Polyester polycarbonate diol, manufacturing method therefor, polyurethane resin–forming composition, and polyurethane resin

Abstract

The present disclosure is related to a polyester polycarbonate diol including a constituent unit (A) represented by formula (A), a constituent unit (B) represented by formula (B), and a terminal hydroxy group, wherein in an X-ray diffraction spectrum obtained via wide-angle X-ray scattering measurement using the polyester polycarbonate diol, which has been immersed in liquid nitrogen for 3 minutes or longer and cooled, as a specimen for measurement, there is a diffraction line due to crystallinity at 2θ=21.3±0.5°. (In formula (A), R1 represents an alkanediyl group and * represents a bond.)　(In formula (B), R2 represents an alkanediyl group and * represents a bond.)

Description

Polyester polycarbonate diol and its manufacturing method, polyurethane resin-forming composition and polyurethane resin

[0001] This disclosure relates to polyester polycarbonate diols, methods for producing the same, polyurethane resin-forming compositions, and polyurethane resins.

[0002] Polycarbonate polyols, like polyester polyols and polyether polyols, are useful as raw materials for producing urethane resins (also called polyurethane resins) by reacting them with polyisocyanate compounds, and are useful as raw materials for adhesives, paints, and the like.

[0003] Polycarbonate polyols are typically produced by reacting a carbonate ester with a diol in the presence of a transesterification catalyst (transesterification reaction). To date, various polycarbonate polyols with different structures have been proposed depending on the purpose (for example, Patent Documents 1-2).

[0004] JP-A-11-1549 Patent No. 6222101

[0005] One aspect of this disclosure aims to provide a polyester polycarbonate diol that contributes to the formation of a polyurethane resin having good low-temperature properties and high tensile strength.

[0006] This disclosure relates to the following embodiments: [1] A polyester polycarbonate diol comprising a constituent unit (A) represented by the following formula (A), a constituent unit (B) represented by the following formula (B), and a terminal hydroxyl group, wherein the polyester polycarbonate diol has a diffraction line of crystalline origin at 2θ = 21.3 ± 0.5° in an X-ray diffraction spectrum obtained by wide-angle X-ray scattering measurement using the polyester polycarbonate diol cooled by immersion in liquid nitrogen for 3 minutes or more as the sample to be measured. [In formula (A), R １ The symbol indicates an alkanediyl group, and the asterisk (*) indicates a bond. [In formula (B), R ２represents an alkanediyl group, and * represents a bond. ] [2] The polyester polycarbonate diol according to [1], wherein the content of the constituent unit (B) is 60 mol% or less based on the total content of the constituent unit (A) and the constituent unit (B). [3] The polyester polycarbonate diol according to [1] or [2], wherein the content of the constituent unit (B) is 20 to 50 mol% based on the total content of the constituent unit (A) and the constituent unit (B). [4] The polyester polycarbonate diol according to any one of [1] to [3], which is liquid at 25°C. [5] R １ A polyester polycarbonate diol according to any one of [1] to [4], wherein it contains only one type of alkanediyl group. [6] R １ It contains only one type of alkanediyl group, and R １[1] to [5] a polyester polycarbonate diol, wherein the alkanediyl group contained as has 6 or more carbon atoms. [7] A method for producing a polyester polycarbonate diol according to any one of [1] to [6], comprising a reaction step of reacting a diol with a cyclic ester and a carbonate ester, wherein the diol is of only one type. [8] A method for producing a polyester polycarbonate diol, comprising a reaction step of reacting a diol with a cyclic ester and a carbonate ester, wherein the diol is of only one type, the amount of the cyclic ester is 10 moles or more with respect to 100 moles of the total number of moles of the cyclic ester and the carbonate ester or the diol, the total number of moles is the sum of the number of moles of the one with the smaller number of moles used and the cyclic ester if the number of moles used of the carbonate ester and the diol is smaller than the other, and the sum of the number of moles used of either the carbonate ester or the diol and the cyclic ester if the number of moles used of the carbonate ester and the diol is the same. [9] The method for producing a polyester polycarbonate diol according to [8], wherein the amount of the cyclic ester is 10 moles or more and 60 moles or less with respect to the total number of moles of 100 moles.

[10] The method for producing a polyester polycarbonate diol according to [8] or [9], wherein the polyester polycarbonate diol has a diffraction line of crystalline origin at 2θ = 21.3 ± 0.5° in an X-ray diffraction spectrum obtained by wide-angle X-ray scattering measurement using the polyester polycarbonate diol cooled by immersion in liquid nitrogen for 3 minutes or more as the sample to be measured.

[11] The method for producing a polyester polycarbonate diol according to any one of [7] to

[10] , wherein the number of carbon atoms in the diol is 6 or more.

[12] The method for producing a polyester polycarbonate diol according to any one of [7] to

[11] , wherein the reaction step is carried out in the presence of two types of catalysts.

[13] The method for producing a polyester polycarbonate diol according to

[12] , wherein the two types of catalysts are potassium bicarbonate and lithium trifluoroacetate, sodium oxalate, or sodium trichloroacetate.

[14] A polyurethane resin-forming composition containing a polyol and a polyisocyanate, wherein the polyol contains a polyester polycarbonate diol according to any one of [1] to [6].

[15] A polyurethane resin which is a reaction product of the polyurethane resin-forming composition according to

[14] .

[0007] According to one aspect of this disclosure, a polyester polycarbonate diol that contributes to the formation of a polyurethane resin having good low-temperature properties and high tensile strength can be provided.

[0008] This figure shows the X-ray diffraction (XRD) spectrum measured using the polyester polycarbonate diol of Example 1.

[0009] Several embodiments of this disclosure are described below. However, this disclosure is not limited to the embodiments described below.

[0010] In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. Unless otherwise specified, the units of the numbers before and after "~" are the same. In numerical ranges described in stages within this specification, the upper or lower limit of one stage may be replaced with the upper or lower limit of another stage. Furthermore, in numerical ranges described within this specification, the upper or lower limit of that range may be replaced with the values ​​shown in the examples. Also, individually stated upper and lower limits can be combined in any way. The materials exemplified below may be used individually or in combination of two or more, unless otherwise specified. The content of each component in a composition, if multiple substances corresponding to each component exist in the composition, means the total amount of those multiple substances present in the composition, unless otherwise specified.

[0011] <Polyester polycarbonate diol> One embodiment of the present disclosure relates to a polyester polycarbonate diol comprising a structural unit (A) represented by the following formula (A), a structural unit (B) represented by the following formula (B), and terminal hydroxy groups. [In formula (A), R １ represents an alkanediyl group, and * represents a bond.] [In formula (B), R ２ represents an alkanediyl group, and * represents a bond.]

[0012] The alkanediyl group represented by R １ and R ２ may be linear or branched. The number of carbon atoms in the alkanediyl group represented by R １ and R ２ may be, for example, 2 to 10. Specific examples of the alkanediyl group include an ethanediyl group, 1,2-propanediyl group, 1,3-propanediyl group, 1,2-butanediyl group, 1,3-butanediyl group, 1,4-butanediyl group, 1,5-pentanediyl group, 2,2-dimethyl-1,3-propanediyl group, 1,6-hexanediyl group, 3-methyl-1,5-pentanediyl group, 1,8-octanediyl group, 2-ethyl-1,6-hexanediyl group, 1,9-nonanediyl group, 2-methyloctane-1,8-diyl group, 2-butyl-2-ethyl-1,3-propanediyl group and the like. Among these, 1,4-butanediyl group, 1,5-pentanediyl group, 1,6-hexanediyl group, 3-methyl-1,5-pentanediyl group, 2-ethyl-1,6-hexanediyl group, 1,9-nonanediyl group, 2-methyloctane-1,8-diyl group and the like are mentioned.

[0013] The type of alkanediyl group contained as R １ may be one type or two or more types. Only one type of alkanediyl group may be contained as R １ .

[0014] The number of carbon atoms of the alkanediyl group contained as R １ may be 6 or more, 7 or more, or 8 or more, and may be 10 or less, 9 or less, 8 or less, or 7 or less. R １The number of carbon atoms in the alkanediyl group included as may be 6-10, 6-9, 7-10, 7-9, 8-10, or 8-9. １ As the number of carbon atoms in the alkanediyl group increases, polyurethane resins with lower glass transition temperatures tend to be formed more easily.

[0015] R １ It contains only one type of alkanediyl group, and R １ The alkanediyl group included may have six or more carbon atoms.

[0016] R １ The alkanediyl group included may be a 1,6-hexanediyl group or a 1,9-nonanediyl group. １ When the alkanediyl group included is a 1,9-nonanediyl group, a polyurethane resin with a lower glass transition temperature is more likely to be formed.

[0017] R ２ The type of alkanediyl group included may be one or more.

[0018] R ２ The number of carbon atoms in the alkanediyl group included may be four or more, and may be 4 to 6 or 5.

[0019] R ２ It contains only one type of alkanediyl group, and R ２ The alkanediyl group included may have 4 or more carbon atoms, or 5 carbon atoms. ２ The alkanediyl group included may be a 1,5-pentanediyl group.

[0020] The content of constituent unit (A) may be 90 mol% or less, 85 mol% or less, 80 mol% or less, or 75 mol% or less, based on the total content of constituent unit (A) and constituent unit (B).

[0021] The content of constituent unit (A) may be 40 mol% or more, 50 mol% or more, 60 mol% or more, or 75 mol% or more, based on the total content of constituent unit (A) and constituent unit (B).

[0022] The content of constituent unit (A) may be 40-95 mol%, 50-85 mol%, 60-80 mol%, or 65-75 mol%, based on the total content of constituent unit (A) and constituent unit (B). When the content of constituent unit (A) is within the above range, a polyurethane resin with good low-temperature properties and high tensile strength is easily formed.

[0023] The content of constituent unit (B) may be 60 mol% or less, based on the total content of constituent unit (A) and constituent unit (B). From the viewpoint of making it easier to form a polyurethane resin with even higher breaking strength, it may be 55 mol% or less, 50 mol% or less, 45 mol% or less, or 40 mol% or less. From the viewpoint of making it easier to form a polyurethane resin with even higher breaking strength and an even higher softening temperature, it may be 35 mol% or less.

[0024] The content of constituent unit (B) may be 6 mol% or more, 8 mol% or more, 10 mol% or more, 12 mol% or more, 15 mol% or more, or 18 mol% or more, based on the total content of constituent unit (A) and constituent unit (B). From the viewpoint of making it easier to form a polyurethane resin that is liquid at 25°C, has an even lower 100% modulus, and an even higher elongation at break, it may be 20 mol% or more, 25 mol% or more, or 30 mol% or more.

[0025] The content of constituent unit (B) may be 10-60 mol%, 15-60 mol%, 20-60 mol%, 25-60 mol%, 10-55 mol%, 15-55 mol%, 20-55 mol%, 25-55 mol%, 10-50 mol%, 15-50 mol%, 20-50 mol%, 25-50 mol%, 10-40 mol%, 15-40 mol%, 20-40 mol%, 25-40 mol%, 10-35 mol%, 15-35 mol%, 20-35 mol%, or 25-35 mol%, based on the total content of constituent unit (A) and constituent unit (B). When the content of constituent unit (B) is within the above range, a polyurethane resin with good hydrolysis resistance, low-temperature properties, and high tensile strength is easily formed.

[0026] When the content of the structural unit (B) is 20 to 35 mol% or 25 to 35 mol% based on the total content of the structural unit (A) and the structural unit (B), a polyurethane resin that is liquid at 25°C, has a further lower 100% modulus, further higher breaking strength and softening temperature, and further higher elongation at break is more easily formed.

[0027] The contents of the structural unit (A) and the structural unit (B) can be calculated from the charged amounts of the raw materials. Details of the calculation method may be as described in the Examples mentioned later.

[0028] The arrangement of the structural units (A) and (B) in the polyester polycarbonate diol may be any of a random arrangement, an alternating arrangement or a block arrangement.

[0029] The polyester polycarbonate diol may further contain other structural units other than the structural units (A) and (B). The content of the other structural units may be 10 mol% or less, or 5 mol% or less based on the total content of the structural units (A) and (B).

[0030] At least one of the terminal hydroxy groups in the polyester polycarbonate diol may be bonded to the structural unit (A) or the structural unit (B) via a linker. The linker may include, for example, an alkanediyl group. The alkanediyl group is R １ and R ２ may be as described for the alkanediyl group in . For example, the polyester polycarbonate diol may include a structure represented by the following formula (C) including a hydroxy group and a linker.

[0031] In formula (C), R ３ represents an alkanediyl group, and * represents a bonding site to -C(=O)- of the structural unit (A) or (B).

[0032] Polyester polycarbonate diols exhibit a diffraction line originating from crystallinity at 2θ = 21.3 ± 0.5° in the X-ray diffraction spectrum obtained by wide-angle X-ray scattering measurement using a polyester polycarbonate diol cooled by immersion in liquid nitrogen for 3 minutes or more as the sample to be measured. The diffraction line originating from crystallinity is a sharp diffraction line that does not contain broad scattering peaks. In this specification, "sharp diffraction line" means a diffraction line with a full width at half maximum of 0.40 or less. Full width at half maximum means full width at half maximum (FWHM).

[0033] The polyester polycarbonate diol may further have a diffraction line originating from crystallinity at 2θ = 23.6 ± 0.5° in the X-ray diffraction spectrum obtained by wide-angle X-ray scattering measurement using the above-mentioned sample, or it may not have such a diffraction line.

[0034] Wide-angle X-ray scattering measurements are performed by the following method. The sample to be measured is obtained by placing a polyester polycarbonate diol (the target of measurement) on a Si non-reflective sample plate, and immersing the sample on the Si non-reflective sample plate in liquid nitrogen for at least 3 minutes. The Si non-reflective sample plate on which the sample to be measured is placed is installed in the sample chamber of the measuring device within 1 minute. Wide-angle X-ray scattering measurements are performed on the sample to be measured placed in the sample chamber under the following conditions: -Conditions- (1) Measuring device: SmartLab (fully automated multi-purpose X-ray diffractometer, manufactured by Rigaku Corporation) (2) X-ray source: CuKα rays, 45kV, 200mA (3) Optical instrument: Parallel beam optical system (4) Scan conditions: 2θ = 5 to 90 deg, 40 deg / min, 0.04 deg / step

[0035] The number-average molecular weight of polyester polycarbonate diols may be, for example, 500 or more, 1000 or more, 1200 or more, 1400 or more, 1600 or more, 1650 or more, 1700 or more, or 1750 or more. The number-average molecular weight of polyester polycarbonate diols may be, for example, 4000 or less, 3500 or less, 3000 or less, 2500 or less, 2200 or less, 2000 or less, 1940 or less, 1900 or less, 1850 or less, or 1800 or less. The number average molecular weight of the polyester polycarbonate diol may be 1650 or more, and 2200 or less, 2000 or less, 1940 or less, 1900 or less, 1850 or less, or 1800 or less, as this facilitates the formation of a polyurethane resin with a better 100% modulus and a better elongation at break. It may also be 1700 or more, and 2200 or less, 2000 or less, 1940 or less, 1900 or less, 1850 or less, or 1800 or less. It may also be 1750 or more, and 2200 or less, 2000 or less, 1940 or less, 1900 or less, 1850 or less, or 1800 or less.

[0036] The number-average molecular weight is the number-average molecular weight on a difunctional polyoxypropylene polyol basis, measured using GPC (Gel Permeation Chromatography). Details of the measurement method are shown in the examples.

[0037] The hydroxyl value of polyester polycarbonate diol may be, for example, 25 mg KOH / g or more, 30 mg KOH / g or more, 35 mg KOH / g or more, 40 mg KOH / g or more, 45 mg KOH / g or more, 50 mg KOH / g or more, 52 mg KOH / g or more, 54 mg KOH / g or more, or 55 mg KOH / g or more. The hydroxyl value of polyester polycarbonate diol may be, for example, 250 mg KOH / g or less, 200 mg KOH / g or less, 150 mg KOH / g or less, 100 mg KOH / g or less, 80 mg KOH / g or less, 70 mg KOH / g or less, 65 mg KOH / g or less, 62 mg KOH / g or less, 60 mg KOH / g or less, or 58 mg KOH / g or less. The hydroxyl value of polyester polycarbonate diol may be 50 mg KOH / g or more and 62 mg KOH / g or less, 60 mg KOH / g or less, or 58 mg KOH / g or less, in order to facilitate the formation of a polyurethane resin with a better 100% modulus and a better elongation at break.

[0038] The hydroxyl value refers to the number of milligrams (mg) of potassium hydroxide equivalent to the number of hydroxyl groups in 1 g of polyester polycarbonate diol. The hydroxyl value is measured according to JIS K1557-1 using a method with an acetylation reagent.

[0039] The properties of polyester polycarbonate diol may be solid at 25°C or liquid at 25°C. Polyester polycarbonate diol may be liquid at 25°C because it has excellent handling properties and makes it easier to streamline the manufacturing process and improve productivity.

[0040] Polyester polycarbonate diols can be produced by a method that includes a reaction step involving the reaction of a diol, a cyclic ester, and a carbonate ester. Only one type of diol may be used in the reaction step.

[0041] The number of carbon atoms in the diol used in the reaction step may be 2 or more, 6 or more, 7 or more, or 8 or more, and may be 10 or less, 9 or less, 8 or less, or 7 or less, and may be 2 to 10, 6 to 10, 6 to 9, 7 to 10, 7 to 9, 8 to 10, or 8 to 9.

[0042] Specific examples of diols include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 2-ethyl-1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, and 2-butyl-2-ethyl-1,3-propanediol.

[0043] The only diol used in the reaction process may be 1,6-hexanediol. In other words, no diol other than 1,6-hexanediol may be used in the reaction process. When only 1,6-hexanediol is used as the diol in the reaction process, the above-mentioned polyester polycarbonate diol is more easily obtained.

[0044] The only diol used in the reaction process may be 1,9-nonanediol. In other words, no diol other than 1,9-nonanediol may be used in the reaction process. When only 1,9-nonanediol is used in the reaction process, the above-mentioned polyester polycarbonate diol is more easily obtained.

[0045] The amount of diol may be 0.8 moles or more, or 0.9 moles or more, and 1.2 moles or less, or 1.1 moles or less, per mole of carbonate ester.

[0046] The amount of diol may be 0.6 moles or more, 0.8 moles or more, 1.0 mole or more, 1.2 moles or more, 1.4 moles or more, 1.6 moles or more, or 1.8 moles or more per mole of cyclic ester, and may be 6.4 moles or less, 4.4 moles or less, 3.4 moles or less, 2.6 moles or less, or 2.4 moles or less. The amount of diol per mole of cyclic ester is 0.6–6.4 moles, 0.6–4.4 moles, 0.6–3.4 moles, 0.6–2.6 moles, 0.6–2.4 moles, 0.8–6.4 moles, 0.8–4.4 moles, 0.8–3.4 moles, 0.8–2.6 moles, 0.8–2.4 moles, 1.0–6.4 moles, 1.0–4.4 moles, 1.0–3.4 moles, 1.0–2.6 moles, 1.0–2.4 moles, 1.2–6.4 moles, and 1.2–4.4 moles. , 1.2 to 3.4 moles, 1.2 to 2.6 moles, 1.2 to 2.4 moles, 1.4 to 6.4 moles, 1.4 to 4.4 moles, 1.4 to 3.4 moles, 1.4 to 2.6 moles, 1.4 to 2.4 moles, 1.6 to 6.4 moles, 1.6 to 4.4 moles, 1.6 to 3.4 moles, 1.6 to 2.6 moles, 1.6 to 2.4 moles, 1.8 to 6.4 moles, 1.8 to 4.4 moles, 1.8 to 3.4 moles, 1.8 to 2.6 moles, or 1.8 to 2.4 moles.

[0047] Examples of cyclic esters include β-propiolactone, β-butyrolactone, γ-butyrolactone, β-valerolactone, γ-valerolactone, δ-valerolactone, α-caprolactone, β-caprolactone, γ-caprolactone, δ-caprolactone, ε-caprolactone, α-methyl-ε-caprolactone, β-methyl-ε-caprolactone, 4-methylcaprolactone, γ-caprylolactone, ε-caprylolactone, ε-palmitractone, and any combination of two or more of these.

[0048] The amount of cyclic ester may be 0.10 moles or more, 0.20 moles or more, 0.30 moles or more, 0.35 moles or more, or 0.40 moles or more per mole of carbonate ester, and may be 1.4 moles or less, 1.0 mole or less, 0.80 moles or less, 0.60 moles or less, 0.55 moles or less, or 0.50 moles or less. The amount of cyclic ester per mole of carbonate is 0.10–1.4 moles, 0.10–1.0 moles, 0.10–0.80 moles, 0.10–0.60 moles, 0.10–0.55 moles, 0.10–0.50 moles, 0.20–1.4 moles, 0.20–1.0 moles, 0.20–0.80 moles, 0.20–0.60 moles, 0.20–0.55 moles, 0.20–0.50 moles, 0.30–1.4 moles, 0.30–1.0 moles, 0.30 The amounts may be up to 0.80 moles, 0.30 to 0.60 moles, 0.30 to 0.55 moles, 0.30 to 0.50 moles, 0.35 to 1.4 moles, 0.35 to 1.0 moles, 0.35 to 0.80 moles, 0.35 to 0.60 moles, 0.35 to 0.55 moles, 0.35 to 0.50 moles, 0.40 to 1.4 moles, 0.40 to 1.0 moles, 0.40 to 0.80 moles, 0.40 to 0.60 moles, 0.40 to 0.55 moles, or 0.40 to 0.50 moles.

[0049] The amount of cyclic ester may be 0.10 moles or more, 0.20 moles or more, 0.30 moles or more, 0.35 moles or more, or 0.40 moles or more per mole of diol, and may be 1.4 moles or less, 1.0 mole or less, 0.80 moles or less, 0.60 moles or less, 0.55 moles or less, or 0.50 moles or less. The amount of cyclic ester per mole of diol is 0.10–1.4 moles, 0.10–1.0 moles, 0.10–0.80 moles, 0.10–0.60 moles, 0.10–0.55 moles, 0.10–0.50 moles, 0.20–1.4 moles, 0.20–1.0 moles, 0.20–0.80 moles, 0.20–0.60 moles, 0.20–0.55 moles, 0.20–0.50 moles, 0.30–1.4 moles, 0.30–1.0 moles, 0.30– The amounts may be 0.80 mol, 0.30–0.60 mol, 0.30–0.55 mol, 0.30–0.50 mol, 0.35–1.4 mol, 0.35–1.0 mol, 0.35–0.80 mol, 0.35–0.60 mol, 0.35–0.55 mol, 0.35–0.50 mol, 0.40–1.4 mol, 0.40–1.0 mol, 0.40–0.80 mol, 0.40–0.60 mol, 0.40–0.55 mol, or 0.40–0.50 mol.

[0050] The amount of cyclic ester may be 6 moles or more, 8 moles or more, 10 moles or more, 12 moles or more, 15 moles or more, 18 moles or more, 20 moles or more, 25 moles or more, or 30 moles or more, and may be 60 moles or less, 55 moles or less, 50 moles or less, 45 moles or less, 40 moles or less, or 35 moles or less, based on 100 moles of the total number of moles of cyclic ester and carbonate ester or diol.

[0051] The amount of cyclic ester may be 20 moles or more, 25 moles or more, or 30 moles or more per 100 moles of the total number of moles of cyclic ester and carbonate ester or diol, from the viewpoint of making it easier to obtain a polyester polycarbonate diol that is liquid at 25°C, has an even lower 100% modulus, and can form a polyurethane resin with an even higher elongation at break. The amount of cyclic ester may be 60 moles or less, 55 moles or less, 50 moles or less, 45 moles or less, or 40 moles or less per 100 moles of the total number of moles of cyclic ester and carbonate ester or diol, from the viewpoint of making it easier to obtain a polyester polycarbonate diol that can form a polyurethane resin with an even higher breaking strength, and may be 35 moles or less from the viewpoint of making it easier to obtain a polyester polycarbonate diol that can form a polyurethane resin with an even higher breaking strength and a higher softening temperature.

[0052] The amount of cyclic ester may be 10-60 moles, 15-60 moles, 20-60 moles, 25-60 moles, 10-55 moles, 15-55 moles, 20-55 moles, 25-55 moles, 10-50 moles, 15-50 moles, 20-50 moles, 25-55 moles, 10-40 moles, 15-40 moles, 20-40 moles, 25-40 moles, 10-35 moles, 15-35 moles, 20-35 moles, or 25-35 moles, based on 100 moles of the total number of moles of cyclic ester and carbonate ester or diol. When the amount of cyclic ester is within the above range, it is easier to obtain a polyester polycarbonate diol that can form a polyurethane resin with good hydrolysis resistance, low-temperature properties, and high tensile strength.

[0053] When the amount of cyclic ester is 20 to 35 moles or 25 to 35 moles per 100 moles of the total number of moles of cyclic ester and carbonate ester or diol, it becomes easier to obtain a polyester polycarbonate diol that is liquid at 25°C, has an even lower 100% modulus, even higher breaking strength and softening temperature, and even greater elongation at break, which can form a polyurethane resin.

[0054] The total number of moles of cyclic ester and carbonate ester or diol (hereinafter also simply referred to as "total number of moles") may be the total number of moles of the carbonate ester or diol used in the reaction step, plus the cyclic ester, if the number of moles of one of the carbonate ester or diol used in the reaction step is less than the other. That is, if the number of moles of diol used in the reaction step is less than the number of moles of carbonate ester used (moles of diol used < moles of carbonate ester used), the total number of moles may be the total number of moles of diol and cyclic ester, and if the number of moles of carbonate ester used in the reaction step is less than the number of moles of diol used (moles of diol used > moles of carbonate ester used), the total number of moles may be the total number of moles of carbonate ester and cyclic ester. If the number of moles of carbonate ester and diol used is the same, the total number of moles may be the total number of moles of either the carbonate ester or diol plus the cyclic ester. If the ratio of moles of diol used to moles of carbonate ester used (moles of diol used / moles of carbonate ester used) is 1.0, it can be determined that the number of moles used is the same. If it is less than 1.0 or greater than 1.0, it can be determined that the number of moles used for one of the carbonate ester or diol is smaller than the other.

[0055] The amount of cyclic ester may be 5 moles or more, 10 moles or more, or 15 moles or more, and 40 moles or less, 35 moles or less, 30 moles or less, or 25 moles or less, per 100 moles of the total number of moles of diol, cyclic ester, and carbonate ester. The amount of cyclic ester may be 5 to 40 moles, 5 to 35 moles, 5 to 30 moles, 5 to 25 moles, 10 to 40 moles, 10 to 35 moles, 10 to 30 moles, 10 to 25 moles, 15 to 40 moles, 15 to 35 moles, 15 to 30 moles, or 15 to 25 moles per 100 moles of the total number of moles of diol, cyclic ester, and carbonate ester.

[0056] Examples of carbonate esters include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, ethylene carbonate, trimethylene carbonate, and 1,2-propylene carbonate. These may be used individually or in combination of two or more. From the viewpoint of availability and ease of setting polymerization reaction conditions, the carbonate ester may be at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate, and ethylene carbonate.

[0057] The amount of carbonate ester may be 0.80 moles or more, or 0.85 moles or more, and 1.15 moles or less, or 1.10 moles or less, per mole of diol. The amount of carbonate ester may be 0.80 to 1.15 moles, 0.80 to 1.10 moles, 0.85 to 1.15 moles, or 0.85 to 1.10 moles per mole of diol.

[0058] The amount of carbonate ester may be 0.70 moles or more, 1.00 moles or more, 1.50 moles or more, 1.75 moles or more, or 1.80 moles or more per mole of cyclic ester, and may be 6.50 moles or less, 4.50 moles or less, 3.50 moles or less, 2.35 moles or less, or 2.30 moles or less per mole of cyclic ester. The amount of carbonate ester may be 0.70 to 6.50 moles, 0.70 to 4.50 moles, 0.70 to 3.50 moles, 0.70 to 2.35 moles, 0.70 to 2.30 moles, 1.00 to 6.50 moles, 1.00 to 4.50 moles, 1.00 to 3.50 moles, 1.00 to 2.35 moles, 1.00 to 2.30 moles, 1.50 to 6.50 moles, or 1.50 to 4.50 moles per mole of cyclic ester. It may be 1.50 to 3.50 moles, 1.50 to 2.35 moles, 1.50 to 2.30 moles, 1.75 to 6.50 moles, 1.75 to 4.50 moles, 1.75 to 3.50 moles, 1.75 to 2.35 moles, 1.75 to 2.30 moles, 1.80 to 6.50 moles, 1.80 to 4.50 moles, 1.80 to 3.50 moles, 1.80 to 2.35 moles, or 1.80 to 2.30 moles.

[0059] The reaction may be carried out in the presence of a catalyst. As the catalyst, known catalysts used as catalysts for ring-opening polymerization of cyclic esters, or for transesterification reactions, can be used. The catalyst may be a metal salt.

[0060] Examples of cations in metal salts include alkali metal ions such as lithium ions, sodium ions, potassium ions, and cesium ions; magnesium ions, calcium ions, iron(II) ions, iron(III) ions, copper(II) ions, aluminum ions, and zinc ions. Examples of anions in metal salts include bicarbonate ions, acetylacetonate, trifluoroacetate, trichloroacetate, oxalate ions, methanesulfonate ions, carbonate ions, sulfate ions, nitrate ions, and methoxide ions. Specific examples of catalysts include lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, lithium acetylacetonate, sodium acetylacetonate, potassium acetylacetonate, lithium trifluoroacetate, sodium trichloroacetate, lithium oxalate, sodium oxalate, potassium oxalate, and sodium methanesulfonate.

[0061] The reaction process may be carried out in the presence of one or more catalysts. It is preferable to carry out the reaction process in the presence of two catalysts because the reaction time is shortened and polyester polycarbonate polyols with a lower color number are more easily obtained.

[0062] When the reaction step is carried out in the presence of two or more catalysts, the mass of each catalyst relative to the total mass of the catalysts may be, for example, 0.10 or more, 0.20 or more, 0.25 or more, 0.30 or more, or 0.40 or more, and may be 0.90 or less, 0.80 or less, 0.70 or less, 0.60 or less, 0.50 or less, or 0.40 or less. When two or more catalysts include potassium bicarbonate, the mass of potassium bicarbonate relative to the total mass of the catalysts may be 0.20 to 0.70 or 0.30 to 0.60. When two or more catalysts include lithium trifluoroacetate, sodium oxalate, or sodium trichloroacetate, the respective masses of lithium trifluoroacetate, sodium oxalate, and sodium trichloroacetate relative to the total mass of the catalysts may be 0.40 to 0.90 or 0.50 to 0.80.

[0063] The catalyst may include a catalyst whose conjugate acid pKa is 3 or less in an aqueous solution at 25°C, and a catalyst whose conjugate acid pKa is 5 or more in an aqueous solution at 25°C.

[0064] A catalyst with a conjugate acid pKa of 3 or less in an aqueous solution at 25°C may be any catalyst used as a ring-opening polymerization catalyst for cyclic esters, wherein the conjugate acid pKa of 3 or less in an aqueous solution at 25°C. Examples of catalysts with a conjugate acid pKa of 3 or less in an aqueous solution at 25°C include lithium trifluoroacetate (conjugate acid pKa: -0.30), sodium trichloroacetate (conjugate acid pKa: 0.65), sodium oxalate (conjugate acid pKa: 1.23), and sodium methanesulfonate (conjugate acid pKa: -2.60).

[0065] A catalyst with a conjugate acid pKa of 5 or higher in an aqueous solution at 25°C may be any catalyst used as a catalyst for transesterification reactions that has a conjugate acid pKa of 5 or higher in an aqueous solution at 25°C. Examples of catalysts with a conjugate acid pKa of 5 or higher in an aqueous solution at 25°C include potassium bicarbonate (conjugate acid pKa: 6.77, 10.33), lithium acetylacetonate (conjugate acid pKa: 8.90), and sodium methoxide (conjugate acid pKa: 15.5).

[0066] A suitable combination of catalysts is potassium bicarbonate and lithium trifluoroacetate. Another suitable combination of catalysts is potassium bicarbonate and sodium oxalate. Yet another suitable combination of catalysts is potassium bicarbonate and sodium trichloroacetate.

[0067] The total catalyst content may be 50 ppm to 250 ppm by mass, 100 ppm to 200 ppm by mass, or 130 ppm to 170 ppm by mass, relative to the total amount of raw materials charged.

[0068] In the reaction step, the diol, cyclic ester, and carbonate ester are reacted in a reaction solution containing the diol, cyclic ester, carbonate ester, and a catalyst added as needed. The reaction may be carried out by heating the reaction solution. The reaction may be carried out while removing low-boiling point components (such as alcohols derived from the carbonate ester) from the reaction system.

[0069] The heating temperature of the reaction solution (reaction temperature) may be, for example, 80-250°C, 100-220°C, 140-180°C, or 150-170°C. The reaction may be carried out while maintaining a constant temperature, or by gradually or continuously increasing the temperature according to the progress of the reaction. The progress of the reaction can be estimated from the amount of distillate distilled.

[0070] The reaction can also be carried out under atmospheric pressure or reduced pressure (for example, under a pressure of 101 to 0.1 kPa). The pressure may be changed stepwise or continuously depending on the progress of the reaction. The reaction can also be started under atmospheric pressure and carried out under reduced pressure (for example, under a pressure of 101 to 0.1 kPa) in the latter half of the reaction. In this case, the distillation rate of the distillate can be increased, and the progress of the reaction can be accelerated. In this specification, atmospheric pressure means a pressure of 101.325 kPa ± 20.000 kPa.

[0071] The heating of the reaction solution preferably includes heating under a pressure of 101.325 kPa ± 20.000 kPa (first heating), followed by heating under reduced pressure of 10.000 kPa or less (second heating). The first and second heating temperatures may each be within the heating temperature (reaction temperature) described above. It is preferable to remove the alcohol derived from the carbonate ester from the reaction system by distillation at 120°C or below. The distillate temperature may be, for example, 77°C or higher and less than 79°C. The reaction time may be 2 to 80 hours, 3 to 60 hours, 4 to 50 hours, 5 to 40 hours, or 6 to 30 hours.

[0072] <Polyurethane Resin Forming Composition> Another embodiment of the present disclosure relates to a polyurethane resin forming composition containing a polyol including the polyester polycarbonate diol described above, and a polyisocyanate.

[0073] (Polyol) The polyol may further contain polyols other than the polyester polycarbonate diols described above.

[0074] The polyol may further contain, for example, a polyhydric alcohol (Z) represented by the following formula (Z) having three or more hydroxyl groups in its molecule. [In formula (Z), R ４ [This represents a hydrogen atom, an alkyl group, or a hydroxyalkyl group.]

[0075] Specific examples of polyhydric alcohols (Z) include trimethylolpropane, trimethylolethane, glycerin, and pentaerythritol. Polyhydric alcohols (Z) may be used alone or in combination of two or more types.

[0076] The polyol may further contain a polyol having an acidic group. In this case, the polyurethane resin will contain an acidic group. Polyurethane resins having an acidic group are suitably used in aqueous urethane resin dispersions, as described later.

[0077] Acidic groups are functional groups (hydrophilic groups) that can impart hydrophilicity to isocyanate-terminated prepolymers obtained, for example, by reaction with isocyanates. Examples of polyols having such acidic groups include dimethylolalkanoates such as dimethylolpropionic acid (DMPA), dimethylolbutanoic acid (DMBA), dimethylolpentanoic acid, and dimethylolnonanoic acid.

[0078] (Polyisocyanates) Polyisocyanates are compounds having two or more isocyanate groups (-N=C=O), preferably compounds having two isocyanate groups (diisocyanates). Examples of polyisocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and their polyisocyanate derivatives. Examples of derivatives include isocyanurates, allophanates, biuretes, dimers, trimers, carbodiimides, uretonimines, and adducts obtained by the reaction of isocyanates with bifunctional or more polyols. Derivatives may be prepolymerized using polyols or the like as modifiers. One type of polyisocyanate may be used alone, or two or more types of polyisocyanates may be used in combination.

[0079] Examples of aromatic polyisocyanates include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate, or mixtures thereof) (TDI), phenylene diisocyanate (m- or p-phenylene diisocyanate, or mixtures thereof), 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate, or mixtures thereof) (MDI), diphenylpropane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylpropane diisocyanate, or mixtures thereof), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xyl Examples include diisocyanates (1,3- or 1,4-xylylene diisocyanate, or mixtures thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate, or mixtures thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,4-, 1,5- or 1,8-naphthalene diisocyanate, or mixtures thereof) (NDI), 2-nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, etc. These may be used individually or in combination of two or more.

[0080] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, 1,2-propylene diisocyanate, tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, pentamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 3-methylpentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, decamethylene diisocyanate, lysine diisocyanate, and trioxyethylene diisocyanate. These may be used individually or in combination of two or more.

[0081] Examples of alicyclic polyisocyanates include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylenebis(cyclohexyl isocyanate (4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate, or mixtures thereof) (hydrogenated diphenylmethane diisocyanate (hydrogenated MDI)), methylcyclohexane diisocyanate (methyl-2,4-cyclohex Examples include diisocyanate or methyl-2,6-cyclohexane diisocyanate, or mixtures thereof), bis(isocyanate-methyl)cyclohexane (1,3- or 1,4-bis(isocyanate-methyl)cyclohexane, or mixtures thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI), norbornene diisocyanate, norbornane diisocyanate methyl, diisocyanate methylbicycloheptane, etc. These may be used individually or in combination of two or more.

[0082] (Molar ratio of polyol to polyisocyanate) The molar ratio of active hydrogen in the polyol to isocyanate groups in the polyisocyanate may be, for example, 0.1 to 9.0, 0.5 to 1.5, or 0.8 to 1.2. When the molar ratio is within this range, the polyurethane resin tends to have better performance.

[0083] (Urethane Formation Catalyst) The polyurethane resin-forming composition may further contain a urethane formation catalyst for the purpose of shortening the reaction time and improving the reaction rate of the urethane formation reaction. Examples of urethane formation catalysts include tertiary amine catalysts such as triethylamine, triethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine, and tetramethylhexamethylenediamine, and metal catalysts such as tin-based catalysts such as stanus octoate, stanus oleate, and dibutyltin dilaurate. These can be used alone or in combination of two or more. Among these, dibutyltin dilaurate is preferably used.

[0084] The amount of catalyst may be 0.001 parts by mass or more, and 100 parts by mass or less, 50 parts by mass or less, 10 parts by mass or less, 1 part by mass or less, 0.5 parts by mass or less, or 0.1 parts by mass or less, per 100 parts by mass of the total amount of polyol and polyisocyanate, or 0.01 parts by mass or more, and 100 parts by mass or less, 50 parts by mass or less, 10 parts by mass or less, 1 part by mass or less, 0.5 parts by mass or less, or 0.1 parts by mass or less.

[0085] (Phosphorus compounds) When a catalyst is used in the urethane reaction, it is preferable to use a phosphorus compound for treating the catalyst. Phosphorus compounds are not particularly limited, but examples include phosphoric acid triesters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, and cresyl-diphenyl phosphate; acidic phosphoric acid esters such as methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, dibutyl phosphate, monobutyl phosphate, monoisodecyl phosphate, and bis(2-ethylhexyl) phosphate; triphenyl phosphate Phosphate, trisnonylphenyl phosphate, tricresyl phosphate, triethyl phosphate, tris(2-ethylhexyl) phosphate, tridecyl phosphate, trilauryl phosphate, tris(tridecyl) phosphate, trioleyl phosphate, diphenyl mono(2-ethylhexyl) phosphate, diphenyl monodecyl phosphate, diphenyl(monodecyl) phosphate, trilauryl phosphate, diethylhydrogen phosphate, bis(2-ethylhexyl) Phosphite esters such as xyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyldipropylene glycol diphosphite, bis(decyl)pentaerythritol diphosphite, tristearyl phosphite, distearylpentaerythritol diphosphite, and tris(2,4-di-tert-butylphenyl) phosphite; also include phosphoric acid, phosphorous acid, and hypophosphorous acid. These can be used individually or in combination of two or more.Among these, acidic phosphate esters are preferred, and 2-ethylhexyl acid phosphate is more preferred.

[0086] The amount of phosphorus compound may be 10 to 2000 parts by mass, 20 to 1000 parts by mass, 30 to 500 parts by mass, or 50 to 500 parts by mass per 100 parts by mass of catalyst.

[0087] (Solvent) The polyurethane resin-forming composition may further contain a solvent (diluting solvent). Examples of solvents that can be used include esters such as ethyl acetate, butyl acetate, propyl acetate, γ-butyrolactone, δ-valerolactone, and ε-caprolactone; amides such as dimethylformamide, diethylformamide, and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; ethers such as tetrahydrofuran, dioxane, and 2-ethoxyethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and aromatic hydrocarbons such as benzene and toluene. One solvent may be used alone, or two or more may be used in combination.

[0088] The total amount of solvent may be 30% by mass or more and 70% by mass or 65% by mass or less, 40% by mass or more and 70% by mass or less, 65% by mass or less, 50% by mass or more and 70% by mass or less, or 65% by mass or less, based on the total amount of the polyurethane resin-forming composition.

[0089] (Other Components) The polyurethane resin-forming composition may further contain other components besides those described above. Examples of other components include chain extenders, surface modifiers, antioxidants, pigments, dyes, flame retardants, hydrolysis inhibitors, lubricants, plasticizers, fillers, antistatic agents, dispersants, storage stabilizers, thickeners, internal release agents, defoamers, and antibacterial agents. The total amount of other components may be 0 to 10% by mass, 0 to 5% by mass, or 0 to 1% by mass, based on the total amount of the polyurethane resin-forming composition.

[0090] <Two-component composition set> Another embodiment of the present disclosure relates to a two-component composition set for preparing the polyurethane resin-forming composition described above. The two-component composition set comprises a first liquid containing at least a polyol and a second liquid containing at least a polyisocyanate. When components other than polyol and polyisocyanate are used, they may be included in the first and / or second liquids, or they may be compounded separately from the first and second liquids. The first and second liquids in the two-component composition set may be stored and transported in separate containers. The two-component composition set can be suitably used, for example, as a coating agent and can also be suitably used in the manufacture of artificial leather, synthetic leather, exterior paints, interior paints, etc. When the two-component composition set is used as a coating agent, for example, after mixing the first and second liquids, the resulting mixture can be applied to a substrate and optionally heated to form a coating film (for example, a cured film containing polyurethane resin).

[0091] <Polyurethane Resin> Another embodiment of the present disclosure relates to a polyurethane resin which is a reactant of the polyurethane resin-forming composition described above. The reactant may be a polycondensate of a polyol and a polyisocyanate or a crosslinked thereof. A crosslinked body means a polycondensate that has been crosslinked with a chain extender or the like.

[0092] Polyurethane resins can be obtained by a urethane reaction in a reaction mixture containing a polyol, a polyisocyanate, and the above components as needed. The urethane reaction may be carried out at room temperature (e.g., 25°C) or under heating (e.g., 40-200°C).

[0093] By using the polyurethane resin-forming composition containing the above-mentioned polyester polycarbonate diol, a polyurethane resin with good low-temperature properties and high tensile strength can be formed. A polyurethane resin can be judged to have good low-temperature properties if its glass transition temperature is -10.0°C or lower. The glass transition temperature of the polyurethane resin may be -10.0°C or lower, -11.0°C or lower, -12.0°C or lower, -15.0°C or lower, -20.0°C or lower, or -22.0°C or lower. The glass transition temperature of the polyurethane resin may be -25.0°C to -10.0°C, -20.0 to -10.0°C, or -15.0 to -10.0°C. The tensile strength of the polyurethane resin may be greater than 17.0 MPa, 20 MPa or higher, or greater than 25 MPa. The tensile strength of the polyurethane resin may be greater than 17.0 MPa and less than or equal to 40 MPa, between 20 MPa and 40 MPa, or greater than 25 MPa and less than or equal to 40 MPa.

[0094] By using the polyurethane resin-forming composition containing the polyester polycarbonate diol described above, a polyurethane resin with good 100% modulus, elongation at break, and softening temperature can be formed. The 100% modulus of the polyurethane resin may be 2.3 or less, 2.0 or less, or 1.8 or less, and may be between 1.60 and 2.0. The elongation at break of the polyurethane resin may be greater than 430%. The softening temperature of the polyurethane resin may be greater than 250°C, and may be between 250°C and 270°C.

[0095] The glass transition temperature, breaking strength, 100% modulus, elongation at break, and softening temperature of the above polyurethane resin can be measured by the method described in the examples below.

[0096] <Coating Agent> Another embodiment of the present disclosure relates to a coating agent comprising the polyurethane resin described above.

[0097] One example of its use as a coating agent is an in-mold coating method that applies RIM (Reaction Injection Molding). Specifically, this in-mold coating method applies RIM to a method in which a plastic substrate is molded in an injection molding die, and then a urethane coating film is formed on the surface of the molded product within the die. In this method, the internal volume of the die is constant, and not only are the density, thickness, and hardness of the urethane coating film stable, but it is also possible to faithfully reproduce the irregularities on the surface of the die and obtain a highly aesthetic appearance.

[0098] <Aqueous Urethane Resin Dispersion> Another embodiment of the present disclosure relates to an aqueous urethane resin dispersion containing an aqueous medium and a polyurethane resin or a neutralized product thereof dispersed in the aqueous medium. The polyurethane resin in the aqueous urethane resin dispersion has acidic groups.

[0099] The aqueous medium may be water, or a solution containing water, an emulsifier, a dispersant, and the like.

[0100] When an aqueous urethane resin dispersion contains a neutralized polyurethane resin, the acidic groups of the polyurethane resin may be neutralized by a neutralizing agent. Examples of neutralizing agents include ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-ethyl-1-propanol, higher alkyl-modified morpholine and other organic amines, alkali metals such as lithium, potassium, and sodium, and inorganic alkalis such as sodium hydroxide and potassium hydroxide. From the viewpoint of improving the durability and smoothness of the coating film, highly volatile neutralizing agents that dissociate easily upon heating, such as ammonia, trimethylamine, and triethylamine, are preferably used. These neutralizing agents can be used alone or in combination of two or more.

[0101] In the production of aqueous urethane resin dispersions, compounds containing anionic polar groups can also be used. Examples of compounds containing anionic polar groups include those consisting of an organic acid having one or more active hydrogen atoms and a neutralizing agent. Examples of organic acids include carboxylates, sulfonates, phosphates, phosphonates, phosphinates, and thiosulfonates. These anionic polar groups contained in the organic acid may be introduced individually or may be associated with metal ions, such as in a chelate.

[0102] In the production of aqueous urethane resin dispersions, a cationic polar group-containing compound can also be used. An example of a cationic polar group-containing compound is a tertiary amine having one or more active hydrogen atoms, and one compound selected from the group consisting of inorganic acid neutralizers, organic acid neutralizers, and quaternizing agents. Furthermore, as a cationic polar group-containing compound, cationic compounds such as primary amine salts, secondary amine salts, tertiary amine salts, and pyridinium salts can also be used.

[0103] Examples of tertiary amines having one or more active hydrogen atoms include N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dipropylethanolamine, N,N-diphenylethanolamine, N-methyl-N-ethylethanolamine, N-methyl-N-phenylethanolamine, N,N-dimethylpropanolamine, N-methyl-N-ethylpropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-methyldipropanolamine, N-phenyldiethanolamine, N-phenyldipropanolamine, N-hydroxyethyl-N-hydroxypropyl-methylamine, N,N'-dihydroxyethylpiperazine, triethanolamine, trisisopropanolamine, N-methyl-bis-(3-aminopropyl)amine, and N-methyl-bis-(2-aminopropyl)amine. Furthermore, primary amines such as ammonia and methylamine, or secondary amines such as dimethylamine, can also be used after the addition of alkylene oxides.

[0104] Examples of inorganic and organic acids include hydrochloric acid, acetic acid, lactic acid, cyanoacetic acid, phosphoric acid, and sulfuric acid.

[0105] Examples of quaternizing agents include dimethyl sulfate, benzyl chloride, bromoacetamide, and chloroacetamide. Alkyl halides such as ethyl bromide, propyl bromide, and butyl bromide can also be used.

[0106] Aqueous urethane resin dispersions can be produced, for example, by sequentially carrying out the following steps: reacting a polyol containing an acidic group with a polyisocyanate in the presence or absence of a solvent to form a urethane prepolymer; neutralizing the acidic groups in the prepolymer with a neutralizing agent; dispersing the neutralized prepolymer in an aqueous medium; and reacting the prepolymer dispersed in the aqueous medium with a chain extender. In each step, a catalyst can be used as needed to accelerate the reaction and control the amount of by-products.

[0107] <Applications> The polyurethane resin-forming composition, the polyurethane resin, the aqueous urethane resin dispersion, and the coating agent can be used in paint compositions suitable for use as clear coatings for automotive exteriors and coatings for automotive interiors. The polyurethane resin-forming composition, the polyurethane resin, the aqueous urethane resin dispersion, and the coating agent can be preferably used in home appliances, office automation (OA) products, leather surface treatment, synthetic leather surface treatment, and the like.

[0108] The contents of this disclosure will be described in more detail below using examples and comparative examples, but this disclosure is not limited to the following examples.

[0109] Synthesis of Polyester Polycarbonate Diols in Examples and Comparative Examples (Example 1) 163.8 g of 1,6-hexanediol, 162.6 g of diethyl carbonate, 73.7 g of ε-caprolactone, 0.020 g of potassium bicarbonate, and 0.040 g of lithium trifluoroacetate were mixed in a 0.5 L two-necked glass reactor (reactor A) equipped with a stirrer, thermometer, heating device, and a rectification column and condenser packed with regular packing material. The resulting mixture was heated at atmospheric pressure at 150-170°C (150°C initially, 170°C towards the end) and reacted for 6.0 hours while removing low-boiling point components (alcohols derived from carbonate esters, etc.). The distillate temperature was kept between 77°C and 79°C. Furthermore, at a reaction temperature of 170°C, the pressure in the flask was gradually reduced to 5.0 kPa over 0.5 hours, and the reaction was continued at 5.0 kPa for another 0.5 hours. Furthermore, the pressure inside the flask was gradually reduced to 0.5 kPa over 0.5 hours, and the reaction was then carried out at 0.5 kPa for 2.0 hours. By the above method, a polyester polycarbonate diol (PCD-1) containing constituent unit (A), constituent unit (B), and terminal hydroxyl groups was obtained.

[0110] In the synthesis of PCD-1, the amount of cyclic ester was 31.8 moles relative to the total number of moles of cyclic ester and diol (100 moles). The amount of cyclic ester was 31.9 moles relative to the total number of moles of cyclic ester and carbonate ester (100 moles).

[0111] In PCD-1, the content of constituent unit (B) was 31.9 mol%, based on the total amount of constituent unit (A) and constituent unit (B).

[0112] (Example 2) Polyester polycarbonate diol (PCD-2) was obtained in the same manner as in Example 1, except that 162.4 g of 1,6-hexanediol, 163.5 g of diethyl carbonate, and 74.1 g of ε-caprolactone were added.

[0113] In the synthesis of PCD-2, the amount of cyclic ester was 32.1 moles relative to the total number of moles of cyclic ester and diol (100 moles). The amount of cyclic ester was 31.9 moles relative to the total number of moles of cyclic ester and carbonate ester (100 moles).

[0114] In PCD-2, the content of constituent unit (B) was 32.1 mol%, based on the total amount of constituent unit (A) and constituent unit (B).

[0115] (Example 3) Polyester polycarbonate diol (PCD-3) was obtained in the same manner as in Example 1, except that 166.2 g of 1,6-hexanediol, 160.9 g of diethyl carbonate, and 72.9 g of ε-caprolactone were added.

[0116] In the synthesis of PCD-3, the amount of cyclic ester was 31.2 moles relative to the total number of moles of cyclic ester and diol (100 moles). The amount of cyclic ester was 31.9 moles relative to the total number of moles of cyclic ester and carbonate ester (100 moles).

[0117] In PCD-3, the content of constituent unit (B) was 31.9 mol%, based on the total amount of constituent unit (A) and constituent unit (B).

[0118] (Example 4) Polyester polycarbonate diol (PCD-4) was obtained in the same manner as in Example 1, except that 184.5 g of 1,6-hexanediol, 186.6 g of diethyl carbonate, and 28.9 g of ε-caprolactone were added.

[0119] In the synthesis of PCD-4, the amount of cyclic ester was 14.0 moles relative to the total number of moles of cyclic ester and diol (100 moles). The amount of cyclic ester was 13.8 moles relative to the total number of moles of cyclic ester and carbonate ester (100 moles).

[0120] In PCD-4, the content of constituent unit (B) was 14.0 mol%, based on the total amount of constituent unit (A) and constituent unit (B).

[0121] (Example 5) Polyester polycarbonate diol (PCD-5) was obtained in the same manner as in Example 1, except that 179.5 g of 1,6-hexanediol, 180.8 g of diethyl carbonate, and 39.7 g of ε-caprolactone were added.

[0122] In the synthesis of PCD-5, the amount of cyclic ester was 18.6 moles relative to the total number of moles of cyclic ester and diol (100 moles). The amount of cyclic ester was 18.5 moles relative to the total number of moles of cyclic ester and carbonate ester (100 moles).

[0123] In PCD-5, the content of constituent unit (B) was 18.6 mol%, based on the total amount of constituent unit (A) and constituent unit (B).

[0124] (Example 6) Polyester polycarbonate diol (PCD-6) was obtained in the same manner as in Example 1, except that 174.2 g of 1,6-hexanediol, 174.7 g of diethyl carbonate, and 51.1 g of ε-caprolactone were added.

[0125] In the synthesis of PCD-6, the amount of cyclic ester was 23.3 moles relative to the total number of moles of cyclic ester and diol (100 moles). The amount of cyclic ester was 23.2 moles relative to the total number of moles of cyclic ester and carbonate ester (100 moles).

[0126] In PCD-6, the content of constituent unit (B) was 23.3 mol%, based on the total amount of constituent unit (A) and constituent unit (B).

[0127] (Example 7) Polyester polycarbonate diol (PCD-7) was obtained in the same manner as in Example 1, except that 156.2 g of 1,6-hexanediol, 153.8 g of diethyl carbonate, 90.0 g of ε-caprolactone, and 0.04 g of potassium bicarbonate were added.

[0128] In the synthesis of PCD-7, the amount of cyclic ester was 37.4 moles relative to the total number of moles of cyclic ester and diol (100 moles). The amount of cyclic ester was 37.7 moles relative to the total number of moles of cyclic ester and carbonate ester (100 moles).

[0129] In PCD-7, the content of constituent unit (B) was 37.7 mol%, based on the total amount of constituent unit (A) and constituent unit (B).

[0130] (Example 8) Polyester polycarbonate diol (PCD-8) was obtained in the same manner as in Example 1, except that 142.0 g of 1,6-hexanediol, 137.3 g of diethyl carbonate, 120.6 g of ε-caprolactone, and 0.04 g of potassium bicarbonate were added.

[0131] In the synthesis of PCD-8, the amount of cyclic ester was 46.8 moles relative to the total number of moles of cyclic ester and diol (100 moles). The amount of cyclic ester was 47.6 moles relative to the total number of moles of cyclic ester and carbonate ester (100 moles).

[0132] In PCD-8, the content of constituent unit (B) was 47.6 mol%, based on the total amount of constituent unit (A) and constituent unit (B).

[0133] (Example 9) Polyester polycarbonate diol (PCD-9) was obtained in the same manner as in Example 1, except that 196.1 g of 1,9-nonanediol, 140.3 g of diethyl carbonate, and 63.6 g of ε-caprolactone were added.

[0134] In the synthesis of PCD-9, the amount of cyclic ester was 31.3 moles relative to the total number of moles of cyclic ester and diol (100 moles). The amount of cyclic ester was 31.9 moles relative to the total number of moles of cyclic ester and carbonate ester (100 moles).

[0135] In PCD-9, the content of constituent unit (B) was 31.9 mol%, based on the total amount of constituent unit (A) and constituent unit (B).

[0136] (Example 10) Polyester polycarbonate diol (PCD-10) was obtained in the same manner as in Example 1, except that 163.8 g of 1,6-hexanediol, 162.6 g of diethyl carbonate, 73.7 g of ε-caprolactone, and 0.04 g of sodium oxalate were added.

[0137] In the synthesis of PCD-10, the amount of cyclic ester was 31.8 moles relative to the total number of moles of cyclic ester and diol (100 moles). The amount of cyclic ester was 31.9 moles relative to the total number of moles of cyclic ester and carbonate ester (100 moles).

[0138] In PCD-10, the content of constituent unit (B) was 31.9 mol%, based on the total amount of constituent unit (A) and constituent unit (B).

[0139] (Example 11) Polyester polycarbonate diol (PCD-11) was obtained in the same manner as in Example 1, except that 163.8 g of 1,6-hexanediol, 162.6 g of diethyl carbonate, 73.7 g of ε-caprolactone, and 0.04 g of sodium trichloroacetate were added.

[0140] In the synthesis of PCD-11, the amount of cyclic ester was 31.8 moles relative to the total number of moles of cyclic ester and diol (100 moles). The amount of cyclic ester was 31.9 moles relative to the total number of moles of cyclic ester and carbonate ester (100 moles).

[0141] In PCD-11, the content of constituent unit (B) was 31.9 mol%, based on the total amount of constituent unit (A) and constituent unit (B).

[0142] (Example 12) Polyester polycarbonate diol (PCD-12) was obtained in the same manner as in Example 1, except that 125.7 g of 1,6-hexanediol, 118.4 g of diethyl carbonate, 156.0 g of ε-caprolactone, and 0.04 g of potassium bicarbonate were added.

[0143] In the synthesis of PCD-12, the amount of cyclic ester was 56.2 moles relative to the total number of moles of cyclic ester and diol (100 moles). The amount of cyclic ester was 57.7 moles relative to the total number of moles of cyclic ester and carbonate ester (100 moles).

[0144] In PCD-12, the content of constituent unit (B) was 57.7 mol%, based on the total amount of constituent unit (A) and constituent unit (B).

[0145] (Comparative Example 1) A reaction apparatus equipped with a stirrer, a thermometer, and a heating device was charged with 700 g of polycarbonate diol (N-980N) and 300 g of polycaprolactone diol (Plaxel 220), and a transesterification reaction was carried out at 190°C for 8 hours to obtain polyester polycarbonate diol (PCD-13).

[0146] In PCD-13, the content of constituent unit (B) was 30.0 mol%, based on the total amount of constituent unit (A) and constituent unit (B).

[0147] (Comparative Example 2) Polyester polycarbonate diol (PCD-14) was obtained in the same manner as in Example 1, except that 86.3 g of 1,6-hexanediol, 65.8 g of 1,4-butanediol, 170.6 g of diethyl carbonate, and 77.3 g of ε-caprolactone were added.

[0148] In the synthesis of PCD-14, the amount of cyclic ester was 31.7 moles relative to the total number of moles of cyclic ester and diol (100 moles). The amount of cyclic ester was 31.9 moles relative to the total number of moles of cyclic ester and carbonate ester (100 moles).

[0149] In PCD-14, the content of constituent unit (B) was 31.9 mol%, based on the total amount of constituent unit (A) and constituent unit (B).

[0150] (Comparative Example 3) N-980N, a polycarbonate diol, was used as PCD-15. In PCD-15, the content of constituent unit (B) was 0.0 mol% based on the total amount of constituent unit (A) and constituent unit (B).

[0151] (Comparative Example 4) Polyester polycarbonate diol (PCD-16) was obtained in the same manner as in Example 1, except that 193.7 g of 1,6-hexanediol, 197.2 g of diethyl carbonate, and 9.1 g of ε-caprolactone were added.

[0152] In the synthesis of PCD-16, the amount of cyclic ester was 4.6 moles relative to the total number of moles of cyclic ester and diol (100 moles). The amount of cyclic ester was 4.6 moles relative to the total number of moles of cyclic ester and carbonate ester (100 moles).

[0153] In PCD-16, the content of constituent unit (B) was 4.6 mol%, based on the total amount of constituent unit (A) and constituent unit (B).

[0154] Analytical Methods for Each Item [Measurement of Number-Average Molecular Weight] GPC analysis was performed on the compositions obtained above under the following conditions to measure the number-average molecular weight of the polyester polycarbonate diol and the composition. The results are shown in Table 1. -Conditions- (1) Measuring instrument: HLC-8420 (manufactured by Tosoh Corporation) (2) Column: TSKgel (manufactured by Tosoh Corporation) ・G3000H-XL ・G3000H-XL ・G2000H-XL ・G2000H-XL (3) Mobile phase: THF (tetrahydrofuran) (4) Detector: RI (refractive index) detector (accessory for HLC-8420) (5) Temperature: 40℃ (6) Flow rate: 1,000 ml / min (7) Calibration curve: A calibration curve was obtained using the following products (all bifunctional polyoxypropylene polyols manufactured by Sanyo Chemical Industries, Ltd.).・ "Sannix PP-200" (number average molecular weight = 200, average number of functional groups: 2) ・ "Sannix PP-400" (number average molecular weight = 400, average number of functional groups: 2) ・ "Sannix PP-1000" (number average molecular weight = 1000, average number of functional groups: 2) ・ "Sannix PP-2000" (number average molecular weight = 2000, average number of functional groups: 2) ・ "Sannix PP-3000" (number average molecular weight = 3200, average number of functional groups: 2) ・ "Sannix PP-4000" (number average molecular weight = 4160, average number of functional groups: 2) (8) Approximation formula for calibration curve: cubic equation (9) Sample solution concentration: 0.5 mass% THF solution

[0155] [Measurement of Hydroxyl Value] The hydroxyl value of the polycarbonate polyol obtained above and the hydroxyl value of the composition obtained above were measured using a method with an acetylation reagent in accordance with JIS K1557-1. The results are shown in Table 1.

[0156] [Wide-angle X-ray scattering measurement] The sample was placed on a Si non-reflective sample plate, immersed in liquid nitrogen for more than 3 minutes to cool the sample, and then mounted on the apparatus within 1 minute to start the measurement. The conditions were as follows. The results are shown in Table 1. Figure 1 is the X-ray diffraction (XRD) spectrum showing the measurement results when using polyester polycarbonate diol in Example 1. -Conditions- (1) Measurement apparatus: SmartLab (manufactured by Rigaku) ​​(2) X-ray source: CuKα rays, 45kV, 200mA (3) Optical instrument: Parallel beam optical system (4) Scan conditions: 2θ = 5 to 90 deg, 40 deg / min, 0.04 deg / step

[0157] [Content of constituent unit (B)] In Examples 1 to 12 and Comparative Examples 2 and 4, the content of constituent unit (B) was calculated based on the amount of cyclic ester (cyclic lactone) charged and the amount of diol or carbonate ester charged. Specifically, the content of constituent unit (B) was calculated using the following formulas (1-1A) or (1-1B). Formula (1-1A): Moles of cyclic ester / (Moles of diol + Moles of cyclic ester) × 100 Formula (1-1B): Moles of cyclic ester / (Moles of carbonate ester + Moles of cyclic ester) × 100

[0158] The content of constituent unit (B) is calculated using formula (1-1A) when the number of moles of diol is less than the number of moles of diol used, using formula (1-1B) when the number of moles of diol is less than the number of moles of diol used, and using either formula (1-1A) or formula (1-1B) when the number of moles of diol and diol are the same.

[0159] In Comparative Examples 1 and 3, the content of constituent unit (B) was determined by the following method. In Comparative Example 1, since constituent unit (A) is polycarbonate diol and constituent unit (B) is polycaprolactone diol, the content of constituent unit (B) was calculated using the following formula: Formula (1-2): Moles of polycaprolactone diol / (Moles of polycarbonate diol + Moles of polycaprolactone diol) × 100

[0160] Physical Properties Evaluation: Urethane cured film coatings (films) were prepared using the following method, and the physical properties (100% modulus, breaking strength, elongation at breaking, softening temperature, and glass transition temperature) of the obtained films were evaluated as samples.

[0161] [Preparation of Urethane Cured Film] First, the polyester polycarbonate diol obtained above, trimethylolpropane, hydrogenated MDI, urethane catalyst, phosphorus compound (JP-508), and diluent were mixed in a 200 mL glass bottle in the proportions (unit: g) shown in Table 2. Immediately after mixing, the mixture was poured onto release paper and cast into a 200 μm thick film using a bar coater. Next, the cast film was cured by heating at 25°C for 30 minutes, 50°C for 30 minutes, 80°C for 30 minutes, 120°C for 1 hour, and 50°C for 12 hours to obtain a urethane cured film.

[0162] [Tensile Properties Evaluation] The tensile properties of the obtained film were measured in accordance with JIS K6251 under the following conditions: (100% modulus, strength at break, and elongation at break) -Conditions- • Test equipment: Tensilon UTA-500 (manufactured by A&D Co., Ltd.) • Measurement conditions: 25℃ × 50% RH • Head speed: 200 mm / min • Dumbbell No. 4

[0163] [Softening Temperature] After obtaining a test specimen from the acquired film using a dumbbell, a 2 cm gauge mark was marked on the specimen, and the thickness at the center of the gauge mark was measured. A weight of a predetermined weight was attached to one of the grips of the test specimen, and the other grip was clamped with a double clip. The specimen was then suspended in a dryer with the clip facing upwards, and the temperature inside the dryer was increased, and the distance between the gauge marks was observed. The temperature at which the distance between the gauge marks reached 4 cm was read as the softening temperature. • Processing equipment: Forced-air constant-temperature dryer DRK633DA (Advantec Co., Ltd.) • Weight of the weight: Thickness at the center of the gauge mark (μm) × 0.05 g • Dumbbell No. 2 (compliant with JIS K6251) • Heating rate: 5℃ / min

[0164] [Glass Transition Temperature] After obtaining a test specimen (width 0.4 cm, length 2.5 cm) from the obtained film using a dumbbell, the thickness at the center of the gauge (approximately 100-200 μm) was measured. The glass transition temperature was defined as the temperature of the peak top of the obtained loss modulus (E'') / storage modulus (E') = tanδ. -Conditions- - Processing device: RHEOVIBRON DDV-01GP Dynamic Viscoelastometer (manufactured by Orientec Co., Ltd.) - Range: -50 to 40°C - Heating rate: 3°C / min - Frequency: 35 Hz - Amplitude: 16 μm - Static tension: 5.00 gf

[0165] [Evaluation Criteria] 100% modulus, fracture strength, fracture elongation, softening temperature, and glass transition temperature were evaluated on a scale of A, B, and C (A: good, B: average, C: poor).

[0166] <100% Modulus> A: 2.0 MPa or less B: Over 2.0 MPa

[0167] <Breaking Strength> A: Over 25.0 MPa B: Over 17.0 MPa and 25.0 MPa or less C: 17.0 MPa or less

[0168] <Elongation at Break> A: Over 430% B: 430% or less

[0169] <Softening temperature> A: Over 250°C B: Below 250°C

[0170] <Glass transition temperature> A: Below -10°C C: Above -10°C

[0171] The overall evaluation of the compositions was rated on a scale of A, B, and C (A: good, B: average, C: poor). The results are shown in Table 3.

[0172] <Overall Evaluation> A: Only A ratings for each physical property B: No C ratings for each physical property, but at least one B rating C: Each physical property rating includes a C rating

[0173] Details of the materials used in the examples and comparative examples are as follows: • 1,6-Hexanediol: Manufactured by BASF-JAPAN • 1,4-Butanediol: Manufactured by Tokyo Chemical Industry Co., Ltd. • Diethyl carbonate: Manufactured by Sigma-Aldrich • ε-Caprolactone: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • N-980N: Nipponran 980N (trade name), polycarbonate diol, manufactured by Tosoh Corporation • PCL-220: Polycaprolactone diol, manufactured by Daicel Corporation • Potassium bicarbonate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • Lithium trifluoroacetate: Manufactured by Tokyo Chemical Industry Co., Ltd. • Trimethylolpropane: Hydrogenated MDI (Sigma-Aldrich), DOTDL (Covestro), Dioctyltin dilaurate, JP-508 (Kishida Chemical Industries), 2-Ethylhexyl acid phosphate, Methyl ethyl ketone (Johoku Chemical Industries), Toluene (Maruzen Petrochemicals), BYK-331 (Fujifilm Wako Pure Chemical Industries), Silicone-based surface modifier (BYK Corporation)

[0174] In the evaluation of "Diffraction lines in XRD measurement" in Table 1, "Present" was used if a diffraction line originating from crystalline material was observed at 2θ = 21.3 ± 0.5° in the spectrum obtained by wide-angle X-ray scattering measurement, and "Absent" was used if it was not observed. In Examples 1 to 3, diffraction lines originating from crystalline material with a full width at half maximum (FMAX) of 0.24 were observed in all cases.

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[0176]

[0177]

[0178]

[0179]

[0180]

Claims

1. A polyester polycarbonate diol comprising a constituent unit (A) represented by the following formula (A), a constituent unit (B) represented by the following formula (B), and a terminal hydroxyl group, wherein the polyester polycarbonate diol, cooled by immersion in liquid nitrogen for 3 minutes or more, has a diffraction line of crystalline origin at 2θ = 21.3 ± 0.5° in the X-ray diffraction spectrum obtained by wide-angle X-ray scattering measurement using the polyester polycarbonate diol as the sample to be measured. [In formula (A), R １ * indicates an alkanediyl group, and * indicates a bond. [In formula (B), R ２ * indicates an alkanediyl group, and * indicates a bond.

2. The polyester polycarbonate diol according to claim 1, wherein the content of the constituent unit (B) is 60 mol% or less, based on the total content of the constituent unit (A) and the constituent unit (B).

3. The polyester polycarbonate diol according to claim 1, wherein the content of the constituent unit (B) is 20 to 50 mol%, based on the total content of the constituent unit (A) and the constituent unit (B).

4. The polyester polycarbonate diol according to claim 1 or 2, which is liquid at 25°C.

5. R １ The polyester polycarbonate diol according to claim 1 or 2, wherein the alkanediyl group included is of only one type.

6. R １ It contains only one type of alkanediyl group, and R １ The polyester polycarbonate diol according to claim 1 or 2, wherein the alkanediyl group contained therein has 6 or more carbon atoms.

7. A method for producing a polyester polycarbonate diol according to claim 1, comprising a reaction step of reacting a diol with a cyclic ester and a carbonate ester, wherein the diol is of only one type.

8. A method for producing a polyester polycarbonate diol, comprising a reaction step of reacting a diol with a cyclic ester and a carbonate ester, wherein the diol is of only one type, the amount of the cyclic ester is 10 moles or more per 100 moles of the total number of moles of the cyclic ester and the carbonate ester or the diol, the total number of moles is the sum of the number of moles of the carbonate ester and the cyclic ester if the number of moles of one of the carbonate ester and the diol used is less than the other, and the sum of the number of moles of either the carbonate ester and the diol and the cyclic ester if the number of moles of the carbonate ester and the diol used are the same.

9. The method for producing a polyester polycarbonate diol according to claim 8, wherein the amount of the cyclic ester is 10 moles or more and 60 moles or less with respect to the total number of moles of 100 moles.

10. The method for producing a polyester polycarbonate diol according to claim 8, wherein the polyester polycarbonate diol has a diffraction line of crystalline origin at 2θ = 21.3 ± 0.5° in the X-ray diffraction spectrum obtained by wide-angle X-ray scattering measurement using the polyester polycarbonate diol that has been cooled by immersion in liquid nitrogen for 3 minutes or more as the sample to be measured.

11. A method for producing a polyester polycarbonate diol according to any one of claims 7 to 10, wherein the number of carbon atoms in the diol is 6 or more.

12. A method for producing a polyester polycarbonate diol according to any one of claims 7 to 10, wherein the reaction step is carried out in the presence of two types of catalysts.

13. The method for producing a polyester polycarbonate diol according to claim 12, wherein the two types of catalysts are potassium bicarbonate and lithium trifluoroacetate, sodium oxalate, or sodium trichloroacetate.

14. A polyurethane resin-forming composition comprising a polyol and a polyisocyanate, wherein the polyol comprises the polyester polycarbonate diol described in claim 1 or 2.

15. A polyurethane resin which is a reaction product of the polyurethane resin-forming composition described in claim 14.

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