Method for producing polyether compound, method for producing polyether compound having reactive silicon group, method for producing polyether compound having urethane bond, and method for producing polyether compound having polymerizable unsaturated group

Abstract

This method for producing a polyether compound having a hydroxyl group comprises polymerizing AO in an AO-containing raw material with a hydroxyl group-containing initiator in the presence of a composite metal cyanide complex catalyst, wherein the total aldehyde content of the AO-containing raw material, as measured by a titration method, is less than 15 ppm with respect to the total mass of the AO-containing raw material. This method for producing a polyether compound having a reactive silicon group further comprises converting the hydroxyl group of the polyether compound into a group having a reactive silicon group. This method for producing a polyether compound having a urethane bond further comprises reacting the polyether compound having a hydroxyl group with a polyisocyanate. This method for producing a polyether compound having a polymerizable unsaturated group further comprises converting the hydroxyl group of the polyether compound into a group having a polymerizable unsaturated group.

Description

Method for producing polyether compounds, method for producing polyether compounds having reactive silicon groups, method for producing polyether compounds having urethane bonds, and method for producing polyether compounds having polymerizable unsaturated groups

[0001] The present invention relates to a method for producing a polyether compound, a method for producing a polyether compound having a reactive silicon group, a method for producing a polyether compound having a urethane bond, and a method for producing a polyether compound having a polymerizable unsaturated group.

[0002] Polyether compounds are used as raw materials for adhesives, paints, sealants, etc. Polyether compounds are produced by polymerizing alkylene oxide with an initiator having active hydrogen. Double metal cyanide complex catalysts are known as polymerization catalysts for obtaining polyether compounds with narrow molecular weight distribution.

[0003] Patent Document 1 discloses a method for producing a hydrolyzable silyl group-containing polyoxyalkylene, which includes a step of ring-opening polymerizing a monoepoxide having a water content of 5 ppm or more but less than 50 ppm to obtain a hydroxyl group-containing polyoxyalkylene, and a step of introducing a hydrolyzable silyl group into the hydroxyl group-containing polyoxyalkylene. It discloses that by using a monoepoxide with a low water content, the obtained hydrolyzable silyl group-containing polyoxyalkylene can exhibit a high modulus after curing.

[0004] Polyether compounds having reactive silicon groups are known to have the property of crosslinking even at room temperature through the formation of siloxane bonds accompanied by hydrolysis of the reactive silicon groups due to moisture, etc., to give rubber-like cured products. Therefore, polyether compounds having reactive silicon groups are already produced industrially and are widely used in applications such as sealants and adhesives.

[0005] Polyether compounds having reactive silicon groups are produced from polyether compounds having hydroxyl groups as raw materials. Polyether compounds having hydroxyl groups are produced by polymerizing alkylene oxide with an initiator having active hydrogen. Double metal cyanide complex catalysts are known as polymerization catalysts for obtaining polyether compounds with narrow molecular weight distribution.

[0006] Polyether compounds having urethane bonds, such as urethane prepolymers, are used as raw materials for adhesives, paints, sealants, coatings, etc. Polyether compounds having urethane bonds are produced using polyether compounds having hydroxyl groups as raw materials. Polyether compounds having hydroxyl groups are produced by polymerizing alkylene oxide with an initiator having active hydrogen. Double metal cyanide complex catalysts are known as polymerization catalysts for obtaining polyether compounds with narrow molecular weight distribution.

[0007] Patent Document 2 discloses a urethane prepolymer composition (G) containing a hydroxyl-terminated urethane prepolymer (E) and a polyalkylene oxide (B). It also discloses that the urethane prepolymer (E) is a reaction product of a polyol and a polyisocyanate (C) and has at least one urethane group and at least one hydroxyl group per molecule. It also discloses that the polyol can be produced using a double metal cyanide complex catalyst.

[0008] Polyether compounds having polymerizable unsaturated groups are used as raw materials for adhesives in fields such as optical component materials and liquid crystal panels (e.g., Patent Document 3). Polyether compounds having polymerizable unsaturated groups are produced using polyether compounds having hydroxyl groups as raw materials. Polyether compounds having hydroxyl groups are produced by polymerizing alkylene oxide with an initiator having active hydrogen. Double metal cyanide complex catalysts are known as polymerization catalysts for obtaining polyether compounds with narrow molecular weight distributions.

[0009] International Publication No. 2023 / 095636 Japanese Patent Application Laid-Open No. 2023-155601 Japanese Patent Application Laid-Open No. 2012-126839

[0010] However, according to the investigations of the present inventors, when a composite metal cyanide complex catalyst is used, the degree of unsaturation of the obtained polyether compound may become high. Patent Document 1 does not disclose anything other than water as an impurity of the monoepoxide.

[0011] An object of the present invention is to provide a production method that can produce a polyether compound with a low degree of unsaturation.

[0012] In addition, according to the investigations of the present inventors, polyether compounds having reactive silicon groups obtained by conventional methods may result in insufficient strength in the cured product.

[0013] Another object of the present invention is to provide a production method that can yield a polyether compound having a reactive silicon group that provides a cured product with excellent strength.

[0014] When a polyether compound having a urethane bond is used for applications such as the above-mentioned adhesives, sealants, etc., it is required to have curability. However, the curability of the polyether compound having a urethane bond produced by the production method described in Patent Document 2 is insufficient.

[0015] Another object of the present invention is to provide a production method that can yield a polyether compound having a urethane bond and exhibiting excellent curability.

[0016] In addition, according to the investigations of the present inventors, polyether compounds having polymerizable unsaturated groups obtained by conventional methods may also result in insufficient strength of the cured product.

[0017] Another object of the present invention is to provide a production method that can yield a polyether compound having a polymerizable unsaturated group that provides a cured product with excellent strength.

[0018] A preferred embodiment of the present invention provides the following means. [1] A method for producing a polyether compound having a hydroxyl group, comprising contacting an initiator having a hydroxyl group with an alkylene oxide-containing raw material in the presence of a double metal cyanide complex catalyst to polymerize the alkylene oxide in the alkylene oxide-containing raw material with the initiator, wherein the total aldehyde content of the alkylene oxide-containing raw material, as measured by titration, is less than 15 ppm relative to the total mass of the alkylene oxide-containing raw material. [2] The method according to [1], wherein the acetaldehyde content of the alkylene oxide-containing raw material is less than 10 ppm relative to the total mass of the alkylene oxide-containing raw material. [3] The method according to [1] or [2], wherein the alkylene oxide-containing raw material contains an alkylene oxide having 3 or more carbon atoms. [4] The method according to any one of [1] to [3], wherein the number of hydroxyl groups in the initiator is 1 to 10. [5] The method according to any one of [1] to [4], wherein the hydroxyl value-based molecular weight of the polyether compound having hydroxyl groups is 1,000 to 100,000. [6] The method according to any one of [1] to [5], wherein a slurry catalyst in which particles of the composite metal cyanide complex catalyst are dispersed in a dispersion medium is used.

[0019] A preferred embodiment of the present invention also provides the following means: [1A] A method for producing a polyether compound having a reactive silicon group, comprising contacting an initiator having a hydroxyl group with an alkylene oxide-containing raw material in the presence of a double metal cyanide complex catalyst, polymerizing the alkylene oxide in the alkylene oxide-containing raw material with the initiator, and converting the hydroxyl group of the resulting polyether compound having a hydroxyl group to a group having a reactive silicon group represented by the following formula 1, wherein the total aldehyde content of the alkylene oxide-containing raw material as measured by titration is less than 15 ppm based on the total mass of the alkylene oxide-containing raw material. ａ X ３－ａFormula 1 In the formula 1, R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, and X represents a hydroxyl group, a halogen atom, or a hydrolyzable group. a is an integer from 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. [2A] The production method according to [1A], wherein the alkylene oxide-containing raw material has an acetaldehyde content of less than 10 ppm based on the total mass of the alkylene oxide-containing raw material.

[0020] A preferred embodiment of the present invention also provides the following means. [1B] A method for producing a polyether compound having a urethane bond, comprising contacting an initiator having a hydroxyl group with an alkylene oxide-containing raw material in the presence of a double metal cyanide complex catalyst to polymerize the alkylene oxide in the alkylene oxide-containing raw material with the initiator, and reacting the resulting polyether compound having a hydroxyl group with a polyisocyanate, wherein the total aldehyde content of the alkylene oxide-containing raw material as measured by titration is less than 15 ppm relative to the total mass of the alkylene oxide-containing raw material. [2B] The production method according to [1B], wherein the acetaldehyde content of the alkylene oxide-containing raw material is less than 10 ppm relative to the total mass of the alkylene oxide-containing raw material.

[0021] A preferred embodiment of the present invention also provides the following means: [1C] A method for producing a polyether compound having a polymerizable unsaturated group, comprising contacting an initiator having a hydroxyl group with an alkylene oxide-containing raw material in the presence of a double metal cyanide complex catalyst to polymerize the alkylene oxide in the alkylene oxide-containing raw material with the initiator, and converting the hydroxyl group of the resulting polyether compound having a hydroxyl group to a group having a polymerizable unsaturated group, wherein the total aldehyde content of the alkylene oxide-containing raw material as measured by titration is less than 15 ppm relative to the total mass of the alkylene oxide-containing raw material. [2C] The production method according to [1C], wherein the acetaldehyde content of the alkylene oxide-containing raw material is less than 10 ppm relative to the total mass of the alkylene oxide-containing raw material.

[0022] According to the present invention, a production method for obtaining a polyether compound having a low degree of unsaturation can be provided.

[0023] The present invention also provides a production method that can yield a polyether compound having a reactive silicon group that provides a cured product with excellent strength.

[0024] According to the present invention, there is also provided a production method that can obtain a polyether compound having a urethane bond and that has excellent curability.

[0025] According to the present invention, there can also be provided a production method for obtaining a polyether compound having a polymerizable unsaturated group, which provides a cured product with excellent strength.

[0026] The meanings and definitions of terms used in this specification are as follows: A numerical range expressed as "to" means a numerical range with the numbers before and after "to" as the lower and upper limits. The lower and upper limits of the numerical ranges disclosed in this specification can be combined in any way to create a new numerical range.

[0027] "Polyether compound" refers to a polyether compound having a hydroxyl group. "Polyether compound" does not have a reactive silicon group, a urethane bond, a polymerizable unsaturated group, or an isocyanate group. "Polyether compound having a reactive silicon group" has a reactive silicon group. "Polyether compound having a reactive silicon group" may have one or more of a hydroxyl group, a urethane bond, a polymerizable unsaturated group, and an isocyanate group. "Polyether compound having a urethane bond" has a urethane bond. "Polyether compound having a urethane bond" may have a hydroxyl group and an isocyanate group. "Polyether compound having a urethane bond" does not have a reactive silicon group or a polymerizable unsaturated group. "Polyether compound having a urethane bond" is also referred to as "prepolymer" hereinafter. "Polyether compound having a polymerizable unsaturated group" has a polymerizable unsaturated group. "Polyether compound having a polymerizable unsaturated group" may have one or more of a hydroxyl group, a urethane bond, and an isocyanate group. The "polyether compound having a polymerizable unsaturated group" does not have a reactive silicon group. Hereinafter, the "polyether compound," "polyether compound having a reactive silicon group," "polyether compound having a urethane bond," and "polyether compound having a polymerizable unsaturated group" will also be collectively referred to as "polyether compounds, etc."

[0028] The "unit" constituting a polyether compound, etc., refers to an atomic group formed directly by polymerization of a monomer. The "main chain" refers to a polymer chain formed by polymerization of two or more monomers. In the polyether compounds, polyether compounds having reactive silicon groups, and polyether compounds having polymerizable unsaturated groups described below, the "main chain" refers to the residue obtained by removing active hydrogen from the initiator and the portion containing repeating units based on alkylene oxide (polyoxyalkylene chain). The polyether compounds, polyether compounds having reactive silicon groups, and polyether compounds having polymerizable unsaturated groups are polymers consisting of a main chain and terminal groups. The "terminal group" of the polyether compounds, polyether compounds having reactive silicon groups, and polyether compounds having polymerizable unsaturated groups refers to an atomic group containing the oxygen atom closest to the molecular end among the oxygen atoms in the polyoxyalkylene chain. However, if the atomic group contains a residue of an initiator, it is not considered an terminal group but is considered part of the main chain. The "number of terminal groups" in the polyether compound, the polyether compound having a reactive silicon group, and the polyether compound having a polymerizable unsaturated group is the same as the number of active hydrogens in the initiator, which will be described later. 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 "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.

[0029] The "silylation rate" of a polyether compound having a reactive silicon group 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 polyether compound having a reactive silicon group. Specifically, the silylation rate is calculated using 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 value can be measured by NMR analysis. When reactive silicon groups are introduced into the terminal groups of a polyether compound using a silylating agent, it may also be the ratio (mol %) of the number of silyl groups of the added silylating agent to the number of terminal groups. However, in this case, a diisocyanate compound is used as the polyisocyanate compound in the method (c1) described below. The term "silylating agent" refers to a compound having a reactive silicon group and a functional group reactive with an active hydrogen-containing group, an unsaturated group, or an isocyanate group. The content of the isocyanate group relative to the total mass of the prepolymer described below is a value measured in accordance with JIS K 7301:1995.

[0030] In this specification, the number average molecular weight (Mn) and weight average molecular weight (Mw) are polystyrene-equivalent molecular weights measured using gel permeation chromatography (GPC) with tetrahydrofuran as an eluent, with a calibration curve prepared using polystyrene polymers of known molecular weights. The molecular weight distribution (Mw / Mn) is the ratio of Mw to Mn.

[0031] The "hydroxyl value" of a polyether compound is a value measured in accordance with Method B (phthalation method) described in JIS K 1557-1:2007. The hydroxyl value-based molecular weight is a value calculated by multiplying the hydroxyl value of the polyether compound by the number of hydroxyl groups in the polyether compound (the number of active hydrogen atoms in the initiator). When two or more polyether compounds with different numbers of hydroxyl groups are contained, the number of hydroxyl groups in the polyether compound is the average number of hydroxyl groups.

[0032] The degree of unsaturation of the polyether compound is measured in accordance with JIS K 1557-3: 2007. The viscosity of the polyether compound is measured using an E-type viscometer.

[0033] The total aldehyde content of the alkylene oxide-containing raw material is the total amount of compounds having a formyl group, and is measured by titration. Details are as described in the Examples. The alkylene oxide content and acetaldehyde content of the alkylene oxide-containing raw material are measured by gas chromatography. Details are as described in the Examples. "ppm" is calculated by mass unless otherwise specified.

[0034] [Method for Producing Polyether Compound] In the method for producing a polyether compound of the present embodiment, an initiator having active hydrogen is brought into contact with an alkylene oxide-containing raw material in the presence of a composite metal cyanide complex catalyst, and the alkylene oxide in the alkylene oxide-containing raw material is polymerized with the initiator.

[0035] (Alkylene oxide-containing raw material) The alkylene oxide-containing raw material contains alkylene oxide (hereinafter also referred to as "AO"). The AO is selected depending on the structural units of the polyoxyalkylene chain of the polyether compound to be produced. Examples of AO include ethylene oxide (hereinafter also referred to as "EO"), propylene oxide (hereinafter also referred to as "PO"), 1,2-butylene oxide, and 2,3-butylene oxide. From the viewpoint of reactivity, the AO is preferably an AO having 3 or more carbon atoms. As the AO having 3 or more carbon atoms, an AO having 3 to 5 carbon atoms is preferred, and PO is more preferred. The AO-containing raw material may contain one type of AO or two or more types of AO.

[0036] The AO-containing raw material may contain, in addition to AO, components other than AO (hereinafter also referred to as "impurities"). The crude product obtained by the AO synthesis reaction contains impurities. Typically, the crude product is purified, but some impurities remain even after the purification process. Furthermore, even for the same product, the impurity content may vary depending on the lot. Examples of impurities include water, aldehydes, acids, methanol, methyl formate, and chlorine, although these differ depending on the AO synthesis method. Examples of aldehydes include formaldehyde, acetaldehyde, and propionaldehyde. The AO-containing raw material may contain one or more impurities.

[0037] The AO content (AO purity) of the AO-containing raw material is preferably 97% by mass or more, more preferably 98% by mass or more, and even more preferably 99% by mass or more, based on the total mass of the AO-containing raw material. The total content of AO and impurities does not exceed 100% by mass, based on the total mass of the AO-containing raw material.

[0038] The total aldehyde content of the AO-containing raw material is less than 15 ppm, preferably less than 14 ppm, and more preferably less than 13 ppm, based on the total mass of the AO-containing raw material. When the aldehyde content is equal to or less than the above upper limit, the degree of unsaturation of the polyether compound can be reduced. The total aldehyde content of the AO-containing raw material is preferably 0 ppm or more, preferably 0.5 ppm or more, based on the total mass of the AO-containing raw material. When the total aldehyde content is equal to or greater than the above lower limit, the performance of the resulting polyether compound is superior. The above upper limit and lower limit can be combined as appropriate.

[0039] The acetaldehyde content of the AO-containing raw material is preferably less than 10 ppm, more preferably less than 9.5 ppm, even more preferably less than 9 ppm, and particularly preferably less than the detection limit, based on the total mass of the AO-containing raw material. The detection limit for acetaldehyde is usually 0.1 ppm. When the acetaldehyde content is equal to or less than the upper limit, the degree of unsaturation of the polyether compound can be reduced.

[0040] The AO-containing raw material may be selected from commercially available AO-containing raw materials having an impurity content within a desired range, or may be produced by a known production method. For example, the target AO-containing raw material may be obtained by synthesizing AO by a known method and adjusting the impurity content of the resulting AO-containing crude product. The target AO-containing raw material may also be obtained by adjusting the impurity content of a commercially available AO-containing raw material. Examples of methods for adjusting the impurity content include a method of reducing the impurity content by a purification treatment and a method of adding impurities. Examples of purification treatment include washing with water and drying.

[0041] The type and content of impurities in the crude product or AO-containing raw material can be adjusted by the AO synthesis method and purification treatment conditions.

[0042] (Initiator) The number of active hydrogens in the initiator is preferably 1 or more, more preferably 1 to 10, even more preferably 1 to 8, and particularly preferably 1 to 6. The number of active hydrogens in the initiator is preferably selected depending on the number of hydroxyl groups per molecule of the polyether compound to be obtained. The number of active hydrogens in the initiator and the number of terminal groups of the polyether compound are the same. One type of initiator may be used alone, or two or more types may be used in combination.

[0043] The initiator preferably has a hydroxyl group as the active hydrogen-containing group. As an initiator having one hydroxyl group, a monohydric alcohol having a linear or branched hydrocarbon group is preferred. Specific examples include 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, and oleyl alcohol. 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, and 1,6-hexanediol. Water is also an example of an initiator having two hydroxyl groups. Examples of initiators having three hydroxyl groups include glycerin, trimethylolpropane, and trimethylolethane. Examples of initiators having four or more hydroxyl groups include pentaerythritol, diglycerin, meso-erythritol, methyl glucoside, sucrose, glucose, sorbitol, dipentaerythritol, trehalose, and diglycerin. Alternatively, a low-molecular-weight polymer obtained by polymerizing an alkylene oxide with such an initiator in the presence of an alkali metal hydroxide may be used as the initiator. The hydroxyl value of the initiator is preferably, for example, 3 to 842 mgKOH / g, and more preferably 7 to 561 mgKOH / g.

[0044] (Composite Metal Cyanide Complex Catalyst) A composite metal cyanide complex catalyst (hereinafter also referred to as "DMC catalyst") functions as a polymerization catalyst for alkylene oxide. The DMC catalyst is a crystalline solid, and contains a reaction product of a metal halide salt and a transition metal cyanide compound, an organic ligand, and water of crystallization (coordinated water, etc.) contained within the crystal. In addition, it may contain impurities unavoidable in the production that are contained in trace amounts in the metal salt, metal compound, etc., and moisture other than water of crystallization. The metal halide salt, transition metal cyanide compound, and organic ligand can be any known ones used in the production of DMC catalysts.

[0045] The DMC catalyst is believed to be represented by the following formula 2: M １ ａ [M ２ (CN) ｂ ] ｃ ・d(M １ ｅ X ｆ )・g(Ligand)・h(H ２ O) Formula 2 In Formula 2, M １ ｅ X ｆ is a metal halide salt, M １ is a metal atom that serves as a cation, X is a halogen atom that serves as a counter anion, and M ２ is a transition metal atom contained in the transition metal cyanide compound and serves as an active site, and Ligand is an organic 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.

[0046] M １ Examples of the metals 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). ２ Examples of X 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 ｆ The metal halide salt represented by the formula (I) is preferably at least one selected from zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, and zinc acetate. ２In view of the interatomic distance between X and X, it is more preferable that the compound contains one or more selected from zinc chloride and zinc bromide. Examples of the ligand (organic ligand) include alcohols, ethers, esters, aldehydes, ketones, amides, nitriles and sulfides, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and polyoxyalkylene poly(or mono)ols. One type of organic ligand may be used, or two or more types may be used. Examples of the alcohol 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. Examples of the polyoxyalkylene poly(or mono)ol include polypropylene diol. A preferred organic ligand is tert-butyl alcohol.

[0047] A preferred example of a DMC catalyst is zinc hexacyanocobaltate (Zn) containing an organic ligand, water, zinc chloride or zinc bromide. ３ [Co(CN) ６ ] ２ ) Its chemical formula is Zn ３ [Co(CN) ６ ] ２ d(ZnCl ２ )・g(Ligand)・h(H ２ O) or Zn ３ [Co(CN) ６ ] ２ d(ZnBr ２ )・g(Ligand)・h(H ２ O) is considered.

[0048] The DMC catalyst is zinc hexacyanocobaltate (Zn) with tert-butyl alcohol as the ligand. ３ [Co(CN) ６ ] ２ The complex may be coordinated with water and zinc chloride.

[0049] The DMC catalyst may be used, for example, in the production of a polyether compound in a solid state, or in the production of a polyether compound in a slurry state in which DMC catalyst particles are dispersed in a dispersion medium (hereinafter also referred to as a "slurry catalyst").

[0050] The slurry catalyst contains a DMC catalyst and a dispersion medium. The slurry catalyst is preferably a slurry that contains a DMC catalyst and a dispersion medium, and may also contain impurities and moisture that are unavoidable in the production process.

[0051] As the dispersion medium for the slurry catalyst, organic solvents known in the art for slurry catalysts can be used. For example, the low-volatility hydroxy compounds described in Japanese Patent No. 3,194,255 can be used. The hydroxy compound is a hydroxyl group-containing compound having 1 to 8 hydroxyl groups and a molecular weight of 100 to 8,000, and a compound having an alcoholic hydroxyl group, such as a polyether compound, is preferred. As the dispersion medium for the slurry catalyst, a second polyether compound is preferred because it does not become an impurity in the product (polyether compound) of alkylene oxide polymerization. In other words, the dispersion medium for the slurry catalyst preferably contains a second polyether compound. The Mn of the second polyether compound used as the dispersion medium is preferably 100 to 8,000, more preferably 600 to 3,000. When the Mn is equal to or greater than the lower limit, it does not act as a catalyst poison, and when it is equal to or less than the upper limit, the slurry catalyst is easy to handle. The initiator used in the polymerization of alkylene oxide may also be used as part of the dispersion medium.

[0052] It is preferable that the dispersion medium of the slurry catalyst is substantially free of water. Specifically, the water content of the dispersion medium is preferably 500 ppm or less, more preferably 200 ppm or less, and may be an undetectable amount. The water content of the dispersion medium is the water content measured by the Karl Fischer measurement method.

[0053] The content of the DMC catalyst relative to the total mass of the slurry catalyst is, for example, preferably 0.001 to 60% by mass, more preferably 0.003 to 50% by mass, and even more preferably 0.006 to 30% by mass. In particular, when the dispersion medium is a second polyether compound, the content of the DMC catalyst relative to the total mass of the slurry catalyst is preferably 1 to 60% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 30% by mass. In particular, when the dispersion medium contains an initiator, the content of the DMC catalyst relative to the total mass of the slurry catalyst is preferably 0.003 to 0.020% by mass, more preferably 0.004 to 0.015% by mass, and even more preferably 0.006 to 0.010% by mass.

[0054] The DMC catalyst can be produced by a known method. For example, a metal halide salt and a transition metal cyanide compound are reacted to obtain a reaction product, and an organic ligand is then coordinated to synthesize the DMC catalyst. After synthesizing the DMC catalyst, the water content of the DMC catalyst may be adjusted.

[0055] A mixture containing a DMC catalyst and water is obtained by reacting a metal halide salt with a transition metal cyanide compound in the presence of water, and then coordinating an organic ligand with the reaction product in the presence of water. Impurities and water may be removed from the mixture, and the water content of the resulting solid may be reduced to a predetermined range, thereby obtaining the DMC catalyst.

[0056] A preferred embodiment of the method for producing a DMC catalyst includes, for example, the following method. First, an aqueous solution of a metal halide salt is reacted with an aqueous solution of a transition metal cyanide compound to produce a reaction product. An aqueous solution of an organic ligand is added to the reaction product and stirred to coordinate the organic ligand, thereby obtaining a mixed solution containing the DMC catalyst and water. The resulting mixed solution is subjected to solid-liquid separation to obtain a solid. The resulting solid is washed with an aqueous solution containing the organic ligand, and the solid-liquid separation operation is performed one or more times, preferably two or more times. The resulting solid may also be dried so that the moisture content falls within the above-mentioned specific range, and pulverized as necessary.

[0057] The concentration of the metal halide salt in the aqueous solution of the metal halide salt is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. It is also preferably equal to or less than the saturated concentration. The concentration of the transition metal cyanide compound in the aqueous solution of the transition metal cyanide compound is preferably 2 to 50% by mass, more preferably 2 to 20% by mass, and even more preferably 3 to 10% by mass. The molar ratio of the metal contained in the metal halide salt to the transition metal contained in the transition metal cyanide compound is preferably 1.6 to 12, and more preferably 1.8 to 8.

[0058] The reaction temperature in the reaction between the aqueous solution of the metal halide salt and the aqueous solution of the transition metal cyanide compound is preferably 10 to 65°C, more preferably 20 to 60°C, and even more preferably 30 to 55°C.

[0059] The concentration of the organic ligand in the aqueous solution of the organic ligand is preferably from 10 to 90% by mass, more preferably from 25 to 75% by mass, and even more preferably from 35 to 65% by mass.

[0060] The temperature at which the organic ligand is coordinated is preferably 10 to 90°C, more preferably 20 to 80°C, and even more preferably 30 to 70°C.

[0061] After the organic ligand is coordinated, it is preferable to carry out solid-liquid separation. For solid-liquid separation, methods known in the art, such as filtration and centrifugation, can be used. The obtained solid contains the DMC catalyst as well as salts (alkali metal halides) produced in the reaction. Therefore, it is preferable to remove the salts by washing the obtained solid. Specifically, an aqueous solution of the organic ligand is added to the obtained solid, the mixture is stirred, and then solid-liquid separation is carried out again. The washing time is preferably 10 to 90 minutes, more preferably 20 to 60 minutes. It is preferable to perform washing multiple times.

[0062] When producing a slurry catalyst, a method can be used in which a mixed solution containing a DMC catalyst and water is obtained as described above, impurities and water are removed from the resulting mixed solution, and then a dispersion medium is added to prepare a slurry containing the DMC catalyst and the dispersion medium. Before adding the dispersion medium, washing with an aqueous solution of an organic ligand may be performed.

[0063] (AO Polymerization) By contacting an initiator with an AO-containing raw material in the presence of a DMC catalyst, AO in the AO-containing raw material is polymerized with the initiator (ring-opening addition polymerization). When a DMC catalyst is used as the AO polymerization catalyst, the Mw / Mn of the polyether compound tends to be smaller and the degree of unsaturation of the polyether compound tends to be smaller than when a polymerization catalyst other than a DMC catalyst is used.

[0064] When the polyoxyalkylene chain of the polyether compound is a random copolymer chain consisting of PO units and EO units, a method of obtaining the polyether compound by contacting an initiator with an AO-containing raw material containing PO and EO in the presence of a DMC catalyst is preferred. The same applies to combinations of two or more AOs other than the combination of PO and EO.

[0065] When the polyoxyalkylene chain of the polyether compound is a block copolymer chain having a block of PO units and a block of EO units, the polyether compound may be obtained by reacting an initiator with an AO-containing raw material containing PO in the presence of a DMC catalyst to obtain a precursor, and then reacting the precursor with the AO-containing raw material containing EO, or the polyether compound may be obtained by reacting an initiator with an AO-containing raw material containing EO in the presence of a DMC catalyst to obtain a precursor, and then reacting the precursor with the AO-containing raw material containing PO, etc. The same applies to combinations of two or more AOs other than the combination of PO and EO.

[0066] The amount of the DMC catalyst used is preferably 1 to 200 ppm, more preferably 5 to 60 ppm, and particularly preferably 10 to 50 ppm, based on the total mass of the polyether compound finally obtained. When the amount of the DMC catalyst used is equal to or greater than the lower limit, the polymerization reaction is likely to proceed. When the amount of the DMC catalyst used is equal to or less than the upper limit, the amount of the DMC catalyst used is reduced, which is economical.

[0067] The polymerization may be carried out continuously or batchwise, but is preferably carried out batchwise. The polymerization temperature is preferably 30 to 180°C, more preferably 70 to 160°C, and even more preferably 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 AO-containing raw material is preferably supplied to the reactor at a rate that maintains the reaction temperature. The reaction atmosphere is preferably an atmosphere that is less susceptible to moisture contamination, and more preferably an inert gas atmosphere such as nitrogen.

[0068] The reaction solution after polymerization contains a polyether compound and a DMC catalyst. It may also contain a stabilizer and trace amounts of impurities. Therefore, it is preferable to purify the reaction solution by filtration.

[0069] [Polyether Compound] The main chain of the polyether compound is a polymer chain consisting of an oxyalkylene chain containing a residue obtained by removing active hydrogen from an initiator and one or more repeating units based on alkylene oxide (hereinafter, repeating units based on a monomer will be simply referred to as "monomer units", for example, repeating units based on AO will be referred to as "AO units"). When the polymer chain contains two or more types of AO units, the AO units may form a block polymer or a random polymer. Examples of the oxyalkylene chain include a polymer chain containing an EO unit, a polymer chain containing a PO unit, a polymer chain containing an EO unit and a PO unit, a polymer chain consisting of an EO unit, a polymer chain consisting of a PO unit, a polymer chain consisting of a butylene oxide unit, a polymer chain consisting of a tetramethylene oxide unit, a polymer chain consisting of an EO unit and a PO unit, and a polymer chain consisting of a PO unit and a butylene oxide unit. As the oxyalkylene chain, a polymer chain consisting of an AO unit having 3 or more carbon atoms is preferred, and a polymer chain consisting of a PO unit is particularly preferred. The terminal groups of the polyether compound are hydroxyl groups, and the number of terminal groups (i.e., the number of hydroxyl groups) of the polyether compound is the same as the number of active hydrogens of the initiator.

[0070] The Mn of the polyether compound is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 60,000. When the Mn is equal to or greater than the lower limit, sufficient flexibility is imparted and good elongation properties are likely to be obtained when the polyether compound is used as an adhesive or coating material. When the Mn is equal to or less than the upper limit, the viscosity of the polyether compound can be kept low, making it easy to handle.

[0071] The hydroxyl value of the polyether compound is preferably 0.5 to 350 mgKOH / g, more preferably 1 to 200 mgKOH / g, and even more preferably 5 to 100 mgKOH / g. When the hydroxyl value is equal to or greater than the lower limit, sufficient curing is likely to be achieved when the compound is resinified. When the hydroxyl value is equal to or less than the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties are likely to be achieved.

[0072] The hydroxyl value-equivalent molecular weight of the polyether compound is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 60,000. When the hydroxyl value-equivalent molecular weight is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are likely to be obtained. When the hydroxyl value-equivalent molecular weight is equal to or less than the upper limit, the viscosity of the polyether compound can be kept low, making it easy to handle.

[0073] The Mw of the polyether compound is preferably 1,200 to 120,000, more preferably 2,000 to 90,000, and even more preferably 3,000 to 70,000. When the Mw is equal to or greater than the lower limit, sufficient flexibility is imparted and good elongation properties are likely to be obtained when used as an adhesive or coating material. When the Mw is equal to or less than the upper limit, the viscosity of the polyether compound can be kept low, making it easy to handle.

[0074] The Mw / Mn of the polyether compound is preferably 1.00 to 1.15, more preferably 1.00 to 1.12, and even more preferably 1.00 to 1.10. When the Mw / Mn is equal to or less than the upper limit, the viscosity of the polyether compound can be kept low, making it easy to handle.

[0075] The degree of unsaturation of the polyether compound is preferably 0.001 to 0.040 meq / g, more preferably 0.002 to 0.030 meq / g, and even more preferably 0.003 to 0.010 meq / g. When the degree of unsaturation is equal to or less than the upper limit, the polyether compound is likely to have good physical properties when used in the applications described below.

[0076] The viscosity of the polyether compound at a measurement temperature of 25° C. is preferably 100 to 100,000 mPa·s, more preferably 200 to 80,000 mPa·s, and even more preferably 400 to 60,000 mPa·s.

[0077] Polyether compounds can be used as lubricants, raw materials for polyurethane foams, adhesives, sealants, coating materials, etc. Furthermore, polyether compounds having reactive silicon groups, prepolymers, and polyether compounds having polymerizable unsaturated groups may be produced by reacting the polyether compounds with compounds that can react with the hydroxyl groups of the polyether compounds.

[0078] [Polyether Compound Having a Reactive Silicon Group] The polyether compound having a reactive silicon group (hereinafter also referred to as "polyether compound A") has a reactive silicon group represented by formula 1 described below.

[0079] The reactive silicon group has a hydroxyl group, a halogen atom, 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 polyether compound A is represented by the following formula 1: -SiR ａ X ３－ａ Formula 1

[0080] In 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.

[0081] 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 of the polyether compound A 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 ready availability.

[0082] In Formula 1, X 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, a siloxane bond is quickly formed, making it easy to form a crosslinked structure in the cured product, and the physical properties of the cured product tend to be good.

[0083] In Formula 1, a is an integer of 0 to 2. When a is 2, R's may be the same or different. When a is 1 or less, X's may be the same or different. Since a low crosslink density due to siloxane bonds tends to reduce the modulus of the cured product, a is preferably 2 or less, and more preferably 1 or less.

[0084] Examples of the reactive silicon group represented by 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. From the viewpoint of high activity and good curability, a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group, and a diethoxymethylsilyl group are preferred, and a trimethoxysilyl group and a dimethoxymethylsilyl group are more preferred.

[0085] Polyether compound A is a polyether compound having an average of 1.0 or more terminal groups per molecule and having a reactive silicon group represented by formula 1, wherein the terminal group is a reactive silicon group, an unsaturated group, an isocyanate group, or a hydroxyl group.

[0086] Polyether compound A has an average of 1.0 or more terminal groups per molecule. The average number of terminal groups is preferably 1.0 to 8.0, more preferably 1.0 to 6.0, and even more preferably 1.0 to 4.0, since this results in a cured product with higher tensile strength and better modulus and elongation. The number of terminal groups of polyether compound A is the same as the number of terminal groups of the polyether compound. The terminal groups of polyether compound A have any of a reactive silicon group, an unsaturated group, an isocyanate group, or a hydroxyl group represented by Formula 1. The respective terminal groups may be the same or different from each other.

[0087] The average number of reactive silicon groups represented by formula 1 per terminal group of polyether compound A is preferably 0.5 to 2.0, more preferably 0.60 to 1.94. When the average number of reactive silicon groups is equal to or greater than the above lower limit, the crosslinking density due to siloxane bonds increases, and a good cured product with a high modulus can be obtained.

[0088] The average number of reactive silicon groups represented by formula 1 per molecule of polyether compound A is preferably 0.6 to 8.0, more preferably 0.8 to 6.0, and even more preferably 1.2 to 4.0. When the average number of reactive silicon groups is equal to or greater than the above lower limit, the crosslinking density due to siloxane bonds increases, and a good cured product with a high modulus can be obtained.

[0089] The Mn of polyether compound A is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and particularly preferably 2,000 to 60,000. When Mn is equal to or greater than the lower limit, the elongation properties of the cured product are improved. When Mn is equal to or less than the upper limit, the viscosity is low and workability is improved.

[0090] The Mw / Mn of the polyether compound A is preferably 1.00 to 1.50, more preferably 1.00 to 1.45, even more preferably 1.00 to 1.40, and most preferably 1.00 to 1.20. When the Mw / Mn is equal to or less than the upper limit, good elongation properties are easily obtained, and the viscosity is reduced, resulting in good workability.

[0091] The viscosity of the polyether compound A at a measurement temperature of 25° C. is preferably 100 to 120,000 mPa·s, more preferably 200 to 100,000 mPa·s, and even more preferably 400 to 80,000 mPa / s. When the viscosity is equal to or less than the upper limit, the polyether compound A is easy to handle.

[0092] [Method for producing polyether compound having reactive silicon group] In the method for producing polyether compound A, the hydroxyl groups of the polyether compound are converted into groups having reactive silicon groups. Examples of the method for producing polyether compound A include the following production methods (a1), (b1), and (c1). Method (a1): Converting the hydroxyl groups of the polyether compound into alkenyloxy groups having a carbon-carbon double bond at the molecular terminal or alkynyloxy groups having a carbon-carbon triple bond at the molecular terminal, and then converting the carbon-carbon double bond at the molecular terminal of the alkenyloxy group or the carbon-carbon triple bond to a reactive silicon group -SiR represented by formula 1 ａ X ３－ａand converting the alkenyloxy group or alkynyloxy group into a group having a reactive silicon group represented by Formula 1. Method (b1): A method of reacting a hydroxyl group of a polyether compound with a silylating agent having a functional group reactive with the hydroxyl group and a reactive silicon group represented by Formula 1 to convert the hydroxyl group into a group having a reactive silicon group represented by Formula 1. Method (c1): A method of converting a hydroxyl group of a polyether compound into a group having an isocyanate group, and then reacting with a silylating agent having a functional group reactive with an isocyanate group and a reactive silicon group represented by Formula 1 to convert the hydroxyl group into a group having a reactive silicon group represented by Formula 1.

[0093] In method (a1), an alkali metal salt is allowed to act on a polyether compound to form an alcoholate, and then the alcoholate is reacted with a halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular terminal or a halogenated hydrocarbon compound having a carbon-carbon triple bond at the molecular terminal to convert the hydroxyl groups of the polyether compound into alkenyloxy groups having a carbon-carbon double bond at the molecular terminal or alkynyloxy groups having a carbon-carbon triple bond at the molecular terminal.

[0094] Examples of alkali metal salts include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. From the viewpoints 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. From the viewpoint of availability, sodium methoxide is particularly preferred. The alkali metal salt may be used in a state dissolved in a solvent.

[0095] 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. Examples of halogenated hydrocarbon compounds containing a carbon-carbon triple bond at the molecular terminal 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 of the halogenated hydrocarbon compounds 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. A halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular terminal and a halogenated hydrocarbon compound having a triple bond at the molecular terminal may be used in combination. The halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular terminal may be used alone or in combination of two or more. The halogenated hydrocarbon compound having a carbon-carbon triple bond at the molecular terminal may be used alone or in combination of two or more.

[0096] Next, a reactive silicon group, —SiR, represented by Formula 1, is bonded to the carbon-carbon double bond at the molecular terminal of the alkenyloxy group or the carbon-carbon triple bond at the molecular terminal of the alkynyloxy group. ａ X ３－ａ The alkenyloxy group or alkynyloxy group is converted into a group having a reactive silicon group represented by Formula 1 by reacting with a silylating agent capable of introducing the following: ａ X ３－ａ, R, X, and a are the same as in Formula 1). Specific examples include dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, methyldiisopropoxysilane, (α-chloromethyl)dimethoxysilane, (α-chloromethyl)diethoxysilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, and 3-mercaptopropyltrimethoxysilane. From the viewpoints of high activity and good curability, trimethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane are preferred, and dimethoxymethylsilane is more preferred.

[0097] In the method (b1), a polyether compound is reacted with a silylating agent. As the silylating agent, an isocyanate silane compound represented by the following formula 3 is preferably used: OCN—(CH ２ ) ｎ -SiR ａ X ３－ａ ...Formula 3 -SiR in Formula 3 ａ X ３－ａ is the same as in Formula 1. n is an integer of 1 to 8, preferably 1 to 3. The reaction between the hydroxyl group of the polyether compound and the isocyanate silane compound converts the hydroxyl group of the polyether compound to —O—C(═O)NH—(CH ２ ) ｎ -SiR ａ X ３－ａ A urethane bond (—O—C(═O)NH—) and —SiR ａ X ３－ａ

[0033] Examples of the isocyanate silane compound include 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, isocyanate methyl trimethoxysilane, isocyanate methyl triethoxysilane, 3-isocyanate propyl methyl dimethoxysilane, 3-isocyanate propyl methyl diethoxysilane, isocyanate methyl methyl dimethoxysilane, and isocyanate methyl methyl diethoxysilane. In view of reactivity with polyether compounds and ease of handling, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, 3-isocyanate propyl methyl dimethoxysilane, and isocyanate methyl trimethoxysilane are preferred.

[0098] The active hydrogen of the polyether compound reacts with the isocyanate group of the isocyanate silane compound represented by Formula 3, thereby introducing a reactive silicon group into the polyether compound. When the active hydrogen-containing group of the polyether compound is a hydroxyl group, the polyoxyalkylene chain (-(R ５ O) ｍ -, R ５ represents an alkylene group, and m represents the number of moles of oxyalkylene groups.) to which a reactive silicon group is bonded via a urethane bond and an organic group. ５ O) ｍ -C(=O)NH-(CH ２ ) ｎ -SiR ａ X ３－ａ A linked structure represented by the following formula is formed.

[0099] This reaction may be carried out in the presence of a urethanization catalyst. The urethanization catalyst is not particularly limited, and known urethanization catalysts can be used as appropriate. Examples include organotin compounds such as dibutyltin dilaurate and dioctyltin dilaurate, metal catalysts such as bismuth compounds, and base catalysts such as organic amines. The reaction temperature is preferably 20 to 200°C, more preferably 50 to 150°C. The urethanization reaction is preferably carried out in an inert gas atmosphere. Nitrogen is preferred as the inert gas.

[0100] The molar ratio of the total number of isocyanate groups in the isocyanate silane compound represented by Formula 3 to the total number of active hydrogens in the polyether compound is preferably set according to the number of reactive silicon groups per molecule of the polyether compound A to be obtained. It is preferable to react the isocyanate silane compound represented by Formula 3 so that the resulting polyether compound A has at least 0.7 reactive silicon groups per molecule. For example, when the active hydrogen-containing group in the polyether compound is a hydroxyl group, NCO / OH, which represents the molar ratio of the total number of isocyanate groups (NCO) in the isocyanate silane compound represented by Formula 3 to the total number of active hydrogens in the polyether compound (total number of hydroxyl groups), is preferably 0.7 to 1.0, more preferably 0.8 to 1.0, and even more preferably 0.9 to 1.0. When NCO / OH is equal to or greater than the lower limit, the strength of the cured product is excellent, and when it is equal to or less than the upper limit, the elongation of the cured product is excellent.

[0101] In method (c1), a polyisocyanate compound is reacted with a hydroxyl group of a polyether compound to convert the hydroxyl group into an isocyanate-containing monovalent organic group (hereinafter also referred to as an "isocyanate-containing group") that has a urethane bond (-O-C(=O)NH-) at the bond terminal with the polyether compound, and then a silylating agent having a functional group reactive with an isocyanate group and a reactive silicon group represented by formula 1 is reacted with the isocyanate-containing group to form a terminal group that is a monovalent organic group (hereinafter also referred to as a "urethane bond- and reactive silicon group-containing group") that has one or more urethane bonds (-O-C(=O)NH-) and a silylating agent residue that has reacted with an isocyanate group. Hereinafter, method (c1) will be described assuming that the polyisocyanate compound is a diisocyanate compound represented by the following formula 4, and that the silylating agent having a functional group reactive with an isocyanate group and a reactive silicon group represented by formula 1 is a compound represented by the following formula 5, but the present invention is not limited thereto.

[0102] OCN-R ３ -NCO Formula 4 R in Formula 4 ３ represents a divalent organic group.

[0103] W-R ４ -SiR ａ X ３－ａ In Formula 5, W represents a functional group (a group having one or more active hydrogen atoms) capable of reacting with a monovalent isocyanate group, R ４ is a divalent organic group, -SiR ａ X ３－ａ is the same as Equation 1.

[0104] When the hydroxyl group of a polyether compound is reacted with a diisocyanate compound represented by formula 4, the isocyanate-containing group is —O—C(═O)NH—R ３ When an isocyanate-containing group is reacted with a silylating agent represented by formula 5, the urethane bond and the reactive silicon-containing group are converted to a group represented by the formula -O-C(=O)NH-R ３ -NHC(=O)-W'-R ４ -SiR ａ X ３－ａ(wherein W' is a divalent group obtained by removing one active hydrogen from W.) For example, when W is a hydroxyl group, the urethane bond and the reactive silicon group-containing group are represented by the formula: -O-C(=O)NH-R ３ -NHC(=O)-OR ４ -SiR ａ X ３－ａ In this case, the urethane bond and reactive silicon group-containing group have two urethane bonds. ２ ), the urethane bond and the reactive silicon group-containing group are —O—C(═O)NH—R ３ -NHC(=O)-NH-R ４ -SiR ａ X ３－ａ It is a group represented by the following formula:

[0105] R ３ is preferably a divalent organic group having 2 to 20 carbon atoms, and examples thereof include an alkylene group, a cycloalkylene group, a bicycloalkylene group, a monocyclic or polycyclic divalent aromatic hydrocarbon group, a divalent group obtained by removing two hydrogen atoms from a cycloalkane having an alkyl group as a substituent, a divalent group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having an alkyl group as a substituent, a divalent group obtained by removing two hydrogen atoms from two or more cycloalkanes which are bonded via an alkylene group and which may have an alkyl group as a substituent, and a divalent group obtained by removing two hydrogen atoms from two or more aromatic hydrocarbons which are bonded via an alkylene group and which may have an alkyl group as a substituent.

[0106] Examples of the diisocyanate compound represented by Formula 4 and other polyisocyanate compounds include aromatic polyisocyanates, non-yellowing aromatic polyisocyanates (compounds that do not have an isocyanate group directly bonded to a carbon atom constituting an aromatic ring), aliphatic polyisocyanates, alicyclic polyisocyanates, and urethane-modified, biuret-modified, allophanate-modified, carbodiimide-modified, and isocyanurate-modified polyisocyanates. Examples of aromatic polyisocyanates include naphthalene-1,5-diisocyanate, polyphenylene polymethylene polyisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. Examples of non-yellowing aromatic polyisocyanates include xylylene diisocyanate and tetramethylxylylene diisocyanate. Examples of aliphatic polyisocyanates include hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, and 2,4,4-trimethyl-hexamethylene diisocyanate. Examples of alicyclic polyisocyanates include isophorone diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate). As the polyisocyanate compound, those having two isocyanate groups are preferred, with hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate being more preferred, and tolylene diisocyanate being even more preferred because it is easier to obtain tensile strength in the cured product. One type of polyisocyanate compound may be used, or two or more types may be used in combination.

[0107] A functional group capable of reacting with an isocyanate group represented by formula 5 and —SiR ａ X ３－ａ R in the silylating agent having ４As the alkyl group, a divalent organic group having 1 to 20 carbon atoms is preferred, a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms, a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms and substituted with an alkyl group having 1 to 4 carbon atoms, a group obtained by removing two hydrogen atoms from a cyclic hydrocarbon having 3 to 10 carbon atoms, or a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 12 carbon atoms is more preferred, a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 8 carbon atoms is even more preferred, and a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 6 carbon atoms is particularly preferred. W is preferably a group having one or two active hydrogen atoms selected from a hydroxyl group, a carboxyl group, a sulfanyl group, an amino group, and an amino group in which one hydrogen atom is substituted with an alkyl group having 1 to 6 carbon atoms, more preferably a hydroxyl group, a sulfanyl group, an amino group, a methylamino group, an ethylamino group, or a butylamino group, and more preferably a hydroxyl group, an amino group, a methylamino group, an ethylamino group, or a butylamino group.

[0108] In the methods (b1) and (c1), the polyether compound A obtained has a reactive silicon group formed via one or more organic groups represented by the following formula (i). That is, the polyether compound A obtained by methods (b1) and (c1) contains one or more organic groups represented by the following formula (i). The polyether compound A obtained by method (b1) contains only one organic group represented by the following formula (i), and the polyether compound A obtained by method (c1) contains two or more organic groups represented by the following formula (i): -C(=O)NH- Formula (i)

[0109] The organic group (i) is a divalent group derived from a urethane bond or a urea bond. When the isocyanate silane compound represented by Formula 3 is used as a silylating agent, the number of organic groups (i) is one.

[0110] The organic group (i) preferably forms a urethane bond (—O—C(═O)NH—, where —O— represents the oxygen atom at the terminal of the polyoxyalkylene chain) with the polyoxyalkylene chain. That is, it is preferable that one organic group (i) is present between the polyoxyalkylene chain and the reactive silicon group in the polyether compound A. When the polyether compound A is produced by the above-mentioned method (b1), the number of organic groups represented by formula (i) contained in the polyether compound A will be one. When the polyether compound A is produced by method (b1), a polyether compound A with a high silylation rate is likely to be obtained. When the polyether compound A is produced by method (b1), a polyether compound A with a narrow molecular weight distribution is likely to be obtained. The viscosity of the polyether compound is suppressed, resulting in good workability. When the isocyanate silane compound represented by formula 3 contains one isocyanate group and one reactive silicon group, the number of reactive silicon groups per molecule of the polyether compound A will be the same as the number of groups (i) per molecule.

[0111] The silylation rate of polyether compound A is preferably 50 to 100 mol%, more preferably 60 to 98 mol%. When the silylation rate is equal to or greater than the lower limit of the above range, the cured product has excellent tensile strength and a high modulus. When the curable composition contains two or more types of polyether compound A, it is sufficient that the average silylation rate of all polyether compounds A is within the above range.

[0112] [Curable Composition Comprising Polyether Compound Having a Reactive Silicon Group] Polyether compound A is used in a curable composition. The curable composition is obtained by mixing polyether compound A with other necessary components. As polyether compound A, only one type may be used, or two or more types may be used in combination. The content of the polyether compound having a reactive silicon group relative to the total mass of the curable composition is preferably 1 to 90 mass%, more preferably 10 to 80 mass%, and even more preferably 20 to 70 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.

[0113] Examples of other components contained in the curable composition include curable compounds other than polyether compound A, 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, blowing agents, solvents, and silicates. Other components include those described in WO 2013 / 180203, WO 2014 / 192842, WO 2016 / 002907, JP 2014-88481, JP 2015-10162, JP 2015-105293, JP 2017-039728, and JP 2017-214541, and can be used in combination without limitation. Two or more of each component may be used in combination.

[0114] The curable composition may be a one-component type in which all of the polyether compound A and other components are blended in advance, sealed, and stored, and then cured by atmospheric moisture after application. Alternatively, it may be a two-component type in which a base composition containing at least the polyether compound A 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. It is preferable that the one-component curable composition does not contain water. It is preferable that the blended components containing water are dehydrated and dried in advance, or that the pressure is reduced during blending and kneading. In two-component curable compositions, 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 perspective of storage stability, it is preferable that the blended components be dehydrated and dried in advance. To improve storage stability, a dehydrating agent may be added to the one-component curable composition or the two-component base composition.

[0115] Suitable applications of the curable composition containing polyether compound A include adhesives, sealants (for example, elastic sealants for construction, sealants for double glazing, rust-proofing and waterproofing sealants for glass edges, sealants for the rear surface 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).

[0116] [Prepolymer] The prepolymer (hereinafter also referred to as "polyether compound B") is a reaction product of a polyether compound and a polyisocyanate. A urethane bond is formed between the polyether compound and the polyisocyanate through a urethane reaction between the hydroxyl groups of the polyether compound and the isocyanate groups of the polyisocyanate. Of the isocyanate groups in the polyisocyanate units introduced into polyether compound B, those that remain unreacted with the hydroxyl groups of polyether compound B become the isocyanate groups at the molecular terminals of polyether compound B. Furthermore, of the hydroxyl groups in the polyether compound units, those that remain unreacted with the isocyanate groups of the polyisocyanate become the hydroxyl groups at the molecular terminals of polyether compound B. In other words, the molecular terminal groups of polyether compound B contain either or both of a hydroxyl group and an isocyanate group.

[0117] The Mn of polyether compound B is preferably 1,000 to 1,000,000, more preferably 1,500 to 500,000, and even more preferably 2,000 to 100,000. When Mn is equal to or greater than the lower limit, sufficient flexibility is imparted and good elongation properties are obtained when used as an adhesive or coating material. When Mn is equal to or less than the upper limit, the viscosity of polyether compound C can be kept low, making it easy to handle.

[0118] The Mw / Mn of the polyether compound B is preferably 1.00 to 1.50, more preferably 1.00 to 1.45, and even more preferably 1.00 to 1.40. When the Mw / Mn is equal to or less than the upper limit, good elongation properties are easily obtained, and the viscosity is reduced, resulting in good workability.

[0119] When the molecular terminal of polyether compound B is an isocyanate group, the content of the isocyanate group relative to the total mass of polyether compound B is preferably 0.1 to 20 mass%, more preferably 0.5 to 18 mass%, and even more preferably 1 to 15 mass%. When the content of the isocyanate group is equal to or greater than the above lower limit, the tensile strength of the cured product is likely to be improved. When the content of the isocyanate group is equal to or less than the above upper limit, gelation is less likely to occur during the reaction.

[0120] The content of the urethane bond relative to the total mass of the polyether compound B is preferably from 0.01 to 40 mass %, more preferably from 0.1 to 30 mass %, and even more preferably from 1 to 15 mass %.

[0121] The viscosity of the polyether compound B at a measurement temperature of 25° C. is preferably 100 to 100,000 mPa·s, more preferably 200 to 50,000 mPa·s, and even more preferably 500 to 30,000 mPa / s. When the viscosity is equal to or less than the upper limit, the polyether compound B is easy to handle.

[0122] [Method for producing prepolymer] In the method for producing polyether compound B, a polyether compound is reacted with a polyisocyanate. If necessary, a urethane catalyst may be used. One type of polyether compound may be used, or two or more types may be used in combination.

[0123] Examples of polyisocyanates include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates. The number of isocyanate groups contained in the polyisocyanate is preferably 2 to 3, and more preferably 2.

[0124] Examples of the aliphatic polyisocyanate include linear aliphatic polyisocyanates such as tetramethylene diisocyanate, dodecamethylene diisocyanate, and hexamethylene diisocyanate, and branched aliphatic polyisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate.

[0125] Examples of alicyclic polyisocyanates include isophorone diisocyanate (3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, IPDI), hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane.

[0126] Examples of aromatic polyisocyanates include tolylene diisocyanate (TDI), 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (diphenylmethane 4,4'-diisocyanate, MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate.

[0127] Examples of the araliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and α,α,α,α-tetramethylxylylene diisocyanate.

[0128] The polyisocyanate is preferably an alicyclic polyisocyanate or an aromatic polyisocyanate, more preferably IPDI, MDI or TDI. One type of polyisocyanate may be used alone, or two or more types may be used in combination.

[0129] The functional groups at the molecular terminals of polyether compound B can be controlled by adjusting the molar ratio of the total number of isocyanate groups in the polyisocyanate to the total number of hydroxyl groups in the polyether compound (hereinafter also referred to as the "NCO / OH ratio"). For example, when producing a polyether compound B having isocyanate groups at its molecular terminals, the NCO / OH ratio is preferably 2 to 10, more preferably 2 to 8, even more preferably 2 to 7, and particularly preferably 2 to 5. When producing a polyether compound B having hydroxyl groups at its molecular terminals, the NCO / OH ratio is preferably 0.1 to 0.8, more preferably 0.2 to 0.7, and even more preferably 0.3 to 0.6.

[0130] The urethanization catalyst is preferably one or more selected from tertiary amine compounds and organometallic compounds. When a highly reactive polyisocyanate is used, the urethanization catalyst may not be used.

[0131] Examples of the tertiary amine compound include triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-undecene-7.

[0132] The organometallic compound is preferably at least one selected from tin compounds and non-tin compounds, such as dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate. Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanium, and butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate; and zirconium compounds such as zirconium naphthenate.

[0133] The urethanization catalyst may be used alone or in combination of two or more. When a urethanization catalyst is used, the amount of the urethanization catalyst used is preferably, for example, 0.001 to 1.0 part by mass per 100 parts by mass of the polyether compound.

[0134] A solvent can be used, if necessary, in the production of polyether compound B. The solvent is preferably one or more selected from ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and aromatic hydrocarbons such as toluene and xylene. One solvent may be used alone, or two or more solvents may be used in combination. When a solvent is used, the amount of the solvent used is not particularly limited, but is preferably 100 to 1,000 parts by mass per 100 parts by mass of the polyether compound.

[0135] Examples of methods for producing the polyether compound B include a method of mixing a polyether compound, a polyisocyanate, and, if necessary, a urethanization catalyst and a solvent. Alternatively, a method may be used in which a polyisocyanate is added dropwise to a mixed liquid obtained by mixing a polyether compound, and, if necessary, a urethanization catalyst and a solvent.

[0136] The reaction temperature is preferably 50 to 120° C., more preferably 50 to 100° C. When the reaction temperature is equal to or higher than the lower limit, the urethane reaction is likely to be accelerated. When the reaction temperature is equal to or lower than the upper limit, side reactions other than the urethane reaction are likely to be suppressed.

[0137] When a urethanization catalyst is used, it is preferable to add a reaction terminator to inactivate the urethanization catalyst after the reaction is completed. Examples of the reaction terminator include acetylacetone. One type of reaction terminator may be used alone, or two or more types may be used in combination.

[0138] If unreacted polyisocyanate remains after the reaction, it is preferable to purify the polyether compound B by removing the polyisocyanate by distillation.

[0139] [Polyurethane composition containing prepolymer] Polyether compound B is used in the polyurethane composition. The polyurethane composition is obtained by mixing polyether compound B with other optional components as necessary. As polyether compound B, only one type may be used, or two or more types may be used in combination. The content ratio of polyether compound B relative to the total mass of the polyurethane composition is 15 to 100 mass%, preferably 30 to 100 mass%. The polyurethane composition may further contain optional components other than polyether compound B.

[0140] Examples of optional components contained in the polyurethane composition include catalysts, fillers, plasticizers, stabilizers, pigments, fibers, dyes, drying agents, adhesion improvers, rheology modifiers, solvents, natural resins, non-reactive polymers, and other additives. Each of the optional components may be used alone, or two or more may be used in combination. When the polyurethane composition contains optional components, the content of the optional components relative to the total mass of the polyurethane composition is preferably more than 0 mass% and 50 mass% or less.

[0141] A cured product can be produced by reacting a polyurethane composition with a curing agent. When the molecular terminal of polyether compound B is an isocyanate group, a curing agent having active hydrogen is used. The active hydrogen-containing group of the curing agent is preferably a hydroxyl group. When the molecular terminal of polyether compound B is a hydroxyl group, a curing agent having an isocyanate group is used. When the molecular terminal of polyether compound B is an isocyanate group, a urethane reaction occurs between the isocyanate group of polyether compound B contained in the polyurethane composition and the active hydrogen-containing group (e.g., a hydroxyl group) of the curing agent, thereby crosslinking polyether compound B with a urethane bond, thereby obtaining a cured product. When the molecular terminal of polyether compound B is a hydroxyl group, a urethane reaction occurs between the hydroxyl group of polyether compound B contained in the polyurethane composition and the isocyanate group of the curing agent, thereby crosslinking polyether compound B with a urethane bond, thereby obtaining a cured product. When a curing agent has a hydroxyl group, the number of hydroxyl groups in the curing agent is preferably 2 or more, more preferably 2 to 4, and even more preferably 2 to 3. Water is an example of a curing agent having two hydroxyl groups. In the case of a curing agent having an isocyanate group, the number of isocyanate groups in the curing agent is preferably 2 or more, more preferably 2 to 4, and even more preferably 2 to 3.

[0142] Examples of the curing agent having a hydroxyl group include the initiator and water described in the method for producing the polyether compound, and examples of the curing agent having an isocyanate group include the polyisocyanate described above.

[0143] When the molecular terminal of polyether compound B is an isocyanate group, the molar ratio of the total amount of isocyanate groups of polyether compound B to the total amount of hydroxyl groups of the curing agent is preferably greater than 1, more preferably from 1.01 to 1.20. When the molecular terminal of polyether compound B is a hydroxyl group, the molar ratio of the total amount of hydroxyl groups of polyether compound B to the total amount of isocyanate groups of the curing agent is preferably greater than 0.8, more preferably from 0.81 to 1.20.

[0144] The polyurethane composition and curing agent may be mixed in a one-component manner, in which all components except the curing agent are premixed to form a one-component polyurethane composition, which is then sealed and stored, and cured by atmospheric moisture after application. Alternatively, a two-component method may be used, in which the polyurethane composition, which is the base composition, and a curing agent composition containing at least a curing agent are stored separately, and the curing agent composition and base composition are mixed before use. In the case of a one-component composition, atmospheric moisture (water) functions as the curing agent. That is, when the molecular terminal of polyether compound B is an isocyanate group, a one-component composition is preferred. It is preferable that the one-component composition does not contain water. It is preferable that the blending components containing water are dehydrated and dried in advance, or that the pressure is reduced during preparation of the one-component composition. In the case of a two-component composition, the curing agent composition may contain water. The base composition is less likely to gel even if it contains a small amount of water, but from the perspective of storage stability, it is preferable to dehydrate and dry the blending components in advance. In the case of a two-component composition, optional components may be included in the curing agent composition. To improve storage stability, a dehydrating agent may be added to the one-component composition or the two-component base composition. The reaction temperature is preferably 20 to 40° C. In the case of a one-component type, the relative humidity at the reaction temperature is preferably 40 to 60%.

[0145] Suitable applications of the polyurethane composition containing polyether compound B include adhesives, sealants (e.g., elastic sealants for construction, sealants for double-glazing, rust-proofing and waterproofing sealants for glass edges, sealants for the rear surface of solar cells, sealants for buildings, sealants for ships, sealants for automobiles, and sealants for roads), coating materials (for paint applications), and electrical insulating materials (insulating coating materials for electric wires and cables). As an adhesive, it is suitable as an elastic adhesive for joining plastics to each other, joining metals to each other, and joining plastics to metals. It is also suitable as an elastic sealant and elastic coating material.

[0146] [Polyether Compound Having a Polymerizable Unsaturated Group] A polyether compound having a polymerizable unsaturated group (hereinafter also referred to as "polyether compound C") is a reaction product of a polyether compound and a compound having a polymerizable unsaturated group. An example of the polymerizable unsaturated group is a carbon-carbon double bond at the molecular terminal. Preferred polymerizable unsaturated groups are a (meth)acryloyl group and a (meth)acryloyloxy group. "(Meth)acryloyl group" is a general term for an acryloyl group and a methacryloyl group. "(Meth)acryloyloxy group" is a general term for an acryloyloxy group and a methacryloyloxy group.

[0147] The polyether compound C has an average of 1.0 or more terminal groups per molecule. In order to improve the crosslinking reaction and curing properties when resinified, the average number of terminal groups is preferably 1.0 to 8.0, more preferably 1.0 to 6.0, and even more preferably 1.0 to 4.0. The number of terminal groups of the polyether compound C is the same as the number of terminal groups of the polyether compound.

[0148] The average number of polymerizable unsaturated groups per terminal group of the polyether compound C is preferably 0.5 to 2.0, more preferably 0.8 to 1.2. When the average number of polymerizable unsaturated groups is equal to or greater than the lower limit, crosslinking reaction and curing properties tend to be good when resinified. When the average number of polymerizable unsaturated groups is equal to or less than the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties tend to be obtained.

[0149] The average number of polymerizable unsaturated groups per molecule of polyether compound C is preferably 1.0 to 8.0, more preferably 1.0 to 6.0, and even more preferably 1.0 to 4.0. When the average number of polymerizable unsaturated groups is equal to or greater than the lower limit, crosslinking reaction and curing properties are likely to be good when resinified. When the average number of polymerizable unsaturated groups is equal to or less than the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties are likely to be obtained.

[0150] The Mn of polyether compound C is preferably 1,000 to 1,000,000, more preferably 1,500 to 500,000, and even more preferably 2,000 to 100,000. When Mn is equal to or greater than the lower limit, sufficient flexibility is imparted and good elongation properties are likely to be obtained when used as an adhesive or coating material. When Mn is equal to or less than the upper limit, the viscosity of polyether compound C can be kept low, making it easy to handle.

[0151] The Mw / Mn of the polyether compound C is preferably 1.00 to 1.50, more preferably 1.00 to 1.45, and even more preferably 1.00 to 1.40. When the Mw / Mn is equal to or less than the upper limit, good elongation properties are easily obtained, and the viscosity is reduced, resulting in good workability.

[0152] When the polyether compound C has a urethane bond, the content of the urethane bond relative to the total mass of the polyether compound C is preferably 0.01 to 40 mass%, more preferably 0.1 to 30 mass%, and even more preferably 1 to 15 mass%.

[0153] The viscosity of the polyether compound C at a measurement temperature of 25° C. is preferably 100 to 100,000 mPa·s, more preferably 200 to 50,000 mPa·s, and even more preferably 500 to 30,000 mPa / s. When the viscosity is equal to or less than the upper limit, the polyether compound C is easy to handle.

[0154] [Method for producing polyether compound having polymerizable unsaturated group] In the method for producing polyether compound C, the hydroxyl group of the polyether compound is converted into a group having a polymerizable unsaturated group. Examples of the method for producing polyether compound C include the following production methods (a2), (b2), and (c2). Method (a2): A method in which a compound having a functional group reactive with a hydroxyl group and a polymerizable unsaturated group (hereinafter also referred to as "compound 1") is reacted with the hydroxyl group of the polyether compound to convert the hydroxyl group into a group having a polymerizable unsaturated group. Method (b2): A method in which a hydroxyl group of the polyether compound is reacted with polyisocyanate to obtain a prepolymer having an isocyanate group at the molecular terminal, and then a compound having a functional group reactive with an isocyanate group and a polymerizable unsaturated group (hereinafter also referred to as "compound 2") is reacted to convert the hydroxyl group into a group having a polymerizable unsaturated group. Method (c2): A method in which a hydroxyl group of a polyether compound is reacted with a polyisocyanate to obtain a prepolymer having a hydroxyl group at the molecular terminal, and then the prepolymer is reacted with compound 1 to convert the hydroxyl group into a group having a polymerizable unsaturated group.

[0155] In the method (b2), the prepolymer having an isocyanate group at the molecular terminal can be the polyether compound B having an isocyanate group at the molecular terminal.In the method (c2), the prepolymer having a hydroxyl group at the molecular terminal can be the polyether compound B having a hydroxyl group at the molecular terminal.

[0156] Compound 1 is preferably a compound having one isocyanate group and a polymerizable unsaturated group, more preferably a (meth)acrylate having one isocyanate group, even more preferably an isocyanate alkyl (meth)acrylate, particularly preferably an isocyanate alkyl (meth)acrylate having 8 or less carbon atoms excluding the carbon in the isocyanate group of the isocyanate alkyl group, and most preferably an isocyanate alkyl (meth)acrylate having 4 or less carbon atoms excluding the carbon in the isocyanate group of the isocyanate alkyl group. "(Meth)acrylate" is a general term for acrylate and methacrylate. Examples of Compound 1 include 2-isocyanate ethyl (meth)acrylate and isocyanate methyl (meth)acrylate. Commercially available products include Karenz-AOI and Karenz-MOI (both product names of Showa Denko K.K.).

[0157] Compound 2 is preferably a compound having an active hydrogen-containing group such as a hydroxyl group or an amino group, and a polymerizable unsaturated group, preferably a (meth)acrylate having an active hydrogen-containing group such as a hydroxyl group or an amino group, more preferably a hydroxyalkyl (meth)acrylate or hydroxycycloalkyl (meth)acrylate having one hydroxyl group, and particularly preferably a hydroxyalkyl (meth)acrylate having an alkyl group with 8 or less carbon atoms. Examples of compound 2 include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate. Commercially available products include Light Ester HO-250(N), Light Ester HOP(N), Light Ester HOA(N), Light Ester HOP-A(N), and Light Ester HOB(N) (all product names of Kyoei Chemical Co., Ltd.), and 4-HBA (product name of Osaka Organic Chemical Industry Ltd.).

[0158] When the composition containing polyether compound C is a photocurable composition, it is preferable that all of the polymerizable unsaturated groups contained in polyether compound C are acryloyloxy groups. Such polyether compound C can be obtained by using compounds 1 and 2 in which the polymerizable unsaturated groups are acryloyloxy groups.

[0159] In methods (a2) and (c2), the molar ratio of the amount of compound 1 used relative to the amount of hydroxyl groups in the polyether compound or the amount of hydroxyl groups in the prepolymer having hydroxyl groups at the molecular terminals is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05. In method (b2), the molar ratio of the amount of compound 2 used relative to the amount of isocyanate groups in the prepolymer having isocyanate groups at the molecular terminals may be greater than 1. Excess compound 2 remains unreacted and may be contained in the composition containing polyether compound C. The molar ratio is preferably 0.8 to 1.5, more preferably 0.9 to 1.3, and even more preferably 0.95 to 1.1.

[0160] In the methods (a2), (b2), and (c2), the reaction between a hydroxyl group and a functional group capable of reacting with the hydroxyl group, and the reaction between an isocyanate group and a functional group capable of reacting with the isocyanate group can be carried out by methods known in the art. When the reaction is between a hydroxyl group and an isocyanate group, the above-mentioned urethane catalyst may be used as necessary.

[0161] [Composition containing polyether compound having polymerizable unsaturated group] The polyether compound C is used in a curable composition. The curable composition is obtained by mixing the polyether compound C with other optional components. As the polyether compound C, only one type may be used, or two or more types may be used in combination. The content of the polyether compound C relative to the total mass of the curable composition is preferably 65 mass% or more, more preferably 75 mass% or more.

[0162] The curable composition may contain, in addition to the polyether compound C, a compound having a polymerizable unsaturated group other than the polyether compound C (hereinafter also referred to as "other compound"), a photopolymerization initiator, and other components.

[0163] Examples of other compounds include other compounds 1 and 2 below. Other compound 1 is a compound other than polyether compound C, and is preferably a compound having one (meth)acryloyloxy group and one or more hydroxyl groups, and preferably one or two hydroxyl groups. Other compound 1 may be a compound having a polyoxyalkylene chain, and in this case, a compound having no urethane bond or urea bond (a compound produced by a method other than methods (a2) to (c2)) is preferred. Other compound may also be a compound having an aliphatic polyester chain obtained by ring-opening addition polymerization of lactone.

[0164] Examples of other compounds 1 include hydroxyalkyl(meth)acrylates, dihydroxyalkyl(meth)acrylates, lactone-modified hydroxyalkyl(meth)acrylates, polyoxyalkylene diol mono(meth)acrylates, and (meth)acrylic acid-monoepoxide adducts.

[0165] The number of carbon atoms in the hydroxyalkyl moiety of the hydroxyalkyl (meth)acrylate is preferably 2 to 8, and more preferably 2 to 6. The number of carbon atoms in the dihydroxyalkyl moiety of the dihydroxyalkyl (meth)acrylate is preferably 2 to 8, and more preferably 2 to 6. Specific examples of hydroxyalkyl (meth)acrylates include the hydroxyalkyl (meth)acrylates exemplified as Compound 2. Of these, 4-hydroxybutyl acrylate and 6-hydroxyhexyl acrylate are preferred in terms of flexibility and low volatility.

[0166] Examples of lactone-modified hydroxyalkyl (meth)acrylates include compounds obtained by ring-opening addition of lactone to the hydroxyalkyl (meth)acrylate exemplified as Compound 2. The number of lactones added is preferably 1 to 3. Examples of lactones include ε-caprolactone, γ-butyrolactone, and γ-valerolactone.

[0167] The (meth)acrylic acid-monoepoxide adduct is preferably a reaction product of (meth)acrylic acid with a glycidyl ether or glycidyl ester, such as a reaction product of (meth)acrylic acid with phenyl glycidyl ether.

[0168] Among these, hydroxyalkyl (meth)acrylate and (meth)acrylic acid-monoepoxide adduct are preferred because they are easily available industrially and contain few impurities.

[0169] Only one type of other compound 1 may be used, or two or more types may be used in combination. When the curable composition contains the other compound 1, the content of the other compound 1 relative to the total mass of the curable composition is preferably 1 to 20 mass%, more preferably 1 to 15 mass%. When the content of the other compound 1 is equal to or greater than the above-mentioned lower limit, the effect of improving adhesion by adding the other compound 1 is likely to be sufficiently obtained. When the content of the other compound 1 is equal to or less than the above-mentioned upper limit, good physical properties in terms of low cure shrinkage are likely to be obtained.

[0170] The other compound 2 is a compound other than the polyether compound C and the other compound 1, and is preferably a compound having one (meth)acryloyloxy group and not containing a urethane bond. As the other compound 2, a (meth)acrylate having a long-chain alkyl group with 8 or more carbon atoms or a (meth)acrylate having an amide group is preferred. Examples of the other compound 2 other than these include alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, and (meth)acrylates having an aliphatic cyclic hydrocarbon group with 7 or less carbon atoms.

[0171] When the curable composition contains a long-chain alkyl (meth)acrylate having 8 or more carbon atoms, air bubbles in the cured product tend to disappear when the curable composition is sealed under reduced pressure and then cured in a higher-pressure atmosphere (vacuum sealing-pressure increase curing method) to form a cured product. The number of carbon atoms in the long-chain alkyl group is preferably 8 to 22, and more preferably 8 to 18. Examples of long-chain alkyl (meth)acrylates include lauryl (meth)acrylate, isostearyl (meth)acrylate, and isodecyl (meth)acrylate. Among these, lauryl acrylate and isostearyl acrylate are preferred in terms of flexibility, low viscosity, and low crystallinity.

[0172] As the (meth)acrylate having an amide group, a compound in which the hydrogen atom bonded to the nitrogen atom of (meth)acrylamide is substituted with a hydrocarbon group such as an alkyl group or a divalent organic group is preferred, because this easily prevents whitening of the cured product of the curable composition under moist and heat conditions. Examples of (meth)acrylamide derivatives include 4-(meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, and N,N-diethyl(meth)acrylamide.

[0173] Only one type of other compound 2 may be used, or two or more types may be used in combination. When the curable composition contains the other compound 2, the content of the other compound 2 relative to the total mass of the curable composition is preferably 1 to 30 mass%, more preferably 1 to 25 mass%. When the content of the other compound 2 is equal to or greater than the above lower limit, the effect of adding the other compound 2 is likely to be sufficiently obtained. When the content of the other compound 2 is equal to or less than the above upper limit, good physical properties in terms of low cure shrinkage are likely to be obtained.

[0174] The curable composition may be a photocurable composition or a thermosetting composition. Photocurable compositions are preferred because they can be cured at low temperatures and have a fast curing rate. When the curable composition is a photocurable composition, it preferably contains a photopolymerization initiator. When a photocurable composition is used in the manufacture of a display device, for example, high temperatures are not required, so there is little risk of damage to the display device due to high temperatures.

[0175] Examples of the photopolymerization initiator include acetophenone-based, ketal-based, benzoin or benzoin ether-based, phosphine oxide-based, benzophenone-based, thioxanthone-based, and quinone-based photopolymerization initiators. Among these, phosphine oxide-based and thioxanthone-based photopolymerization initiators are preferred, with phosphine oxide-based being preferred in that coloration after the photopolymerization reaction is easily suppressed. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

[0176] The photopolymerization initiator is not particularly limited, and commercially available products can also be used. Examples of commercially available products include IRGACURE 819, IRGACURE TPO, IRGACURE 184, IRGACURE 2959, IRGACURE 1173, IRGACURE 127, IRGACURE 907, IRGACURE OXE01, and IRGACURE OXE02, manufactured by BASF. When the curable composition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total of the curable components.

[0177] Examples of other components include tackifiers such as rosin esters, terpene phenols, and hydrogenated terpene phenols, plasticizers such as adipates and phthalates, polyether compounds having no polymerizable unsaturated groups, and polyether polyols having alkoxylated molecular ends. When the curable composition contains a plasticizer, flexibility and adhesion tend to be improved. The content of these compounds relative to the total mass of the curable composition is preferably 48% by mass or less, more preferably 28% by mass or less.

[0178] Examples of other components include polymerization inhibitors, photocuring accelerators, chain transfer agents, light stabilizers (such as ultraviolet absorbers and radical scavengers), antioxidants, flame retardants, adhesion improvers (such as silane coupling agents), pigments, and dyes. Among these, it is preferable to include a polymerization inhibitor and a light stabilizer. In particular, by including a polymerization inhibitor in an amount smaller than that of the polymerization initiator, the storage stability of the curable composition can be improved and the molecular weight after curing can be easily adjusted.

[0179] Examples of the polymerization inhibitor include hydroquinone-based (such as 2,5-di-tert-butylhydroquinone), catechol-based (such as p-tert-butylcatechol), anthraquinone-based, phenothiazine-based, and hydroxytoluene-based polymerization inhibitors.

[0180] The ultraviolet absorber is used to prevent photodegradation of the curable composition and improve weather resistance. Examples of the ultraviolet absorber include benzotriazole-based, triazine-based, benzophenone-based, and benzoate-based ultraviolet absorbers. As the benzotriazole-based ultraviolet absorber, for example, those described in paragraph

[0076] of WO 2014 / 017328 can be used.

[0181] The light stabilizer is used to prevent photodegradation of the curable composition and improve weather resistance. Examples of the light stabilizer include hindered amine light stabilizers. As the hindered amine light stabilizer, those described in paragraph

[0077] of WO 2014 / 017328 can be used.

[0182] The antioxidant is used to prevent oxidation of the curable composition and improve weather resistance and heat resistance. Examples of the antioxidant include phenolic and phosphorus-based antioxidants. As the phenolic antioxidant, for example, those described in paragraph

[0078] of WO 2014 / 017328 can be used. As the phosphorus-based antioxidant, those described in paragraph

[0078] of WO 2014 / 017328 can be used.

[0183] Also usable are products containing a mixture of a plurality of antioxidants, light stabilizers, etc. Examples include IRGASTAB PUR68 and TINUVIN B75 manufactured by BASF.

[0184] When the curable composition contains other components, the total content of the other components is preferably 100 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less, per 100 parts by mass of the curable component.

[0185] The content of the chain transfer agent in the curable composition is preferably small, preferably 3 parts by mass or less, more preferably 2 parts by mass or less, per 100 parts by mass of the curable component, and particularly preferably no chain transfer agent is contained.

[0186] Suitable applications of the curable composition containing a polyether compound having a polymerizable unsaturated group include pressure-sensitive adhesives in the fields of various building and decoration materials, packaging materials, printing materials, display materials, electrical and electronic component materials, optical component materials, liquid crystal panels, and the like.

[0187] Hereinafter, the embodiments will be described in more detail with reference to examples, but the present invention is not limited to the following description.

[0188] [Total Aldehydes in AO-Containing Raw Materials] The total aldehyde content relative to the total mass of the AO-containing raw materials was determined by titration. Specifically, the total aldehyde content was measured using the following reagents and the following procedure. (1) Reagents: Sodium bisulfite Starch solution (5 g / L): Dissolve 5 g of starch (soluble) in approximately 100 mL of water, pour into 1 L of hot water while stirring, and cool and store. 0.05 mol / L (0.1 N) iodine solution 0.005 mol / L (0.01 N) iodine solution: A solution obtained by diluting 0.05 mol / L (0.1 N) iodine solution 10 times. Sodium bicarbonate reagent (2) Procedure: 1) Using a measuring cylinder, measure 150 mL of distilled water pre-cooled to 0-10°C into a 500 mL Erlenmeyer flask with a ground stopper. 2) Weigh out 0.05 g of sodium bisulfite reagent using a balance and add it. 3) Weigh out 36 mL of sample using a measuring cylinder and transfer it to the flask. Then, re-stopper the flask, mix, and store the flask at 0-10°C for 15 minutes. 4) Add 150 mL of distilled water pre-cooled to 0-10°C using a measuring cylinder, and approximately 2 mL of starch solution. 5) Titrate with 0.05 mol / L iodine solution until just before the endpoint, and continue titrating with 0.005 mol / L iodine solution until the blue color no longer disappears within 1 minute. 6) Add 1 g of sodium bicarbonate reagent and mix. 7) Titrate with 0.005 mol / L iodine solution until the light blue color no longer disappears within 1 minute, and read the titration volume. 8) Calculate the total aldehyde content using the following formula. A = (V × 0.00029) / (36 × 0.83) × 100 Here, A represents the total aldehyde content (%), and V represents the titer (mL) of the 0.005 mol / L iodine solution.

[0189] [Acetaldehyde and AO Contents in AO-Containing Raw Material] The acetaldehyde content (ppm) and AO content (mass%) relative to the total mass of the AO-containing raw material were measured using a gas chromatograph (detector: flame ionization detector (FID)) under the following conditions: Column: capillary, 60 m x 0.32 mmφ, DB-1301 ms, film thickness 1.0 μm Oven temperature: 35°C (12 min) → 10°C / min → 100°C (12 min) INJ / DET temperature: 180 / 180°C Carrier gas: He Air flow rate: 400 mL / min H２ Flow rate: 30 mL / min Carrier flow rate (pressure): 1.3609 mL / min (24.056 psi) Septum purge flow rate: 5 mL / min Split ratio: 50:1 Split flow rate: 68.047 mL / min Total flow: 74.407 mL / min Gas saver: 20 mL / min Injection port: Back Injection method: Microsyringe, injection volume 2 μL

[0190] [Hydroxyl value and hydroxyl value-equivalent molecular weight] The hydroxyl value (OHV) was calculated in accordance with Method B of JIS K 1557-1:2007. The OHV-equivalent molecular weight was calculated based on the formula "56,100 / hydroxyl value of polyether compound × number of hydroxyl groups of polyether compound." The number of hydroxyl groups of the polyether compound is the number of hydroxyl groups of the initiator used.

[0191] [Degree of Unsaturation] The degree of unsaturation (USV) of the polyether compound was measured in accordance with JIS K 1557-3:2007.

[0192] [Silylation rate] The silylation rate is １ Measurement was performed by the H-NMR internal standard method.

[0193] [Tensile Test of Cured Product of Polyether Compound Having Reactive Silicon Group] A curable composition was prepared by adding additives in the formulation shown in Table 1 to 100 parts by mass of a polyether compound having a reactive silicon group. The curable composition to be measured was filled into a 2 mm thick mold and cured at a temperature of 25°C and a humidity of 50% for 3 days, and then further cured at a temperature of 50°C and a humidity of 65% for 4 days. The obtained cured product was punched out using a dumbbell mold to obtain a dumbbell-shaped test piece. A tensile test was performed on this dumbbell-shaped test piece using a Tensilon testing machine at a tensile speed of 500 mm / min, and the stress at 50% elongation (M50, N / mm ２ ), strength (N / mm ２ ) and elongation (%) were measured.

[0194]

[0195] Abbreviations in Table 1 are as follows: Whiten SB: heavy calcium carbonate, manufactured by Shiraishi Kogyo Co., Ltd. White Glazing CCR: gelatinous calcium carbonate, manufactured by Shiraishi Kogyo Co., Ltd. DINP: Vinicizer 90, diisononyl phthalate, manufactured by Kao Corporation Disparlon 6500: fatty acid amide wax, manufactured by Kusumoto Chemicals Co., Ltd. KBM-1003: vinyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. KBM-403: 3-glycidyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. KBM-603: 3-(2-aminoethylamino)propyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. IRGANOX 1010: hindered phenol-based antioxidant, manufactured by BASF Japan Co., Ltd. TINUVIN 326: benzotriazole-based ultraviolet absorber, manufactured by BASF Japan Co., Ltd. U860: dioctyltin bis(isooctylthioglycolate), manufactured by Nitto Chemicals Co., Ltd.

[0196] [Mn] The molecular weight of the polyether compound was analyzed using a GPC system (Tosoh Corporation product name HLC-8320) and an RI detector. Two TSK-GEL Super HZ4000 (4.6 mm x 150 mm) columns and two Super HZ2500 (4.6 mm x 150 mm) columns were connected in series in this order. Tetrahydrofuran (THF) was used as the eluent at a flow rate of 0.35 ml / min, the column temperature was set to 40 ° C., and Mn was calculated by converting it using a calibration curve created using a polystyrene standard sample (Agilent Technologies product name Easical PS-2, molecular weight range 580 to 400,000).

[0197] [Adhesion] The polyurethane composition was applied to a substrate film (a 25 μm-thick polyethylene terephthalate (PET) film) using an applicator to a thickness of 10 μm, and then left to dry and harden in a thermostatic chamber at 130°C to form an adhesive layer. The substrate film on which the adhesive layer was formed was cut into a width of 25 mm and a length of 150 mm to prepare an evaluation sample. The adhesive layer of the evaluation sample was bonded to a glass plate (float glass) in an atmosphere of 23°C and 50% RH, and the evaluation sample was placed on a horizontal surface with the substrate film side facing up. A 2.0 kg roller was moved back and forth once from the substrate film side to press the adhesive layer and the glass plate together. After aging for 30 minutes in an atmosphere of 23°C and 50% RH, the adhesive strength of the adhesive layer was measured by peeling the interface between the adhesive layer of the evaluation sample and the glass plate using a universal tensile tester (manufactured by A&D Co., Ltd., product name: Tensilon RTG-1310) at a peel angle of 180° and a pulling rate of 300 mm / min. The measured adhesive strength was evaluated according to the following criteria: A: adhesive strength is 0.10 N / 25 mm or less; B: adhesive strength is greater than 0.10 N / 25 mm.

[0198] [Coatability] The polyurethane composition was applied to a 25 μm thick PET film using an applicator to a thickness of 10 μm. The polyurethane composition applied to the PET film was visually inspected for the presence or absence of foreign matter and cissing, and evaluated according to the following criteria: A: No foreign matter or cissing was present, and the composition was applied cleanly (smooth). B: No foreign matter or cissing was present, and the composition was not applied cleanly (uneven).

[0199] [Curability] The polyurethane composition was applied to a 25 μm thick PET film using an applicator to a thickness of 10 μm, and then left to dry and cure in a thermostatic chamber at 130° C. to form an adhesive layer. 16 hours and 24 hours after the adhesive layer was formed, the presence or absence of tack on the surface of the adhesive layer was confirmed and evaluated according to the following criteria: AA: No tack after 16 hours; A: No tack after 24 hours; B: Tack present after 24 hours.

[0200] [Physical Properties of Cured Product] A mixed liquid (curable composition) of 100 parts by mass of a polyether compound having a polymerizable unsaturated group and 0.3 parts by mass of a photopolymerization initiator (Irgacure-819, manufactured by BASF) was poured into a silicone mold having a width of 5 mm, a length of 15 mm, and a thickness of 2 mm. Under a nitrogen environment, a conveyor-type UV irradiator (manufactured by ORC) was used to irradiate the cured product with an HgXe lamp at an illuminance of 100 mW / cm. ２ , cumulative light intensity 3000 mJ / cm ２ The test sample was cured under the following conditions: The cured product was used as a test sample. The test sample was measured for elongation (%), 100% modulus (M100, MPa), and breaking strength (MPa) at a tensile speed of 300 mm / min using a tensile testing device (Tensilon VTM (manufactured by Toyo Boardwin Co., Ltd.)).

[0201] [AO-Containing Raw Material] Twelve types of PO (PO (1) to (12)) obtained from different sources and from different lots were used as the AO-containing raw material. The acetaldehyde content and total aldehyde content of each of PO (1) to (12) are shown in Table 2 below. The PO content (PO purity) of each of PO (1) to (12) was 99% or more.

[0202] [Production Example 1: Preparation of Polyol P1 (Initiator)] PO (1) was polymerized with propylene glycol in the presence of a KOH catalyst, followed by dealkalization and purification to obtain polyoxypropylene diol (hereinafter also referred to as "Polyol P1"). The average number of hydroxyl groups per molecule of Polyol P1 was 2, and the molecular weight in terms of OHV was 1,000.

[0203] [Production Example 2: Preparation of Polyol P2 (Initiator)] PO (1) was polymerized with glycerin in the presence of a KOH catalyst, followed by dealkalization and purification to obtain polyoxypropylene triol (hereinafter also referred to as "Polyol P2"). The average number of hydroxyl groups per molecule of Polyol P2 was 3, and the molecular weight in terms of OHV was 1,000.

[0204] [Production Example 3: Preparation of Polyol P3 (Initiator)] PO (1) was polymerized with n-butyl alcohol in the presence of a KOH catalyst, followed by dealkalization and purification to obtain polyoxypropylene monool (hereinafter also referred to as "Polyol P3"). Polyol P3 had an average number of hydroxyl groups per molecule of 1 and an OHV-equivalent molecular weight of 400.

[0205] [Production Example 4: Preparation of Polyol P4 (Initiator)] Sorbitol was polymerized with PO (1) in the presence of a KOH catalyst, followed by dealkalization and purification to obtain a polyoxypropylene polyol (hereinafter also referred to as "Polyol P4"). Polyol P4 had an average of 6 hydroxyl groups per molecule and an OHV-equivalent molecular weight of 880.

[0206] Below, Examples 1 to 4, 9, 10, and 12 are working examples, and Examples 5 to 8 and 11 are comparative examples, which relate to polyether compounds having hydroxyl groups.

[0207] Example 1 Using polyol P1 as an initiator, PO (1) was polymerized in the presence of a tert-butyl alcohol zinc hexacyanocobaltate complex catalyst (hereinafter referred to as "TBA-DMC catalyst") until the OHV-equivalent molecular weight reached 12,000, to obtain polyether compound 1. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 1.

[0208] [Example 2] Using polyol P1 as an initiator, PO (2) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 18,000, yielding polyether compound 2. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 2.

[0209] [Example 3] Using polyol P2 as an initiator, PO (3) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 15,000, yielding polyether compound 3. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 3.

[0210] [Example 4] Using polyol P1 as an initiator, PO (4) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 22,000, yielding polyether compound 4. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 4.

[0211] Example 5 Polyether compound 5 was produced in the same manner as in Example 1, except that PO(5) was used instead of PO(1).

[0212] Example 6 Polyether compound 6 was produced in the same manner as in Example 2, except that PO(6) was used instead of PO(2).

[0213] Example 7 Polyether compound 7 was produced in the same manner as in Example 3, except that PO(7) was used instead of PO(3).

[0214] Example 8 Polyether compound 8 was produced in the same manner as in Example 4, except that PO(8) was used instead of PO(4).

[0215] Example 9 Using polyol P3 as an initiator, PO (9) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 4,000, yielding polyether compound 9. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 9.

[0216] Example 10 Using polyol P4 as an initiator, PO (10) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 42,000, yielding polyether compound 10. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 10.

[0217] Example 11 Polyether compound 11 was produced in the same manner as in Example 10, except that PO(11) was used instead of PO(10).

[0218] Example 12 Using polyol P1 as an initiator, PO (12) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 12,000, yielding polyether compound 12. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 12.

[0219] Table 2 shows the number of functional groups, OHV-equivalent molecular weight, and USV of the initiator of each polyether compound.

[0220]

[0221] Comparing Example 1 and Example 5, in which polyether compounds were produced under the same conditions except for the AO-containing raw material, the USV was lower in Example 1. Similar trends were also confirmed in the comparisons between Example 2 and Example 6, Example 3 and Example 7, Example 4 and Example 8, and Example 10 and Example 11.

[0222] Below, Examples 1A to 4A and 9A are working examples, and Examples 5A to 8A are comparative examples, which relate to polyether compounds having reactive silicon groups.

[0223] [Example 1A] Using polyol P1 as an initiator, PO (1) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 12,000, yielding a polyether compound 1 having a hydroxyl group. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 1.

[0224] To 150 g of polyether compound 1, 0.0075 g of Neostan U-860 manufactured by Nitto Kasei Co., Ltd. and 4.97 g of 3-isocyanatopropyltriethoxysilane (NCO content: 20.5% by mass) were added, and the mixture was allowed to react at 80°C for 3 hours. The NCO / OH molar ratio of the isocyanate content of 3-isocyanatopropyltriethoxysilane to the hydroxyl group content of polyether compound 1 was set to 0.97. The reaction was terminated when it was confirmed by IR that there was no absorption due to NCO, yielding polyether compound A1 having a reactive silicon group.

[0225] [Example 2A] Using polyol P1 as an initiator, PO (2) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 18,000, yielding polyether compound 2 having hydroxyl groups. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 2. Next, polyether compound A2 having reactive silicon groups was obtained in the same manner as in Example 1A, except that polyether compound 2 was used instead of polyether compound 1 and the amount of 3-isocyanatopropyltriethoxysilane added was 3.31 g.

[0226] [Example 3A] Using polyol P2 as an initiator, PO (3) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 15,000, yielding a polyether compound 3 having a hydroxyl group. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 3. Next, polyether compound A3 having a reactive silicon group was obtained in the same manner as in Example 1A, except that polyether compound 3 was used instead of polyether compound 1 and the amount of 3-isocyanatopropyltriethoxysilane added was 5.96 g.

[0227] [Example 4A] Using polyol P1 as an initiator, PO (4) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 22,000, yielding polyether compound 4 having hydroxyl groups. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 4. Next, polyether compound A4 having reactive silicon groups was obtained in the same manner as in Example 1A, except that polyether compound 4 was used instead of polyether compound 1 and the amount of 3-isocyanatopropyltriethoxysilane added was 2.71 g.

[0228] Example 5A Polyether compound 5 having a hydroxyl group and polyether compound A5 having a reactive silicon group were prepared in the same manner as in Example 1A, except that PO(5) was used instead of PO(1).

[0229] Example 6A Polyether compound 6 having a hydroxyl group and polyether compound A6 having a reactive silicon group were prepared in the same manner as in Example 2A, except that PO(6) was used instead of PO(2).

[0230] Example 7A Polyether compound 7 having a hydroxyl group and polyether compound A7 having a reactive silicon group were prepared in the same manner as in Example 3A, except that PO(7) was used instead of PO(3).

[0231] Example 8A Polyether compound 8 having a hydroxyl group and polyether compound A8 having a reactive silicon group were prepared in the same manner as in Example 4A, except that PO(8) was used instead of PO(4).

[0232] [Example 9A] Using polyol P1 as an initiator, PO (12) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 12,000, yielding polyether compound 9. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 9. Next, polyether compound A9 having a reactive silicon group was obtained in the same manner as in Example 1A, except that polyether compound 9 was used instead of polyether compound 1.

[0233] Table 3 shows the number of functional groups of the initiator of the polyether compound of each example, the molecular weight in terms of OHV, USV, the silylation rate of polyether compound A of each example, and the results of tensile tests on the cured products.

[0234]

[0235] Comparing Example 1A and Example 5A, in which polyether compound A was produced under the same conditions except for the AO-containing raw material, Example 1A had superior strength and elongation of the cured product. Similar trends were also confirmed in comparisons between Example 2A and Example 6A, Example 3A and Example 7A, Example 4A and Example 8A, and Example 9A and Example 5A.

[0236] Below, Examples 1B to 3B are working examples, and Examples 4B to 6B are comparative examples, which relate to polyether compounds having a urethane bond.

[0237] [Production Example (a-1)] Using polyol P4 as an initiator, PO (1) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 42,000, to obtain a polyether compound (a-1) having a hydroxyl group. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of the polyether compound (a-1).

[0238] [Production Example (a-2)] Using polyol P1 as an initiator, PO (2) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 10,000, to obtain a polyether compound (a-2) having a hydroxyl group. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of the polyether compound (a-2).

[0239] [Production Example (a-3)] Using polyol P2 as an initiator, PO (3) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 10,000, to obtain a polyether compound (a-3). The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of the polyether compound (a-3).

[0240] [Production Example (b-1)] A polyether compound (b-1) having a hydroxyl group was produced in the same manner as in Production Example (a-1), except that PO (5) was used instead of PO (1).

[0241] [Production Example (b-2)] A polyether compound (b-2) having a hydroxyl group was produced in the same manner as in Production Example (a-2), except that PO (6) was used instead of PO (2).

[0242] [Production Example (b-3)] A polyether compound (b-3) having a hydroxyl group was produced in the same manner as in Production Example (a-3), except that PO (7) was used instead of PO (3).

[0243] Table 4 shows the number of functional groups, OHV-equivalent molecular weight, Mn, and USV of the initiator for each polyether compound.

[0244]

[0245] [Example 1B] 100 parts by mass of polyether compound (a-1), 7.0 parts by mass of a polyisocyanate compound (Coronate HX, manufactured by Tosoh Corporation, isocyanate group content 21.3% by mass), 0.04 parts by mass of Narcem ferric iron manufactured by Nippon Chemical Industry Co., Ltd. as a catalyst, and ethyl acetate as a solvent in an amount such that the overall solids concentration became 50% by mass were uniformly mixed and subjected to a urethanization reaction to obtain a polyurethane composition containing a polyether compound having a urethane bond.

[0246] [Examples 2B to 6B] Polyurethane compositions containing polyether compound B having a urethane bond were obtained in the same manner as in Example 1B, except that a polyether compound shown in Table 5 was used instead of 100 parts by mass of polyether compound (a-1) and the amount of polyisocyanate compound was changed to a value shown in Table 5.

[0247] The average number of functional groups, Mn, and Mn per average number of functional groups of the polyether compound used in each example, as well as the evaluation results of the adhesion, coatability, and curability of the polyurethane composition of each example, are shown in Table 5. In Table 5, the values ​​for "Properties of polyether compound" for Examples 2B and 5B are average values ​​for a mixture of two types of polyether compounds.

[0248]

[0249] Comparing Examples 1B and 4B, in which polyurethane compositions were produced under the same conditions except for the AO-containing raw material, Example 1B had superior curability. Similar trends were also observed in comparing Examples 2B and 5B, and Examples 3B and 6B.

[0250] Below, Examples 1C to 4C and 9C are working examples, and Examples 5C to 8C are comparative examples, which relate to polyether compounds having a polymerizable unsaturated group.

[0251] [Example 1C] Using polyol P1 as an initiator, PO (1) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 12,000, yielding a polyether compound 1 having a hydroxyl group. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound A.

[0252] To 150 g of polyether compound 1, 0.015 g of dibutyltin dilaurate and 3.42 g of 2-isocyanatoethyl acrylate (NCO content: 29.8% by mass) were added, and the mixture was allowed to react at 80°C for 2 hours. The NCO / OH molar ratio of the amount of isocyanate in 2-isocyanatoethyl acrylate to the amount of hydroxyl groups in polyether compound 1 was set to 0.97. The reaction was terminated when it was confirmed by IR that there was no absorption derived from NCO, yielding polyether compound C1 having a polymerizable unsaturated group.

[0253] [Example 2C] Using polyol P1 as an initiator, PO (2) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 18,000, yielding polyether compound 2 having a hydroxyl group. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 2. Next, polyether compound C2 having a polymerizable unsaturated group was obtained in the same manner as in Example 1C, except that polyether compound 2 was used instead of polyether compound 1 and the amount of 2-isocyanatoethyl acrylate added was 2.28 g.

[0254] [Example 3C] Using polyol P2 as an initiator, PO (3) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 15,000, yielding polyether compound 3 having a hydroxyl group. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 3. Next, polyether compound C3 having a polymerizable unsaturated group was obtained in the same manner as in Example 1C, except that polyether compound 3 was used instead of polyether compound 1 and the amount of 2-isocyanatoethyl acrylate added was 4.10 g.

[0255] [Example 4C] Using polyol P1 as an initiator, PO (4) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 22,000, yielding polyether compound 4 having a hydroxyl group. The polymerization was carried out with the addition of 0.1% by mass of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 4. Next, polyether compound C3 having a polymerizable unsaturated group was obtained in the same manner as in Example 1C, except that polyether compound 4 was used instead of polyether compound 1 and the amount of 2-isocyanatoethyl acrylate added was 1.86 g.

[0256] Example 5C Polyether compound 5 having a hydroxyl group and polyether compound C5 having a polymerizable unsaturated group were prepared in the same manner as in Example 1C, except that PO(5) was used instead of PO(1).

[0257] Example 6C Polyether compound 6 having a hydroxyl group and polyether compound C6 having a polymerizable unsaturated group were prepared in the same manner as in Example 2C, except that PO(6) was used instead of PO(2).

[0258] Example 7C Polyether compound 7 having a hydroxyl group and polyether compound C7 having a polymerizable unsaturated group were prepared in the same manner as in Example 3C, except that PO(7) was used instead of PO(3).

[0259] Example 8C Polyether compound 8 having a hydroxyl group and polyether compound C8 having a polymerizable unsaturated group were prepared in the same manner as in Example 4C, except that PO(8) was used instead of PO(4).

[0260] [Example 9C] Using polyol P1 as an initiator, PO (12) was polymerized in the presence of a TBA-DMC catalyst until the OHV-equivalent molecular weight reached 12,000, yielding polyether compound 9. The polymerization was carried out with the addition of 0.1 mass% of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst used was such that the concentration of the TBA-DMC catalyst was 50 ppm relative to the total mass of polyether compound 9. Next, polyether compound C9 having a polymerizable unsaturated group was obtained in the same manner as in Example 1C, except that polyether compound 9 was used instead of polyether compound 1.

[0261] Table 6 shows the number of functional groups of the initiator of each polyether compound, the molecular weight in terms of OHV, USV, and physical properties of the cured product of each polyether compound C.

[0262]

[0263] Comparing Examples 1C and 5C, in which Polyether Compound C was produced under the same conditions except for the AO-containing raw material, Example 1C had a superior breaking strength of the cured product. Similar trends were also observed in comparisons between Examples 2C and 6C, between Examples 3C and 7C, between Examples 4C and 8C, and between Examples 9C and 5C.

[0264] According to the present invention, a production method for obtaining a polyether compound having a low degree of unsaturation can be provided.

[0265] The present invention also provides a production method that can yield a polyether compound having a reactive silicon group that provides a cured product with excellent strength.

[0266] According to the present invention, there is also provided a production method that can obtain a polyether compound having a urethane bond and that has excellent curability.

[0267] According to the present invention, there can also be provided a production method for obtaining a polyether compound having a polymerizable unsaturated group, which provides a cured product with excellent strength.

[0268] This application claims priority based on Japanese Patent Application No. 2024-112667 filed with the Japan Patent Office on July 12, 2024, Japanese Patent Application No. 2024-112619 filed with the Japan Patent Office on July 12, 2024, Japanese Patent Application No. 2024-112611 filed with the Japan Patent Office on July 12, 2024, and Japanese Patent Application No. 2024-112644 filed with the Japan Patent Office on July 12, 2024, and the entire contents of these Japanese applications are incorporated herein by reference.

Claims

1. A method for producing a polyether compound having a hydroxyl group, comprising contacting an initiator having a hydroxyl group with an alkylene oxide-containing raw material in the presence of a composite metal cyanide complex catalyst to polymerize the alkylene oxide in the alkylene oxide-containing raw material with the initiator, wherein the total aldehyde content of the alkylene oxide-containing raw material as measured by titration is less than 15 ppm based on the total mass of the alkylene oxide-containing raw material.

2. The method of claim 1, wherein the alkylene oxide-containing feedstock has an acetaldehyde content of less than 10 ppm based on the total mass of the alkylene oxide-containing feedstock.

3. The method according to claim 1 or 2, wherein the alkylene oxide-containing raw material contains an alkylene oxide having 3 or more carbon atoms.

4. The method of any one of claims 1 to 3, wherein the number of hydroxyl groups in the initiator is 1 to 10.

5. The method according to any one of claims 1 to 4, wherein the hydroxyl value-based molecular weight of the hydroxyl-containing polyether compound is 1,000 to 100,000.

6. The production method according to any one of claims 1 to 5, wherein a slurry catalyst in which particles of the composite metal cyanide complex catalyst are dispersed in a dispersion medium is used.

7. A method for producing a polyether compound having a reactive silicon group, which comprises converting the hydroxyl group of the polyether compound having a hydroxyl group obtained by the production method according to any one of claims 1 to 6 into a group having a reactive silicon group represented by the following formula 1: -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, and X represents a hydroxyl group, a halogen atom, or a hydrolyzable group. 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.

8. A method for producing a polyether compound having a urethane bond, which comprises reacting a polyether compound having a hydroxyl group obtained by the method according to any one of claims 1 to 6 with a polyisocyanate.

9. A method for producing a polyether compound having a polymerizable unsaturated group, which comprises converting the hydroxyl group of a polyether compound having a hydroxyl group obtained by the production method described in any one of claims 1 to 6 into a group having a polymerizable unsaturated group.

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