Composite metal cyanide complex catalyst, 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

The present invention relates to a particulate composite metal cyanide complex catalyst wherein: the 50% cumulative volume particle diameter of the composite metal cyanide complex catalyst is 0.01-4.0 µm as determined from the volume-based cumulative particle size distribution obtained by a laser diffraction scattering method; and the content of the particles having a particle diameter of 11 µm or more relative to the total volume of the composite metal cyanide complex catalyst is 10 vol% or less.

Description

Composite metal cyanide complex catalyst, 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

[0001] The present invention relates to a composite metal cyanide complex catalyst, 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. This application claims priority to Japanese Patent Application Nos. 2024-109224, 2024-109226, 2024-109231, and 2024-109225, filed on July 5, 2024, the contents of which are incorporated herein by reference.

[0002] Polyether compounds are used as raw materials for adhesives, paints, sealants, coatings, 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 composite metal cyanide complex catalyst, which includes the steps of contacting an aqueous solution of a metal halide compound with an aqueous solution of a cyanide transition metal compound in a laminar flow state to obtain a liquid containing a composite metal cyanide complex, and mixing the liquid containing the composite metal cyanide complex with an organic ligand to obtain a dispersion containing a composite metal cyanide complex catalyst having an organic ligand. The composite metal cyanide complex catalyst produced by the above production method has a specific surface area measured by the BET method of 20 to 150 m. ２ / g, and the pore volume of 3 nm or less measured by the DFT method based on the specific surface area is 0.05 × 10 －３ ~10 x 10 －３ cc / g.

[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] Patent Document 2 discloses an oxyalkylene polymer having a urethane bond and an alkoxysilyl group, which is obtained by subjecting a polymer having a polyoxyalkylene chain and a hydroxy group to a urethanization reaction with a compound having an alkoxysilyl group and an isocyanate group. It also discloses that the polymer having a polyoxyalkylene chain and a hydroxy group can be obtained by ring-opening polymerization of an alkylene oxide with a compound having an active hydrogen atom in the presence of a double metal cyanide complex catalyst.

[0007] 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.

[0008] Patent Document 3 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.

[0009] Polyether compounds having polymerizable unsaturated groups are used as raw materials for pressure-sensitive adhesives, adhesives, paints, sealants, coatings, etc. in fields such as optical component materials and liquid crystal panels. 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.

[0010] Patent Document 4 discloses a method for producing an oligomer having a polyoxyalkylene chain, a group having a urethane bond derived from an isocyanate group-containing compound, and an acryloyloxy group by reacting the obtained isocyanate group-terminated urethane prepolymer with isophorone diisocyanate in the presence of a composite metal cyanide complex catalyst, and by reacting the obtained isocyanate group-terminated urethane prepolymer with 2-hydroxyethyl acrylate.

[0011] Japanese Patent No. 5109093 Japanese Patent No. 5521326 Japanese Patent Application Laid-Open No. 2023-155601 Japanese Patent No. 7255604

[0012] When a polyether compound is used for applications such as the above-mentioned adhesives and coatings, solid impurities in the polyether compound may cause problems. Therefore, after the polyether compound is produced, it may be purified by filtration to remove impurities. The inventors of the present application produced a polyether compound using the composite metal cyanide complex catalyst described in Patent Document 1 and purified it by filtration, but found that the filtration rate was slow and clogging occurred.

[0013] When a polyether compound having a reactive silicon group is used for applications such as the above-mentioned sealants, adhesives, and paints, solid impurities in the polyether compound having a reactive silicon group may cause problems. Therefore, after producing the polyether compound having a reactive silicon group, purification by filtration may be performed to remove impurities. When a polyol (a polymer having a polyoxyalkylene chain and a hydroxyl group) produced using a composite metal cyanide complex catalyst is used to produce a polyether compound having a reactive silicon group (an oxyalkylene polymer having a urethane bond and an alkoxysilyl group) by the production method described in Patent Document 1 and then purified by filtration, there is a problem that the filtration rate is slow and clogging occurs.

[0014] Furthermore, when polyether compounds having reactive silicon groups are used in applications such as the above-mentioned sealants and adhesives, they are required to have high stretch durability. However, the stretch durability of the cured products obtained from the polyether compounds having reactive silicon groups produced by the production method described in Patent Document 2 is insufficient.

[0015] When a polyether compound having a urethane bond is used in applications such as the above-mentioned adhesives, paints, sealants, and coatings, solid impurities in the polyether compound having a urethane bond may cause problems. Therefore, after producing a polyether compound having a urethane bond, purification by filtration may be performed to remove impurities. When a urethane prepolymer (a polyether compound having a urethane bond) is produced by the production method described in Patent Document 3 using a polyol produced using a composite metal cyanide complex catalyst and then purified by filtration, problems arise in that the filtration rate is slow and clogging occurs.

[0016] When a polyether compound having a polymerizable unsaturated group is used for applications such as the above-mentioned pressure-sensitive adhesives, adhesives, paints, sealants, and coatings, solid impurities in the polyether compound having a polymerizable unsaturated group may cause problems. Therefore, after producing a polyether compound having a polymerizable unsaturated group, purification by filtration may be performed to remove impurities. When an oligomer (polyether compound having a polymerizable unsaturated group) having a polyoxyalkylene chain, a group having a urethane bond derived from an isocyanate group-containing compound, and an acryloyloxy group is produced by the production method described in Patent Document 4 and purified by filtration, there are problems such as a slow filtration rate and clogging.

[0017] The present invention has been made in consideration of the above circumstances, and aims to provide a composite metal cyanide complex catalyst that can improve filterability in the purification process of a polyether compound, and a method for producing a polyether compound using the composite metal cyanide complex catalyst. Another object of the present invention is to provide a method for producing a polyether compound having a reactive silicon group that provides excellent stretch durability of the cured product and improves filterability in the purification process. Another object of the present invention is to provide a method for producing a polyether compound having a urethane bond that can improve filterability in the purification process. Another object of the present invention is to provide a method for producing a polyether compound having a polymerizable unsaturated group that can improve filterability in the purification process.

[0018] The present invention provides the following means: [1] A particulate composite metal cyanide complex catalyst, wherein the 50% cumulative volume particle diameter of the composite metal cyanide complex catalyst, as determined from a volume-based cumulative particle size distribution obtained by a laser diffraction scattering method, is 0.01 to 4.0 μm, and the content of particles having a particle diameter of 11 μm or more relative to the total volume of the composite metal cyanide complex catalyst is 10% by volume or less. [2] A particulate composite metal cyanide complex catalyst, wherein the 50% cumulative volume particle diameter D, as determined from a volume-based cumulative particle size distribution obtained by a laser diffraction scattering method, is 0.01 to 4.0 μm. ５０ is 0.01 to 4.0 μm, the content of the particles having a particle diameter of 11 μm or more relative to the total volume of the composite metal cyanide complex catalyst is 10% by volume or less, and the 10% cumulative volume particle diameter calculated from the volume-based cumulative particle size distribution is D １０ , 90% cumulative volume particle diameter is D ９０ When (D ９０ -D １０ ) / D ５０ A double metal cyanide complex catalyst having a molecular weight distribution of 1.00 to 1.15. [3] The double metal cyanide complex catalyst according to [1] or [2], wherein the content of particles having a particle size of 11 μm or more relative to the total volume of the double metal cyanide complex catalyst is 5 vol% or less. [4] A method for producing a polyether compound, comprising polymerizing an alkylene oxide with an initiator having active hydrogen in the presence of the double metal cyanide complex catalyst according to any one of [1] to [3]. [5] The method for producing a polyether compound according to [4], wherein the number average molecular weight of the polyether compound is 500 to 100,000. [6] The method for producing a polyether compound according to [4] or [5], wherein the molecular weight distribution of the polyether compound is 1.00 to 1.15. [7] The method for producing a polyether compound according to any one of [4] to [6], wherein the total degree of unsaturation of the polyether compound is 0.001 to 0.040 meq / g. [8] The method for producing a polyether compound according to any one of [4] to [7], wherein the amount of the composite metal cyanide complex catalyst used is 1 to 200 ppm by mass relative to the total mass of the polyether compound.

[0019] [1A] A method for producing a polyether compound having a reactive silicon group, comprising polymerizing an initiator having active hydrogen with an alkylene oxide in the presence of a double metal cyanide complex catalyst to obtain a composition containing a polyether compound having a hydroxyl group, and converting the hydroxyl group of the polyether compound in the composition to a group having a reactive silicon group represented by the following formula 1, wherein the double metal cyanide complex catalyst is in the form of particles, the double metal cyanide complex catalyst has a 50% cumulative volume particle size of 0.01 to 4.0 μm as determined from a volume-based cumulative particle size distribution obtained by a laser diffraction scattering method, and the content of particles having a particle size of 11 μm or more relative to the total volume of the double metal cyanide complex catalyst is 10% by volume or less. 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. [2A] A method for producing a polyether compound having a reactive silicon group, comprising polymerizing an initiator having active hydrogen and an alkylene oxide in the presence of a double metal cyanide complex catalyst to obtain a composition containing a polyether compound having a hydroxyl group, and converting the hydroxyl group of the polyether compound in the composition to a group having a reactive silicon group represented by the following formula 1, wherein the double metal cyanide complex catalyst is in the form of particles, and the 50% cumulative volume particle diameter D is determined from a volume-based cumulative particle size distribution of the double metal cyanide complex catalyst obtained by a laser diffraction scattering method. ５０ is 0.01 to 4.0 μm, the content of the particles having a particle diameter of 11 μm or more relative to the total volume of the composite metal cyanide complex catalyst is 10% by volume or less, and the 10% cumulative volume particle diameter calculated from the volume-based cumulative particle size distribution is D １０ , 90% cumulative volume particle diameter is D ９０ When (D ９０ -D １０ ) / D ５０A method for producing a polyether compound having a reactive silicon group, wherein —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 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. [3A] The method for producing a polyether compound having a reactive silicon group according to [1A] or [2A], wherein the content of particles having a particle diameter of 11 μm or more relative to the total volume of the double metal cyanide complex catalyst is 5 vol% or less. [4A] The method for producing a polyether compound having a reactive silicon group according to any one of [1A] to [3A], wherein the number average molecular weight of the polyether compound having a hydroxyl group is 500 to 100,000. [5A] The method for producing a polyether compound having a reactive silicon group according to any one of [1A] to [4A], wherein the molecular weight distribution of the polyether compound having a hydroxyl group is 1.00 to 1.15. [6A] The method for producing a polyether compound having a reactive silicon group according to any one of [1A] to [5A], wherein the total degree of unsaturation of the polyether compound having a hydroxyl group is 0.001 to 0.040 meq / g. [7A] The method for producing a polyether compound having a reactive silicon group according to any one of [1A] to [6A], wherein the amount of the double metal cyanide complex catalyst used relative to the total mass of the polyether compound having a hydroxyl group is 1 to 200 ppm by mass.

[0020] [1B] A method for producing a polyether compound having a urethane bond, comprising reacting a composition containing a polyether compound having a hydroxyl group obtained by polymerizing an initiator having active hydrogen with an alkylene oxide in the presence of a double metal cyanide complex catalyst with a polyisocyanate, wherein the double metal cyanide complex catalyst is in the form of particles, the double metal cyanide complex catalyst has a 50% cumulative volume particle diameter of 0.01 to 4.0 μm as determined from a volume-based cumulative particle size distribution obtained by a laser diffraction scattering method, and the content of particles having a particle diameter of 11 μm or more relative to the total volume of the double metal cyanide complex catalyst is 10% by volume or less. [2B] A method for producing a polyether compound having a urethane bond, comprising polymerizing an initiator having active hydrogen and an alkylene oxide in the presence of a composite metal cyanide complex catalyst, and reacting the resulting composition containing a polyether compound having a hydroxyl group with a polyisocyanate, wherein the composite metal cyanide complex catalyst is in the form of particles, and the 50% cumulative volume particle diameter D is determined from the volume-based cumulative particle size distribution of the composite metal cyanide complex catalyst obtained by a laser diffraction scattering method. ５０ is 0.01 to 4.0 μm, the content of the particles having a particle diameter of 11 μm or more relative to the total volume of the composite metal cyanide complex catalyst is 10% by volume or less, and the 10% cumulative volume particle diameter calculated from the volume-based cumulative particle size distribution is D １０ , 90% cumulative volume particle diameter is D ９０ When (D ９０ -D １０ ) / D ５０[3B] A method for producing a polyether compound having a urethane bond according to [1B] or [2B], wherein the content of the particles having a particle diameter of 11 μm or more relative to the total volume of the double metal cyanide complex catalyst is 5 vol% or less. [4B] A method for producing a polyether compound having a urethane bond according to any of [1B] to [3B], wherein the number average molecular weight of the polyether compound having a hydroxyl group is 500 to 100,000. [5B] A method for producing a polyether compound having a urethane bond according to any of [1B] to [4B], wherein the molecular weight distribution of the polyether compound having a hydroxyl group is 1.00 to 1.15. [6B] A method for producing a polyether compound having a urethane bond according to any of [1B] to [5B], wherein the total degree of unsaturation of the polyether compound having a hydroxyl group is 0.001 to 0.040 meq / g. [7B] The method for producing a polyether compound having a urethane bond according to any one of [1B] to [6B], wherein the amount of the double metal cyanide complex catalyst used is 1 to 200 ppm by mass relative to the total mass of the polyether compound having a hydroxyl group.

[0021] [1C] A method for producing a polyether compound having a polymerizable unsaturated group, comprising polymerizing an initiator having active hydrogen and an alkylene oxide in the presence of a double metal cyanide complex catalyst to obtain a composition containing a polyether compound having a hydroxyl group, and converting the hydroxyl group of the polyether compound having a hydroxyl group in the composition to a group having a polymerizable unsaturated group, wherein the double metal cyanide complex catalyst is in a particulate form, the double metal cyanide complex catalyst has a 50% cumulative volume particle size of 0.01 to 4.0 μm as determined from a volume-based cumulative particle size distribution obtained by a laser diffraction scattering method, and the content of particles having a particle size of 11 μm or more relative to the total volume of the double metal cyanide complex catalyst is 10% by volume or less. [2C] A method for producing a polyether compound having a polymerizable unsaturated group, comprising polymerizing an initiator having active hydrogen and an alkylene oxide in the presence of a double metal cyanide complex catalyst to obtain a composition containing a polyether compound having a hydroxyl group, and converting the hydroxyl group of the polyether compound having a hydroxyl group in the composition into a group having a polymerizable unsaturated group, wherein the double metal cyanide complex catalyst is in a particulate form, and the 50% cumulative volume particle diameter D is determined from a volume-based cumulative particle size distribution of the double metal cyanide complex catalyst obtained by a laser diffraction scattering method. ５０ is 0.01 to 4.0 μm, the content of the particles having a particle diameter of 11 μm or more relative to the total volume of the composite metal cyanide complex catalyst is 10% by volume or less, and the 10% cumulative volume particle diameter calculated from the volume-based cumulative particle size distribution is D １０ , 90% cumulative volume particle diameter is D ９０ When (D ９０ -D １０ ) / D ５０[3C] A method for producing a polyether compound having a polymerizable unsaturated group according to [1C] or [2C], wherein the content of the particles having a particle diameter of 11 μm or more relative to the total volume of the double metal cyanide complex catalyst is 5 vol% or less. [4C] A method for producing a polyether compound having a polymerizable unsaturated group according to any of [1C] to [3C], wherein the number average molecular weight of the polyether compound having a hydroxyl group is 500 to 100,000. [5C] A method for producing a polyether compound having a polymerizable unsaturated group according to any of [1C] to [4C], wherein the molecular weight distribution of the polyether compound having a hydroxyl group is 1.00 to 1.15. [6C] A method for producing a polyether compound having a polymerizable unsaturated group according to any of [1C] to [5C], wherein the total degree of unsaturation of the polyether compound having a hydroxyl group is 0.001 to 0.040 meq / g. [7C] The method for producing a polyether compound having a polymerizable unsaturated group according to any one of [1C] to [6C], wherein the amount of the double metal cyanide complex catalyst used is 1 to 200 ppm by mass relative to the total mass of the polyether compound having a hydroxyl group.

[0022] According to the present invention, there are provided a composite metal cyanide complex catalyst capable of improving filterability in the purification process of a polyether compound, and a method for producing a polyether compound using the composite metal cyanide complex catalyst. According to the present invention, there is also provided a method for producing a polyether compound having a reactive silicon group, which provides excellent stretch durability of the cured product and improves filterability in the purification process. According to the present invention, there is also provided a method for producing a polyether compound having a urethane bond, which improves filterability in the purification process. According to the present invention, there is also provided a method for producing a polyether compound having a polymerizable unsaturated group, which improves filterability in the purification process.

[0023] The meanings and definitions of terms used in this specification are as follows: A numerical range expressed as "to" means that the numerical values ​​before and after "to" are the lower and upper limits of the numerical range.

[0024] The particle size distribution of the composite metal cyanide complex catalyst particles can be determined by a laser diffraction scattering method. Hereinafter, the X% cumulative volume particle diameter determined from the volume-based cumulative particle size distribution obtained by the laser diffraction scattering method is referred to as D Ｘ Also expressed as: D Ｘ represents the particle size obtained by accumulating up to a certain X% of the total volume of the particle size distribution obtained by the laser diffraction scattering method, where the volume of the entire particle size distribution is taken as 100%. The particle size distribution in the reaction liquid (composition) after the production of the polyether compound can also be determined by dynamic light scattering particle size distribution measurement. Hereinafter, the X% cumulative volume particle size determined from the volume-based cumulative particle size distribution obtained by dynamic light scattering particle size distribution measurement will be referred to as d Ｘ Also expressed as d Ｘ represents the particle size obtained by accumulating up to a specific X% of the total volume of the particle size distribution obtained by dynamic light scattering particle size distribution measurement, where the volume is 100%. Also, the X% cumulative light intensity particle size calculated from the light intensity-based cumulative particle size distribution in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement is called d Ｘ ' is also expressed as '. Ｘ ' represents the particle size obtained by accumulating up to a certain X% of the light intensity of the entire particle size distribution in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement, with the light intensity being 100%.

[0025] "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. A "polyether compound having a polymerizable unsaturated group" does not have a reactive silicon group. Hereinafter, "polyether compounds," "polyether compounds having a reactive silicon group," "polyether compounds having a urethane bond," and "polyether compounds having a polymerizable unsaturated group" are collectively referred to as "polyether compounds, etc." 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. The "main chain" in the polyether compounds, polyether compounds having a reactive silicon group, and polyether compounds having a polymerizable unsaturated group described below refers to the residue obtained by removing active hydrogen from the initiator and the portion containing repeating units based on alkylene oxide (polyoxyalkylene chain). Polyether compounds, polyether compounds having a reactive silicon group, and polyether compounds having a polymerizable unsaturated group are polymers consisting of a main chain and terminal groups.The "end group" of a polyether compound, a polyether compound having a reactive silicon group, or a polyether compound having a polymerizable unsaturated group 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 end group but is considered part of the main chain. The "number of end groups" in a polyether compound, a polyether compound having a reactive silicon group, or a polyether compound having a polymerizable unsaturated group is the same as the number of active hydrogen atoms in the initiator, as described below. 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 or a hydrogen atom derived from a hydroxyl group of water.

[0026] 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 value of the silylation rate can be measured by NMR analysis. Alternatively, it may be the ratio (mol %) of the number of silyl groups of the silylating agent added to the number of terminal groups when the reactive silicon groups are introduced into the terminal groups of the polyether compound using the silylating agent described below. 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.

[0027] In this specification, the number average molecular weight (Mn) and weight average molecular weight (Mw) are polystyrene-equivalent molecular weights measured using GPC with tetrahydrofuran as an eluent and a calibration curve prepared using polystyrene polymers of known molecular weights. The molecular weight distribution (Mw / Mn) is the ratio of Mw to Mn.

[0028] 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.

[0029] The total degree of unsaturation of the polyether compound can be measured in accordance with JIS K 1557-3: 2007. The viscosity of the polyether compound, polyether compound having a reactive silicon group, prepolymer, and polyether compound having a polymerizable unsaturated group can be measured using an E-type viscometer.

[0030] <<Duoth Metal Cyanide Complex Catalyst>> The duoth metal cyanide complex catalyst of this embodiment is in the form of particles. The 50% cumulative volume particle diameter of the duoth metal cyanide complex catalyst, determined from a volume-based cumulative particle size distribution obtained by a laser diffraction scattering method, is 0.01 to 4.0 μm. The content of particles having a particle diameter of 11 μm or more relative to the total volume of the duoth metal cyanide complex catalyst is 10 vol % or less.

[0031] 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 (such as coordinated water) contained within the crystal. In addition, the catalyst may contain impurities unavoidable in the production and moisture other than water of crystallization that are contained in trace amounts in the metal salts and metal compounds. The metal halide salts, transition metal cyanide compounds, and organic ligands can be those known in the production of DMC catalysts.

[0032] The DMC catalyst is believed to be represented by the following formula 2: M １ ａ１ [M ２ (CN) ｂ１ ] ｃ１ d1 (M １ ｅ１ X １ ｆ１ )・g1(Ligand)・h1(H ２ O) Formula 2 In the above formula 2, M １ ｅ１ X １ ｆ１ is a metal halide salt, M １ is the metal atom that becomes a cation, X １ 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. a1, b1, c1, d1, e1, f1, g1, and h1 are integers, and a1, b1, c1, e1, and f1 are numbers that result in electrical neutrality.

[0033] The above 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 the 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). １ Examples of M include Cl, Br, and I. １ ｅ１ X １ ｆ１ 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. ２ and X １In terms of the interatomic distance between the cations, it is more preferable that the cations contain 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.

[0034] 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 d1(ZnCl ２ )・g1(Ligand)・h1(H ２ O) or Zn ３ [Co(CN) ６ ] ２ d1 (ZnBr ２ )・g1(Ligand)・h(H ２ O) is considered.

[0035] 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.

[0036] DMC catalyst particles D ５０is 0.01 to 4.0 μm, preferably 0.05 to 3.5 μm, more preferably 0.1 to 3.0 μm, even more preferably 0.1 μm or more but less than 3.0 μm, and particularly preferably 0.5 to 2.5 μm. ５０ When the value of D is equal to or greater than the lower limit, the catalyst has sufficient catalytic activity as a polymerization catalyst for alkylene oxide. ５０ When the value is equal to or less than the upper limit, the filterability in the purification step of the polyether compound or the like is likely to be improved.

[0037] The content of particles having a particle diameter of 11 μm or more relative to the total volume of the DMC catalyst is 10% by volume or less, preferably 5% by volume or less, more preferably 4% by volume or less, and even more preferably 3% by volume or less. When the content of particles having a particle diameter of 11 μm or more is below the upper limit, filterability is likely to be improved in the purification process of polyether compounds, etc. The content of particles having a particle diameter of 11 μm or more relative to the total volume of the DMC catalyst is preferably 0 to 10% by volume, more preferably 0 to 5% by volume, even more preferably 0 to 4% by volume, and particularly preferably 0 to 3% by volume.

[0038] The content of particles having a particle diameter of 0.15 to 1 μm relative to the total volume of the DMC catalyst is preferably 5% by volume or more, more preferably 7% by volume or more, and even more preferably 10% by volume or more. The upper limit is not particularly limited, but may be, for example, 50% by volume or less, or 30% by volume or less. The content of particles having a particle diameter of 0.15 to 1 μm relative to the total volume of the DMC catalyst is preferably 5 to 50% by volume, more preferably 7 to 50% by volume, and even more preferably 7 to 30% by volume. When the content of particles having a particle diameter of 0.15 to 1 μm is equal to or greater than the above lower limit, the filterability in the purification process of polyether compounds and the like is easily improved.

[0039] The content of particles having a particle size of 0.1 to 0.2 μm relative to the total volume of the DMC catalyst is preferably 3% by volume or less, more preferably 1% by volume or less, and even more preferably 0% by volume. When the content of particles having a particle size of 0.1 to 0.2 μm is equal to or less than the upper limit, filterability in the purification process of polyether compounds and the like is likely to be improved.

[0040] DMC catalyst particles D １０is preferably 0.01 to 2.0 μm, more preferably 0.05 to 1.8 μm, and even more preferably 0.1 to 1.5 μm. １０ When the amount of the alkylene oxide is within the above range, the catalyst has sufficient catalytic activity as a polymerization catalyst for alkylene oxide, a polyether compound having a narrow molecular weight distribution can be obtained, and the filterability in the purification step of the polyether compound or the like is likely to be improved.

[0041] DMC catalyst particles D ９０ is preferably 1 to 15 μm, more preferably 1.5 to 10 μm, and even more preferably 2 to 8 μm. ９０ When the amount of the alkylene oxide is within the above range, the catalyst has sufficient catalytic activity as a polymerization catalyst for alkylene oxide, a polyether compound having a narrow molecular weight distribution can be obtained, and the filterability in the purification step of the polyether compound or the like is likely to be improved.

[0042] The particle size distribution of the DMC catalyst particles in the range of 0.1 to 10 μm is preferably unimodal, having only one peak. A unimodal distribution tends to improve filterability in the purification process of polyether compounds, etc. A unimodal distribution means that there is only one peak in the particle size distribution in the range of 0.1 to 10 μm. More specifically, when the particle size with the highest frequency in the particle size distribution in the range of 0.1 to 10 μm is taken as the peak particle size, the frequency of plots monotonically decreases (i.e., does not increase) from the peak particle size to the minimum particle size and the maximum particle size.

[0043] DMC catalyst (D ９０ -D １０ ) / D ５０ is preferably 0.1 to 3.0, more preferably 0.5 to 2.5, even more preferably 1.0 to 2.0, and most preferably 1.05 to 1.50. (D ９０ -D １０ ) / D ５０ indicates the height of the particle size distribution, and when the particle size distribution of the DMC catalyst particles is monomodal, (D ９０ -D １０ ) / D ５０ is likely to be equal to or less than the upper limit. (D ９０ -D １０ ) / D ５０When the amount of the alkylene oxide is within the above range, the catalyst has sufficient catalytic activity as a polymerization catalyst for alkylene oxide, a polyether compound having a narrow molecular weight distribution can be obtained, and the filterability in the purification step of the polyether compound or the like is likely to be improved.

[0044] DMC catalyst D ９０ / D １０ is preferably 1.5 to 8.0, more preferably 2.0 to 6.5, and even more preferably 2.5 to 4.5. ９０ / D １０ indicates that the particle size distribution is narrow, and when the particle size distribution of the DMC catalyst particles is narrow, D ９０ / D １０ is likely to be below the upper limit. ９０ / D １０ When the amount of the alkylene oxide is within the above range, the catalyst has sufficient catalytic activity as a polymerization catalyst for alkylene oxide, a polyether compound having a narrow molecular weight distribution can be obtained, and the filterability in the purification step of the polyether compound or the like is likely to be improved.

[0045] The DMC catalyst may be used, for example, in the production of a polyether compound in the above-mentioned solid state, or in the state of a slurry in which DMC catalyst particles are dispersed in a dispersion medium (hereinafter also referred to as a "slurry catalyst") in the production of a polyether compound.

[0046] 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.

[0047] 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 compounds having alcoholic hydroxyl groups, such as polyether compounds, are preferred. As the dispersion medium for the slurry catalyst, polyether compounds are preferred because they do not become impurities in the product (polyether compound) of alkylene oxide polymerization. The Mn of the 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, the catalyst is less likely to poison the catalyst, while when it is equal to or less than the upper limit, the slurry catalyst is easier to handle. In addition, the initiator used in the polymerization of alkylene oxide may be used as part of the dispersion medium.

[0048] It is preferable that the dispersion medium of the slurry catalyst contains substantially no water. Specifically, the water content of the dispersion medium is preferably 500 ppm by mass or less, more preferably 200 ppm by mass or less, and may be an undetectable amount. The water content of the dispersion medium is preferably 0 to 500 ppm by mass, more preferably 0 to 200 ppm by mass. The water content of the dispersion medium and the water content relative to the total mass of the slurry catalyst described below are the water contents measured by Karl Fischer measurement method.

[0049] 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 polyether compound, the content of the DMC catalyst relative to the total mass of the slurry catalyst is preferably 0.1 to 60% by mass, more preferably 0.5 to 40% by mass, and even more preferably 1 to 30% by mass. The content of water relative to the total mass of the slurry catalyst is, for example, preferably 0 to 10,000 ppm by mass, more preferably 10 to 6,000 ppm by mass, and even more preferably 100 to 4,000 ppm by mass.

[0050] <Method for Producing DMC Catalyst> The DMC catalyst of this embodiment can be produced by reacting a metal halide salt with a transition metal cyanide compound, and then coordinating an organic ligand with the resulting reaction product. After synthesis of the DMC catalyst, the water content of the DMC catalyst may be adjusted.

[0051] 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.

[0052] A preferred embodiment of the method for producing the DMC catalyst of this embodiment is, 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.

[0053] 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 metal halide salt in the aqueous solution of the metal halide salt is preferably 10% by mass or more and less than the saturated concentration, more preferably 30% by mass or more and less than the saturated concentration, and even more preferably 50% by mass or more and less than the saturated concentration. The concentration of the cyanide transition metal compound in the aqueous solution of the cyanide transition metal 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 cyanide transition metal compound is preferably 1.6 to 12, and more preferably 1.8 to 8.

[0054] According to the study by the inventors of the present application, the DMC catalyst ５０It was found that the content of particles having a particle size of 11 μm or more relative to the total volume of the DMC catalyst is greatly dependent on the mixing conditions of the aqueous solution of the metal halide salt and the aqueous solution of the transition metal cyanide compound.

[0055] The mixing of the aqueous solution of the metal halide salt and the aqueous solution of the cyanide transition metal compound is preferably carried out by dropping one aqueous solution into the other aqueous solution. Note that, rather than dropping the aqueous solution of the metal halide salt into the aqueous solution of the cyanide transition metal compound, it is preferable to drop the aqueous solution of the cyanide transition metal compound into the aqueous zinc halide solution. Dropping the aqueous solution of the cyanide transition metal compound into the aqueous zinc halide solution makes it easier to obtain a DMC catalyst that satisfies the above-mentioned particle size and particle size distribution. The ratio of the drop rate (mol / hour) calculated as the transition metal in the cyanide transition metal compound to the total amount (mol) of metal derived from the metal halide salt contained in the aqueous metal halide salt solution is preferably 0.30 (mol / hour / mol) or less, more preferably 0.25 (mol / hour / mol) or less, and even more preferably 0.20 (mol / hour / mol) or less. The lower limit of the ratio is not particularly limited, but may be 0.01 (mol / hour / mol) or more, or may be 0.1 (mol / hour / mol) or more. The ratio is preferably 0.01 to 0.30 (mol / hour / mol), more preferably 0.01 to 0.25 (mol / hour / mol), and even more preferably 0.1 to 0.20 (mol / hour / mol). If the ratio is equal to or less than the upper limit, the DMC catalyst ５０ , and the content of particles having a particle diameter of 11 μm or more relative to the total volume of the DMC catalyst can be easily controlled within the above-mentioned range. The dropwise addition time of the aqueous solution of the transition metal cyanide compound is preferably 40 minutes or more, more preferably 60 minutes or more, and even more preferably 80 minutes or more. The upper limit of the dropwise addition time may be, for example, 180 minutes or less, or 150 minutes or less. The dropwise addition time is preferably 40 to 180 minutes, more preferably 60 to 180 minutes, and even more preferably 60 to 150 minutes. When the dropwise addition time is equal to or greater than the above-mentioned lower limit, the D of the DMC catalyst can be easily controlled. ５０When the dropping rate is equal to or less than the upper limit, the DMC catalyst can be produced more efficiently.

[0056] When mixing the aqueous solution of the metal halide salt and the aqueous solution of the transition metal cyanide compound, it is preferable to stir the mixture thoroughly. The stirring blade to be used is preferably a half-moon stirring blade, a full-zone stirring blade, an anchor-type stirring blade, or the like. When using a half-moon stirring blade in a 500 mL flask, the diameter is preferably 60 mm or more, and more preferably 70 mm or more.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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 obtained mixed solution, and then a dispersion medium is added to prepare a slurry containing the DMC catalyst and the dispersion medium. Note that washing with an aqueous solution of an organic ligand may be performed before adding the dispersion medium.

[0062] <<Method for Producing Polyether Compound>> In the method for producing a polyether compound of the present embodiment, an alkylene oxide is polymerized with an initiator having active hydrogen in the presence of the DMC catalyst.

[0063] The number of active hydrogens in the initiator is preferably 1 or more, more preferably 2 to 10, even more preferably 2 to 8, and particularly preferably 2 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.

[0064] 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, diglycerin, and polyglycerin. 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.

[0065] The alkylene oxide is selected depending on the structural units of the polyoxyalkylene chain of the resulting polyether compound. Examples of alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide. Among these, ethylene oxide and propylene oxide are preferred, and propylene oxide is more preferred.

[0066] When a DMC catalyst is used as the polymerization catalyst, the Mw / Mn of the polyether compound tends to be smaller and the total degree of unsaturation of the polyether compound tends to be smaller than when a polymerization catalyst other than a DMC catalyst is used.

[0067] When the polyoxyalkylene chain of the polyether compound is a random copolymer chain composed of propylene oxide units and ethylene oxide units, a method of obtaining the polyether compound by reacting a mixture of propylene oxide and ethylene oxide with an initiator in the presence of a DMC catalyst is preferred.

[0068] When the polyoxyalkylene chain of the polyether compound is a copolymer chain having a block composed of propylene oxide units and a block composed of ethylene oxide units, the polyether compound may be obtained by reacting propylene oxide with an initiator in the presence of a DMC catalyst to obtain a precursor, and then reacting ethylene oxide with the precursor; or the polyether compound may be obtained by reacting ethylene oxide with an initiator in the presence of a DMC catalyst to obtain a precursor, and then reacting propylene oxide with the precursor.

[0069] The amount of DMC catalyst used relative to the total mass of the resulting polyether compound is preferably 1 to 200 ppm by mass, more preferably 2 to 100 ppm by mass, and even more preferably 5 to 50 ppm by mass. When the amount of DMC catalyst used is equal to or greater than the lower limit, the polymerization reaction is likely to proceed. When the amount of DMC catalyst used is equal to or less than the upper limit, the amount of DMC catalyst used is reduced, which is economical.

[0070] 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 lower limit is not particularly limited, but is, for example, atmospheric pressure. The polymerization pressure is preferably atmospheric pressure or more and 1.0 MPa or less, more preferably atmospheric pressure or more and 0.8 MPa or less, and even more preferably atmospheric pressure or more and 0.3 MPa or less. The alkylene oxide is preferably supplied to the reactor at a rate that maintains the above 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.

[0071] The reaction solution after polymerization contains a polyether compound and a DMC catalyst. It may also contain a stabilizer and may contain trace amounts of impurities. Therefore, it is preferable to purify the reaction solution by filtration. The pore size of the filter paper is, for example, preferably 0.1 to 10 μm, more preferably 0.3 to 6 μm. The DMC catalyst is pulverized during the reaction and contained as fine particles. The 50% cumulative volume particle size determined from the volume-based cumulative particle size distribution obtained by dynamic light scattering particle size distribution measurement in the reaction solution is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm, and even more preferably 1 to 30 nm. The 50% cumulative light intensity particle size determined from the light intensity-based cumulative particle size distribution in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement in the reaction solution is preferably 1.0 μm or less, more preferably 0.9 μm or less, and even more preferably 0.8 μm or less. The lower limit of the 50% cumulative light intensity particle diameter may be, for example, 0.01 μm or more, or 0.1 μm or more. The 50% cumulative light intensity particle diameter is preferably 0.01 to 1.0 μm, more preferably 0.01 to 0.9 μm, and even more preferably 0.1 to 0.8 μm. The peak particle diameter determined from the light intensity-based cumulative particle size distribution in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement of the reaction solution is preferably 1.0 μm or less, more preferably 0.9 μm or less, and even more preferably 0.8 μm or less. The lower limit of the peak particle diameter may be, for example, 0.01 μm or more, or 0.1 μm or more. The peak particle diameter is preferably 0.01 to 1.0 μm, more preferably 0.01 to 0.9 μm, and even more preferably 0.1 to 0.8 μm.

[0072] The content of the DMC catalyst relative to the total mass of the reaction solution is preferably 1 to 200 ppm by mass, more preferably 2 to 100 ppm by mass, and even more preferably 5 to 50 ppm by mass. The content of the DMC catalyst is determined based on the amount of the DMC catalyst used in producing the polyether compound. The content of the polyether compound relative to the total mass of the reaction solution is preferably 98.0% by mass or more, more preferably 99.0% by mass or more, and even more preferably 99.5% by mass or more.

[0073] <Polyether Compound> The main chain of the polyether compound is a polymer chain consisting of a residue obtained by removing active hydrogen from an initiator and an oxyalkylene chain containing one or more repeating units based on alkylene oxide (hereinafter, a repeating unit based on a monomer will be simply referred to as a "monomer unit", for example, a repeating unit based on alkylene oxide will be referred to as an "alkylene oxide unit"). When the polymer chain contains two or more types of alkylene oxide units, these alkylene oxide units may form a block polymer or a random polymer. Examples of the oxyalkylene chain include a polymer chain containing an ethylene oxide unit, a polymer chain containing a propylene oxide unit, a polymer chain containing an ethylene oxide unit and a propylene oxide unit, a polymer chain containing an ethylene oxide unit, a polymer chain containing a propylene oxide unit, a polymer chain containing a butylene oxide unit, a polymer chain containing a tetramethylene oxide unit, a polymer chain containing an ethylene oxide unit and a propylene oxide unit, and a polymer chain containing a propylene oxide unit and a butylene oxide unit. Polymer chains having ethylene oxide units, polymer chains having propylene oxide units, polymer chains having ethylene oxide units and propylene oxide units, polymer chains consisting of propylene oxide units, and polymer chains consisting of ethylene oxide units and propylene oxide units are preferred, and polymer chains consisting of propylene oxide units are particularly preferred. The terminal groups of the polyether compound are hydroxyl groups. The number of terminal groups of the polyether compound (i.e., the number of hydroxyl groups) is the same as the number of active hydrogens of the initiator.

[0074] The Mn of the polyether compound is preferably 500 to 100,000, more preferably 1,000 to 100,000, even more preferably 1,500 to 80,000, and particularly preferably 2,000 to 60,000. When the Mn 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 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 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.

[0076] The hydroxyl value-equivalent molecular weight of the polyether compound is preferably 500 to 100,000, more preferably 1,000 to 100,000, even more preferably 1,500 to 80,000, and particularly 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 easier to handle.

[0077] The Mw of the polyether compound is preferably 600 to 120,000, more preferably 1,200 to 120,000, even more preferably 2,000 to 90,000, and particularly preferably 3,000 to 70,000. When the Mw 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 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.

[0078] 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.

[0079] The total degree of unsaturation of the polyether compound is preferably from 0.001 to 0.040 meq / g, more preferably from 0.002 to 0.030 meq / g, and even more preferably from 0.003 to 0.010 meq / g.

[0080] The viscosity of the polyether compound at a measurement temperature of 25° C. is preferably 100 to 30,000 mPa·s, more preferably 200 to 20,000 mPa·s, and even more preferably 400 to 10,000 mPa·s.

[0081] <Uses of Polyether Compounds> Polyether compounds can be used as lubricating oils, raw materials for polyurethane foams, adhesives, sealants, coating materials, etc. Furthermore, by reacting the polyether compounds with compounds that can react with the hydroxyl groups of the polyether compounds, they may be converted into polyether compounds having reactive silicon groups, prepolymers, polyether compounds having polymerizable unsaturated groups, etc.

[0082] <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.

[0083] (Reactive Silicon Group) 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

[0084] In the above formula 1, R represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group. R is preferably at least one group selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms and triorganosiloxy groups.

[0085] 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.

[0086] In the above 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 rapidly 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.

[0087] In the above formula 1, a is an integer of 0 to 2. When a is 2, R may be the same or different from each other. When a is 1 or less, X may be the same or different from each other. 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.

[0088] Examples of the reactive silicon group represented by the above formula 1 include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a methyldiisopropoxysilyl group, an (α-chloromethyl)dimethoxysilyl group, and an (α-chloromethyl)diethoxysilyl group. 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.

[0089] 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 above, wherein the terminal group is the reactive silicon group, an unsaturated group, an isocyanate group, or a hydroxyl group.

[0090] 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 2.0 to 6.0, and even more preferably 2.0 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 above polyether compound. The terminal groups of polyether compound A have any of the reactive silicon group, unsaturated group, isocyanate group, or hydroxyl group represented by formula 1 above. The respective terminal groups may be the same or different from each other.

[0091] The average number of reactive silicon groups represented by the above 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, making it possible to obtain a good cured product with a high modulus.

[0092] The average number of reactive silicon groups represented by the above 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, making it possible to obtain a good cured product with a high modulus.

[0093] The Mn of polyether compound A is preferably 500 to 100,000, more preferably 1,000 to 100,000, even 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.

[0094] 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.

[0095] The viscosity of the polyether compound A at a measurement temperature of 25° C. is preferably 100 to 100,000 mPa·s, more preferably 200 to 70,000 mPa·s, and even more preferably 400 to 30,000 mPa / s. When the viscosity is equal to or less than the upper limit, the polyether compound A is easy to handle.

[0096] <Method for producing polyether compound having reactive silicon group> In the method for producing polyether compound A, the hydroxyl groups of a polyether compound are converted into groups having a reactive silicon group represented by the above formula 1. Examples of methods for producing polyether compound A include the following methods (a1), (b1), and (c1). Method (a1): Converting the hydroxyl groups of a polyether compound into alkenyloxy groups having a carbon-carbon double bond or alkynyloxy groups having a carbon-carbon triple bond at the molecular terminal, and then converting the reactive silicon group -SiR represented by the above formula 1 into the carbon-carbon double bond at the molecular terminal of the alkenyloxy group or the carbon-carbon triple bond of the alkynyloxy group. ａ X ３－ａa silylating agent capable of introducing a functional group reactive with the hydroxyl group and the reactive silicon group represented by the formula 1, thereby converting the alkenyloxy group or alkynyloxy group into a group having a reactive silicon group represented by the 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 the reactive silicon group represented by the formula 1, thereby converting the hydroxyl group into a group having a reactive silicon group represented by the 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 the isocyanate group and the reactive silicon group represented by the formula 1, thereby converting the hydroxyl group into a group having a reactive silicon group represented by the formula 1.

[0097] 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 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 or alkynyloxy groups having a carbon-carbon triple bond at the molecular terminal.

[0098] 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.

[0099] 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 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, 1-bromo- Examples of the halogenated hydrocarbon compound include 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 carbon-carbon triple bond 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 may be used alone or in combination of two or more.

[0100] Next, a reactive silicon group, —SiR, represented by the above formula 1, is bonded to the carbon-carbon double bond at the molecular terminal of the alkenyloxy group or the carbon-carbon triple bond 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 the above 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 above). Specific examples include dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, methyldiisopropoxysilane, (α-chloromethyl)dimethoxysilane, (α-chloromethyl)diethoxysilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, and 3-mercaptopropyltrimethoxysilane. From the viewpoints of high activity and good curability, trimethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane are preferred, and dimethoxymethylsilane is more preferred.

[0101] 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 the above formula 3 ａ X ３－ａ is the same as in formula 1 above. 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.

[0034] As the isocyanate silane compound, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, 3-isocyanate propyl methyl dimethoxysilane, isocyanate methyl methyl dimethoxysilane, and isocyanate methyl trimethoxysilane are preferred in view of their reactivity with polyether compounds and ease of handling.

[0102] The active hydrogen of the polyether compound reacts with the isocyanate group of the isocyanate silane compound represented by the above 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.

[0103] 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.

[0104] 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 number of reactive silicon groups per molecule of the resulting polyether compound A is at least 0.7. 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.

[0105] 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") having a urethane bond (-O-C(=O)NH-) at the bond terminal side 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 the above 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") having one or more urethane bonds (-O-C(=O)NH-) and a silylating agent residue 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 the above formula 1 is a compound represented by the following formula 5, but the present invention is not limited thereto.

[0106] OCN-R ３ —NCO Formula 4 R in the above formula 4 ３ represents a divalent organic group.

[0107] W-R ４ -SiR ａ X ３－ａ Formula 5 In the above formula 5, W represents a functional group (a group having one or more active hydrogens) 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 above.

[0108] When the diisocyanate compound represented by the above formula 4 is reacted with the hydroxyl group of the polyether compound, the isocyanate-containing group is —O—C(═O)NH—R ３ When the isocyanate-containing group is reacted with the silylating agent represented by the 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 each represented by —O—C(═O)NH—R ３ -NHC(=O)-NH-R ４ -SiR ａ X ３－ａ It is a group represented by the formula:

[0109] 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 may have an alkyl group as a substituent and are bonded via an alkylene group, and a divalent group obtained by removing two hydrogen atoms from two or more aromatic hydrocarbons which may have an alkyl group as a substituent and are bonded via an alkylene group.

[0110] Examples of the diisocyanate compound represented by the above formula 4 and other polyisocyanate compounds include aromatic polyisocyanates, non-yellowing aromatic polyisocyanates (which refer to compounds that do not have an isocyanate group directly bonded to a carbon atom constituting an aromatic ring), aliphatic polyisocyanates, and alicyclic polyisocyanates, as well as urethane-modified products, biuret-modified products, allophanate-modified products, carbodiimide-modified products, and isocyanurate-modified products obtained from the above polyisocyanates.

[0111] 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). The polyisocyanate compound is preferably one having two isocyanate groups, more preferably hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, or 2,6-tolylene diisocyanate, and even more preferably tolylene diisocyanate because it is easy 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.

[0112] The functional group capable of reacting with an isocyanate group represented by the above 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 the group consisting of 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.

[0113] In the cases of 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) per terminal group. Note that the polyether compound A obtained by method (b1) contains only one organic group represented by the following formula (i) per terminal group, while the polyether compound A obtained by method (c1) contains two or more organic groups represented by the following formula (i) per terminal group. -C(=O)NH- Formula (i)

[0114] The organic group (i) is a divalent group derived from a urethane bond or a urea bond. When the isocyanate silane compound represented by the above formula 3 is used as a silylating agent, there is one organic group (i) per terminal group.

[0115] 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 the above formula (i) per terminal group contained in the polyether compound A is one. When the polyether compound A is produced by the method (b1), a polyether compound A with a high silylation rate is likely to be obtained. When the polyether compound A is produced by the method (b1), a polyether compound A with a narrow molecular weight distribution is likely to be obtained. The viscosity of the polyether compound A is suppressed, resulting in good workability. When the isocyanate silane compound represented by the above formula 3 contains one isocyanate group and one reactive silicon group, the number of reactive silicon groups per molecule of the polyether compound A is the same as the number of groups (i) per molecule.

[0116] 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.

[0117] The reaction solution after producing polyether compound A contains polyether compound A and a DMC catalyst. It may also contain a stabilizer and may contain trace amounts of impurities. Therefore, it is preferable to purify the reaction solution by filtration. The pore size of the filter paper is, for example, preferably 0.1 to 10 μm, more preferably 0.3 to 6 μm. Since the DMC catalyst does not contribute to the urethanization reaction, it is believed that the particle size is almost unchanged from that of the DMC catalyst in the composition containing the polyether compound. The 50% cumulative volume particle size calculated from the volume-based cumulative particle size distribution obtained by dynamic light scattering particle size distribution measurement of the reaction solution is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm, and even more preferably 1 to 30 nm. The 50% cumulative light intensity particle size calculated from the light intensity-based cumulative particle size distribution in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement of the reaction solution is preferably 1.0 μm or less, more preferably 0.9 μm or less, and even more preferably 0.8 μm or less. The lower limit of the 50% cumulative light intensity particle diameter may be, for example, 0.01 μm or more, or 0.1 μm or more. The 50% cumulative light intensity particle diameter is preferably 0.01 to 1.0 μm, more preferably 0.01 to 0.9 μm, and even more preferably 0.1 to 0.8 μm. The peak particle diameter determined from the light intensity-based cumulative particle size distribution in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement of the reaction solution is preferably 1.0 μm or less, more preferably 0.9 μm or less, and even more preferably 0.8 μm or less. The lower limit of the peak particle diameter may be, for example, 0.01 μm or more, or 0.1 μm or more. The peak particle diameter is preferably 0.01 to 1.0 μm, more preferably 0.01 to 0.9 μm, and even more preferably 0.1 to 0.8 μm. The content of the DMC catalyst relative to the total mass of the reaction liquid is preferably from 1 to 200 ppm by mass, more preferably from 2 to 100 ppm by mass, and even more preferably from 5 to 50 ppm by mass.

[0118] (Curable composition containing polyether compound having reactive silicon group) The polyether compound having reactive silicon group 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 polyether compound A 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 will have better tensile strength and elongation properties.

[0119] 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.

[0120] 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.

[0121] (Uses of Curable Compositions Comprising Polyether Compounds Having Reactive Silicon Groups) Suitable uses of the curable compositions 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).

[0122] <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 by a urethane reaction between the hydroxyl group of the polyether compound and the isocyanate group of the polyisocyanate. Of the isocyanate groups in the polyisocyanate units introduced into polyether compound B, those that remain unreacted with the hydroxyl group of the polyether compound 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 group 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.

[0123] The Mn of polyether compound B is preferably 500 to 1,000,000, more preferably 1,000 to 1,000,000, even more preferably 1,500 to 500,000, and particularly 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 B can be kept low, making it easy to handle.

[0124] 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.

[0125] 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 25 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.

[0126] 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 %.

[0127] 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.

[0128] <Method for producing prepolymer> In the method for producing polyether compound B, a polyether compound is reacted with a polyisocyanate. If necessary, a urethanization catalyst may be used. One type of polyether compound may be used, or two or more types may be used in combination.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] Examples of the araliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and α,α,α,α-tetramethylxylylene diisocyanate.

[0134] 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.

[0135] 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.

[0136] 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.

[0137] Examples of the tertiary amine compound include triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-undecene-7.

[0138] 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.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] If unreacted polyisocyanate remains after the reaction, it is preferable to purify the polyether compound B by removing the polyisocyanate by distillation.

[0145] The reaction solution after producing polyether compound B contains polyether compound B and a DMC catalyst. It may also contain a stabilizer and may contain trace amounts of impurities. Therefore, it is preferable to purify the reaction solution by filtration. The pore size of the filter paper is, for example, preferably 0.1 to 10 μm, more preferably 0.3 to 6 μm. Since the DMC catalyst does not contribute to the urethanization reaction, it is believed that the particle size is almost unchanged from the DMC catalyst in the composition containing the polyether compound. The 50% cumulative volume particle size calculated from the volume-based cumulative particle size distribution obtained by dynamic light scattering particle size distribution measurement of the reaction solution is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm, and even more preferably 1 to 30 nm. The 50% cumulative light intensity particle size calculated from the light intensity-based cumulative particle size distribution in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement of the reaction solution is preferably 1.0 μm or less, more preferably 0.9 μm or less, and even more preferably 0.8 μm or less. The lower limit of the 50% cumulative light intensity particle diameter may be, for example, 0.01 μm or more, or 0.1 μm or more. The 50% cumulative light intensity particle diameter is preferably 0.01 to 1.0 μm, more preferably 0.01 to 0.9 μm, and even more preferably 0.1 to 0.8 μm. The peak particle diameter determined from the light intensity-based cumulative particle size distribution in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement of the reaction solution is preferably 1.0 μm or less, more preferably 0.9 μm or less, and even more preferably 0.8 μm or less. The lower limit of the peak particle diameter may be, for example, 0.01 μm or more, or 0.1 μm or more. The peak particle diameter is preferably 0.01 to 1.0 μm, more preferably 0.01 to 0.9 μm, and even more preferably 0.1 to 0.8 μm. The content of the DMC catalyst relative to the total mass of the reaction liquid is preferably from 1 to 200 ppm by mass, more preferably from 2 to 100 ppm by mass, and even more preferably from 5 to 50 ppm by mass.

[0146] (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 preferably 15 to 100 mass%, more preferably 30 to 100 mass%. The polyurethane composition may further contain optional components other than polyether compound B.

[0147] 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.

[0148] 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. In addition, water is 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.

[0149] 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.

[0150] 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.

[0151] 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. Although the base composition is less likely to gel even with a small amount of water, it is preferable to dehydrate and dry the blending components in advance from the standpoint of storage stability. In the case of a two-component composition, the above-mentioned 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%.

[0152] (Uses of Polyurethane Compositions Comprising Prepolymers) Suitable uses of polyurethane compositions comprising 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, the composition is suitable as an elastic adhesive for joining plastics together, joining metals together, and joining plastics and metals. The composition is also suitable as an elastic sealant or elastic coating material.

[0153] <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.

[0154] 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 2.0 to 6.0, and even more preferably 2.0 to 4.0. The number of terminal groups of the polyether compound C is the same as the number of terminal groups of the above polyether compound.

[0155] 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.

[0156] The average number of polymerizable unsaturated groups per molecule of polyether compound C is preferably 1.0 to 8.0, more preferably 1.5 to 6.0, and even more preferably 2.0 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 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.

[0157] The Mn of polyether compound C is preferably 500 to 1,000,000, more preferably 1,000 to 1,000,000, even more preferably 1,500 to 500,000, and particularly 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.

[0158] 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.

[0159] 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%.

[0160] 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.

[0161] <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 the 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 the above-mentioned compound 1 to convert the hydroxyl group into a group having a polymerizable unsaturated group.

[0162] 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.

[0163] 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.).

[0164] 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.).

[0165] When the composition containing polyether compound C is a photocurable composition, it is preferred 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.

[0166] 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.

[0167] In the methods (a2), (b2), and (c2), the reaction between a hydroxyl group and the functional group capable of reacting with the hydroxyl group, and the reaction between an isocyanate group and the 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.

[0168] The reaction solution after producing polyether compound C contains polyether compound C and a DMC catalyst. It may also contain a stabilizer and may contain trace amounts of impurities. Therefore, it is preferable to purify the reaction solution by filtration. The pore size of the filter paper is, for example, preferably 0.1 to 10 μm, more preferably 0.3 to 6 μm. Since the DMC catalyst does not contribute to the urethanization reaction, it is believed that the particle size is almost unchanged from that of the DMC catalyst in the composition containing the polyether compound. The 50% cumulative volume particle size calculated from the volume-based cumulative particle size distribution obtained by dynamic light scattering particle size distribution measurement of the reaction solution is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm, and even more preferably 1 to 30 nm. The 50% cumulative light intensity particle size calculated from the light intensity-based cumulative particle size distribution in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement of the reaction solution is preferably 1.0 μm or less, more preferably 0.9 μm or less, and even more preferably 0.8 μm or less. The lower limit of the 50% cumulative light intensity particle diameter may be, for example, 0.01 μm or more, or 0.1 μm or more. The 50% cumulative light intensity particle diameter is preferably 0.01 to 1.0 μm, more preferably 0.01 to 0.9 μm, and even more preferably 0.1 to 0.8 μm. The peak particle diameter determined from the light intensity-based cumulative particle size distribution in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement of the reaction solution is preferably 1.0 μm or less, more preferably 0.9 μm or less, and even more preferably 0.8 μm or less. The lower limit of the peak particle diameter may be, for example, 0.01 μm or more, or 0.1 μm or more. The peak particle diameter is preferably 0.01 to 1.0 μm, more preferably 0.01 to 0.9 μm, and even more preferably 0.1 to 0.8 μm. The content of the DMC catalyst relative to the total mass of the reaction liquid is preferably from 1 to 200 ppm by mass, more preferably from 2 to 100 ppm by mass, and even more preferably from 5 to 50 ppm by mass.

[0169] (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.

[0170] 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.

[0171] Examples of the other compound 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 not having a urethane bond or a urea bond (a compound produced by a method other than the above methods (a2) to (c2)) is preferred. Other compound 1 may also be a compound having an aliphatic polyester chain obtained by ring-opening addition polymerization of a lactone.

[0172] 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.

[0173] The number of carbon atoms in the hydroxyalkyl moiety of the hydroxyalkyl (meth)acrylate is preferably 2 to 8, more preferably 2 to 6. The number of carbon atoms in the dihydroxyalkyl moiety of the dihydroxyalkyl (meth)acrylate is preferably 2 to 8, more preferably 2 to 6. Specific examples of the hydroxyalkyl (meth)acrylate include the hydroxyalkyl (meth)acrylates exemplified above as Compound 2. Of these, 4-hydroxybutyl acrylate and 6-hydroxyhexyl acrylate are preferred in terms of flexibility and low volatility.

[0174] Examples of lactone-modified hydroxyalkyl (meth)acrylates include compounds obtained by ring-opening addition of lactone to the hydroxyalkyl (meth)acrylates exemplified above as Compound 2. The number of lactones added is preferably 1 to 3. Examples of lactones include ε-caprolactone, γ-butyrolactone, and γ-valerolactone.

[0175] The (meth)acrylic acid-monoepoxide adduct is preferably a reaction product of (meth)acrylic acid with a glycidyl ether or glycidyl ester, such as (meth)acrylic acid with phenyl glycidyl ether.

[0176] Among these, hydroxyalkyl (meth)acrylate and (meth)acrylic acid-monoepoxide adduct are preferred because they are easily available industrially and contain few impurities.

[0177] 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.

[0178] 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.

[0179] 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.

[0180] 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.

[0181] 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.

[0182] 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.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] 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.

[0188] 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.

[0189] 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.

[0190] 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.

[0191] 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.

[0192] 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.

[0193] 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.

[0194] (Applications of Curable Compositions Comprising Polyether Compounds Having Polymerizable Unsaturated Groups) Suitable applications of the curable compositions comprising polyether compound C include pressure-sensitive adhesives in the fields of various building materials, packaging materials, printing materials, display materials, electrical and electronic component materials, optical component materials, liquid crystal panels, and the like.

[0195] The composite metal cyanide complex catalyst of the present invention has a 50% cumulative volume particle size of 0.01 to 4.0 μm as determined from a volume-based cumulative particle size distribution obtained by a laser diffraction scattering method, and the content of particles having a particle size of 11 μm or more relative to the total volume of the composite metal cyanide complex catalyst is 10 volume % or less, thereby improving the filterability of compositions containing polyether compounds produced using the composite metal cyanide complex catalyst. Furthermore, the filterability of compositions containing polyether compounds having reactive silicon groups, compositions containing polyether compounds having urethane bonds, and compositions containing polyether compounds having polymerizable unsaturated groups, all of which are produced from the composition containing the polyether compound, is also improved. Furthermore, (D ９０ -D １０ ) / D ５０ , D ９０ / D １０ Controlling the parameters such as these will further improve the filterability.

[0196] As mentioned above, when the inventors of the present application produced a polyether compound using the DMC catalyst described in Patent Document 1 and purified it by filtration, they discovered problems such as a slow filtration rate and clogging. Therefore, it can be concluded that the DMC catalyst described in Patent Document 1 has a 50% cumulative volume particle size of 0.01 to 4.0 μm as determined from the volume-based cumulative particle size distribution obtained by laser diffraction scattering, and that the content of particles having a particle size of 11 μm or more relative to the total volume of the DMC catalyst is not 10% by volume or less. In particular, it is believed that the DMC catalyst described in Patent Document 1 does not have a content of particles having a particle size of 11 μm or more relative to the total volume of the DMC catalyst of 10% by volume or less. The characteristic that the content of particles having a particle size of 11 μm or more relative to the total volume of the DMC catalyst is 10% by volume or less can be determined by laser diffraction scattering, as described below, but it is extremely difficult (impossible to determine) to determine this by observation with an electron microscope such as a scanning electron microscope.

[0197] For example, consider a spherical particle with a diameter of 1 μm (hereinafter also referred to as "particle A") and a spherical particle with a diameter of 11.1 μm (hereinafter also referred to as "particle B"). In this case, the volume of particle A is 0.52 μm. ３ ((4π / 3)×0.5３ ) and the volume of particle B is 716 μm ３ ((4π / 3)×5.55 ３ ), and the volumes are significantly different. Suppose that particle A is 89% by volume and particle B is 11% by volume. If the number of particle A is X and the number of particle B is Y, then (0.52 μm ３ ×X pieces) / (716μm ３ Since the equation X / Y (number of particles A) = 89 / 11 holds, X / Y = 11141. That is, even if there are 11141 particles A and 1 particle B, the requirement that "the content of particles having a particle diameter of 11 μm or more is 10% by volume or less" is not satisfied. On the other hand, when there are 11141 particles A and 1 particle B, the level is such that observation with an electron microscope such as a scanning electron microscope can be judged to be sufficient to determine that "particles have a uniform particle diameter of 1 μm." From this perspective, even if the level is such that "the particle size uniformity is high" when observed with an electron microscope such as a scanning electron microscope, it is unclear whether the characteristic that "the content of particles having a particle diameter of 11 μm or more is 10% by volume or less" is satisfied. If the particle diameter of particle A is assumed to be 2.5 μm, the X / Y ratio calculated above is 706. In this case, there are 706 particles A and 1 particle B, which is also a level at which the particle diameter is sufficiently determined to be "uniform particles of 2.5 μm." Furthermore, when observing with an electron microscope such as a scanning electron microscope, the size of particles outside the selected field of view is not taken into consideration. In the above, the particle diameter of particle B was adopted as 11.1 μm, which is near the lower limit, but if this particle diameter is increased, X / Y will become even larger.

[0198] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following descriptions.

[0199] [Particle size distribution (laser diffraction scattering method)] The particle size distribution of the DMC catalyst particles before use in the polymerization reaction was measured by laser diffraction scattering method. Specifically, the DMC catalyst was dispersed in methanol, and the particle size distribution of the obtained dispersion was measured using a particle size distribution measuring device (SALD-2300 manufactured by Shimadzu Corporation), and a volume-based cumulative particle size distribution was obtained. From the obtained cumulative particle size distribution, D ＸThe content of particles having a particle diameter of 11 μm or more relative to the total volume of the DMC catalyst, and the content of particles having a particle diameter of 0.15 to 1 μm relative to the total volume of the DMC catalyst were determined.

[0200] [Particle size distribution (dynamic light scattering particle size distribution measurement)] The particle size distribution in the reaction solution containing the polyether compound and DMC catalyst produced in Examples 1 to 10 described below was measured by dynamic light scattering particle size distribution measurement. Specifically, a dynamic light scattering measurement device (Microtrac Bell Corporation particle size distribution measurement device: NANOTRAC WAVE II-UT151) was used, methanol was selected as the dispersion solvent, and the particle size distribution of the reaction solution containing the polyether compound and DMC catalyst was measured, and a cumulative particle size distribution based on light intensity and a cumulative particle size distribution based on light intensity in the range of 0.1 to 6.5 μm were obtained. From the obtained volume-based cumulative particle size distribution, d ５０ , the peak particle diameter and d from the cumulative particle size distribution based on light intensity in the range of 0.1 to 6.5 μm ５０ ' was asked.

[0201] [Hydroxyl value and hydroxyl value-equivalent molecular weight] The hydroxyl value was calculated in accordance with Method B of JIS K 1557-1: 2007. The hydroxyl value-equivalent molecular weight was calculated based on the formula "56,100 / hydroxyl value of polyether compound × number of hydroxyl groups in polyether compound".

[0202] [Mn, Mw, Mw / Mn] Several types of monodisperse polystyrenes with different degrees of polymerization were used as standard samples for molecular weight measurement. A gel permeation chromatograph analyzer HLC-8420GPC (product name of Tosoh Corporation) was used to measure the molecular weight of polystyrene. A calibration curve was created based on the relationship between the molecular weight and retention time of the polystyrene. A polyether compound, a polyether compound having a reactive silicon group, or a polyether compound having a polymerizable unsaturated group was diluted to 0.5% by mass with tetrahydrofuran and passed through a filter with a pore size of 0.5 μm to obtain a measurement sample. Using the obtained measurement sample, tetrahydrofuran was used as the solvent. The sample pump was set to a flow rate of 0.350 mL / min, the reference pump was set to a flow rate of 0.350 mL / min, the detector temperature was set to 40 ° C, the collection time was 6 to 15 minutes, and the peaks appearing at the collection time of 6 to 11 minutes were analyzed to determine Mn, Mw, and Mw / Mn.

[0203] [Total Unsaturation Degree] The total unsaturation degree of the polyether compound was measured in accordance with JIS K 1557-3:2007.

[0204] [Viscosity] The viscosity of the polyether compound, the polyether compound having a reactive silicon group, the polyether compound having a urethane bond, and the polyether compound having a polymerizable unsaturated group was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: RE85U) at a measurement temperature of 25°C and rotor No. 1.

[0205] [Filterability: Polyether Compound] A glass filter container was attached to the weighed container, and a 5.0 μm filter paper (PTFE filter, diameter 47 mm) was further attached. 100 g of the reaction solution containing the polyether compound and DMC catalyst obtained in Examples 1 to 10 described below was added to 100 g of methyl ethyl ketone as a dilution solvent, and the resulting sample was poured into the filter paper from the top and filtered. Natural filtration was allowed for 30 minutes, and the amount of filtered sample was measured. The larger the amount of filtered sample, the better the filterability. If the amount of filtered sample is 15.0 g or more, the filterability is considered to be good, and if the amount of filtered sample is less than 15.0 g, the filterability is considered to be poor.

[0206] [Filterability: Polyether Compound Having a Reactive Silicon Group] A glass filter container was attached to a weighed container, and a 5.0 μm filter paper (PTFE filter, diameter 25 mm) was further attached. 10 g of the reaction solution containing the polyether compound having a reactive silicon group and the DMC catalyst obtained in Examples 1A to 6A described below was added to 10 g of methyl ethyl ketone as a dilution solvent, and the resulting sample was poured into the filter paper from the top and filtered. Natural filtration was allowed for 30 minutes, and the amount of filtered sample was measured. The larger the amount of filtered sample, the better the filterability. If the amount of filtered sample is 3.00 g or more, the filterability is considered to be good, and if the amount of filtered sample is less than 3.00 g, the filterability is considered to be poor.

[0207] [Filterability: Polyether Compound Having Urethane Bonds] A glass filter container was attached to a weighed container, and a 5.0 μm filter paper (PTFE filter, diameter 25 mm) was further attached. 10 g of the reaction solution containing the polyether compound having a urethane bond and the DMC catalyst obtained in Examples 1B to 6B described below was added to 10 g of methyl ethyl ketone as a dilution solvent, and the resulting sample was poured into the filter paper from the top and filtered. The mixture was allowed to naturally filter for 30 minutes, and the amount of the filtered sample was weighed. The larger the amount of filtered sample, the better the filterability. If the amount of filtered sample was 2.00 g or more, the filterability was considered good, and if the amount of filtered sample was less than 2.00 g, the filterability was considered poor.

[0208] [Filterability: Polyether Compound Having a Polymerizable Unsaturated Group] A glass filter container was attached to a weighed container, and a 5.0 μm filter paper (PTFE filter, diameter 25 mm) was further attached. 10 g of the reaction solution containing the polyether compound having a polymerizable unsaturated group and the DMC catalyst obtained in Examples 1C to 6C described below was added to 10 g of methyl ethyl ketone as a dilution solvent, and the resulting sample was poured into the filter paper from the top and filtered. The mixture was allowed to naturally filter for 30 minutes, and the amount of the filtered sample was weighed. The larger the amount of filtered sample, the better the filterability. If the amount of filtered sample was 2.5 g or more, the filterability was considered good, and if the amount of filtered sample was less than 2.5 g, the filterability was considered poor.

[0209] [Number of Reactive Silicon Groups] The number of reactive silicon groups (silylation rate) contained in a polyether compound having a reactive silicon group was measured by the internal standard method of 1H-NMR.

[0210] [Stretching durability: Polyether compound having a reactive silicon group] The test was conducted in accordance with the fatigue resistance classification CR90 of the fatigue resistance test described in 5.22 of JIS A 1439:2016. Anodized aluminum whose surface had been treated with a primer (MP-2000, product name of Cemedine Co., Ltd.) was used as the adherend. The modulus (represented as "M50" in Table 4, unit: N / mm) was the stress at 50% elongation. ２ ), the tensile strength, which is the maximum cohesive strength (shown as "Tmax" in Table 4; unit: N / mm ２ The elongation at maximum point (shown as "Emax" in Table 4, unit: %) was measured. Cracks in the cured product near the adhesive interface between the adherend and the cured product were observed every 500 stretches, and the number of stretches (shown as "durability" in Table 4, unit: times) at which the cracks reached 2.5 mm or more was recorded. The higher the number of stretches, the better the stretch durability.

[0211] Tensile Properties: Polyether Compounds Having Reactive Silicon Groups: 1 part by mass of dibutyltin dilaurate was added to 100 parts by mass of polyether compounds A-1 to A-6 having reactive silicon groups obtained in Examples 1A to 6A. The mixture was thoroughly mixed and degassed under vacuum. The mixture was then coated onto a film having a thickness of 100 μm using an applicator and aged at 23°C and 50% relative humidity for 5 days and at 50°C for 3 days to obtain dumbbell-shaped No. 3 test pieces as cured products. Tensile tests were conducted using the test pieces at a pulling rate of 100 mm / min in accordance with JIS K 6251:2017, the tensile test method for vulcanized rubber. The stress at 50% elongation (shown as "M50" in Table 3, unit: MPa), maximum tensile strength (shown as "Tmax" in Table 3, unit: MPa), and maximum elongation (shown as "Emax" in Table 3, unit: %) were measured. The higher the M50 and Tmax values, the higher the tensile strength. The higher the Emax value, the better the elongation properties.

[0212] [Isocyanate Group Content] The isocyanate group content relative to the total mass of the polyether compound having a urethane bond was measured in accordance with JIS K 7301:1995.

[0213] <DMC Catalyst> Hereinafter, Production Example 1 is an example, and Production Examples 2 to 4 are comparative examples.

[0214] [Production Example 1] Propylene oxide (hereinafter also referred to as "PO") was polymerized with propylene glycol in the presence of a KOH catalyst, followed by dealkalization and purification to obtain a polyoxypropylene diol (hereinafter also referred to as "Polyol P1"). Polyol P1 had an average number of hydroxyl groups per molecule of 2 and an Mn of 1,000. A zinc chloride aqueous solution consisting of 10.2 g of zinc chloride and 10 g of water was prepared in a 500 mL flask. While stirring the zinc chloride aqueous solution at 300 rpm using an 80 mm diameter half-moon stirring blade, a potassium hexacyanocobaltate aqueous solution consisting of 4.2 g of potassium hexacyanocobaltate and 75 g of water was added dropwise to the zinc chloride aqueous solution at a constant rate over 90 minutes. During this time, the mixed solution in the flask was maintained at 40°C. After the dropwise addition of the potassium hexacyanocobaltate aqueous solution was completed, the mixture in the flask was stirred for an additional 30 minutes, after which a mixture consisting of 80 g of tert-butyl alcohol (hereinafter also referred to as "TBA"), 80 g of water, and 0.6 g of polyol P1 was added, and the mixture was stirred at 40°C for 30 minutes, and then at 60°C for an additional 60 minutes. The resulting mixture was filtered under pressure (0.25 MPa) using a 125 mm diameter circular filter plate and quantitative filter paper for fine particles (Advantec product name, No. 5C) to obtain a solid containing a composite metal cyanide complex (hereinafter referred to as the "filter cake"). The filter cake was transferred to a flask, and a mixture consisting of 36 g of TBA and 84 g of water was added. The mixture was stirred for 30 minutes, and then filtered under pressure under the same conditions as above. The obtained filter cake was transferred to a flask, and a mixture of 108 g of TBA and 12 g of water was added and stirred for 30 minutes to obtain a dispersion in which the composite metal cyanide complex catalyst was dispersed in the TBA-water mixture. 120 g of polyol P1 was added to the dispersion, and then volatile components were distilled off under reduced pressure at 80°C for 3 hours, and then further distilled off at 115°C for 3 hours to obtain TBA-DMC catalyst slurry A. The concentration of TBA-DMC catalyst contained in TBA-DMC catalyst slurry A was 5.33% by mass. The particle size distribution of the obtained TBA-DMC catalyst was measured. D Ｘ, the content of particles having a particle diameter of 11 μm or more relative to the total volume of the TBA-DMC catalyst, and the content of particles having a particle diameter of 0.15 to 1 μm relative to the total volume of the TBA-DMC catalyst, (D ９０ -D １０ ) / D ５０ , D ９０ / D １０ The results are shown in Table 1 (the same applies to Production Examples 2 to 4 below). Note that no particles with a particle size of 0.1 to 0.2 μm were observed. Furthermore, the particle size distribution of the TBA-DMC catalyst particles in the range of 0.1 to 10 μm measured by laser diffraction scattering was monomodal, with only one peak.

[0215] [Production Example 2] A 67% by mass aqueous zinc chloride solution was introduced into one branch conduit connected to a 600 mL first reactor, and a 5.5% by mass aqueous potassium hexacyanocobaltate solution was introduced into the other. The two solutions were combined at a branch just before the first reactor, and the combined solution was introduced into the first reactor. The zinc chloride aqueous solution was continuously fed at a rate of 12.3 g / min (6.83 mL / min assuming a specific gravity of 1.80 g / mL), and the potassium hexacyanocobaltate aqueous solution was continuously fed at a rate of 31.5 g / min (31.5 mL / min assuming a specific gravity of 1.0 g / mL) (Zn / Co atomic ratio = 11.5). The combined solution was stirred at 300 rpm in the first reactor, which was maintained at 40°C, using a stirring blade. The reaction solution from the first reactor was then introduced into a second reactor, which was maintained at 60°C, via a conduit. The average residence time in the first reactor was 15.7 minutes. This average residence time was calculated by dividing the volume of the portion of the first reactor where mixing and stirring was sufficient (600 mL) by the rate of the supplied liquid (38.2 mL / min). Simultaneously with the supply of the reaction liquid, a 50% by mass TBA aqueous solution was supplied to the second reactor, having an internal volume of 2,300 mL, at 63.2 g / min (71.0 mL / min assuming a specific gravity of 0.89 g / mL). The liquid in the second reactor was stirred at 300 rpm with a stirring blade, and the dispersion produced in the second reactor was pumped from the second reactor through a conduit into a storage tank and stored there. The average residence time of the liquid in the second reactor was 21.5 minutes. This average residence time was calculated by dividing the volume of the portion of the second reactor where mixing and stirring was sufficient (2,300 mL) by the rate of the supplied liquid (109.3 mL / min). The proportion of TBA in the steady state was 29.5% by mass relative to the amount of liquid in the second reactor. The amount of TBA introduced was calculated based on the amount of zinc hexacyanocobaltate (Zn ) converted from the amount of potassium hexacyanocobaltate used as a raw material. ３ [Co(CN) ６ ] ２) equivalent to approximately 9.7 times the mass of the dispersion liquid stored in the storage tank. Next, 1,100 g of the dispersion liquid stored in the storage tank was filtered, and a solid containing a composite metal cyanide complex (hereinafter referred to as the "filter cake") was obtained in approximately 25 minutes. 112 g of the filter cake and 500 g of a 30% by mass TBA aqueous solution were mixed at room temperature and stirred at 300 rpm for 1 hour, followed by filtration, and the filter cake containing the composite metal cyanide complex was separated in approximately 20 minutes. The TBA-DMC catalyst content in the filter cake was 28.0% by mass. 30 g of the filter cake was mixed with 90 g of polyol P1 and stirred at room temperature for 3 hours. Volatile components were then distilled off for 5 hours at 80°C under a reduced pressure of 0.005 MPa to obtain TBA-DMC catalyst slurry B. The concentration of the TBA-DMC catalyst contained in TBA-DMC catalyst slurry B was 8.53% by mass.

[0216] Production Example 3 A TBA-DMC catalyst slurry C was obtained in the same manner as in Production Example 1, except that the stirring blades used in stirring the aqueous zinc chloride solution were changed to half-moon blades with a diameter of 40 mm. The concentration of the TBA-DMC catalyst contained in TBA-DMC catalyst slurry C was 5.50 mass%.

[0217] Production Example 4 A TBA-DMC catalyst slurry D was obtained in the same manner as in Production Example 1, except that the dropwise addition time of the aqueous potassium hexacyanocobaltate solution was changed from 90 minutes to 10 minutes. The concentration of the TBA-DMC catalyst contained in TBA-DMC catalyst slurry D was 5.40 mass%.

[0218]

[0219] <Polyether Compound> Below, Examples 1, 2, 7, and 9 are working examples, and Examples 3 to 6, 8, and 10 are comparative examples.

[0220] Example 1: Propylene glycol was polymerized with PO in the presence of a KOH catalyst, followed by dealkalization and purification to obtain a polyoxypropylene diol (hereinafter also referred to as "Polyol P2"). Polyol P2 had an average number of hydroxyl groups per molecule of 2 and an Mn of 700. Using Polyol P2 as an initiator, 3,300 g of PO was polymerized in the presence of TBA-DMC catalyst slurry A to obtain polyether compound a-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 slurry A used was such that the TBA-DMC catalyst concentration was 44 ppm by mass relative to the total mass of polyether compound a-1. The hydroxyl value, hydroxyl value-equivalent molecular weight, Mn, Mw, Mw / Mn, total unsaturation, and viscosity of polyether compound a-1 are shown in Table 2 (the same applies to Examples 2 to 10). In addition, the d measured by dynamic light scattering particle size distribution measurement for the TBA-DMC catalyst ５０ , peak particle size in the range of 0.1 to 6.5 μm, d in the range of 0.1 to 6.5 μm ５０ The results are shown in Table 2 (hereinafter, the same applies to Examples 2 to 10). A filterability test was carried out using the obtained polyether compound a-1. The results are shown in Table 2 (hereinafter, the same applies to Examples 2 to 10).

[0221] Example 2 Polyether compound a-2 was obtained in the same manner as in Example 1, except that the amount of TBA-DMC catalyst slurry A used was changed so that the concentration of the TBA-DMC catalyst was 30 ppm by mass.

[0222] Example 3 Polyether compound a-3 was obtained in the same manner as in Example 1, except that TBA-DMC catalyst slurry B was used instead of TBA-DMC catalyst slurry A.

[0223] Example 4 Polyether compound a-4 was obtained in the same manner as in Example 3, except that the amount of TBA-DMC catalyst slurry B used was changed so that the concentration of the TBA-DMC catalyst was 30 ppm by mass.

[0224] Example 5 Polyether compound a-5 was obtained in the same manner as in Example 1, except that TBA-DMC catalyst slurry C was used instead of TBA-DMC catalyst slurry A.

[0225] Example 6 Polyether compound a-6 was obtained in the same manner as in Example 1, except that TBA-DMC catalyst slurry D was used instead of TBA-DMC catalyst slurry A.

[0226] Example 7 PO 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"). The average number of hydroxyl groups per molecule of polyol P3 was 1, and Mn was 400. Using polyol P3 as an initiator, 3,600 g of PO was polymerized in the presence of TBA-DMC catalyst slurry A to obtain polyether compound a-7. 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 slurry A used was such that the concentration of the TBA-DMC catalyst was 44 ppm by mass relative to the total mass of polyether compound a-7.

[0227] Example 8 Polyether compound a-8 was obtained in the same manner as in Example 7, except that TBA-DMC catalyst slurry B was used instead of TBA-DMC catalyst slurry A.

[0228] Example 9: Sorbitol was polymerized with PO in the presence of a KOH catalyst, followed by dealkalization and purification to obtain polyoxypropylene hexaol (hereinafter also referred to as "polyol P4"). The average number of hydroxyl groups per molecule of polyol P4 was 6, and the Mn was 874. Using polyol P4 as an initiator, 5,126 g of PO was polymerized in the presence of TBA-DMC catalyst slurry A to obtain polyether compound a-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 slurry A used was such that the concentration of the TBA-DMC catalyst was 44 ppm by mass relative to the total mass of polyether compound a-9.

[0229] Example 10 A polyether compound a-10 was obtained in the same manner as in Example 9, except that the TBA-DMC catalyst slurry B was used instead of the TBA-DMC catalyst slurry A.

[0230]

[0231] As shown in Table 2, it was found that Examples 1, 2, 7, and 9 had improved filterability compared to Examples 3 to 6, 8, and 10. In Examples 1 to 10, the d ５０ are similar (rather, d in Examples 4 to 6 ５０ The d in Examples 1 and 2 is ５０ Also, d in Example 8 is slightly smaller than ５０ The d in Example 7 is ５０ ), and it was found that most of the particles were extremely small. ５０ is extremely small compared to the pore size of the filter paper, which is 5.0 μm. ５０ The difference in filterability is due to the peak particle size in the range of 0.1 to 6.5 μm and d ５０ On the other hand, the peak particle size and d ５０ The difference between the peak particle diameter and d' is very small, and it is an unexpected effect that such a small difference would cause a difference in filterability. ５０ In order to control the D of the TBA-DMC catalyst before polymerization, ５０ It was also found that adjusting the content of particles having a particle size of 11 μm or more relative to the total volume of the TBA-DMC catalyst before polymerization was effective. Furthermore, the Mw / Mn of polyether compounds a-1, a-2, a-7, and a-9 was smaller than the Mw / Mn of polyether compounds a-3 to a-6, a-8, and a-10, and it was thought that this smaller Mw / Mn also contributed to the improvement of filterability.

[0232] <Polyether Compound Having a Reactive Silicon Group> Below, Examples 1A, 2A, and 7A are working examples, and Examples 3A to 6A and 8A are comparative examples.

[0233] [Example 1A] To 150 g of polyether compound a-1 in a composition containing polyether compound a-1 obtained in Example 1, a TBA-DMC catalyst, and a stabilizer, 0.0075 g of Neostan U-860 manufactured by Nitto Kasei Co., Ltd. and 14.5 g of 3-isocyanatopropyltriethoxysilane (NCO content: 20.5% by mass) were added and reacted at 80 ° C. for 3 hours. The NCO / OH molar ratio of the isocyanate amount of 3-isocyanatopropyltriethoxysilane to the amount of hydroxyl groups in polyether compound a-1 was set to 0.97. The reaction was terminated by confirming the absence of NCO-derived absorption by IR. The Mn, Mw, Mw / Mn, viscosity, and silylation rate of the resulting reactive silicon group-containing polyether compound A-1 are shown in Table 3 (the same applies to Examples 2A to 6A below). Filterability tests and evaluation of tensile properties were performed using the resulting reactive silicon group-containing polyether compound A-1. The results are shown in Table 3 (the same applies to Examples 2A to 6A below).

[0234] [Example 2A] Polyether compound A-2 having a reactive silicon group was obtained in the same manner as in Example 1A, except that the composition containing polyether compound a-2 obtained in Example 2, a TBA-DMC catalyst, and a stabilizer was used instead of the composition containing polyether compound a-1, a TBA-DMC catalyst, and a stabilizer.

[0235] [Example 3A] Polyether compound A-3 having a reactive silicon group was obtained in the same manner as in Example 1A, except that the composition containing polyether compound a-3 obtained in Example 3, a TBA-DMC catalyst, and a stabilizer was used instead of the composition containing polyether compound a-1, a TBA-DMC catalyst, and a stabilizer.

[0236] [Example 4A] Polyether compound A-4 having a reactive silicon group was obtained in the same manner as in Example 1A, except that the composition containing polyether compound a-4 obtained in Example 4, a TBA-DMC catalyst, and a stabilizer was used instead of the composition containing polyether compound a-1, a TBA-DMC catalyst, and a stabilizer.

[0237] [Example 5A] Polyether compound A-5 having a reactive silicon group was obtained in the same manner as in Example 1A, except that the composition containing polyether compound a-5 obtained in Example 5, a TBA-DMC catalyst, and a stabilizer was used instead of the composition containing polyether compound a-1, a TBA-DMC catalyst, and a stabilizer.

[0238] [Example 6A] Polyether compound A-6 having a reactive silicon group was obtained in the same manner as in Example 1A, except that a composition containing polyether compound a-6 obtained in Example 6, a TBA-DMC catalyst, and a stabilizer was used instead of the composition containing polyether compound a-1, a TBA-DMC catalyst, and a stabilizer.

[0239]

[0240] [Example 7A] Using polyol P2 as an initiator, 14,300 g of PO was polymerized in the presence of TBA-DMC catalyst slurry A to obtain polyether compound a-11. The polymerization was carried out with the addition of 0.1 mass% of Irganox 1076 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst slurry A used was such that the TBA-DMC catalyst concentration was 50 ppm by mass relative to the total mass of polyether compound a-11. The hydroxyl value, hydroxyl value-equivalent molecular weight, Mn, Mw, Mw / Mn, total unsaturation, and viscosity of polyether compound a-11 are shown in Table 4 (the same applies to Example 8A below).

[0241] A methanol solution of 1.05 molar equivalents of sodium methoxide was added relative to the hydroxyl groups of polyether compound a-11 in a composition containing polyether compound a-11, a TBA-DMC catalyst, and a stabilizer, to alcoholate polyether compound a-11. Next, the methanol was distilled off by heating under reduced pressure, and an excess amount of allyl chloride relative to the amount of hydroxyl groups in polyether compound a-11 was added to convert the terminal groups to allyloxy groups. Next, in the presence of hexachloroplatinic (IV) acid hexahydrate, 0.77 molar equivalents of dimethoxymethylsilane were added relative to the converted allyloxy groups of polyether compound a-11, and the reaction was carried out at 70 °C for 5 hours to obtain polyether compound A-7 having reactive silicon groups. The Mn, Mw, Mw / Mn, and silylation rate of the resulting polyether compound A-7 having reactive silicon groups are shown in Table 4 (the same applies to Example 8A below).

[0242] [Example 8A] Polyether compound a-12 and polyether compound A-8 having a reactive silicon group were obtained in the same manner as in Example 7A, except that in the production of polyether compound a-11, TBA-DMC catalyst slurry B was used instead of TBA-DMC catalyst slurry A.

[0243]

[0244] (Other Components) The additives listed in Tables 5 and 6 are as follows. White Glazing CCR: Colloidal calcium carbonate, product name of Shiraishi Kogyo Co., Ltd. Whiten SB: Heavy calcium carbonate, product name of Shiraishi Kogyo Co., Ltd. R820: Titanium oxide, product name of Ishihara Sangyo Kaisha, Ltd. PREMINOL S 4012: High molecular weight polyol having two hydroxyl groups per molecule and Mn of 13,000, product name of AGC. Sanso Cizer EPS: 4,5-epoxycyclohexane-1,2-dicarboxylate-di-2-ethylhexyl, product name of New Japan Chemical Co., Ltd. Disparlon 305: Hydrogenated castor oil-based thixotropic agent, product name of Kusumoto Chemicals Co., Ltd. Balloon 80GCA: Organic balloon, product name of Matsumoto Yushi Co., Ltd. M309: Aronix M-309: Light-curing resin, product name of Toagosei Co., Ltd. KBM-403: 2-glycidyloxypropyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd. IRGANOX1135: Hindered phenol-based antioxidant, product name of BASF Corporation. TINUVIN326: Benzotriazole-based ultraviolet absorber, product name of BASF Corporation. Tung oil: Air-oxidation curing compound, product of Kimura Corporation. Stannoct: Stannous octoate, product name of Yoshitomi Pharmaceutical Co., Ltd. Laurylamine: Reagent, product of Junsei Chemical Co., Ltd. DINP: Sanso Cizer DINP, diisononyl phthalate, product name of New Japan Chemical Co., Ltd. Glomax LL: Calcined kaolin, product name of Takehara Chemical Industry Co., Ltd.

[0245]

[0246]

[0247] <Preparation of Curable Composition> A base composition was prepared by mixing 100 parts by mass of polyether compounds A-7 and A-8 having reactive silicon groups obtained in Examples 7A and 8A with additives in the amounts (parts by mass) shown in Table 5. This base composition was mixed with a curing agent composition in the amount shown in Table 6, and stretch durability was evaluated. The results are shown in Table 4.

[0248] As shown in Table 3, it was found that Examples 1A and 2A had improved filterability compared to Examples 3A to 6A. In Examples 1A to 6A, the d ５０are similar (rather, d in Examples 4 to 6 ５０ The d in Examples 1 and 2 is ５０ ), and it was found that most of the particles were extremely small. In addition, since the TBA-DMC catalyst does not contribute to the silylation reaction, it is thought that the particle size in the reaction solution during the production of polyether compounds having reactive silicon groups is also of a similar order. ５０ is extremely small compared to the pore size of the filter paper, which is 5.0 μm. ５０ The difference in filterability is due to the peak particle size in the range of 0.1 to 6.5 μm and d ５０ On the other hand, in Examples 1A, 2A, and 3A to 6A, the peak particle size and d ５０ The difference between the peak particle diameter and d' is very small, and it is an unexpected effect that such a small difference would cause a difference in filterability. ５０ In order to control the D of the TBA-DMC catalyst before the polymerization reaction, ５０ It was also found that adjusting the content of particles with a particle size of 11 μm or more relative to the total volume of the TBA-DMC catalyst before the polymerization reaction was effective. Furthermore, it was found that Examples 1A and 2A provided cured products with superior strength and elongation compared to Examples 3A to 6A. Furthermore, as shown in Table 4, it was found that Example 7A provided cured products with improved stretch durability compared to Example 8A.

[0249] <Polyether Compound Having Urethane Bond> Below, Examples 1B and 2B are working examples, and Examples 3B to 6B are comparative examples.

[0250] [Example 1B] To 150 g of polyether compound a-1 in a composition containing polyether compound a-1 obtained in Example 1, a TBA-DMC catalyst, and a stabilizer, 0.015 g of dibutyltin dilaurate and 16.6 g of isophorone diisocyanate (NCO content: 37.8% by mass) were added and reacted at 80°C for 2 hours. The NCO / OH molar ratio of the isocyanate content of isophorone diisocyanate to the hydroxyl group content of polyether compound a-1 was set to 2.0. The reaction was terminated upon confirming that the NCO content of the resulting polyether compound B-1 having urethane bonds reached the theoretical value of approximately 1.9% by mass. The isocyanate group content and viscosity of the resulting polyether compound B-1 having urethane bonds are shown in Table 7 (the same applies hereinafter to Examples 2B to 6B). A filterability test was conducted using the resulting polyether compound B-1 having urethane bonds. The results are shown in Table 7 (the same applies hereinafter to Examples 2B to 6B).

[0251] Example 2B Polyether compound B-2 having a urethane bond was obtained in the same manner as in Example 1B, except that the composition containing polyether compound a-2 obtained in Example 2, a TBA-DMC catalyst, and a stabilizer was used instead of the composition containing polyether compound a-1, a TBA-DMC catalyst, and a stabilizer.

[0252] [Example 3B] Polyether compound B-3 having a urethane bond was obtained in the same manner as in Example 1B, except that a composition containing polyether compound a-3 obtained in Example 3, a TBA-DMC catalyst, and a stabilizer was used instead of the composition containing polyether compound a-1, a TBA-DMC catalyst, and a stabilizer.

[0253] Example 4B Polyether compound B-4 having a urethane bond was obtained in the same manner as in Example 1B, except that a composition containing polyether compound a-4 obtained in Example 4, a TBA-DMC catalyst, and a stabilizer was used instead of the composition containing polyether compound a-1, a TBA-DMC catalyst, and a stabilizer.

[0254] [Example 5B] Polyether compound B-5 having a urethane bond was obtained in the same manner as in Example 1B, except that a composition containing polyether compound a-5 obtained in Example 5, a TBA-DMC catalyst, and a stabilizer was used instead of the composition containing polyether compound a-1, a TBA-DMC catalyst, and a stabilizer.

[0255] Example 6 Polyether compound B-6 having a urethane bond was obtained in the same manner as in Example 1B, except that a composition containing polyether compound a-6 obtained in Example 6, a TBA-DMC catalyst, and a stabilizer was used instead of the composition containing polyether compound a-1, a TBA-DMC catalyst, and a stabilizer.

[0256]

[0257] As shown in Table 7, it was found that Examples 1B and 2B had improved filterability compared to Examples 3B to 6B. In Examples 1B to 6B, the d ５０ are similar (rather, d in Examples 4 to 6 ５０ The d in Examples 1 and 2 is ５０ It was found that most of the particles were extremely small. Furthermore, since the TBA-DMC catalyst does not contribute to the urethane reaction, the particle size in the reaction solution during the production of a polyether compound having a urethane bond is also thought to be of a similar order of magnitude. ５０ is extremely small compared to the pore size of the filter paper, which is 5.0 μm. ５０ The difference in filterability is due to the peak particle size in the range of 0.1 to 6.5 μm and d ５０ On the other hand, in Examples 1B, 2B, and 3B to 6B, the peak particle size and d ５０ The difference between the peak particle diameter and d ５０In order to control the D of the TBA-DMC catalyst before the polymerization reaction, ５０ It has also been found that adjusting the content of particles having a particle size of 11 μm or more relative to the total volume of the TBA-DMC catalyst before the polymerization reaction is effective. Furthermore, the Mw / Mn of polyether compounds a-1 and a-2 is smaller than the Mw / Mn of polyether compounds a-3 to a-6, and therefore it is thought that the Mw / Mn of polyether compounds B-1 and B-2 having urethane bonds is also smaller than the Mw / Mn of polyether compounds B-3 to B-6 having urethane bonds, and this smaller Mw / Mn is also thought to contribute to improved filterability.

[0258] <Polyether Compound Having a Polymerizable Unsaturated Group> Below, Examples 1C and 2C are working examples, and Examples 3C to 6C are comparative examples.

[0259] [Example 1C] To 150 g of polyether compound a-1 in a composition containing polyether compound a-1 obtained in Example 1, a TBA-DMC catalyst, and a stabilizer, 0.015 g of dibutyltin dilaurate and 10.3 g of 2-isocyanatoethyl acrylate (NCO content: 29.8% by mass) were added and reacted at 80°C for 2 hours. The molar ratio of the isocyanate content of 2-isocyanatoethyl acrylate to the hydroxyl group content of polyether compound a-1, NCO / OH, was set to 0.97. The reaction was terminated upon confirmation of the absence of NCO-derived absorption by IR. The Mn, Mw, Mw / Mn, and viscosity of the obtained polyether compound C-1 having a polymerizable unsaturated group are shown in Table 8 (the same applies hereinafter to Examples 2C to 6C). A filterability test was conducted using the obtained polyether compound C-1 having a polymerizable unsaturated group. The results are shown in Table 8 (the same applies hereinafter to Examples 2C to 6C).

[0260] [Example 2C] Polyether compound C-2 having a polymerizable unsaturated group was obtained in the same manner as in Example 1C, except that the composition containing polyether compound a-2 obtained in Example 2, a TBA-DMC catalyst, and a stabilizer was used instead of the composition containing polyether compound a-1, a TBA-DMC catalyst, and a stabilizer.

[0261] [Example 3C] Polyether compound C-3 having a polymerizable unsaturated group was obtained in the same manner as in Example 1C, except that a composition containing polyether compound a-3 obtained in Example 3, a TBA-DMC catalyst, and a stabilizer was used instead of the composition containing polyether compound a-1, a TBA-DMC catalyst, and a stabilizer.

[0262] Example 4C Polyether compound C-4 having a polymerizable unsaturated group was obtained in the same manner as in Example 1C, except that a composition containing polyether compound a-4 obtained in Example 4, a TBA-DMC catalyst, and a stabilizer was used instead of the composition containing polyether compound a-1, a TBA-DMC catalyst, and a stabilizer.

[0263] [Example 5C] Polyether compound C-5 having a polymerizable unsaturated group was obtained in the same manner as in Example 1C, except that a composition containing polyether compound a-5 obtained in Example 5, a TBA-DMC catalyst, and a stabilizer was used instead of the composition containing polyether compound a-1, a TBA-DMC catalyst, and a stabilizer.

[0264] [Example 6C] Polyether compound C-6 having a polymerizable unsaturated group was obtained in the same manner as in Example 1C, except that a composition containing polyether compound a-6 obtained in Example 6, a TBA-DMC catalyst, and a stabilizer was used instead of the composition containing polyether compound a-1, a TBA-DMC catalyst, and a stabilizer.

[0265]

[0266] As shown in Table 8, it was found that Examples 1C and 2C had improved filterability compared to Examples 3C to 6C. In Examples 1C to 6C, d ５０ are similar (rather, d in Examples 4 to 6 ５０ The d in Examples 1 and 2 is ５０ ), and it was found that most of the particles were extremely small. In addition, since the TBA-DMC catalyst does not contribute to the urethane reaction, it is thought that the particle size in the reaction solution during the production of polyether compounds having urethane bonds is also of a similar order. ５０is extremely small compared to the pore size of the filter paper, which is 5.0 μm. ５０ The difference in filterability is due to the peak particle size in the range of 0.1 to 6.5 μm and d ５０ On the other hand, in Examples 1C, 2C, and 3C to 6C, the peak particle size and d ５０ The difference between the peak particle diameter and d' is very small, and it is an unexpected effect that such a small difference would cause a difference in filterability. ５０ In order to control the D of the TBA-DMC catalyst before polymerization, ５０ It has been found that adjusting the content of particles having a particle size of 11 μm or more relative to the total volume of the TBA-DMC catalyst before polymerization is effective. Furthermore, the Mw / Mn of polyether compounds C-1 and C-2 having polymerizable unsaturated groups is smaller than the Mw / Mn of polyether compounds C-3 to C-6 having polymerizable unsaturated groups, and this smaller Mw / Mn is also thought to contribute to improved filterability.

[0267] Use of the composite metal cyanide complex catalyst of the present invention increases the filterability of the resulting polyether compounds, polyether compounds having reactive silicon groups, polyether compounds having urethane bonds, and polyether compounds having polymerizable unsaturated groups, and therefore has high industrial applicability.

Claims

1. A particulate composite metal cyanide complex catalyst, wherein the composite metal cyanide complex catalyst has a 50% cumulative volume particle diameter of 0.01 to 4.0 μm as determined from a volume-based cumulative particle size distribution obtained by a laser diffraction scattering method, and the content of particles having a particle diameter of 11 μm or more relative to the total volume of the composite metal cyanide complex catalyst is 10% by volume or less.

2. The double metal cyanide complex catalyst according to claim 1, wherein the content of particles having a particle size of 11 μm or more relative to the total volume of the double metal cyanide complex catalyst is 5% by volume or less.

3. A method for producing a polyether compound, which comprises polymerizing an alkylene oxide with an initiator having active hydrogen in the presence of the composite metal cyanide complex catalyst according to claim 1 or 2.

4. The method for producing a polyether compound according to claim 3, wherein the number average molecular weight of the polyether compound is 500 to 100,000.

5. The method for producing a polyether compound according to claim 3 or 4, wherein the molecular weight distribution of the polyether compound is 1.00 to 1.

15.

6. The method for producing a polyether compound according to any one of claims 3 to 5, wherein the polyether compound has a total degree of unsaturation of 0.001 to 0.040 meq / g.

7. The method for producing a polyether compound according to any one of claims 3 to 6, wherein the amount of the composite metal cyanide complex catalyst used is 1 to 200 ppm by mass relative to the total mass of the polyether compound.

8. A method for producing a polyether compound having a reactive silicon group, comprising obtaining a composition containing a polyether compound by the method for producing a polyether compound according to any one of claims 3 to 7, and converting the hydroxyl groups of the polyether compound in the composition into groups having a reactive silicon group represented by the following formula 1: -SiR ａ X ３－ａ 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.

9. A method for producing a polyether compound having a urethane bond, comprising obtaining a composition containing a polyether compound by the method for producing a polyether compound according to any one of claims 3 to 7, and reacting the polyether compound in the obtained composition with a polyisocyanate.

10. A method for producing a polyether compound having a polymerizable unsaturated group, comprising obtaining a composition containing a polyether compound by the method for producing a polyether compound according to any one of claims 3 to 7, and converting a hydroxyl group of the polyether compound in the composition into a group having a polymerizable unsaturated group.

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