Method for producing composition, method for producing oxyalkylene polymer, method for producing curable composition, and method for producing cured product

Abstract

To provide a method for producing a composition containing an oxyalkylene polymer A, the oxyalkylene polymer A having reduced viscosity, a hydroxyl group, and a carbon-carbon double bond at a molecular end; a method for producing an oxyalkylene polymer B more efficiently by employing the composition, the oxyalkylene polymer B having a reactive silicon group on its main chain, being free of the reactive silicon group at its terminal group, and having a hydroxyl group; a method for producing a curable composition comprising the oxyalkylene polymer B; and a method for producing a cured product employing the curable composition.SOLUTION: There is provided a method for producing a composition containing an oxyalkylene polymer A, the oxyalkylene polymer A having a hydroxyl group and a carbon-carbon double bond at a molecular end, wherein the method comprises obtaining the oxyalkylene polymer A by polymerizing an alkylene oxide with an initiator that has an active hydrogen-containing group and a carbon-carbon double bond at a molecular end, in the presence of a double metal cyanide complex catalyst having an alcohol as a ligand.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a composition, a method for producing an oxyalkylene polymer, a method for producing a curable composition, and a method for producing a cured product. [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 are already being produced industrially and are widely used in applications such as sealants, adhesives, and paints.

[0004] In order to make the curable composition easier to handle, a plasticizer is used to reduce the viscosity of the curable composition. Low-molecular-weight compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester and diisononyl phthalate are widely used as the plasticizer. However, the use of a low-molecular-weight compound as a plasticizer can cause bleeding in the resulting cured product.

[0005] Reactive plasticizers are known as plasticizers that can suppress bleed-out. Low-molecular-weight oxyalkylene polymers containing one reactive silicon group and one hydroxyl group per molecule are known as reactive plasticizers. The reactive silicon groups of the oxyalkylene polymers are incorporated into the cured product through reaction, thereby suppressing bleed-out.

[0006] Patent Document 1 discloses a method for producing a low-molecular-weight oxyalkylene polymer having one reactive silicon group and one hydroxyl group per molecule. Specifically, the method involves using a polyoxypropylene polymer having an average molecular weight of 1,500 and an unsaturated group and a hydroxyl group per molecule as an initiator, polymerizing propylene oxide in the presence of a zinc hexacyanocobaltate glyme complex to obtain a precursor having an unsaturated group and a hydroxyl group per molecule, and then hydrosilylating the precursor polymer with methyldimethoxysilane in the presence of a platinum divinyltetramethyldisiloxane catalyst to produce a polymer having a reactive silicon group and a hydroxyl group per molecule. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-294659 Summary of the Invention [Problem to be solved by the invention]

[0008] Patent Document 1 discloses that the zinc hexacyanocobaltate glyme complex inhibits the hydrosilylation reaction, and therefore, after obtaining a precursor polymer, a carboxylic acid compound such as succinic anhydride is added to inactivate the zinc hexacyanocobaltate glyme complex before the hydrosilylation reaction is carried out. The inactivation treatment of the zinc hexacyanocobaltate glyme complex makes the production process inefficient. Furthermore, reactive plasticizers are required to have low viscosity, but the viscosity of the polymer having a reactive silicon group and an unsaturated group in one molecule produced by the production method described in Patent Document 1 is not sufficiently low. The viscosity of the polymer having a reactive silicon group and an unsaturated group in one molecule is greatly affected by the viscosity of the precursor polymer.

[0009] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a composition containing an oxyalkylene polymer A having a lower viscosity and a hydroxyl group and a carbon-carbon double bond at the molecular terminal; a method for producing an oxyalkylene polymer B having a reactive silicon group in the main chain, no reactive silicon group at the terminal group, and a hydroxyl group using the above composition more efficiently; a method for producing a curable composition containing the above oxyalkylene polymer B; and a method for producing a cured product using the above curable composition. [Means for solving the problem]

[0010] The present invention includes the following [1] to

[17] . [1] A method for producing a composition containing an oxyalkylene polymer A having a hydroxyl group and a carbon-carbon double bond at the molecular terminal, the method comprising: polymerizing an alkylene oxide with an initiator having an active hydrogen-containing group and a carbon-carbon double bond at the molecular terminal in the presence of a double metal cyanide complex catalyst whose ligand is an alcohol to obtain the oxyalkylene polymer A. [2] The method for producing a composition according to [1], wherein the amount of the double metal cyanide complex catalyst used is 100 to 1,500 ppm by mass relative to the total mass of the initiator. [3] The method for producing a composition according to [1] or [2], wherein the oxyalkylene polymer A has a number average molecular weight of 3,000 to 20,000. [4] The method for producing a composition according to any one of [1] to [3], wherein the oxyalkylene polymer A has a molecular weight distribution of 1.30 or less. [5] The method for producing a composition according to any one of [1] to [4], wherein the double metal cyanide complex catalyst is a zinc hexacyanocobaltate complex of tert-butyl alcohol as a ligand. [6] The method for producing a composition according to any one of [1] to [5], wherein the oxyalkylene polymer A has 1 to 3 hydroxyl groups and 1 to 3 carbon-carbon double bonds at the molecular terminals. [7] The method for producing a composition according to [6], wherein the oxyalkylene polymer A has one hydroxyl group and one carbon-carbon double bond at the molecular terminal. [8] A method for producing an oxyalkylene polymer B having a reactive silicon group represented by the following formula 1 in its main chain, having no reactive silicon group at its terminal groups, and having a hydroxyl group, comprising reacting a composition produced by the method for producing a composition according to any one of [1] to [7] with a silylating agent in the presence of a hydrosilylation catalyst to obtain the oxyalkylene polymer B. -SiR 1 a1 X 1 3-a1 formula 1 In the formula 1, R 1 represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, and X 1 represents a hydroxyl group, a halogen atom, or a hydrolyzable group. a1 is an integer of 0 to 2. 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 from each other. [9] The method for producing an oxyalkylene polymer B according to [8], wherein the amount of the hydrosilylation catalyst used is 1 to 15 ppm by mass, calculated as the metal contained in the hydrosilylation catalyst, relative to the total mass of the composition.

[10] The method for producing an oxyalkylene polymer B according to [8] or [9], wherein the oxyalkylene polymer B has a number average molecular weight of 3,000 to 20,000.

[11] The method for producing an oxyalkylene polymer B according to any one of [8] to

[10] , wherein the molecular weight distribution of the oxyalkylene polymer B is 1.30 or less.

[12] The method for producing an oxyalkylene polymer B according to any one of [8] to

[11] , wherein the hydrosilylation catalyst is a platinum complex.

[13] The method for producing an oxyalkylene polymer B according to

[12] , wherein the platinum complex is a platinum-vinylsiloxane complex.

[14] The method for producing an oxyalkylene polymer B according to any one of [8] to

[13] , wherein the oxyalkylene polymer B has 1 to 3 hydroxyl groups and 1 to 3 reactive silicon groups.

[15] The method for producing an oxyalkylene polymer B according to

[14] , wherein the oxyalkylene polymer B has one hydroxyl group and one reactive silicon group.

[16] A method for producing a curable composition, comprising mixing a polymer B produced by the method for producing an oxyalkylene polymer B according to any one of [8] to

[15] above with an oxyalkylene polymer C having a reactive silicon group represented by the following formula 2 at its terminal group and having a number average molecular weight of 10,000 to 100,000: -SiR 2 a2 X 2 3-a2 formula 2 In the formula 2, R 2 represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, and X 2 represents a hydroxyl group, a halogen atom, or a hydrolyzable group. a2 is an integer of 0 to 2. When a2 is 2, R 2 may be the same or different, and when a2 is 0 or 1, X 2 may be the same or different from each other.

[17] A method for producing a cured product, comprising curing a curable composition produced by the method for producing a curable composition according to

[16] . [Effects of the Invention]

[0011] According to the present invention, there are provided a method for producing a composition containing an oxyalkylene polymer A having a lower viscosity and a hydroxyl group and a carbon-carbon double bond at the molecular terminal; a method for more efficiently using the above composition to produce an oxyalkylene polymer B having a reactive silicon group in the main chain, no reactive silicon group at the terminal group, and a hydroxyl group; a method for producing a curable composition containing the above oxyalkylene polymer B; and a method for producing a cured product using the above curable composition. DETAILED DESCRIPTION OF THE INVENTION

[0012] 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 a polymer means an atomic group formed directly by polymerization of a monomer. The term "main chain" refers to a polymer chain formed by polymerization of two or more monomers. In the oxyalkylene polymer described below, the "main chain" refers to a portion containing a residue of an initiator and a repeating unit based on alkylene oxide (polyoxyalkylene chain). An oxyalkylene polymer is a polymer consisting of a main chain and terminal groups. 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. The term "precursor polymer" refers to a polymer before the introduction of reactive silicon groups, and is an oxyalkylene polymer having a hydroxyl terminal group obtained by polymerizing alkylene oxide with active hydrogen of an initiator. Polymer A described below is a precursor polymer.

[0013] The "silylation rate" of polymer B described below is the ratio of the number of reactive silicon groups to the total number of reactive silicon groups and carbon-carbon double bonds in the oxyalkylene polymer. Specifically, the silylation rate is calculated by the following formula: Silylation rate (%) = 100 × number of reactive silicon groups / [number of reactive silicon groups + number of carbon-carbon double bonds]

[0014] The "silylation rate" of polymer C described below is the ratio of the number of reactive silicon groups to the total number of reactive silicon groups, hydroxyl groups, unsaturated groups, and isocyanate groups in the terminal groups of the oxyalkylene polymer. Specifically, the silylation rate is calculated by the following formula: Silylation rate (%) = 100 × number of reactive silicon groups / [number of reactive silicon groups + number of hydroxyl groups + number of isocyanate groups + (number of carbon-carbon double bonds) + (number of carbon-carbon triple bonds) × 2] The silylation rate can be measured by NMR analysis. Alternatively, it may be the ratio (mol %) of the number of silyl groups of the silylating agent added to the oxyalkylene polymer terminal groups when the reactive silicon groups are introduced into the terminal groups of the oxyalkylene polymer by the silylating agent described below to the number of terminal groups. The term "silylating agent" refers to a compound having a reactive silicon group and a functional group that reacts with a hydroxyl group, an unsaturated group, or an isocyanate group.

[0015] 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.

[0016] 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.

[0017] In this specification, the number average molecular weight (Mn) and weight average molecular weight (Mw) are polystyrene-equivalent molecular weights measured using GPC with tetrahydrofuran as an eluent and a calibration curve prepared using polystyrene polymers of known molecular weights. The molecular weight distribution (Mw / Mn) is the ratio of Mw to Mn.

[0018] <<Method for producing composition>> The method for producing a composition according to the present embodiment is a method for producing a composition containing an oxyalkylene polymer A (hereinafter also referred to as "polymer A") having a hydroxyl group and a carbon-carbon double bond at the molecular terminal. The method for producing the composition includes obtaining polymer A by polymerizing alkylene oxide with an initiator having an active hydrogen-containing group and a carbon-carbon double bond at the molecular terminal in the presence of a double metal cyanide complex catalyst having an alcohol ligand.

[0019] (initiator) The initiator has an active hydrogen-containing group and a carbon-carbon double bond at the molecular terminal. The number of active hydrogens contained in the initiator is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. The number of carbon-carbon double bonds contained in the molecular terminal of the initiator is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0020] Examples of initiators include compound 1, in which at least one carbon-carbon bond at the molecular terminal of a saturated hydrocarbon compound is substituted with a carbon-carbon double bond and at least one hydrogen atom is substituted with an active hydrogen-containing group, and low-molecular-weight compound 2 obtained by polymerizing alkylene oxide with compound 1. Among these, low-molecular-weight compound 2 is preferred. The saturated hydrocarbon compound may have an ethereal oxygen atom. Examples of the saturated hydrocarbon compound include linear or branched alkanes having 3 to 10 carbon atoms. The initiator may be used alone or in combination of two or more kinds.

[0021] The degree of unsaturation of the initiator is preferably from 0.40 to 4.00 mmol / g, more preferably from 1.00 to 3.00 mmol / g, and even more preferably from 1.00 to 2.00 mmol / g. The hydroxyl value of the initiator is preferably from 30 to 120 mgKOH / g, more preferably from 25 to 110 mgKOH / g, and even more preferably from 20 to 100 mgKOH / g. The hydroxyl value-based molecular weight of the initiator is preferably 500 to 2,000, more preferably 500 to 1,800, and even more preferably 500 to 1,500. The Mn of the initiator is preferably from 750 to 3,000, more preferably from 750 to 2,700, and even more preferably from 750 to 2,300. When the hydroxyl value and Mn of the initiator cannot be measured, the formula weight is used as the molecular weight converted into hydroxyl value and Mn.

[0022] (Double cyanide complex catalyst with alcohol ligand) A composite metal cyanide complex catalyst (hereinafter also referred to as "A-DMC catalyst") in which the ligand is an alcohol is a ring-opening polymerization catalyst. The A-DMC catalyst is a crystalline solid and contains a reaction product of a metal halide salt and a transition metal cyanide compound, a ligand, and water of crystallization (such as coordinated water) encapsulated in the crystal. In addition, it may contain trace amounts of impurities unavoidable during production in the metal salts and metal compounds, as well as moisture other than water of crystallization.

[0023] Examples of the metal that becomes a cation (the metal contained in the transition metal cyanide compound) and the metal in the metal halide salt include zinc, iron, cobalt, nickel, aluminum, strontium, manganese, chromium, copper, tin, lead, molybdenum, and tungsten, with zinc, iron, cobalt, and nickel being preferred, and zinc being more preferred.

[0024] Examples of halogen in the metal halide salt include fluorine, chlorine, bromine, and chlorine, with chlorine being preferred.

[0025] Examples of the metal in the transition metal cyanide compound include cobalt, iron, chromium, manganese, and vanadium, with cobalt, iron, chromium, and manganese being preferred, and cobalt being more preferred.

[0026] The ligand is an alcohol, and examples thereof include tert-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, and ethylene glycol mono-tert-butyl ether, with tert-butyl alcohol being preferred. The ligands may be used alone or in combination of two or more kinds.

[0027] The A-DMC catalyst is preferably a zinc hexacyanocobaltate (Zn3[Co(CN)6]2) complex with tert-butyl alcohol as the ligand. Water and zinc chloride may be coordinated to the complex.

[0028] The A-DMC catalyst is believed to be represented by Formula 1A below: M 1 a [M 2 (CN) b ] c d(M 1 e X f )·g(Ligand)·h(H2O) 1A In the above formula 1A, M 1 e X f is a metal halide salt, and M 1 is a metal atom that becomes a cation, X is a halogen atom that becomes a counter anion, and M 2 is the transition metal atom contained in the transition metal cyanide compound and serves as the active site, and Ligand is the ligand. a, b, c, d, e, f, g, and h are integers, and a, b, c, e, and f are numbers that result in electrical neutrality.

[0029] The above M 1 Examples of such elements include Zn(II), Fe(II), Fe(III), Co(II), Ni(II), Al(III), Sr(II), Mn(II), Cr(III), Cu(II), Sn(II), Pb(II), Mo(IV), Mo(VI), W(IV) and W(VI). The above M 2 Examples of such elements include Co(III), Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), V(IV), and V(V). Examples of X include Cl, Br, and I. M 1 e X fThe metal halide salt represented by the formula (I) is preferably one or more selected from zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, and zinc acetate. 2 In view of the interatomic distance between and X, it is more preferable that the compound contains at least one selected from zinc chloride and zinc bromide. Ligand is alcohol.

[0030] According to the investigations of the present inventors, it has been found that the use of an A-DMC catalyst in which the ligand is an alcohol has the following three advantages over the use of a DMC catalyst in which the ligand is a non-alcohol, such as a glyme (hereinafter also referred to as "other DMC catalysts"). The first advantage is that when the A-DMC catalyst is used, the viscosity of the resulting polymer A is reduced compared to when other DMC catalysts are used. The second advantage is that when the A-DMC catalyst is used, the amount of catalyst required can be reduced compared to when other DMC catalysts are used. Reducing the amount of catalyst required can suppress inhibition of the reaction with the silylating agent in the subsequent step. Furthermore, the third advantage is that the A-DMC catalyst is less likely to inhibit the reaction with the silylating agent in the subsequent step compared to other DMC catalysts. Due to the second and third advantages, there is no need to perform a deactivation treatment on the A-DMC catalyst, and it can be used directly in the reaction with the silylating agent.

[0031] The amount of the A-DMC catalyst used relative to the total mass of the initiator is preferably 100 to 1500 ppm by mass, more preferably 100 to 1200 ppm by mass, even more preferably 100 to 1000 ppm by mass, and particularly preferably 200 to 500 ppm by mass. When the amount of the A-DMC catalyst used is equal to or greater than the lower limit of the above range, polymerization proceeds easily. When the amount is equal to or less than the upper limit, the reaction with the silylating agent in the subsequent step is less likely to be inhibited.

[0032] (Alkylene oxide) The alkylene oxide is selected depending on the structural units of the polyoxyalkylene chain of the polymer A to be obtained. 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.

[0033] (Reaction conditions) 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.

[0034] <Polymer A> Polymer A has a hydroxyl group and a carbon-carbon double bond at the molecular terminal, but does not have a reactive silicon group described below. The number of hydroxyl groups in polymer A is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. The number of hydroxyl groups in polymer A is the same as the number of active hydrogens in the initiator. In addition, the number of hydroxyl groups in polymer A is the same as the number of terminal groups of polymer A. The number of carbon-carbon double bonds at the molecular terminals of polymer A is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. The number of carbon-carbon double bonds at the molecular terminals of polymer A is the same as the number of carbon-carbon double bonds at the molecular terminals of the initiator.

[0035] Polymer A is a polymer consisting of a main chain and terminal groups. The main chain of polymer A is a polymer chain comprising a residue obtained by removing active hydrogen from the initiator and a polyoxyalkylene chain comprising one or more repeating units based on alkylene oxide (hereinafter, a repeating unit based on a monomer will be simply referred to as a "monomer unit", for example, a repeating unit based on alkylene oxide will be referred to as an "alkylene oxide unit"). The main chain of polymer A is preferably a polymer chain comprising a residue obtained by removing active hydrogen from the initiator and a polyoxyalkylene chain comprising one or more alkylene oxide units. Note that the carbon-carbon double bond at the molecular terminal is contained in the residue obtained by removing active hydrogen from the initiator, and therefore the carbon-carbon double bond at the molecular terminal is contained in the main chain. The terminal group of polymer A is a hydroxyl group.

[0036] In the case of a polymer chain having two or more types of alkylene oxide units, the alkylene oxide units may form a block polymer or a random polymer.

[0037] 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%.

[0038] The degree of unsaturation of polymer A is preferably from 0.04 to 0.4 mmol / g, more preferably from 0.08 to 0.4 mmol / g, and even more preferably from 0.1 to 0.4 mmol / g. The hydroxyl value of the polymer A is preferably from 2.5 to 20.0 mgKOH / g, more preferably from 5.0 to 20.0 mgKOH / g, and even more preferably from 7.5 to 20.0 mgKOH / g. The hydroxyl value-based molecular weight of the polymer A is preferably from 2,000 to 14,000, more preferably from 2,000 to 10,000, and even more preferably from 2,000 to 7,000. The Mn of the polymer A is preferably from 3,000 to 20,000, more preferably from 3,000 to 15,000, and even more preferably from 3,000 to 10,000. The Mw / Mn of polymer A is preferably 1.30 or less, more preferably from 1.10 to 1.30, and even more preferably from 1.10 to 1.20. The viscosity of polymer A at 25° C. is preferably from 500 to 10,000 mPa·s, more preferably from 500 to 5,000 mPa·s, and even more preferably from 500 to 2,000 mPa·s.

[0039] <Composition> The composition contains polymer A and an A-DMC catalyst. The composition may contain a stabilizer in addition to polymer A and the A-DMC catalyst. The content of the A-DMC catalyst relative to the total mass of polymer A is preferably 20 to 200 ppm by mass, more preferably 20 to 180 ppm by mass, and even more preferably 20 to 150 ppm by mass. When the composition contains a stabilizer, the content of the stabilizer relative to the total mass of polymer A is preferably 500 to 2000 ppm by mass.

[0040] <Method for producing oxyalkylene polymer B> The method for producing oxyalkylene polymer B of this embodiment is a method for producing an oxyalkylene polymer B (hereinafter also referred to as "polymer B") that has a reactive silicon group represented by formula 1 described below in its main chain, does not have the reactive silicon group in its terminal group, and has a hydroxyl group. The method includes reacting a composition containing polymer A produced by the above method for producing a composition with a silylating agent in the presence of a hydrosilylation catalyst to obtain oxyalkylene polymer B. Polymer B does not have the reactive silicon group in its terminal group. Polymer B has the reactive silicon group in its main chain. In the method for producing polymer B of this embodiment, it is not necessary to perform a deactivation treatment for the A-DMC catalyst contained in the above composition.

[0041] <Reactive silicon group> The reactive silicon group has a halogen atom, 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 B is represented by the following formula 1: -SiR 1 a1 X 1 3-a1 formula 1

[0042] In the above formula 1, R 1 represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group. R 1 is preferably at least one selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms and triorganosiloxy groups.

[0043] R 1 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 of the polymer having a reactive silicon group and the stability of the curable composition. 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.

[0044] In the above formula 1, X 1 represents a hydroxyl group, a halogen atom, 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.

[0045] In the above formula 1, a1 is an integer of 0 to 2. When a1 is 2, R 1 may be the same or different. When a1 is 1 or less, X 1 may be the same or different. If the crosslinking density by siloxane bonds is low, the modulus of the cured product will decrease, so a is preferably 2 or less, and a1 is more preferably 1 or less.

[0046] 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.

[0047] (hydrosilylation catalyst) The hydrosilylation catalyst is preferably a catalyst containing a metal of 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 preferably a simple substance of the Group 8 metal, a support in which the Group 8 metal is supported on a support, a metal salt, or a complex with an organic compound. Specifically, platinum complexes such as platinum itself, solid platinum supported on a support such as alumina, silica, or carbon black, metal salts such as hexachloroplatinic acid (IV) hexahydrate, chloroplatinic acid complexes with alcohols, aldehydes, ketones, or the like as ligands, 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], and platinum-phosphite complexes [Pt{P(OPh)3}4] are preferred.

[0048] Platinum olefin complexes, platinum-acetylacetonate complexes, and platinum-vinylsiloxane complexes are more preferred, and platinum-vinylsiloxane complexes are even more preferred. These Group 8 metal catalysts may be used alone or in combination of two or more.

[0049] The hydroxyl groups of polymer B may undergo an alcohol exchange reaction with the hydrolyzable groups (alkoxy groups) in the reactive silicon, resulting in polymerization of polymer B. Polymerization of polymer B causes an increase in viscosity. The inventors of the present application have found that the alcohol exchange reaction can be suppressed by using a platinum-vinylsiloxane complex as a hydrosilylation catalyst.

[0050] The amount of the hydrosilylation catalyst used relative to the total mass of the composition is preferably 1 to 15 ppm by mass, more preferably 1 to 10 ppm by mass, and even more preferably 1 to 5 ppm by mass, calculated as the metal contained in the hydrosilylation catalyst. When the amount of the hydrosilylation catalyst used is equal to or greater than the lower limit of the above range, the hydrosilylation reaction is likely to proceed. When the amount is equal to or less than the upper limit, the alcohol exchange reaction is inhibited, and the viscosity is likely to decrease.

[0051] (Silylating agent) Examples of silylating agents include compounds having both a group capable of reacting with the carbon-carbon double bond at the molecular terminal to form a bond (e.g., a sulfanyl group) and a reactive silicon group represented by the above formula 1, and hydrosilane compounds (e.g., HSiR 1 a1 X 1 3-a1 , R 1 , X 1 , a1 is the same as in formula 1 above). Specific examples include dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, methyldiisopropoxysilane, (α-chloromethyl)dimethoxysilane, (α-chloromethyl)diethoxysilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, and 3-mercaptopropyltrimethoxysilane. In view of high activity and good curability, trimethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane are preferred, and dimethoxymethylsilane is more preferred.

[0052] The molar ratio of the amount of the silylating agent used to the total amount of carbon-carbon double bonds at the molecular terminals contained in polymer A is preferably from 0.6 to 0.85, more preferably from 0.7 to 0.85, and even more preferably from 0.75 to 0.85. The silylation rate of the polymer B is preferably from 60 to 85 mol %, more preferably from 70 to 85 mol %, and even more preferably from 75 to 85 mol %.

[0053] (Reaction conditions) 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.

[0054] The reaction can be carried out in the presence or absence of a solvent. When polymer A is a solid or a highly viscous liquid, it is preferable to use a solvent to reduce the viscosity of the reaction solution. The solvent for the hydrosilylation reaction is not particularly limited, but examples include hydrocarbon solvents such as heptane, benzene, toluene, and xylene, halogenated hydrocarbon compounds, alcohols, glycols, ethers, esters, ketones, nitriles, and amides.

[0055] The gas phase of the reactor during the hydrosilylation reaction is preferably an inert gas such as nitrogen or helium.

[0056] <Polymer B> Polymer B has a reactive silicon group in its main chain, but does not have a reactive silicon group at its terminal group but has a hydroxyl group. Polymer B may have an unsaturated group in its main chain. The unsaturated group is preferably a carbon-carbon double bond located at a position other than the molecular terminal. The number of hydroxyl groups in polymer B is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. The number of hydroxyl groups in polymer B is the same as the number of hydroxyl groups in polymer A. In addition, the number of hydroxyl groups in polymer B is the same as the number of terminal groups of polymer B.

[0057] The average number of reactive silicon groups in the main chain of polymer B is preferably 0.75 to 2.4, more preferably 0.75 to 1.6, and even more preferably 0.75 to 0.85. When the silylation rate is 100%, the number of reactive silicon groups in polymer B is the same as the number of carbon-carbon double bonds at the molecular terminals of polymer A.

[0058] Polymer B is a polymer consisting of a main chain and terminal groups. The main chain of polymer B is a polymer chain comprising a derivative unit in which a reactive silicon group has been introduced into the residue remaining after removal of active hydrogen from the initiator, and a polyoxyalkylene chain comprising one or more alkylene oxide units. The main chain of polymer B is preferably a polymer chain comprising a derivative unit in which a reactive silicon group has been introduced into the residue remaining after removal of active hydrogen from the initiator, and a polyoxyalkylene chain comprising one or more alkylene oxide units. The derivative unit is an atomic group obtained by reacting the silylating agent with a carbon-carbon double bond at the molecular terminal in the residue remaining after removal of active hydrogen from the initiator. The reactive silicon group is obtained by converting the carbon-carbon double bond at the molecular terminal derived from the initiator residue of polymer A, and therefore the reactive silicon group is included in the main chain. The polyoxyalkylene chain is the same as the example of polymer A. The terminal groups of polymer B are hydroxyl groups and do not contain reactive silicon groups.

[0059] The Mn of the polymer B is preferably from 3,000 to 20,000, more preferably from 3,000 to 15,000, and even more preferably from 3,000 to 10,000. The Mw / Mn of polymer B is preferably 1.30 or less, more preferably from 1.10 to 1.30, and even more preferably from 1.10 to 1.20. The viscosity of Polymer B at 25° C. is preferably from 500 to 10,000 mPa·s, more preferably from 500 to 5,000 Pa·s, and even more preferably from 500 to 2000 mPa·s.

[0060] <Method for producing curable composition> The method for producing a cured composition of this embodiment is a method for producing a curable composition by mixing polymer B with an oxyalkylene polymer C (hereinafter also referred to as "polymer C") having a reactive silicon group represented by the following formula 2 at its terminal group and having an Mn of 10,000 to 100,000. The curable composition may contain a vinyl polymer having a reactive silicon group, which will be described later, and other components. The curable composition of this embodiment may contain two or more types of polymer B. -SiR 2a2 X 2 3-a2 formula 2 In the above formula 2, R 2 represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, and X 2 represents a hydroxyl group, a halogen atom, or a hydrolyzable group. a2 is an integer of 0 to 2. When a2 is 2, R 2 may be the same or different, and when a2 is 0 or 1, X 2 may be the same or different from each other.

[0061] <Polymer C> Polymer C is an oxyalkylene polymer having a reactive silicon group represented by the above formula 2 at its terminal group and Mn of 10,000 to 100,000. When polymer C has a plurality of terminal groups, the terminal groups preferably have the above reactive silicon group, unsaturated group, isocyanate group, or hydroxyl group. 2 , X 2 , a2 are R in the above formula 1, 1 , X 1 , a1 is the same. The curable composition of the present embodiment may contain two or more types of polymer C.

[0062] Polymer C is a polymer consisting of a main chain and terminal groups. The main chain of polymer C is a polymer chain comprising a residue obtained by removing active hydrogen from an initiator and a polyoxyalkylene chain comprising one or more alkylene oxide units. The main chain of polymer C is preferably a polymer chain comprising a residue obtained by removing active hydrogen from an initiator and a polyoxyalkylene chain comprising one or more alkylene oxide units. It is preferable that the main chain does not comprise a reactive silicon group. The polyoxyalkylene chain is the same as the example of polymer A. The polymer C has a reactive silicon group as a terminal group. When the polymer C has a plurality of terminal groups, the terminal groups preferably have the reactive silicon group, unsaturated group, isocyanate group, or hydroxyl group.

[0063] The number of terminal groups in one molecule of polymer C is preferably 2 to 8, more preferably 2 to 7, and even more preferably 2 to 6. When the number of terminal groups is within the above range, the cured product has higher tensile strength and better modulus and elongation. When there are two or more terminal groups, the respective terminal groups may be the same or different.

[0064] The average number of reactive silicon groups per terminal group of polymer C is preferably 0.5 to 1.7, more preferably 0.5 to 1.0, and even more preferably 0.5 to 0.75. If the average number is equal to or greater than the lower limit of the above range, the crosslinking density due to siloxane bonds will be high, making it easier to obtain a good cured product with a high modulus.

[0065] The average number of reactive silicon groups per molecule of polymer C is preferably 1.0 to 9.6, more preferably 1.0 to 6.0, and even more preferably 1.0 to 4.8. If it is at least the lower limit of the above range, the crosslinking density due to siloxane bonds will be high, making it easier to obtain a good cured product with a high modulus.

[0066] The Mn of polymer C is preferably 10,000 to 100,000, more preferably 10,000 to 90,000, even more preferably 10,000 to 80,000, and particularly preferably 10,000 to 70,000. When the Mn is equal to or greater than the lower limit of the above range, the elongation properties of the cured product are improved. When the Mn is equal to or less than the upper limit of the above range, the viscosity is low and workability is improved.

[0067] The molecular weight distribution of polymer C is preferably 1.30 or less. A smaller molecular weight distribution is preferable, more preferably 1.10 to 1.30, even more preferably 1.10 to 1.30, and particularly preferably 1.10 to 1.20, because good elongation properties are easily obtained and the viscosity is reduced, resulting in good workability.

[0068] <Method of producing polymer C> The method for producing polymer C includes producing a precursor polymer and silylating the resulting precursor polymer.

[0069] (Preparation of precursor polymer) The precursor polymer can be prepared by polymerizing an initiator and an alkylene oxide in the presence of a ring-opening polymerization catalyst. The number of active hydrogens in the initiator is preferably 2 to 8, more preferably 2 to 7, and even more preferably 2 to 6. It is preferable to select the number depending on the number of reactive silicon groups per molecule of the polymer C to be obtained. The initiator may be used alone or in combination of two or more kinds.

[0070] The initiator preferably has a hydroxyl group as the active hydrogen-containing group. The initiator having one hydroxyl group is preferably a monohydric alcohol having a linear or branched hydrocarbon group, such as methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-butyl alcohol, tert-butyl alcohol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, oleyl alcohol, or a low-molecular-weight polyoxyalkylene monool. 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.

[0071] The alkylene oxide is selected depending on the constituent units of the polyoxyalkylene chain of the precursor polymer and polymer C to be obtained. 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.

[0072] 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 the precursor polymer tends to be narrow and the degree of unsaturation of the precursor polymer tends 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 tert-butyl alcohol is coordinated as a 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 tert-butyl alcohol as a ligand is preferred.

[0073] The Mn of the precursor polymer is preferably from 10,000 to 100,000, more preferably from 10,000 to 90,000, still more preferably from 10,000 to 80,000, and particularly preferably from 10,000 to 70,000. It is preferable to set it according to the Mn of the polymer C to be obtained. The Mw / Mn of the precursor polymer is preferably set so that the Mw / Mn of polymer C is 1.30 or less. For example, the Mw / Mn of the precursor polymer is preferably 1.25 or less, more preferably 1.20 or less, and even more preferably 1.15 or less. The lower limit is not particularly limited. For example, it is 1.00 or more, and preferably 1.01 or more. The above lower and upper limits can be combined arbitrarily. For example, the Mw / Mn of the precursor polymer is preferably 1.10 to 1.30, more preferably 1.15 to 1.30, even more preferably 1.20 to 1.30, and particularly preferably 1.25 to 1.30.

[0074] (silylation) Examples of the silylation method include the following methods (a) to (c). Method (a): A method in which the hydroxyl groups of a precursor polymer are converted into alkenyloxy groups having a carbon-carbon double bond at the molecular terminal, and then a silylating agent capable of introducing a reactive silicon group represented by the above formula 2 is reacted with the carbon-carbon double bond at the molecular terminal of the alkenyloxy group to convert the alkenyloxy group into a group having the reactive silicon group represented by the above formula 2. Method (b): A method in which a silylating agent having a functional group reactive with the hydroxyl group of a precursor polymer and a reactive silicon group represented by the above formula 2 is reacted with the hydroxyl group to convert the hydroxyl group into a group having the reactive silicon group represented by the above formula 2. Method (c): A method in which the hydroxyl groups of a precursor polymer are converted into groups having an isocyanate group, and then the precursor polymer is reacted with a silylating agent having a functional group reactive with an isocyanate group and a reactive silicon group represented by the above formula 2 to convert the hydroxyl groups into groups having a reactive silicon group represented by the above formula 2.

[0075] As the above methods (a) to (c), the methods described in paragraphs

[0029] to

[0056] of WO 2023 / 1282298 can be applied.

[0076] The silylation rate of polymer C is preferably 50 to 100 mol %, more preferably 60 to 98 mol %. When the silylation rate is at least the lower limit of the above range, the cured product has excellent tensile strength and a high modulus.

[0077] <Polymer D> The curable composition of this embodiment may contain a vinyl polymer (hereinafter also referred to as "polymer D") having, on average, one or more reactive silicon groups represented by the above formula 1 per molecule. The curable composition of this embodiment may contain two or more types of polymer D. Polymer D contributes to weather resistance, water resistance, and the like. The reactive silicon group in polymer D may be introduced at the end of the main chain, at the side chain, or at both the end of the main chain and the side chain. The average number of reactive silicon groups per molecule of polymer D is preferably 0.8 or more. From the viewpoint of tensile strength after curing, it is preferably 1.0 or more, more preferably 1.2 or more. From the viewpoint of good elongation of the cured product, it is preferably 4.0 or less, more preferably 3.0 or less. The average number of reactive silicon groups per molecule of polymer D is calculated by multiplying the concentration of reactive silicon groups in polymer D (mol / g) by the number average molecular weight of polymer D. The concentration of reactive silicon groups in polymer D (mol / g) can be measured by NMR. As the monomer constituting the main chain of polymer D, for example, known monomers as described in JP-B-3-14068, JP-A-6-211922, and JP-A-11-130931 can be used. Examples of monomers containing a reactive silicon group and an unsaturated group to be copolymerized with the above-mentioned monomers include vinyldimethoxymethylsilane, vinyldiethoxymethylsilane, vinylmethyldichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, tris(2-methoxyethoxy)vinylsilane, 3-(dimethoxymethylsilyl)propyl(meth)acrylate, 3-(trimethoxysilyl)propyl(meth)acrylate, and 3-(triethoxysilyl)propyl(meth)acrylate. Two or more of these may be used. The content of the (meth)acrylic acid ester monomer relative to all the monomers constituting the polymer D is preferably 50% by mass or more, more preferably 70% by mass or more, and may be 100% by mass.

[0078] Polymer D can be polymerized by a conventionally known polymerization method described in JP-A Nos. 2006-257405, 2006-37076, 2008-45059, etc. Conventionally known secondary materials such as initiators required for polymerization can also be used, and reaction conditions such as reaction temperature and reaction pressure can also be appropriately selected. Examples of polymerization methods include solution polymerization, emulsion polymerization, suspension polymerization, or bulk polymerization using a radical polymerization initiator, as well as living radical polymerization. Examples of living radical polymerization methods include those using cobalt porphyrin complexes, as disclosed in the Journal of the American Chemical Society (J. Am. Chem. Soc.), Vol. 116, p. 7943, 1994; those using nitroxide radicals, as disclosed in JP-A-2003-500378; and atom transfer radical polymerization (ATRP), as disclosed in JP-A-11-130931, using organic halides or sulfonyl halide compounds as initiators and transition metal complexes as catalysts. Polymers obtained by living radical polymerization tend to have narrow molecular weight distributions and low viscosity. It is also possible to use a commercially available polymer D. Examples of commercially available products that can be used include the XMAP series (trade name of Kaneka Corporation), the ARUFON US-6000 series (e.g., US-6110, US-6120, US-6170, etc., all of which are product names of Toagosei Co., Ltd.), and the Actflow NE series (e.g., NE-1000, NE-3000, all of which are product names of Soken Chemical & Engineering Co., Ltd.).

[0079] The Mn of polymer D is preferably from 500 to 100,000, more preferably from 800 to 80,000, and even more preferably from 1,000 to 60,000. When the Mn is at least the lower limit of the above range, the cured product tends to have excellent elongation properties and weather resistance, and when it is no greater than the upper limit, the workability is superior. The Mw / Mn of the polymer D is preferably 4.0 or less, more preferably 3.0 or less. When it is equal to or less than the above upper limit, the workability is more excellent.

[0080] <Curable composition> The content of polymer B relative to the total mass of the curable composition is preferably 5 to 40 mass%, more preferably 5 to 30 mass%, and even more preferably 5 to 20 mass%. When it is equal to or less than the upper limit of the above range, the cured product has better tensile strength and elongation properties. The content of polymer C relative to the total mass of the curable composition is preferably 10 to 60 mass%, more preferably 10 to 50 mass%, and even more preferably 10 to 40 mass%. When the content is equal to or greater than the lower limit of the above range, 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 of the above range, the cured product has better tensile strength and a higher modulus.

[0081] The combined content of polymer B and polymer C relative to the total mass of the curable composition is preferably 15 to 80 mass%, more preferably 15 to 70 mass%, and even more preferably 15 to 60 mass%. When it is at least the lower limit of the above range, the curability is good, and the cured product has excellent tensile strength and a high modulus.

[0082] The content of the polymer B is preferably 10 to 50 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 10 to 30 parts by mass, relative to 100 parts by mass of the total content of the polymer B and the polymer C. When the content is equal to or greater than the lower limit of the above range, the viscosity of the curable composition decreases, and the tensile strength of the cured product becomes superior. When the content is equal to or less than the upper limit of the above range, the tensile strength and modulus become superior.

[0083] When the curable composition contains polymer D, the content of polymer D is preferably 20 to 100 parts by mass, more preferably 30 to 100 parts by mass, and even more preferably 40 to 100 parts by mass, relative to 100 parts by mass of the total of polymers C. When the content is equal to or less than the upper limit of the above range, the weather resistance of the cured product of the curable composition becomes better.

[0084] The content of components other than polymers B to D relative to the total mass of the curable composition is preferably from 40 to 80 mass %, more preferably from 40 to 70 mass %, and even more preferably from 40 to 60 mass %.

[0085] [Other ingredients] Examples of the other components include curable compounds other than polymers A to D, such as epoxy resins, 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.

[0086] The curable composition may be a one-component type in which the polymer and all other components are mixed in advance and stored in a sealed container, and then 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. 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.

[0087] [Application] 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). In particular, it is suitable for applications requiring good tensile strength and reduced bleed-out in the cured product, such as floor adhesives. [Example]

[0088] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following descriptions.

[0089] [Hydroxyl value and hydroxyl value-equivalent molecular weight] The hydroxyl value was calculated in accordance with JIS K 1557: 2007. The hydroxyl value-based molecular weight was calculated based on the formula "56,100 / (hydroxyl value of polymer)×number of active hydrogen atoms in initiator."

[0090] [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.

[0091] [Silylation rate] The silylation rate is 1 H-NMR analysis was performed.

[0092] [Measurement of unsaturation degree] The unsaturation degree of the polymer was measured according to the Wijs method. Specifically, approximately 2 g of polymer was placed in an Erlenmeyer flask, accurately weighed, and dissolved in 40 ml of chloroform. Wijs reagent was accurately measured and added using a 20 ml volumetric pipette, and the flask was then left in a cool, dark place for 1 hour. A potassium iodide solution (2 g) dissolved in 100 ml of water was added to the potassium iodide solution, to which several drops of starch solution had been added. N / 10 sodium thiosulfate was then added dropwise with stirring, and the end point was determined when the solution in the flask became colorless and transparent. The unsaturated value was calculated from the end point using the following formula. The blank titration was performed using chloroform without polymer, as described above. Unsaturated group value (mmol / g) = ((blank test titer (ml) - sample titer (ml)) x titer of sodium thiosulfate solution) ÷ (20 x sample (g))

[0093] [Viscosity measurement] The viscosity of the polymer was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: RE80 type) under conditions of a measurement temperature of 25°C and rotor No. 4.

[0094] [Tensile property test] The adherend was an anodized aluminum plate coated with the primer MP-2000 (product name of Cemedine Co., Ltd.), and test specimens were prepared in accordance with the test method for architectural sealants in JIS A 1439 5.2 (2016), and tensile property tests were conducted. Specifically, the curable composition was poured into the space formed by sandwiching a spacer between the two aluminum plates, and then cured for 7 days at a temperature of 23°C and a relative humidity of 50%, and then further cured for 7 days at a temperature of 50°C and a relative humidity of 65% to obtain a test specimen. The obtained test specimen was subjected to a tensile property test using a Tensilon testing machine, and the stress at 50% elongation (referred to as "M50" in Table 3; unit: N / mm 2 ), maximum cohesive strength (referred to as "Tmax" in Table 3. Unit: N / mm 2 ), and maximum elongation (referred to as "Emax" in Table 3, unit: %) were measured.

[0095] [Paint contamination test] The curable composition was applied to an aluminum plate in a 50 mm x 50 mm x 10 mm pattern and cured for 48 hours at 23°C and 50% relative humidity. A one-component aqueous reactive curing silicone resin paint (Odefresh Si100II, manufactured by Nippon Paint Co., Ltd.) was then applied over the coating. After curing at 50°C for one week and then at 23°C for one day, thoroughly dried contaminant powder was sprinkled over the entire surface and allowed to stand for 10 minutes. Unadhered contaminant powder was sifted off. A sample with minimal contaminant powder and maintaining the color of the curable composition was rated "excellent," while a sample with significant contaminant powder and a loss of color was rated "poor." The contaminant powder used was JIS Test Powder Type 1, 8 (Kanto Rohm) (manufactured by the Japan Powder Industry and Engineering Association). The paint contamination was measured using the above-mentioned paint contamination evaluation method. A sample with almost no contamination powder attached and maintaining the color of the curable composition was rated as "Excellent" (◎), and a sample with a large amount of contamination powder attached and impairing the color of the curable composition was rated as "Poor" (×).

[0096] Below, Examples 1, 2, and 5 to 10 are working examples, and Examples 3, 4, and 11 are comparative examples.

[0097] (Example 1) The initiator used was a linear polyether (obtained by ring-opening addition polymerization of propylene oxide to allyl alcohol, hereafter referred to as "Polyether Z1") having one allyl group and one hydroxyl group at each end. The hydroxyl value-based molecular weight of Polyether Z1 was 600, the hydroxyl value determined by hydroxyl value titration was 89.6 mg KOH / g, and the degree of unsaturation determined by iodine value titration was 1.45 mmol / g. A reaction vessel was charged with 1,000 g of polyether Z1 and 0.41 g of a zinc hexacyanocobaltate complex catalyst for tert-butyl alcohol (hereinafter referred to as "TBA-DMC catalyst") and dehydrated by nitrogen substitution. To activate the catalyst, 100 g of propylene oxide was charged and heated to 100°C. After an induction period, the reaction temperature rose sharply and then dropped. After confirming the drop in reaction temperature, an additional 7,180 g of propylene oxide was added dropwise over approximately 5 hours, and the polymerization addition reaction was carried out while maintaining the internal temperature at 100-110°C. After the dropwise addition was completed, heating was continued for another hour, and then degassing was performed under reduced pressure to remove traces of unreacted propylene oxide, yielding Composition 1 containing Polymer A-1. The type of catalyst used and the amount of catalyst used relative to the total mass of the initiator are shown in Table 1 (the same applies to Examples 2 to 4 below).

[0098] Polymer A-1 is a linear oxyalkylene polymer having one hydroxyl group and one carbon-carbon double bond at the molecular terminal. Polymer A-1 has one terminal group, which is a hydroxyl group. The degree of unsaturation, hydroxyl value, hydroxyl value-based molecular weight, Mn, Mw / Mn, and viscosity of Polymer A-1 are shown in Table 1 (the same applies to Examples 2 and 4 below). The content of the DMC catalyst in Composition 1 relative to the total mass of Polymer A-1 is also shown in Table 1 (the same applies to Examples 2 and 4 below).

[0099] (Example 2) Composition 2 containing Polymer A-2 was obtained in the same manner as in Example 1, except that the amount of TBA-DMC catalyst charged was changed to 0.98 g. Polymer A-2 is a linear oxyalkylene polymer having one hydroxyl group and one carbon-carbon double bond at the molecular terminal.

[0100] (Example 3) A reaction was carried out in the same manner as in Example 1, except that a glyme zinc hexacyanocobaltate complex catalyst (hereinafter referred to as "Glyme-DMC catalyst") was used instead of the TBA-DMC catalyst and the amount of Glyme-DMC catalyst charged was changed to 0.41 g. However, polymerization did not proceed and a polymer could not be obtained.

[0101] (Example 4) A composition 4 containing polymer a-1 was obtained in the same manner as in Example 3, except that the amount of Glyme-DMC catalyst charged was changed to 1.23 g. Polymer a-1 is a linear oxyalkylene polymer having one hydroxyl group and one carbon-carbon double bond at the molecular terminal.

[0102] [Table 1]

[0103] In Examples 1 and 2, in which the TBA-DMC catalyst was used, polymerization proceeded sufficiently, resulting in lower Mw / Mn and viscosity, despite the use of a smaller amount of catalyst than in Example 4, in which the Glyme-DMC catalyst was used. In Example 3, in which the same amount of Glyme-DMC catalyst as in Example 1 was used, polymerization did not proceed sufficiently.

[0104] (Example 5) To 1000 g of composition 1 containing polymer A-1 obtained in Example 1, 0.037 g of a 3 mass% isopropyl alcohol solution of platinum-vinylsiloxane complex and 15.2 g of dimethoxymethylsilane were added as hydrosilylation catalysts, in that order. The amount of dimethoxymethylsilane added was 0.8 molar equivalents relative to the total number of carbon-carbon double bonds at the molecular terminals contained in polymer A-1. The hydrosilylation reaction was carried out at 50°C for 2 hours, followed by degassing under reduced pressure to obtain polymer B-1. Polymer B-1 is a linear oxyalkylene polymer containing one hydroxyl group and one reactive silicon group (dimethoxymethylsilyl group). Polymer B-1 contains a reactive silicon group in the main chain, a hydroxyl group at the terminal group, and no reactive silicon group. The amount of platinum-vinylsiloxane complex (calculated as platinum) used relative to the total mass of Composition 1, the silylation rate, Mn, Mw / Mn, and viscosity of Polymer B-1 are shown in Table 2 (the same applies to Examples 6 to 11 below). In the table, "Pt-VTS" means platinum-vinylsiloxane complex.

[0105] (Example 6) Polymer B-2 was obtained in the same manner as in Example 5, except that the amount of a 3 mass% isopropyl alcohol solution of a platinum-vinylsiloxane complex added as a hydrosilylation catalyst was changed to 0.087 g. Polymer B-2 is a linear oxyalkylene polymer having one hydroxyl group and one reactive silicon group (dimethoxymethylsilyl group). Polymer B-2 has a reactive silicon group in the main chain but does not have a reactive silicon group at the terminal group.

[0106] (Example 7) Polymer B-3 was obtained in the same manner as in Example 5, except that 0.15 g of a 3 mass% isopropyl alcohol solution of platinum-vinylsiloxane complex was added as a hydrosilylation catalyst. Polymer B-3 is a linear oxyalkylene polymer having one hydroxyl group and one reactive silicon group (dimethoxymethylsilyl group). Polymer B-3 has a reactive silicon group in the main chain and a hydroxyl group at the terminal group, but does not have a reactive silicon group.

[0107] (Example 8) Polymer B-4 was obtained in the same manner as in Example 5, except that the amount of a 3 mass% isopropyl alcohol solution of a platinum-vinylsiloxane complex added as a hydrosilylation catalyst was changed to 0.40 g. Polymer B-3 is a linear oxyalkylene polymer having one hydroxyl group and one reactive silicon group (dimethoxymethylsilyl group). Polymer B-4 has a reactive silicon group in the main chain and a hydroxyl group at the terminal group, but does not have a reactive silicon group.

[0108] (Example 9) Polymer B-5 was obtained in the same manner as in Example 5, except that hexachloroplatinic (IV) acid hexahydrate (chloroplatinic acid hexahydrate) was used instead of the 3 mass% isopropyl alcohol solution of platinum-vinylsiloxane complex, and the amount of chloroplatinic acid hexahydrate added was changed to 0.007 g. Polymer B-5 is a linear oxyalkylene polymer having one hydroxyl group and one reactive silicon group (dimethoxymethylsilyl group). Polymer B-5 has a reactive silicon group in the main chain and hydroxyl groups at the terminal groups, but does not have a reactive silicon group.

[0109] (Example 10) Polymer B-6 was obtained in the same manner as in Example 5, except that composition 2 was used instead of composition 1. Polymer B-6 is a linear oxyalkylene polymer having one hydroxyl group and one reactive silicon group (dimethoxymethylsilyl group). Polymer B-6 has a reactive silicon group in the main chain and a hydroxyl group at the terminal group, but does not have a reactive silicon group.

[0110] (Example 11) Polymer b-1 was obtained in the same manner as in Example 6, except that composition 4 was used instead of composition 1. Polymer b-1 is a linear oxyalkylene polymer having one hydroxyl group and one reactive silicon group (dimethoxymethylsilyl group). Polymer b-1 has a reactive silicon group in the main chain and a hydroxyl group at the terminal group, but does not have a reactive silicon group.

[0111] [Table 2]

[0112] In Examples 5 to 10, which used compositions obtained using the TBA-DMC catalyst, the viscosity of the polymer having reactive silicon groups was low and the silylation rate was high, making deactivation of the TBA-DMC catalyst unnecessary. On the other hand, in Example 11, which used a composition obtained using the Glyme-DMC catalyst, the viscosity of the polymer having reactive silicon groups was high and the silylation rate was low, making deactivation of the Glyme-DMC catalyst necessary. Furthermore, when Example 5 (using Composition 1) and Example 10 (using Composition 2), which use different amounts of TBA-DMC catalyst, are compared, the silylation rate is the same, indicating that the silylation rate does not change depending on the amount of TBA-DMC catalyst used. This suggests that the TBA-DMC catalyst is less likely to inhibit the reaction with the silylating agent than the Glyme-DMC catalyst.

[0113] [Reference examples 1~5] Curable compositions were prepared using the polymer B-2 obtained in Example 6. Specifically, the curable compositions were prepared using the polymer and additives in the blending amounts (parts by mass) shown in Table 3. The above-mentioned tensile property test and paint contamination test were carried out using the obtained curable compositions. The results are shown in Table 3. Polymers C-1 to C-4 and polymers D-1 and D-2 were synthesized as follows.

[0114] (Synthesis Example 1: Synthesis of Polymer C-1) Propylene oxide was polymerized using sorbitol as an initiator and TBA-DMC catalyst to obtain an oxypropylene polymer (precursor polymer). The precursor polymer had a molecular weight of 42,000 calculated based on hydroxyl groups. Next, 1.05 molar equivalents of sodium methoxide in methanol was added relative to the hydroxyl groups of the precursor polymer to alcoholate the precursor polymer. The methanol was then distilled off by heating under reduced pressure, and an excess amount of allyl chloride relative to the amount of hydroxyl groups in the precursor polymer was added to convert the terminal groups to allyl groups. Next, in the presence of hexachloroplatinic acid (IV) hexahydrate, 0.5 molar equivalents of dimethoxymethylsilane relative to the converted allyl groups of the precursor polymer were added, and the reaction was carried out at 70°C for 5 hours to obtain Polymer C-1. Polymer C-1 is an oxyalkylene polymer having reactive silicon groups (dimethoxymethylsilyl groups). Polymer C-1 has reactive silicon groups at the terminal groups but no reactive silicon groups in the main chain.

[0115] (Synthesis Example 2: Synthesis of Polymer C-2) Propylene oxide was polymerized using propylene glycol as an initiator and TBA-DMC catalyst to obtain an oxypropylene polymer (precursor polymer). The precursor polymer had a hydroxyl group-based molecular weight of 10,000. Next, 1.05 molar equivalents of sodium methoxide in methanol was added relative to the hydroxyl groups of the precursor polymer to alcoholate the precursor polymer. Next, the methanol was distilled off by heating under reduced pressure, and an excess amount of allyl chloride relative to the amount of hydroxyl groups in the precursor polymer was added to convert the terminal groups to allyl groups. Next, in the presence of hexachloroplatinic acid (IV) hexahydrate, 0.5 molar equivalents of dimethoxymethylsilane relative to the converted allyl groups of the precursor polymer were added, and the reaction was carried out at 70°C for 5 hours to obtain Polymer C-2. Polymer C-2 is an oxyalkylene polymer having reactive silicon groups (dimethoxymethylsilyl groups). Polymer C-2 has reactive silicon groups at the terminal groups but no reactive silicon groups in the main chain.

[0116] (Synthesis Example 3: Synthesis of Polymer C-3) Propylene oxide was polymerized using propylene glycol as an initiator and Glyme-DMC catalyst as a catalyst to obtain an oxypropylene polymer (precursor polymer). The precursor polymer had a molecular weight calculated based on hydroxyl groups of 16,000. Next, 1.05 molar equivalents of sodium methoxide in methanol solution relative to the hydroxyl groups of the precursor polymer were added to alcoholate the precursor polymer. Next, the methanol was distilled off by heating under reduced pressure, and an excess amount of allyl chloride relative to the amount of hydroxyl groups in the precursor polymer was added to convert the terminal groups to allyl groups. Next, in the presence of hexachloroplatinic acid (IV) hexahydrate, 0.78 molar equivalents of dimethoxymethylsilane relative to the converted allyl groups of the precursor polymer were added, and the reaction was carried out at 70°C for 5 hours to obtain Polymer C-3. Polymer C-3 is an oxyalkylene polymer having reactive silicon groups (dimethoxymethylsilyl groups). Polymer C-3 has reactive silicon groups at the terminal groups but does not have reactive silicon groups in the main chain.

[0117] (Synthesis Example 4: Synthesis of Polymer C-4) Propylene oxide was polymerized using glycerin as an initiator and Glyme-DMC catalyst as a catalyst to obtain an oxypropylene polymer (precursor polymer). The precursor polymer had a molecular weight of 20,000 calculated based on hydroxyl groups. Next, 1.05 molar equivalents of sodium methoxide in methanol was added relative to the hydroxyl groups of the precursor polymer to alcoholate the precursor polymer. Next, the methanol was distilled off by heating under reduced pressure, and an excess amount of allyl chloride relative to the amount of hydroxyl groups in the precursor polymer was added to convert the terminal groups to allyl groups. Next, in the presence of hexachloroplatinic acid (IV) hexahydrate, 0.78 molar equivalents of methyldimethoxysilane relative to the converted allyl groups of the precursor polymer were added, and the reaction was carried out at 70°C for 5 hours to obtain Polymer C-4. Polymer C-4 is an oxyalkylene polymer having reactive silicon groups (dimethoxymethylsilyl groups). Polymer C-4 has reactive silicon groups at the terminal groups but no reactive silicon groups in the main chain.

[0118] (Synthesis Example 5: Synthesis of Polymer D-1) 257.1 g of ethyl acetate was added to a pressure-resistant reactor equipped with a stirrer, and the temperature was raised to approximately 70° C. While maintaining the temperature inside the reaction vessel at approximately 70° C. and stirring under a nitrogen atmosphere, a mixed solution of 57.4 g of methyl methacrylate, 430.6 g of n-butyl acrylate, 86.1 g of stearyl methacrylate, 15.8 g of 3-methacryloxypropylmethyldimethoxysilane (KBM-502, product name of Shin-Etsu Silicones), 5.7 g of 2,2′-azobis-2,4-dimethylvaleronitrile (V-65, product name of Wako Pure Chemical Industries, Ltd.), and 0.8 g of dodecyl mercaptan was added dropwise to the ethyl acetate over 2 hours to polymerize, thereby obtaining polymer D-1, which is a (meth)acrylic acid ester polymer having dimethoxymethylsilyl groups in its side chains.

[0119] (Synthesis Example 6: Synthesis of Polymer D-2) In this example, living radical polymerization was used to synthesize the following polymer d1 by reacting a compound having two alkenyl groups at the end of the polymerization reaction, and the following polymer d2 was obtained by substituting the bromo group with a methyl ester, followed by the following polymer D-2 having a dimethoxymethylsilyl group at the main chain terminal.

[0120] A 2-L flask was charged with 8.39 g of cuprous bromide and 112 mL of acetonitrile, and the mixture was heated and stirred at 70°C for 20 minutes under a nitrogen stream. To this was added 17.6 g of diethyl 2,5-dibromoadipate, 130 mL of ethyl acrylate, 720 mL of butyl acrylate, and 251 g of stearyl acrylate, and the mixture was heated and stirred at 70°C for an additional 40 minutes. To this was added 0.41 mL of pentamethyldiethylenetriamine (hereinafter referred to as "triamine") to initiate the reaction. Heating and stirring were continued at 70°C, and an additional 2.05 mL of triamine was added. 330 minutes after the start of the reaction, 244 mL of 1,7-octadiene and 4.1 mL of triamine were added, and the mixture was continued to heat and stir at 70°C. Heating was stopped 570 minutes after the start of the reaction. The resulting reaction solution was diluted with toluene and filtered, and the filtrate was subjected to a heat treatment under reduced pressure to obtain an acrylic acid ester polymer (polymer d1) having an alkenyl group at its terminal. The Mn of polymer d1 is 22800, the molecular weight distribution is 1.40, 1 The average number of alkenyl groups per molecule of polymer d1 determined by 1 H-NMR analysis was 2.0.

[0121] Under a nitrogen atmosphere, the entire amount of the obtained polymer d1, 17.2 g of potassium acetate, and 700 mL of N,N-dimethylacetamidomethyl (hereinafter referred to as DMAc) were added to a 2 L flask and heated with stirring at 100 °C for 10 hours. The reaction solution was heated under reduced pressure to remove DMAc, and toluene was added and filtered. The filtrate was heated under reduced pressure to remove volatiles, and the remainder was added to a 2 L flask. 100 g of an adsorbent (a 1:1 mixture by mass of Kyoward 500SN and Kyoward 700SN (both Kyowa Chemical products)) was added, and the mixture was heated with stirring at 130 °C for 9 hours under a nitrogen stream. The mixture was diluted with toluene, filtered to remove the adsorbent, and the toluene in the filtrate was distilled off under reduced pressure to obtain a polymer (polymer d2).

[0122] In a 1 L pressure-resistant reactor, 700 g of polymer d2, 22.2 mL of dimethoxymethylhydrosilane, 7.71 mL of methyl orthoformate, and a platinum catalyst (1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zero-valent platinum) were added. The amount of the platinum catalyst used was 9 × 10 relative to the alkenyl groups of polymer d1. -3 The mixture in the reaction vessel was heated and stirred at 100°C for 195 minutes. The volatile matter in the mixture was distilled off under reduced pressure to obtain polymer D-2, which is a polymer having dimethoxymethylsilyl groups at the main chain terminals. The average number of reactive silicon groups per molecule was 1 The number was determined to be 2.0 by H-NMR analysis.

[0123] [Other ingredients] Other ingredients listed in Table 3 are as follows: Epicoat 828: Epoxy resin, Mitsubishi Chemical Corporation product name. Epicure H3: Epoxy resin hardener, Mitsubishi Chemical Corporation product name. Polymer E-1: An oxyalkylene polymer having a hydroxyl group-based molecular weight of 10,000 obtained by polymerizing propylene oxide using propylene glycol as an initiator in the presence of a TBA-DMC catalyst. Disparlon #6500: Thixotropic agent, product name of Kusumoto Chemicals. 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. 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. IRGANOX 1010 (referred to as Ir1010 in the table): hindered phenol antioxidant, product name of BASF. TINUVIN 326 (referred to as Ti326 in the table): Benzotriazole light stabilizer, product name of BASF. U-220H: Dibutyltin bis(acetylacetonate), tin catalyst, product name of Nitto Kasei Co., Ltd.

[0124] [Table 3]

[0125] As shown in Table 3, Reference Examples 1 to 5 containing Polymer B-2 had good tensile properties and good paint contamination resistance.

Claims

1. A method for producing a composition containing an oxyalkylene polymer A having a hydroxyl group and a carbon-carbon double bond at a molecular terminal, comprising the steps of: A method for producing a composition, comprising polymerizing an alkylene oxide with an initiator having an active hydrogen-containing group and a carbon-carbon double bond at the molecular terminal in the presence of a double metal cyanide complex catalyst whose ligand is an alcohol, to obtain an oxyalkylene polymer A.

2. The method for producing a composition according to claim 1, wherein the amount of the double metal cyanide complex catalyst used is 100 to 1500 ppm by mass relative to the total mass of the initiator.

3. The method for producing a composition according to claim 1, wherein the number average molecular weight of the oxyalkylene polymer A is 3,000 to 20,000.

4. The method for producing a composition according to claim 1, wherein the molecular weight distribution of the oxyalkylene polymer A is 1.30 or less.

5. 2. The method for producing a composition according to claim 1, wherein the double metal cyanide complex catalyst is a zinc hexacyanocobaltate complex having tert-butyl alcohol as a ligand.

6. 2. The method for producing a composition according to claim 1, wherein the oxyalkylene polymer A has 1 to 3 hydroxyl groups and 1 to 3 carbon-carbon double bonds at the molecular terminals.

7. 7. The method for producing a composition according to claim 6, wherein the oxyalkylene polymer A has one hydroxyl group and one carbon-carbon double bond at the molecular terminal.

8. A method for producing an oxyalkylene polymer B having a reactive silicon group represented by the following formula 1 in its main chain, and having no reactive silicon group but a hydroxyl group in its terminal group, comprising: A method for producing an oxyalkylene polymer B, comprising reacting a composition produced by the method for producing a composition according to claim 1 with a silylating agent in the presence of a hydrosilylation catalyst to obtain an oxyalkylene polymer B. -SiR １ ａ１ X １ ３－ａ１ Formula 1 In the formula 1, R １ represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, and X １ represents a hydroxyl group, a halogen atom, or a hydrolyzable group. a1 is an integer of 0 to 2. 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 from each other.

9. 9. The method for producing oxyalkylene polymer B according to claim 8, wherein the amount of the hydrosilylation catalyst used is 1 to 15 ppm by mass, calculated as the metal contained in the hydrosilylation catalyst, relative to the total mass of the composition.

10. The method for producing an oxyalkylene polymer B according to claim 8, wherein the number average molecular weight of the oxyalkylene polymer B is 3,000 to 20,000.

11. The method for producing an oxyalkylene polymer B according to claim 8, wherein the molecular weight distribution of the oxyalkylene polymer B is 1.30 or less.

12. The method for producing an oxyalkylene polymer B according to claim 8, wherein the hydrosilylation catalyst is a platinum complex.

13. The method for producing an oxyalkylene polymer B according to claim 12, wherein the platinum complex is a platinum-vinylsiloxane complex.

14. 9. The method for producing an oxyalkylene polymer B according to claim 8, wherein the oxyalkylene polymer B has 1 to 3 hydroxyl groups and 1 to 3 reactive silicon groups.

15. The method for producing an oxyalkylene polymer B according to claim 14, wherein the oxyalkylene polymer B has one hydroxyl group and one reactive silicon group.

16. A method for producing a curable composition, comprising mixing a polymer B produced by the method for producing an oxyalkylene polymer B according to any one of claims 8 to 15, and an oxyalkylene polymer C having a reactive silicon group represented by the following formula 2 at a terminal group and having a number average molecular weight of 10,000 to 100,000: -SiR ２ ａ２ X ２ ３－ａ２ Formula 2 In the formula 2, R ２ represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, and X ２ represents a hydroxyl group, a halogen atom, or a hydrolyzable group. a2 is an integer of 0 to 2. When a2 is 2, R ２ may be the same or different, and when a2 is 0 or 1, X ２ may be the same or different from each other.

17. A method for producing a cured product, comprising curing a curable composition produced by the method for producing a curable composition according to claim 16.

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