Curable resin composition and cured product thereof

Abstract

To provide a curable resin composition which can give a cured product showing high strength.SOLUTION: A curable resin composition contains a polyoxyalkylene-based polymer (A) having a reactive silyl group and a branch structure, and 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 12 carbon atoms on a silicon atom. The polyoxyalkylene-based polymer (A) may have the branch structure in a polymer skeleton, and may have the branch structure in a terminal structure.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] Although the physical properties after curing can be improved by blending a polysilsesquioxane-based polymer with an organic polymer having a reactive silyl group, further improvements in the physical properties are desired.

[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 can give a cured product exhibiting high strength. [Means for solving the problem]

[0008] The present inventors conducted intensive research to solve the above-mentioned problems and found that the problems can be solved by using in combination a polyoxyalkylene polymer having a reactive silyl group and a specific structure, 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 and a branched structure; and 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 12 carbon atoms on a silicon atom. Preferably, the polyoxyalkylene polymer (A) has the above-mentioned branched structure in the polymer skeleton. Preferably, the polyoxyalkylene polymer (A) has the branched structure in its terminal structure. The polyoxyalkylene polymer (A) preferably has a terminal structure represented by the general formula (3) described below. Preferably, the polyoxyalkylene polymer (A) has an average of 2.0 or more reactive silyl groups per molecule. 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 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. 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 and which can give a cured product exhibiting high strength. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, an embodiment of the present invention will be described in detail. 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 linear or branched. A linear polymer backbone can be formed by using an initiator having one or two hydroxyl groups in one molecule in a polymerization method for forming the polymer backbone, and a branched polymer backbone can be formed by using an initiator having three or more hydroxyl groups in one molecule.

[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] The polyoxyalkylene polymer (A) has a branched structure. By having the polyoxyalkylene polymer (A) have a branched structure, it is possible to enjoy the effect of improving the strength of the cured product by blending the polysilsesquioxane polymer (B). The branched structure may exist in the polymer skeleton of the polyoxyalkylene polymer (A) (when the polymer skeleton is the above-mentioned branched chain type), or may exist in the terminal structure of the polyoxyalkylene polymer (A). The branched structure in the terminal structure will be described later.

[0016] <Reactive silyl group> The polyoxyalkylene polymer (A) has a reactive silyl group, which is 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, and can be specifically represented by the following general formula (1). -Si(R 1 ) 3-a (X) a (1) In formula (1), R1 each independently 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. a is 1, 2, or 3.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] R 1Specific 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.

[0022] R 1 Suitable 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.

[0023] 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.

[0024] a is 1, 2, or 3. a is preferably 2 or 3.

[0025] Specific examples of the reactive silyl group include, but are not limited to, trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, 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, trimethoxysilyl group, triethoxysilyl group, and (methoxymethyl)dimethoxysilyl group are preferred because they can obtain a cured product with good mechanical properties. From the viewpoint of activity, trimethoxysilyl group, (chloromethyl)dimethoxysilyl group, and (methoxymethyl)dimethoxysilyl group are more preferred, and trimethoxysilyl group and (methoxymethyl)dimethoxysilyl group are particularly preferred. From the viewpoint of stability, dimethoxymethylsilyl group and triethoxysilyl group are more preferred, and dimethoxymethylsilyl group is particularly preferred.

[0026] 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. In particular, since the effect of improving the strength of the cured product by blending the polysilsesquioxane polymer (B) is excellent, the average number of reactive silyl groups per molecule of the polymer (A) is preferably 2.0 or more, more preferably 2.2 or more, and particularly preferably 2.5 or more. In addition, the upper limit of the average number is not particularly limited, but is preferably 6 or less, and 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.

[0027] In addition, the average ratio of the number of reactive silyl groups to the number of terminals of the polymer skeleton in one molecule of the polyoxyalkylene polymer (A) is not particularly limited, and may be 1.0 or less, or may be more than 1.0. Since the cured product can exhibit high strength, the average ratio is preferably more than 1.0, more preferably 1.1 or more, even more preferably 1.3 or more, and particularly preferably 1.5 or more. In addition, the upper limit of the average ratio is not particularly limited, but is preferably 5 or less, more preferably 3 or less. The numerical value of the average ratio can be calculated from the results of NMR measurement.

[0028] In the present specification, the average ratio of the number of reactive silyl groups to the number of polymer skeleton terminals refers to the number of reactive silyl groups contained on average per terminal structure of the polymer skeleton, and is expressed as the average number of reactive silyl groups in one polymer molecule / the number of polymer skeleton terminals in one polymer molecule. The number of polymer skeleton terminals in one polymer molecule is 2 when the polymer skeleton is entirely linear, and 3 or more when the polymer skeleton is entirely branched. In addition, when the polymer skeleton is a mixture of linear and branched chains, the number can be between 2 and 3.

[0029] In the polyoxyalkylene polymer (A), the terminal structure having a reactive silyl group is not particularly limited, but representative examples include terminal structures represented by the following general formula (2) or (3).

[0030] -OR 6 -CH(R 7 )-CH2-Si(R 1 ) 3-a (X) a (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 , X, and a are the same as described above for formula (1).

[0031] 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.

[0032] 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.

[0033] [ka]

[0034] In formula (3), R 8 R represents a direct bond or a divalent bonding group having 1 to 6 carbon atoms. 9 represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. n is an integer from 1 to 10. 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 , R 6 , R 7 , X, and a are the same as described above for formulas (1) and (2).

[0035] R 8 R may be a divalent organic group having 1 to 6 carbon atoms. The organic group is preferably a hydrocarbon group or a hydrocarbon group containing an oxygen atom. The number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2. 8 As the alkyl group, -CH2OCH2-, -CH2O- and -CH2- are preferable, and -CH2OCH2- is more preferable.

[0036] R 9is preferably hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, more preferably hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and even more preferably hydrogen or a hydrocarbon group having 1 to 2 carbon atoms. Particularly preferred is a hydrogen atom or a methyl group, and most preferably a hydrogen atom.

[0037] The terminal structure represented by general formula (3) shows an example of a branched structure in the above-mentioned terminal structure, and represents one terminal structure bonded to one end of the polymer skeleton. Although two or more reactive silyl groups are shown in formula (3), formula (3) does not show two or more ends, but shows that two or more reactive silyl groups are present in one terminal structure. In addition, formula (3) does not include the repeating units in the polymer skeleton, except for the oxygen at the left end. In other words, the n structures in parentheses present in formula (3) do not correspond to the repeating units in the polymer skeleton.

[0038] <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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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, 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.

[0043] <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.

[0044] (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).

[0045] The initiator having a hydroxyl group is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, low molecular weight polyoxypropylene triol, butanol, allyl alcohol, low molecular weight polyoxypropylene monoallyl ether, low molecular weight polyoxypropylene monoalkyl ether, etc. Among these, by using an initiator having three or more hydroxyl groups in one molecule, a polyoxyalkylene polymer having a branched polymer skeleton can be formed.

[0046] 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.

[0047] (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.

[0048] 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.

[0049] (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.

[0050] 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.

[0051] 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.

[0052] 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)

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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, and can be represented by the following general formula (8).

[0057] [ka]

[0058] In formula (8), R 8 and R 9 are the same as those described above for general formula (3), 8 and R 9 It is the same group as

[0059] Specific examples of the epoxy compound (E2) having a carbon-carbon unsaturated bond are not particularly limited, but allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and butadiene monoxide are preferred in terms of reaction activity, with allyl glycidyl ether being particularly preferred.

[0060] 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 epoxy compound (E2) is reacted, the organic halide (E1) having a carbon-carbon unsaturated bond can be reacted continuously. 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. When the reactive silyl group described below is introduced into the polyoxyalkylene polymer (F) having a carbon-carbon unsaturated bond in the terminal structure obtained by the method of using the epoxy compound (E2) and the organic halide (E1) in combination, the terminal structure represented by the general formula (3) can be formed.

[0061] (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.

[0062] Specific examples of the hydrosilane compound (G) having a reactive silyl group include halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, and bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, and diethoxymethysilane; silane, dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, bis(chloromethyl)methoxysilane, (methoxymethyl)methylmethoxysilane, (methoxymethyl)dimethoxysilane, bis(methoxymethyl)methoxysilane, (methoxymethyl)diethoxysilane, (ethoxymethyl)diethoxysilane, (3,3,3-trimethoxysilane, (fluoropropyl)dimethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, [(chloromethyl)dimethoxysilyloxy]dimethylsilane, [(chloromethyl)diethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(methoxymethyl)diethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilyloxy]dimethylsilane, [(3,3,3-trimethoxysilane], alkoxysilanes such as [fluoropropyl]dimethoxysilyloxy]dimethylsilane; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; ketoximate silanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane; and isopropenyloxysilanes (deacetone type) such as triisopropenyloxysilane, (chloromethyl)diisopropenyloxysilane, and (methoxymethyl)diisopropenyloxysilane.

[0063] 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.

[0064] <<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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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).

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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%).

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] <<Curing catalyst>> The curable resin composition according to the present disclosure preferably contains a curing catalyst for the purpose of promoting a reaction of hydrolysis and dehydration condensation of reactive silyl groups possessed by the polyoxyalkylene polymer (A) and the polysilsesquioxane polymer (B), i.e., a curing reaction.

[0091] As the curing catalyst, a conventionally known catalyst can be used, and specifically, an organic tin compound, a metal carboxylate, an amine compound, a carboxylic acid, an alkoxy metal, an inorganic acid, etc. can be used.

[0092] Specific examples of organic tin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), a reaction product of dibutyltin oxide and a silicate compound, a reaction product of dibutyltin oxide and a phthalic acid ester, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate), a reaction product of dioctyltin oxide and a silicate compound, etc. Dioctyltin compounds are preferred due to the increasing interest in the environment in recent years.

[0093] Specific examples of the metal carboxylate include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, cesium carboxylate, etc. The carboxylate group can be a combination of the following carboxylic acid with various metals.

[0094] Specific examples of the amine compound include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; amino group-containing silane coupling agents; and ketimine compounds.

[0095] Specific examples of carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

[0096] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate titanium tetrakis(acetylacetonate) and diisopropoxy titanium bis(ethylacetoacetate), aluminum compounds such as aluminum tris(acetylacetonate) and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis(acetylacetonate).

[0097] As other curing catalysts, fluorine anion-containing compounds, photoacid generators and photobase generators can also be used.

[0098] The curing catalyst may be a combination of two or more different catalysts. For example, the combination of the amine compound and a carboxylic acid or the amine compound and an alkoxy metal may provide an effect of improving reactivity.

[0099] From the viewpoint of achieving both an improvement in the curing reaction rate and workability during curing, the amount of the curing catalyst is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, and particularly preferably 0.1 to 10 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer (A) and the polysilsesquioxane polymer (B) in total.

[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 described in more detail below with reference to 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-8120GPC 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. 50 μl of platinum divinyldisiloxane complex solution (3% by weight of platinum in isopropanol solution) was added to 500 g of this polymer (Q-1), and 6.4 g of dimethoxymethylsilane was slowly added dropwise while stirring. After reacting at 100°C for 2 hours, 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 ends. It was found that polymer (A-1) had an average of 0.7 dimethoxymethylsilyl groups at one end and an average of 2.2 dimethoxymethylsilyl groups per molecule. Polymer (A-1) is a polymer with a branched structure in the polymer skeleton.

[0110] (Synthesis Example 2) 500 g of the polymer (Q-1) obtained in Synthesis Example 1 was mixed with 50 μl of a platinum divinyldisiloxane complex solution (a 3% by weight platinum solution in isopropanol), and 6.9 g of trimethoxysilane was slowly added dropwise while stirring. After reacting at 100° C. for 2 hours, unreacted trimethoxysilane was distilled off under reduced pressure to obtain polyoxypropylene (A-2) having a number average molecular weight of 26,200 and trimethoxysilyl groups at the ends. It was found that the polymer (A-2) had an average of 0.7 trimethoxysilyl groups at one end and an average of 2.0 trimethoxysilyl groups per molecule. The polymer (A-2) is a polymer having a branched structure in the polymer skeleton.

[0111] (Synthesis Example 3) Using polyoxypropylene glycol with a number average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized with zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (P-3) with hydroxyl groups at both ends, a number average molecular weight of 27,900 (terminal group equivalent molecular weight 17,700), and a molecular weight distribution Mw / Mn = 1.21. Next, 1.0 molar equivalent of sodium methoxide was added to the hydroxyl groups of this hydroxyl-terminated polyoxypropylene (P-3) as a 28% methanol solution. After distilling off the methanol by vacuum devolatilization, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl groups of the polymer (P-3) and reacted at 130°C for 2 hours. Then, 0.28 molar equivalent of a methanol solution of sodium methoxide was added to remove methanol, and 1.79 molar equivalent of allyl chloride was added to convert the terminal hydroxyl groups to allyl groups. The obtained unpurified polyoxypropylene was mixed and stirred with n-hexane and water, and then the water was removed by centrifugation. 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-3) having multiple carbon-carbon unsaturated bonds at the terminals was obtained. It was found that the polymer (Q-3) had an average of 2.0 carbon-carbon unsaturated bonds introduced at one terminal. 50 μl of platinum divinyldisiloxane complex solution (isopropanol solution containing 3% by weight of platinum) was added to 500 g of the obtained (Q-3), and 9.6 g of dimethoxymethylsilane was slowly added dropwise while stirring. The mixed solution was reacted at 100° C. for 2 hours, and the unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (A-3) having a number average molecular weight of 28,500 and multiple dimethoxymethylsilyl groups at the terminals. It was found that the polymer (A-3) had an average of 1.7 dimethoxymethylsilyl groups at one terminal and an average of 3.4 dimethoxymethylsilyl groups in one molecule. The polymer (A-3) has a terminal structure represented by the general formula (3) and is a polymer having a branched structure in the terminal structure.

[0112] (Synthesis Example 4) Sodium methoxide was added as a 28% methanol solution in an amount of 1.2 molar equivalents to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene (P-3) obtained in Synthesis Example 3. 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-3) to convert the terminal hydroxyl groups to allyl groups, and the 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-4) having allyl groups at its terminals was obtained. 50 μl of platinum divinyldisiloxane complex solution (3% by weight of platinum in isopropanol solution) was added to 500 g of this polymer (Q-4), and 3.8 g of dimethoxymethylsilane was slowly added dropwise while stirring. The mixed solution was reacted at 100°C for 2 hours, and then unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (A-4) having a number average molecular weight of about 28,500 and dimethoxymethylsilyl groups at the terminals. It was found that polymer (A-4) had an average of 0.6 dimethoxymethylsilyl groups at one terminal and an average of 1.2 dimethoxymethylsilyl groups per molecule. Polymer (A-4) is a polymer without a branched structure.

[0113] (Synthesis Example 5) 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 polymers (A-1) to (A-4) obtained in Synthesis Examples 1 to 4 were mixed with the methanol solution so that the solid content ratio (weight ratio) of the polymers (A-1) to (A-4):(B-1) was 70:30 as shown in Table 1, and the methanol was distilled off at 140°C to obtain polymer mixtures (AB-1) to (AB-4).

[0114] [Table 1]

[0115] (Examples 1 to 3 and Comparative Examples 1 to 5) As shown in Table 2, 100 parts by weight of polymer mixture (AB-1) to (AB-4) or polyoxypropylene (A-1) to (A-4) and 50 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., product name: Hakuenka CCR) were mixed and thoroughly kneaded, and then passed through a small triple paint roll three times. After this, dehydration was carried out under reduced pressure at 120°C for 2 hours, and then cooled to below 50°C. After that, 3 parts by weight of vinyltrimethoxysilane (manufactured by Momentive Performance Materials, Inc., product name: Silquest A-171), 2 parts by weight of γ-(2-aminoethyl)aminopropyltrimethoxysilane (manufactured by Momentive Performance Materials, Inc., product name: Silquest A-1120) as an adhesion promoter, and 0.2 parts by weight of dibutyltin bisacetylacetonate (manufactured by Nitto Kasei Kogyo Co., Ltd., product name: Neostan U-220H) or 1.5 parts by weight of tin(II) octylate (manufactured by Nitto Kasei Kogyo Co., Ltd., product name: Neostan U-28) and 0.25 parts by weight of laurylamine (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing catalyst were added and kneaded to obtain a curable composition.

[0116] (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, and then placed 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 manufactured by Shimadzu Corporation to measure the breaking strength (TB). The "breaking strength increase rate due to component (B)" was calculated by multiplying the breaking strength of Examples 1 to 3 and Comparative Example 1 using the polymer mixtures (AB-1) to (AB-4) by the breaking strength of Comparative Examples 2 to 5 using the corresponding polymers (A-1) to (A-4), and multiplying the result by 100.

[0117] [Table 2]

[0118] From Table 2, it can be seen that in Examples 1 to 3, which contain polyoxypropylene having a branched structure and a polysilsesquioxane-based polymer, the breaking strength of the cured product is large, and the rate of increase in breaking strength is high compared to Comparative Examples 2 to 4, which contain the same polyoxypropylene but do not contain a polysilsesquioxane-based polymer. On the other hand, it can be seen that in Comparative Example 1, which contains polyoxypropylene and a polysilsesquioxane-based polymer without a branched structure, the breaking strength is smaller than that of Comparative Example 5, which does not contain a polysilsesquioxane-based polymer.

Claims

1. A polyoxyalkylene polymer (A) having a reactive silyl group and a branched structure, and The composition contains a polysilsesquioxane-based 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 12 carbon atoms on a silicon atom, The polyoxyalkylene polymer (A) has an average of 2.0 or more reactive silyl groups per molecule of the curable resin composition.

2. A polyoxyalkylene polymer (A) having a reactive silyl group and a branched structure, and The composition contains a polysilsesquioxane-based 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 12 carbon atoms on a silicon atom, The curable resin composition, wherein the polyoxyalkylene polymer (A) has the above-mentioned branched structure in its terminal structure and has a terminal structure represented by general formula (3). 【Chemistry 1】 (In the formula, R １ Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group. Each independently represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. 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. ８ represents a direct bond or a divalent linking group having 1 to 6 carbon atoms. ９ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms; and n is an integer from 1 to 10.

3. The curable resin composition according to claim 1 , wherein the polyoxyalkylene polymer (A) has the branched structure in a terminal structure.

4. The curable resin composition according to claim 3 , wherein the polyoxyalkylene polymer (A) has a terminal structure represented by general formula (3). 【Chemistry 2】 (In the formula, R １ Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group. Each independently represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3. 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. ８ represents a direct bond or a divalent linking group having 1 to 6 carbon atoms. ９ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms; and n is an integer from 1 to 10.

5. The curable resin composition according to any one of claims 1 to 4, wherein the proportion of the polysilsesquioxane polymer (B) is 1 to 60% by weight based on the total weight of the polyoxyalkylene polymer (A) and the polysilsesquioxane polymer (B).

6. The curable resin composition according to any one of claims 1 to 5, 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.

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

8. An adhesive comprising the curable resin composition according to any one of claims 1 to 6.

9. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 6.

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