly limited, but preferred specific examples include lithium chloride, sodium chloride, potassium chloride, rabidium chloride, cesium chloride, magnesium chloride, calcium chloride, strontium chloride, lithium bromide, sodium bromide, potassium bromide, rabidium bromide, cesium bromide, magnesium bromide, calcium bromide, strontium bromide, lithium iodide, sodium iodide, potassium iodide, rabidium iodide, cesium iodide, magnesium iodide, calcium iodide, and strontium iodide.

[0077] The amount of the condensation catalyst added can be appropriately adjusted, and may be, for example, about 50 ppm to 3% by weight based on the alkoxysilane component. However, in order to improve the stability of the polysilsesquioxane polymer (B), it is preferable to use a smaller amount of the condensation catalyst within a range in which the effect of shortening the reaction time by the condensation catalyst can be achieved.

[0078] The reaction temperature when carrying out the hydrolysis and dehydration condensation steps can be appropriately set by those skilled in the art, but for example, the reaction liquid is preferably heated to a range of 50 to 110° C. In addition, the reaction time when carrying out the hydrolysis and dehydration condensation steps can be appropriately set by those skilled in the art, but may be, for example, about 10 minutes to 12 hours.

[0079] The content of the polysilsesquioxane polymer (B) in the curable resin composition according to the present disclosure can be appropriately determined taking into consideration the curability of the composition, the strength of the obtained cured product, and the like. The content of the polysilsesquioxane polymer (B) in the total of the polyoxyalkylene polymer (A) and the polysilsesquioxane polymer (B) is preferably an amount such that the proportion of the polysilsesquioxane polymer (B) is 1 to 60% by weight, more preferably 5 to 50% by weight, even more preferably 10 to 45% by weight, and particularly preferably 15 to 40% by weight.

[0080] After producing the polysilsesquioxane polymer (B), a step of removing alcohol generated by hydrolysis of the alkoxysilane component during the production may be carried out. This step is preferably carried out after mixing the polyoxyalkylene polymer (A) with the polysilsesquioxane polymer (B) containing the alcohol. This makes it possible to obtain a mixture in which the content of volatile components such as alcohol is reduced while uniformly mixing the polyoxyalkylene polymer (A) and the polysilsesquioxane polymer (B). The alcohol removal step can be carried out by subjecting the mixture to reduced pressure distillation to distill off the alcohol. The conditions for reduced pressure distillation can be appropriately set by those skilled in the art, but the temperature may be, for example, about 60 to 160°C.

[0081] <<Curing catalyst (C)>> The curable resin composition according to the present disclosure contains a curing catalyst (C) for the purpose of promoting the reaction of hydrolysis and dehydration condensation of reactive silyl groups possessed by the polyoxyalkylene polymer (A) and the polysilsesquioxane polymer (B), i.e., the curing reaction. In order to obtain a cured product having good curability and high strength, a tin compound having a structure in which a carbonyloxy group is bonded to a tin atom, a carboxylic acid, or a compound having an amidine skeleton is used as the curing catalyst (C). These curing catalysts may be used alone or in combination of two or more.

[0082] Comparing the polyoxyalkylene polymer (A) having a reactive silyl group represented by the general formula (1) with the polysilsesquioxane polymer (B), the latter has a significantly faster curing rate. Therefore, when the polyoxyalkylene polymer (A) and the polysilsesquioxane polymer (B) are cured in the presence of a curing catalyst such as dibutyltin bisacetylacetonate, the curing of only the polysilsesquioxane polymer (B) proceeds preferentially, resulting in the formation of a cured product that is weak in strength and brittle. However, when the specific curing catalyst (C) described above is used, the curing rates of the polyoxyalkylene polymer (A) and the polysilsesquioxane polymer (B) become similar, and the curing proceeds relatively uniformly, making it possible to form a cured product exhibiting high strength.

[0083] The tin compound containing a structure in which a carbonyloxy group is bonded to a tin atom, which is one type of curing catalyst (C), is a tin salt of a carboxylic acid and can be represented, for example, by the following general formula (8) or (9). Sn(OCOR 3 )2(8) (R 4 )2Sn(OCOR 3 )2(9)

[0084] In formula (8) or (9), R 3 R is the same or different, and represents a substituted or unsubstituted, saturated or unsaturated hydrocarbon group. 4 R is the same or different, and represents a substituted or unsubstituted, saturated or unsaturated hydrocarbon group. 3 The number of carbon atoms in the hydrocarbon group represented by R is preferably 1 to 20, more preferably 6 to 18, and even more preferably 8 to 12. 4 The number of carbon atoms in the hydrocarbon group represented by the formula (OCOR) is preferably 1 to 20, more preferably 2 to 16, and even more preferably 3 to 10. 3 The portion corresponds to the carbonyloxy group. The tin compound is a tin salt of a carboxylic acid. As the carboxylic acid constituting the tin compound, various carboxylic acids exemplified later as a type of carboxylic acid of the curing catalyst (C) can be used.

[0085] Specific examples of the tin compound include dialkyltin carboxylates such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctanoate, dibutyltin bis(methyl maleate), dibutyltin bis(ethyl maleate), dibutyltin bis(butyl maleate), dibutyltin bis(isooctyl maleate), dibutyltin bis(tridecyl maleate), dibutyltin bis(benzyl maleate), dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), and dioctyltin bis(isooctyl maleate); and divalent tin compounds such as tin octylate, tin naphthenate, and tin stearate.

[0086] The carboxylic acid, which is one of the curing catalysts (C), is not particularly limited, but a monovalent, divalent, or trivalent carboxylic acid can be used. Among them, a monovalent or divalent carboxylic acid is preferred, and a monovalent carboxylic acid is more preferred. Either an aliphatic carboxylic acid or an aromatic carboxylic acid can be used, but an aliphatic carboxylic acid is preferred. The aliphatic carboxylic acid may be either a saturated fatty acid or an unsaturated fatty acid. The hydrocarbon group in the carboxylic acid group may be a straight chain or a branched chain. The carbon number of the carboxylic acid may be, for example, 1 to 20, preferably 6 to 18, and more preferably 8 to 12. The carboxylic acid may have a functional group other than a carboxyl group, but preferably does not have a functional group other than a carboxyl group.

[0087] Specific examples of the carboxylic acid include formic acid; linear saturated fatty acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, and lacteric acid; and undecylenic acid. Monoenoic acid, such as Linderic acid, Tsuzuic acid, Physeteric acid, Myristoleic acid, 2-hexadecenoic acid, 6-hexadecenoic acid, 7-hexadecenoic acid, palmitoleic acid, petroselinic acid, oleic acid, elaidic acid, asclepinic acid, vaccenic acid, gadoleic acid, gondoic acid, cetoleic acid, erucic acid, brassidic acid, selacholeic acid, xymenic acid, lumecic acid, acrylic acid, methacrylic acid, angelic acid, crotonic acid, isocrotonic acid, and 10-undecenoic acid. Saturated fatty acids: linoelaidic acid, linoleic acid, 10,12-octadecadienoic acid, hiragonic acid, α-eleostearic acid, β-eleostearic acid, punicic acid, linolenic acid, 8,11,14-eicosatrienoic acid, 7,10,13-docosatrienoic acid, 4,8,11,14-hexadecatetraenoic acid, moroctic acid, stearidonic acid, arachidonic acid, 8,12,16,19-docosatetraenoic acid, 4,8,12,15,18-eicosapentaenoic acid, sardine acid, nicotinic acid, linole ... Polyenic unsaturated fatty acids such as sinoic acid and docosahexaenoic acid; branched fatty acids such as 1-methylbutyric acid, isobutyric acid, 2-ethylbutyric acid, isovaleric acid, tuberculostearic acid, pivalic acid, neodecanoic acid; fatty acids with triple bonds such as propiolic acid, talic acid, stearic acid, crepenic acid, xymenic acid, 7-hexadecanoic acid; alicyclic carboxylic acids such as naphthenic acid, malvalic acid, sterculic acid, hydnocarbic acid, shormooglic acid, and golric acid;Oxygen-containing fatty acids such as acetoacetic acid, ethoxyacetic acid, glyoxylic acid, glycolic acid, gluconic acid, savinic acid, 2-hydroxytetradecanoic acid, iprolic acid, 2-hydroxyhexadecanoic acid, yarapinolic acid, uniperilic acid, ambrettolic acid, alluritic acid, 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, ricinoleic acid, camrolenoic acid, licanic acid, ferronic acid, and cerebronic acid; and halogen-substituted monocarboxylic acids such as chloroacetic acid, 2-chloroacrylic acid, and chlorobenzoic acid. Further, examples of the aliphatic dicarboxylic acid include saturated dicarboxylic acids such as adipic acid, azelaic acid, pimelic acid, suberic acid, sebacic acid, ethylmalonic acid, glutaric acid, oxalic acid, malonic acid, succinic acid, and oxydiacetic acid; and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, acetylenedicarboxylic acid, and itaconic acid. Examples of the aliphatic polycarboxylic acid include tricarboxylic acids such as aconitic acid, citric acid, and isocitric acid. Examples of the aromatic carboxylic acid include aromatic monocarboxylic acids such as benzoic acid, 9-anthracene carboxylic acid, atrolactic acid, anisic acid, isopropyl benzoic acid, salicylic acid, and toluic acid; and aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, carboxyphenylacetic acid, and pyromellitic acid. Further, examples of the amino acids include alanine, leucine, threonine, aspartic acid, glutamic acid, arginine, cysteine, methionine, phenylalanine, tryptophan, and histidine.

[0088] The compound having an amidine skeleton, which is one type of curing catalyst (C), can be represented by the following general formula (10). R 11 N=CR 12 -NR 13 2(10) In formula (10), R 11 , R 12 , and two R 13 R each independently represents a hydrogen atom or an organic group. 11 , R 12 , and two R 13Any two or more of these may be bonded to form a cyclic structure.

[0089] R 11 R is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group in which the carbon atom adjacent to the nitrogen atom (the carbon atom at the α-position) does not have an unsaturated bond, in order to enhance the curability of the curable resin composition. 11 The number of carbon atoms is preferably 1 to 10, and more preferably 1 to 6, because they are easily available.

[0090] R 12 is a hydrogen atom or -NR 14 2, and preferably an organic group represented by -NR 14 It is more preferable that the organic group represented by the formula: 14 each independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. In this case, the amidine compound represented by the general formula (10) is called a guanidine compound.

[0091] Also, R 12 Since the physical properties of the resulting cured product are good, -NR 15 -C(=NR 16 )-NR 17 2, or -N=C(NR 18 2)-NR 19 It is preferable that R is an organic group represented by the formula: 15 , R 16 and two R 17 Each of R independently represents a hydrogen atom or an organic group having 1 to 6 carbon atoms. 18 and two R 19 each independently represents a hydrogen atom or an organic group having 1 to 6 carbon atoms. In this case, the amidine compound represented by the general formula (10) is called a biguanide compound.

[0092] Two R in the general formula (10) 13In view of ease of availability and of enhancing the curability of the curable resin composition, preferably represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0093] The number of carbon atoms contained in the amidine compound is preferably 2 or more, more preferably 6 or more, and particularly preferably 7 or more. The upper limit of the number of carbon atoms contained in the amidine compound is not particularly limited, but is preferably 10,000 or less. The molecular weight of the amidine compound is preferably 60 or more, more preferably 120 or more, and particularly preferably 130 or more. The upper limit of the molecular weight of the amidine compound is not particularly limited, but is preferably 100,000 or less.

[0094] Examples of the amidine compound include, but are not limited to, pyrimidine compounds such as pyrimidine, 2-aminopyrimidine, 6-amino-2,4-dimethylpyrimidine, 2-amino-4,6-dimethylpyrimidine, 1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1-ethyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-diethyl-1,4,5,6-tetrahydropyrimidine, 1-n-propyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 2-hydroxy-4,6-dimethylpyrimidine, 1,3-diazanaphthalene, and 2-hydroxy-4-aminopyrimidine; imidazoline compounds such as 2-imidazoline, 2-methyl-2-imidazoline, 2-ethyl-2-imidazoline, 2-propyl-2-imidazoline, 2-vinyl-2-imidazoline, 1-(2-hydroxyethyl)-2-methyl-2-imidazoline, 1,3-dimethyl-2-iminoimidazolidine, and 1-methyl-2-iminoimidazolidine-4-one; amidine compounds such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 2,9-diazabicyclo[4.3.0]nona-1,3,5,7-tetraene, and 6-(dibutylamino)-1,8-diazabicyclo[5,4,0]undec-7-ene (DBA-DBU); Guanidine, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, 1,1-dimethylguanidine, 1,3-dimethylguanidine, 1,2-diphenylguanidine, 1,1,2-trimethylguanidine, 1,2,3-trimethylguanidine, 1,1,3,3-tetramethylguanidine, 1,1,2,3,3-pentamethylguanidine, 2-ethyl-1,1,3,3-tetramethylguanidine, 1,1,3,3-tetramethyl-2-n-propylguanidine, 1,1,3,3-tetramethyl-2-isopropylguanidine, 2-n-butyl-1,1,3,3-tetramethylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, 1,2,3-Tricyclohexylguanidine, 1-benzyl-2,3-dimethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-ethyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-propyl-1,5,7-triazabicyclo[4.4.0] guanidine compounds such as dec-5-ene, 7-isopropyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-cyclohexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-n-octyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene; Biguanide, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-(2-ethylhexyl)biguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, 1-morpholinobiguanide, Examples of the biguanide compounds include 1-n-butyl-N2-ethylbiguanide, 1,1'-ethylenebisbiguanide, 1,5-ethylenebiguanide, 1-[3-(diethylamino)propyl]biguanide, 1-[3-(dibutylamino)propyl]biguanide, and N',N''-dihexyl-3,12-diimino-2,4,11,13-tetraazatetradecanediamine; and the like. Among these, guanidine compounds are preferred due to their good curability, and phenylguanidine is particularly preferred.

[0095] From the viewpoint of achieving both an improvement in the curing reaction rate and workability during curing, the amount of the curing catalyst (C) added is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 15 parts by weight, even more preferably 0.1 to 10 parts by weight, still more preferably 0.5 to 7 parts by weight, and particularly preferably 1 to 5 parts by weight, relative to 100 parts by weight in total of the polyoxyalkylene polymer (A) and the polysilsesquioxane polymer (B).

[0096] (curing promoter) The curable resin composition may further contain an amine compound as a curing promoter. By using such a curing promoter in combination with the curing catalyst (C), the curing speed of the curable resin composition and / or the strength of the cured product can be further improved. The effect achieved by the curing promoter is particularly remarkable when the curing catalyst (C) is the divalent tin compound or carboxylic acid.

[0097] The amine compound is an amine compound other than the compound having the amidine skeleton, and is not particularly limited, but a monovalent, divalent, or trivalent amine compound can be used. Among them, a monovalent or divalent carboxylic acid is preferable. Either an aliphatic amine compound or an aromatic amine compound can be used, but an aliphatic amine compound is preferable. The aliphatic amine compound may be either a saturated aliphatic or an unsaturated aliphatic amine. The hydrocarbon group in the aliphatic amine compound may be a straight chain or a branched chain. The carbon number of the amine compound may be, for example, 1 to 20, preferably 3 to 18, and more preferably 6 to 14. The amine compound may have a functional group other than an amino group, but preferably does not have a functional group other than an amino group.

[0098] Specific examples of the amine compound include aliphatic primary amines such as butylamine, octylamine, 2-ethylhexylamine, laurylamine, stearylamine, and oleylamine; aliphatic secondary amines such as dibutylamine; aliphatic tertiary amines such as triethylamine, triamylamine, trihexylamine, and trioctylamine; aliphatic unsaturated amines such as triallylamine and oleylamine; aromatic amines such as aniline, laurylaniline, stearylaniline, and triphenylamine; pyridine, 2-aminopyridine, 2-(dimethylamino)pyridine, 4-(dimethylaminopyridine), 2-hydroxypyridine, imidazole, 2-ethyl-4-methylimidazole, morpholine, N-methylmorpholine, piperidine, 2-piperidinemethanol, 2-(2-piperidinol), ... Nitrogen-containing heterocyclic compounds such as 1,4-diazabicyclo(2,2,2)octane (DABCO), aziridine, etc.; monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, propylenediamine, hexamethylenediamine, N-methyl-1,3-propanediamine, N,N'-dimethyl-1,3-propanediamine, diethylenetriamine, triethylenetetramine, triethylenediamine, benzylamine, 3-methoxypropylamine, 3-lauryloxypropylamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine (DEAPA), 3-dibutylaminopropylamine, 3-morpholinopropylamine, 2-(1-piperazinyl)ethylamine, xylylenediamine, etc.

[0099] The amount of the amine compound is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, even more preferably 0.05 to 3 parts by weight, and particularly preferably 0.1 to 1 part by weight, per 100 parts by weight of the polyoxyalkylene polymer (A) and the polysilsesquioxane polymer (B) in total, from the viewpoint of improving the curing speed and / or the strength of the cured product.

[0100] <<Curable resin composition>> The curable resin composition according to the present disclosure may contain various additives, if necessary, in addition to the polyoxyalkylene polymer (A), the polysilsesquioxane polymer (B), and the curing catalyst. Examples of the additives include fillers, adhesion promoters, plasticizers, antisagging agents, antioxidants, light stabilizers, UV absorbers, physical property regulators, compounds containing epoxy groups, photocurable substances, oxygen-curable substances, and organic resins other than the polyoxyalkylene polymer (A).

[0101] In addition, for the purpose of adjusting various physical properties of the curable resin composition or the cured product, additives other than those described above may be added to the curable resin composition as necessary. Examples of such additives include tackifier resins, solvents, diluents, epoxy resins, surface improvers, foaming agents, curability regulators, flame retardants, silicates, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, and fungicides.

[0102] The curable resin composition can be prepared as a one-component type in which all ingredients are mixed in advance, sealed, and stored, and then cured by moisture in the air after application. The one-component type curable resin composition preferably does not substantially contain water, and the water content is preferably 5% by weight or less, and more preferably 1% by weight or less. In addition, it can also be prepared as a two-component type in which ingredients such as a curing catalyst, a filler, a plasticizer, and water are mixed as a curing agent, and the curing agent and a base agent containing a polyoxyalkylene polymer (A) and a polysilsesquioxane polymer (B) are mixed before use. The base agent of the two-component type preferably does not substantially contain water, and the water content is preferably 5% by weight or less, and more preferably 1% by weight or less. From the viewpoint of workability, the one-component type is preferred.

[0103] The curable resin composition is formed into a desired shape by a method such as coating, casting, or filling before curing. The curable resin composition formed by coating, casting, or filling can be cured at room temperature or under heating. The heat curing conditions are not particularly limited, but a temperature of 60 to 220°C and a time of 1 to 120 minutes are preferable, and a temperature of 100 to 200°C and a time of 5 to 60 minutes are more preferable.

[0104] The curable resin composition according to the present disclosure can be used as an adhesive, a pressure sensitive adhesive, a sealant for sealing in buildings, ships, automobiles, buses, roads, home appliances, etc., a mold release agent, a paint, a spraying agent, etc. In addition, the cured product obtained by curing the curable resin composition can be suitably used as a waterproof material, a waterproof coating material, a vibration isolating material, a vibration damping material, a soundproofing material, a foam material, etc. EXAMPLES

[0105] The present invention will be explained in more detail below by way of examples, but the present invention is not limited to these examples.

[0106] The number average molecular weight in the examples is a GPC molecular weight measured under the following conditions. Liquid delivery system: Tosoh HLC-8220GPC Column: Tosoh TSK-GEL H type Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40℃

[0107] The terminal-converted molecular weight in the examples is a molecular weight calculated by determining the hydroxyl value according to the measurement method of JIS K 1557 and the iodine value according to the measurement method of JIS K 0070, taking into consideration the structure of the organic polymer (the degree of branching determined by the polymerization initiator used).

[0108] The average number of silyl groups introduced per terminal of the polymer (A) shown in the examples was calculated by NMR measurement.

[0109] (Synthesis Example 1) Using polyoxypropylene triol with a number average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (P-1) with a number average molecular weight of 24,600 (terminal group equivalent molecular weight 17,400) having hydroxyl groups at the ends and a molecular weight distribution Mw / Mn = 1.31. Sodium methoxide was added in an amount of 1.2 molar equivalents to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene (P-1) as a 28% methanol solution. After the methanol was distilled off by vacuum devolatilization, 1.5 molar equivalents of allyl chloride was added to the hydroxyl groups of the polymer (P-1) to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by devolatilization under reduced pressure. The obtained unpurified polyoxypropylene was mixed with n-hexane and water and stirred, after which the water was removed by centrifugation, and the metal salts in the polymer were removed by devolatilizing the hexane from the obtained hexane solution under reduced pressure. As a result, polyoxypropylene (Q-1) having allyl groups at its terminals was obtained. 500g of this polymer (Q-1) was mixed with 50μl of platinum divinyldisiloxane complex solution (3% by weight of platinum in isopropanol solution), and 6.4g of dimethoxymethylsilane was slowly added dropwise while stirring. After reacting for 2 hours at 100℃, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (A-1) having a number average molecular weight of 26,200 and dimethoxymethylsilyl groups at the terminals. It was found that polymer (A-1) had an average of 0.7 dimethoxymethylsilyl groups at one terminal and an average of 2.2 dimethoxymethylsilyl groups per molecule.

[0110] (Synthesis Example 2) 297.5 g of phenyltrimethoxysilane, 392.3 g of methyltrimethoxysilane, 94.3 g of water, and 0.4 g of a 10% LiBr aqueous solution were added at room temperature, and the mixture was heated and reacted for 6 hours under reflux of methanol to obtain a methanol solution of polysilsesquioxane polymer (B-1) having methoxysilyl groups and / or silanol groups and further having phenyl groups and methyl groups on silicon atoms and having a number average molecular weight of 900. The polymer (A-1) obtained in Synthesis Example 1 and the above methanol solution were mixed so that the solid content ratio of (A-1):(B-1) was 70:30, and the methanol was distilled off at 140°C to obtain a polymer mixture (AB-1).

[0111] Example 1 、2、5 ~7 , Reference Examples 3 and 4 and Comparative Examples 1 to 4) 100 parts by weight of the polymer mixture (AB-1) and 50 parts by weight of surface-treated gelatinous calcium carbonate (Shiraishi Kogyo Co., Ltd., product name: Hakuenka CCR) were mixed and thoroughly kneaded, and then passed through a small three-roll paint roll three times. After this, dehydration was carried out under reduced pressure at 120°C for 2 hours, and after cooling to below 50°C, 3 parts by weight of vinyltrimethoxysilane (Momentive Performance Materials, Inc., product name: Silquest A-171), 2 parts by weight of γ-(2-aminoethyl)aminopropyltrimethoxysilane (Momentive Performance Materials, Inc., product name: Silquest A-1120), and the curing catalyst and curing promoter shown in Table 1 were added and kneaded to obtain a curable composition.

[0112] Each Example 、Reference example The curing catalysts and curing promoters used in the comparative examples are as follows: Tin(II) octoate (Neostan U-28, manufactured by Nitto Chemical Industry Co., Ltd.) Dibutyltin dilaurate (Neostan U-100, manufactured by Nitto Chemical Industry Co., Ltd.) Dioctyltin dilaurate (Neostan U-810, manufactured by Nitto Kasei Kogyo Co., Ltd.) Neodecanoic acid (Versatic 10, Japan Epoxy Resin Co., Ltd.) Phenylguanidine solution (48% BBSA solution, manufactured by Nippon Carbide Industries Co., Ltd.) BBSA (Nn-butylbenzenesulfonamide, manufactured by Proviron) Reaction product of dioctyltin salt and ethyl orthosilicate (Neostan S-1, manufactured by Nitto Kasei Kogyo Co., Ltd.) Dibutyltin bisacetylacetonate (Neostan U-220H, manufactured by Nitto Chemical Industry Co., Ltd.) Dibutyltin bis(dodecyl mercaptide) (manufactured by Nitto Chemical Industry Co., Ltd.) Titanium ethyl acetoacetate (Orgatics TC-750, Matsumoto Fine Chemical Co., Ltd.) Laurylamine (Wako Pure Chemical Industries, Ltd.) 3-(Diethylamino)propylamine (DEAPA, Wako Pure Chemical Industries, Ltd.)

[0113] (curable) The time when each curable composition was spread with a spatula was set as the starting time, and the surface of the composition was confirmed by touching it with the spatula, and the time until the composition no longer stuck to the spatula (skin time) was measured. The results are shown in Table 1.

[0114] (Tensile properties) Each curable composition was cut into a 3 mm thick sheet specimen and placed at 23°C and 50% RH for 3 days, then in a 50°C dryer for 4 days to completely cure. After punching out a No. 3 dumbbell, a tensile test was performed at a tensile speed of 200 mm / min using an autograph made by Shimadzu Corporation to measure the breaking strength (TB). The results are shown in Table 1.

[0115] [Table 1]

[0116] As shown in Table 1, Example 1 contained a tin compound having a structure in which a carbonyloxy group is bonded to a tin atom, a carboxylic acid, or a compound having an amidine skeleton as a curing catalyst. 、2、5 ~7 , Reference Examples 3 and 4 It can be seen that, while the curing properties are relatively good, the strength of the cured product is higher than that of Comparative Examples 1 to 4, which contain a curing catalyst that does not correspond to the above-mentioned compounds.

[0117] Example 8 、Reference example 9 and Comparative Examples 5-6) As shown in Table 2, 100 parts by weight of polymer mixture (AB-1) or polyoxypropylene (A-1), 120 parts by weight of surface-treated gelatinous calcium carbonate (Shiraishi Kogyo Co., Ltd., product name: Hakuenka CCR), 20 parts by weight of titanium oxide (Ishihara Sangyo Kaisha, Ltd., product name: Typake R-820), 55 parts by weight of phthalate ester plasticizer (J-Plus Corporation, product name: DIDP), 2 parts by weight of thixotropic agent (Kusumoto Chemicals Co., Ltd., product name: Disparlon 6500), 1 part by weight of light stabilizer (Ciba Specialty Chemicals Co., Ltd., product name: Tinuvin 770), and 1 part by weight of ultraviolet absorber (Ciba Specialty Chemicals Co., Ltd., product name: Tinuvin 326) were mixed and thoroughly kneaded, and then passed through a small three-roll paint roll three times. This was followed by dehydration under reduced pressure at 120°C for 2 hours, and then cooling to below 50°C. After that, 2 parts by weight of vinyltrimethoxysilane (manufactured by Momentive Performance Materials, Inc., product name: Silquest A-171), 3 parts by weight of γ-(2-aminoethyl)aminopropyltrimethoxysilane (manufactured by Momentive Performance Materials, Inc., product name: Silquest A-1120) as an adhesion promoter, and the curing catalyst shown in Table 2 were added and kneaded to obtain a curable composition. The skinning time of each curable composition was measured in the same manner as above. The results are shown in Table 2.

[0118] [Table 2]

[0119] As shown in Table 2, Example 8 and Example 9, which contain polyoxypropylene having a methyldimethoxysilyl group and a polysilsesquioxane-based polymer, Reference example It can be seen that Comparative Example 9 has a shorter skinning time than Comparative Examples 5 and 6, which contain polyoxypropylene having a methyldimethoxysilyl group but no polysilsesquioxane polymer. In other words, it can be seen that the curing speed is improved by blending polyoxypropylene having a methyldimethoxysilyl group with a polysilsesquioxane polymer.

Claims

1. A polyoxyalkylene polymer (A) having a reactive silyl group represented by the following general formula (1): A polysilsesquioxane polymer (B) having an alkoxysilyl group and / or a silanol group, and further having an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms on a silicon atom; and The composition contains at least one curing catalyst (C) selected from the group consisting of a tin compound having a structure in which a carbonyloxy group is bonded to a tin atom and represented by the following general formula (8), a carboxylic acid, and a guanidine compound which is a compound having an amidine skeleton: The content of the polyoxyalkylene polymer (A) in the curable resin composition is 10 to 90% by weight. -Si(R １ )(X) ２ (1) (In the formula, R １ represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group. Each X independently represents a hydroxyl group or a hydrolyzable group. Sn(OCOR3)2(8) (In the formula, R 3 is the same or different and represents a substituted or unsubstituted, saturated or unsaturated hydrocarbon group.)

2. 2. The curable resin composition according to claim 1, wherein the content of the polyoxyalkylene polymer (H) having a reactive silyl group represented by the following general formula (1') is 0% by weight or more and less than 10% by weight. -Si(X') ３ (1') (In the formula, each X' independently represents a hydroxyl group or a hydrolyzable group.)

3. 3. The curable resin composition according to claim 1, wherein the proportion of the polysilsesquioxane polymer (B) is 1 to 60% by weight based on the total of the polyoxyalkylene polymer (A) and the polysilsesquioxane polymer (B).

4. The curable resin composition according to any one of claims 1 to 3, wherein the content of the curing catalyst (C) is 0.1 to 10 parts by weight based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the polysilsesquioxane polymer (B).

5. The curable resin composition according to any one of claims 1 to 4, wherein a molar ratio of the alkyl group to the aryl group (the alkyl group:the aryl group) in the polysilsesquioxane-based polymer (B) is 10:90 to 90:

10.

6. A sealant comprising the curable resin composition according to any one of claims 1 to 5.

7. An adhesive comprising the curable resin composition according to any one of claims 1 to 5.

8. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 5.

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