Curable composition, cured product, and method for producing curable composition

Abstract

To provide a curable composition from which a cured product having good tensile strength and excellent tear strength is obtained, a cured product of the curable composition, and a method for producing the cured composition.SOLUTION: A curable composition comprising a polymer A and a polymer B, wherein the polymer A has two or more terminal groups in one molecule, and the terminal groups do not have a divalent organic group represented by - C (= O) NH - and have at least one group selected from the group consisting of a reactive silicon group, an unsaturated group, and a hydroxyl group, the polymer A is an oxyalkylene polymer having a silylation ratio of 85 to 100 mol%, and the polymer B is an oxyalkylene polymer having two or more terminal groups per molecule, the terminal groups each having at least one group selected from the group consisting of a reactive silicon group, an unsaturated group, and a hydroxy group, the average total number of reactive silicon groups, unsaturated groups, and hydroxy groups per terminal group being more than 1.0, and the silylation ratio of the polymer B being smaller than the silylation ratio of the polymer A.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable composition, a cured product, and a method for producing the curable composition. [Background technology]

[0002] Polymers containing at least one reactive silicon group per molecule are known to crosslink through the formation of siloxane bonds accompanied by hydrolysis of the reactive silicon group due to moisture, etc., even at room temperature, resulting in the formation of rubber-like cured products.

[0003] Among these polymers having reactive silicon groups, those whose main chain skeletons are oxyalkylene polymers, saturated hydrocarbon polymers, alkyl acrylate polymers, and alkyl methacrylate polymers have already been industrially produced and are widely used in applications such as sealants, adhesives, and paints. When using curable compositions containing these polymers having reactive silicon groups for the above applications, the cured products are required to have excellent tear strength and tensile strength. Cured products with good tensile strength are less likely to break.

[0004] Patent Document 1 discloses a curable composition containing polyoxypropylene having an average of 1.6 dimethoxymethylsilyl groups at each terminal and an average of 3.2 dimethoxymethylsilyl groups per molecule, with a number-average molecular weight of 15,300, and polyoxypropylene having an average of 0.8 dimethoxymethylsilyl groups at each terminal and an average of 1.6 dimethoxymethylsilyl groups per molecule, with a number-average molecular weight of 14,600. It is disclosed that the cured product of the curable composition has excellent tear strength. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 6096320 Summary of the Invention [Problem to be solved by the invention]

[0006] The tear strength of the cured product of the curable composition described in Patent Document 1 is insufficient. When a curable composition containing a polymer having a reactive silicon group is used for the above-mentioned applications, tensile strength is required in addition to tear strength. On the other hand, the tensile strength of the cured product of the curable composition described in Patent Document 1 is insufficient.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a curable composition that can give a cured product having good tensile strength and excellent tear strength, a cured product of the curable composition, and a method for producing the cured composition. [Means for solving the problem]

[0008] The present invention includes the following [1] to

[10] . [1] A curable composition comprising a polymer A and a polymer B, wherein the polymer A is an oxyalkylene polymer having two or more terminal groups per molecule, the terminal groups having no divalent organic group represented by -C(=O)NH-, and at least one group selected from the group consisting of a reactive silicon group represented by the following formula 1, an unsaturated group, and a hydroxyl group, and a silylation rate calculated by the following formula f1 is 85 to 100 mol %; and the polymer B is an oxyalkylene polymer having two or more terminal groups per molecule, the terminal groups having at least one group selected from the group consisting of a reactive silicon group represented by the following formula 1, an unsaturated group, and a hydroxyl group, and the average total number of the reactive silicon groups, the unsaturated groups, and the hydroxyl groups per terminal group is greater than 1.0, and the silylation rate calculated by the following formula f1 is lower than that of the polymer A. -SiR a X 3-a formula 1 In the formula 1, R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, X represents a hydroxyl group or a hydrolyzable group, and a is an integer of 0 to 2. When a is 2, R may be the same or different from each other, and when a is 0 or 1, X may be the same or different from each other. The reactive silicon group of the polymer A and the reactive silicon group of the polymer B may be the same or different from each other.

number

[10] The method for producing a curable composition according to [9], wherein the amount of the silylating agent added is 0.90 times or more by mole relative to the total amount of unsaturated groups in the unsaturated group-containing oxyalkylene polymer. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a curable composition that can give a cured product having good tensile strength and excellent tear strength, a cured product of the curable composition, and a method for producing the cured composition. DETAILED DESCRIPTION OF THE INVENTION

[0010] The meanings and definitions of terms used in this specification are as follows: A numerical range expressed by "to" means that the numerical values ​​before and after "to" are the lower and upper limits of the numerical range. The "unit" constituting the oxyalkylene polymer means an atomic group formed directly by polymerization of the alkylene oxide monomer. The oxyalkylene polymer is a polymer consisting of a main chain containing a polyoxyalkylene chain and terminal groups. The "main chain" in the oxyalkylene polymer means a residue obtained by removing active hydrogen from an initiator and a portion containing repeating units based on alkylene oxide (polyoxyalkylene chain). The "end group" of an oxyalkylene polymer refers to an atomic group containing the oxygen atom in the polyoxyalkylene chain that is closest to the molecular end. However, if the atomic group contains a residue of an initiator, it is not considered to be an end group but is considered to be part of the main chain. The "active hydrogen-containing group" refers to at least one group selected from the group consisting of a hydroxyl group bonded to a carbon atom, a carboxyl group, an amino group, a monovalent functional group obtained by removing one hydrogen atom from a primary amine, a hydrazide group, and a sulfanyl group. The term "active hydrogen" refers to a hydrogen atom derived from the active hydrogen-containing group and a hydrogen atom derived from the hydroxyl group of water. The term "unsaturated group" refers to a carbon-carbon double bond or a carbon-carbon triple bond. The carbon-carbon double bond and the carbon-carbon triple bond may be located at or outside the molecular terminals.

[0011] The "number of terminal groups" in the oxyalkylene polymer is the same as the number of active hydrogen atoms in the initiator, which will be described later. The "degree of unsaturation" can be measured in accordance with the unsaturation measurement method (Wijs method). The degree of unsaturation indicates the proportion of carbon-carbon double bonds or carbon-carbon triple bonds in the polymer.

[0012] The number average molecular weight (Mn) and weight average molecular weight (Mw) are polystyrene-equivalent molecular weights measured using GPC with tetrahydrofuran as the eluent and a calibration curve prepared using polystyrene polymers of known molecular weight. The molecular weight distribution (Mw / Mn) is the ratio of Mw to Mn.

[0013] The silylation rate can be measured by NMR analysis. The term "silylating agent" refers to a compound having a functional group that reacts with an unsaturated group and a reactive silicon group.

[0014] ≪Curable composition≫ The curable composition of this embodiment includes polymer A and polymer B. Polymer A is an oxyalkylene polymer having two or more terminal groups per molecule, which terminal groups do not contain a divalent organic group represented by -C(=O)NH-, but contain at least one group selected from the group consisting of a reactive silicon group represented by formula 1 below, an unsaturated group, and a hydroxyl group, and the silylation rate calculated by formula f1 below is 85 to 100 mol%. Polymer B is an oxyalkylene polymer having two or more terminal groups per molecule, which terminal groups contain at least one group selected from the group consisting of a reactive silicon group represented by formula 1 below, an unsaturated group, and a hydroxyl group, the average total number of the reactive silicon groups, unsaturated groups, and hydroxyl groups per terminal group exceeds 1.0, and the silylation rate calculated by formula f1 below is lower than the silylation rate of polymer A.

[0015] (reactive silicon group) The reactive silicon group has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can form a siloxane bond to crosslink. The reaction to form the siloxane bond is accelerated by a curing catalyst. The reactive silicon group in Polymer A and Polymer B is represented by the following formula 1: -SiR a X 3-a formula 1

[0016] In the above formula 1, R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group. R is preferably at least one group selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms and triorganosiloxy groups.

[0017] R is preferably at least one group selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, an α-chloroalkyl group, and a triorganosiloxy group. It is more preferably at least one group selected from the group consisting of a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, an α-chloromethyl group, a trimethylsiloxy group, a triethylsiloxy group, and a triphenylsiloxy group. A methyl group or an ethyl group is preferred in view of the good curability and stability of the curable composition containing polymer A and polymer B. An α-chloromethyl group is preferred in view of the fast curing rate of the cured product. A methyl group is particularly preferred in view of its easy availability.

[0018] In the above formula 1, X represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a sulfanyl group, and an alkenyloxy group. An alkoxy group is preferred because it is mildly hydrolyzable and easy to handle. The alkoxy group is preferably a methoxy group, an ethoxy group, or an isopropoxy group, and more preferably a methoxy group or an ethoxy group. When the alkoxy group is a methoxy group or an ethoxy group, it is easy to rapidly form a siloxane bond and form a crosslinked structure in the cured product, and the physical properties of the cured product tend to be good.

[0019] In the above formula 1, a is an integer of 0 to 2. When a is 2, R may be the same or different from each other. When a is 1 or less, X may be the same or different from each other. If the crosslinking density due to siloxane bonds is low, the modulus of the cured product will decrease, so a is preferably 2 or less, and more preferably 1 or less.

[0020] Examples of the reactive silicon group represented by the above formula 1 include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a methyldiisopropoxysilyl group, an (α-chloromethyl)dimethoxysilyl group, and an (α-chloromethyl)diethoxysilyl group. In terms of high activity and good curability, a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group, and a diethoxymethylsilyl group are preferred, and a dimethoxymethylsilyl group is more preferred.

[0021] The reactive silicon group in polymer A and the reactive silicon group in polymer B may be the same or different. When polymer A has multiple reactive silicon groups, the multiple reactive silicon groups may be the same or different. When polymer B has multiple reactive silicon groups, the multiple reactive silicon groups may be the same or different.

[0022] The reactive silicon group contained in polymer A is preferably a reactive silicon group represented by the following formula 3. In one embodiment, the reactive silicon group contained in polymer B is preferably a reactive silicon group represented by the following formula 3. -OR 11 -SiR 12 a2 X 2 3-a2 formula 3

[0023] R 12 , X 2 , a2 are the same as R, X, and a in the above formula 1, respectively. R 11 is a linear alkylene group having 1 to 20 carbon atoms. 11 The number of carbon atoms in R is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. 11 When is a linear alkylene group, the curing rate of the curable composition containing polymer A and polymer B is likely to be improved. Furthermore, when the number of carbon atoms is within the above range, the curing rate is likely to be further improved.

[0024] <Polymer A> Polymer A is an oxyalkylene polymer having two or more terminal groups per molecule, the terminal groups not containing a divalent organic group represented by -C(=O)NH-, but containing at least one group selected from the group consisting of a reactive silicon group represented by formula 1 above, an unsaturated group, and a hydroxyl group, and having a silylation rate calculated by formula f1 below of 85 to 100 mol%.

[0025]

number

[0026] Polymer A is a polymer consisting of a main chain and terminal groups. The main chain of polymer A contains a residue obtained by removing active hydrogen from the initiator and a polyoxyalkylene chain composed of one or more repeating units based on alkylene oxide (hereinafter, repeating units based on alkylene oxide will be simply referred to as "alkylene oxide units"). The main chain of polymer A preferably comprises a residue obtained by removing active hydrogen from the initiator and a polyoxyalkylene chain composed of one or more alkylene oxide units.

[0027] When the polyoxyalkylene chain has two or more types of alkylene oxide units, these alkylene oxide units may form a block chain or a random copolymer chain.

[0028] Examples of polyoxyalkylene chains include polymer chains having ethylene oxide units, polymer chains having propylene oxide units, polymer chains having ethylene oxide units and propylene oxide units, polymer chains consisting of ethylene oxide units, polymer chains consisting of propylene oxide units, polymer chains consisting of butylene oxide units, polymer chains consisting of tetramethylene oxide units, polymer chains consisting of ethylene oxide units and propylene oxide units, and polymer chains consisting of propylene oxide units and butylene oxide units. Polymer chains having ethylene oxide units, polymer chains having propylene oxide units, polymer chains having ethylene oxide units and propylene oxide units, polymer chains consisting of propylene oxide units, and polymer chains consisting of ethylene oxide units and propylene oxide units are preferred, with polymer chains consisting of propylene oxide units being particularly preferred. Furthermore, when polymer A has a polymer chain containing ethylene oxide units, the content of ethylene oxide units relative to the total mass of polymer A is preferably 0.1 to 30 mass%, more preferably 10 to 20 mass%. When the content of ethylene oxide units in polymer A is equal to or greater than the above lower limit, it is preferred in that the curing rate is faster, and when it is equal to or less than the above upper limit, it is preferred in that the viscosity can be easily reduced. When polymer A has a polymer chain containing ethylene oxide units and propylene oxide units, or a polymer chain consisting of ethylene oxide units and propylene oxide units, the content of ethylene oxide units relative to the total mass of polymer A is preferably 0.1 to 30 mass%, more preferably 10 to 20 mass%. When the content of ethylene oxide units in polymer A is equal to or greater than the lower limit, it is preferred in that the curing rate is faster, and when it is equal to or less than the upper limit, it is preferred in that the viscosity can be easily reduced. When polymer A has a polymer chain containing ethylene oxide units and propylene oxide units, the content of propylene oxide units relative to the total mass of polymer A is preferably 50 to 99.9 mass%, more preferably 70 to 90 mass%.

[0029] Polymer A has two or more terminal groups per molecule. The number of terminal groups is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 4, since this results in a cured product with higher tensile strength and better modulus and elongation. The terminal groups of polymer A have at least one group selected from the group consisting of a reactive silicon group, an unsaturated group, and a hydroxyl group, as represented by the above formula 1. The respective terminal groups may be the same or different.

[0030] The silylation rate of polymer A is 85 to 100 mol%, more preferably 88 to 100 mol%, and even more preferably 90 to 100 mol%. When the silylation rate is equal to or higher than the lower limit, a cured product having good tensile strength and excellent tear strength is likely to be obtained.

[0031] The terminal group of polymer A may have a plurality of reactive silicon groups or a plurality of unsaturated groups, or may have both a reactive silicon group and an unsaturated group.

[0032] When the terminal groups of polymer A have a plurality of reactive silicon groups, at least one of the terminal groups preferably has a group represented by the following formula 2, and at least one of the terminal groups is preferably a group represented by the following formula 2:

[0033] [ka]

[0034] In the above formula 2, R 2 , R 3 each independently represents a divalent organic group having 1 to 6 carbon atoms and no carbon-carbon unsaturated bond. The organic group may contain a heteroatom. Examples of the heteroatom include an oxygen atom, a nitrogen atom, and a sulfur atom.

[0035] R 2 , R 3 Examples include -CH2-, -C2H4-, -C3H6-, -C4H8-, and -C5H 10 -, -C6H 12Examples include -, -C(CH3)2-, -CH2O-, -CH2-O-CH2-, -CH2-O-CH2-O-CH2-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CH=N-, and -CH=NN=CH-. R 2 is preferably —CH2—O—CH2—, —CH2O—, or —CH2—, and more preferably —CH2—O—CH2—. R 3 is preferably —CH2— or —C2H4—, and more preferably —CH2—.

[0036] R in the above formula 2 4 , R 5 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. Examples of the straight-chain alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples of branched alkyl groups include an isopropyl group, an s-butyl group, a t-butyl group, a 2-methylbutyl group, a 2-ethylbutyl group, a 2-propylbutyl group, a 3-methylbutyl group, a 3-ethylbutyl group, a 3-propylbutyl group, a 2-methylpentyl group, a 2-ethylpentyl group, a 2-propylpentyl group, a 3-methylpentyl group, a 3-ethylpentyl group, a 3-propylpentyl group, a 4-methylpentyl group, a 4-ethylpentyl group, a 4-propylpentyl group, a 2-methylhexyl group, a 2-ethylhexyl group, a 2-propylhexyl group, a 3-methylhexyl group, a 3-ethylhexyl group, a 3-propylhexyl group, a 4-methylhexyl group, a 4-ethylhexyl group, a 4-propylhexyl group, a 5-methylhexyl group, a 5-ethylhexyl group, and a 5-propylhexyl group. R 4 , R 5 are each independently preferably a hydrogen atom, a methyl group, or an ethyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0037] In the above formula 2, n represents an integer of 1 to 10, preferably 1 to 7, more preferably 1 to 5, and even more preferably 1.

[0038] R 1 , X 1 , a1 are the same as R, X, and a in formula 1 above, respectively.

[0039] The average number of reactive silicon groups per terminal group of polymer A is preferably 0.85 to 3.80, more preferably 0.88 to 3.00, and even more preferably 0.90 to 1.00. When the average number is equal to or greater than the above lower limit, a cured product having good tensile strength and excellent tear strength is likely to be obtained.

[0040] The average number of unsaturated groups per terminal group of the polymer A is preferably from 0 to 0.30, more preferably from 0.03 to 0.20, and even more preferably from 0.05 to 0.15. The average number of hydroxyl groups per terminal group of polymer A is preferably 0.10 or less, more preferably 0.05 or less, and even more preferably 0.

[0041] The average number of reactive silicon groups per molecule of polymer A is preferably 1.70 to 8.00, more preferably 1.75 to 6.00, and even more preferably 1.80 to 3.00. When the average number is equal to or greater than the above lower limit, a cured product having good tensile strength and excellent tear strength is likely to be obtained.

[0042] The average number of unsaturated groups per molecule of polymer A is preferably from 0 to 1.80, more preferably from 0 to 1.20, still more preferably from 0 to 0.90, and particularly preferably from 0.10 to 0.30. The average number of hydroxyl groups per molecule of polymer A is preferably 0.60 or less, more preferably 0.30 or less, and even more preferably 0.

[0043] The Mn of polymer A is preferably 5,000 to 100,000, more preferably 10,000 to 80,000, even more preferably 15,000 to 60,000, and particularly preferably 25,000 to 60,000. When it is equal to or greater than the lower limit, the elongation properties of the cured product are improved. When it is equal to or less than the upper limit, the viscosity is low and workability is improved.

[0044] The molecular weight distribution of polymer A is preferably 1.80 or less. A smaller molecular weight distribution is preferable, more preferably 1.00 to 1.60, even more preferably 1.02 to 1.50, and particularly preferably 1.04 to 1.40, because good elongation properties are easily obtained and the viscosity is reduced, resulting in good workability.

[0045] The viscosity of polymer A at 25° C. is preferably from 1 to 50 Pa·s, more preferably from 1 to 40 Pa·s, and even more preferably from 1 to 30 Pa·s.

[0046] <Polymer B> Polymer B is an oxyalkylene polymer having two or more terminal groups per molecule, the terminal groups having at least one group selected from the group consisting of a reactive silicon group represented by formula 1 above, an unsaturated group, and a hydroxyl group, the average total number of the reactive silicon groups, the unsaturated groups, and the hydroxyl groups per terminal group being greater than 1.0, and the silylation rate calculated by formula f1 above being lower than the silylation rate of polymer A.

[0047] Polymer B is a polymer consisting of a main chain and terminal groups. The main chain of polymer B contains a residue obtained by removing active hydrogen from the initiator and a polyoxyalkylene chain composed of one or more types of alkylene oxide units. The main chain of polymer B preferably contains a residue obtained by removing active hydrogen from the initiator and a polyoxyalkylene chain composed of one or more types of alkylene oxide units. The polyoxyalkylene chain is the same as the example of polymer A.

[0048] Polymer B has two or more terminal groups per molecule. The number of terminal groups is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 4, since this results in a cured product with higher tensile strength and better modulus and elongation. The terminal groups of polymer B have at least one group selected from the group consisting of a reactive silicon group represented by formula 1 above, an unsaturated group, and a hydroxyl group. The respective terminal groups may be the same or different. It is preferable that the terminal groups of polymer B do not have a divalent organic group represented by -C(=O)NH-.

[0049] The silylation rate of polymer B is lower than that of polymer A. The silylation rate of polymer B is preferably less than 85 mol%, more preferably 50 mol% or more but less than 85 mol%, and even more preferably 70 mol% or more but less than 85 mol%. When the silylation rate is less than the above upper limit, a cured product having good tensile strength and excellent tear strength is likely to be obtained.

[0050] The ratio of the silylation rate of polymer A to the silylation rate of polymer B is preferably from 1.05 to 1.50, more preferably from 1.10 to 1.40, and even more preferably from 1.20 to 1.30.

[0051] The terminal group of polymer B may have a plurality of reactive silicon groups or a plurality of unsaturated groups, or may have both a reactive silicon group and an unsaturated group.

[0052] The average total number of reactive silicon groups, unsaturated groups, and hydroxyl groups per terminal group exceeds 1.0, preferably 1.0 to 2.0, more preferably 1.4 to 2.0, and even more preferably 1.6 to 2.0.

[0053] At least one of the terminal groups of polymer B preferably has a group represented by formula 2 above, and at least one of the terminal groups is preferably a group represented by formula 2 above. When at least one of the terminal groups of polymer B has a group represented by formula 2 above, the ratio of the number of terminal groups having the group represented by formula 2 above to the total number of terminal groups of polymer B is preferably 0.4 or more, more preferably 0.5 or more, and even more preferably 0.6 or more.

[0054] The average number of reactive silicon groups per terminal group of polymer B is preferably 0.85 to 1.70, more preferably 0.90 to 1.65, and even more preferably 1.00 to 1.60. When the average number is equal to or greater than the above lower limit, a cured product having good tensile strength and excellent tear strength is likely to be obtained.

[0055] The ratio of the average number of reactive silicon groups per terminal group of polymer A to the average number of reactive silicon groups per terminal group of polymer B is preferably 0.5 to 1.0, more preferably 0.5 to 0.8, and even more preferably 0.5 to 0.7.

[0056] The average number of unsaturated groups per terminal group of polymer B is preferably from 0.05 to 1.00, more preferably from 0.03 to 0.50, and even more preferably from 0 to 0.30. The average number of hydroxyl groups per terminal group of polymer B is preferably 0.20 or less, more preferably 0.10 or less, and even more preferably 0.

[0057] The average number of reactive silicon groups per molecule of polymer B is preferably 2.00 to 3.40, more preferably 2.00 to 3.30, and even more preferably 2.00 to 3.20. When the average number is equal to or greater than the above lower limit, a cured product having good tensile strength and excellent tear strength is likely to be obtained.

[0058] The ratio of the average number of reactive silicon groups per molecule of polymer A to the average number of reactive silicon groups per molecule of polymer B is preferably from 0.5 to 5.0, more preferably from 0.5 to 4.0, and even more preferably from 0.5 to 3.0.

[0059] The average number of unsaturated groups per molecule of polymer B is preferably from 0.10 to 2.00, more preferably from 0.06 to 1.00, and even more preferably from 0 to 0.60. The average number of hydroxyl groups per molecule of polymer B is preferably 0.40 or less, more preferably 0.20 or less, and even more preferably 0.

[0060] The Mn of polymer B is preferably 3,000 to 50,000, more preferably 5,000 to 30,000, even more preferably 7,500 to 25,000, and particularly preferably 10,000 to 25,000. When it is equal to or greater than the lower limit, the elongation properties of the cured product are improved. When it is equal to or less than the upper limit, the viscosity is low and workability is improved.

[0061] The ratio of Mn of polymer A to Mn of polymer B is preferably from 0.5 to 4.0, more preferably from 0.5 to 3.0, and even more preferably from 0.5 to 2.5.

[0062] The molecular weight distribution of polymer B is preferably 1.80 or less. A smaller molecular weight distribution is preferable, more preferably 1.00 to 1.60, even more preferably 1.02 to 1.50, and particularly preferably 1.04 to 1.40, because good elongation properties are easily obtained and the viscosity is reduced, resulting in good workability.

[0063] The viscosity of Polymer B at 25° C. is preferably from 1 to 50 Pa·s, more preferably from 1 to 40 Pa·s, and even more preferably from 1 to 30 Pa·s.

[0064] <Methods of producing polymer A and polymer B> The method for producing polymer A and polymer B includes reacting an unsaturated group-containing oxyalkylene polymer having an unsaturated group at a molecular terminal (hereinafter simply referred to as "unsaturated group-containing oxyalkylene polymer") with a silylating agent. The unsaturated group-containing oxyalkylene polymer can be produced by converting the hydroxyl groups of an oxyalkylene polymer having a terminal hydroxyl group into a group having an unsaturated group at the molecular terminal.

[0065] (Method for producing an oxyalkylene polymer having a hydroxyl terminal group) An oxyalkylene polymer having a hydroxyl group as a terminal group can be produced by polymerizing an alkylene oxide with an initiator having active hydrogen in the presence of a ring-opening polymerization catalyst.

[0066] The initiator has active hydrogen. The number of active hydrogens contained in the initiator is preferably 2 or more, more preferably 2 to 8, still more preferably 2 to 6, and particularly preferably 2 to 4. The number of active hydrogens contained in the initiator is the same as the number of terminal groups of polymer A and polymer B. Therefore, the initiator may be selected according to the number of terminal groups of polymer A and polymer B. The initiator may be used alone or in combination of two or more kinds.

[0067] The initiator preferably has a hydroxyl group as the active hydrogen-containing group. Examples of initiators having two hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, and low-molecular-weight polyoxypropylene glycol. Examples of initiators having three hydroxyl groups include glycerin, trimethylolpropane, trimethylolethane, and low-molecular-weight polyoxypropylenetriol. Examples of initiators having four or more hydroxyl groups include pentaerythritol, sucrose, sorbitol, dipentaerythritol, trehalose, and diglycerin. Alternatively, a low molecular weight polymer obtained by polymerizing an alkylene oxide with the above initiator in the presence of an alkali metal hydroxide may be used as the initiator.

[0068] The alkylene oxide is selected depending on the constituent units of the polyoxyalkylene chains of the polymer A and the polymer B. Examples of alkylene oxides include ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide, of which ethylene oxide and propylene oxide are preferred, and propylene oxide is more preferred.

[0069] Examples of the ring-opening polymerization catalyst include composite metal cyanide complexes and alkali metal hydroxides (such as potassium hydroxide). The use of a composite metal cyanide complex is preferred in that the molecular weight distribution of an oxyalkylene polymer having a hydroxyl terminal group is likely to be narrow, and the total degree of unsaturation of an oxyalkylene polymer having a hydroxyl terminal group is likely to be low. The composite metal cyanide complex may be a known compound, such as those disclosed in International Publication No. 2003 / 062301, International Publication No. 2004 / 067633, Japanese Patent Application Laid-Open No. 2004-269776, Japanese Patent Application Laid-Open No. 2005-15786, International Publication No. 2013 / 065802, or Japanese Patent Application Laid-Open No. 2015-010162. The composite metal cyanide complex is preferably a composite metal cyanide complex in which glyme or t-butyl alcohol is coordinated as an organic ligand to the catalyst skeleton. The catalyst skeleton is more preferably Zn3[Co(CN)6]2 (i.e., zinc hexacyanocobaltate complex). In particular, a composite metal cyanide complex using t-butyl alcohol as an organic ligand is preferred.

[0070] When the polyoxyalkylene chains of polymer A and polymer B are random copolymer chains, a method of producing an oxyalkylene polymer having a hydroxyl group as a terminal group is preferred, in which an alkylene oxide including propylene oxide is polymerized with an initiator in the presence of a composite metal cyanide complex. For example, a preferred method is to react a mixture of ethylene oxide and propylene oxide with an initiator in the presence of a double metal cyanide complex to obtain an oxyalkylene polymer having hydroxyl groups as terminal groups.

[0071] When the polyoxyalkylene chains of polymer A and polymer B have a block chain or random copolymer chain composed of an oxyalkylene group and a block chain composed of an oxyethylene group, a preferred method is to polymerize an alkylene oxide using an initiator in the presence of a double metal cyanide complex, and then polymerize ethylene oxide in the presence of an alkali metal hydroxide to produce an oxyalkylene polymer having a hydroxyl group as a terminal group. For example, a preferred method is to polymerize propylene oxide with an initiator in the presence of a double metal cyanide complex, and then polymerize ethylene oxide in the presence of an alkali metal hydroxide to obtain an oxyalkylene polymer having hydroxyl groups as terminal groups. Alternatively, a preferred method is to react a mixture of ethylene oxide and propylene oxide with an initiator in the presence of a double metal cyanide complex, and then polymerize the ethylene oxide in the presence of an alkali metal hydroxide to obtain an oxyalkylene polymer having hydroxyl groups as terminal groups. In an oxyalkylene polymer having a hydroxyl group as a terminal group, it is preferred that a block chain consisting of an oxyethylene group is bonded to the terminal group of the polyoxyalkylene chain, since this will result in better deep curing properties.

[0072] The Mn of the oxyalkylene polymer having a hydroxyl group as a terminal group is preferably from 3,000 to 100,000, more preferably from 5,000 to 80,000, still more preferably from 7,500 to 60,000, and particularly preferably from 10,000 to 60,000. It is preferably set depending on the Mn of polymer A and polymer B.

[0073] The Mw / Mn of the oxyalkylene polymer having a hydroxyl terminal group is preferably set so that the Mw / Mn of polymer A and polymer B is equal to or less than the above-mentioned upper limit. For example, the Mw / Mn of the oxyalkylene polymer having a hydroxyl terminal group is preferably 1.80 or less, more preferably 1.00 to 1.60, even more preferably 1.02 to 1.50, and particularly preferably 1.04 to 1.40.

[0074] The total degree of unsaturation of the oxyalkylene polymer having hydroxyl terminal groups is preferably 0.1 meq / g or less, more preferably 0.05 meq / g or less, even more preferably 0.03 meq / g or less, and particularly preferably 0.01 meq / g or less. When it is below the above upper limit, excellent deep curing properties are achieved. The lower limit is not particularly limited. For example, 0.0001 meq / g or more is preferred. The total degree of unsaturation of the oxyalkylene polymer having hydroxyl terminal groups is preferably 0.0001 to 0.1 meq / g, more preferably 0.0001 to 0.05 meq / g, even more preferably 0.0001 to 0.03 meq / g, and most preferably 0.0001 to 0.01 meq / g.

[0075] The polymerization may be carried out continuously or batchwise, but is preferably carried out batchwise. The polymerization temperature is preferably from 30 to 180°C, more preferably from 70 to 160°C, and even more preferably from 90 to 140°C. The polymerization pressure is preferably 1.0 MPa or less, more preferably 0.8 MPa or less, and even more preferably 0.3 MPa or less. The alkylene oxide is preferably fed to the reactor at a rate that allows the above reaction temperature to be maintained. The reaction atmosphere is preferably one that is less susceptible to moisture contamination, and more preferably an inert gas atmosphere such as nitrogen.

[0076] (Method for producing unsaturated group-containing oxyalkylene polymer) Methods for converting the hydroxyl groups of an oxyalkylene polymer having hydroxyl terminal groups into groups having unsaturated groups at the molecular terminals include a method in which an alkali metal salt is reacted with an oxyalkylene polymer having hydroxyl terminal groups, followed by reaction with a halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular terminal (Method 1); a method in which an alkali metal salt is reacted with an oxyalkylene polymer having hydroxyl terminal groups, followed by reaction with an epoxy compound having a carbon-carbon double bond at the molecular terminal, followed by reaction with an alkali metal salt, followed by reaction with a halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular terminal (Method 2); and a method in which an alkali metal salt is reacted with an oxyalkylene polymer having hydroxyl terminal groups, followed by reaction with a halogenated hydrocarbon compound having a carbon-carbon triple bond at the molecular terminal (Method 3).

[0077] When the average total number of reactive silicon groups, unsaturated groups, and hydroxyl groups per terminal group of polymer A is 1.0 or less, the above method 1 is adopted. When the average total number of reactive silicon groups, unsaturated groups, and hydroxyl groups per terminal group of polymer A is more than 1.0, the above method 2 or method 3 is adopted. When the average total number of reactive silicon groups, unsaturated groups, and hydroxyl groups per terminal group of polymer A is more than 1.0 and the reactive silicon group possessed by polymer A is a reactive silicon group represented by the above formula 3, the above method 2 is adopted. When polymer B is produced, the above method 2 or method 3 is employed.

[0078] Examples of alkali metal salts include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. In terms of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide, and potassium ethoxide are preferred, and sodium methoxide and potassium ethoxide are more preferred, with sodium methoxide being particularly preferred in terms of availability. The alkali metal salt may be used in a state of being dissolved in a solvent.

[0079] Examples of halogenated hydrocarbon compounds containing a carbon-carbon double bond at the molecular terminal include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. Allyl chloride and methallyl chloride are preferred.

[0080] In the above methods 1 and 2, when producing polymer A having a reactive silicon group represented by formula 3, it is preferable to use a linear halogenated hydrocarbon compound containing a carbon-carbon double bond at the molecular terminal. Preferred linear halogenated hydrocarbon compounds containing a carbon-carbon double bond at the molecular terminal are vinyl chloride, allyl chloride, vinyl bromide, allyl bromide, vinyl iodide, and allyl iodide. Two or more halogenated hydrocarbon compounds having a carbon-carbon double bond at the molecular terminal may be used in combination.

[0081] Halogenated hydrocarbon compounds containing a carbon-carbon triple bond at the molecular end include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne, 1-chloro-2-pentyne, 1,4-dichloro-2-butyne, 5-chloro-1-pentyne, 6-chloro-1-hexyne, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, ... Examples include bromo-2-octyne, 1-bromo-2-pentyne, 1,4-dibromo-2-butyne, 5-bromo-1-pentyne, 6-bromo-1-hexyne, propargyl iodide, 1-iodo-2-butyne, 4-iodo-1-butyne, 1-iodo-2-octyne, 1-iodo-2-pentyne, 1,4-diiodo-2-butyne, 5-iodo-1-pentyne, and 6-iodo-1-hexyne. Propargyl chloride, propargyl bromide, and propargyl iodide are preferred. Two or more halogenated hydrocarbon compounds having a carbon-carbon triple bond at the molecular terminal may be used in combination.

[0082] Examples of epoxy compounds having a carbon-carbon double bond at the molecular terminal include allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monoxide, and 1,4-cyclopentadiene monoepoxide. Allyl glycidyl ether is preferred.

[0083] As the epoxy compound having a carbon-carbon double bond at the molecular terminal, a compound represented by the following formula 4 is preferred.

[0084] [ka] R in the above formula 4 2 , R 5 is R in the above formula 2 2 , R 5 is the same as

[0085] (Method for introducing reactive silicon groups) The introduction of the reactive silicon group involves reacting the unsaturated group-containing oxyalkylene polymer with a silylating agent (silylation reaction), which is preferably carried out in the presence of a Group 8 metal catalyst.

[0086] (Silylating agent) Examples of the silylating agent include compounds having both a group (e.g., a sulfanyl group) capable of reacting with the carbon-carbon double bond at the molecular terminal of the unsaturated group-containing oxyalkylene polymer to form a bond and a reactive silicon group represented by the above formula 1, and hydrosilane compounds (e.g., HSiR a X 3-a, R, X, and a are the same as in formula 1 above). Specific examples include trimethoxysilane, triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, diisopropoxymethylsilane, (α-chloromethyl)dimethoxysilane, and (α-chloromethyl)diethoxysilane. In terms of high activity and good curability, trimethoxysilane, triethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane are preferred, and dimethoxymethylsilane or trimethoxysilane is more preferred.

[0087] The amount of the silylating agent added in the production of polymer A is preferably 0.85 molar times or more, more preferably 0.95 molar times or more, and even more preferably 1.00 molar times or more, relative to the total amount of unsaturated groups in the unsaturated group-containing oxyalkylene polymer. When a cocatalyst described below is not used, the amount of the silylating agent added in the production of polymer B may be the same as in the production of polymer A. When a cocatalyst described below is used, the amount of the silylating agent added is preferably 0.50 to 0.85 molar times, more preferably 0.60 to 0.85 molar times, and even more preferably 0.70 to 0.85 molar times, relative to the total amount of unsaturated groups in the unsaturated group-containing oxyalkylene polymer.

[0088] (Group 8 metal catalyst) The Group 8 metal catalyst is a catalyst containing a metal from Group 8 of the short periodic table. The Group 8 metal is preferably at least one metal selected from the group consisting of cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum, more preferably at least one metal selected from the group consisting of ruthenium, palladium, and platinum, and even more preferably platinum. The Group 8 metal catalyst is used as the Group 8 metal itself, a metal salt, or a complex with an organic compound. Specifically, preferred are platinum metal supported on a carrier such as platinum itself, solid platinum supported on a carrier such as alumina, silica, or carbon black, chloroplatinic acid complexes having an alcohol, aldehyde, or ketone as a ligand, or chloroplatinic acid complexes, platinum-olefin complexes [e.g., Pt(CH2=CH2)2(PPh3), Pt(CH2=CH2)2Cl2], platinum-acetylacetonate complexes [Pt(C5H7O2)2], platinum-vinylsiloxane complexes [Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4], platinum-phosphine complexes [Ph(PPh3)4, Pt(PBu3)4], platinum-phosphite complexes [Pt{P(OPh)3}4], and the like.

[0089] These Group 8 metal catalysts may be used alone or in combination of two or more. Chloroplatinic acid, platinum olefin complexes, platinum-acetylacetonate complexes, and platinum-vinylsiloxane complexes are preferred due to their high reactivity. Specifically, a solution of hexachloroplatinic acid (IV) hexahydrate and platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is preferred.

[0090] Although there are no particular limitations on the amount of the Group 8 metal catalyst used, the amount of the Group 8 metal catalyst used relative to the unsaturated group-containing oxyalkylene polymer is preferably 1.0 to 20 ppm by mass, more preferably 1.5 to 10 ppm by mass. When the amount of the Group 8 metal catalyst used is equal to or greater than the above lower limit, the silylation reaction proceeds sufficiently, and when it is equal to or less than the above upper limit, it is preferable from the standpoint of cost.

[0091] It is known that even when a silylation reaction is carried out using a Group 8 metal catalyst and an excess amount of silylating agent relative to the number of moles of carbon-carbon double bonds at the molecular terminals of an unsaturated group-containing oxyalkylene polymer, the silylation rate does not reach 100 mol%. This is thought to be because during the silylation reaction, the carbon-carbon double bonds at the molecular terminals of the unsaturated group-containing oxyalkylene polymer are transferred to the interior of the molecule, and the transferred carbon-carbon double bonds do not react with the silylating agent. In this case, the upper limit of the silylation rate is less than 85 mol%. To achieve a silylation rate of 85 mol% or more, it is preferable to use the following co-catalyst. By using a co-catalyst, the silylation rate can be increased to 85 mol% or more. That is, it is preferable to use a co-catalyst to produce polymer A.

[0092] <Co-catalyst> The co-catalyst preferably contains either or both of a carboxylic acid compound having a carbon-carbon triple bond and a carboxylic acid compound having a carbon-carbon double bond. In this specification, a carboxylic acid compound refers to a compound having a carboxy group and a derivative thereof. Examples of the derivative include esters and carboxylic acid anhydrides. The carboxylic acid compound having a carbon-carbon triple bond may be used alone or in combination of two or more types. The carboxylic acid compound having a carbon-carbon double bond may be used alone or in combination of two or more types. The co-catalyst may contain either a carboxylic acid compound having a carbon-carbon triple bond or a carboxylic acid compound having a carbon-carbon double bond, and preferably contains both a carboxylic acid compound having a carbon-carbon triple bond and a carboxylic acid compound having a carbon-carbon double bond.

[0093] (Carboxylic acid compounds with carbon-carbon triple bonds) Examples of carboxylic acid compounds having a carbon-carbon triple bond include monocarboxylic acids having a carbon-carbon triple bond, dicarboxylic acids having a carbon-carbon triple bond, carboxylic acid anhydrides having a carbon-carbon triple bond, and esters having a carbon-carbon triple bond.

[0094] A monocarboxylic acid having a carbon-carbon triple bond is a compound in which a hydrogen atom bonded to a carbon in a hydrocarbon compound having a carbon-carbon triple bond is substituted with a carboxy group. A dicarboxylic acid having a carbon-carbon triple bond is a compound in which two hydrogen atoms bonded to carbon in a hydrocarbon compound having a carbon-carbon triple bond are substituted with carboxy groups. The carboxylic acid anhydride having a carbon-carbon triple bond is a compound obtained by dehydration condensation of carboxy groups of two of the above-mentioned carboxylic acids having a carbon-carbon triple bond, a compound obtained by dehydration condensation of a carboxy group of the above-mentioned carboxylic acid having a carbon-carbon triple bond and a carboxy group of a carboxylic acid not having a carbon-carbon triple bond, or a compound obtained by dehydration condensation of two carboxy groups in one molecule of a dicarboxylic acid having a carbon-carbon triple bond. An ester having a carbon-carbon triple bond is a compound in which the hydrogen atom in the carboxy group of the carboxylic acid having a carbon-carbon triple bond is substituted with a monovalent hydrocarbon group. The monovalent hydrocarbon group is preferably a monovalent saturated hydrocarbon group, and examples thereof include a linear or branched alkyl group and a cycloalkyl group. Among these, a methyl group and an ethyl group are preferred.

[0095] Examples of the hydrocarbon compound having a carbon-carbon triple bond include a compound having a carbon-carbon triple bond in which at least one carbon-carbon single bond in a saturated hydrocarbon compound is replaced with a carbon-carbon triple bond. Examples of the saturated hydrocarbon compound include linear or branched alkanes. The hydrogen atoms in the compound having a carbon-carbon triple bond may be substituted with a substituent. Examples of the substituent include an aromatic group, a hydroxyl group, and the like.

[0096] The number of carbon atoms in the carboxylic acid compound having a carbon-carbon triple bond is preferably 3 or more and 17 or less, more preferably 3 or more and 10 or less, and particularly preferably 4 or more and 10 or less. The number of carbon atoms in the monocarboxylic acid compound having a carbon-carbon triple bond is preferably 3 or more and 17 or less, more preferably 3 or more and 10 or less. The number of carbon atoms in the dicarboxylic acid having a carbon-carbon triple bond is preferably 4 or more and 10 or less. The number of carbon atoms in the carboxylic anhydride having a carbon-carbon triple bond is preferably 4 or more and 10 or less. The number of carbon atoms in the ester having a carbon-carbon triple bond is preferably 4 or more and 17 or less, more preferably 4 or more and 10 or less.

[0097] The number of carbon-carbon triple bonds in one molecule of the carboxylic acid compound having a carbon-carbon triple bond is preferably one or two, and more preferably one.

[0098] The carboxylic acid compound having a carbon-carbon triple bond is preferably a carboxylic acid compound having a carbon-carbon triple bond at the α-position carbon. Examples of the carboxylic acid compound having a carbon-carbon triple bond at the α-position carbon include a monocarboxylic acid having a carbon-carbon triple bond at the α-position carbon, a dicarboxylic acid having a carbon-carbon triple bond at the α-position carbon, a carboxylic acid anhydride having a carbon-carbon triple bond at the α-position carbon, or an ester having a carbon-carbon triple bond at the α-position carbon. Preferred are monocarboxylic acids having a carbon-carbon triple bond at the α-position carbon and esters having a carbon-carbon triple bond at the α-position carbon, and more preferred are monocarboxylic acids having a carbon-carbon triple bond at the α-position carbon. In the case of dicarboxylic acids, there are dicarboxylic acids having carbon-carbon triple bonds at both α-positions and dicarboxylic acids having a carbon-carbon triple bond at only one α-position, but dicarboxylic acids having carbon-carbon triple bonds at both α-positions are preferred.

[0099] Preferred monocarboxylic acids having a carbon-carbon triple bond at the α-carbon include phenylpropiolic acid, propiolic acid, 2-butynoic acid, 2-heptynoic acid, 2-methyl-3-butynoic acid, 2-hydroxy-3-butynoic acid, and 3-butynoic acid, with phenylpropiolic acid being more preferred. Examples of dicarboxylic acids having a carbon-carbon triple bond at the α-carbon include acetylenedicarboxylic acid. Examples of carboxylic acid anhydrides having a carbon-carbon triple bond at the α-carbon include propiolic anhydride. Examples of esters having a carbon-carbon triple bond at the α-carbon include methyl phenylpropiolate. When a carboxylic acid compound having a carbon-carbon triple bond at the α-carbon has two or more triple bonds in one molecule, it may have a carbon-carbon triple bond at a carbon other than the α-carbon.

[0100] (Carboxylic acid compounds with carbon-carbon double bonds) Examples of carboxylic acid compounds having a carbon-carbon double bond include monocarboxylic acids having a carbon-carbon double bond, dicarboxylic acids having a carbon-carbon double bond, carboxylic anhydrides having a carbon-carbon double bond, and esters having a carbon-carbon double bond. A carboxylic acid compound having both a carbon-carbon triple bond and a carbon-carbon double bond in one molecule is considered to be a carboxylic acid compound having a carbon-carbon triple bond. In other words, the term "carboxylic acid compound having a carbon-carbon double bond" as used herein refers to a carboxylic acid compound that has a carbon-carbon double bond but does not have a carbon-carbon triple bond.

[0101] A monocarboxylic acid having a carbon-carbon double bond is a compound in which a hydrogen atom bonded to a carbon in a hydrocarbon compound having a carbon-carbon double bond is substituted with a carboxy group. A dicarboxylic acid having a carbon-carbon double bond is a compound in which two hydrogen atoms bonded to carbon in a hydrocarbon compound having a carbon-carbon double bond are substituted with carboxy groups. The carboxylic acid anhydride having a carbon-carbon double bond is a compound obtained by dehydration condensation of carboxy groups of two of the above-mentioned carboxylic acids having carbon-carbon double bonds, a compound obtained by dehydration condensation of a carboxy group of the above-mentioned carboxylic acid having a carbon-carbon double bond and a carboxy group of a carboxylic acid not having a carbon-carbon double bond, or a compound obtained by dehydration condensation of two carboxy groups in one molecule of a dicarboxylic acid having a carbon-carbon double bond. The ester having a carbon-carbon double bond is a compound in which the hydrogen atom in the carboxyl group of the monocarboxylic acid having a carbon-carbon double bond is substituted with a monovalent hydrocarbon group. The monovalent hydrocarbon group is preferably a monovalent saturated hydrocarbon group, and examples thereof include a linear or branched alkyl group and a cycloalkyl group. Among these, a methyl group and an ethyl group are preferred.

[0102] Examples of the hydrocarbon compound having a carbon-carbon double bond include a compound having a carbon-carbon double bond in which at least one carbon-carbon single bond in a saturated hydrocarbon compound is replaced with a carbon-carbon double bond. Examples of the saturated hydrocarbon compound include linear or branched alkanes and cycloalkanes. The hydrogen atoms in the compound having a carbon-carbon double bond may be substituted with a substituent. Examples of the substituent include an aromatic group, a hydroxyl group, and the like.

[0103] The carbon number of the carboxylic acid compound having a carbon-carbon double bond is preferably 3 to 18, more preferably 4 to 18, and even more preferably 4 to 10. The "carbon number" of the carboxylic acid compound having a carbon-carbon double bond does not include the number of carbon atoms in the branched chains, but refers to the number of carbon atoms in the main chain. The "main chain" refers to the longest molecular chain including the double bond. For example, in the case of methacrylic acid, the number of carbon atoms in the main chain including the double bond is counted as 3, not including the number of carbon atoms in the methyl group.

[0104] The number of double bonds in one molecule of the carboxylic acid compound having a carbon-carbon double bond is preferably one or two, and more preferably one.

[0105] As the carboxylic acid compound having a carbon-carbon double bond, a carboxylic acid compound having a carbon-carbon double bond at the α-position carbon is preferred. Examples of the carboxylic acid compound having a carbon-carbon double bond at the α-position carbon include a monocarboxylic acid having a carbon-carbon double bond at the α-position carbon, a dicarboxylic acid having a carbon-carbon double bond at the α-position carbon, a carboxylic acid anhydride having a carbon-carbon double bond at the α-position carbon, or an ester having a carbon-carbon double bond at the α-position carbon. Monocarboxylic acids having a carbon-carbon double bond at the α-position carbon and esters having a carbon-carbon double bond at the α-position carbon are preferred, and monocarboxylic acids having a carbon-carbon double bond at the α-position carbon are more preferred. In the case of dicarboxylic acids, there are dicarboxylic acids having carbon-carbon double bonds at both α-positions and dicarboxylic acids having a carbon-carbon double bond at only one α-position, but dicarboxylic acids having carbon-carbon double bonds at both α-positions are preferred.

[0106] Preferred monocarboxylic acids having a carbon-carbon double bond at the α-carbon include acrylic acid, methacrylic acid, 3-methyl-2-hexenoic acid, 2-hexenoic acid, crotonic acid, sorbic acid, 2-nonenoic acid, 2-decenoic acid, 2-heptadecenoic acid, and 2-octadecenoic acid, with crotonic acid being more preferred. Preferred esters having a carbon-carbon double bond at the α-carbon include ethyl crotonate. Preferred dicarboxylic acids having a carbon-carbon double bond at the α-carbon include maleic acid. Preferred carboxylic acid anhydrides having a carbon-carbon double bond at the α-carbon include maleic anhydride. Preferred carboxylic acid halides having a carbon-carbon double bond at the α-carbon include crotonic acid chloride. When a carboxylic acid compound having a carbon-carbon double bond at the α-carbon has two or more double bonds in one molecule, it may have a carbon-carbon double bond at a carbon other than the α-carbon.

[0107] (Silane compounds) It is preferable that the co-catalyst further contains a silane compound represented by the following formula 5. When the silane compound is contained, the silylation rate is more likely to be improved. HSiR 6 3 formula 5

[0108] In the above formula 5, R 6 R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group. 6 may be the same or different from each other.

[0109] R 6 is preferably at least one selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group. It is more preferably at least one selected from the group consisting of a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, and a benzyl group. A methyl group or an ethyl group is preferred, and an ethyl group is particularly preferred. Furthermore, R 1 are preferably the same.

[0110] Examples of the silane compound include trimethylsilane, triethylsilane, triisopropylsilane, triphenylsilane, dimethylethylsilane, and dimethylphenylsilane, with triethylsilane being preferred. When the silane compound is contained as the co-catalyst, any combination of a carboxylic acid compound having a carbon-carbon triple bond and the silane compound, a carboxylic acid compound having a carbon-carbon double bond and the silane compound, or a carboxylic acid compound having a carbon-carbon triple bond, a carboxylic acid compound having a carbon-carbon double bond and the silane compound may be used, and it is preferable that a carboxylic acid compound having a carbon-carbon triple bond, a carboxylic acid compound having a carbon-carbon double bond and the silane compound are contained.

[0111] When a carboxylic acid compound having a carbon-carbon triple bond is used as a co-catalyst, the molar ratio of the carboxylic acid compound having a carbon-carbon triple bond to the Group 8 metal catalyst is preferably 0.01 to 25, more preferably 0.05 to 20, and particularly preferably 0.1 to 10. When the molar ratio is equal to or greater than the lower limit, the silylation rate is further improved. When the molar ratio is equal to or less than the upper limit, the amount of acid in the solution is reduced, thereby preventing viscosity increase.

[0112] When a carboxylic acid compound having a carbon-carbon double bond is used as a co-catalyst, the amount of the carboxylic acid compound having a carbon-carbon double bond is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol, per mol of unsaturated group in the unsaturated group-containing oxyalkylene polymer. When the amount is equal to or greater than the lower limit, the silylation rate is further improved. When the amount is equal to or less than the upper limit, the amount of acid in the solution is reduced, and thickening of the curable composition containing polymer A and polymer B is suppressed.

[0113] When the silane compound represented by the above formula 5 is used as a co-catalyst, the molar ratio of the silane compound to the total of the carboxylic acid compound having a carbon-carbon triple bond and the carboxylic acid compound having a carbon-carbon double bond is preferably 0.05 to 20, more preferably 0.1 to 10. When the molar ratio is equal to or greater than this lower limit, the silylation rate is further improved. In addition, the amount of acid in the solution is reduced, thereby preventing viscosity increase.

[0114] It is preferable to disperse the Group 8 metal catalyst and dissolve and dilute the co-catalyst in various solvents to stabilize the Group 8 metal catalyst and co-catalyst and make them easier to handle. Preferred solvents include hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, and xylene, halogenated hydrocarbon compounds, alcohols, glycols, ethers, esters, ketones, nitriles, and amides. Among these, alcohols, ketones, nitriles, and amides are preferred, with isopropyl alcohol, acetone, N,N-dimethylformamide (DMF), and acetonitrile being more preferred, and acetonitrile being particularly preferred. The Group 8 metal catalyst and co-catalyst may be diluted in two or more solvents.

[0115] <Method of adding Group 8 metal catalyst, co-catalyst, and silylating agent> There are no particular limitations on the method of adding the Group 8 metal catalyst, co-catalyst, and silylating agent during the silylation reaction, such as the order of addition.

[0116] When a carboxylic acid compound having a carbon-carbon triple bond is used as a co-catalyst, a premix may be prepared by dispersing a Group 8 metal catalyst and dissolving a carboxylic acid compound having a carbon-carbon triple bond in a solvent to form colloidal particles of the Group 8 metal catalyst, and then adding the resulting premix to the unsaturated group-containing oxyalkylene polymer, followed by the addition of a silylating agent to carry out the silylation reaction. Alternatively, the Group 8 metal catalyst and the carboxylic acid compound having a carbon-carbon triple bond may be added to a reaction solution containing an unsaturated group-containing organic polymer, followed by the addition of a silylating agent to carry out the hydrosilylation. Pre-forming colloidal particles of the Group 8 metal catalyst improves the dispersibility of the Group 8 metal catalyst, facilitating the silylation reaction, and therefore adding a premix to the reaction solution is preferred.

[0117] When a carboxylic acid compound having a carbon-carbon double bond is contained as a co-catalyst, the Group 8 metal catalyst and the carboxylic acid compound having a carbon-carbon double bond may be added to the unsaturated group-containing oxyalkylene polymer, and then a silylating agent may be added to carry out the silylation reaction.

[0118] When a carboxylic acid compound having a carbon-carbon triple bond and a carboxylic acid compound having a carbon-carbon double bond are used in combination as co-catalysts, the carboxylic acid compound having a carbon-carbon double bond may be added to the unsaturated group-containing oxyalkylene polymer, a premix containing the Group 8 metal catalyst and the carboxylic acid compound having a carbon-carbon triple bond may be further added, and then a silylating agent may be added to carry out the silylation reaction. Alternatively, the Group 8 metal catalyst, the carboxylic acid compound having a carbon-carbon triple bond, and the carboxylic acid compound having a carbon-carbon double bond may be added separately to a reaction solution containing the unsaturated group-containing organic polymer, and then a silylating agent may be added to carry out the hydrosilylation.

[0119] When a silane compound is contained as a co-catalyst, the silane compound may be added to the unsaturated group-containing oxyalkylene polymer, or the silane compound may be added to a premix containing the Group 8 metal catalyst and a carboxylic acid compound having a carbon-carbon triple bond.

[0120] (Reaction conditions) The silylation reaction can be carried out in the absence of a solvent or in the presence of a solvent. Examples of solvents that can be used for the silylation reaction include hydrocarbons, halogenated hydrocarbons, ethers, and esters, with heptane, hexane, cyclohexane, benzene, toluene, and xylene being preferred. When the unsaturated group-containing oxyalkylene polymer is a solid or a highly viscous liquid, it is preferred to use a solvent to reduce the viscosity of the reaction solution.

[0121] The gas phase of the reactor during the silylation reaction may consist solely of an inert gas such as nitrogen or helium, or may contain oxygen or the like.

[0122] When oxygen is introduced into the gas phase, the hydrosilylation reaction can be carried out in the presence of an antioxidant to prevent oxidation of the reaction solvent. The antioxidant is not particularly limited, but phenolic antioxidants or amine-based antioxidants that function as radical chain inhibitors can be used. Examples of phenolic antioxidants that can be used include 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), tetrakis{methylene-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}methane, and 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane. Examples of the amine-based antioxidant that can be used include phenyl-β-naphthylamine, α-naphthylamine, N,N'-di-sec-butyl-p-phenylenediamine, phenothiazine, and N,N'-diphenyl-p-phenylenediamine.

[0123] The reaction may be carried out continuously or batchwise, but is preferably carried out batchwise. The reaction temperature is preferably 50 to 120°C, more preferably 50 to 110°C, and even more preferably 50 to 100°C. The reaction pressure is preferably from 0.01 to 0.2 MPa, more preferably from 0.01 to 0.15 MPa, and even more preferably from 0.01 to 0.1 MPa.

[0124] (Adjustment of silylation rate) The silylation rates of polymer A and polymer B may be adjusted by controlling the amount of silylating agent added relative to the total amount of unsaturated groups in the unsaturated group-containing oxyalkylene polymer, as described above, or by not using a co-catalyst during the production of polymer B.

[0125] <Curable composition> The content of polymer A relative to the total mass of the curable composition is preferably 1 to 50 mass%, more preferably 5 to 40 mass%, and even more preferably 10 to 30 mass%. When it is not more than the upper limit, the cured product has better tensile strength and elongation properties. The content of polymer B relative to the total mass of the curable composition is preferably 1 to 40 mass%, more preferably 3 to 30 mass%, and even more preferably 5 to 20 mass%. When the content is equal to or greater than the lower limit, the viscosity of the curable composition decreases and the elongation properties become better. When the content is equal to or less than the upper limit, the cured product has better tensile strength and a higher modulus.

[0126] The combined content of polymer A and polymer B relative to the total mass of the curable composition is preferably 1 to 50 mass%, more preferably 5 to 45 mass%, and even more preferably 10 to 40 mass%. When it is at least the above lower limit, the curability is good, and the cured product has excellent tensile strength and a high modulus.

[0127] The content of the polymer A is preferably 1 to 99 parts by mass, more preferably 30 to 90 parts by mass, and even more preferably 50 to 95 parts by mass, relative to 100 parts by mass of the total content of the polymer A and the polymer B. When the content is equal to or greater than the lower limit, the viscosity of the curable composition decreases, and the tensile strength of the cured product is superior. When the content is equal to or less than the upper limit, the tensile strength and modulus are superior.

[0128] The content of components other than polymer A and polymer B relative to the total mass of the curable composition is preferably from 30 to 90 mass %, more preferably from 40 to 90 mass %, and even more preferably from 50 to 85 mass %.

[0129] [Other ingredients] Examples of the other components include polymers other than polymer A and polymer B, curable compounds, epoxy resin curing agents, curing catalysts (silanol condensation catalysts), fillers, plasticizers, thixotropy-imparting agents, stabilizers, adhesion-imparting agents, physical property adjusters, dehydrating agents, adhesion-imparting resins, reinforcing materials such as fillers, surface modifiers, flame retardants, foaming agents, solvents, and silicates. Other components can be used in combination without limitation with conventionally known components described in International Publication No. 2013 / 180203, International Publication No. 2014 / 192842, International Publication No. 2016 / 002907, JP 2014-88481 A, JP 2015-10162 A, JP 2015-105293 A, JP 2017-039728 A, JP 2017-214541 A, etc. Two or more types of each component may be used in combination.

[0130] Examples of polymers other than polymer A and polymer B include an oxyalkylene polymer having an average of 1.0 or more terminal groups per molecule, the terminal groups being at least one group selected from the group consisting of a divalent organic group represented by -C(=O)NH-, a reactive silicon group represented by formula 1 above, an unsaturated group, and a hydroxyl group, and having a silylation rate calculated by formula f1 above of 50 to 99 mol%; an oxyalkylene polymer having an average of 1.0 or more and less than 2.0 terminal groups per molecule, the terminal groups not having a divalent organic group represented by formula 1 above, an unsaturated group, and at least one group selected from the group consisting of a reactive silicon group represented by formula 1 above, an unsaturated group, and a hydroxyl group, and having a silylation rate calculated by formula f1 above of 50 to 99 mol%; an oxyalkylene polymer not having a reactive silicon group; a polymer other than an oxyalkylene polymer having a reactive silicon group; and a polymer other than an oxyalkylene polymer not having a reactive silicon group.

[0131] The curable composition may be a one-component type in which the polymer and all other ingredients are mixed in advance, stored in a sealed container, and cured by moisture in the air after application, or a two-component type in which a base composition containing at least a polymer having a reactive silicon group and a curing agent composition containing at least a curing catalyst are stored separately and the curing agent composition and the base composition are mixed before use. In the case of a two-component type, the "total mass of the curable composition" in the above-mentioned content of polymer A and polymer B should be read as "total mass of the base composition and the curing agent composition." The one-component curable composition preferably does not contain water. It is preferable that the components containing water are dehydrated and dried in advance, or that the components are dehydrated under reduced pressure during mixing and kneading. In the two-component curable composition, the curing agent composition may contain water. The base composition is unlikely to gel even if it contains a small amount of water, but from the viewpoint of storage stability, it is preferable to dehydrate and dry the blended components in advance. In order to improve storage stability, a dehydrating agent may be added to the one-component curable composition or the two-component base composition.

[0132] <Method for producing curable composition> The curable composition of the present embodiment can be produced by mixing polymer A produced by the method for producing polymer A described above, polymer B produced by the method for producing polymer B described above, and, if necessary, the other components described above.

[0133] ≪Cured product≫ The cured product of this embodiment is a cured product of the above-mentioned curable composition. The reactive silicon groups of polymer A and polymer B undergo a hydrolysis reaction due to moisture in the air, and the silanols generated by the hydrolysis reaction undergo an intermolecular condensation reaction to give a crosslinked cured product.

[0134] <Uses of the curable composition> Suitable applications of the curable composition of the present embodiment include adhesives, sealants (for example, elastic sealants for construction, sealants for double glazing, anti-rust and waterproof sealants for glass edges, sealants for the backside of solar cells, sealants for buildings, sealants for ships, sealants for automobiles, and sealants for roads), and electrical insulating materials (insulating coating materials for electric wires and cables). [Example]

[0135] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following descriptions.

[0136] [Mn, Mw / Mn] The measurement device used was a gel permeation chromatograph analyzer HLC-8420GPC (product name of Tosoh Corporation). The column used was a TSKgel SupermultiporeHZ-M (product name of Tosoh Corporation), and the solvent was tetrahydrofuran. The sample pump was set to a flow rate of 0.350 mL / min, the reference pump was set to a flow rate of 0.350 mL / min, the detector temperature was set to 40°C, and the collection time was 6 to 15 minutes. Mn, Mw, and Mw / Mn were determined by analyzing the peaks that appeared between 6 and 11 minutes of collection time. A calibration curve was prepared using polystyrene as a standard material.

[0137] [Silylation rate] The silylation rate is 1 H-NMR analysis was performed.

[0138] [Curing speed evaluation] Measurement was carried out in accordance with "5.19 Finger Tack Drying Time Test" of JIS A 1439:2016, and when evaluated by finger contact after drying at 23°C for 24 hours, products in which the curable composition was insufficiently cured and adhered to the finger were rated as "X", and products in which the curable composition was sufficiently cured and did not adhere to the finger were rated as "O".

[0139] [Tensile property test] The curable composition to be measured was filled into a 2 mm thick mold, and cured for 3 days at a temperature of 23°C and a humidity of 50%, and then cured for a further 4 days at a temperature of 50°C and a humidity of 65%. The resulting cured product was punched out using a dumbbell mold to obtain a test piece. The test piece was subjected to a tensile test using a Tensilon testing machine at a tensile speed of 500 mm / min, and the modulus (M50, unit: N / mm), which is the stress at 50% elongation, was measured. 2 ), the maximum cohesive strength (Tmax, unit: N / mm 2 ) and maximum elongation (E, unit: %) were measured.

[0140] [Tear strength test] A cured product was obtained in the same manner as in the [Tensile property test]. The obtained cured product was punched out using an angle mold to obtain a test piece. This test piece was subjected to a tear test at a tear speed of 500 mm / min to measure the tear strength (N / mm).

[0141] [Manufacturing Example 1] Propylene oxide was polymerized using propylene glycol as an initiator and a zinc hexacyanocobaltate complex (hereinafter referred to as "TBA-DMC catalyst") with t-butyl alcohol as a ligand as a catalyst to obtain oxypropylene polymer A1, an oxyalkylene polymer having hydroxyl groups at the terminal groups. The number average molecular weight of oxypropylene polymer A1 was 25,000.

[0142] Sodium methoxide was added in an amount of 1.05 molar equivalents relative to the hydroxyl groups of oxypropylene polymer A1, and methanol was distilled off under reduced pressure. Allyl chloride was then added in an excess amount relative to the hydroxyl groups of oxypropylene polymer A1 to react, and unreacted allyl chloride was removed under reduced pressure. Metal salts were removed by purification, and the hydroxyl groups of oxypropylene polymer A1 were converted to allyloxy groups, yielding unsaturated group-containing oxyalkylene polymer A1.

[0143] Crotonic acid was added to the unsaturated group-containing oxyalkylene polymer A1 in an amount of 1 mole per mole of unsaturated group, followed by the addition of a platinum catalyst (hexachloroplatinic acid (IV) hexahydrate), phenylpropiolic acid, and a solution (premix) of triethylsilane dissolved in acetonitrile. The amount of hexachloroplatinic acid (IV) hexahydrate added was 6.5 mg per 1000 g of the unsaturated group-containing oxyalkylene polymer A1, the amount of phenylpropiolic acid added was 9.2 mg per 1000 g of the unsaturated group-containing oxyalkylene polymer A1, and the amount of triethylsilane added was 7.3 mg per 1000 g of the unsaturated group-containing oxyalkylene polymer A1. 0.9 moles of dimethoxymethylsilane was added as a silylating agent to 1 mole of unsaturated groups in the unsaturated group-containing oxyalkylene polymer A1, and the silylation reaction was carried out at 70°C for 3 hours. After that, the unreacted silylating agent was removed under reduced pressure to obtain polymer A-1, which is a reactive silicon group-containing oxyalkylene polymer. 11 The number of reactive silicon groups per terminal group, the number of reactive silicon groups per molecule, the silylation rate, Mn, and Mw / Mn are shown in Table 1 (hereinafter, polymers A-2 to A-6, B-1, B-2, and C-1 will be shown in the same manner. However, R 11 indicates polymer A only).

[0144] [Manufacturing Example 2] Polymer A-2, a reactive silicon group-containing oxyalkylene polymer, was obtained in the same manner as in Production Example 1, except that the amount of dimethoxymethylsilane added was changed to 1.0 mole per mole of unsaturated group in unsaturated group-containing oxyalkylene polymer A1.

[0145] [Manufacturing Example 3] Polymer A-3, a reactive silicon group-containing oxyalkylene polymer, was obtained in the same manner as in Production Example 1, except that glycerin was used as the initiator instead of propylene glycol.

[0146] [Manufacturing Examples 4 and 5] Polymers A-4 and A-5, which are reactive silicon group-containing oxyalkylene polymers, were obtained in the same manner as in Production Example 3, except that the amount of alkylene oxide supplied and the reaction conditions (reaction temperature and time) were changed so that the Mn values ​​were as shown in Table 1.

[0147] [Manufacturing Example 6] Sodium methoxide in an amount of 1.05 molar equivalents relative to the hydroxyl groups of the oxypropylene polymer A1 of Production Example 1 was added, and methanol was distilled off under reduced pressure. Thereafter, methallyl chloride (3-chloro-2-methyl-1-propene) in an amount excess relative to the hydroxyl groups of the oxypropylene polymer A1 was added, and the mixture was reacted at 130°C for 2 hours, after which unreacted methallyl chloride was removed under reduced pressure. The mixture was purified to remove metal salts, and the hydroxyl groups of the oxypropylene polymer A1 were converted to methallyloxy groups, yielding an unsaturated group-containing oxyalkylene polymer A6. A silylation reaction was carried out in the same manner as in Production Example 1, except that unsaturated group-containing oxyalkylene polymer a1 was used instead of unsaturated group-containing oxyalkylene polymer A1, to obtain polymer A-6, which is a reactive silicon group-containing oxyalkylene polymer.

[0148] [Manufacturing Example 7] To the hydroxyl groups of the oxypropylene polymer A1 of Production Example 1, 1.05 molar equivalents of a methanol solution of sodium methoxide were added to alcoholate the oxypropylene polymer A1. Next, the methanol was distilled off by heating under reduced pressure, and 1.05 molar equivalents of allyl glycidyl ether was added relative to the amount of hydroxyl groups in the oxypropylene polymer A1, followed by a reaction at 130°C for 2 hours. Subsequently, an additional 0.28 molar equivalents of a methanol solution of sodium methoxide relative to the hydroxyl groups of the oxypropylene polymer A1 was added to remove the methanol, and an excess amount of allyl chloride was added relative to the hydroxyl groups of the oxypropylene polymer A1, followed by a reaction at 130°C for 2 hours to convert the terminal groups to allyloxy groups, yielding an unsaturated group-containing oxyalkylene polymer B1. The unsaturated group-containing oxyalkylene polymer B1 had an average of 2.0 unsaturated groups per terminal group and an average of 4.0 unsaturated groups per molecule. Next, in the presence of a platinum divinyldisiloxane complex, 0.80 moles of methyldimethoxysilane was added per mole of unsaturated group in the unsaturated group-containing oxyalkylene polymer B1, and the mixture was allowed to react at 70°C for 5 hours to obtain polymer B-1, a reactive silicon group-containing oxyalkylene polymer having a methyldimethoxysilyl group introduced into the terminal group.

[0149] [Manufacturing Example 8] Propylene oxide was polymerized using propylene glycol as an initiator and TBA-DMC as a catalyst to obtain oxypropylene polymer B2, an oxyalkylene polymer having hydroxyl groups at its terminals. The number average molecular weight of oxypropylene polymer B2 was 15,000.

[0150] A methanol solution of 1.05 molar equivalents of sodium methoxide was added relative to the hydroxyl groups of oxypropylene polymer B2 to alcoholate the oxypropylene polymer B2. Next, the methanol was distilled off by heating under reduced pressure, and 1.05 molar equivalents of allyl glycidyl ether was added relative to the amount of hydroxyl groups in oxypropylene polymer B2, followed by a reaction at 130°C for 2 hours. Subsequently, a methanol solution of 0.28 molar equivalents of sodium methoxide relative to the hydroxyl groups of oxypropylene polymer B2 was added to remove the methanol. An excess of allyl chloride was added relative to the hydroxyl groups of oxypropylene polymer B2, and the reaction was continued at 130°C for 2 hours to convert the terminal groups to allyloxy groups, yielding an unsaturated group-containing oxyalkylene polymer B2. The unsaturated group-containing oxyalkylene polymer B2 had an average of 2.0 unsaturated groups per terminal group and an average of 4.0 unsaturated groups per molecule. Next, in the presence of a platinum divinyldisiloxane complex, 0.80 moles of methyldimethoxysilane was added per mole of unsaturated group in the unsaturated group-containing oxyalkylene polymer B1, and the mixture was allowed to react at 70°C for 5 hours to obtain polymer B-2, a reactive silicon group-containing oxyalkylene polymer having a methyldimethoxysilyl group introduced into the terminal group.

[0151] [Manufacturing Example 9] Hexachloroplatinic acid (IV) hexahydrate as a platinum catalyst was added to the unsaturated group-containing oxyalkylene polymer A1 of Production Example 1. The amount of hexachloroplatinic acid (IV) hexahydrate added was 6.5 mg per 1000 g of the unsaturated group-containing oxyalkylene polymer A1. 0.75 moles of dimethoxymethylsilane was added as a silylating agent relative to 1 mole of unsaturated groups in the unsaturated group-containing oxyalkylene polymer A1, and the mixture was reacted at 70°C for 3 hours. After that, the unreacted silylating agent was removed under reduced pressure to obtain polymer C-1, which is a reactive silicon group-containing oxyalkylene polymer.

[0152] [Table 1]

[0153] [Other ingredients] Other ingredients listed in Tables 2 and 3 are as follows: Hakuenka CCR: Colloidal calcium carbonate with a fatty acid-treated surface, a product name of Shiraishi Calcium Co., Ltd. Whiten SB: Untreated heavy calcium carbonate, product name of Shiraishi Calcium Co., Ltd. DINP: Vinicizer 90, diisononyl phthalate, Kao product. Disparlon #6500 (referred to as Disparlon in the table): a thixotropic agent, product name of Kusumoto Chemicals Co., Ltd. Irganox 1010: Hindered phenolic antioxidant, BASF product name. KBM-1003: Vinyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd. KBM-603: 3-(2-aminoethylamino)propyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd. KBM-403: Glycidoxypropyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd. DBTDL: dibutyltin dilaurate;

[0154] [Preparation of Curable Composition] (Examples 1 to 14) Curable compositions were prepared using the polymers and additives in the amounts (parts by mass) shown in Tables 2 and 3. The curable compositions obtained were used to carry out the above-mentioned curing rate evaluation, tensile property test, and tear property test. Examples 1 to 8 are working examples, and Examples 9 to 14 are comparative examples. The results are shown in Tables 2 and 3.

[0155] [Table 2]

[0156] [Table 3]

[0157] As shown in Table 2, the cured products of the curable compositions of Examples 1 to 8 containing polymer A and polymer B of the present invention had high Tmax and excellent tear strength. As shown in Table 3, Example 9, which contained polymer C-1 having a low silylation rate and polymer B instead of polymer A having a high silylation rate, was inferior in both tensile strength and tear strength. Example 10, which contained only polymer B without polymer A having a high silylation rate, was superior in tear strength but inferior in tensile strength. Examples 11 to 14, which contained only polymer A without polymer B, were inferior in both tensile strength and tear strength. Note that, when R in the above formula 3 is 11 It was found that in Example 7, which contained Polymer A-6 and Polymer B, each of which has a reactive silicon group where the group is a branched alkylene group, the curing rate was slow, although the tensile strength and tear strength were excellent.

Claims

1. A curable composition comprising a polymer A and a polymer B, The polymer A is an oxyalkylene polymer having two or more terminal groups per molecule, the terminal groups not containing a divalent organic group represented by —C(═O)NH— but containing at least one group selected from the group consisting of a reactive silicon group represented by the following formula 1, an unsaturated group, and a hydroxyl group, and having a silylation rate calculated by the following formula f1 of 85 to 100 mol %, The polymer B is an oxyalkylene polymer having two or more terminal groups per molecule, the terminal groups having at least one group selected from the group consisting of a reactive silicon group, an unsaturated group, and a hydroxyl group, represented by the following formula 1, the average total number of the reactive silicon groups, the unsaturated groups, and the hydroxyl groups per terminal group being greater than 1.0, and a silylation rate calculated by the following formula f1 being smaller than the silylation rate of the polymer A. -SiR ａ X ３－ａ Formula 1 In the formula 1, R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, X represents a hydroxyl group or a hydrolyzable group, and a is an integer of 0 to 2. When a is 2, R may be the same or different from each other, and when a is 0 or 1, X may be the same or different from each other. The reactive silicon group of the polymer A and the reactive silicon group of the polymer B may be the same or different. [Equation 1]

2. The curable composition according to claim 1 , wherein at least one of the terminal groups in the polymer B has a group represented by the following formula 2: 【Chemistry 1】 In the formula 2, R ２ , R ３ each independently represents a divalent organic group having 1 to 6 carbon atoms and no carbon-carbon unsaturated bond, and R ４ , R ５ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. n represents an integer of 1 to 10. R １ , X １ , a1 are the same as R, X, and a in the formula 1. When a1 is 2, R １ may be the same or different, and when a1 is 0 or 1, X １ may be the same or different. １ ３－ａ１ X １ ａ１ may be the same or different from each other.

3. 2. The curable composition according to claim 1, wherein the number average molecular weight of the polymer A is 5,000 to 100,000.

4. The curable composition according to claim 1 , wherein the silylation rate of the polymer B is less than 85 mol %.

5. The curable composition according to claim 1 , wherein the reactive silicon group of the polymer A is a reactive silicon group represented by the following formula 3: -OR １１ -SiR １２ ａ２ X ２ ３－ａ２ Formula 3 In the formula 3, R １１ is a linear alkylene group having 1 to 20 carbon atoms, and R １２ , X ２ , a2 are the same as R, X, and a in the formula 1. When a2 is 2, R １２ may be the same or different, and when a2 is 0 or 1, X ２ may be the same or different from each other.

6. 2. The curable composition according to claim 1, wherein the content of the polymer A is 1 to 99 parts by mass relative to 100 parts by mass of the total content of the polymer A and the polymer B.

7. The curable composition according to claim 1, wherein a total content of the polymer A and the polymer B relative to the total mass of the curable composition is 1 to 50 mass%.

8. A cured product of the curable composition according to any one of claims 1 to 7.

9. A method for producing the curable composition according to any one of claims 1 to 7, comprising: obtaining the polymer A by reacting an unsaturated group-containing oxyalkylene polymer with a silylating agent in the presence of a Group 8 metal catalyst and a co-catalyst containing either or both of a carboxylic acid compound having a carbon-carbon triple bond and a carboxylic acid compound having a carbon-carbon double bond at the α-position carbon; A method for producing a curable composition, comprising mixing the polymer A and the polymer B.

10. The method for producing a curable composition according to claim 9 , wherein the amount of the silylating agent added is 0.90 times or more by mole based on the total amount of unsaturated groups in the unsaturated group-containing oxyalkylene polymer.

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