Composition

Abstract

Provided is a composition comprising a polyether compound and a composite metal cyanide complex catalyst, which can improve filterability in a polyether compound purification process. [Solution] A composition comprising a polyether compound and a composite metal cyanide complex catalyst, wherein the composite metal cyanide complex catalyst is in particulate form, and the 50% cumulative light intensity particle size of the composition calculated from a 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 1.0 μm or less.

Description

[Technical field]

[0001] The present invention relates to a composition. [Background technology]

[0002] Polyether compounds are used as raw materials for adhesives, paints, sealants, coatings, etc. Polyether compounds are produced by polymerizing alkylene oxides with an initiator having active hydrogen. Composite 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 by the DFT method based on the specific surface area is 0.05 × 10 -3 ~10×10 -3 It is disclosed that it is cc / g. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5109093 Summary of the Invention [Problem to be solved by the invention]

[0005] When the polyether compound is used for applications such as the above-mentioned adhesives and coatings, solid impurities in a composition containing the polyether compound may cause problems. Therefore, after the polyether compound is produced, purification by filtration may be performed 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 there was a problem in that the filtration speed was slow and clogging occurred.

[0006] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a composition containing a polyether compound and a double metal cyanide complex catalyst, which can improve filterability in a polyether compound purification process. [Means for solving the problem]

[0007] The present invention provides the following means. [1] A composition comprising a polyether compound and a double metal cyanide complex catalyst, wherein the double metal cyanide complex catalyst is in a particulate form, and the composition has a 50% cumulative light intensity particle size of 1.0 μm or less, as determined from a cumulative particle size distribution based on light intensity in a range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement. [2] The composition according to [1], wherein the peak particle size of the composition calculated from a cumulative particle size distribution based on light intensity in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement is 1.0 μm or less. [3] The composition according to [1] or [2], wherein the 50% cumulative volume particle size of the composition is 0.1 to 100 nm, as determined from a volume-based cumulative particle size distribution obtained by dynamic light scattering particle size distribution measurement. [4] The composition according to any one of [1] to [3], wherein the polyether compound has a number average molecular weight of 1,000 to 100,000. [5] The composition according to any one of [1] to [4], wherein the molecular weight distribution of the polyether compound is 1.00 to 1.15. [6] The composition according to any one of [1] to [5], wherein the polyether compound has a total degree of unsaturation of 0.001 to 0.040 meq / g. [7] The composition according to any one of [1] to [6], wherein the content of the double metal cyanide complex catalyst relative to the total mass of the polyether compound is 1 to 200 ppm by mass. Effect of the Invention

[0008] According to the present invention, it is possible to provide a composition containing a polyether compound and a double metal cyanide complex catalyst, which can improve filterability in a purification process of the polyether compound. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The meanings and definitions of terms used in this specification are as follows: A numerical range expressed by "to" means that the numerical values ​​before and after the "to" are the lower and upper limits of the numerical range.

[0010] 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 It indicates 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, which is taken as 100%. The particle size distribution in the composition 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 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 dynamic light scattering particle size distribution measurement, which is taken as 100%. Also, d represents the X% cumulative light intensity particle size obtained from the cumulative particle size distribution based on light intensity in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement. X '. d 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 set to 100%.

[0011] The "unit" constituting a polyether compound or the like means an atomic group formed directly by polymerization of a monomer. The term "main chain" refers to a polymer chain formed by polymerization of two or more monomers. In the polyether compound, the polyether compound having a reactive silicon group, and the polyether compound having a polymerizable unsaturated group described below, the "main chain" refers to a residue obtained by removing active hydrogen from an initiator and a portion including a repeating unit based on an alkylene oxide (polyoxyalkylene chain). The polyether compound, the polyether compound having a reactive silicon group, and the polyether compound having a polymerizable unsaturated group are polymers consisting of a main chain and terminal groups. The "end group" of the polyether compound, the polyether compound having a reactive silicon group, and the polyether compound having a polymerizable unsaturated group means an atomic group containing the oxygen atom closest to the molecular end among the oxygen atoms in the polyoxyalkylene chain. However, when the atomic group contains a residue of an initiator, it is not considered as an end group, but as a part of the main chain. The "number of end groups" in the polyether compound, the polyether compound having a reactive silicon group, and the polyether compound having a polymerizable unsaturated group is the same number as the number of active hydrogens of the initiator 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 term "active hydrogen" refers to a hydrogen atom derived from the above active hydrogen-containing group and a hydrogen atom derived from a hydroxyl group of water.

[0012] 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 group of the polyether compound having a reactive silicon group. Specifically, the silylation rate is calculated by the following formula: Silylation rate (%) = 100 × number of reactive silicon groups / [number of reactive silicon groups + number of hydroxyl groups + number of isocyanate groups + (number of carbon-carbon double bonds) + (number of carbon-carbon triple bonds) × 2] The value of the silylation rate can be measured by NMR analysis. It may also 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 group is introduced to the terminal group of the polyether compound by the silylating agent described later. However, in this case, a diisocyanate compound is used as the polyisocyanate compound in the method (c1) described later. The term "silylating agent" refers to a compound having a reactive silicon group and a functional group that reacts with an active hydrogen-containing group, an unsaturated group, or an isocyanate group. The content of isocyanate groups relative to the total mass of the prepolymer described below is a value measured in accordance with JIS K 7301:1995.

[0013] In this specification, the number average molecular weight (Mn) and the 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 with known molecular weights. The molecular weight distribution (Mw / Mn) is the ratio of Mw to Mn.

[0014] The "hydroxyl value" of the 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 calculated by: 56,100 / hydroxyl value of polyether compound x number of hydroxyl groups of polyether compound (number of active hydrogens of initiator). When two or more polyether compounds with different numbers of hydroxyl groups are contained, the number of hydroxyl groups of the polyether compound is the average number of hydroxyl groups.

[0015] The total degree of unsaturation of a polyether compound can be measured in accordance with JIS K 1557-3:2007. The viscosity of the polyether compound, the polyether compound having a reactive silicon group, the prepolymer, and the polyether compound having a polymerizable unsaturated group can be measured using an E-type viscometer.

[0016] ≪Composition≫ The composition of the present embodiment includes a polyether compound and a composite metal cyanide complex catalyst. The 50% cumulative light intensity particle size calculated from the cumulative particle size distribution based on light intensity in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement of the composition is 1.0 μm or less. In this way, it is considered that the filterability can be improved in the purification process of the polyether compound by controlling the particle size and particle size distribution in the composition.

[0017] <Polyether compounds> 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 is simply referred to as a "monomer unit", for example, a repeating unit based on alkylene oxide is referred to as an "alkylene oxide unit".) In the case of a polymer chain having two or more types of alkylene oxide units, the alkylene oxide units may form a block polymer or a random polymer. Examples of the oxyalkylene chain include a polymer chain having an ethylene oxide unit, a polymer chain having a propylene oxide unit, a polymer chain having an ethylene oxide unit and a propylene oxide unit, a polymer chain consisting of an ethylene oxide unit, a polymer chain consisting of a propylene oxide unit, a polymer chain consisting of a butylene oxide unit, a polymer chain consisting of a tetramethylene oxide unit, a polymer chain consisting of an ethylene oxide unit and a propylene oxide unit, and a polymer chain consisting of a propylene oxide unit and a butylene oxide unit. A polymer chain having an ethylene oxide unit, a polymer chain having a propylene oxide unit, a polymer chain having an ethylene oxide unit and a propylene oxide unit, a polymer chain consisting of a propylene oxide unit, and a polymer chain consisting of an ethylene oxide unit and a propylene oxide unit are preferred, and a polymer chain consisting of a propylene oxide unit is 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.

[0018] The Mn of the polyether compound is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 60,000. When the Mn is equal to or greater than the lower limit, sufficient flexibility is imparted when the polyether compound is used as an adhesive or coating material, and good elongation properties are easily obtained. When the Mn is equal to or less than the upper limit, the viscosity of the polyether compound can be kept low, making the polyether compound easy to handle.

[0019] 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 more than the lower limit, sufficient curing is easily obtained when 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 easily obtained.

[0020] The hydroxyl value-based molecular weight of the polyether compound is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 60,000. When the hydroxyl value-based 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 easily obtained. When the hydroxyl value-based molecular weight is equal to or less than the upper limit, the viscosity of the polyether compound can be kept low, making it easy to handle.

[0021] The Mw of the polyether compound is preferably 1,200 to 120,000, more preferably 2,000 to 90,000, and even more preferably 3,000 to 70,000. When the Mw is equal to or greater than the lower limit, sufficient flexibility is imparted when used as an adhesive or coating material, and good elongation properties are easily 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.

[0022] The Mw / Mn of the polyether compound is preferably from 1.00 to 1.15, more preferably from 1.00 to 1.12, and even more preferably from 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.

[0023] 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 further preferably from 0.003 to 0.010 meq / g.

[0024] The viscosity of the polyether compound at a measurement temperature of 25° C. is preferably from 100 to 30,000 mPa·s, more preferably from 200 to 20,000 mPa·s, and even more preferably from 400 to 10,000 mPa·s.

[0025] <Double metal cyanide complex catalyst> The composite metal cyanide complex catalyst is in the form of particles. The composite metal cyanide complex catalyst before use as a polymerization catalyst preferably 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. 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 before use as a polymerization catalyst is preferably 10 volume % or less. Hereinafter, the composite metal cyanide complex catalyst is also referred to as the "DMC catalyst", the composite metal cyanide complex catalyst before use as a polymerization catalyst is also referred to as the "DMC catalyst (F)", and the DMC catalyst contained in the composition of the present embodiment is also referred to as the "DMC catalyst (U)".

[0026] The 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 crystal water (coordination water, etc.) contained in the crystal. In addition, the catalyst may contain impurities that are unavoidable during production and moisture other than crystal water that are contained in trace amounts in the metal salts and metal compounds. The metal halide salt, transition metal cyanide compound, and organic ligand that can be used are those known in the production of DMC catalysts.

[0027] The DMC catalyst is believed to be represented by Formula 1 below. M 1 a1 [M 2 (CN) b1 ] c1 d1(M 1 e1 X 1 f1 )·g1(Ligand)·h1(H 2 O) Equation 1 In the above formula 1, 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 2is 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 are electrically neutral.

[0028] The above M 1 Examples of such elements include Zn(II), Fe(II), Fe(III), Co(II), Ni(II), Al(III), Sr(II), Mn(II), Cr(III), Cu(II), Sn(II), Pb(II), Mo(IV), Mo(VI), W(IV) and W(VI). The above M 2 Examples of such elements include Co(III), Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), V(IV), and V(V). Above X 1 Examples of the fluorine atom include Cl, Br, and I. M 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 1 In terms of the interatomic distance, it is more preferable that the zinc oxide layer contains at least one selected from zinc chloride and zinc bromide. Examples of the ligand (organic ligand) include alcohol, ether, ester, aldehyde, ketone, amide, nitrile and sulfide, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and polyoxyalkylene poly(or mono)ol. The organic ligand may be one type or two or more types. 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. As the organic ligand, tert-butyl alcohol is preferable.

[0029] A preferred example of the DMC catalyst is zinc hexacyanocobaltate (Zn hexacyanocobaltate) 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 to be the case.

[0030] The DMC catalyst is zinc hexacyanocobaltate (Zn 3 [Co(CN) 6 ] 2 ) complex is preferred. The complex may be coordinated with water and zinc chloride.

[0031] D of DMC catalyst (F) particles 50is preferably 0.01 to 4.0 μm, more preferably 0.05 to 3.5 μm, even more preferably 0.1 to 3.0 μm, particularly preferably 0.1 μm or more and less than 3.0 μm, and most preferably 0.5 to 2.5 μm. 50 When the above lower limit is exceeded, the catalyst has sufficient catalytic activity as a polymerization catalyst for alkylene oxide. 50 When the content is equal to or less than the upper limit, the filterability is likely to be improved in the purification step of the polyether compound.

[0032] The content of particles having a particle size of 11 μm or more relative to the total volume of the DMC catalyst (F) is preferably 10 vol% or less, more preferably 5 vol% or less, even more preferably 4 vol% or less, and particularly preferably 3 vol% or less. When the content of particles having a particle size of 11 μm or more is equal to or less than the upper limit, the filterability in the purification step of the polyether compound is likely to be improved.

[0033] The content of particles having a particle diameter of 0.15 to 1 μm relative to the total volume of the DMC catalyst (F) is preferably 5 vol% or more, more preferably 7 vol% or more, and even more preferably 10 vol% or more. The upper limit is not particularly limited, but may be, for example, 50 vol% or less, or 30 vol% or less. When the content of particles having a particle diameter of 0.15 to 1 μm is equal to or more than the lower limit, the filterability in the purification step of the polyether compound is likely to be improved.

[0034] The content of particles having a particle size of 0.1 to 0.2 μm relative to the total volume of the DMC catalyst (F) is preferably 3 vol% or less, more preferably 1 vol% or less, and even more preferably 0 vol%. When the content of particles having a particle size of 0.1 to 0.2 μm is equal to or less than the above upper limit, filterability is likely to be improved in the purification step of the polyether compound.

[0035] D of DMC catalyst (F) particles 10 is preferably 0.01 to 2.0 μm, more preferably 0.05 to 1.8 μm, and further preferably 0.1 to 1.5 μm. 10When the amount of the alkylene oxide is within the above range, the alkylene oxide 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 is likely to be improved.

[0036] D of DMC catalyst (F) particles 90 is preferably 1 to 15 μm, more preferably 1.5 to 10 μm, and further preferably 2 to 8 μm. 90 When the amount of the alkylene oxide is within the above range, the alkylene oxide 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 is likely to be improved.

[0037] The particle size distribution of the DMC catalyst (F) particles in the range of 0.1 to 10 μm is preferably unimodal, i.e., has only one peak. A unimodal distribution tends to improve filterability in the purification step of the polyether compound. Being unimodal means that the particle size distribution in the range of 0.1 to 10 μm has only one peak.

[0038] DMC catalyst (F) (D 90 -D 10 ) / D 50 is preferably 0.1 to 3.0, more preferably 0.5 to 2.5, further 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 (F) particles is monomodal, (D 90 -D 10 ) / D 50 is likely to be below the upper limit. (D 90 -D 10 ) / D 50 When the amount of the alkylene oxide is within the above range, the alkylene oxide 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 is likely to be improved.

[0039] DMC catalyst (F) 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. When the particle size distribution of the DMC catalyst (F) particles is narrow, D 90 / D 10 is likely to be 4.5 or less. D 90 / D 10 When the amount of the alkylene oxide is within the above range, the alkylene oxide 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 is likely to be improved.

[0040] The DMC catalyst (F) may be used, for example, in the above-mentioned solid state for the production of a polyether compound, or may be used in the state of a slurry in which particles of the DMC catalyst (F) are dispersed in a dispersion medium (hereinafter also referred to as a "slurry catalyst") for the production of a polyether compound.

[0041] The slurry catalyst contains the DMC catalyst (F) and a dispersion medium. The slurry catalyst preferably contains the DMC catalyst (F) and a dispersion medium, and may also contain impurities and moisture that are unavoidable during production.

[0042] As the dispersion medium of the slurry catalyst, a known organic solvent for slurry catalysts can be used. For example, a hardly volatile hydroxy compound described in Japanese Patent No. 3194255 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 8000, and a compound having an alcoholic hydroxyl group such as a polyether compound is preferred. As the dispersion medium for the slurry catalyst, a polyether compound is preferred since it does not become an impurity for the product (polyether compound) of polymerization of alkylene oxide. The Mn of the polyether compound used as the dispersion medium is preferably from 100 to 8,000, more preferably from 600 to 3,000. When Mn is at least the above lower limit value, it is less likely to be a catalyst poison, and when it is at most the above upper limit value, the handling property of the slurry catalyst is excellent. Also, an initiator for polymerizing alkylene oxide may be used as part of the dispersion medium.

[0043] The dispersion medium of the slurry catalyst preferably contains substantially no water. Specifically, the water content of the dispersion medium is preferably 500 mass ppm or less, more preferably 200 mass ppm or less, and may even be an undetectable amount. The water content of the dispersion medium is the water content measured by the Karl Fischer measurement method.

[0044] The content of the DMC catalyst (F) relative to the total mass of the slurry catalyst is, for example, preferably from 0.001 to 60% by mass, more preferably from 0.003 to 50% by mass, and still more preferably from 0.006 to 30% by mass. In particular, when the dispersion medium is a polyether compound, the content of the DMC catalyst (F) relative to the total mass of the slurry catalyst is preferably from 0.1 to 60% by mass, more preferably from 0.5 to 40% by mass, and still more preferably from 1 to 30% by mass. In particular, when the dispersion medium contains the above initiator, the content of the DMC catalyst (F) relative to the total mass of the slurry catalyst is preferably from 0.003 to 0.02% by mass, more preferably from 0.004 to 0.015% by mass, and still more preferably from 0.006 to 0.01% by mass.

[0045] <Method for producing DMC catalyst (F)> The DMC catalyst (F) of the present embodiment can be produced by coordinating an organic ligand to a reaction product obtained by reacting a metal halide salt and a transition metal cyanide compound. Further, after synthesizing the DMC catalyst (F), the water content of the DMC catalyst (F) may be adjusted.

[0046] A metal halide salt and a transition metal cyanide compound are reacted in the presence of water to obtain a reaction product, and an organic ligand is coordinated in the presence of water to obtain a mixture containing DMC catalyst (F) and water. Impurities and water may be removed from the resulting mixture to reduce the moisture content of the resulting solid to a predetermined range, thereby obtaining DMC catalyst (F).

[0047] A preferred embodiment of the method for producing the DMC catalyst (F) of the present 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 generate 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 DMC catalyst (F) 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 an organic ligand, and the solid-liquid separation operation is carried out at least once, preferably at least twice. The resulting solid may be dried so that the moisture content falls within the above-mentioned specific range, and may be pulverized as necessary.

[0048] 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. The concentration of the cyanide transition metal compound in the aqueous solution of the cyanide transition metal compound is preferably from 2 to 50 mass %, more preferably from 2 to 20 mass %, and even more preferably from 3 to 10 mass %. The molar ratio of the metal contained in the metal halide salt to the transition metal contained in the transition metal cyanide compound is preferably 1.6-12, and more preferably 1.8-8.

[0049] According to the study by the inventors of the present application, the D 50 It was found that the content of particles with a particle size of 11 μm or more relative to the total volume of the DMC catalyst (F) 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.

[0050] The mixing of the aqueous solution of the metal halide salt and the aqueous solution of the transition metal cyanide compound is preferably carried out by dropping the aqueous solution of the transition metal cyanide compound into the aqueous zinc halide solution rather than dropping the aqueous solution of the metal halide salt into the aqueous solution of the transition metal cyanide compound. Dropping the aqueous solution of the transition metal cyanide 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 transition metal cyanide compound to the total amount (mol) of metal derived from the metal halide salt contained in the metal halide salt aqueous 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. When the ratio is equal to or less than the upper limit, the DMC catalyst D 50 Furthermore, it becomes easier to control the content of particles having a particle size of 11 μm or more relative to the total volume of the DMC catalyst within the above-mentioned range. The drop time of the aqueous solution of the transition metal cyanide compound is preferably 30 minutes or more, more preferably 60 minutes or more, and even more preferably 80 minutes or more. The upper limit of the drop time may be, for example, 180 minutes or less, or 150 minutes or less. When the drop time is the lower limit or more, the DMC catalyst (F) is 50 When the dropping rate is equal to or lower than the upper limit, the DMC catalyst (F) can be produced more efficiently.

[0051] 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. As the stirring blade to be used, a half-moon stirring blade, a full-zone type stirring blade, an anchor type stirring blade, etc. are preferable. When using a half-moon stirring blade in a 500 mL flask, the diameter is preferably 60 mm or more, more preferably 70 mm or more.

[0052] 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 further preferably 30 to 55°C.

[0053] 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 further preferably from 35 to 65% by mass.

[0054] The temperature when coordinating the organic ligand is preferably from 10 to 90°C, more preferably from 20 to 80°C, and further preferably from 30 to 70°C.

[0055] After the organic ligand is coordinated, it is preferable to carry out solid-liquid separation. For solid-liquid separation, a method known in the art, such as filtration or centrifugation, can be adopted. The obtained solid contains the DMC catalyst (F) as well as a salt (alkali metal halide) generated by the reaction. Therefore, it is preferable to remove the salt 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 carry out washing multiple times.

[0056] When producing a slurry catalyst, a method can be used in which a mixed liquid containing the DMC catalyst (F) and water is obtained as described above, impurities and water are removed from the obtained mixed liquid, and then a dispersion medium is added to prepare a slurry containing the DMC catalyst (F) and the dispersion medium. Note that washing with an aqueous solution of an organic ligand may be performed before adding the dispersion medium.

[0057] (Particle size and DMC catalyst (U) content in composition) The composition of the present embodiment includes a polyether compound and a DMC catalyst (U). It may also include a stabilizer and may contain a trace amount of impurities. Therefore, it is preferable to purify the composition 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 (U) is very small compared to the DMC catalyst (F). This is considered to be due to the fact that it is pulverized and made into fine particles by the polymerization reaction of the alkylene oxide described below. The 50% cumulative volume particle size calculated from the volume-based cumulative particle size distribution obtained by dynamic light scattering particle size distribution measurement in the composition 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 diameter obtained from the cumulative particle size distribution based on light intensity in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement in the composition is 1.0 μm or less, preferably 0.9 μm or less, and 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 peak particle diameter obtained from the cumulative particle size distribution based on light intensity in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement in the composition 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.

[0058] The content of the DMC catalyst (U) relative to the total mass of the composition is preferably 1 to 200 ppm by mass, more preferably 2 to 100 ppm by mass, and further preferably 5 to 50 ppm by mass. The content of the DMC catalyst (U) is determined based on the amount of the DMC catalyst (F) used in producing the polyether compound. The content of the polyether compound relative to the total mass of the composition is preferably 98.0 mass % or more, more preferably 99.0 mass % or more, and even more preferably 99.5 mass % or more.

[0059] <Production method of 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 (F).

[0060] The number of active hydrogens in the initiator is preferably 1 or more, more preferably 2 to 10, further preferably 2 to 8, and particularly preferably 2 to 6. The number of active hydrogens in the initiator is preferably selected according to 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 in the polyether compound are the same. The initiator may be used alone or in combination of two or more kinds.

[0061] The initiator preferably has a hydroxyl group as the active hydrogen-containing group. The initiator having one hydroxyl group is preferably a monohydric alcohol having a linear or branched hydrocarbon group, specifically, 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 these initiators in the presence of an alkali metal hydroxide may be used as the initiator. The hydroxyl value of the initiator is, for example, preferably from 3 to 842 mgKOH / g, and more preferably from 7 to 561 mgKOH / g.

[0062] The alkylene oxide is selected depending on the constituent units of the polyoxyalkylene chain of the resulting polyether compound. Examples of the 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.

[0063] 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, compared to when a polymerization catalyst other than a DMC catalyst is used.

[0064] When the polyoxyalkylene chain of the polyether compound is a random copolymer chain consisting of 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 (F) is preferred.

[0065] 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 (F) to obtain a precursor, which is then reacted with ethylene oxide, or the polyether compound may be obtained by reacting ethylene oxide with an initiator in the presence of a DMC catalyst (F) to obtain a precursor, which is then reacted with propylene oxide,

[0066] The amount of DMC catalyst (F) 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 (F) used is equal to or more than the above lower limit, the polymerization reaction is likely to proceed. When the amount of DMC catalyst (F) used is equal to or less than the above upper limit, the amount of DMC catalyst (F) used is suppressed, which is economical.

[0067] The polymerization may be carried out in a continuous manner or a batch manner, but is preferably carried out in a batch manner. The polymerization temperature is preferably from 30 to 180°C, more preferably from 70 to 160°C, and further preferably from 90 to 140°C. The polymerization pressure is preferably 1.0 MPa or less, more preferably 0.8 MPa or less, and even more preferably 0.3 MPa or less. The alkylene oxide is preferably fed to the reactor at a rate such that the above reaction temperature is maintained. The reaction atmosphere is preferably one which is less susceptible to moisture contamination, and is more preferably an inert gas atmosphere such as nitrogen.

[0068] <Applications of polyether compounds> The polyether compound can be used as a lubricant, a raw material for polyurethane foam, an adhesive, a sealing material, a coating material, etc. In addition, the polyether compound may be reacted with a compound capable of reacting with a hydroxyl group of the polyether compound to produce a polyether compound having a reactive silicon group, a prepolymer, a polyether compound having a polymerizable unsaturated group, etc.

[0069] <Polyether compound having 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 2 described below.

[0070] (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 the polyether compound A is represented by the following formula 2. -SiR a X 3-a formula 2

[0071] In the above formula 2, 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 a hydrocarbon group having 1 to 20 carbon atoms and a triorganosiloxy group.

[0072] 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. More preferably, R is 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 terms of the good curability of the polyether compound A and the stability of the curable composition. An α-chloromethyl group is preferred in terms of the fast curing rate of the cured product. A methyl group is particularly preferred in terms of easy availability.

[0073] In the above formula 2, 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, it is easy to form a siloxane bond quickly and form a crosslinked structure in the cured product, and the physical properties of the cured product tend to be good.

[0074] In the above formula 2, a is an integer of 0 to 2. When a is 2, R may be the same or different. When a is 1 or less, X may be the same or different. When the crosslink density by the siloxane bond is low, the modulus of the cured product is likely to decrease, so a is preferably 2 or less, and more preferably 1 or less.

[0075] Examples of the reactive silicon group represented by the above formula 2 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, a (α-chloromethyl)dimethoxysilyl group, and a (α-chloromethyl)diethoxysilyl group. In terms of high activity and good curability, a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group, and a diethoxymethylsilyl group are preferred, and a trimethoxysilyl group and a dimethoxymethylsilyl group are more preferred.

[0076] 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 the above formula 2, wherein the terminal group is the above reactive silicon group, an unsaturated group, an isocyanate group, or a hydroxyl group.

[0077] The polyether compound A has an average of 1.0 or more terminal groups per molecule. Since the cured product has a higher tensile strength and better modulus and elongation, 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 A is the same as the number of terminal groups of the above polyether compound. The terminal group of the polyether compound A has any one of a reactive silicon group, an unsaturated group, an isocyanate group, or a hydroxyl group represented by the above formula 2. The respective terminal groups may be the same or different from each other.

[0078] The average number of reactive silicon groups represented by the above formula 2 per terminal group of the 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 more than the above lower limit, the crosslinking density by siloxane bonds is high, and a good cured product with a high modulus can be obtained.

[0079] The average number of reactive silicon groups represented by the above formula 2 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 more than the above lower limit, the crosslinking density due to siloxane bonds is high, and a good cured product with a high modulus can be obtained.

[0080] The Mn of the polyether compound A is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 60,000. When Mn is equal to or more 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 the workability is good.

[0081] The Mw / Mn of the polyether compound A is preferably 1.00 to 1.50, more preferably 1.00 to 1.45, further 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.

[0082] 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 above upper limit, handling is excellent.

[0083] <Method for producing polyether compound having reactive silicon group> In the method for producing the polyether compound A, the hydroxyl groups of the polyether compound are converted to groups having a reactive silicon group represented by the above formula 2. The method for producing the polyether compound A may be the following method (a1), (b1), or (c1). Method (a1): Converting the hydroxyl groups of a polyether compound into alkenyloxy groups having a carbon-carbon double bond at the molecular terminal or alkynyloxy groups having a carbon-carbon triple bond at the molecular terminal, and then converting the carbon-carbon double bond at the molecular terminal of the alkenyloxy group or the carbon-carbon triple bond at the molecular terminal of the alkynyloxy group into a reactive silicon group -SiR represented by the above formula 2. a X 3-a A method of converting an alkenyloxy group or an alkynyloxy group into a group having a reactive silicon group represented by the above formula 2 by reacting with a silylating agent capable of introducing the following formula: Method (b1): A method in which a hydroxyl group of a polyether compound is reacted with a silylating agent having a functional group reactive with the hydroxyl group and a reactive silicon group represented by the above formula 2, to convert the hydroxyl group into a group having the reactive silicon group represented by the above formula 2. Method (c1): A method in which a hydroxyl group of a polyether compound is converted to a group having an isocyanate group, and then a silylating agent having a functional group capable of reacting with an isocyanate group and a reactive silicon group represented by the above formula 2 is reacted to convert the hydroxyl group to a group having a reactive silicon group represented by the above formula 2.

[0084] In method (a1), an alkali metal salt is allowed to act on a polyether compound to convert it into an alcoholate, and then a halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular terminal or a halogenated hydrocarbon compound having a carbon-carbon triple bond at the molecular terminal is allowed to react with the polyether compound to convert the hydroxyl groups of the polyether compound into alkenyloxy groups having a carbon-carbon double bond at the molecular terminal or alkynyloxy groups having a carbon-carbon triple bond at the molecular terminal.

[0085] Examples of the alkali metal salt 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.

[0086] Examples of halogenated hydrocarbon compounds containing a carbon-carbon double bond at the molecular end 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. Halogenated hydrocarbon compounds containing a carbon-carbon triple bond at the molecular end include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne, 1-chloro-2-pentyne, 1,4-dichloro-2-butyne, 5-chloro-1-pentyne, 6-chloro-1-hexyne, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, 1-butyne, Examples of the iodine include bromo-2-octyne, 1-bromo-2-pentyne, 1,4-dibromo-2-butyne, 5-bromo-1-pentyne, 6-bromo-1-hexyne, propargyl iodide, 1-iodo-2-butyne, 4-iodo-1-butyne, 1-iodo-2-octyne, 1-iodo-2-pentyne, 1,4-diiodo-2-butyne, 5-iodo-1-pentyne, and 6-iodo-1-hexyne. Propargyl chloride, propargyl bromide, and propargyl iodide are preferred. A halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular terminal and a halogenated hydrocarbon compound having a triple bond at the molecular terminal may be used in combination. The halogenated hydrocarbon compound having a carbon-carbon double bond at the molecular terminal may be used alone or in combination of two or more. The halogenated hydrocarbon compound having a carbon-carbon triple bond at the molecular terminal may be used alone or in combination of two or more.

[0087] Next, a reactive silicon group, -SiR, represented by the above formula 2, is bonded to the carbon-carbon double bond at the molecular terminal of the alkenyloxy group or the carbon-carbon triple bond at the molecular terminal of the alkynyloxy group. a X 3-a The alkenyloxy group or alkynyloxy group is converted into a group having a reactive silicon group represented by the above formula 2 by reacting with a silylating agent capable of introducing the following: a X 3-a , R, X, and a are the same as those in the above formula 2). Specific examples include dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, methyldiisopropoxysilane, (α-chloromethyl)dimethoxysilane, (α-chloromethyl)diethoxysilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, and 3-mercaptopropyltrimethoxysilane. In terms of high activity and good curing properties, trimethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane are preferred, and dimethoxymethylsilane is more preferred.

[0088] 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 In the above formula 3, -SiR a X 3-a is the same as in the above formula 2. n is an integer of 1 to 8, and preferably 1 to 3. The reaction between the hydroxyl group of the polyether compound and the above isocyanate silane compound converts the hydroxyl group of the polyether compound to -OC(=O)NH-(CH 2 ) n -SiR a X 3-aThe urethane bond (-OC(=O)NH-) and -SiR a X 3-a is converted to an end group having the formula: Examples of the isocyanate silane compound include 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, isocyanate methyl trimethoxy silane, isocyanate methyl triethoxy silane, 3-isocyanate propyl methyl dimethoxy silane, 3-isocyanate propyl methyl diethoxy silane, isocyanate methyl methyl dimethoxy silane, and isocyanate methyl methyl diethoxy silane. As the isocyanate silane compound, 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, 3-isocyanate propyl methyl dimethoxy silane, isocyanate methyl methyl dimethoxy silane, and isocyanate methyl trimethoxy silane are preferred from the viewpoints of reactivity with polyether compounds and ease of handling.

[0089] 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.) is bonded to a reactive silicon group via a urethane bond and an organic group to obtain a polyether compound A. 5 O) m -C(=O)NH-(CH 2 ) n -SiR a X 3-a A linking structure represented by the following formula is formed.

[0090] This reaction may be carried out in the presence of a urethanization catalyst. The urethanization catalyst is not particularly limited, and a known urethanization catalyst can be appropriately used. For example, an organic tin compound such as dibutyltin dilaurate and dioctyltin dilaurate, a metal catalyst such as a bismuth compound, and a base catalyst such as an organic amine can be mentioned. The reaction temperature is preferably 20 to 200°C, more preferably 50 to 150°C. In addition, the urethanization reaction is preferably carried out under an inert gas atmosphere. As the inert gas, nitrogen is preferable.

[0091] The molar ratio of the total number of isocyanate groups of the isocyanate silane compound represented by the above formula 3 to the total number of active hydrogens of 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 the above formula 3 so that the number of reactive silicon groups per molecule of the obtained polyether compound A is at least 0.7. For example, when the active hydrogen-containing group of the polyether compound is a hydroxyl group, NCO / OH, which represents the molar ratio of the total number of isocyanate groups (NCO) of the isocyanate silane compound represented by the above formula 3 to the total number of active hydrogens (total number of hydroxyl groups) of the polyether compound, 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.

[0092] In method (c1), a polyisocyanate compound is reacted with a hydroxyl group of a polyether compound to convert the hydroxyl group into a monovalent organic group containing an isocyanate group (hereinafter also referred to as an "isocyanate-containing group") having a urethane bond (-OC(=O)NH-) at the bond terminal side with the polyether compound, and then a silylating agent having a functional group capable of reacting with an isocyanate group and a reactive silicon group represented by the above formula 2 is reacted with the isocyanate-containing group to form an end group which 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 (-OC(=O)NH-) and a silylating agent residue reacted with an isocyanate group. Hereinafter, the 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 capable of reacting with an isocyanate group and a reactive silicon group represented by the above formula 2 is a compound represented by the following formula 5, but the present invention is not limited thereto.

[0093] OCN-R 3 -NCO formula 4 R in the above formula 4 3 represents a divalent organic group.

[0094] WR 4 -SiR a X 3-a formula 5 In the above formula 5, W is a functional group capable of reacting with a monovalent isocyanate group (a group having one or more active hydrogens), R 4 is a divalent organic group, -SiR a X 3-a is the same as Equation 2 above.

[0095] When the diisocyanate compound represented by the above formula 4 is reacted with the hydroxyl group of the polyether compound, the above isocyanate-containing group is -OC(=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 represented by the formula -OC(=O)NH-R 3 -NHC(=O)-W'-R4 -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: -OC(=O)NH-R 3 -NHC(=O)-OR 4 -SiR a X 3-a In this case, the urethane bond and the reactive silicon group-containing group have two urethane bonds. 2 ), the urethane bond and the reactive silicon group-containing group are represented by -OC(=O)NH-R 3 -NHC(=O)-NH-R 4 -SiR a X 3-a It is a group represented by the following formula:

[0096] R 3 As the alkylene group, a divalent organic group having 2 to 20 carbon atoms is preferable, 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 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 bonded via an alkylene group.

[0097] 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.

[0098] Aromatic polyisocyanates include, for example, naphthalene-1,5-diisocyanate, polyphenylenepolymethylene 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 the aliphatic polyisocyanate 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 a tensile strength of the cured product. The polyisocyanate compound may be used alone or in combination of two or more kinds.

[0099] A functional group capable of reacting with an isocyanate group represented by the above formula 5 and -SiR a X 3-a In the silylating agent having R4 As the alkyl group, a divalent organic group having 1 to 20 carbon atoms is preferable, 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 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 preferable, a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 8 carbon atoms is even more preferable, and a group obtained by removing two hydrogen atoms from a linear hydrocarbon having 1 to 6 carbon atoms is particularly preferable. W is preferably a group having one or two active hydrogens 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.

[0100] In the case of the methods (b1) and (c1), the polyether compound A obtained has a reactive silicon group formed via one or more organic groups represented by the following formula (i). That is, the polyether compound A obtained by the methods (b1) and (c1) contains one or more organic groups represented by the following formula (i). Note that the polyether compound A obtained by the method (b1) contains only one organic group represented by the following formula (i), and the polyether compound A obtained by the method (c1) contains two or more organic groups represented by the following formula (i). -C(=O)NH- Formula (i)

[0101] 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, the number of organic groups (i) is one.

[0102] The organic group (i) preferably forms a urethane bond (-OC(=O)NH-, -O- represents the oxygen atom at the end of the polyoxyalkylene chain) with the polyoxyalkylene chain. That is, it is preferable that one organic group (i) exists 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) contained in the polyether compound A is one. When the polyether compound A is produced by the method (b1), it is easy to obtain a polyether compound A having a high silylation rate. When the polyether compound A is produced by the method (b1), it is easy to obtain a polyether compound A having a narrow molecular weight distribution. The viscosity of the polyether compound A is suppressed, so that the workability is good. 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 polyether compound A is the same as the number of groups (i) per molecule.

[0103] The silylation rate of the polyether compound A is preferably 50 to 100 mol %, more preferably 60 to 98 mol %. When the silylation rate is equal to or higher 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 compounds A, the average silylation rate of all the polyether compounds A may be within the above range.

[0104] (Curable composition containing polyether compound having reactive silicon group) The polyether compound having a reactive silicon group is used in a curable composition. The curable composition is obtained by mixing the polyether compound A with other necessary components. As the 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 has better tensile strength and elongation properties.

[0105] 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, foaming agents, solvents, and silicates. Other components may be used in combination with any of the conventionally known components described in International Publication No. 2013 / 180203, International Publication No. 2014 / 192842, International Publication No. 2016 / 002907, JP 2014-88481 A, JP 2015-10162 A, JP 2015-105293 A, JP 2017-039728 A, JP 2017-214541 A, etc. Two or more types of each component may be used in combination.

[0106] The curable composition may be a one-component type in which the polyether compound A and all other components are mixed in advance, sealed, and stored, and then cured by moisture in the air after application, or a two-component type in which a base composition containing at least the polyether compound A and a hardener composition containing at least a curing catalyst are stored separately, and the hardener composition and the base composition are mixed before use. It is preferable that the one-liquid type curable composition does not contain water. It is preferable that the blended components containing water are dehydrated and dried in advance, or that the components are dehydrated under reduced pressure during blending and kneading. In the two-part curable composition, the curing agent composition may contain water. The base composition is unlikely to gel even if it contains a small amount of moisture, but from the viewpoint of storage stability, it is preferable to dehydrate and dry the blended components in advance. In order to improve storage stability, a dehydrating agent may be added to the one-part curable composition or the two-part base composition.

[0107] (Use of curable composition containing polyether compound having reactive silicon group) Suitable applications of the curable composition containing polyether compound A include adhesives, sealants (e.g., elastic sealants for architecture, sealants for insulating glass, anti-rust and waterproof sealants for glass ends, sealants for the rear surfaces 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).

[0108] <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. Among the isocyanate groups in the polyisocyanate unit introduced into the polyether compound B, the isocyanate group remaining unreacted with the hydroxyl group of the polyether compound becomes the isocyanate group at the molecular end of the polyether compound B. In addition, among the hydroxyl groups in the polyether compound unit, the hydroxyl group remaining unreacted with the isocyanate group of the polyisocyanate becomes the hydroxyl group at the molecular end of the polyether compound B. That is, the molecular end group of the polyether compound B contains either one or both of a hydroxyl group and an isocyanate group.

[0109] The Mn of the polyether compound B is preferably 1,000 to 1,000,000, more preferably 1,500 to 500,000, and even more preferably 2,000 to 100,000. When the Mn is equal to or greater than the lower limit, sufficient flexibility is imparted and good elongation properties are obtained when the polyether compound B is used as an adhesive or coating material. When the Mn is equal to or less than the upper limit, the viscosity of the polyether compound B can be kept low, making it easy to handle.

[0110] 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.

[0111] 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 from 0.1 to 25 mass%, more preferably from 0.5 to 18 mass%, and further preferably from 1 to 15 mass%. When the content of isocyanate groups 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 isocyanate groups is equal to or less than the above upper limit, gelation is unlikely to occur during the reaction.

[0112] 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 further preferably from 1 to 15 mass %.

[0113] 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 above upper limit, handling is excellent.

[0114] <Prepolymer manufacturing method> In the method for producing the polyether compound B, a polyether compound is reacted with a polyisocyanate. If necessary, a urethane catalyst may be used. The polyether compound may be used alone or in combination of two or more kinds.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] Examples of araliphatic polyisocyanates include dialkyldiphenylmethane diisocyanates, tetraalkyldiphenylmethane diisocyanates, and α,α,α,α-tetramethylxylylene diisocyanate.

[0120] As the polyisocyanate, alicyclic polyisocyanates and aromatic polyisocyanates are preferred, and IPDI, MDI and TDI are more preferred. One type of polyisocyanate may be used alone, or two or more types may be used in combination.

[0121] The functional group at the molecular end of the polyether compound B can be controlled by adjusting the molar ratio of the total amount of isocyanate groups of the polyisocyanate to the total amount of hydroxyl groups of the polyether compound (hereinafter also referred to as "NCO / OH ratio"). For example, when producing a polyether compound B having an isocyanate group at the molecular end, 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 a hydroxyl group at the molecular end, 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.

[0122] 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.

[0123] Examples of the tertiary amine compound include triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-undecene-7.

[0124] The organometallic compound is preferably one or more selected from tin-based compounds and non-tin-based compounds. Examples of tin compounds include 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-based compounds include titanium-based compounds such as dibutyltitanium dichloride, tetrabutyltitanium trichloride, and butoxytitanium trichloride; lead-based compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate; and zirconium-based compounds such as zirconium naphthenate.

[0125] The urethanization catalyst may be used alone or in combination of two or more kinds. 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.

[0126] In the production of the polyether compound B, a solvent can be used, if necessary. 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. The solvent may be used alone or in combination of two or more kinds. When a solvent is used, the amount of the solvent used is not particularly limited, but is preferably 100 to 1000 parts by mass per 100 parts by mass of the polyether compound.

[0127] Examples of the method 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 of adding a polyisocyanate dropwise to a mixed liquid obtained by mixing a polyether compound, and, if necessary, a urethanization catalyst and a solvent may be used.

[0128] 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 promoted. 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.

[0129] When a urethanization catalyst is used, it is preferable to inactivate the urethanization catalyst after the completion of the reaction by adding a reaction terminator such as acetylacetone. The reaction terminator may be used alone or in combination of two or more kinds.

[0130] When unreacted polyisocyanate remains after the reaction, it is preferable to purify polyether compound B by removing the polyisocyanate by distillation.

[0131] (Polyurethane composition containing prepolymer) The polyether compound B is used in a polyurethane composition. The polyurethane composition is obtained by mixing the polyether compound B with other optional components as necessary. As the polyether compound B, only one type may be used, or two or more types may be used in combination. The content of polyether compound B relative to the total mass of the polyurethane composition is 15 mass % or more and 100 mass % or less, and preferably 30 to 100 mass %. The polyurethane composition may further contain optional components other than polyether compound B.

[0132] 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 in combination of two or more. 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.

[0133] A cured product can be produced by reacting a polyurethane composition with a curing agent. When the molecular end 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 end of polyether compound B is a hydroxyl group, a curing agent having an isocyanate group is used. When the molecular end of polyether compound B is an isocyanate group, the isocyanate group of polyether compound B contained in the polyurethane composition and the active hydrogen-containing group (e.g., hydroxyl group) of the curing agent undergo a urethane reaction to crosslink polyether compound B with a urethane bond, thereby obtaining a cured product. When the molecular end of polyether compound B is a hydroxyl group, the hydroxyl group of polyether compound B contained in the polyurethane composition and the isocyanate group of the curing agent undergo a urethane reaction to crosslink polyether compound B with a urethane bond, thereby obtaining a cured product. In the case of a curing agent having 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. Note that 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.

[0134] Examples of the curing agent having a hydroxyl group include the initiators and water described in the method for producing the polyether compound. The curing agent having an isocyanate group is exemplified by the above-mentioned polyisocyanates.

[0135] 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 more than 1, more preferably 1.0 to 1.2. 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 more than 0.8, more preferably 0.8 to 1.2.

[0136] The method of mixing the polyurethane composition and the curing agent may be a one-component type in which the polyurethane composition, which is a one-component composition obtained by previously mixing everything except the curing agent, is sealed and stored, and then cured by moisture in the air after application. Alternatively, a two-component type 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 the base composition are mixed before use may be used. In the case of the one-component type, moisture (water) in the air functions as the curing agent. That is, when the molecular end of the polyether compound B is an isocyanate group, the one-component type is preferred. The one-liquid composition preferably does not contain water. It is preferable that the blended components containing water are dehydrated and dried in advance, or dehydrated under reduced pressure during preparation of the one-liquid composition. In the case of the two-liquid type, the hardener composition may contain water. The base composition is unlikely to gel even if it contains a small amount of water, but from the viewpoint of storage stability, it is preferable to dehydrate and dry the blended components in advance. In the case of the two-liquid type, the above-mentioned optional components may be included in the hardener composition. In order to improve storage stability, a dehydrating agent may be added to the one-liquid composition or the two-liquid base composition. The reaction temperature is preferably 20 to 40° C. In the case of a one-liquid type, the relative humidity at the above reaction temperature is preferably 40 to 60%.

[0137] (Use of polyurethane composition containing prepolymer) Suitable applications of the polyurethane composition containing polyether compound B include adhesives, sealants (e.g., elastic sealants for architecture, sealants for insulating glass, anti-rust and waterproof sealants for glass ends, sealants for the rear surfaces of solar cells, sealants for buildings, sealants for ships, sealants for automobiles, and sealants for roads), coating materials (for paint applications), and electrical insulating materials (insulating coating materials for electric wires and cables). As an adhesive, it is suitable as an elastic adhesive for joining plastics together, metals together, and plastics and metals, and is also suitable as an elastic sealing material and elastic coating material.

[0138] <Polyether compound having 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 end. As the polymerizable unsaturated group, a (meth)acryloyl group or a (meth)acryloyloxy group is preferable. "(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.

[0139] 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.

[0140] The average number of polymerizable unsaturated groups per one 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 are likely to be good when resinified. When the average number of polymerizable unsaturated groups is equal to or less than the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties are likely to be obtained.

[0141] The average number of polymerizable unsaturated groups per molecule of the 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 are likely to be good when resinified. When the average number of polymerizable unsaturated groups is equal to or less than the upper limit, sufficient flexibility is imparted to the resin, and good elongation properties are likely to be obtained.

[0142] The Mn of the polyether compound C is preferably 1,000 to 1,000,000, more preferably 1,500 to 500,000, and even more preferably 2,000 to 100,000. When the Mn is equal to or greater than the lower limit, sufficient flexibility is imparted when the polyether compound C is used as an adhesive or coating material, and good elongation properties are easily obtained. When the Mn is equal to or less than the upper limit, the viscosity of the polyether compound C can be kept low, making it easy to handle.

[0143] 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.

[0144] 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 from 0.01 to 40 mass%, more preferably from 0.1 to 30 mass%, and further preferably from 1 to 15 mass%.

[0145] 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 above upper limit, handling is excellent.

[0146] <Method of producing polyether compound having polymerizable unsaturated group> In the method for producing the polyether compound C, a hydroxyl group of the polyether compound is converted into a group having a polymerizable unsaturated group. The method for producing the polyether compound C may be the following method (a2), (b2) or (c2). Method (a2): A method in which a hydroxyl group of a polyether compound is reacted with a compound having a functional group capable of reacting with the hydroxyl group and a polymerizable unsaturated group (hereinafter also referred to as "compound 1") to convert the hydroxyl group into a group having a polymerizable unsaturated group. Method (b2): A method in which a hydroxyl group of a polyether compound is reacted with a polyisocyanate to obtain a prepolymer having an isocyanate group at the molecular end, 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 end, 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.

[0147] In the method (b2), the prepolymer having an isocyanate group at the molecular end can be the above-mentioned polyether compound B having an isocyanate group at the molecular end.In the method (c2), the prepolymer having a hydroxyl group at the molecular end can be the above-mentioned polyether compound B having a hydroxyl group at the molecular end.

[0148] 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, isocyanate methyl (meth)acrylate, etc. Commercially available products include Karenz-AOI and Karenz-MOI (both are product names of Showa Denko KK).

[0149] 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, more preferably a (meth)acrylate having an active hydrogen-containing group such as a hydroxyl group or an amino group, further preferably a hydroxyalkyl (meth)acrylate or hydroxycycloalkyl (meth)acrylate having one hydroxyl group, and particularly preferably a hydroxyalkyl (meth)acrylate in which the alkyl group has 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, 6-hydroxyhexyl (meth)acrylate, etc. Commercially available products include Light Ester HO-250(N), Light Ester HOP(N), Light Ester HOA(N), Light Ester HOP-A(N), Light Ester HOB(N) (all of which are Kyoei Chemical Co., Ltd. product names), and 4-HBA (Osaka Organic Chemical Industry Co., Ltd. product name).

[0150] When the composition containing polyether compound C is a photocurable composition, it is preferable that all of the polymerizable unsaturated groups contained in polyether compound C are acryloyloxy groups. Such polyether compound C can be obtained by using compounds 1 and 2 in which the polymerizable unsaturated groups are acryloyloxy groups.

[0151] In the methods (a2) and (c2), the molar ratio of the amount of compound 1 used 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 the method (b2), the molar ratio of the amount of compound 2 used relative to the amount of isocyanate groups in the prepolymer having an isocyanate group at the molecular terminal may be more than 1. Excess compound 2 remains unreacted, but 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.

[0152] In the methods (a2), (b2) and (c2), the reaction between a hydroxyl group and a functional group capable of reacting with the hydroxyl group and the reaction between an isocyanate group and a functional group capable of reacting with the isocyanate group can be carried out by a method 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.

[0153] (Composition containing a polyether compound having a 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, and more preferably 75 mass % or more.

[0154] 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 compounds"), a photopolymerization initiator, and other components.

[0155] Examples of the other compounds include the following other compounds 1 and 2. The other compound 1 is a compound other than the polyether compound C, and is preferably a compound having one (meth)acryloyloxy group and one or more hydroxyl groups, and preferably has one or two hydroxyl groups. The other compound 1 may be a compound having a polyoxyalkylene chain, and in this case, a compound having no urethane bond or urea bond (a compound produced by a method other than the above methods (a2) to (c2)) is preferred. The other compound 1 may be a compound having an aliphatic polyester chain obtained by ring-opening addition polymerization of lactone.

[0156] 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.

[0157] 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 as the above compound 2. Among them, 4-hydroxybutyl acrylate and 6-hydroxyhexyl acrylate are preferred in terms of flexibility and low volatility.

[0158] Examples of lactone-modified hydroxyalkyl (meth)acrylates include compounds obtained by ring-opening addition of lactone to the hydroxyalkyl (meth)acrylates exemplified as the above compound 2. The number of lactones added is preferably 1 to 3. Examples of lactones include ε-caprolactone, γ-butyrolactone, and γ-valerolactone.

[0159] The (meth)acrylic acid-monoepoxide adduct is preferably a reaction product of (meth)acrylic acid with a glycidyl ether or a glycidyl ester, and examples thereof include (meth)acrylic acid and phenyl glycidyl ether.

[0160] Among these, hydroxyalkyl (meth)acrylate and (meth)acrylic acid-monoepoxide adduct are preferred because they are easily available industrially and contain few impurities.

[0161] The other compounds 1 may be used alone or in combination of two or more. When the curable composition contains Other Compound 1, the content of Other Compound 1 with respect to the total mass of the curable composition is preferably 1 to 20% by mass, more preferably 1 to 15% by mass. When the content of Other Compound 1 is at least the above lower limit value, the effect of improving the adhesion by adding Other Compound 1 can be easily obtained sufficiently. When the content of Other Compound 1 is at most the above upper limit value, good physical properties can be easily obtained in terms of low curing shrinkage rate.

[0162] Other Compound 2 is a compound other than polyether compound C and Other Compound 1, and is preferably a compound having one (meth)acryloyloxy group and not containing a urethane bond. As Other Compound 2, (meth)acrylate having a long-chain alkyl group with 8 or more carbon atoms and (meth)acrylate having an amide group are preferable. Examples of Other Compound 2 other than these include alkyl (meth)acrylate with 7 or less carbon atoms, alkoxyalkyl (meth)acrylate, (meth)acrylate having an aliphatic cyclic hydrocarbon group, and the like.

[0163] When the curable composition contains long-chain alkyl (meth)acrylate with 8 or more carbon atoms, when forming a cured product by a method of confining the curable composition under reduced pressure and curing it in an atmosphere of higher pressure (reduced-pressure sealing - pressure-increasing curing method), the bubbles in the cured product are likely to disappear. The number of carbon atoms of the long-chain alkyl group is preferably 8 to 22, more preferably 8 to 18. Examples of the long-chain alkyl (meth)acrylate include lauryl (meth)acrylate, isostearyl (meth)acrylate, isodecyl (meth)acrylate, and the like. Among them, lauryl acrylate and isostearyl acrylate are preferable in terms of flexibility, low viscosity, and low crystallinity.

[0164] 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, since it is easy to suppress whitening of the cured product of the curable composition under moist and hot conditions. Examples of (meth)acrylamide derivatives include 4-(meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, and N,N-diethyl(meth)acrylamide.

[0165] The other compounds 2 may be used alone or in combination of two or more. When the curable composition contains the other compound 2, the content of the other compound 2 is preferably 1 to 30 mass%, more preferably 1 to 25 mass%, based on the total mass of the curable composition. When the content of the other compound 2 is equal to or more than the above lower limit, the effect of adding the other compound 2 is easily 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 easily obtained.

[0166] The curable composition may be a photocurable composition or a thermosetting composition. A photocurable composition is preferred because it can be cured at a low temperature and has a high curing rate. When the curable composition is a photocurable composition, it is preferred to contain a photopolymerization initiator. When the 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.

[0167] 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, and phosphine oxide-based photopolymerization initiators are preferred in that coloring after photopolymerization reaction is easily suppressed. The photopolymerization initiator may be used alone or in combination of two or more types.

[0168] The photopolymerization initiator is not particularly limited, and commercially available products can be used, such as IRGACURE 819, IRGACURE TPO, IRGACURE 184, IRGACURE 2959, IRGACURE 1173, IRGACURE 127, IRGACURE 907, IRGACURE OXE01, and IRGACURE OXE02, both 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, based on 100 parts by mass of the total of the curable components.

[0169] 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 are likely 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.

[0170] Examples of other components include polymerization inhibitors, photocuring accelerators, chain transfer agents, light stabilizers (UV absorbers, radical scavengers, etc.), antioxidants, flame retardants, adhesion improvers (silane coupling agents, etc.), pigments, dyes, etc. 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.

[0171] Examples of the polymerization inhibitor include hydroquinone-based (2,5-di-tert-butylhydroquinone, etc.), catechol-based (p-tert-butylcatechol, etc.), anthraquinone-based, phenothiazine-based, and hydroxytoluene-based polymerization inhibitors.

[0172] Ultraviolet absorbers are used to prevent photo-degradation of curable compositions and improve weather resistance. Examples of ultraviolet absorbers include benzotriazole-based, triazine-based, benzophenone-based, benzoate-based ultraviolet absorbers, etc. As the benzotriazole-based ultraviolet absorber, for example, those described in paragraph

[0076] of International Publication No. 2014 / 017328 can be used.

[0173] Light stabilizers are used to prevent photo-degradation of curable compositions and improve weather resistance. Examples of light stabilizers include hindered amine-based light stabilizers. As the hindered amine-based light stabilizer, those described in paragraph

[0077] of International Publication No. 2014 / 017328 can be used.

[0174] Antioxidants are used to prevent oxidation of curable compositions and improve weather resistance and heat resistance. Examples of antioxidants include phenolic and phosphorus-based antioxidants. As the phenolic antioxidant, for example, those described in paragraph

[0078] of International Publication No. 2014 / 017328 can be used. As the phosphorus-based antioxidant, those described in paragraph

[0078] of International Publication No. 2014 / 017328 can be used.

[0175] Also, products obtained by mixing a plurality of antioxidants, light stabilizers, etc. can be used. Examples include IRGASTAB PUR68, TINUVIN B75, etc. manufactured by BASF.

[0176] 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 with respect to 100 parts by mass of the curable component.

[0177] In the curable composition, the content of the chain transfer agent is preferably low. With respect to 100 parts by mass of the curable component, it is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and particularly preferably not containing a chain transfer agent.

[0178] (Use of a curable composition containing a polyether compound having a coincident unsaturated group) As the use of the curable composition containing the polyether compound C, adhesives in various fields such as various building materials, packaging materials, printing materials, display materials, electric and electronic component materials, optical component materials, and liquid crystal panels are suitable.

Examples

[0179] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following description.

[0180] [Particle size distribution (laser diffraction scattering method)] The particle size distribution of the particles of the DMC catalyst before use in the polymerization reaction was measured by the 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) to obtain a volume-based cumulative particle size distribution. From the obtained cumulative particle size distribution, D X , the content of particles having a particle diameter of 11 μm or more with respect to the total volume of the DMC catalyst, and the content of particles having a particle diameter of 0.15 to 1 μm with respect to the total volume of the DMC catalyst were determined.

[0181] [Particle size distribution (dynamic light scattering type particle size distribution measurement)] The particle size distribution in the composition containing the polyether compound and the DMC catalyst produced in Examples 1 to 6 described later was measured by dynamic light scattering type particle size distribution measurement. Specifically, using a dynamic light scattering type measuring device (particle size distribution measuring device of Microtrac Bell Corporation: NANOTRAC WAVE II-UT151), methanol was selected as the dispersion solvent, and the particle size distribution of the composition containing the polyether compound and the DMC catalyst was measured to obtain a volume-based cumulative particle size distribution and a light intensity-based cumulative particle size distribution in the range of 0.1 to 6.5 μm. From the obtained volume-based cumulative particle size distribution, d 50 , the peak particle diameter and d were determined from the light intensity-based cumulative particle size distribution in the range of 0.1 to 6.5 μm 50 ’.

[0182] [Hydroxyl value and hydroxyl value-converted molecular weight] The hydroxyl value was calculated in accordance with JIS K 1557-1: 2007, Method B. The hydroxyl value-based molecular weight was calculated based on the formula "56,100 / hydroxyl value of polyether compound x number of hydroxyl groups of polyether compound."

[0183] [Mn, Mw, Mw / Mn] As standard samples for molecular weight measurement, several types of monodisperse polystyrenes with different degrees of polymerization were measured using a gel permeation chromatograph analyzer HLC-8420GPC (product name of Tosoh Corporation), and a calibration curve was created based on the relationship between the molecular weight of polystyrene and retention time. The polyether compound 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, Mn, Mw, and Mw / Mn were obtained by analyzing the peaks that appeared at 6 to 11 minutes of collection time, using tetrahydrofuran as a solvent, setting the sample pump to a flow rate of 0.350 mL / min, setting the reference pump to a flow rate of 0.350 mL / min, setting the detector temperature to 40°C, and setting the collection time to 6 to 15 minutes.

[0184] [Total unsaturation] The total degree of unsaturation of the polyether compound was measured in accordance with JIS K 1557-3:2007.

[0185] [viscosity] The viscosity of the polyether compound was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: RE85U) under conditions of a measurement temperature of 25° C. and rotor No. 1.

[0186] [Filterability] 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 composition containing the polyether compound and DMC catalyst (U) obtained in Examples 1 to 6 described below was added to 100 g of methyl ethyl ketone as a dilution solvent, and the obtained sample was poured into the upper surface of the filter paper and filtered. Natural filtration was performed for 30 minutes, and the amount of the filtered sample was measured. The larger the amount of the filtered sample, the better the filterability. When the amount of the filtered sample is 15 g or more, the filterability is judged to be good, and when the amount of the filtered sample is less than 15 g, the filterability is judged to be not good.

[0187] [Production Example 1] In the presence of a KOH catalyst, propylene glycol was polymerized with propylene oxide (hereinafter also referred to as "PO"), and the resulting product was purified by dealkalization to obtain polyoxypropylene diol (hereinafter also referred to as "polyol P1"). The average number of hydroxyl groups per molecule of polyol P1 was 2, and Mn was 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 a half-moon stirring blade with a diameter of 80 mm, a potassium hexacyanocobaltate aqueous solution consisting of 4.2 g of potassium hexacyanocobaltate and 75 g of water was dropped into the zinc chloride aqueous solution at a constant rate over 90 minutes. During this time, the mixed solution in the flask was kept at 40°C. After the dropping of the potassium hexacyanocobaltate aqueous solution was completed, the mixture in the flask was stirred for another 30 minutes, and then 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 another 60 minutes. The resulting mixture was filtered under pressure (0.25 MPa) using a circular filter plate with a diameter of 125 mm 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 of 36 g of TBA and 84 g of water was added and 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. After adding 120 g of polyol P1 to the dispersion, the volatile components were distilled off under reduced pressure at 80° C. for 3 hours, and then the volatile components were distilled off at 115° C. for 3 hours to obtain a slurry A of TBA-DMC catalyst (F). The concentration of TBA-DMC catalyst (F) contained in the slurry A of TBA-DMC catalyst (F) was 5.33% by mass. The particle size distribution of the obtained TBA-DMC catalyst (F) 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 (F), 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 (F), (D 90 -D 10 ) / D 50 , and 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 particles of TBA-DMC catalyst (F) in the range of 0.1 to 10 μm measured by a laser diffraction scattering method was unimodal with only one peak.

[0188] [Production Example 2] A 67% by mass aqueous zinc chloride solution was introduced from one side of a branch conduit connected to a first reactor having an internal volume of 600 mL, and a 5.5% by mass aqueous potassium hexacyanocobaltate solution was introduced from the other side, and the two solutions were joined at a branch just before the first reactor, and the combined liquid was introduced into the first reactor. The aqueous zinc chloride solution was continuously supplied at a rate of 12.3 g / min (6.83 mL / min assuming a specific gravity of 1.80 g / mL), and the aqueous potassium hexacyanocobaltate solution was continuously supplied 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 liquid was stirred at 300 rpm by a stirring blade in the first reactor kept at 40°C, and then the reaction liquid from the first reactor was introduced into the second reactor kept at 60°C through a conduit. The average residence time in the first reactor was 15.7 minutes, which was calculated by dividing the volume of the portion of the first reactor where mixing and stirring was sufficiently performed (600 mL) by the flow rate of the 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 2300 mL at 63.2 g / min (71.0 mL / min assuming a specific gravity of 0.89 g / mL). In the second reactor, the liquid was stirred at 300 rpm with a stirring blade, and the dispersion produced in the second reactor was sent from the second reactor through a conduit to a storage tank and stored therein. The average residence time of the liquid in the second reactor was 21.5 minutes. This average residence time was calculated by dividing 2,300 mL, which is the volume of the portion of the second reactor where mixing and stirring was sufficiently performed, by 109.3 mL / min, which is the rate of the liquid being supplied. The proportion of TBA in the steady state was 29.5 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 3 [Co(CN) 6 ] 2 ) is approximately 9.7 times the mass of Next, 1100 g of the dispersion stored in the storage tank was filtered, and a solid containing a composite metal cyanide complex (hereinafter referred to as a "filter cake") was obtained in about 25 minutes. 112 g of the filter cake and 500 g of a 30% by mass TBA aqueous solution were mixed at room temperature, stirred at 300 rpm for 1 hour, and then filtered to separate a filter cake containing a composite metal cyanide complex in about 20 minutes. The content of TBA-DMC catalyst (F) 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, and then volatile components were distilled off at 80° C. and under reduced pressure of 0.005 MPa for 5 hours to obtain a slurry B of TBA-DMC catalyst (F). The concentration of TBA-DMC catalyst (F) contained in the slurry B of TBA-DMC catalyst (F) was 8.53 mass%.

[0189] [Production Example 3] A slurry C of TBA-DMC catalyst (F) was obtained in the same manner as in Production Example 1, except that the stirring blade was changed to a half-moon disk having a diameter of 40 mm in stirring the aqueous zinc chloride solution. The concentration of TBA-DMC catalyst (F) in the slurry C of TBA-DMC catalyst (F) was 5.50 mass%.

[0190] [Production Example 4] A slurry D of TBA-DMC catalyst (F) 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 TBA-DMC catalyst (F) in the slurry D of TBA-DMC catalyst (F) was 5.40 mass%.

[0191] [Table 1]

[0192] Below, Examples 1 and 2 are working examples, and Examples 3 to 6 are comparative examples.

[0193] [Example 1] In the presence of KOH catalyst, PO was polymerized with propylene glycol, and the resulting mixture was purified by dealkalization to obtain polyoxypropylene diol (hereinafter also referred to as "polyol P2"). The average number of hydroxyl groups per molecule of polyol P2 was 2, and Mn was 700. Using polyol P2 as an initiator, 3,300 g of PO was polymerized in the presence of TBA-DMC catalyst (F) slurry A to obtain polyether compound a-1. The polymerization was carried out by adding 0.1 mass % of Irganox 1010 manufactured by BASF as a stabilizer. The amount of TBA-DMC catalyst (F) slurry A used was such that the concentration of the TBA-DMC catalyst was 44 mass ppm relative to the total mass of polyether compound a-1. The hydroxyl value, hydroxyl value converted molecular weight, Mn, Mw, Mw / Mn, total degree of unsaturation, and viscosity of polyether compound a-1 are shown in Table 2 (hereinafter, the same is shown for Examples 2 to 6). After the reaction, the TBA-DMC catalyst (U) in the composition containing the polyether compound a-1, the TBA-DMC catalyst (U), and the stabilizer was measured by dynamic light scattering particle size distribution measurement. 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 6). A filterability test was carried out using the obtained composition. The results are shown in Table 2 (hereinafter, the same applies to Examples 2 to 6).

[0194] [Example 2] A composition containing polyether compound a-2, TBA-DMC catalyst (U), and a stabilizer was obtained in the same manner as in Example 1, except that the amount of TBA-DMC catalyst (F) slurry A was changed so that the concentration of the TBA-DMC catalyst was 30 ppm by mass.

[0195] [Example 3] A composition containing polyether compound a-3, TBA-DMC catalyst (U), and a stabilizer was obtained in the same manner as in Example 1, except that TBA-DMC catalyst (F) slurry B was used instead of TBA-DMC catalyst (F) slurry A.

[0196] [Example 4] A composition containing polyether compound a-4, TBA-DMC catalyst (U), and a stabilizer was obtained in the same manner as in Example 3, except that the amount of TBA-DMC catalyst (F) slurry B used was changed so that the concentration of the TBA-DMC catalyst was 30 ppm by mass.

[0197] [Example 5] A composition containing polyether compound a-5, TBA-DMC catalyst (U), and a stabilizer was obtained in the same manner as in Example 1, except that TBA-DMC catalyst (F) slurry C was used instead of TBA-DMC catalyst (F) slurry A.

[0198] [Example 6] A composition containing polyether compound a-6, TBA-DMC catalyst (U), and a stabilizer was obtained in the same manner as in Example 1, except that TBA-DMC catalyst (F) slurry D was used instead of TBA-DMC catalyst (F) slurry A.

[0199] [Table 2]

[0200] As shown in Table 2, it was found that the filterability was improved in Examples 1 and 2 compared to Examples 3 to 6. In Examples 1 to 6, d 50 are similar (rather, d in Examples 4 to 6 50 The d in Examples 1 and 2 is 50 (slightly smaller than 10 ... 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 difference in the d range of 0.1 to 6.5 μm based on the trace components in the composition. 50 On the other hand, in Examples 1 and 2 and Examples 3 to 6, the d range of 0.1 to 6.5 μm is 50 The difference in the d' is very small, and it is an unexpected effect that such a small difference would cause a difference in filterability. 50In controlling the ', the D of TBA-DMC catalyst (F) 50 It was also found that it was effective to adjust the content of particles with a particle size of 11 μm or more relative to the total volume of the TBA-DMC catalyst (F).

Claims

1. A composition comprising a polyether compound and a double metal cyanide complex catalyst, The composite metal cyanide complex catalyst is in particulate form, The composition has a 50% cumulative light intensity particle size of 1.0 μm or less, as determined from a cumulative particle size distribution based on light intensity in the range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement.

2. The composition according to claim 1, wherein the composition has a peak particle size of 1.0 μm or less as determined from a cumulative particle size distribution based on light intensity in a range of 0.1 to 6.5 μm obtained by dynamic light scattering particle size distribution measurement.

3. 3. The composition according to claim 1, wherein the 50% cumulative volume particle size of the composition is 0.1 to 100 nm, as determined from a volume-based cumulative particle size distribution obtained by dynamic light scattering particle size distribution measurement.

4. The composition according to claim 1 or 2, wherein the number average molecular weight of the polyether compound is from 1,000 to 100,000.

5. The composition according to claim 1 or 2, wherein the molecular weight distribution of the polyether compound is from 1.00 to 1.

15.

6. The composition according to claim 1 or 2, wherein the polyether compound has a total degree of unsaturation of 0.001 to 0.040 meq / g.

7. 3. The composition according to claim 1, wherein the content of the double metal cyanide complex catalyst relative to the total mass of the polyether compound is 1 to 200 ppm by mass.

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