Polyether polyol composition

Abstract

To provide a polyether polyol composition which has a high thermal decomposition temperature, is excellent in compatibility with a urethane raw material, has good reactivity as a urethane raw material, and can exhibit excellent tensile resistance when formed into a polyurethane.SOLUTION: The polyether polyol composition comprises a polyalkylene ether glycol and a polyether polyol represented by formula (1). (In the above formula (1), R represents a divalent hydrocarbon group having 2 to 10 carbon atoms, n is an integer of 2 to 40, m is an integer of 1 or more, and s is an integer of 1 to 30.). In Formula (1), a plurality of R's may be the same as or different from each other. ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyether polyol composition, and more particularly to a polyether polyol composition containing a polyalkylene ether glycol and a polyether polyol having an oxymethylene structure in the main chain. [Background technology]

[0002] The polyether polyol composition has the general formula HO-(RO) m The polyether polyol contains a polyether polyol having primary hydroxyl groups at both ends, represented by the formula -H (m is an integer of 2 or more, and R is an alkylene group), and the polyether polyol is generally produced by ring-opening polymerization of a cyclic ether. Among them, polytetramethylene ether glycol (hereinafter sometimes abbreviated as "PTMG") obtained by ring-opening polymerization of tetrahydrofuran (hereinafter sometimes abbreviated as "THF") is a linear polyether glycol having hydroxyl groups at both ends, and has the general formula HO-[(CH2)4O] n -H (n is an integer of 2 or more), and is extremely useful as a raw material for polyurethane and polyester, which require stretchability and elasticity.

[0003] In recent years, in fields requiring high-modulus, high-strength polyurethanes and polyesters, the use of high-molecular-weight PTMG has been desired. However, high-molecular-weight PTMG has a high viscosity and is difficult to handle. However, the introduction of oxymethylene groups into the PTMG has made it possible to reduce the viscosity.

[0004] Patent Document 1 describes a method for producing a polyol in which an oxymethylene group is introduced into PTMG, the polyol being purified by steam distillation using a solid acid catalyst such as montmorillonite and the like, and using PTMG having a number average molecular weight of 650 to 3000, or PTMG having a number average molecular weight of 650 to 3000, and glycol, and paraformaldehyde or formaldehyde as raw materials, in the presence of calcium hydroxide.

[0005] Patent Document 2 describes a polyol having a number average molecular weight of 2000 to 13000, which is produced by using PTMG having a number average molecular weight of 1000 to 3000 and paraformaldehyde or formaldehyde as raw materials, and introducing oxymethylene groups into PTMG using a solid acid catalyst such as Amberlyst at a temperature of 60°C to 110°C.

[0006] Patent Document 3 describes the production of a polyether polyol having a number average molecular weight of at least 1270, less than 200 hydroxyl groups, and an oxymethylene structure, using an alkylene diol such as pentanediol or a polyol such as PTMG and paraformaldehyde as raw materials, and using an acidic catalyst such as sulfuric acid or p-toluenesulfonic acid at a temperature not exceeding 130°C.

[0007] Polyurethanes obtained using polyether polyols as raw materials are used in applications such as elastic fibers such as spandex, thermoplastic elastomers, thermosetting elastomers, artificial leather, and synthetic leather, and in the field of the elastic fibers, there is an increasing demand for materials that are excellent in flexibility, elastic recovery, and chemical resistance.

[0008] However, while polyurethanes using polytetramethylene ether glycol, which are known as such polyurethanes, are excellent in flexibility, elongation, and elastic recovery, they have the problem of reduced flexibility at low temperatures due to the crystallinity of the soft segment.Furthermore, they have the problem of poor chemical resistance to oleic acid contained in oils and fats secreted by the human body, which is required for clothing applications (Comparative Example 4 of Patent Document 4).

[0009] Patent Document 5 describes a polyol with enhanced amorphousness, which is obtained by introducing a monomer having a side chain (e.g., 3-alkyltetrahydrofuran) into polytetramethylene ether glycol as a means of suppressing the crystallinity of polytetramethylene glycol. It is known that polyurethanes using these polyols can exhibit good flexibility even in low temperature ranges because the alkyl side chains of the polyol suppress the crystallinity of the soft segment, but the effects on durability such as resistance to oleic acid are not clearly stated.

[0010] Patent Document 6 proposes a high molecular weight polytetramethylene ether glycol having a number average molecular weight of 3500 to 5500, which is known to have better flexibility and elastic recovery than polytetramethylene ether glycol having a number average molecular weight of less than 3500. However, the effects on flexibility and elastic recovery in the low temperature range are not clearly stated. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Special Publication No. 7-505176 [Patent Document 2] Japanese Patent Application Publication No. 57-53529 [Patent Document 3] British Patent No. 850178 [Patent Document 4] Japanese Patent Publication No. 2021-152239 [Patent Document 5] Japanese Patent Application Publication No. 63-235320 [Patent Document 6] Japanese Patent Application Publication No. 2017-025282 Summary of the Invention [Problem to be solved by the invention]

[0012] When polyurethane is produced using, as a raw material, a polyether polyol composition obtained solely from a previously known polyether polyol having an oxyalkylene structure having two or more carbon atoms, such as PTMG, the resulting polyurethane has poor compatibility with solvents and therefore insufficient reactivity. Furthermore, polyurethanes produced using the polyether polyol compositions are unsatisfactory in terms of flexibility at low temperatures and chemical resistance, such as resistance to oleic acid.

[0013] The present invention has been made in view of the above problems, and an object of the present invention is to provide a polyether polyol composition that has excellent compatibility with solvents during urethane production and enables polyurethane to be produced through a good reaction. Another object of the present invention is to provide a polyurethane having improved flexibility at low temperatures and chemical resistance such as resistance to oleic acid, the polyurethane being for use in elastic fibers, and polyurethane elastic fibers using the polyurethane for elastic fibers. [Means for solving the problem]

[0014] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by preparing a polyether polyol composition containing a polyalkylene ether glycol and a polyether polyol represented by a specific structural formula, and have thus completed the present invention. That is, the gist of the present invention lies in the following [1] to

[13] . [1] A polyether polyol composition comprising a polyalkylene ether glycol and a polyether polyol represented by the following formula (1):

[0015] [ka] (In the above formula (1), R represents a divalent hydrocarbon group having 2 to 10 carbon atoms, n is an integer of 2 to 40, m is an integer of 1 or more, and s is an integer of 1 to 30. In addition, in formula (1), multiple R may be the same or different.)

[0016] [2] The polyether polyol composition according to [1], wherein the ratio of the mass of the polyalkylene ether glycol to the mass of the polyether polyol represented by the formula (1) is within the range of 15:85 to 55:45. [3] The polyether polyol composition according to [1] or [2], wherein the polyether polyol represented by the formula (1) has a number average molecular weight of 600 or more. [4] The polyether polyol composition according to any one of [1] to [3], wherein R in the formula (1) is an n-butylene group. [5] A polyurethane containing a structural unit derived from a compound having a plurality of isocyanate groups, a structural unit derived from a chain extender, a structural unit derived from a polyalkylene ether glycol, and a structural unit derived from a polyether polyol represented by the following formula (2):

[0017] [ka] (In the above formula (2), R represents a divalent hydrocarbon group having 2 to 10 carbon atoms, n is an integer of 2 to 40, m is an integer of 1 or more, and s is an integer of 1 to 30. In addition, in formula (2), multiple R may be the same or different.)

[0018] [6] The polyurethane according to [5], wherein the ratio of the mass of the structural unit derived from the polyalkylene ether glycol to the mass of the structural unit derived from the polyether polyol represented by formula (2) is within the range of 15:85 to 55:45. [7] The polyurethane according to [5] or [6], wherein the polyether polyol represented by the formula (2) has a number average molecular weight of 600 or more. [8] The polyurethane according to any one of [5] to [7], wherein R in the formula (2) is an n-butylene group. [9] The polyurethane according to any one of [5] to [8], wherein the structural unit derived from the chain extender is a structural unit derived from at least one compound selected from the group consisting of polyols and polyamines, and the compound is at least one compound selected from the group consisting of ethylenediamine, propylenediamine, isophoronediamine, and hexamethylenediamine.

[10] The polyurethane according to any one of [5] to [9], wherein the structural unit derived from the chain extender is a structural unit derived from at least one compound selected from the group consisting of polyols and polyamines, and the compound is at least one compound selected from the group consisting of 1,4-butanediol, ethylene glycol, propylene glycol, and 1,6-hexanediol.

[11] The polyurethane according to any one of [5] to

[10] , wherein the compound having a plurality of isocyanate groups is at least one compound selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,6-hexamethylene diisocyanate, and isophorone diisocyanate.

[12] The polyurethane according to any one of [5] to

[11] is for use in elastic fibers.

[13] Polyurethane elastic fiber using the polyurethane for elastic fiber described in

[12] . [Effects of the Invention]

[0019] According to the present invention, it is possible to provide a polyether polyol composition which has excellent compatibility with solvents during urethane production and enables polyurethane to be produced through a good reaction. Furthermore, according to the present invention, it is possible to provide a polyurethane having improved flexibility at low temperatures and chemical resistance such as resistance to oleic acid, the polyurethane being for use in elastic fibers, and polyurethane elastic fibers using the polyurethane for elastic fibers. [Brief explanation of the drawings]

[0020] [Figure 1] 2 is a graph showing the viscoelasticity measurement results (E′ (Pa) / temperature (° C.)) of the polyurethane described in Example 2-1 and the polyurethane described in Comparative Example 2-1. [Figure 2] 1 is a graph showing the viscoelasticity measurement results (E′ (Pa) / temperature (° C.)) of the polyurethane described in Example 2-2 and the polyurethane described in Comparative Example 2-1. DETAILED DESCRIPTION OF THE INVENTION

[0021] The present invention will be specifically described below, but the present invention is not limited to the embodiments described below as long as it does not depart from the gist of the invention.

[0022] <Polyether polyol composition> The polyether polyol composition of the present invention contains a polyether polyol composition comprising a polyalkylene ether glycol and a polyether polyol having an oxymethylene structure.

[0023] <Polyalkylene ether glycol> The polyalkylene ether glycol of the present invention, when used as a urethane raw material, has excellent compatibility with the urethane raw material, has good reactivity as a urethane raw material, and when made into a polyurethane, can provide a polyether polyol that can exhibit excellent tensile strength. Therefore, it preferably contains a structural unit derived from a diol having a divalent aliphatic hydrocarbon group having 2 to 10 carbon atoms, and more preferably contains a structural unit derived from a diol having a divalent acyclic aliphatic hydrocarbon group having 2 to 10 carbon atoms. Examples of the structural unit derived from a diol having a divalent acyclic aliphatic hydrocarbon group having 2 to 10 carbon atoms include structural units derived from linear polyols such as ethylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol; structural units derived from linear polyols such as 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol; Examples of structural units include those derived from branched polyols such as neopentyl glycol, 2-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-1,6-hexanediol, 3-butyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,4-dibutyl-1,5-pentanediol, and 2,2-dibutyl-1,3-propanediol. Of these, structural units derived from at least one polyol selected from the group consisting of 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are more preferred.

[0024] Examples of structural units derived from diols having a divalent cycloaliphatic hydrocarbon group having 2 to 10 carbon atoms include 1,3-cyclopentanediol, 1,4-cyclohexanediol, erythritan, isosorbide, 1,4-cyclohexanedimethanol, 2,2-bis(4-hydroxycyclohexyl)-propane, 1,3-cyclohexanedimethanol, 2,7-norbornanediol, tricyclo[5.2.1.0] 2,6 Examples of suitable structural units include those derived from alicyclic polyols such as decane dimethanol. Of these, structural units derived from at least one polyol selected from the group consisting of erythritan, isosorbide, and 1,4-cyclohexane dimethanol are more preferred. The polyalkylene ether glycol used in the present invention can be at least one type or a combination of two or more types of structural units derived from diols having a divalent aliphatic hydrocarbon group having 2 to 10 carbon atoms, as described above, without any particular limitations.

[0025] <Polyether polyol having an oxymethylene structure> The polyether polyol composition of the present invention contains a polyol having an oxymethylene structure represented by the following formula (1).

[0026] [ka]

[0027] (In the above formula (1), R represents a divalent hydrocarbon group having 2 to 10 carbon atoms, n is an integer of 1 to 40, m is an integer of 1 or more, and s is an integer of 1 to 30. In addition, in formula (1), multiple R may be the same or different.)

[0028] The divalent hydrocarbon group (R) having 2 to 10 carbon atoms in the formula (1) is preferably a divalent aliphatic hydrocarbon group having 2 to 10 carbon atoms, and more preferably a divalent acyclic aliphatic hydrocarbon group having 2 to 10 carbon atoms, because when the polyether polyol represented by the formula (1) is used as a urethane raw material, it can provide a polyether polyol that has excellent compatibility with the urethane raw material, has good reactivity as a urethane raw material, and is capable of exhibiting excellent tensile strength when made into a polyurethane. Examples of the divalent acyclic aliphatic hydrocarbon group having 2 to 10 carbon atoms include hydrocarbon groups derived from linear polyols such as ethylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol; hydrocarbon groups derived from 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-methyl-1,4-butanediol, and 3-methyl-1,5- Examples of suitable branched polyols include hydrocarbon groups derived from branched polyols such as pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-1,6-hexanediol, 3-butyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,4-dibutyl-1,5-pentanediol, and 2,2-dibutyl-1,3-propanediol. Of these, hydrocarbon groups derived from at least one polyol selected from the group consisting of 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are more preferred.

[0029] Examples of divalent alicyclic hydrocarbon groups having 2 to 10 carbon atoms include 1,3-cyclopentanediol, 1,4-cyclohexanediol, erythritan, isosorbide, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,7-norbornanediol, tricyclo[5.2.1.0 2,6] Examples include hydrocarbon groups derived from alicyclic polyols such as decanedimethanol. Among these, hydrocarbon groups derived from at least one polyol selected from the group consisting of erythritan, isosorbide, and 1,4-cyclohexanedimethanol are more preferred. The polyether polyol represented by the formula (1) in the present invention can be any one or a combination of two or more of the structural units derived from the diol having a divalent aliphatic hydrocarbon group having 2 to 10 carbon atoms, without any particular limitations.

[0030] The lower limit of the molecular weight distribution of the polyether polyol represented by formula (1) is preferably 1.85 or more, more preferably 1.90 or more, even more preferably 2.00 or more, and particularly preferably 2.30 or more. The upper limit is not particularly limited, but is preferably 3.50 or less, more preferably 3.40 or less, even more preferably 3.30 or less, and particularly preferably 3.20 or less. By keeping the molecular weight distribution within this range, when a polyether polyol composition containing a polyether polyol having an oxymethylene group and a polyalkylene ether glycol is used as a urethane raw material, it is easy to obtain a polyurethane that has excellent compatibility with the urethane raw material, good reactivity as a urethane raw material, and improved flexibility at low temperatures, elastic recovery, and chemical resistance such as oleic acid resistance. The molecular weight distribution can be measured by GPC (gel permeation chromatography).

[0031] The number-average molecular weight of the polyether polyol represented by formula (1) is preferably 600 to 9900, more preferably 800 to 5900, and even more preferably 1000 to 5200. By setting the number-average molecular weight within this range, the viscosity is low and easy to handle. When a polyether polyol composition containing the polyether polyol represented by formula (1) and a polyalkylene ether glycol is used as a urethane raw material, it becomes easy to obtain a polyurethane that has excellent compatibility with the urethane raw material, good reactivity as a urethane raw material, and improved flexibility at low temperatures, elastic recovery, and chemical resistance such as oleic acid resistance. The number-average molecular weight of the polyether polyol can be determined by measuring the hydroxyl value of the polyether polyol according to the method described in JIS K1557-1:2007 and calculating the number-average molecular weight, by GPC (gel permeation chromatography) measurement, or by other methods. 1 It can be measured by H-NMR measurement (proton nuclear magnetic resonance spectroscopy).

[0032] (Production of polyether polyol represented by formula (1)) <Raw material 1> The raw material for producing the polyether polyol represented by the formula (1) of the present invention includes a raw material that is the basis of the formula (1). The raw material is at least one compound selected from the group consisting of formaldehyde, paraformaldehyde, and trioxane (hereinafter, sometimes referred to as "raw material 1"). Formaldehyde is generally used as an aqueous solution called formalin, and when formaldehyde is used as a raw material, it becomes necessary to remove a large amount of water from the reaction system to purify the polyether polyol. Therefore, trioxane and paraformaldehyde are preferred as raw material 1, and paraformaldehyde is more preferred, as they allow efficient production of polyether polyol.

[0033] The amount of raw material 1 is preferably 0.1% by mass or more and 35% by mass or less, more preferably 0.5% by mass or more and 30% by mass or less, and even more preferably 1% by mass or more and 25% by mass or less, based on the total amount of raw materials. By adjusting the amount within this range, the thermal stability of the produced polyether polyol may be improved.

[0034] <Raw material 2> The raw materials include, in addition to raw material 1, a polyol other than raw material 1 (hereinafter, sometimes referred to as "raw material 2"). Raw material 2 is a polyether polyol other than raw material 1 and / or a polyol other than raw material 1.

[0035] As the polyether polyol other than raw material 1 (hereinafter sometimes referred to as "raw material 2-1"), when a polyether polyol composition containing the polyether polyol represented by formula (1) and a polyalkylene ether glycol is used as a urethane raw material, it is possible to provide a polyether polyol that has excellent compatibility with the urethane raw material, has good reactivity as a urethane raw material, and exhibits excellent tensile strength when formed into a polyurethane. Aliphatic polyether polyols are preferred, and acyclic aliphatic polyether polyols are more preferred. Examples of acyclic aliphatic polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, copolymerized polytetramethylene ether glycol of 3-methyltetrahydrofuran and tetrahydrofuran, copolymerized polyether polyol of neopentyl glycol and tetrahydrofuran, copolymerized polyether polyol of ethylene oxide and tetrahydrofuran, and copolymerized polyether glycol of propylene oxide and tetrahydrofuran. Among these, polytetramethylene ether glycol is even more preferred. Cycloaliphatic polyether polyols include 1,3-cyclopentanediol, 1,4-cyclohexanediol, erythritan, 1,4-cyclohexanedimethanol, 2-bis(4-hydroxycyclohexyl)-propane, 1,3-cyclohexanedimethanol, 2,7-norbornanediol, and tricyclo[5.2.1.0 2,6Among them, polyether polyols obtained by polymerizing 1,4-cyclohexanedimethanol are more preferred.

[0036] The number average molecular weight of raw material 2-1 is preferably 100 to 5000, more preferably 150 to 4000, even more preferably 200 to 3000, and particularly preferably 200 to 900. By setting the number average molecular weight within this range, it is possible to achieve a balanced physical property between the viscosity-reducing effect of oxymethylene and the mechanical properties of the polyether polyol itself. Furthermore, by setting the number average molecular weight within this range, when a polyether polyol composition containing the polyether polyol represented by formula (1) and a polyalkylene ether glycol is used as a urethane raw material, it is possible to provide a polyether polyol that has excellent compatibility with urethane raw materials, good reactivity as a urethane raw material, and exhibits excellent tensile strength when made into a polyurethane.

[0037] As the polyol other than raw material 1 (hereinafter sometimes referred to as "raw material 2-2"), when a polyether polyol composition containing the polyether polyol represented by the formula (1) and a polyalkylene ether glycol is used as a urethane raw material, it is possible to provide a polyether polyol that has excellent compatibility with the urethane raw material, has good reactivity as a urethane raw material, and can exhibit excellent tensile strength when made into a polyurethane. Therefore, an acyclic aliphatic polyol is preferred, and an acyclic aliphatic polyol is more preferred. Examples of the acyclic aliphatic polyol include ethylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), and the like. Examples of suitable polyols include 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, 3-methyl-pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-1,6-hexanediol, 3-butyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,4-dibutyl-1,5-pentanediol, 2,2-dibutyl-1,3-propanediol, etc. Among these, at least one polyol selected from the group consisting of 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol is more preferred. Cycloaliphatic polyols include 1,3-cyclopentanediol, 1,4-cyclohexanediol, erythritan, isosorbide, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,7-norbornanediol, tricyclo[5.2.1.0 2,6 Among them, at least one polyol selected from the group consisting of erythritan, isosorbide, and 1,4-cyclohexanedimethanol is more preferred.

[0038] It is preferable that raw material 2 contains raw material 2-1, since this allows the desired number average molecular weight of the polyether polyol to be efficiently obtained.

[0039] <Homogeneous acid catalyst> The catalyst used in the present invention for producing the polyether polyol represented by formula (1) is a homogeneous acid catalyst. The polyether polyol represented by formula (1) is produced using raw materials 1 and 2 in the presence of the homogeneous acid catalyst. The homogeneous acid catalyst has an acidity (pKa) in acetonitrile of less than 7.6, preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.0 or less. While the lower limit is not particularly limited, -1.0 is preferred. Examples of homogeneous acid catalysts having an acidity (pKa) in acetonitrile within the above range include trifluoromethanesulfonic acid (pKa = 2.6), fluorosulfonic acid (pKa = 1.5), tetrafluoroboric acid (pKa = 1.8), perchloric acid (pKa = -0.7), hydrobromic acid (pKa = 5.4), hydroiodic acid (pKa = 2.8), 4-chlorobenzenesulfonic acid (pKa = 7.0), 2,5-dichlorobenzenesulfonic acid, 3-nitrobenzenesulfonic acid (pKa = 6.4), 4-nitrobenzenesulfonic acid, Examples of suitable fluorocarbons include 2,4,6-trifluoromethanesulfonyl phenol (pKa=6.3), 2,4,6-tri(trifluoromethanesulfonyl)phenol (pKa=4.44), 2,4,6-tri(fluorosulfonyl)phenol (pKa=5.22), 1,2,3-tricyanocyclopentadiene (pKa=1.44), 2,3,5-tricyanocyclopentadiene (pKa=3.65), 1,2,4-tricyano-3-methylcyclopentadiene (pKa=3.4), and bis(trifluoromethanesulfonyl)imide (pKa=0.3).

[0040] From the viewpoint of suppressing the modification of the hydroxyl groups at the terminals of the produced polyether polyol and improving its thermal stability, the homogeneous acid catalyst is preferably a Brønsted acid containing a halogen, a halogenated alkyl group, or a halogenated aromatic group as a substituent, more preferably a Brønsted acid containing a halogenated alkyl group or a halogenated aromatic group as a substituent, and even more preferably a Brønsted acid containing a halogenated alkyl group as a substituent. Examples of the homogeneous catalyst described above include trifluoromethanesulfonic acid, perfluorooctane sulfonic acid, fluorosulfonic acid, chlorosulfonic acid, 2,5-dichlorobenzenesulfonic acid, pentafluorobenzenesulfonic acid, and bis(trifluoromethanesulfonyl)imide.

[0041] The amount of the homogeneous acid catalyst is preferably 0.001 mol % or more and 0.5 mol % or less, more preferably 0.005 mol % or more and 0.1 mol % or less, and even more preferably 0.01 mol % or more and 0.05 mol % or less, relative to the amount of hydroxyl groups in the raw material 2. When the amount of the homogeneous acid catalyst is within the above range, the thermal stability of the produced polyether polyol represented by the formula (1) may be improved. The amount of hydroxyl groups in raw material 2 is calculated by dividing the amount of raw material 2 used in the production of polyether polyol by the molecular weight of raw material 2 to obtain the number of moles, and then multiplying the result by 2. When raw material 2 is a polyol, i.e., raw material 2-2, the molecular weight is the number average molecular weight.

[0042] <Reaction process> The reaction to produce a polyether polyol represented by formula (1) using raw materials 1 and 2 as raw materials in the presence of a homogeneous acid catalyst is carried out in a reaction system. The reaction system may be a batch system or a continuous system, with the batch system being preferred due to the ease of removing water by-produced in the reaction system. The homogeneous acid catalyst may be dissolved in a solvent inert to the reaction (e.g., water) and added as a solution to the reaction system. If necessary, a solvent that does not affect the reaction may be present in the reaction system. Examples of such solvents include tetrahydrofuran, cyclopentyl methyl ether, benzene, toluene, xylene, and cyclohexane. However, toluene, xylene, and cyclohexane are preferred from the viewpoint of stability against the homogeneous acid catalyst. The reaction starts when raw material 1, raw material 2, and the homogeneous acid catalyst coexist in the reaction system. The reaction temperature is preferably 60°C or higher and 130°C or lower, more preferably 70°C or higher and 120°C or lower, and even more preferably 90°C or higher and 110°C or lower. By using this reaction temperature range, moisture generated in the reaction system can be easily removed from the reaction system even under normal pressure. The reaction pressure is preferably 10 kPa or higher and 1000 kPa or lower, more preferably 50 kPa or higher and 500 kPa or lower, and even more preferably 90 kPa or higher and 150 kPa or lower. Using this reaction pressure range may allow the raw materials to be maintained within the reaction system and may also allow moisture to be efficiently removed. Once it has been confirmed that the raw material 1 has been consumed, that is, that the reaction has been completed, removal of the solvent and water from the reaction system may begin. The temperature is preferably 60°C or higher and 180°C or lower, more preferably 90°C or higher and 160°C or lower, and even more preferably 100°C or higher and 150°C or lower. By setting the temperature within this range, water and solvent generated during the reaction can be efficiently removed from the reaction system. Furthermore, the pressure is preferably 1 Pa or higher and 50 kPa or lower, more preferably 10 Pa or higher and 10 kPa or lower, and even more preferably 50 Pa or higher and 1 kPa or lower. Setting the pressure within this range may enable efficient removal of the solvent and water. After removing the solvent and water, heating under reduced pressure may be continued as necessary. The temperature is preferably 60°C or higher, more preferably 100°C or higher, and even more preferably 130°C or higher, in order to promote depolymerization, as described below. Furthermore, in order to prevent decomposition of the product, the temperature is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 150°C or lower. By using the reaction temperature within this range, the sites where oxymethylene groups in the polyether polyol represented by formula (1) are continuously bonded can be depolymerized, resulting in a structure in which structural units derived from raw material 2 and oxymethylene groups are alternately bonded, which may improve heat resistance. The reaction pressure is preferably 1 Pa or higher and 50 kPa or lower, more preferably 10 Pa or higher and 10 kPa or lower, and even more preferably 50 Pa or higher and 1 kPa or lower.

[0043] After an appropriate time has elapsed since the start of the reaction, taking into consideration the number average molecular weight of the desired polyether polyol represented by the formula (1), a deactivator for the homogeneous acid catalyst, such as magnesium hydroxide, aluminum oxide, or hydrotalcite, can be added to the reaction system to deactivate the homogeneous catalyst and terminate the reaction.

[0044] After the reaction is complete, the polyether polyol represented by formula (1) may be purified. Specifically, the deactivator is removed. Methods for removing the deactivator include filtration. If the viscosity of the polyether polyol represented by formula (1) is high and filtration is difficult, a solvent may be added to facilitate filtration. The solvent may be removed by discharging the solvent from the system by heating under reduced pressure.

[0045] (Proportion of Polyether Polyol Composition) In the ratio of the mass of the polyalkylene ether glycol contained in the polyether polyol composition of the present invention to the mass of the polyether polyol represented by formula (1), the weight ratio of the polyalkylene ether glycol is preferably 15:85 or more. Furthermore, in the above ratio, the weight ratio of the polyalkylene ether glycol is preferably 55:45 or less, more preferably 50:50 or less, even more preferably 45:55 or less, and particularly preferably 40:60 or less. When the ratio of the mass of the polyalkylene ether glycol contained in the polyether polyol composition to the mass of the polyether polyol represented by formula (1) satisfies the above range, a polyether polyol composition that has excellent compatibility with solvents during urethane production and allows polyurethane to be produced through a good reaction is more likely to be obtained, and when converted into a urethane, polyurethanes that have improved flexibility at low temperatures and chemical resistance, such as resistance to oleic acid, tend to be more likely to be obtained.

[0046] [Uses of polyether polyol composition] The polyether polyol composition of the present invention is useful as a raw material for polyurethanes suitable for applications such as elastic fibers, thermoplastic polyurethanes, and coating materials because of its excellent reactivity, flexibility at low temperatures, and chemical resistance such as resistance to oleic acid.

[0047] [Polyurethane] The polyurethane of the present invention can be produced by a conventional polyurethane reaction using a polyalkylene ether glycol, a polyether polyol represented by the following formula (2), a polyisocyanate compound, and a chain extender in predetermined proportions.

[0048] [ka]

[0049] (In the above formula (2), R represents a divalent hydrocarbon group having 2 to 10 carbon atoms, n is an integer of 2 to 40, m is an integer of 1 or more, and s is an integer of 1 to 30. In addition, in formula (2), multiple R may be the same or different.)

[0050] The polyalkylene ether glycol used in the polyurethane of the present invention is the polyalkylene ether glycol described in the polyether polyol composition of the present invention. Furthermore, as the polyether polyol represented by formula (2) used in the polyurethane of the present invention, the polyether polyol represented by formula (1) described in the polyether polyol composition of the present invention is used.

[0051] As a method for producing the polyurethane of the present invention, for example, a polyether polyol composition containing the polyalkylene ether glycol and the polyether polyol represented by formula (2) can be reacted with a polyisocyanate and a chain extender at a temperature ranging from room temperature to 200°C to produce the polyurethane. Alternatively, a polyether polyol composition containing the polyalkylene ether glycol and the polyether polyol represented by formula (2) can be first reacted with an excess of polyisocyanate to produce a prepolymer having an isocyanate group at its terminal, and then a chain extender can be used to increase the degree of polymerization to produce polyurethane.

[0052] <Polyisocyanate> Examples of polyisocyanates that can be used in producing polyurethane using a polyether polyol composition containing the polyalkylene ether glycol and the polyether polyol represented by formula (2) include various known aliphatic, alicyclic, and aromatic polyisocyanate compounds. For example, aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and dimer diisocyanate in which the carboxyl groups of dimer acid are converted to isocyanate groups; alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and 1,4-bis(isocyanatomethyl)cyclohexane. Cyanates: aromatic diisocyanates such as xylylene diisocyanate, 4,4'-diphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate, and m-tetramethylxylylene diisocyanate. These may be used alone or in combination of two or more.

[0053] Among these, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate are preferred because they provide a polyurethane with a good balance of physical properties and are available industrially in large quantities at low cost.

[0054] <Chain extender> The chain extender used in producing polyurethane is a low molecular weight compound having at least two active hydrogens that react with isocyanate groups when producing a prepolymer having an isocyanate group, which will be described later. Typical examples of the chain extender include polyols and polyamines. The polyol used as a chain extender refers to a polyol other than the polyalkylene ether glycol and the polyether polyol represented by the formula (2).

[0055] Specific examples thereof include straight-chain diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol; 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, and 2,4-heptanediol. Diols with branched chains such as 1,4-dimethylolhexane, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, and dimer diol; diols with ether groups such as diethylene glycol and propylene glycol; and diols with alicyclic structures such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 1,4-dihydroxyethylcyclohexane. diols containing aromatic groups such as xylylene glycol, 1,4-dihydroxyethylbenzene, and 4,4'-methylenebis(hydroxyethylbenzene); polyols such as glycerin, trimethylolpropane, and pentaerythritol; hydroxyamines such as N-methylethanolamine and N-ethylethanolamine; ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, and 4,4'-diaminodiamine. Examples include polyamines such as cyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4,4'-diphenylmethanediamine, methylenebis(o-chloroaniline), xylylenediamine, diphenyldiamine, tolylenediamine, hydrazine, piperazine, and N,N'-diaminopiperazine; and water.

[0056] These chain extenders may be used alone or in combination of two or more. Among these, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, ethylenediamine, 1,3-diaminopropane, isophoronediamine, and 4,4'-diaminodicyclohexylmethane are preferred in terms of the favorable balance of physical properties of the resulting polyurethane and their industrial availability in large quantities at low cost. Furthermore, the chain extender used in producing a prepolymer having a hydroxyl group, which will be described later, is a low-molecular-weight compound having at least two isocyanate groups, and specific examples thereof include the compounds described in the <Polyisocyanate> section.

[0057] <Chain terminator> When producing polyurethane, a chain terminator having one active hydrogen group can be used as needed to control the molecular weight of the resulting polyurethane. Examples of these chain terminators include aliphatic monools having one hydroxyl group, such as methanol, ethanol, propanol, butanol, and hexanol, and aliphatic monoamines having one amino group, such as diethylamine, dibutylamine, n-butylamine, and morpholine. These may be used alone or in combination of two or more.

[0058] <Catalyst> When producing the polyurethane of the present invention, a catalyst may be used in the urethanization reaction. Examples of the urethanization reaction catalyst include organotin compounds, organozinc compounds, organobismuth compounds, organotitanium compounds, organozirconium compounds, and amine compounds. The urethanization reaction catalyst may be used alone or in combination of two or more. When a urethanization reaction catalyst is used, it is preferable to adjust the amount to 0.1 to 100 ppm by mass relative to the mass of the polyurethane for elastic fiber produced. By using a urethanization reaction catalyst within this range, the molecular weight of the polyurethane is maintained at a sufficiently high level, and the inherent physical properties of the polyurethane are more likely to be effectively exhibited.

[0059] Among the urethanization reaction catalysts, organic tin compounds are preferred. Examples of organic tin compounds include tin-containing acylate compounds and tin-containing mercaptocarboxylic acid salts, and more specifically, tin octoate, monomethyltin mercaptoacetate, monobutyltin triacetate, monobutyltin monooctylate, monobutyltin monoacetate, monobutyltin maleate, monobutyltin maleic acid benzyl ester salt, monooctyltin maleate, monooctyltin thiodipropionate, monooctyltin tris(isooctylthioglycolate), monophenyltin triacetate, dimethyltin maleate salt, dimethyltin bis(ethylene glycol monothioglycolate), dimethyltin bis(mercaptoacetic acid) salt, dimethyltin bis(3-mercaptopropionic acid) salt, dimethyltin bis(isooctylmercaptoacetate), dibutyltin diacetate. dibutyltin dioctoate, dibutyltin distearate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin maleate polymer, dibutyltin maleate ester salt, dibutyltin bis(mercaptoacetic acid), dibutyltin bis(mercaptoacetic acid alkyl ester) salt, dibutyltin bis(3-mercaptopropionic acid alkoxybutyl ester) salt, dibutyltin bisoctylthioglycol ester salt, dibutyltin(3-mercaptopropionic acid) salt, dioctyltin maleate, dioctyltin maleate ester salt, dioctyltin maleate polymer, dioctyltin dilaurate, dioctyltin bis(isooctylmercaptoacetate), dioctyltin bis(isooctylthioglycolate), dioctyltin bis(3-mercaptopropionic acid) salt, and the like.

[0060] According to the present invention, when an aliphatic isocyanate compound and / or an alicyclic isocyanate compound is used as a raw material, it is preferable to use an organotin compound as a catalyst because the reactivity of these compounds is lower than that of aromatic isocyanate compounds. In particular, when using 4,4'-dicyclohexylmethane diisocyanate, which has low reactivity, it is even more preferable to use an organotin compound as a catalyst.

[0061] [Polyurethane manufacturing method] The polyurethane of the present invention can be efficiently produced by the following methods: a method of continuously reacting a polyether polyol composition containing a polyalkylene ether glycol and a polyether polyol represented by formula (2), a polyisocyanate compound, and a chain extender in one shot (single-step method); a method of first reacting a polyether polyol composition containing a polyalkylene ether glycol and a polyether polyol represented by formula (2) with an excess of a polyisocyanate compound to produce a prepolymer having isocyanate groups at the molecular chain terminals, which is then reacted with a chain extender to increase the degree of polymerization (two-step method (a)); or a method of first reacting a polyisocyanate compound with an excess of a polyalkylene ether glycol and a polyether polyol represented by formula (2) to produce a prepolymer having hydroxyl groups at the molecular chain terminals, which is then reacted with a chain extender to increase the degree of polymerization (two-step method (b)).

[0062] As a method for producing the polyurethane of the present invention by reacting a polyether polyol composition containing the polyalkylene ether glycol and the polyether polyol represented by formula (2) with a polyisocyanate compound and a chain extender, a general experimental method or an industrially used production method can be used.

[0063] <One step method> The one-stage method, also known as the one-shot method, is a method in which a polyether polyol composition containing a polyalkylene ether glycol and a polyether polyol represented by formula (2), and other polyols, a polyisocyanate compound, and a chain extender, which are used as needed, are charged all at once to carry out a reaction.

[0064] <Two step method> The two-stage method is also called the prepolymer method and is mainly the following method. (a) A method for producing a polyurethane by first reacting a polyether polyol composition containing a polyalkylene ether glycol and a polyether polyol represented by formula (2), and other polyols with an excess of a polyisocyanate compound at a reaction equivalent ratio of polyisocyanate compound / (the polyether polyol composition of the present invention and other polyols) of more than 1 to 10.0, to produce a prepolymer having isocyanate groups at the molecular chain terminals, and then adding a chain extender to the prepolymer. (b) A method of producing a polyurethane by first reacting a polyisocyanate compound with a polyether polyol composition containing an excess of polyalkylene ether glycol and a polyether polyol represented by formula (2) and another polyol at a reaction equivalent ratio of polyisocyanate compound / (polyalkylene ether glycol, polyether polyol represented by formula (2), and another polyol) of 0.1 or more and less than 1.0 to produce a prepolymer having hydroxyl groups at the molecular chain terminals, and then reacting this with a polyisocyanate compound having isocyanate groups at the terminals as a chain extender.

[0065] The two-stage process can be carried out in the absence of a solvent or in the presence of a solvent. The production of polyurethane by the two-stage process can be carried out by any of the following methods (1) to (3). (1) Without using a solvent, a polyisocyanate compound, a polyalkylene ether glycol, and a polyether polyol composition containing the polyether polyol represented by formula (2) are directly reacted with other polyols to synthesize a prepolymer, which is then used as is in the chain extension reaction. (2) A prepolymer is synthesized by the method described in (1), then dissolved in a solvent and used in the subsequent chain extension reaction. (3) A solvent is used from the beginning, and a polyether polyol composition containing a polyisocyanate compound, a polyalkylene ether glycol, and a polyether polyol represented by formula (2) is reacted with other polyols, followed by a chain extension reaction.

[0066] In the case of method (1), it is important to obtain polyurethane in the presence of a solvent during the chain extension reaction by, for example, dissolving the chain extender in the solvent or dissolving the prepolymer and chain extender in the solvent simultaneously.

[0067] In addition, catalysts, stabilizers, etc. may be added as needed in the production of polyurethane.

[0068] <Reaction molar ratio> In any of the above production methods, the urethane-forming reaction for producing the polyurethane of the present invention is carried out so that the reaction molar ratio of polyol:polyisocyanate compound:chain extender is 1:1.5-4:0.5-3. If the molar ratio of the polyisocyanate compound to 1 mole of polyol is less than 1.5, the strength of the resulting polyurethane will be insufficient, and if it exceeds 4, the flexibility of the resulting polyurethane will be insufficient. It is preferable to use 1.5 to 4 moles, particularly 2 to 3 moles, of the polyisocyanate compound per mole of polyol. Furthermore, if the molar ratio of the chain extender to 1 mole of polyol is less than 0.5, the strength of the resulting polyurethane will be insufficient, and if it exceeds 3, the flexibility of the resulting polyurethane will be insufficient. The chain extender is preferably used in an amount of 0.5 to 3 moles, particularly 1 to 2 moles, per mole of polyol.

[0069] <Molecular weight> The molecular weight of the polyurethane of the present invention is adjusted appropriately depending on the application and is not particularly limited, but is preferably 50,000 to 500,000, and more preferably 100,000 to 300,000, as the weight average molecular weight (Mw) calculated in terms of polystyrene as measured by gel permeation chromatography (GPC). If the weight average molecular weight (Mw) is less than the lower limit, sufficient strength and hardness may not be obtained, while if it is greater than the upper limit, handling properties such as processability tend to be impaired.

[0070] <Additives> The polyurethane of the present invention can be used as a polyurethane composition by adding or mixing an internal mold release agent, a filler, a plasticizer, a colorant (dye or pigment), a stabilizer (for example, an antioxidant, a UV stabilizer, or a heat stabilizer), a flame retardant, a crosslinking agent, a reaction accelerator, a reinforcing agent, or the like, within a range that does not impair the properties of the polyurethane of the present invention.

[0071] Examples of internal mold release agents include fatty acid amides, fatty acid esters, fatty acids, and fatty acid salts. Examples of fatty acid amides include caproic acid amide, lauric acid amide, myristic acid amide, stearic acid amide, oleic acid amide, ethylene bisstearic acid amide, and ethylene bisoleic acid amide. Examples of fatty acid esters include esters of long-chain fatty acids and alcohols, specifically sorbitan monolaurate, butyl stearate, butyl laurate, octyl palmitate, and stearyl stearate. Examples of fatty acids include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, montanic acid, lindenic acid, oleic acid, erucic acid, and linoleic acid. Examples of fatty acid salts include metal (e.g., barium, zinc, magnesium, calcium, etc.) salts of the above fatty acids.

[0072] Examples of fillers include talc, calcium carbonate, chalk, calcium sulfate, clay, kaolin, silica, glass, fumed silica, mica, wollastonite, feldspar, aluminum silicate, calcium silicate, alumina, alumina hydrates such as alumina trihydrate, glass microspheres, ceramic microspheres, thermoplastic resin microspheres, barite, wood flour, glass fiber, carbon fiber, marble dust, cement dust, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, titanium dioxide, titanates, combinations thereof, etc. The filler is preferably talc, calcium carbonate, barium sulfate, silica, glass, glass fiber, alumina, titanium dioxide, or a combination thereof, and more preferably talc, calcium carbonate, barium sulfate, glass fiber, or a combination thereof. Fillers that can be used include those described in Zweifel Hans et al., "Plastics Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th Edition, Chapter 17, pp. 901-948 (2001).

[0073] Examples of plasticizers include mineral oil, abietic acid esters, adipates, alkylsulfonic acid esters, azelates, benzoates, chlorinated paraffins, citrates, epoxides, glycol ethers and their esters, glutarates, hydrocarbon oils, isobutyrates, oleates, pentaerythritol derivatives, phosphates, phthalates, polybutenes, ricinoleates, sebacates, sulfonamides, trimellitates, pyromellitates, biphenyl derivatives, stearates, difuran esters, fluorine-containing plasticizers, hydroxybenzoates, isocyanate ester adducts, polycyclic aromatic compounds, natural product derivatives, siloxane-based plasticizers, tar-based products, thioesters, thioethers, and combinations thereof. The content of plasticizer in the polyurethane composition is preferably 0 to 15% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass. As the plasticizer, those described in George Wypych's "Handbook of Plasticizers," Chem Tec Publishing, Toronto-Scarborough, Ontario (2004) can be used.

[0074] Examples of colorants (dyes and pigments) include inorganic pigments such as metal oxides (e.g., iron oxide, zinc oxide, titanium dioxide), mixed metal oxides, carbon black, and combinations thereof; organic pigments such as anthraquinone, anthanthrone, azo compounds, monoazo compounds, arylamides, benzimidazolone, BONA lake, diketopyrrolopyrrole, dioxazine, disazo compounds, diarylide compounds, flavanthrone, indanthrone, isoindolinone, isoindoline, monoazo salts, naphthol, β-naphthol, naphthol AS, naphthol lake, perylene, perinone, phthalocyanine, pyranthrone, quinacridone, quinophthalone, and combinations thereof; and combinations of inorganic and organic pigments. The content of the colorant in the polyurethane composition is preferably 0 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.25 to 2% by mass. As the colorant, those described in Zweifel Hans et al., "Plastics Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th Edition, Chapter 15, pp. 813-882 (2001) can be used.

[0075] Examples of antioxidants include aromatic amines or hindered amines such as alkyldiphenylamines, phenyl-α-naphthylamines, alkyl-substituted phenyl-α-naphthylamines, aralkyl-substituted phenyl-α-naphthylamines, alkylated p-phenylenediamines, and tetramethyl-diaminodiphenylamine; phenolic compounds such as 2,6-di-t-butyl-4-methylphenol; 1,3,5-trimethyl-2,4,6-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)benzene; Examples of antioxidants include tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane (e.g., IRGANOX™ 1010, manufactured by Ciba Specialty Chemicals); acryloyl-modified phenol; octadecyl-3,5-di-t-butyl-4-hydroxycinnamate (e.g., IRGANOX™ 1076, manufactured by Ciba Specialty Chemicals); phosphites; phosphonite esters; hydroxylamines; benzofuranone derivatives; and combinations thereof. The content of the antioxidant in the polyurethane composition is preferably 0 to 5 mass%, more preferably 0.0001 to 2.5 mass%, even more preferably 0.001 to 1 mass%, and particularly preferably 0.001 to 0.5 mass%. As the antioxidant, those described in Zweifel Hans et al., "Plastics Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th Edition, Chapter 1, pp. 1-140 (2001) can be used.

[0076] Examples of UV stabilizers include benzophenone, benzotriazole, aryl ester, oxanilide, acrylic ester, formamidine, carbon black, hindered amine, nickel quencher, hindered amine, phenolic compound, metal salt, zinc compound, and combinations thereof. The content of the UV stabilizer in the polyurethane composition is preferably 0 to 5% by mass, more preferably 0.01 to 3% by mass, even more preferably 0.1 to 2% by mass, and particularly preferably 0.1 to 1% by mass. UV stabilizers that can be used include those described in "Plastics Additives Handbook" by Zweifel Hans et al., Hanser Gardner Publications, Cincinnati, Ohio, 5th Edition, Chapter 2, pp. 141-426 (2001).

[0077] Examples of heat stabilizers include phosphorus-based heat stabilizers, and commercially available products thereof include trade names Irgafos 38, 126, and P-EPQ manufactured by Ciba Specialty Chemicals, and trade names Adekastab PEP-4C, 11C, 24, and 36 manufactured by Asahi Denka Kogyo Co., Ltd. When a phosphorus-based heat stabilizer is used, the content of the heat stabilizer in the polyurethane composition is preferably 0.05 to 1% by mass.

[0078] Examples of the flame retardant include halogen-based organic flame retardants such as polybromodiphenyl ether, ethylene bisbrominated phthalimide, bis(brominated phenyl)ethane, bis(brominated phenyl)terephthalamide, and perchloropentacyclodecane; phosphorus-based organic flame retardants; nitrogen-based organic flame retardants; and inorganic flame retardants such as antimony trioxide, aluminum hydroxide, and magnesium hydroxide.

[0079] Examples of crosslinking agents include organic peroxides such as alkyl peroxides, aryl peroxides, peroxyesters, peroxycarbonates, diacyl peroxides, peroxyketals, and cyclic peroxides; silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, and 3-methacryloyloxypropyltrimethoxysilane; and radical crosslinkers having multiple (preferably three or more) carbon-carbon double bonds in the molecule, such as trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and toluacrylformal. Examples of crosslinking agents that can be used include those described in "Plastics Additives Handbook" by Zweifel Hans et al., 5th Edition, Chapter 14, pp. 725-812 (2001), published by Hanser Gardner Publications, Cincinnati, Ohio. Of these, radical crosslinking agents are preferred, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and toluacrylformal are more preferred, and trimethylolpropane triacrylate and trimethylolpropane trimethacrylate are even more preferred.

[0080] These additives may be used alone or in any combination of two or more in any ratio.

[0081] The amount of these additives added, expressed as a mass ratio relative to the polyurethane of the present invention, preferably has a lower limit of 0.01 mass%, more preferably 0.05 mass%, and even more preferably 0.1 mass%, and an upper limit of preferably 10 mass%, more preferably 5 mass%, and even more preferably 1 mass%. If the amount of additive added is too small, the effect of adding the additive cannot be fully obtained, while if the amount is too large, precipitation or turbidity may occur during processing of the polyurethane.

[0082] <Polyurethane applications> The polyurethane of the present invention has excellent flexibility and elastic recovery at low temperatures and chemical resistance such as resistance to oleic acid, and therefore can be suitably used as elastic fibers for clothing applications and the like.

[0083] [Polyurethane elastic fiber] Methods for producing polyurethane elastic fibers using the polyurethane of the present invention include, for example, a melt spinning method in which the polyurethane of the present invention is formed into pellets and the pelleted polyurethane is spun while melting; a wet spinning method in which the polyurethane of the present invention is dissolved in the presence of an appropriate solvent and then extruded from a nozzle into a coagulating liquid of a non-solvent, where it is solidified by a chemical reaction to form fibers; and a dry spinning method in which polyurethane dissolved in an appropriate solvent is ejected from a spinneret (nozzle), and the solvent is vaporized with hot air to form fibers.These methods are not particularly limited, and the effects of the present invention can be achieved by any of these known methods.

[0084] The spinning apparatus and spinning conditions used in producing polyurethane elastic fibers using the polyurethane of the present invention vary depending on the desired fiber diameter and shape, and are not particularly limited and may be appropriately set accordingly. The fineness (fiber diameter) of the polyurethane elastic fiber can be appropriately selected based on the shape retention performance and production costs of the elastic fiber product, but from the standpoint of ease of production and cost, it is preferably in the range of 11 to 800 dtex, more preferably 17 to 622 dtex, and even more preferably 17 to 156 dtex.

[0085] The elastic fiber made of the polyurethane of the present invention can be used as a bare yarn as it is, or can be covered with other fibers to be used as a covered yarn. Examples of other fibers include conventionally known fibers such as polyamide fibers, wool, cotton, and polyester fibers, with polyester fibers being preferred. The elastic fiber made of the polyurethane of the present invention may also contain a dye-disperse dye.

[0086] <Uses of polyurethane other than elastic fibers> The polyurethane of the present invention has excellent solvent resistance and good flexibility and mechanical strength, and therefore, in addition to applications for elastic fibers, can be widely used in foams, elastomers, paints, fibers, pressure-sensitive adhesives, adhesives, flooring materials, sealants, medical materials, artificial leather, synthetic leather, coating agents, water-based polyurethane paints, active-energy radiation-curable polymer compositions, and the like.

[0087] In particular, when the polyurethane of the present invention is used in applications such as artificial leather, synthetic leather, breathable waterproof fabric, waterproof fabric, water-based polyurethane, adhesive, elastic fiber, medical material, flooring material, paint, coating agent, etc., it has a good balance of solvent resistance, flexibility, and mechanical strength, and therefore can impart good properties such as high durability and sufficient flexibility as well as resistance to physical impact in areas that come into contact with human skin or are used with cosmetic agents or disinfectant alcohol. Furthermore, it can be suitably used in automotive applications requiring heat resistance and outdoor applications requiring weather resistance.

[0088] The polyurethane of the present invention can be used in polyurethane elastomers, such as cast polyurethane elastomers. Specific applications include rolls such as rolling mill rolls, papermaking rolls, office equipment rolls, and pretensioning rolls; solid tires and casters for forklifts, automobile new trams, dollies, and transport vehicles; and industrial products such as conveyor belt idlers, guide rolls, pulleys, steel pipe linings, rubber screens for ore, gears, connection rings, liners, pump impellers, cyclone cones, and cyclone liners. It can also be used in office automation equipment belts, paper feed rolls, cleaning blades for copying machines, snow plows, toothed belts, surf rollers, and the like.

[0089] The polyurethane of the present invention is also applicable to applications as a thermoplastic elastomer. For example, it can be used in tubes and hoses, spiral tubes, fire hoses, etc., in pneumatic equipment used in the food and medical fields, painting equipment, analytical equipment, physicochemical equipment, metering pumps, water treatment equipment, industrial robots, etc. In addition, it can be used as belts such as round belts, V-belts, and flat belts in various power transmission mechanisms, spinning machines, packaging equipment, printing machines, etc. In addition, it can be used in footwear heel tops and soles, equipment parts such as couplings, packing, ball joints, bushings, gears, and rolls, sports goods, leisure goods, watch straps, etc. Furthermore, it can be used in automotive parts such as oil stoppers, gearboxes, spacers, chassis parts, interior parts, and tire chain replacements. It can also be used in films such as keyboard films and automotive films, curl cords, cable sheaths, bellows, conveyor belts, flexible containers, binders, synthetic leather, dipping products, adhesives, etc.

[0090] The polyurethane elastomer of the present invention can be further made into a foamed polyurethane elastomer or a polyurethane foam. The method for making the polyurethane elastomer into a foamed polyurethane elastomer or a polyurethane foam may be, for example, chemical foaming using water or mechanical foaming such as mechanical froth, or other methods such as spray foaming, slab foaming, injection molding, or molding to obtain a rigid foam, or slab foaming or molding to obtain a flexible foam. Specific applications of the polyurethane elastomer foam or polyurethane foam include electronic devices, heat insulating materials and vibration damping materials for railway rails and buildings, automobile seats, automobile ceiling cushions, bedding such as mattresses, insoles, midsoles, shoe soles, etc.

[0091] The polyurethane of the present invention can also be used as a solvent-based two-component paint and can be applied to wood products such as musical instruments, Buddhist altars, furniture, decorative plywood, sporting goods, etc. It can also be used as a tar epoxy urethane for automobile repair.

[0092] The polyurethane of the present invention can be used as a component of moisture-curing one-component paints, blocked isocyanate-based solvent paints, alkyd resin paints, urethane-modified synthetic resin paints, ultraviolet-curing paints, water-based urethane paints, etc., and can be applied, for example, to paints for plastic bumpers, strippable paints, coating agents for magnetic tapes, overprint varnishes for floor tiles, flooring materials, paper, wood grain printed films, etc., wood varnishes, coil coats for high processing, optical fiber protective coatings, solder resists, top coats for metal printing, base coats for vapor deposition, white coats for food cans, etc.

[0093] The polyurethane of the present invention can also be used as a pressure sensitive adhesive or adhesive for food packaging, shoes, footwear, magnetic tape binders, decorative paper, wood, structural members, etc., and can also be used as a component of low temperature adhesives and hot melts. The polyurethane of the present invention can be used as a binder in magnetic recording media, inks, castings, fired bricks, graft materials, microcapsules, granular fertilizers, granular agricultural chemicals, polymer cement mortar, resin mortar, rubber chip binders, recycled foam, glass fiber sizing, and the like.

[0094] The polyurethane of the present invention can be used as a component of a fiber processing agent for shrink-proofing, wrinkle-proofing, water-repellent finishing, etc.

[0095] The polyurethane of the present invention can be used as a sealant / caulking for concrete walls, induction joints, around sashes, wall-type PC (Precast Concrete) joints, ALC (Autoclaved Lightweight Concrete) joints, board joints, sealants for composite glass, heat-insulating sash sealants, automotive sealants, rooftop waterproof sheets, etc.

[0096] The polyurethane of the present invention can be used as a medical material, and can be used as a blood-compatible material for tubes, catheters, artificial hearts, artificial blood vessels, artificial valves, etc., and as a disposable material for catheters, tubes, bags, surgical gloves, artificial kidney potting materials, etc.

[0097] By modifying the terminals, the polyurethane of the present invention can be used as a raw material for UV-curable coating materials, electron beam-curable coating materials, photosensitive resin compositions for flexographic printing plates, photocurable optical fiber coating compositions, etc. [Example]

[0098] The present invention will be described in more detail below based on examples, but the present invention is not limited to the following examples.

[0099] [Evaluation method] The polyalkylene ether glycol or polyether polyol compositions used in the following examples and comparative examples were evaluated using the following methods.

[0100] <Molecular weight and molecular weight distribution> The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polyether polyol represented by the formula (1) were measured using a GPC (gel permeation chromatography) measuring device (HLC-8420GPC, manufactured by Tosoh Corporation), and the molecular weight distribution (Mw / Mn) was calculated. Measurement method by GPC: The weight average molecular weight Mw and number average molecular weight Mn in terms of polystyrene were determined by GPC measurement under the following conditions. Equipment: Tosoh HLC-8420 Column: TSKgel Super HZM-N (4.6mmI.D.×15cmL×4) Reference column: TSKgel Super H-RC (6.0mm I.D. x 15cm L x 1) Eluent: THF (tetrahydrofuran) Flow rate: 0.35mL / min Column temperature: 40℃ RI detector: RI (built-in in the device HLC-8420)

[0101] [Method for evaluating polyalkylene ether glycol or polyether polyol composition] <Hydroxyl value / number average molecular weight> The hydroxyl value of the polyalkylene ether glycol was measured by a method using an acetylation reagent in accordance with JIS K1557-1. The hydroxyl value of the polyether polyol represented by the formula (1) was determined in accordance with the American Society for Testing and Materials (ASTM) by urethanizing the hydroxyl groups of a tetrahydrofuran solution with p-toluenesulfonyl isocyanate, hydrolyzing the excess urethanizing reagent with water, and titrating the sulfonylamide ester formed from the hydroxyl groups of the sample with a base. The number average molecular weight (Mn) was calculated from the obtained hydroxyl value according to the following formula (I). Number average molecular weight = 2 × 56.1 / (hydroxyl value × 10 -3 ) …(I)

[0102] <Viscosity> The viscosity of the polyalkylene ether glycol or polyether polyol composition was measured at each temperature using a viscometer (ViscoQC100 and PTD100 cone-plate type manufactured by Anton Paar). Measurement method using a viscometer: The viscosity was measured at each temperature under the following conditions. Apparatus: Anton Paar ViscoQC100 Temperature control: Anton Paar PTD100 cone plate (Peltier temperature control system) Measuring jig: CP40 Measurement temperature: 25℃, 40℃, 60℃, 80℃

[0103] <Low crystallinity> The polyalkylene ether glycol or polyether polyol composition was allowed to stand in a refrigerator maintained at 10°C, and after 2 hours, the appearance was visually inspected and evaluated as follows. White solid: × Cloudy liquid: △ Transparent liquid: 〇

[0104] <Solvent compatibility> The polyalkylene ether glycol or polyether polyol composition was mixed with various solvents in a weight ratio of 50:50, and the appearance was checked after 24 hours and evaluated as follows. Insoluble or separated: × Not completely dissolved (hazy in the liquid): △ Emulsion: ▲ Dissolution: 〇

[0105] [Evaluation method for polyurethane] <Molecular weight and molecular weight distribution> Polyurethane was dissolved in dimethylacetamide (containing approximately 0.3 wt% anhydrous lithium bromide) to a concentration of 0.07 wt% to prepare the sample for GPC analysis. GPC analysis was performed using a Tosoh HLC-8420 GPC system (two TSKgel SuperAWM-H columns) under the following conditions: sample injection volume of approximately 40 μL, column temperature of 40°C, dimethylacetamide (containing approximately 0.3 wt% anhydrous lithium bromide) as the mobile phase, and a flow rate of 0.6 mL / min. The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the polyurethane were measured in terms of standard polystyrene using a commercially available monodisperse polystyrene solution as the standard sample, and the molecular weight distribution (Mw / Mn) was calculated.

[0106] <Tensile test> The polyurethane solution was applied to a fluororesin sheet (Fluorine Tape Nitoflon 900, thickness 0.1 mm, manufactured by Nitto Denko Corporation) using a 500 μm applicator, and dried at 80°C for 1 hour and then at 100°C for 0.5 hours. The polyurethane film was then dried under vacuum at 100°C for 0.5 hours and then allowed to stand at 23°C and 60% RH for at least 12 hours. 1 cm x 15 cm test pieces were cut from the resulting polyurethane film. Tensile tests were performed on these test pieces in accordance with JIS K6301 (2010) using a tensile tester (Shimadzu Corporation, product name "AGS-X") at a chuck distance of 50 mm, a tensile speed of 500 mm / min, and temperatures of 23°C or -10°C and relative humidity of 60%. The stresses at which the test pieces reached 100%, 200%, and 300% elongation were measured as the 100% modulus, 200% modulus, and 300% modulus, respectively. The elongation and strength at break of the test pieces were also measured. Higher elongation and strength indicate better flexibility and mechanical strength. When the test piece is stretched to 100%, 200%, and 300%, the stress (100% modulus, 200% modulus, 300% modulus) is measured. The closer the strength ratio of each modulus measured at -10°C to each modulus measured at 23°C (e.g., 100% modulus (-10°C) / 100% modulus (23°C)) is to 1.0, the better the low-temperature flexibility at -10°C is.

[0107] <Crystallinity evaluation method> Using a dynamic viscoelasticity measuring device (manufactured by UBM Corporation, product name "Rheogel-E4000"), the storage modulus (E') and loss modulus (E") were measured in tension mode over a temperature range of -100 to 250°C, at a heating rate of 3°C / min, and a frequency of 1 Hz. E' correlates with hardness at each temperature, and generally decreases as the temperature rises and the material transitions from a glassy to a rubbery state. When the urethane is highly crystalline, this decrease in E' associated with the transition from the glassy to rubbery state is paralleled by an increase in E' due to crystallization, which is observed as an inflection point. The transition region from glass to rubber is defined as -80°C to 0°C, and the inflection point of E' in this region is considered to be due to urethane crystallization, and was judged according to the following criteria. Good: No inflection point due to crystallization was observed. Low crystallinity means the urethane has excellent low-temperature properties. ×: An inflection point due to crystallization was observed. Due to high crystallinity, the low-temperature properties of the urethane were poor.

[0108] <Oleic acid resistance> A 3cm x 3cm test piece was cut from the polyurethane film and placed in a 250ml glass bottle containing 50ml of oleic acid, the test solvent, and left to stand at 80°C for 16 hours. After the test, the test piece was removed and lightly wiped with a paper wiper, then weighed on a precision balance and the weight change (increase) from before the test was calculated. A weight change rate closer to 0% indicates better resistance to oleic acid.

[0109] [Production and Evaluation of Polyether Polyol Represented by Formula (1)] The compounds described in the Synthesis Examples, Examples and Comparative Examples are abbreviated as follows: POM-PTMG: Polyether polyol represented by the formula (1) PTMG: Polytetramethylene ether glycol BG: 1,4-butanediol MDI: 4,4'-diphenylmethane diisocyanate PTMG#250: Polytetramethylene ether glycol manufactured by Mitsubishi Chemical Corporation, with a number average molecular weight (Mn) based on the hydroxyl value of 650 PTMG#2000: Polytetramethylene ether glycol manufactured by Mitsubishi Chemical Corporation, with a number average molecular weight (Mn) based on the hydroxyl value of 2000 PFA: Paraformaldehyde TfOH: trifluoromethanesulfonic acid DMF: Dehydrated N,N-dimethylformamide, manufactured by Wako Pure Chemical Industries, Ltd. MDI: 4,4'-diphenylmethane diisocyanate

[0110] [Synthesis Example 1] A 1 L glass four-neck flask equipped with a magnetic stirrer and a Dean-Stark trap was charged with 535.7 g of PTMG#250, 68.7 g of PFA, 0.55 mL of TfOH (10% aqueous solution), and 160 mL of toluene, and the atmosphere was purged with nitrogen gas. The separable flask was heated in a 120°C oil bath, and the reaction was carried out at atmospheric pressure for 4 hours while removing water under reflux conditions. The internal temperature was then cooled to 50°C, the pressure was reduced to 11 mmHg, and the toluene was removed from the system. The pressure was then reduced to 8 mmHg, and the reaction was carried out for 3 hours at a maximum temperature of 150°C. Thereafter, the internal temperature was cooled to 100°C, and 6 g of hydrotalcite was added to the reaction liquid to deactivate the catalyst TfOH. Thereafter, the hydrotalcite was removed by pressure filtration using a PTFE membrane filter, and a polyether polyol represented by the above formula (1) was obtained. The polyether polyol represented by formula (1) produced in Synthesis Example 1 is referred to as "POM-PTMG1." The properties and physical property evaluation results of POM-PTMG1 are shown in Table 1.

[0111] [Table 1]

[0112] [Example 1-1] A polyol composition was prepared by mixing PTMG#2000 (50 parts by mass) and POM-PTMG1 (50 parts by mass) obtained in Synthesis Example 1. The evaluation results of the physical properties are shown in Table 2.

[0113] [Example 1-2] A polyol composition was prepared by mixing PTMG#2000 (25 parts by mass) and POM-PTMG1 (75 parts by mass) obtained in Synthesis Example 1. The evaluation results of the physical properties are shown in Table 2.

[0114] [Comparative Example 1-1] The evaluation results of the physical properties of PTMG#2000 are shown in Table 2.

[0115] [Table 2]

[0116] The following can be seen from Table 2. The polyether polyol compositions described in the examples have lower viscosity, lower crystallinity, and better compatibility with solvents than polyalkylene ether glycols having similar number average molecular weights. Therefore, when used as a raw material for polyurethanes, for example, the polyether polyol compositions of the present invention are easy to handle and have excellent handling properties.

[0117] [Example 2-1] <Production of polyurethane> A separable flask equipped with a thermocouple, condenser, and stirrer was placed on a 60°C oil bath. 34.91 g of POM-PTMG1, 34.96 g of PTMG2000, 6.13 g of BG, and 236.87 g of DMF, all preheated to 80°C, were placed in the separable flask. 0.0179 g of Neostan U-830 (hereinafter sometimes referred to as "U-830"; manufactured by Nitto Kasei Co., Ltd.) was added as a urethanization catalyst. Next, 23.99 g of MDI was added, and the contents of the separable flask were stirred at 60 rpm under a nitrogen atmosphere to initiate the urethanization reaction. After the heat generated by the MDI addition subsided, the oil bath was heated to 70°C, and stirring was continued for 1 hour. Subsequently, MDI was added in portions to adjust the molecular weight, and polyurethane was produced. The evaluation results of the polyurethane's properties and physical properties are shown in Table 3 and Figure 1.

[0118] [Example 2-2] Polyurethanes were produced in the same manner as in Example 1, except that the amounts of polyurethane raw materials were changed as shown in Table 3. The properties and physical properties of the polyurethanes were evaluated and are shown in Table 3 and FIG.

[0119] [Comparative Example 2-1] A polyurethane was produced in the same manner as in Example 1, except that POM-PTMG1 was not used as the polyurethane raw material and the amounts were changed as shown in Table 3. The evaluation results of the properties and physical properties of the polyurethane are shown in Table 3 and Figs.

[0120] [Table 3]

[0121] The following can be seen from Table 3, Figures 1 and 2. As shown in Figures 1 and 2, the polyurethanes described in the examples have low crystallinity, as the storage modulus decreases gradually as they transition from a glassy state to a rubbery state after the glass transition point. Furthermore, as shown in Table 3, the change in modulus measured at -10°C is smaller than that measured at 23°C, which indicates that flexibility is easily maintained even at temperatures as low as -10°C, i.e., they have excellent low-temperature flexibility. Furthermore, since the weight change rate of the oleic acid resistance is small, the chemical resistance is good and it is useful for elastic fibers. On the other hand, in the polyurethane of the comparative example, a peak due to crystallization is observed during the transition from the glassy state to the rubbery state after the glass transition point, as shown in Figures 1 and 2. Furthermore, as shown in Table 3, the change in modulus measured at -10°C is greater than that measured at 23°C, which clearly indicates that flexibility deteriorates due to crystallization at temperatures as low as -10°C, i.e., low-temperature flexibility is poor. In addition, the weight change rate of oleic acid resistance is high and chemical resistance is low.

Claims

1. A polyether polyol composition comprising a polyalkylene ether glycol and a polyether polyol represented by the following formula (1): 【Chemistry 1】 (In the above formula (1), R represents a divalent hydrocarbon group having 2 to 10 carbon atoms, n is an integer of 2 to 40, m is an integer of 1 or more, and s is an integer of 1 to 30. In addition, in formula (1), multiple Rs may be the same or different.)

2. The polyether polyol composition according to claim 1, wherein the ratio of the mass of the polyalkylene ether glycol to the mass of the polyether polyol represented by formula (1) is within the range of 15:85 to 55:

45.

3. 3. The polyether polyol composition according to claim 1, wherein the polyether polyol represented by formula (1) has a number average molecular weight of 600 or more.

4. 3. The polyether polyol composition according to claim 1, wherein R in formula (1) is an n-butylene group.

5. A polyurethane comprising a structural unit derived from a compound having a plurality of isocyanate groups, a structural unit derived from a chain extender, a structural unit derived from a polyalkylene ether glycol, and a structural unit derived from a polyether polyol represented by the following formula (2): 【Chemistry 2】 (In the above formula (2), R represents a divalent hydrocarbon group having 2 to 10 carbon atoms, n is an integer of 2 to 40, m is an integer of 1 or more, and s is an integer of 1 to 30. In addition, in formula (2), multiple Rs may be the same or different.)

6. The polyurethane according to claim 5, wherein the ratio of the mass of the structural units derived from the polyalkylene ether glycol to the mass of the structural units derived from the polyether polyol represented by formula (2) is within the range of 15:85 to 55:

45.

7. 7. The polyurethane according to claim 5, wherein the polyether polyol represented by formula (2) has a number average molecular weight of 600 or more.

8. 7. The polyurethane according to claim 5, wherein R in formula (2) is an n-butylene group.

9. 7. The polyurethane according to claim 5, wherein the structural unit derived from the chain extender is a structural unit derived from at least one compound selected from the group consisting of polyols and polyamines, and the compound is at least one compound selected from the group consisting of ethylenediamine, propylenediamine, isophoronediamine, and hexamethylenediamine.

10. The polyurethane according to claim 5 or 6, wherein the structural unit derived from the chain extender is a structural unit derived from at least one compound selected from the group consisting of polyols and polyamines, and the compound is at least one compound selected from the group consisting of 1,4-butanediol, ethylene glycol, propylene glycol, and 1,6-hexanediol.

11. The polyurethane according to claim 5 or 6, wherein the compound having a plurality of isocyanate groups is at least one compound selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,6-hexamethylene diisocyanate, and isophorone diisocyanate.

12. The polyurethane according to claim 5 or 6, which is for use in elastic fibers.

13. A polyurethane elastic fiber using the polyurethane for elastic fibers according to claim 12.

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