Polyol composition

Abstract

A polyol composition. [Problem] To provide a uniform polyol composition containing a polyester polyol and a polycarbonate polyol, which does not require copolymerization and has excellent quality stability, and the like. [Solution] A polyol composition, which is a polyol composition containing a polycarbonate polyol and a polyester polyol, characterized in that no phase separation occurs in a state of being left to stand at 80°C for 4 hours.

Description

Technical Field

[0001] This invention relates to polyol compositions comprising polycarbonate polyols and polyester polyols, etc. Background Technology

[0002] Previously, polyurethane resins were widely used in synthetic leather, adhesives, furniture coatings, and automotive coatings. Among the raw materials for polyurethane resins, polyether polyols, polyester polyols, and polycarbonate polyols are used as the polyol components that react with isocyanates. In recent years, in order to improve the softness (tactile feel) of polyurethane resins and achieve a sustainable society, there has been a demand for polyol components that balance low viscosity with heat resistance, hydrolysis resistance, and other properties, based on the perspective of reducing solvents and ensuring long-term use.

[0003] According to non-patent literature 1, polyurethanes that typically use polyether polyols as the polyol component exhibit excellent flexibility and hydrolysis resistance, but poor heat resistance and weather resistance. Conversely, polyurethanes using polyester polyols show improved heat resistance and weather resistance, but poor hydrolysis resistance. In contrast, polyurethanes using polycarbonate polyols are considered to have the best durability in terms of heat resistance, chemical resistance, and hydrolysis resistance, but their high viscosity leaves room for improvement in flexibility and workability.

[0004] To address the aforementioned issues, various studies have been conducted on introducing ester bonds and ether bonds into polycarbonate polyols. For example, Patent Document 1 describes a method for synthesizing copolycarbonate diols by subjecting polycarbonate diols to transesterification. Patent Document 2 describes a polycarbonate polyol having a specific polyester structure. Patent Document 3 discloses a coating composition using a specific polycarbonate diol composition. Furthermore, Patent Documents 4 and 5 describe polycarbonate polyols having ester bonds in repeating structural units.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 3-252420

[0008] Patent Document 2: Japanese Patent Application Publication No. 2019-151813

[0009] Patent Document 3: International Publication No. 2019 / 131617

[0010] Patent Document 4: Japanese Patent Application Publication No. 2022-137002

[0011] Patent Document 5: International Publication No. 2023 / 080134

[0012] Non-patent literature

[0013] Non-Patent Document 1: "Collection of Cases on Material Selection, Structure Control and Modification of Polyurethane (Japanese: ポリウレタンの材料選定、構造制御と改質 事例集)", Items 51 to 62, published by Technical Information Association Co., Ltd., first edition issued in December 2014 Content of the Invention

[0014] Problem to be Solved by the Invention

[0015] However, in the techniques described in Patent Documents 1 to 5, a method such as copolymerization is used to introduce ester bonds and ether bonds, so there is room for further improvement in the production method of the polyol composition.

[0016] Accordingly, the present invention has been accomplished in view of the above circumstances, and an object of the present invention is to provide a uniform polyol composition containing polyester polyol and polycarbonate polyol that does not require copolymerization and is excellent in quality stability.

[0017] Means for Solving the Problem

[0018] The inventors of the present invention have conducted intensive studies repeatedly and as a result, found that by combining a specific polycarbonate polyol and a specific polyester polyol, a uniform polyol composition that is liquid at normal temperature can be synthesized, and by using the present polyol composition, a polyurethane excellent in flexibility (texture), hydrolysis resistance, low-temperature properties, heat resistance and moist heat resistance can be produced, thereby completing the present invention.

[0019] That is, the present invention provides various specific embodiments shown below.

[0020] <1>

[0021] A polyol composition, characterized in that the polyol composition comprises a polycarbonate polyol and a polyester polyol, and does not undergo phase separation when allowed to stand at 80°C for 4 hours.

[0022] <2>

[0023] The polyol composition according to <1>, which satisfies the following formula (Formula 1).

[0024] |x-y|<(x+y) / 4 ……(Formula 1)

[0025] (In (Formula 1), x is the upper viscosity of the polyol composition at 23°C, and y is the lower viscosity of the polyol composition at 23°C.)

[0026] <3>

[0027] according to <1> or <2> The polyol composition wherein the polycarbonate polyol has a viscosity of 30,000 mPa·s or higher at 23 degrees.

[0028] <4>

[0029] according to <1> ~ <3> The polyol composition according to any one of the following methods, wherein the 23-degree viscosity of the polyester polyol is less than 20,000 mPa·s.

[0030] <5>

[0031] according to <1> ~ <4> The polyol composition according to any one of the following methods, wherein the 23-degree viscosity of the polyol composition is less than the 23-degree viscosity of the polycarbonate polyol.

[0032] <6>

[0033] according to <1> ~ <5> The polyol composition described in any one of the above-mentioned polyester polyols has repeating structural units represented by the following general formula (I).

[0034] The above-mentioned polycarbonate polyols have repeating structural units as shown in the following general formula (II).

[0035] The difference between the average number of carbon atoms of R1 in the following general formula (I) and the average number of carbon atoms of R3 in the following general formula (II) is less than 1.7.

[0036]

[0037] (In general formula (I), R1 is a divalent aliphatic hydrocarbon group, branched or cyclic, or aromatic hydrocarbon group with 2 or more but less than 20 carbon atoms, optionally containing heteroatoms. R2 is a divalent aliphatic hydrocarbon group, branched or cyclic, or aromatic hydrocarbon group with 2 or more but less than 10 carbon atoms, optionally containing heteroatoms. When multiple R1 and R2 exist, they may be the same or different from each other.)

[0038]

[0039] (In general formula (II), R3 is a divalent aliphatic hydrocarbon group, branched or cyclic, or aromatic hydrocarbon group with 2 or more but less than 20 carbon atoms, optionally containing heteroatoms. When multiple R3s exist, they may be the same or different from each other.)

[0040] <7>

[0041] according to <1> ~ <6> The polyol composition according to any one of the following methods, wherein the 23-degree viscosity of the polyol composition is less than 1,000,000 mPa·s.

[0042] <8>

[0043] according to <1> ~ <7> The polyol composition described in any one of the following statements is transparent.

[0044] <9>

[0045] according to <1> ~ <8> The polyol composition described in any one of the following methods has a volatile component / non-volatile component ratio of 75% by mass or more.

[0046] <10>

[0047] according to <6> The polyol composition wherein R1 in the above general formula (I) is a divalent linear aliphatic hydrocarbon group having 2 or more and 10 or fewer carbon atoms, and comprises at least two such groups.

[0048] <11>

[0049] according to <6> The polyol composition comprises at least one linear, branched, or cyclic aliphatic hydrocarbon group in which the difference between the number of carbon atoms of R1 in the above general formula (I) and the average number of carbon atoms of R3 in the above general formula (II) is greater than 2.

[0050] <12>

[0051] according to <6> The polyol composition wherein, relative to the total mass of the repeating structural units shown in general formula (I) and general formula (II), the content of the repeating structural units shown in general formula (II) is 5% by mass or more and 95% by mass or less.

[0052] <13>

[0053] according to <6> The polyol composition wherein, relative to the total mass of the repeating structural units shown in general formula (I) and general formula (II), the content of the repeating structural units shown in general formula (II) is 30% by mass or more and 70% by mass or less.

[0054] <14>

[0055] according to <1> or <6> The polyol composition wherein R1 in the general formula (I) is a structure derived from an aliphatic dicarboxylic acid selected from the group consisting of sebacic acid, azelaic acid, adipic acid, dimer acid, glutaric acid, succinic acid, nonamethylene dicarboxylic acid and decamethylene dicarboxylic acid, and includes at least two of them.

[0056] <15>

[0057] according to <6> ~ <14> The polyol composition described in any one of the following statements has a number average molecular weight of 250 or more and 10,000 or less.

[0058] <16>

[0059] according to <6> The polyol composition wherein R3 in the above general formula (II) has two or more aliphatic structures with 2 to 20 carbon atoms.

[0060] <17>

[0061] A polymer that makes <1> or <6> The above-described polyol composition is obtained by polymerizing a compound having a functional group that reacts with the hydroxyl group of the polyol composition.

[0062] <18>

[0063] An adhesive comprising <17> The aforementioned polymer.

[0064] <19>

[0065] A coating comprising <17> The aforementioned polymer.

[0066] <20>

[0067] A sealing material comprising <17> The aforementioned polymer.

[0068] <21>

[0069] A synthetic leather comprising <17> The aforementioned polymer.

[0070] In addition, the present invention provides various specific methods as shown below. [1]

[0072] A polyol composition comprising a polycarbonate polyol and a polyester polyol,

[0073] The polycarbonate polyol has a viscosity of 30,000 mPa·s or higher at 23 degrees.

[0074] The polyester polyol has a viscosity of less than 20,000 mPa·s at 23 degrees.

[0075] The viscosity deviation of the polyol composition satisfies the following formula (Formula 1).

[0076] |xy|<(x+y) / 4……(Formula 1)

[0077] (In Formula 1, x is the upper viscosity of the polyol composition at 23°C, and y is the lower viscosity of the polyol composition at 23°C.) [2]

[0079] According to the polyol composition described in [1], wherein the polyester polyol has repeating structural units represented by the following general formula (I),

[0080] The polycarbonate polyol has repeating structural units as shown in the following general formula (II).

[0081] The difference between the average number of carbon atoms of R1 in the following general formula (I) and the average number of carbon atoms of R3 in the following general formula (II) is less than 1.7.

[0082]

[0083] (In general formula (I), R1 is a divalent aliphatic hydrocarbon group, branched or cyclic, or aromatic hydrocarbon group with 2 or more but less than 20 carbon atoms, optionally containing heteroatoms. R2 is a divalent aliphatic hydrocarbon group, branched or cyclic, or aromatic hydrocarbon group with 2 or more but less than 10 carbon atoms, optionally containing heteroatoms. When multiple R1 and R2 exist, they may be the same or different from each other.)

[0084]

[0085] (In general formula (II), R3 is a divalent aliphatic hydrocarbon group, branched or cyclic, or aromatic hydrocarbon group with 2 or more but less than 20 carbon atoms, optionally containing heteroatoms. When multiple R3s exist, they may be the same or different from each other.) [3]

[0087] According to the polyol composition described in [2], wherein R1 in the aforementioned general formula (I) is a divalent linear aliphatic hydrocarbon group having 2 or more and 10 or less carbon atoms, and comprises at least two types. [4]

[0089] According to the polyol composition described in [2] or [3], the content of the repeating structural unit shown in the aforementioned general formula (II) is 5% by mass or more and 95% by mass or less, relative to the total mass of the repeating structural unit shown in the aforementioned general formula (I) and the repeating structural unit shown in the aforementioned general formula (II). [5]

[0091] The polyol composition according to any one of [2] to [4], wherein R1 in the general formula (I) is a structure of an aliphatic dicarboxylic acid selected from the group consisting of sebacic acid, azelaic acid, adipic acid, dimer acid, glutaric acid, succinic acid, nonamethylene dicarboxylic acid and decamethylene dicarboxylic acid, including at least two of them. [6]

[0093] The polyol composition according to any one of [1] to [4] has a number average molecular weight of 250 or more and 10,000 or less. [7]

[0095] The polyol composition according to any one of [2] to [6], wherein R3 in the general formula (II) has two or more aliphatic structures with 2 to 20 carbon atoms. [8]

[0097] A polyurethane obtained by polymerizing the polyol composition described in any one of [1] to [7] with an isocyanate compound. [9]

[0099] An adhesive comprising the polyurethane described in [8].

[10]

[0101] A coating comprising the polyurethane described in [8].

[11]

[0103] A sealing material comprising the polyurethane described in [8].

[12]

[0105] A synthetic leather comprising the polyurethane described in [8].

[0106] The effects of the invention

[0107] According to the present invention, a polyol composition with excellent operability and quality stability can be achieved. In addition, by using the polyol composition of the present invention, a polyurethane with excellent physical property balance of softness (touch), low temperature properties, heat resistance, hydrolysis resistance and appearance can be manufactured. Attached Figure Description

[0108] Figure 1 This is a schematic diagram illustrating the method for measuring the upper and lower viscosity of a polyol composition at 23°C. Detailed Implementation

[0109] Hereinafter, a method for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. Furthermore, the present invention is not limited to the following description and can be implemented in various modifications within its scope.

[0110] <Polyol Compositions>

[0111] The polyol composition of this embodiment is characterized in that it comprises polycarbonate polyol and polyester polyol, and the polyol composition does not undergo phase separation when left to stand at 80°C for 4 hours.

[0112] Here, phase separation refers to the existence of multiple phases in a liquid (solution or molten state). Specifically, it includes, for example, the separation into multiple phases in a static state (it should be noted that even if the boundaries are not clearly defined, phase separation is considered complete if multiple layers can be identified). Even if the multiple phases are all transparent or similar in color, phase separation is considered complete if multiple phases can be identified by methods such as illuminating the liquid or using a black background. It should be noted that in cases where solids float in the liquid or precipitates are present, the presence or absence of phase separation is determined by whether multiple phases can be observed simply by examining the liquid itself.

[0113] The viscosity at 23 degrees of the polycarbonate polyol is preferably 30,000 mPa·s or more, more preferably 50,000 mPa·s or more, and even more preferably 100,000 mPa·s or more. The viscosity at 23 degrees of the polyester polyol is preferably 20,000 mPa·s or less, more preferably 19,000 mPa·s or less, and even more preferably 18,000 mPa·s or less. This results in an excellent balance between viscosity when forming the polyol composition and durability when forming the polyurethane.

[0114] In this specification, when using a variety of polycarbonate polyols or a variety of polyester polyols, the average viscosity calculated using the method described in the examples will be taken as the 23-degree viscosity of the polycarbonate polyol or the 23-degree viscosity of the polyester polyol.

[0115] In addition, the preferred viscosity deviation satisfies the following formula (Formula 1).

[0116] |xy|<(x+y) / 4……(Formula 1)

[0117] (In Formula 1, x is the upper viscosity of the polyol composition at 23°C, and y is the lower viscosity of the polyol composition at 23°C. x and y were measured according to [Evaluation 1] described in the examples below and using [Physical Property 4].)

[0118] Viscosity deviation refers to the viscosity difference between the upper and lower parts of a blend when two or more polyols with different viscosities are blended. When this viscosity difference satisfies the above formula (1), the viscosity deviation is small, and there is a tendency to obtain a homogeneous polyol composition. Furthermore, a polyol composition that satisfies the following formula (2) is more preferred, and a polyol composition that satisfies the following formula (3) is even more preferred. The homogeneity of the polyol composition that satisfies the following formula (3) is particularly excellent.

[0119] |xy|<(x+y) / 8……(Formula 2)

[0120] |xy|<(x+y) / 16……(Formula 3)

[0121] (In Equations 2 and 3, x is the upper viscosity of the polyol composition at 23°C, and y is the lower viscosity of the polyol composition at 23°C. x and y were measured according to [Evaluation 1] described in the examples below and using [Physical Property 4].)

[0122] It should be noted that in this embodiment, room temperature refers to 23°C.

[0123] In addition, in this embodiment, liquid refers to a state that exhibits fluidity even to a slight degree.

[0124] In one manner, the polyol composition has repeating structural units as shown in general formula (I) as a polyester polyol and repeating structural units as shown in general formula (II) as a polycarbonate polyol.

[0125]

[0126] (In general formula (I), R1 is a divalent aliphatic hydrocarbon group, branched or cyclic, or aromatic hydrocarbon group with 2 or more but less than 20 carbon atoms, optionally containing heteroatoms. R2 is a divalent aliphatic hydrocarbon group, branched or cyclic, or aromatic hydrocarbon group with 2 or more but less than 10 carbon atoms, optionally containing heteroatoms. When multiple R1 and R2 exist, they may be the same or different from each other.)

[0127]

[0128] (In general formula (II), R3 is a divalent aliphatic hydrocarbon group, branched or cyclic, or aromatic hydrocarbon group with 2 or more but less than 20 carbon atoms, optionally containing heteroatoms. When multiple R3s exist, they may be the same or different from each other.)

[0129] The polyol composition of this embodiment is typically cured using a curing agent such as a polyisocyanate, and can be formulated into polyurethane for use as various molding compounds, adhesives, coatings, etc.

[0130] <<Hydroxy value of the composition>>

[0131] The hydroxyl value of the polyol composition in this embodiment is 20~700 mgKOH / g, preferably 40~230 mgKOH / g, and more preferably 50~130 mgKOH / g.

[0132] The polyol composition of this embodiment tends to exhibit excellent strength and chemical resistance of the resulting polyurethane by having a hydroxyl value of 40 mg KOH / g or higher. Furthermore, the polyol composition of this embodiment tends to exhibit improved softness (touch) and low-temperature properties of the resulting polyurethane by having a hydroxyl value of 200 mg KOH / g or lower.

[0133] The hydroxyl values ​​of the polycarbonate polyol and polyester polyol contained in the polyol composition of this embodiment are preferably 40 to 75 mg KOH / g. By using polycarbonate polyols and / or polyester polyols with hydroxyl values ​​of 100 to 700 mg KOH / g, there is a tendency to further improve uniformity. In this case, it is more preferable to use polycarbonate polyols with 100 to 700 mg KOH / g, and by keeping their content at 50% by mass or less, there is a tendency to have an excellent balance between softness and low-temperature properties.

[0134] <<Number Average Molecular Weight>>

[0135] The number-average molecular weight (Mn) of the polyol composition of this embodiment is preferably 250 or more and 10,000 or less, more preferably 400 or more and 8,000 or less, even more preferably 500 or more and 5,000 or less, and particularly preferably 500 or more and 3,000 or less. By setting the number-average molecular weight to the upper limit mentioned above, the polyol composition of this embodiment tends to have a lower viscosity and improved operability when manufacturing polyurethane. Furthermore, by setting the number-average molecular weight to the lower limit mentioned above, the polyurethane manufactured using the polyol composition of this embodiment tends to have excellent flexibility.

[0136] <<Average number of carbon atoms>>

[0137] In one embodiment, the polyol composition comprises a polycarbonate polyol and a polyester polyol, wherein the difference between the average number of carbon atoms of R1 in the above general formula (I) and the average number of carbon atoms of R3 in the above general formula (II) is 1.7 or less in absolute value, more preferably 1.5 or less, and even more preferably 1.3 or less.

[0138] The polyol composition of this embodiment is not theoretically limited, and it can be considered that by making the difference between the average number of carbon atoms of R1 in the above general formula (I) and the average number of carbon atoms of R3 in the above general formula (II) less than 1.7, the polarity difference between the polycarbonate polyol and the polyester polyol tends to be narrowed, and the resulting polyol composition has excellent uniformity. Here, polarity refers to the charge shift caused by the difference in electronegativity between atoms. In addition, by making the difference between the average number of carbon atoms of R1 in the above general formula (I) and the average number of carbon atoms of R3 in the above general formula (II) less than 1.3, the polyol composition of this embodiment tends to have further improved compatibility and suppressed viscosity deviation.

[0139] The average number of carbon atoms in R1 of the above general formula (I) and the average number of carbon atoms in R3 of the above general formula (II) can be calculated by the methods described in [Property 5] and [Property 6] in the following examples.

[0140] [Repeating structural unit (I)]

[0141] The following describes in detail the repeating structural unit (I) in the polyol composition of this embodiment.

[0142] (R1)

[0143] In general formula (I), each R1 is independently a divalent aliphatic hydrocarbon group, branched or cyclic, or aromatic hydrocarbon group with 2 or more but less than 20 carbon atoms, optionally having heteroatoms. When multiple R1s exist, they may be the same or different from each other.

[0144] R1 in general formula (I) is not particularly limited, and can include, for example, straight-chain or branched alkylene groups with 2 to 20 carbon atoms. Specifically, it is not particularly limited, and can include, for example, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, propylene, isobutylene, 2-methyltetramethylene, 2-methylpentamethylene, 3-methylpentamethylene, isononamethylene, 2-methylnonamethylene, etc. Furthermore, R1 in general formula (I) is not particularly limited, and can include, for example, substituted or unsubstituted cycloalkylene groups with 3 to 20 carbon atoms. Specifically, there are no particular limitations; examples include cyclopentylene, cyclohexylene, 1,2-dimethylenecyclopentylene, 1,3-dimethylenecyclopentylene, 1,2-dimethylenecyclohexylene, 1,3-dimethylenecyclohexylene, 1,4-dimethylenecyclohexylene, 4,4'-dimethylenedicyclohexylene, and 2,2-dicyclohexylpropane. Furthermore, R1 in general formula (I) is not particularly limited; examples include substituted or unsubstituted aryl groups with 6 to 20 carbon atoms. Specifically, there are no particular limitations; examples include phenylene, 1,2-dimethylenephenylene, 1,3-dimethylenephenylene, 1,4-dimethylenephenylene, naphthylene, 4,4'-dimethylenediphenylene, and 2,2-diphenylpropane. Furthermore, there are no particular limitations on the specific examples of heteroatoms in R1 of general formula (I). Examples include boron, oxygen, nitrogen, phosphorus, and sulfur. It can also have five-membered heterocyclic structures such as tetrahydrofuran, tetrahydrothiophene, and tetrahydropyrrole, or six-membered heterocyclic structures such as tetrahydropyran and pyridine. From the viewpoint of generality, it is preferable to include an oxygen-containing five-membered ring structure derived from isosorbide.

[0145] R1 in general formula (I) is preferably derived from a structure of sebacic acid, azelaic acid, adipic acid, dimer acid, glutaric acid, succinic acid, nonamethylene dicarboxylic acid, or decamethylene dicarboxylic acid, and more preferably from a structure of sebacic acid, adipic acid, or succinic acid. By using such aliphatic dicarboxylic acids, there is a tendency to obtain cured products with excellent flexibility. In addition, R1 in general formula (I) is preferably selected from at least two of the group consisting of divalent linear aliphatic hydrocarbon groups with 2 or more and 10 or fewer carbon atoms. In this case, the polyol composition of this embodiment tends to have its crystallization at room temperature suppressed and its uniformity at room temperature improved.

[0146] (R2)

[0147] In general formula (I), R2 is a divalent aliphatic hydrocarbon group, branched or cyclic, or aromatic hydrocarbon group with 2 or more but less than 20 carbon atoms, optionally containing heteroatoms. When multiple R2s are present, they may be identical or different from each other.

[0148] As for R2 in general formula (I), there is no particular limitation, and examples include linear or branched alkylene groups having 2 to 20 carbon atoms. Specifically, there is no particular limitation, and examples include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, propylene, isobutylene, 2-methyltetramethylene, 2-methylpentamethylene, 3-methylpentamethylene, isononamethylene, 2-methylnonamethylene, etc. Furthermore, as for R2 in general formula (I), there is no particular limitation, and examples include substituted or unsubstituted cycloalkylene groups having 3 to 20 carbon atoms. Specifically, there are no particular limitations; examples include cyclopentylene, cyclohexylene, 1,2-dimethylenecyclopentylene, 1,3-dimethylenecyclopentylene, 1,2-dimethylenecyclohexylene, 1,3-dimethylenecyclohexylene, 1,4-dimethylenecyclohexylene, 4,4'-dimethylenedicyclohexylene, and 2,2-dicyclohexylpropane. Furthermore, R2 in general formula (I) is not particularly limited; examples include substituted or unsubstituted aryl groups with 6 to 20 carbon atoms. Specifically, there are no particular limitations; examples include phenylene, 1,2-dimethylenephenylene, 1,3-dimethylenephenylene, 1,4-dimethylenephenylene, naphthylene, 4,4'-dimethylenediphenylene, and 2,2-diphenylpropane. Furthermore, there are no particular limitations on the specific examples of heteroatoms in R2 of general formula (I). Examples include boron, oxygen, nitrogen, phosphorus, and sulfur. It can also have five-membered heterocyclic structures such as tetrahydrofuran, tetrahydrothiophene, and tetrahydropyrrole; or six-membered heterocyclic structures such as tetrahydropyran and pyridine. From the viewpoint of generality, it is preferable to include an oxygen-containing five-membered ring structure derived from isosorbide.

[0149] Of these, R2 is preferably a diol compound having a straight-chain alkylene group with 3 to 12 carbon atoms or a branched alkylene group with 4 to 9 carbon atoms, from the viewpoint of obtaining a polyurethane with excellent softness (tactile feel), chemical resistance, low-temperature properties, and heat resistance. More preferably, it is a diol compound having a straight-chain alkylene group with 3 to 6 carbon atoms or a branched alkylene group with 3 to 6 carbon atoms. Furthermore, there are no particular limitations on the plant-derived, i.e., biologically derived, raw materials used; for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, isosorbide, etc., can be used.

[0150] In general formula (I), m is a number of 1 or more, preferably 2 to 30, and more preferably 5 to 15.

[0151] [Repeating Structural Unit (II)]

[0152] Next, the details of the repeating structural unit (II) will be explained.

[0153] (R3)

[0154] In general formula (I), R3 is a divalent aliphatic hydrocarbon group, branched or cyclic, or aromatic hydrocarbon group with 2 or more but less than 20 carbon atoms, optionally containing heteroatoms. When multiple R3s exist, they may be identical or different from each other.

[0155] As a divalent straight-chain aliphatic hydrocarbon group in R3, the number of carbon atoms is 2 or more and 15 or less, preferably 3 or more and 12 or less, and more preferably 3 or more and 10 or less.

[0156] Specific examples of divalent straight-chain aliphatic hydrocarbon groups in R3 are not particularly limited, and examples include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptene, and octene. From a general point of view, trimethylene, butylene, pentamethylene, hexane, and decamethylene are preferred.

[0157] As a divalent branched aliphatic hydrocarbon group in R3, the number of carbon atoms is 3 or more and 15 or less, preferably 3 or more and 12 or less, and more preferably 3 or more and 10 or less.

[0158] Specific examples of divalent branched aliphatic hydrocarbon groups in R3 are not particularly limited, but examples include: isopropylene, isobutylene, tert-butylene, isopentylene, 2,2-dimethyltrimethylene, isohexylene, isoheptylene, isooctylene, etc. From a general viewpoint, isobutylene, isopentylene, or isohexylene are preferred.

[0159] As a divalent cyclic aliphatic hydrocarbon group in R3, the number of carbon atoms is 3 or more and 15 or less, preferably 6 or more and 15 or less, and more preferably 6 or more and 10 or less.

[0160] Specific examples of divalent cyclic aliphatic hydrocarbon groups in R3 are not particularly limited, such as cyclobutylene, cyclopentylene, cyclohexylene, and cycloheptylene. Among them, from a general point of view, cyclohexylene is preferred.

[0161] As a divalent aromatic hydrocarbon group in R3, it has 6 or more and 15 or less carbon atoms, preferably 6 or more and 12 or less, and more preferably 6 or more and 10 or less.

[0162] There are no particular limitations on specific examples of divalent aromatic hydrocarbon groups in R3, such as phenylene, naphthylene, etc.

[0163] There are no particular limitations on the specific heteroatoms in R3. Examples include boron, oxygen, nitrogen, phosphorus, and sulfur. These heteroatoms can have five-membered heterocyclic structures such as tetrahydrofuran, tetrahydrothiophene, and tetrahydropyrrole; or six-membered heterocyclic structures such as tetrahydropyran and pyridine. From a generality perspective, structures derived from isosorbide are preferred.

[0164] Of these, R3, from the viewpoint of obtaining polyurethane with excellent softness (tactile feel), chemical resistance, low-temperature properties, and heat resistance, is preferably a diol compound having a straight-chain alkylene group with 3 to 12 carbon atoms or a branched alkylene group with 4 to 9 carbon atoms; more preferably, it is a diol compound having a straight-chain alkylene group with 3 to 6 carbon atoms or a branched alkylene group with 3 to 6 carbon atoms. Furthermore, there are no particular limitations on the plant-derived, i.e., biologically derived, raw materials; for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, etc., can be used.

[0165] In addition, in this embodiment, in addition to difunctional diols, polyol compounds with three or more functions can also be used as raw materials for polyols as needed.

[0166] There are no particular limitations on polyols with three or more functionalities; examples include trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, and glycerol. By using polyols with three or more functionalities, the average number of hydroxyl groups in a molecule can be easily adjusted to the range of 1.7 to 3.5.

[0167] Furthermore, the polycarbonate polyol contained in the polyol composition of this embodiment is preferably one in which R3 in at least a portion of the general formula (II) of the polycarbonate polyol is selected from at least two of the group consisting of divalent linear and branched aliphatic hydrocarbon groups having 2 or more and 15 or fewer carbon atoms. In this case, there is a tendency to obtain a polycarbonate polyol composition that is liquid at room temperature.

[0168] In general formula (II), n is a number of 1 or more, preferably 2 to 50, and more preferably 5 to 25.

[0169] In the polyol composition of this embodiment, regarding the content ratio of the repeating structural unit (hereinafter also referred to as "polyester structural unit") shown in general formula (I) and the content ratio of the repeating structural unit (hereinafter also referred to as "polycarbonate structural unit") shown in general formula (II), relative to the total mass of the repeating structural units shown in general formula (I) and general formula (II), the content of the repeating structural unit shown in general formula (II) is preferably 5% by mass or more and 95% by mass or less, more preferably 30% by mass or more and 90% by mass or less, and even more preferably 50% by mass or more and 80% by mass or less. By setting the content ratio of polycarbonate structural unit to polyester structural unit within the above range, the polyol composition of this embodiment tends to produce polyurethane with excellent flexibility and hydrolysis resistance.

[0170] The method for manufacturing the polycarbonate polyol and polyester polyol included in the polyol composition of this embodiment is not particularly limited. For example, a difunctional diol compound, a polyol with three or more functions as needed, a diacid, and a carbonate can be used as raw materials to synthesize the polyol through an ester exchange reaction as described in, for example, "Polymer Reviews, Vol. 9, pp. 9-20".

[0171] The polyol composition of this embodiment preferably contains polycarbonate-structured molecules with hydroxyl groups at both ends. That is, the polycarbonate-structured molecules in the polyol composition of this embodiment are preferably polycarbonate diols. Due to impurities in various raw materials used in the manufacture of the polyol composition and / or byproducts of the terminal structures produced during the manufacture of the polyol, or to control the rate and state of the urethane esterification reaction for the intended use of the polyol composition, sometimes a portion of the terminal hydroxyl groups is converted to alkyl, aryl, or other groups that do not react with isocyanate groups. In this embodiment, such a situation is also considered, and the terminal groups of the aforementioned polycarbonate diol also include cases where, strictly speaking, not 100 mol% of both ends are hydroxyl groups. From this viewpoint, the ratio of hydroxyl groups to the total molar amount of terminal groups is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 98 mol% or more.

[0172] In this embodiment, the two-terminal structures of the polyol contained in the polyol composition can be confirmed, for example, by the method of determining the ratio of terminal primary OH groups described in Japanese Patent No. 3874664 (Reference 1). In addition to ethanol, solvents such as tetrahydrofuran, acetone, and methanol can also be used as solvents for recovering the fraction.

[0173] <<Manufacturing Methods>>

[0174] The method for manufacturing the polyol composition of this embodiment is not particularly limited, and the following method can be cited: after pre-manufacturing polycarbonate polyol and polyester polyol, these polycarbonate polyols and polyester polyols are mixed, and the manufacturing process is carried out at a temperature of 150°C or below under stirring, in the presence or absence of a transesterification catalyst. In order to suppress the transesterification reaction, the temperature range of 50 to 120°C is more preferred, and the temperature range of 60 to 80°C is even more preferred.

[0175] The dicarboxylic acid that can be used in the synthesis of the polyester polyol included in the polyol composition of this embodiment is not particularly limited, and examples include aliphatic and / or aromatic dicarboxylic acids. Aliphatic dicarboxylic acids are not particularly limited, and examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, etc. Aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, etc.

[0176] To obtain a cured product with excellent flexibility, aliphatic dicarboxylic acids are particularly preferred, among which succinic acid, glutaric acid, adipic acid, and sebacic acid are preferred. These dicarboxylic acids can also be used in the form of alcohol esters, such as dimethyl succinate, dimethyl glutarate, and dimethyl adipate. These dicarboxylic acids can be used alone, and more preferably in combination. By using multiple dicarboxylic acids in combination, the polyester polyol tends to become liquid at room temperature, resulting in a polyol composition with excellent workability. Furthermore, there are no particular limitations on the plant-derived, i.e., biologically derived, raw materials; for example, succinic acid and sebacic acid can be used.

[0177] The carbonates that can be used in the synthesis of the polycarbonate polyols included in the polyol composition of this embodiment are not particularly limited. Examples include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate; diaryl carbonates such as diphenyl carbonate; and alkyl carbonates such as ethylene carbonate, 1,3-propylene carbonate, 1,2-propylene carbonate, 1,2-butyl carbonate, 1,3-butyl carbonate, and 1,2-pentyl carbonate. From the viewpoint of ease of obtaining the desired product and ease of setting the polymerization reaction conditions, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate are preferred as carbonates.

[0178] When manufacturing the polycarbonate polyol contained in the polyol composition of this embodiment, a catalyst may or may not be added. When a catalyst is added, it can be freely selected from catalysts commonly used in transesterification reactions. There are no particular limitations on the catalyst; for example, metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, zirconium, hafnium, cobalt, germanium, tin, lead, antimony, arsenic, and cerium, as well as their metal salts, metal alkoxides, and organic compounds containing such metals can be used. Among the above catalysts, metal alkoxides are preferred. Alkoxides of titanium, zirconium, and hafnium (Group 4 of the periodic table) are less affected by the generated water and can maintain high activity, therefore they are particularly preferred.

[0179] Furthermore, the amount of catalyst used is typically 0.00001 to 0.1% by mass of the difunctional diol compound used as a raw material and, if necessary, the trifunctional or higher polyol, preferably 0.001 to 0.05% by mass, and more preferably 0.01 to 0.03% by mass. If the amount of catalyst is 0.0001% by mass or more, the reaction rate can be increased, and productivity improved. If the amount of catalyst is 0.1% by mass or less, the resulting polycarbonate polyol has an excellent color tone.

[0180] As described above, the method for manufacturing the polycarbonate polyol contained in the polyol composition of this embodiment can use difunctional diol compounds, polyols with three or more functions as needed, and carbonates as raw materials, and synthesize them through transesterification reaction.

[0181] More specifically, the transesterification reaction is carried out according to the following steps.

[0182] First, using one or more difunctional diol compounds in a specified ratio, one or more trifunctional polyols in a specified ratio are mixed with one or more carbonates in a specified ratio as needed, and the transesterification reaction is carried out under normal or reduced pressure, in the absence or presence of a transesterification catalyst, preferably at a temperature of 100 to 200°C, more preferably at a temperature of 140 to 180°C.

[0183] Next, by distilling off the alcohol from the carbonate and the water from the dicarboxylic acid (or, in the case of using a dicarboxylic acid, a monohydric alcohol derived from the dicarboxylic acid), a polycarbonate polyol with a molecular weight of, for example, around 300 to 500 g / mol is obtained.

[0184] Next, under reduced pressure, preferably at 130-230°C, more preferably at 150-200°C, unreacted carbonate and difunctional diol, and optionally trifunctional or higher polyols, are distilled off. A condensation reaction of the diacid and water (or a monohydric alcohol derived from the diacid if a diacid is used) generates water. Through this condensation reaction, a polycarbonate polyol with a desired hydroxyl value can be obtained. Specifically, for example, shortening the reaction time of the condensation reaction tends to increase the hydroxyl value of the resulting polycarbonate polyol, while extending the reaction time tends to decrease the hydroxyl value.

[0185] The average number of hydroxyl groups in polycarbonate polyols can be adjusted by controlling the initial feed ratio of each component, the amount of each raw material distilled during manufacturing, and the amount of reaction products.

[0186] There are no particular limitations on the method for manufacturing polycarbonate polyols and polyester polyols, and known methods can be used. For example, the carbonate compound described above can be reacted with a diol compound in the presence of an transesterification catalyst to obtain a polycarbonate polyol. Alternatively, the diacid compound described above can be reacted with a diol compound in the presence of an transesterification catalyst to obtain a polyester polyol.

[0187] The carbonates that can be used in the synthesis of the polycarbonate polyol used in this embodiment are not particularly limited, and examples include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate; diaryl carbonates such as diphenyl carbonate; and alkyl carbonates such as ethylene carbonate, 1,3-propyl carbonate, 1,2-propyl carbonate, 1,2-butyl carbonate, 1,3-butyl carbonate, and 1,2-pentyl carbonate. From the viewpoint of ease of acquisition and ease of setting polymerization reaction conditions, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate are preferred as carbonates.

[0188] The difunctional diol compounds that can be used in the synthesis of polycarbonate polyols and polyester polyols used in this embodiment are not particularly limited. Examples include diols with a divalent straight-chain aliphatic or alicyclic hydrocarbon skeleton having 2 to 15 carbon atoms, and branched alkylene diols having 4 to 15 carbon atoms.

[0189] Diol compounds are divalent straight-chain aliphatic or alicyclic hydrocarbon skeletons with 2 to 15 carbon atoms. Specifically, there are no particular limitations, but examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanediol.

[0190] As a branched alkylene diol compound having 4 to 15 carbon atoms, specifically, without particular limitation, examples include 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 2-ethyl-1,6-hexanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, etc.

[0191] In addition, cyclic diols and diols with aromatic rings can be listed.

[0192] As a cyclic diol, there is no particular limitation; examples include 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanediethanol, 2-bis(4-hydroxycyclohexyl)propane, 1,8-cyclooctanediethanol, isosorbide, etc.

[0193] As a diol with an aromatic ring, there are no particular limitations; examples include p-phenylenediethanol, p-tetrachlorophenylenediethanol, 1,4-bis(hydroxyethoxy)benzene, and 2,2-bis[(4-hydroxyethoxy)phenyl]propane.

[0194] The dicarboxylic acids that can be used in the synthesis of the polyester polyol used in this embodiment are not particularly limited, and examples include aliphatic and / or aromatic dicarboxylic acids. Aliphatic dicarboxylic acids are not particularly limited, and examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, etc. Aromatic dicarboxylic acids are not particularly limited, and examples include phthalic acid, isophthalic acid, terephthalic acid, etc. For obtaining a cured product with excellent flexibility, aliphatic dicarboxylic acids are particularly preferred, with succinic acid, glutaric acid, adipic acid, and sebacic acid being the most preferred. Furthermore, these dicarboxylic acids can also be used in the form of alcohol esters, such as dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl sebate, etc. These dicarboxylic acids can be used alone or in combination.

[0195] Commercially available polycarbonate polyols used in this embodiment are not particularly limited, and examples include:

[0196] Made by Asahi Kasei Co., Ltd.; trade names "DURANOL T5651", "DURANOL T5652", "DURANOL T5650E", "DURANOL T5650J", "DURANOL T4671", "DURANOL T4672", "DURANOL G3452", "DURANOLG3450J", "DURANOL BPN02", "DURANOL FL012", "DURANOL GE502", "DURANOL GE501", "DURANOL AKN11", "DURANOL AK021E", "DURANOL DK031E";

[0197] Manufactured by Ube Industries; Trade names: “ETERNACOLL PH-50”, “ETERNACOLL PH-100”, “ETERNACOLL PH-200”, “ETERNACOLL PH-300”, “ETERNACOLL UHC50-100”, “ETERNACOLL UHC50-200”, “ETERNACOLL UC-100”, “ETERNACOLL UM-90 (1 / 3)”, “ETERNACOLL UM-90 (1 / 1)”, “ETERNACOLL UM-90 (3 / 1)”, “ETERNACOLL UP-50”, “ETERNACOLL UP-100”, “ETERNACOLL UP-200”;

[0198] Made by Kuraray Co., Ltd.; trade names "Kuraray Polyol C-2065N", "Kuraray Polyol C-1090", "Kuraray Polyol C-2090", "Kuraray Polyol C-3090", "Kuraray Polyol C-1050", "Kuraray Polyol C-2050", "Kuraray Polyol C-3050", "Kuraray Polyol C-1015N", "Kuraray Polyol C-2015N";

[0199] Made by Daicel Corporation; Product names: "PLACCEL 220EC", "PLACCEL CD205", "PLACCEL CD205PL", "PLACCEL CD220PL";

[0200] Manufactured by Tosoh Corporation; Product names: "NIPPOLLAN 965", "NIPPOLLAN 963", "NIPPOLLAN 964", "NIPPOLLAN 968";

[0201] Manufactured by Mitsubishi Chemical Corporation; trade names include "BENEBiOL NL1030B", "BENEBiOL NL2030B", "BENEBiOL HS0830B", "BENEBiOL HS0840B", "BENEBiOL HS0840H", "BENEBiOL HS0850H", "BENEBiOL HS0830S", "BENEBiOL HS0840S", "BENEBiOL NL1030DS", "BENEBiOL NL1030S", and "BENEBiOL NL2030S".

[0202] They can be used individually or in combination of two or more.

[0203] Commercially available polyester polyols used in this embodiment are not particularly limited. Examples include the "KYOWAPOL" series manufactured by Kyowa Hakko Chemical Co., Ltd.; the "Kuraray Polyol" series manufactured by Kuraray Co., Ltd., with trade names "P-510", "F-2010", "P-5010", "P-2050", and "P-2010"; the "PLACCEL" series manufactured by Daicel Co., Ltd.; the "POLYLITE" series manufactured by DIC Co., Ltd., with trade names "OD-x-2251", "OD-x-2420", and "OD-x-2692"; the "NIPPOLLAN" series manufactured by Tosoh Co., Ltd., with trade names "NIPPOLLAN 1004" and "NIPPOLLAN 141"; the "URIC SE" series manufactured by Ito Oil Co., Ltd., with trade name "SE-2013C"; polyesters obtained by ring-opening polymerization of castor oil-modified polyols, ε-caprolactone, and other cyclic ester compounds, and their copolyesters.

[0204] Regarding the polycarbonate polyol and polyester polyol used in the manufacture of the polyol composition of this embodiment, in order to deactivate the transesterification catalyst used in its manufacture, it is preferable to add a catalyst poison such as a phosphate ester compound.

[0205] When the polycarbonate polyol or polyester polyol used as a raw material contains catalyst poisons or the like from the transesterification reaction catalyst used in its manufacture, there is usually a tendency for the transesterification reaction between the polycarbonate polyol and the polyester polyol to be difficult to carry out. Therefore, by increasing the reaction temperature in the manufacturing process, the synthesis time can be further shortened.

[0206] On the other hand, if the polycarbonate polyol or polyester polyol used as raw material does not contain a catalyst poison for transesterification, a necessary amount of catalyst poison such as a phosphate ester compound can be added again.

[0207] [Polyurethane]

[0208] In the method of manufacturing polyurethane using the polyol composition of this embodiment (hereinafter also referred to as "component (a)"), a curing agent such as a polyisocyanate (hereinafter also referred to as "component (b)") and a chain extender as needed (hereinafter also referred to as "component (c)") are typically used.

[0209] As a method for manufacturing polyurethane using the polyol composition of this embodiment, it may be a method of preparing a curable composition by mixing a mixture of constituent components (a), (b), and (c) in a one-time manner. Alternatively, it may be a method of preparing an isocyanate-terminated prepolymer composition obtained by reacting component (a) with component (b) in advance, and preparing a curable composition by mixing a mixture of the isocyanate-terminated prepolymer composition and component (c).

[0210] The curable composition of this embodiment is prepared by using the above-described polyol composition and reacting it with an organic diisocyanate and / or a chain extender.

[0211] As the polyisocyanate used when manufacturing polyurethane using the polyol composition of this embodiment, a polyisocyanate with an average number of 2 to 10 functional groups per molecule (component (b)) is typically used.

[0212] The polyisocyanate used as component (b) is not particularly limited, and examples include aromatic diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof, diphenylmethane-4,4'-diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-biphenyl diisocyanate (TODI), and polymethylene polyphenylene polyisocyanate (PMDI); aromatic diisocyanates such as diphenylmethylene diisocyanate (XDI) and phenylene diisocyanate; and aliphatic diisocyanates such as 4,4'-methylene dicyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and cyclohexane diisocyanate (hydrogenated XDI).

[0213] As component (b), the polyisocyanate may also be a polyisocyanate having an average of 2.1 or more isocyanate groups per molecule. There are no particular limitations on the polyisocyanate having an average of 2.1 or more isocyanate groups per molecule, and for example, aromatic polyisocyanates such as crude MDI and crude TDI; derivatives of aliphatic isocyanates such as HDI and IPDI, specifically diisocyanate derivatives such as biuret, urethane, diurea, and isocyanurate; and polyol adducts.

[0214] As a polyisocyanate having 2.1 or more isocyanate groups per molecule, there are no particular limitations. Examples include polyisocyanates with trade names such as Sumidur 44S and 44V70 (both manufactured by Sumika Bayer Urethane), Desmodur HL (manufactured by Sumika Bayer Urethane), a copolymer of TDI and HDI, and various DURANATEs manufactured by Asahi Kasei Corporation, namely DURANATE 24A-100, DURANATE 22A-75PX, DURANATE 18H-70B, DURANATE21S-75E, DURANATE THA-100, DURANATE TPA-100, DURANATE MFA-75X, DURANATE TSA-100, DURANATE TSS-100, DURANATE TSE-100, DURANATE D-101, DURANATE D-201, DURANATE P-301-75E, etc. DURANATE Available in the form of WB40-80D, DURANATE WT20-100, DURANATE WT30-100, etc.

[0215] As the polyisocyanate component (b), aromatic polyisocyanates such as MDI are preferred. Using aromatic polyisocyanates tends to yield cured products with excellent mechanical properties. When aromatic polyisocyanates such as MDI are used as component (b) in a curable composition, the curable composition can be suitably used as an adhesive between the base fabric and the outer layer of synthetic leather.

[0216] In addition, when an aliphatic polyisocyanate such as hydrogenated MDI is used as component (b) in the curing composition, synthetic leather with excellent weather resistance can be obtained by the curing composition. Therefore, it is suitable as a curing composition for synthetic leather used in the surface layer.

[0217] Alternatively, a so-called capped isocyanate can be made by capping the polyisocyanate of component (b) with known capping agents such as butanol, 2-ethylhexanol, methyl ethyl ketone oxime, lactams, phenols, imidazoles, and active methylene compounds.

[0218] When manufacturing polyurethane using the polyol composition of this embodiment, a chain extender (component (c)) may be used as needed. The chain extender is used to improve the abrasion resistance and strength of the resulting polyurethane; however, it may sometimes reduce the flexibility of the resulting polyurethane, so it may be used appropriately as needed. There are no particular limitations on the chain extender; examples include short-chain diols such as ethylene glycol and 1,4-butanediol; polyols such as trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, and glycerol. Furthermore, there are no particular limitations on the chain extender; examples include diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, toluenediamine, phenylenediamine, diphenyldiamine, diaminodiphenylmethane, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), and water.

[0219] The amount of chain extender added relative to the total of components (a) and (b) is preferably 30% by mass or less, more preferably 3% by mass or more and 20% by mass or less, and even more preferably 5% by mass or more and 10% by mass or less. Furthermore, by using a polyol as a chain extender, the crosslinking density of the resulting polyurethane can be increased, thereby improving its strength, abrasion resistance, and chemical resistance.

[0220] When expressed as [isocyanate equivalent of component (b)] / [total hydroxyl equivalent of components (a) and (c)], the amounts of the polyol composition of component (a), the polyisocyanate of component (b), and the chain extender of component (c) are preferably adjusted to 0.7 to 1.3, more preferably to 0.8 to 1.2, and even more preferably to 0.9 to 1.1. By making [isocyanate equivalent of component (b)] / [total hydroxyl equivalent of components (a) and (c)] 0.7 or more and 1.3 or less, the molecular weight of the resulting polyurethane can be moderately controlled, tending to have excellent mechanical properties such as strength, elongation, and abrasion resistance.

[0221] When using the polyol composition of this embodiment to manufacture polyurethane, an inactive organic solvent may be included as needed to adjust the workability during polyurethane manufacturing. The content of the inactive organic solvent relative to the polyurethane is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. Adding an inactive organic solvent is effective in reducing the viscosity of the curable composition, improving its workability, and further improving the appearance of the resulting cured product.

[0222] There are no particular limitations on inactive organic solvents as long as they are substantially inactive for polyisocyanates, but they are preferably free of active hydrogen. Examples of inactive organic solvents include hydrocarbons such as pentane, hexane, heptane, octane, decane, petroleum ether, petroleum benzine, ligroin, petroleum spirits, cyclohexane, and methylcyclohexane; fluorinated inactive liquids such as trichlorofluoroethane, tetrachlorodifluoroethane, and perfluoroether; and perfluorocyclohexane, perfluorobutyltetrahydrofuran, perfluoronaphthalene, perfluoron-butylamine, perfluoropolyether, and dimethylpolysiloxane. These can be used alone or in mixtures. Other examples of inactive organic solvents include methyl ethyl ketone (also referred to as MEK), acetone, ethyl acetate, butyl acetate, toluene, and xylene, either alone or in mixtures.

[0223] In the curable composition of this embodiment, polyols other than the polycarbonate polyol and polyester polyol contained in the polyol composition may be used in combination as needed. There are no particular limitations on the polyols other than polycarbonate polyol and polyester polyol, and examples include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, polyacrylic acid polyols, and oil-modified polyols.

[0224] The amount of polyols other than polycarbonate polyols and polyester polyols added is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, relative to the total mass of polycarbonate polyols and polyester polyols and polyols other than polycarbonate polyols and polyester polycarbonates.

[0225] <Other Additives>

[0226] When using the polyol composition of this embodiment to manufacture polyurethane, curing accelerators (catalysts), fillers, flame retardants, dyes, organic or inorganic pigments, release agents, flow modifiers, plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, defoamers, leveling agents, colorants, foaming agents, etc., may be added depending on the application.

[0227] There are no particular limitations on what can be used as a curing accelerator; examples include amines and metal catalysts.

[0228] There are no particular limitations on what constitutes an amine curing accelerator. Examples include triethylamine and N,N-dimethylcyclohexylamine as monoamines, tetramethylethylenediamine as diamines, as well as alkanolamines, cyclic amines, dimethylethanolamine, and ether amines.

[0229] As a metal catalyst, there are no particular limitations. Examples include potassium acetate, potassium 2-ethylhexanoate, calcium acetate, lead octanoate, dibutyltin dilaurate, tin octanoate, bismuth neodecanoate, bismuth oxycarbonate, bismuth 2-ethylhexanoate, zinc octanoate, zinc neodecanoate, phosphine, and phosphorine.

[0230] As fillers and pigments, there are no particular limitations. Examples include fabrics, glass fibers, carbon fibers, polyamide fibers, mica, kaolin, bentonite, metal powders, azo pigments, carbon black, clay, silica, talc, gypsum, alumina white, barium carbonate, and calcium carbonate.

[0231] As a release agent, flow regulator, or leveling agent, there are no particular limitations. Examples include silicone, AEROSIL, wax, stearates, and polysiloxanes such as BYK-331 (manufactured by BYK Chemical).

[0232] As additives used when manufacturing polyurethane using the polyol composition of this embodiment, antioxidants, light stabilizers, and heat stabilizers are preferably used.

[0233] As antioxidants, there are no particular limitations. For example, phosphoric acid, aliphatic, aromatic or alkyl-substituted aromatic esters of phosphorous acid, hypophosphite derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkyl pentaerythritol diphosphite, dialkyl bisphenol A diphosphite, and other phosphorus compounds can be used; phenolic derivatives, especially hindered phenolic compounds, thioether compounds, dithiocarboxylic acid salts, mercaptobenzimidazole compounds, mesolepisine thiourea compounds, thiodipropionate, and other sulfur-containing compounds can be used; tin compounds such as tin maleate and dibutyltin monooxide can also be used. They can be used alone or in combination of two or more.

[0234] [Synthetic Leather]

[0235] The synthetic leather in this embodiment comprises the polyurethane described above.

[0236] The synthetic leather used in this embodiment is not particularly limited, and examples include synthetic leather in which a base fabric, an adhesive layer, an intermediate layer, and an epidermis are sequentially layered. In such synthetic leather, it is preferable that at least one of the group consisting of the base fabric, adhesive layer, intermediate layer, and epidermis comprises the aforementioned polyurethane.

[0237] Various materials can be used as the base fabric (substrate) without particular limitation, such as fibrous substrates. Fibrous substrates are also without particular limitation, including materials formed by shaping fibers into nonwoven fabrics, woven fabrics, mesh fabrics, etc., or materials formed by bonding the fibers of a fiber assembly with elastic polymers. The fibers used in this fiber assembly are also without particular limitation, including natural fibers such as cotton, hemp, and wool; regenerated or semi-synthetic fibers such as rayon and cellulose acetate; and synthetic fibers such as polyamide, polyester, polyacrylonitrile, polyvinyl alcohol, and polyolefins. These fibers can be spun individually or in blends. Other substrates are also without particular limitation, including paper, release paper, polyester and polyolefin plastic films, metal plates such as aluminum, and glass plates.

[0238] In the synthetic leather of this embodiment, the aforementioned polyurethane is preferably used for the adhesive layer, intermediate layer, and epidermal layer. Furthermore, during the formation of each layer, crosslinking agents, other resins, antioxidants, UV absorbers, hydrolysis inhibitors, pigments, dyes, colorants, flame retardants, organic solvents, etc., may be added as needed.

[0239] The method for manufacturing synthetic leather in this embodiment is not particularly limited as long as the above-mentioned polyurethane is used, and any known method for manufacturing synthetic leather can be used.

[0240] [Paint or coating composition]

[0241] The coating or coating agent composition (coating) of this embodiment is made using the above-described polyol composition.

[0242] As a method for manufacturing coatings or coating agent compositions (coatings) using the above-described polyol compositions, manufacturing methods known in the industry can be used. For example, it is possible to manufacture: a two-component solvent-based coating composition in which a coating agent obtained from the above-described polyol composition is mixed with a curing agent containing a polyisocyanate just before coating; a one-component solvent-based coating composition comprising a urethane prepolymer having isocyanate terminal groups obtained by reacting the above-described polycarbonate diol with a polyisocyanate; and a one-component solvent-based coating composition comprising a polyurethane resin obtained by reacting the above-described polycarbonate diol, an organic polyisocyanate, and a chain extender.

[0243] In the coating or coating composition (coating) of this embodiment, for example, curing accelerators (catalysts), leveling agents, fillers, dispersants, flame retardants, dyes, organic or inorganic pigments, release agents, flow modifiers, plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, defoamers, colorants, solvents, and other additives may be added depending on the application. By appropriately including these other additives, coating compositions with different properties, such as smooth coatings and transparent coatings, can be obtained.

[0244] As a curing accelerator (catalyst), there are no particular limitations. Examples of commonly used substances include monoamines, diamines, other triamines, cyclic amines, alkanolamines, ether amines, and metal catalysts.

[0245] As a monoamine, there are no particular limitations; examples include triethylamine and N,N-dimethylcyclohexylamine. As a diamine, there are no particular limitations; examples include tetramethylethylenediamine.

[0246] As an alcoholamine, there are no particular limitations; examples include dimethylethanolamine, etc.

[0247] As a metal catalyst, there are no particular limitations. Examples include potassium acetate, potassium 2-ethylhexanoate, calcium acetate, lead octanoate, dibutyltin dilaurate, tin octanoate, bismuth neodecanoate, bismuth oxycarbonate, bismuth 2-ethylhexanoate, zinc octanoate, zinc neodecanoate, phosphine, and phosphazene.

[0248] Specific examples of organic solvents are not particularly limited, such as amide solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, carbonate solvents, aromatic hydrocarbon solvents, etc.

[0249] These organic solvents can be used alone or in mixtures of two or more solvents.

[0250] [Sealing material]

[0251] The sealant composition of this embodiment comprises the polyurethane described above. The sealant material of this embodiment, by comprising the polyurethane described above, tends to exhibit excellent dimensional stability and durability.

[0252] [Adhesive]

[0253] The adhesive composition of this embodiment comprises the polyurethane described above. By comprising the polyurethane described above, the adhesive of this embodiment tends to exhibit excellent dimensional stability, adhesion, and durability.

[0254] <Applications>

[0255] Synthetic leather obtained using polyurethane manufactured using the polyol composition of this embodiment can be used in automotive interior materials such as car seats, furniture such as sofas, clothing, shoes, bags, and other general merchandise. It is also used as a laminating adhesive for various films and as a surface protectant.

[0256] Aqueous polyurethane produced using the polyol composition of this embodiment can be used as a coating, coating agent, and various other materials, in addition to the synthetic leather described above.

[0257] Example

[0258] The following are specific embodiments and comparative examples to further illustrate this implementation method. However, this implementation method is not limited by these embodiments and comparative examples as long as it does not depart from its spirit. In this embodiment, unless otherwise specified, "parts" and "%" are based on mass.

[0259] The physical properties and evaluations in the examples and comparative examples described below were measured and evaluated using the methods shown below.

[0260] [Physical Property 1] Hydroxyl value

[0261] The hydroxyl value of polycarbonate diol (composition) is determined by the following method.

[0262] First, using a volumetric flask, pyridine was added to 12.5 g of acetic anhydride to prepare 50 mL of acetylation reagent. Next, 2.5 g of the sample was accurately weighed into a 100 mL round-bottom flask. Then, using a full-capacity pipette, 5 mL of the acetylation reagent and 10 mL of toluene were added to the round-bottom flask. A condenser was then attached, and the solution in the round-bottom flask was heated and stirred at 100 °C for 1 hour. Next, 2.5 mL of distilled water was added to the round-bottom flask using a full-capacity pipette, and the solution was further heated and stirred for 10 minutes. After cooling the solution in the round-bottom flask for 2-3 minutes, 12.5 mL of ethanol was added to the round-bottom flask. Finally, 2-3 drops of phenolphthalein were added as an indicator, and titration was performed with 0.5 mol / L ethanolic potassium hydroxide solution. Next, 5 mL of the acetylation reagent, 10 mL of toluene, and 2.5 mL of distilled water were placed into a 100 mL round-bottom flask. The solution in the round-bottom flask was heated and stirred for 10 minutes, and then titrated (blank test) was performed in the same manner. Based on the results, the hydroxyl value of the polycarbonate diol (composition) was calculated using the following formula (i).

[0263] Hydroxyl value (mg-KOH / g)={(FE)×28.05×f} / G……(i)

[0264] It should be noted that in equation (i), E represents the titration volume of the sample (mL), F represents the titration volume of the blank test (mL), G represents the sample mass (g), and f represents the factor of the titrant.

[0265] [Physical Property 2] Number-average molecular weight (A)

[0266] The number-average molecular weight (A) of the polycarbonate polyol (composition) and the polyester polyol (composition) is calculated based on the hydroxyl value obtained in [Property 1] and using the following formula (ii).

[0267] Number average molecular weight (A) = 2 / (H × 10) -3 / 56.11) ……(ii)

[0268] It should be noted that in formula (ii), H represents the hydroxyl value (mg-KOH / g) of the polycarbonate polyol (composition) and the polyester polyol (composition).

[0269] It should be noted that in the following examples and comparative examples, the average number-average molecular weight Mn when using various polycarbonate polyols and / or polyester polyols is calculated based on the hydroxyl values ​​obtained in [Property 1] and the average hydroxyl value is calculated using the following formula (iii). The calculated value is then substituted into the above formula (ii) to calculate the number-average molecular weight.

[0270] Average hydroxyl value = Σ(x n ·H n ……(iii)

[0271] (x) n The mixing ratio of specific polyols, H n (The hydroxyl value of a specific polyol measured before mixing)

[0272] [Physical Property 3] Molecular Weight (B)

[0273] A portion of the polyurethane film obtained in the application examples and comparative examples described below was cut off, and an N,N-dimethylformamide solution was prepared with a polyurethane concentration of 0.1% by mass. Using a GPC apparatus (Tosoh Corporation, product name "HLC-8320" (column: 4 Tskgel SuperHM-H columns), the eluent was a solution of 2.6 g lithium bromide dissolved in 1 L of dimethylformamide), the number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the polyurethane, converted to standard polystyrene, were determined. Furthermore, the molecular weight distribution (Mw / Mn) was calculated from these results.

[0274] [Physical Property 4] Determination of Melt Viscosity

[0275] After preheating the polycarbonate polyol, polyester polyol, or polyol composition to 50°C, a rotational viscometer (rheometer (Anton Paar, MCR102, cone: CP25-1)) was used to measure the temperature during a heating process from 20°C to 80°C (heating rate: 2°C / min, shear rate: 20min). -1 Data acquisition time: constant, each point is 0.5 min) to determine viscosity, and the melt viscosity at 23℃ is measured.

[0276] Alternatively, instead of the above method, a rotational viscometer (Type E viscometer (Toki Sangyo Co., Ltd., TVE-22HT, cone: No. 6)) can be used to measure the melt viscosity at 23°C.

[0277] It should be noted that, in the examples and comparative examples described below, the average viscosity at 23°C when using various polycarbonate polyols or polyester polyols was calculated using the following formula (iv).

[0278] Average viscosity = Σ(x n ·R n ) ……(iv)

[0279] (x) n : The mixing ratio of specific polyols, R n (The viscosity of a specific polyol at 23°C, measured before mixing)

[0280] [Physical Property 5] Content of repeating structural unit (II) in polycarbonate polyol composition

[0281] Take 1 g of the polycarbonate polyol composition sample obtained in the examples and comparative examples described below into a 100 mL round-bottom flask, add 30 g of methanol and 8 g of 28% sodium methoxide methanol solution, and react at 100 °C for 1 hour. After cooling the reaction solution to room temperature, add 2-3 drops of phenolphthalein to the indicator and neutralize with hydrochloric acid. After cooling in a refrigerator for 1 hour, filter the solution and analyze it using gas chromatography (GC). GC analysis was performed using a GC-14B gas chromatograph (manufactured by Shimadzu Corporation, Japan) equipped with a DB-WAX column (manufactured by J&W, USA), with diethylene glycol diethyl ether as an internal standard and a flame ionization detector (FID) as the detector, for quantitative analysis of each component. It should be noted that the column temperature profile was set at 60 °C for 5 minutes, then increased to 250 °C at a rate of 10 °C / min.

[0282] The composition of polycarbonate diol is determined based on the alcohol components detected by the above analysis results.

[0283] [Physical Property 6] Content of repeating structural units (I) in the polyester polyol composition

[0284] Take 1 g of the polyester polyol composition sample obtained in the examples and comparative examples described below into a 100 mL round-bottom flask, add 30 g of methanol and 8 g of 28% sodium methoxide methanol solution, and react at 100 °C for 1 hour. After cooling the reaction solution to room temperature, add 2-3 drops of phenolphthalein to the indicator and neutralize with hydrochloric acid. After cooling in a refrigerator for 1 hour, filter the solution and analyze it using gas chromatography (GC). GC analysis was performed using a GC-14B gas chromatograph (manufactured by Shimadzu Corporation, Japan) equipped with a DB-WAX column (manufactured by J&W, USA), with diethylene glycol diethyl ether as an internal standard and a flame ionization detector (FID) as the detector, to quantitatively analyze each component. The column temperature profile shows the column held at 60 °C for 5 minutes, then increased to 250 °C at a rate of 10 °C / min.

[0285] The composition of polyester polyols is determined based on the alcohol components and methyl ester components derived from dicarboxylic acids detected by the above analysis results.

[0286] Next, deuterated chloroform was used as a solvent to treat the polyester polyol composition sample at a concentration of 0.1 g / L. 1 ¹H-NMR determination. The detected alcohol components and components derived from dicarboxylic acids were assigned, and the content ratio of each component was calculated using the integral ratio of each signal.

[0287] [Physical Property 7] Determination of the transparency (haze value) of polyol compositions

[0288] The polyol composition was filled into an optical glass cuvette (70 mm in length, 20 mm in width, and 55 mm in height), heated at 80°C for more than 3 hours, and after confirming that there were no air bubbles, the transparency was evaluated using a haze meter (Nippon Denshoku Kogyo Co., Ltd., NDH2000) based on the integrating sphere photoelectric photometry method.

[0289] Measurements were performed in liquid mode (horizontal cuvette) using a halogen lamp (5V2A) as the light source. The measuring diameter was Φ20mm, and the measurement environment was room temperature 23±2℃ and humidity 50±10%. Total transmittance (Tt) and diffuse transmittance (Td) were measured, and the haze value was calculated using the following formula (v).

[0290] Haze value (%) = (Td / Tt) × 100 …… (v)

[0291] It should be noted that a haze level of 25% or lower is considered the acceptable threshold for transparency.

[0292] [Physical Property 8] Determination of the volatile / non-volatile component ratio of polyol compositions

[0293] For the polyol composition, the volatile / non-volatile ratio is determined as follows. First, accurately weigh a pre-dried aluminum dish with a bottom diameter of 38 mm. Then, accurately weigh a specified amount (approximately 1 g) of the polyol composition into the dish, as the pre-drying mass (W1). Next, maintain the dish in an oven at 105°C for 1 hour. Then, after the dish reaches room temperature, accurately weigh the remaining polyol composition in the dish, as the post-drying mass (W2). Next, calculate the volatile / non-volatile ratio of the polyol composition using the following formula (vi). It should be noted that the non-volatile component is always 75% by mass or more.

[0294] Volatile component / non-volatile component ratio (%) = W2 / W1 × 100 …… (vi)

[0295] [Evaluation 1] Evaluation of viscosity deviation

[0296] According to the composition in Table 1, the polyol composition was measured in 10g increments into 20mL of a thick-walled glass bottle (Nipro: VIALBC 27X55R(1.5)). The mixture was stirred at 80°C for 5 minutes, then allowed to stand at 80°C for 3.5 hours, and then at 20°C for 24 hours. Visual inspection confirmed that no phase separation occurred in the polyol composition within the thick-walled glass bottle. Then, the following... Figure 1 The viscosity at 23°C was measured at the upper and lower parts located at a distance of more than 1.5 cm, according to the measurement method of "Physical Property 4".

[0297] [Evaluation Criteria]

[0298] × (difference): Does not satisfy the following formula (1-1).

[0299] 〇 (Good): Satisfies the following formula (1-1).

[0300] ◎ (Very good): Satisfies the following formula (1-2).

[0301] |xy|<(x+y) / 4……(Formula 1-1)

[0302] |xy|<(x+y) / 16……(Formula 1-2)

[0303] (In the formula, x is the upper viscosity of the polyol composition at 23°C, and y is the lower viscosity of the polyol composition at 23°C. x and y are measured according to [Physical Property 4] above.)

[0304] [Evaluation 2] Compatibility Evaluation

[0305] The compatibility of the polyol compositions obtained in the following examples and comparative examples is evaluated as follows. According to the composition in Table 1, the polyol composition was measured in 10g increments into 20mL of a thick-walled glass bottle and allowed to stand at 80°C for 4 hours. The compatibility was evaluated based on the appearance of the resulting solution. Regarding the evaluation criteria, after visually determining whether phase separation had occurred, samples that did not clearly separate into upper and lower phases were tested according to the determination method in "Physical Property 7". Samples with a content below 25% were classified as transparent, and those with a content above 25% were classified as cloudy. Except for ○, the composition of the polyol varied over time depending on the location of the polyol, therefore, it is a composition with poor quality stability and transparency.

[0306] [Evaluation Criteria]

[0307] 〇 (Good): Transparent and no phase separation has occurred.

[0308] △ (Decent): Leukorrhea

[0309] × (Difference): Separated into 2 layers

[0310] [Evaluation 3] Room temperature tensile test

[0311] According to JIS K6301 (2010), a tensile testing machine (Orientec, product name "Tensilon", model: RTE-1210) was used to conduct tensile tests on a strip of polyurethane test piece with a width of 10 mm, a length of 100 mm, and a thickness of approximately 50 μm, at a chuck spacing of 20 mm, a tensile speed of 40 mm / min, and a temperature of 23°C (relative humidity of 55%). The stress (100% modulus), the strength at the point of break, and the elongation at the point of break were measured.

[0312] [Evaluation 4] Low-temperature tensile test

[0313] According to JIS K6301 (2010), a polyurethane test piece, 10 mm wide, 100 mm long, and approximately 50 μm thick, was placed in a tensile testing machine (Orientec, product name "Tensilon", model "RTE-1210") equipped with a thermostatic bath (Orientec, model "TLF-R3T-EW"). After resting at -20°C for 5 minutes, a tensile test was performed at a tensile speed of 100 mm / min. The stress (100% modulus), breaking strength, and elongation at break were measured at the point of 100% elongation.

[0314] [Rating 5] Evaluation of softness

[0315] Similar to the above <Room Temperature Tensile Test>, the 100% modulus was determined. In the case of polyurethane synthesized from a polyol composition with a number average molecular weight of 1,800 to 2,200, the softness was evaluated according to the following criteria.

[0316] ◎ (Very good): 100% of the modulus is less than 4MPa.

[0317] 〇 (Good): 100% modulus is above 4MPa and less than 5MPa.

[0318] × (Difference): Cases where the modulus is 5 MPa or higher.

[0319] [Evaluation 6] Evaluation of low-temperature flexibility

[0320] Similar to the above-mentioned <Low Temperature Tensile Test>, 100% modulus determination was performed. In the case of polyurethane synthesized from a polyol composition with a number average molecular weight of 1,800 to 2,200, the softness was evaluated according to the following criteria.

[0321] ◎ (Very good): 100% of the modulus is less than 20MPa.

[0322] 〇 (Good): 100% modulus is above 20MPa and less than 30MPa.

[0323] × (Difference): Cases where the modulus is 30 MPa or higher.

[0324] [Evaluation 7] Evaluation of heat resistance

[0325] A polyurethane film was made into a strip with a width of 10 mm, a length of 100 mm, and a thickness of approximately 50 μm, and heated in a Gill oven at 120 °C for 7 days. For the heated sample, the breaking strength was measured in the same manner as in the <Room Temperature Tensile Test> above, and the percentage of breaking strength retention before and after heating was calculated using the following formula.

[0326] Fracture strength retention rate (%) = Fracture strength after heating / Fracture strength before heating × 100

[0327] In addition, the evaluation shall be conducted according to the following criteria.

[0328] ◎ (Very good): The fracture strength retention rate is above 80%.

[0329] 〇 (Good): The fracture strength retention rate is above 30% but less than 80%.

[0330] × (Poor): Cases where the fracture strength retention rate is less than 30%.

[0331] [Evaluation 8] Evaluation of hydrolysis resistance

[0332] A polyurethane film was made into a strip with a width of 10 mm, a length of 100 mm, and a thickness of approximately 50 μm. It was then heated in a constant temperature and humidity bath at 85°C and 85% relative humidity for 14 days. For the heated sample, the elongation at break was measured in the same manner as in the <Room Temperature Tensile Test> described above. The retention rate of elongation at break before and after heating (%) was calculated using the following formula.

[0333] Elongation at break retention rate (%) = Elongation at break after heating / Elongation at break before heating × 100

[0334] In addition, the evaluation shall be conducted according to the following criteria.

[0335] ◎ (Very good): The elongation at break is maintained at 80% or more.

[0336] 〇 (Good): The elongation at break is maintained at 30% or more but less than 80%.

[0337] × (Poor): Cases where the elongation at break retention rate is less than 30%.

[0338] In addition, the abbreviations used in the table and in this document are as follows.

[0339] A-1: Polyester polyol (manufactured by Kuraray Corporation, "Kuraray Polyol P-2010" (trade name), number average molecular weight: about 2,000, condensate of 3-methyl-1,5-pentanediol (hereinafter also referred to as "3MPD") and adipic acid), number average molecular weight: about 2,000, average number of carbon atoms in R1 in general formula (I): 4)

[0340] A-2: Polyester polyol (manufactured by Kuraray Corporation, "Kuraray Polyol P-2050" (trade name), number average molecular weight: about 2,000, condensate of 3MPD and sebacic acid), number average molecular weight: about 2,000, average number of carbon atoms in R1 in general formula (I): 8)

[0341] Synthesis example of A-3: Synthesis of polyester polyol (succinic acid / sebacic acid / 1,3-propanediol = 37 / 20 / 64 moles)

[0342] First, 200 parts by mass of sebacic acid, 220 parts by mass of succinic acid, and 241 parts by mass of 1,3-propanediol were added to a glass reactor equipped with a stirrer, reflux condenser, heating device, thermometer, etc., to initiate the reaction. Then, the reaction was carried out under a nitrogen stream at 200-250°C for 15-20 hours with heating and stirring. During this period, water generated by the esterification reaction was distilled off the system to obtain polyester polyol A-3 with a hydroxyl value of 56.1 mgKOH / g. Number average molecular weight: approximately 2,000; average number of carbon atoms in R1 of general formula (I): 4.1 (The method for calculating the average number of carbon atoms is not particularly limited; for example, it can be calculated using the following method. Based on the polyester polyol's...) 1 The H-NMR spectrum was calculated by dividing the integral ratio of the signal from succinic acid (2.5–2.7 ppm) by the integral ratio of the signal from sebacic acid (2.2–2.3 ppm) when the chloroform concentration was measured in the range of 7.2–7.3 ppm. From this, the succinic acid / sebacic acid ratio was calculated, and the average number of carbon atoms was determined.

[0343] Example of A-4 synthesis: Synthesis of polyester polyols (adipic acid / sebacic acid / 3-methyl-1,5-pentanediol = 67 / 74 / 84 moles)

[0344] First, 15 parts by mass of sebacic acid, 98 parts by mass of adipic acid, and 99 parts by mass of 1,3-propanediol are added to a glass reactor equipped with a stirrer, reflux condenser, heating device, thermometer, etc., to initiate the reaction. Then, the reaction is carried out under a nitrogen stream at 200-250°C for 15-20 hours with heating and stirring. During this period, water generated by the esterification reaction is distilled off the system to obtain polyester polyol A-4 with a hydroxyl value of 56.1 mgKOH / g. Number average molecular weight: approximately 2,000; average number of carbon atoms in R1 of general formula (I): 4.4 (The method for calculating the average number of carbon atoms is not particularly limited; for example, it can be calculated using the following method. Based on the polyester polyol's...) 1 From the 1H-NMR spectrum, calculate the following for measurements taken in the chloroform range of 7.2–7.3 ppm: ((integral ratio of the signal from adipic acid to sebacic acid at 2.2–2.4 ppm) × 2 - (integral ratio of the signal from sebacic acid at 1.2–1.3 ppm)) ÷ (integral ratio of the signal from sebacic acid at 1.2–1.3 ppm). From this, calculate the adipic acid / sebacic acid ratio and the average number of carbon atoms.

[0345] [Synthesis Example 1] Preparation of Polycarbonate Diol P-1

[0346] In a 1L glass flask (hereinafter referred to as the "reactor") equipped with a distillation column filled with a regularly packed material and a stirring device, 230g of 1,5-pentanediol, 250g of 1,6-hexanediol, and 400g of ethylene carbonate were added, followed by 0.0468g of tetra-n-butoxide titanium as a catalyst. The reactor was immersed in an oil bath at 180°C, and while a portion of the distillate was extracted, the reaction was carried out at a reaction temperature of 165°C for 12 hours. Next, the reactor was directly connected to a condenser, and the oil bath temperature was raised to 180°C, while the pressure was slowly reduced, and the reaction was carried out for another 3 hours to obtain polycarbonate diol P-1, which is liquid at room temperature. The obtained polycarbonate diol P-1 has a hydroxyl value of 55.2 mg-KOH / g and a number-average molecular weight of 2,033. Furthermore, its viscosity at 23°C is 75,000 mPa·s.

[0347] [Synthesis Example 2] Preparation of Polycarbonate Diol P-2

[0348] In a 1L glass flask (hereinafter referred to as the "reactor") equipped with a distillation column filled with a regularly packed material and a stirring device, 270g of 1,6-hexanediol, 250g of 1,4-butanediol, and 445g of ethylene carbonate were added, followed by 0.0960g of tetra-n-butoxide titanium as a catalyst. The reactor was immersed in an oil bath at 140–160°C, and while partially removing the distillate, the reaction was carried out at a reaction temperature of 90–160°C for 20 hours. Next, the reactor was directly connected to a condenser, and the oil bath temperature was raised to 180°C. The pressure was then slowly reduced, and the reaction was carried out for another 8 hours to obtain polycarbonate diol P-2, which is liquid at room temperature. The obtained polycarbonate diol P-2 has a hydroxyl value of 56.1 mg-KOH / g and a number-average molecular weight of 2,000. Furthermore, its viscosity at 23°C is 109,000 mPa·s.

[0349] [Synthesis Example 3] Preparation of Polycarbonate Diol P-3

[0350] In a 1L glass flask (hereinafter referred to as the "reactor") equipped with a distillation column filled with a regularly packed material and a stirring device, 230g of 1,5-pentanediol, 250g of 1,6-hexanediol, and 400g of ethylene carbonate were added, followed by 0.0468g of tetra-n-butoxide titanium as a catalyst. The reactor was immersed in an oil bath at 180°C, and while a portion of the distillate was extracted, the reaction was carried out at a reaction temperature of 165°C for 12 hours. Next, the reactor was directly connected to a condenser, and the oil bath temperature was raised to 165°C. The pressure was then slowly reduced, and the reaction was carried out for another hour to obtain polycarbonate diol P-3, which is liquid at room temperature. The obtained polycarbonate diol P-3 has a hydroxyl value of 224.0 mg-KOH / g and a number-average molecular weight of 501. Furthermore, its viscosity at 23°C is 1,900 mPa·s.

[0351] [Synthesis Example 4] Preparation of Polycarbonate Diol P-4

[0352] In a 1L glass flask (hereinafter referred to as the "reactor") equipped with a distillation column filled with a regularly packed material and a stirring device, 162g of 1,6-hexanediol, 350g of 1,4-butanediol, and 445g of ethylene carbonate were added, followed by 0.0960g of tetra-n-butoxide titanium as a catalyst. The reactor was immersed in an oil bath at 140-160°C, and while partially removing the distillate, the reaction was carried out at a reaction temperature of 90-160°C for 20 hours. Then, the reactor was directly connected to a condenser, the oil bath temperature was raised to 180°C, and the pressure was slowly reduced for an additional 8 hours of reaction, yielding polycarbonate diol P-4, which is liquid at room temperature. The obtained polycarbonate diol P-4 has a hydroxyl value of 56.1 mg-KOH / g and a number-average molecular weight of 2,000. Furthermore, its viscosity at 23°C is 157,000 mPa·s.

[0353] [Synthesis Example 5] Preparation of Polycarbonate Diol P-5

[0354] In a 1L glass flask (hereinafter referred to as the "reactor") equipped with a distillation column filled with a regularly packed material and a stirring device, 383g (5.1mol) of 1,3-propanediol and 450g (5.1mol) of ethylene carbonate were added, followed by 0.0960g of tetra-n-butoxide as a catalyst. The reactor was immersed in an oil bath at 140–160°C, and a portion of the distillate was extracted while the reaction was carried out at 90–160°C for 20 hours. Then, the reactor was directly connected to a condenser, the oil bath temperature was raised to 180°C, and the pressure was slowly reduced for an additional 8 hours of reaction, yielding polycarbonate diol P-5, which is liquid at room temperature. The obtained polycarbonate diol P-5 has a hydroxyl value of 56.1 mg-KOH / g and a number-average molecular weight of 2,000. Furthermore, its viscosity at 23°C is 445,000 mPa·s.

[0355] [Synthesis Example 6] Preparation of Polycarbonate Diol P-6

[0356] In a 1L glass flask (hereinafter referred to as the "reactor") equipped with a distillation column filled with a regularly packed material and a stirring device, 383g (5.1mol) of 1,3-propanediol and 450g (5.1mol) of ethylene carbonate were added, followed by 0.0960g of tetra-n-butoxide as a catalyst. The reactor was immersed in an oil bath at 140–160°C, and a portion of the distillate was extracted while the reaction was carried out at 90–160°C for 20 hours. Then, the reactor was directly connected to a condenser, the oil bath temperature was raised to 165°C, and the pressure was slowly reduced for an additional hour to obtain polycarbonate diol P-6, which is liquid at room temperature. The obtained polycarbonate diol P-6 has a hydroxyl value of 224.0 mg-KOH / g and a number-average molecular weight of 501. Furthermore, its viscosity at 23°C is 5,230 mPa·s.

[0357] [Synthesis Example 7] Preparation of Polycarbonate Diol P-7

[0358] In a 1L glass flask (hereinafter referred to as the "reactor") equipped with a distillation column filled with a regularly packed material and a stirring device, 219g (1.5mol) of isosorbide, 315g (3.5mol) of 1,4-butanediol, and 440g (5.0mol) of ethylene carbonate were added, followed by 0.0960g of tetra-n-butoxide as a catalyst. The reactor was immersed in an oil bath at 140–160°C, and a portion of the distillate was extracted while the reaction was carried out at 90–160°C for 20 hours. Then, the reactor was directly connected to a condenser, the oil bath temperature was raised to 165°C, and the pressure was slowly reduced for an additional 2 hours to obtain polycarbonate diol P-7, which is liquid at room temperature. The obtained polycarbonate diol P-7 has a hydroxyl value of 140.2 mg-KOH / g and a number-average molecular weight of 800. Furthermore, its viscosity at 23°C is 526,000 mPa·s.

[0359] [Synthesis Example 8] Preparation of Polycarbonate Diol P-8

[0360] In a 1L glass flask (hereinafter referred to as the "reactor") equipped with a distillation column filled with a regularly packed material and a stirring device, 250g of 2-methyl-1,3-propanediol, 250g of 1,4-butanediol, and 445g of ethylene carbonate were added, followed by 0.0960g of tetra-n-butoxide as a catalyst. The reactor was immersed in an oil bath at 180°C, and while partially removing the distillate, the reaction was carried out at a reaction temperature of 165°C for 12 hours. Next, the reactor was directly connected to a condenser, and the oil bath temperature was raised to 180°C. The pressure was then slowly reduced, and the reaction was carried out for another 3 hours to obtain polycarbonate diol P-8, which is liquid at room temperature. The obtained polycarbonate diol P-8 has a hydroxyl value of 56.1 mg-KOH / g and a number-average molecular weight of 2,000. Furthermore, its viscosity at 23°C is 751,000 mPa·s.

[0361] [Example 1] Preparation of polyol composition SA-1

[0362] Based on Table 1, the types and amounts of each raw material were added as follows: 200g of polycarbonate polyol P-1, 300g of polycarbonate polyol P-3, 100g of polyester polyol A-1, and 400g of polyester polyol A-2. The mixture was stirred at 80°C for 3 hours to obtain polyol composition SA-1. Additionally, through... 1 The obtained SA-1 was analyzed by H-NMR and GC-MS measurements. The results showed that it possessed repeating structural units represented by general formula (A1), general formula (B1), and general formula (B2). Furthermore, since it did not undergo transesterification, it could be obtained through… 1 H-NMR measurements confirmed the absence of any new signals other than those originating from the polyols before stirring.

[0363]

[0364] (In general formula (A1), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 7.2.

[0365]

[0366] (In general formula (B1), R) 31 It is an aliphatic hydrocarbon group with 5 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 5.5.

[0367] [Examples 2-18]

[0368] The types and amounts of each raw material were changed as described in Table 1. All other reactions were carried out under the same conditions and methods as in Example 1 to obtain the polyol compositions SA-2 to SA-21 of Examples 2 to 21. The viscosity deviation and compatibility of the obtained polyol compositions SA-1 to SA-21 were determined using the methods described above. The results are shown in Table 1.

[0369] In addition, the obtained polyol compositions SA-2 to SA-21 contain repeating structural units shown in the following general formulas (A2) to (A21) and repeating structural units shown in the following general formulas (B2) to (B21) respectively.

[0370]

[0371] (In general formula (A2), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 6.8.

[0372]

[0373] (In general formula (B2), R) 31 It is an aliphatic hydrocarbon group with 4, 5, or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 5.3.

[0374]

[0375] (In general formula (A3), R) 11 R is an aliphatic hydrocarbon group with 4 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 4.

[0376]

[0377] (In general formula (B3), R) 31 It is an aliphatic hydrocarbon group with 5 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 5.5.

[0378]

[0379] (In general formula (A4), R) 11 R is an aliphatic hydrocarbon group with 2 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 3 carbon atoms. Additionally, R... 11 The average number of carbon atoms is 4.1.

[0380]

[0381] (In general formula (B4), R) 31 It is an aliphatic hydrocarbon group with 5 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 5.5.

[0382]

[0383] (In general formula (A5), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 6.8.

[0384]

[0385] (In general formula (B5), R) 31 It is an aliphatic hydrocarbon group with 5 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 5.5.

[0386]

[0387] (In general formula (A6), R) 11 R is an aliphatic hydrocarbon group with 2 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 3 carbon atoms. Additionally, R... 11 The average number of carbon atoms is 4.1.

[0388]

[0389] (In general formula (B6), R) 31 It is an aliphatic hydrocarbon group with 3 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 3.

[0390]

[0391] (In general formula (A7), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 4.4.

[0392]

[0393] (In general formula (B7), R) 31 It is an aliphatic hydrocarbon group with 5 or 6 carbon atoms. Additionally, R... 31The average number of carbon atoms is 5.5.

[0394]

[0395] (In general formula (A8), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 4.4.

[0396]

[0397] (In general formula (B8), R) 31 It is an aliphatic hydrocarbon group with 5 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 5.5.

[0398]

[0399] (In general formula (A9), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 6.4.

[0400]

[0401] (In general formula (B9), R) 31 It is an aliphatic hydrocarbon group with 4, 5, or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 5.3.

[0402]

[0403] (In general formula (A10), R) 11 R is an aliphatic hydrocarbon group with 2 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 3 carbon atoms. Additionally, R... 11 The average number of carbon atoms is 4.1.

[0404]

[0405] (In general formula (B10), R) 31 It is an aliphatic hydrocarbon group with 4 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 5.

[0406]

[0407] (In general formula (A11), R) 11R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 6.

[0408]

[0409] (In general formula (B11), R) 31 It is an aliphatic hydrocarbon group with 4, 5, or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 5.3.

[0410]

[0411] (In general formula (A12), R) 11 R is an aliphatic hydrocarbon group with 4 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 4.

[0412]

[0413] (In general formula (B12), R) 31 It is an aliphatic hydrocarbon group with 4 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 4.6.

[0414]

[0415] (In general formula (A13), R) 11 R is an aliphatic hydrocarbon group with 2 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 3 carbon atoms. Additionally, R... 11 The average number of carbon atoms is 4.1.

[0416]

[0417] (In general formula (B13), R) 31 It is an aliphatic hydrocarbon group with 4 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 4.6.

[0418]

[0419] (In general formula (A14), R) 11 R is an aliphatic hydrocarbon group with 2 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 3 carbon atoms. Additionally, R... 11 The average number of carbon atoms is 4.1.

[0420]

[0421] (In general formula (B14), R) 31 It is an aliphatic hydrocarbon group with 4 carbon atoms or a cyclic aliphatic hydrocarbon group with 6 carbon atoms and 2 oxygen atoms. Additionally, R... 31 The average number of carbon atoms is 4.6.

[0422]

[0423] (In general formula (A15), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 5.2.

[0424]

[0425] (In general formula (B15), R) 31 It is an aliphatic hydrocarbon group with 5 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 5.5.

[0426]

[0427] (In general formula (A16), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 4.8.

[0428]

[0429] (In general formula (B16), R) 31 It is an aliphatic hydrocarbon group with 4 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 4.6.

[0430]

[0431] (In general formula (A17), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 4.4.

[0432]

[0433] (In general formula (B17), R) 31It is an aliphatic hydrocarbon group with 4 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 4.6.

[0434]

[0435] (In general formula (A18), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 4.4.

[0436]

[0437] (In general formula (B18), R) 31 It is an aliphatic hydrocarbon group with 4 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 4.6.

[0438]

[0439] (In general formula (A19), R) 11 R is an aliphatic hydrocarbon group with 2 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 3 carbon atoms. Additionally, R... 11 The average number of carbon atoms is 4.1.

[0440]

[0441] (In general formula (B19), R) 31 It is an aliphatic hydrocarbon group with 4 carbon atoms containing a branched structure. Additionally, R... 31 The average number of carbon atoms is 4.0.

[0442]

[0443] (In general formula (A20), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 5.2.

[0444]

[0445] (In general formula (B20), R) 31 It is an aliphatic hydrocarbon group with 4, 5, or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 5.3.

[0446]

[0447] (In general formula (A21), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 5.6.

[0448]

[0449] (In general formula (B21), R) 31 It is an aliphatic hydrocarbon group with 5 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 5.5.

[0450] [Comparative Examples 1-8] Preparation of polyol compositions SB-1-SB-8

[0451] The types and amounts of each raw material were changed as described in Table 1. All other reactions were carried out under the same conditions and methods as in Example 1 to obtain the polyol compositions SB-1 to SB-8 of Comparative Examples 1 to 8. The viscosity deviation and compatibility of the obtained polyol compositions SB-1 to SB-8 were measured using the methods described above. The results are shown in Table 1.

[0452] In addition, the obtained polyol compositions SB-1 to SB-8 contain repeating structural units shown in the following general formulas (A22) to (A29) and repeating structural units shown in the following general formulas (B22) to (B29) respectively.

[0453]

[0454] (In general formula (A22), R) 11 R is an aliphatic hydrocarbon group with 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 8.

[0455]

[0456] (In general formula (B22), R) 31 It is an aliphatic hydrocarbon group with 4 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 4.6.

[0457]

[0458] (In general formula (A23), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R...11 The average number of carbon atoms is 7.6.

[0459]

[0460] (In general formula (B23), R) 31 It is an aliphatic hydrocarbon group with 4 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 4.6.

[0461]

[0462] (In general formula (A24), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 7.2.

[0463]

[0464] (In general formula (B24), R) 31 It is an aliphatic hydrocarbon group with 4 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 4.6.

[0465]

[0466] (In general formula (A25), R) 11 R is an aliphatic hydrocarbon group with 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 8.

[0467]

[0468] (In general formula (B25), R) 31 It is an aliphatic hydrocarbon group with 5 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 5.5.

[0469]

[0470] (In general formula (A26), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 7.6.

[0471]

[0472] (In general formula (B26), R) 31 It is an aliphatic hydrocarbon group with 4, 5, or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 5.3.

[0473]

[0474] (In general formula (A27), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 7.6.

[0475]

[0476] (In general formula (B27), R) 31 It is an aliphatic hydrocarbon group with 5 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 5.5.

[0477]

[0478] (In general formula (A28), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 7.2.

[0479]

[0480] (In general formula (B28), R) 31 It is an aliphatic hydrocarbon group with 4, 5, or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 5.3.

[0481]

[0482] (In general formula (A29), R) 11 R is an aliphatic hydrocarbon group with 4 or 8 carbon atoms. 21 It is an aliphatic hydrocarbon group with 5 carbon atoms and one branched chain. Additionally, R... 11 The average number of carbon atoms is 7.4.

[0483]

[0484] (In general formula (B29), R) 31 It is an aliphatic hydrocarbon group with 5 or 6 carbon atoms. Additionally, R... 31 The average number of carbon atoms is 5.5.

[0485] [Table 1]

[0486]

[0487] [Application Example 1] Synthesis of polyurethane film PA-1

[0488] In a 500 mL detachable flask equipped with a thermocouple and a condenser, 38 g of polyol composition SA-5, 224 g of dimethylformamide (hereinafter sometimes abbreviated as DMF), and 0.26 g (50 ppm relative to the total mass of MDI and the polyol composition) of a 1% dibutyltin dilaurate toluene solution were added, and the mixture was heated in an oil bath at 40 °C. While stirring the solution in the flask at 100 rpm under a nitrogen atmosphere, 14.8 g of MDI (3.09 times the OH [mol] of the polyol composition) was added dropwise, and the solution was stirred further for about 1.5 hours. The isocyanate group concentration was analyzed to confirm that the theoretical amount had been consumed, and the prepolymer was obtained. Then, the necessary amount of 1,4-butanediol (1,4-BD) (3.2 g), calculated from the residual isocyanate, was added to the flask in portions. After stirring the solution in the flask for about 1 hour, about 1 g of ethanol was added, and the solution in the flask was stirred for another 30 minutes to obtain a polyurethane solution with a number average molecular weight of 93,600.

[0489] Using a 0.8 mm thick coater, the obtained polyurethane solution was dropped onto the upper part of a glass plate (JIS R3202, 2 mm × 100 mm × 150 mm) to achieve a dry film thickness of 50–150 μm. The film was dried on a hot plate at 60 °C for 2 hours, followed by drying in an oven at 80 °C for 12 hours. Then, it was allowed to stand at a constant temperature and humidity of 23 °C and 55% RH for at least 12 hours to obtain the polyurethane film PA-1. The obtained polyurethane film PA-1 was evaluated for various physical properties using the above method. The evaluation results are shown in Table 2.

[0490] [Application Examples 2-6]

[0491] In the manufacture of the polyurethane film in Application Example 1, the polyol composition SA-5 used was changed to the polyol compositions SA-10, SA-13, SA-16, SA-18, and SA-21 manufactured in the examples, respectively. Otherwise, the reaction was carried out under the same conditions as in Application Example 1 to obtain polyurethane films PA-2 to PA-6. The obtained polyurethane films PA-2 to PA-6 were evaluated for various physical properties using the methods described above. The evaluation results are shown in Table 2.

[0492] [Comparative Application Examples 1-7]

[0493] In the manufacture of the polyurethane film in Application Example 1, the polyol composition SA-5 used was changed to precursors P-1, P-2, P-4, P-5, A-1, A-2, and A-3 used to synthesize the polyol composition. Otherwise, the reaction was carried out under the same conditions as in Application Example 1 to obtain polyurethane films PB-1 to PB-7. The obtained polyurethane films PB-1 to PB-7 were evaluated for various physical properties using the method described above. The evaluation results are shown in Table 2.

[0494] [Table 2]

[0495]

[0496] As shown in Table 1, compared with polyol compositions that do not meet the specific conditions, polyol compositions containing repeating structural units (I) and repeating structural units (II) and meeting the specific conditions are homogeneous polyol compositions with no viscosity deviation and excellent transparency.

[0497] Furthermore, as shown in Table 2, compared with polyurethanes obtained from polycarbonate polyols or polyester polyols constituting the polyol composition, the polyurethanes obtained from the polyol compositions of the examples exhibit excellent flexibility at room temperature and low temperature, as well as an excellent balance with durability such as heat resistance and resistance to damp heat.

[0498] Industrial availability

[0499] The polyol composition comprising polycarbonate polyol and polyester polyol of this embodiment can achieve high solids content in the manufacture of coatings and polyurethanes, and is useful as a raw material for coatings and polycarbonate-based polyurethanes. Furthermore, polyurethanes manufactured using the polyol composition of this embodiment have advantages such as softness, low-temperature flexibility, and excellent durability, and can be suitable for a wide range of applications including elastic fibers, synthetic or artificial leather, coatings, and high-performance elastomers.

Claims

1. A polyol composition, characterized in that, It is a polyol composition containing polycarbonate polyol and polyester polyol, which does not undergo phase separation when left to stand at 80°C for 4 hours.

2. The polyol composition according to claim 1, wherein it satisfies the following formula (Formula 1). |xy|<(x+y) / 4……(Formula 1) In (Formula 1), x is the upper viscosity of the polyol composition at 23°C, and y is the lower viscosity of the polyol composition at 23°C.

3. The polyol composition according to claim 1, wherein, The polycarbonate polyol has a viscosity of 30,000 mPa·s or higher at 23 degrees.

4. The polyol composition according to claim 1, wherein, The polyester polyol has a viscosity of less than 20,000 mPa·s at 23 degrees.

5. The polyol composition according to claim 1, wherein, The viscosity of the polyol composition at 23 degrees is less than that of the polycarbonate polyol at 23 degrees.

6. The polyol composition according to claim 1, wherein, The polyester polyol has repeating structural units as shown in the following general formula (I). The polycarbonate polyol has repeating structural units as shown in the following general formula (II). The difference between the average number of carbon atoms of R1 in general formula (I) and the average number of carbon atoms of R3 in general formula (II) is 1.7 or less. In general formula (I), R1 is a divalent aliphatic hydrocarbon group, branched or cyclic, or aromatic hydrocarbon group with 2 or more but less than 20 carbon atoms, optionally containing heteroatoms; R2 is a divalent aliphatic hydrocarbon group, branched or cyclic, or aromatic hydrocarbon group, optionally containing heteroatoms. When multiple R1 and R2 exist, they may be the same or different from each other. In general formula (II), R3 is a divalent aliphatic hydrocarbon group, branched or cyclic hydrocarbon group, with 2 or more but less than 20 carbon atoms, which may optionally have heteroatoms. When multiple R3s exist, they may optionally be the same or different from each other.

7. The polyol composition according to claim 1 or 6, wherein, The 23-degree viscosity of the polyol composition is below 1,000,000 mPa·s.

8. The polyol composition according to claim 1 or 6, wherein it is transparent.

9. The polyol composition according to claim 1 or 6, wherein the ratio of volatile components to non-volatile components is 75% by mass or more.

10. The polyol composition according to claim 6, wherein, In the general formula (I), R1 is a divalent, straight-chain aliphatic hydrocarbon group with 2 or more but less than 10 carbon atoms, and includes at least two types.

11. The polyol composition according to claim 6, comprising at least one linear, branched or cyclic aliphatic hydrocarbon group in which the difference between the number of carbon atoms of R1 in general formula (I) and the average number of carbon atoms of R3 in general formula (II) is greater than 2.

12. The polyol composition according to claim 6, wherein, The content of the repeating structural unit shown in general formula (II) is 5% by mass or more and 95% by mass or less, relative to the total mass of the repeating structural unit shown in general formula (I) and the repeating structural unit shown in general formula (II).

13. The polyol composition according to claim 6, wherein, The content of the repeating structural unit shown in general formula (II) is 30% by mass or more and 70% by mass or less, relative to the total mass of the repeating structural unit shown in general formula (I) and the repeating structural unit shown in general formula (II).

14. The polyol composition according to claim 6, wherein, In the general formula (I), R1 is a structure derived from an aliphatic dicarboxylic acid selected from the group consisting of sebacic acid, azelaic acid, adipic acid, dimer acid, glutaric acid, succinic acid, nonamethylene dicarboxylic acid, and decamethylene dicarboxylic acid, including at least two of them.

15. The polyol composition according to claim 1 or 6, wherein the number average molecular weight is 250 or more and 10,000 or less.

16. The polyol composition according to claim 6, wherein, R3 in the general formula (II) has two or more aliphatic structures with 2 to 20 carbon atoms.

17. A polymer obtained by polymerizing the polyol composition of claim 1 or 6 with a compound having a functional group that reacts with the hydroxyl groups of the polyol composition.

18. An adhesive comprising the polymer of claim 17.

19. A coating comprising the polymer of claim 17.

20. A sealing material comprising the polymer of claim 17.

21. A synthetic leather comprising the polymer of claim 17.

Images