Polycarbonate polyol, polyurethane, adhesive, coating material, sealing material, aqueous polyurethane, aqueous dispersion composition, and synthetic leather

Abstract

Provided are: a polycarbonate polyol which is capable of providing a polyurethane having excellent heat resistance and weather resistance in which coloring due to heat or the like during the production of the polyurethane is suppressed over time; a polyurethane; an adhesive; a coating material; the present invention is characterized by having a repeating structural unit represented by formula (1) and a structural unit represented by formula (2). (In formula (1), R1 represents an arbitrary divalent aliphatic hydrocarbon group) (In formula (2), R2 represents an arbitrary monovalent aliphatic hydrocarbon group, and R3 represents an arbitrary divalent aliphatic hydrocarbon group)

Description

Technical Field

[0001] This invention relates to polycarbonate polyols, polyurethanes, adhesives, coatings, sealing materials, water-based polyurethanes, water-dispersible compositions, and synthetic leather. Background Technology

[0002] Like polyester polyols and polyether polyols, polycarbonate polyols are useful as raw materials for the manufacture of polyurethane resins, urethane acrylates, engineering plastics, adhesives, coatings, etc., when reacted with isocyanate compounds. They are also used as modifiers for polyesters. Polyurethanes and engineering plastics manufactured using polycarbonate polyols having repeating units represented by -[ORO(CO)]- (where R represents a divalent hydrocarbon group) have advantages such as excellent hydrolysis resistance, weather resistance, heat resistance, and ease of industrial manufacturing.

[0003] For example, Patent Document 1 describes a method for manufacturing polycarbonate polyols that can reduce the generation of dioxane as a byproduct during the manufacturing of polycarbonate polyols and can produce polyurethanes with excellent flexibility, mechanical strength, and solvent resistance.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2024-003246 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] However, the polycarbonate polyols disclosed in Patent Document 1 sometimes become colored when heated during the manufacture of polyurethane. Furthermore, there are further issues regarding the coloring of the resulting polyurethane after weathering tests.

[0009] The present invention was made in view of the aforementioned problems. Specifically, an object of the present invention is to provide polycarbonate polyols, etc., which can provide, for example, polyurethanes with excellent heat resistance and weather resistance, where coloring caused by heat during polyurethane manufacturing is suppressed over time. Another object of the present invention is to provide polyurethanes with excellent weather resistance (heat resistance) and suppressed coloring, adhesives, coatings, sealing materials, water-based polyurethanes, water-dispersible compositions, and synthetic leather, etc.

[0010] Solution for solving the problem

[0011] The inventors conducted in-depth research on the aforementioned issues. As a result, they developed a new polycarbonate polyol with a specific structure having olefinic unsaturated bonds, and discovered that the aforementioned issues could be resolved by using this polycarbonate polyol, thus completing the present invention.

[0012] That is, the present invention provides various specific methods as shown below.

[0013] <1>

[0014] A polycarbonate polyol, characterized in that it has repeating structural units as shown in formula (1) and structural units as shown in formula (2).

[0015]

[0016] (In formula (1), R1 is any divalent aliphatic hydrocarbon group.)

[0017]

[0018] (In formula (2), R2 is any monovalent aliphatic hydrocarbon group, and R3 is any divalent aliphatic hydrocarbon group.)

[0019] <2>

[0020] according to <1> The polycarbonate polyol wherein the content of the structural unit shown in the aforementioned formula (2) is 0.001ppm to 30,000ppm.

[0021] <3>

[0022] according to <1> The polycarbonate polyols mentioned above contain a content of 5 ppm to 170 ppm of the structural unit shown in the aforementioned formula (2).

[0023] <4>

[0024] according to <1> ~ <3> The polycarbonate polyol in any one of the above-mentioned formulas (1) has a structural unit as shown in formula (11) formed by bonding the repeating structural unit shown in formula (1) to the structural unit shown in formula (2).

[0025]

[0026] (In formula (11), R1 is any divalent aliphatic hydrocarbon group, R2 is any monovalent aliphatic hydrocarbon group, and R3 is any divalent aliphatic hydrocarbon group.)

[0027] <5>

[0028] according to <1> ~ <4> The polycarbonate polyol described in any one of the above statements also has the structural unit shown in the following formula (3).

[0029]

[0030] (In formula (3), R5 is any divalent aliphatic hydrocarbon group, and R4 is an aliphatic hydrocarbon group with 1 to 12 carbon atoms.)

[0031] <6>

[0032] according to <5> The polycarbonate polyol wherein the mass ratio of the structural unit shown in the aforementioned formula (2) to the sum of the structural unit shown in the aforementioned formula (2) and R4 in the aforementioned formula (3) is 0.000001~0.20.

[0033] <7>

[0034] according to <1> ~ <6> The polycarbonate polyol described in any one of the above has a terminal hydroxyl purity of 90 mol% to 98 mol%.

[0035] <8>

[0036] according to <1> ~ <7> The polycarbonate polyol in any one of the above-mentioned formula (1) comprises two or more repeating structural units of formula (1) with different R1.

[0037] <9>

[0038] according to <1> ~ <7> The polycarbonate polyol in any one of the above-mentioned formula (1) comprises two or more aliphatic structures with 2 to 20 carbon atoms, different from the aforementioned R1.

[0039] <10>

[0040] according to <9> The polycarbonate polyol, wherein in the aforementioned formula (1), the ratio of the two aliphatic hydrocarbon groups of R1 is 0.1 to 0.9.

[0041] <11>

[0042] according to <1> ~ <7> The polycarbonate polyol mentioned in any one of the following statements, wherein,

[0043] The repeating structural unit shown in the aforementioned formula (1) includes an aliphatic structure with 5 carbon atoms in R1 and an aliphatic structure with 6 carbon atoms in R1.

[0044] The content of the structural unit shown in the aforementioned formula (2) is 5ppm to 170ppm.

[0045] <12>

[0046] according to <1> ~ <11> The polycarbonate polyol described in any one of the following has a number average molecular weight of 300 or more and 5000 or less.

[0047] <13>

[0048] according to <1> ~ <12> The polycarbonate polyol mentioned in any one of the above has a hydroxyl value of 20 mg KOH / g to 700 mg KOH / g.

[0049] <14>

[0050] according to <1> ~ <13> The polycarbonate polyol mentioned in any one of the following statements, wherein,

[0051] The structural unit shown in the aforementioned formula (2) is derived from the structure of unsaturated monohydroxy alcohols with 4 to 9 carbon atoms.

[0052] <15>

[0053] A polyol composition comprising: <1> ~ <14> The polycarbonate polyol mentioned in any one of the above statements is a polyol compound having an ester structure and / or an ether structure.

[0054] <16>

[0055] according to <15> The polyol composition wherein the molar ratio of the aforementioned polycarbonate polyol to the total of the polycarbonate structure, ester structure and ether structure contained in the aforementioned polyol compound having an ester structure and / or an ether structure is in the range of 20:80 to 80:20.

[0056] <17>

[0057] according to <15> The polyol composition wherein the molar ratio of the aforementioned polycarbonate polyol to the total of the polycarbonate structure, ester structure and ether structure contained in the aforementioned polyol compound having an ester structure and / or an ether structure is in the range of 30:70 to 75:25.

[0058] <18>

[0059] A polyurethane, which is <1> ~ <14> The polycarbonate polyol or any one of the above <15> ~ <17> The polymer of any one of the polyol compositions and the isocyanate compound.

[0060] <19>

[0061] An adhesive comprising <18> The polyurethane mentioned above.

[0062] <20>

[0063] A coating comprising <18> The polyurethane mentioned above.

[0064] <21>

[0065] A sealing material comprising <18> The polyurethane mentioned above.

[0066] <22>

[0067] A water-based polyurethane, which uses <1> ~ <14> The polycarbonate polyol or any one of the above <15> ~ <17> The polyol composition obtained from any one of the above.

[0068] <23>

[0069] An aqueous dispersion composition, which is used <1> ~ <14> The polycarbonate polyol or any one of the above <15> ~ <17> The polyol composition obtained from any one of the above.

[0070] <24>

[0071] A type of synthetic leather, which is made using <1> ~ <14> The polycarbonate polyol or any one of the above <15> ~ <17> The polyol composition obtained from any one of the above.

[0072] <25>

[0073] An automotive interior material comprising <24> The aforementioned synthetic leather.

[0074] <26>

[0075] A sort of <1> The method for manufacturing the polycarbonate polyol includes:

[0076] In a polyol having the repeating structural unit shown in formula (1) above, a hydroxyl compound containing an unsaturated bond having the structural unit shown in formula (2) above is added.

[0077] The reaction is carried out under normal or reduced pressure at 120°C to 180°C by heating and stirring.

[0078] The effects of the invention

[0079] According to the present invention, polycarbonate polyols and the like can be provided, which can provide, for example, polyurethanes with excellent heat resistance and weather resistance, where coloring caused by heat during the manufacture of polyurethanes is suppressed over time. Furthermore, by using the polycarbonate polyols of the present invention, polyurethanes with excellent heat resistance and weather resistance and suppressed coloring, adhesives, coatings, sealing materials, water-based polyurethanes, water-dispersible compositions, and synthetic leathers can also be provided. Detailed Implementation

[0080] The following describes in detail the method for implementing the present invention (hereinafter referred to as "this embodiment"). It should be noted that the present invention is not limited to the following embodiment, and can be implemented in various modifications within its scope.

[0081] It should be noted that when describing the general formulas of compounds used in this specification, unless otherwise specified in the specification, the definitions according to the Nomenclature rule as defined in IUPAC shall be used, and conventional names may be used in the names of specific groups and example compounds. Furthermore, in this specification, the number of atoms, the number of substituents, and the total number of atoms are all expressed as integers.

[0082] [Polycarbonate polyols]

[0083] The polycarbonate polyol of this embodiment is characterized by having repeating structural units as shown in formula (1) and structural units as shown in formula (2).

[0084]

[0085] (In formula (1), R1 is any divalent aliphatic hydrocarbon group.)

[0086]

[0087] (In formula (2), R2 is any monovalent aliphatic hydrocarbon group, and R3 is any divalent aliphatic hydrocarbon group.)

[0088] The polycarbonate polyol of this embodiment possesses a specific structure with olefinic unsaturated bonds as described above, thereby suppressing the coloring of the polycarbonate polyol and the sharp increase in viscosity during polyurethane manufacturing. Furthermore, by using the polycarbonate polyol of this embodiment, polyurethane with excellent mechanical properties such as tensile strength, elongation at break, scratch resistance, adhesion, heat resistance, and weather resistance can be obtained.

[0089] <The repeating structural unit shown in equation (1)>

[0090] The polycarbonate polyol of this embodiment has a repeating structural unit as shown in formula (1) above. In formula (1) above, R1 is not particularly limited as long as it is any divalent aliphatic hydrocarbon group, for example, it can be a divalent linear, branched or cyclic aliphatic hydrocarbon group with 2 or more and 20 or less carbon atoms containing heteroatoms. R1 can be any of linear, branched or alicyclic, preferably linear or branched. In addition, the number of carbon atoms in the aliphatic hydrocarbon group of R1 is more preferably 2 to 12, further preferably 2 to 10, and particularly preferably 2 to 6. By keeping the number of carbon atoms in the aliphatic hydrocarbon group of R1 within the preferred range, the chemical resistance, tensile strength and other mechanical strength of the obtained polyurethane tend to be improved.

[0091] Furthermore, when the polycarbonate polyol of this embodiment has two or more repeating structural units shown in the above formula (1) with different R1, R1 preferably has two or more aliphatic structures with 2 to 20 carbon atoms. When there are two or more R1, the resulting polycarbonate polyol has a low viscosity, which not only improves the production rate of polyurethane, but also tends to improve the elongation, softness and scratch resistance of the resulting polyurethane, so it is preferred. Furthermore, for example, when used as an adhesive composition, it tends to have excellent adhesive strength and retention rate after a damp heat resistance test (the conditions of the damp heat resistance test are not limited, for example, under the conditions of 85°C and 85% humidity), so it is preferred. As the second type of R1, aliphatic hydrocarbon groups with 2 or more and 10 or less carbon atoms are more preferred, and aliphatic hydrocarbon groups with 2 or more and 6 or less carbon atoms are even more preferred. From the perspective of the excellent strength and elongation of polyurethane, the aliphatic hydrocarbon group of R1 is preferably selected from two or more aliphatic hydrocarbon groups with 3 or more and 7 or fewer carbon atoms, and more preferably from two or more aliphatic hydrocarbon groups with 3 or more and 6 or fewer carbon atoms. Specifically, combinations of carbon atoms in the selected aliphatic hydrocarbon groups are particularly preferred, including combinations of 3 and 4, 3 and 5, 3 and 6, 4 and 5, 4 and 6, and 5 and 6. From the perspective of excellent flexibility, the aliphatic hydrocarbon group of R1 is preferably selected from two or more aliphatic hydrocarbon groups with 6 or more and 10 or fewer carbon atoms, and more preferably from two or more aliphatic hydrocarbon groups with 8 or more and 10 or fewer carbon atoms.

[0092] When using two aliphatic hydrocarbon groups as R1, their ratio can be appropriately set according to the desired performance, without particular limitation. From the viewpoint of obtaining a polycarbonate polyol with low viscosity, it is preferable to set the amount added in the range of 0.01 to 0.99, based on the molar ratio of the first type of R1 to the second type of R2. More preferably, it is 0.05 to 0.95, further preferably 0.1 to 0.9, particularly preferably 0.2 to 0.8, and most preferably 0.3 to 0.7. By being within the above-preferred range, the resulting polycarbonate diol has a lower viscosity and excellent processability. There is a tendency for the polyurethane using the obtained polycarbonate diol to further improve its flexibility, tensile strength, and other mechanical strength, and there is a tendency for the adhesive strength of the obtained adhesive composition to further improve.

[0093] In one manner, the overall structure of the repeating structural unit shown in equation (1) above can be formed by transesterification of carbonate with a hydroxyl compound. Specific examples of transesterification reactions and the carbonate as the raw material for the carbonate skeleton will be described later.

[0094] In one embodiment, R1 of the polycarbonate polyol can be formed from an aliphatic diol. Examples of aliphatic diol raw materials in this case 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, 1,14-tetradecanediol, and other diols without side chains; 2-methyl-1,8-octanediol, 2-ethyl-1... Diols with side chains, such as 6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethyl-1,3-propanediol; and cyclic diols, such as 1,4-cyclohexanediol and 2-bis(4-hydroxycyclohexyl)propane, are used, but are not particularly limited to these. They can be used alone or in combination of two or more. From the viewpoints of productivity, elongation, flexibility, abrasion resistance, chemical resistance, and mechanical strength of the obtained polyurethane, the use of two or more aliphatic diol raw materials is preferred. Examples of preferred aliphatic diol raw materials include 1,3-propanediol (PnDO), 1,4-butanediol (BDO), 1,5-pentanediol (PDO), 1,6-hexanediol (HDO), 1,7-heptanediol (HeDO), 1,8-octanediol (ODO), 1,9-nonanediol (NDO), 1,10-decanediol (DDO), 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol. Among these, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol are more preferred.

[0095] It should be noted that, within the range that does not excessively impair the performance of the polycarbonate polyol of this embodiment, the structure derived from alcohol other than R1 mentioned above can have a structure derived from a polyfunctional compound having three or more hydroxyl groups in one molecule, such as trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, bis(trimethylol)propane, dipentaerythritol, etc. By having a structure derived from a polyfunctional compound, the crosslinking density of the obtained polyurethane is improved, and the mechanical properties such as chemical resistance, coating hardness, scratch resistance, and stress resistance are improved. The valence of the polyfunctional compound is preferably 3 or more and 8 or less, more preferably 3 or more and 6 or less, and even more preferably 3 or more and 4 or less. Here, if too many polyfunctional compounds having three or more hydroxyl groups in one molecule are used, crosslinking may sometimes occur during the polymerization reaction of the polycarbonate polyol, causing gelation. Therefore, when using a polyfunctional compound having three or more hydroxyl groups in one molecule as a raw material, the proportion of the polyfunctional compound having three or more hydroxyl groups in one molecule is preferably 0.01% by mass or more and 20% by mass or less relative to the total amount of the raw material diol that forms R1, more preferably 0.01% by mass or more and 10% by mass or less, and even more preferably 0.1% by mass or more and 5% by mass or less.

[0096] <Structural unit shown in equation (2)>

[0097] The polycarbonate polyol of this embodiment has the structural unit shown in formula (2) above. In formula (2) above, R2 is not particularly limited as long as it is any monovalent aliphatic hydrocarbon group, for example, it can be a straight-chain, branched or cyclic monovalent aliphatic hydrocarbon group with 1 or more and 10 or less carbon atoms having heteroatoms. R2 can be any of straight-chain, branched or alicyclic, preferably straight-chain or branched. In addition, the number of carbon atoms of the aliphatic hydrocarbon group of R2 is more preferably 1 or more and 6 or less, further preferably 1 or more and 3 or less, particularly preferably 1 or more and 2 or less, and most preferably 1. In formula (2) above, R3 is not particularly limited as long as it is any divalent aliphatic hydrocarbon group, for example, it can be a straight-chain, branched or cyclic divalent aliphatic hydrocarbon group with 1 or more and 10 or less carbon atoms having heteroatoms. R3 can be any of straight-chain, branched or alicyclic, preferably straight-chain or branched. Furthermore, the number of carbon atoms in R3 is more preferably 1 or more and 6 or less, even more preferably 1 or more and 4 or less, and particularly preferably 1 or more and 3 or less. Within the above-mentioned preferred range, the resulting polycarbonate diol exhibits superior heat resistance, and there is a tendency for the heat resistance and weather resistance of polyurethanes using the obtained polycarbonate diol to be further improved.

[0098] Furthermore, as the overall structure of the above formula (2), it is preferable to include the portion of a monohydroxy compound with 4 or more but less than 12 carbon atoms and having an internal olefinic unsaturated bond after removing the hydroxyl group; more preferably, the hydroxyl group is not directly bonded to the unsaturated bond. Additionally, this hydroxyl group is preferably a primary hydroxyl group or a secondary hydroxyl group, more preferably a primary hydroxyl group. The structural unit shown in the above formula (2) is preferably derived from an unsaturated monohydroxy alcohol with 4 to 12 carbon atoms, preferably 4 to 9 carbon atoms.

[0099] In one manner, the structural unit of the polycarbonate polyol of this embodiment, as shown in formula (2) above, may be formed from an unsaturated aliphatic monohydric alcohol. Examples of unsaturated aliphatic monohydric alcohol raw materials at this time include 2-buten-1-ol, 2-penten-1-ol, 3-penten-1-ol, 3-methyl-2-penten-1-ol, 3-methyl-3-penten-1-ol, 2-hexen-1-ol, 3-hexen-1-ol, 4-hexen-1-ol, 2-hepten-1-ol, 3-hepten-1-ol, 4-hepten-1-ol, 5-hepten-1-ol, 2-octen-1-ol, 3-octen-1-ol, 4-octen-1-ol, 5-octen-1-ol, 6-octen-1-ol, 2-nonen-1-ol, 3-nonen-1-ol, 4-nonen-1-ol, 5-nonen-1-ol, 6-nonen-1-ol, 7-nonen-1-ol, 2-decen-1-ol, 3- Decen-1-ol, 4-decen-1-ol, 5-decen-1-ol, 6-decen-1-ol, 7-decen-1-ol, 8-decen-1-ol, 2-undecen-1-ol, 3-undecen-1-ol, 4-undecen-1-ol, 5-undecen-1-ol, 6-undecen-1-ol, 7-undecen-1-ol, 8-undecen-1-ol, 9-undecen-1-ol, 2-dodecen-1-ol, 3-dodecen-1-ol, 4-dodecen-1-ol, 5-dodecen-1-ol, 6-dodecen-1-ol, 7-dodecen-1-ol, 8-dodecen-1-ol, 9-dodecen-1-ol, 10-dodecen-1-ol, etc., but not specifically limited to these. They can be used alone or in combination of two or more.

[0100] (The content of the structural units shown in equation (2))

[0101] The content of the structural unit shown in formula (2) in the polycarbonate polyol of this embodiment can be appropriately set according to the desired performance and is not particularly limited. Measured by the amount of alcohol forming the structural unit shown in formula (2) relative to 100% by mass of the total polycarbonate polyol, it is preferably 0.001 ppm or more and 30,000 ppm or less, more preferably 1 ppm or more and 30,000 ppm or less, further preferably 10 ppm or more and 20,000 ppm or less, particularly preferably 100 ppm or more and 10,000 ppm or less, especially more preferably 200 ppm or more and 5,000 ppm or less, more preferably 500 ppm or more and 3,000 ppm or less, particularly preferably 5 ppm or more and 170 ppm or less, and most preferably 40 ppm or more and 100 ppm or less. Within this preferred numerical range, the resulting polycarbonate polyol tends to be more difficult to color during manufacturing, and coloring at temperatures above 150°C is further suppressed. Furthermore, the coloring of the resulting polyurethane is suppressed, and there is a tendency for increased light stability.

[0102] (Purity of terminal hydroxyl groups)

[0103] In the polycarbonate polyol of this embodiment, the amount of terminal hydroxyl groups relative to all terminal groups (terminal hydroxyl purity) can be appropriately set according to the desired performance, and is not particularly limited, but preferably 90 mol% or more, more preferably 92 mol% or more, and even more preferably 94 mol% or more. The terminal hydroxyl purity can be 100 mol% or less, preferably 99 mol% or less, and more preferably 98 mol% or less. Within this preferred numerical range, there is a tendency to easily form coating compositions with better drying properties, and coating films and / or polyurethanes with better durability.

[0104] It should be noted that the total number of terminal groups in polycarbonate polyols is the value calculated using the following formula based on the average number of functional groups (F) and number-average molecular weight (Mn) of polycarbonate polyols using W (g).

[0105] Total number of terminal groups = W / Mn F

[0106] As a method to control the amount of hydroxyl groups in all the terminal groups of the polycarbonate polyol of this embodiment within the above-mentioned range, for example, there is a method of adding a monohydric alcohol and performing heat treatment. The amount of monohydric alcohol added can be calculated based on the purity of the terminal hydroxyl groups in the polycarbonate diol before heat treatment, the hydroxyl value, the amount of polycarbonate diol treated, and the molecular weight of the monohydric alcohol added during heat treatment.

[0107] The polycarbonate polyol of this embodiment preferably has a structural unit as shown in the following formula (11) formed by bonding the repeating structural unit shown in formula (1) above with the structural unit shown in formula (2) above.

[0108]

[0109] (In formula (11), R1 is any divalent aliphatic hydrocarbon group, R2 is any monovalent aliphatic hydrocarbon group, and R3 is any divalent aliphatic hydrocarbon group, which have the same meaning as R1~R3 ​​in formula (1) and formula (2) above.)

[0110] In the polycarbonate polyol of this embodiment, terminal groups other than hydroxyl groups may be present. There are no particular limitations on the terminal groups other than hydroxyl groups, and examples include alkyl, vinyl, and aryl groups.

[0111] It should be noted that, in this embodiment, the amount of hydroxyl groups in the terminal groups can be determined using the methods described in the examples described later.

[0112] <Structural unit shown in equation (3)>

[0113] The polycarbonate polyol of this embodiment may also have the structural unit shown in the following formula (3).

[0114]

[0115] (In formula (3), R5 is any divalent aliphatic hydrocarbon group, and R4 is an aliphatic hydrocarbon group with 1 to 12 carbon atoms.)

[0116] In order to adjust the amount of terminal hydroxyl groups (terminal hydroxyl purity) to the aforementioned range, the polycarbonate polyol of this embodiment preferably also has the structural unit shown in formula (3) above. The structural unit shown in formula (3) is not particularly limited, and can be formed, for example, by transesterification reaction of a monohydroxy compound without unsaturated bonds with a carbonate as described later. By adjusting the amount of terminal hydroxyl groups (terminal hydroxyl purity) to the aforementioned range using the structural unit shown in formula (3), it is possible to suppress the sharp increase in viscosity of the polyurethane obtained by reacting with isocyanate without excessively impairing the effect of this embodiment, and there is a tendency to obtain a polyurethane with excellent durability. In the above formula (3), R4 is any aliphatic hydrocarbon group with 1 to 12 carbon atoms, more preferably 1 or more and 6 or less, further preferably 1 or more and 3 or less, particularly preferably 1 or more and 2 or less, and most preferably 1.

[0117] The hydroxyl compounds without unsaturated bonds used herein are not particularly limited, and examples include saturated primary alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isoamyl alcohol, isodecanol, 2-ethyl-1-hexanol, 1-nonanol, 1-octanol, and 1-decanol; saturated secondary alcohols such as isopropanol, cyclohexanol, and cyclopentanol; and saturated tertiary alcohols such as tert-butanol; etc., but are not particularly limited to these. Among these, saturated primary alcohols are more reactive than other alcohols, and therefore are preferred as monohydric alcohols used herein.

[0118] In formula (3) above, R5 is not particularly limited to any divalent aliphatic hydrocarbon group, such as a divalent linear, branched, or cyclic aliphatic hydrocarbon group containing 2 or more but less than 20 carbon atoms. R5 can be any of linear, branched, or alicyclic, preferably linear or branched. Furthermore, the number of carbon atoms in the aliphatic hydrocarbon group of R5 is more preferably 2 to 12, further preferably 2 to 10, and particularly preferably 2 to 6.

[0119] (The mass ratio of the structural unit shown in Equation (2) to the sum of the structural unit shown in Equation (2) and R4 in Equation (3))

[0120] In one embodiment, the mass ratio of the structural unit shown in formula (2) to the sum of the structural unit shown in formula (2) and R4 in formula (3), calculated as the ratio of the amount of alcohol forming the structural unit shown in formula (2) to the amount of alcohol forming the structure of R4 in formula (3), is preferably 0.000001 or more, more preferably 0.000001 or more and 0.20 or less, even more preferably 0.00001 or more and 0.10 or less, particularly preferably 0.00003 or more and 0.05 or less, and most preferably 0.00005 or more and 0.01 or less. Within the above-preferred range, the resulting polycarbonate diol exhibits superior heat resistance, further suppresses the sharp increase in viscosity of the polyurethane obtained by reacting with isocyanate, and tends to further improve the heat resistance, weather resistance, and durability of the obtained polyurethane.

[0121] It should be noted that, in addition to the repeating structural unit shown in formula (1), the structural unit shown in formula (2), and the structural unit shown in formula (3) as needed, the polycarbonate polyol of this embodiment may also include other structures. For example, the polycarbonate polyol of this embodiment may also include ester structures, ether structures, etc.

[0122] [Manufacturing method of polycarbonate polyols]

[0123] The method for manufacturing the polycarbonate polyol of this embodiment can be carried out by any method known in the art, as long as a polycarbonate polyol having the above-described structure can be obtained, and is not particularly limited. For example, it can be manufactured by polymerizing a hydroxyl compound (e.g., a polyfunctional diol) with a carbonate compound (e.g., carbonate) using a transesterification reaction. For example, it can be synthesized by the transesterification reaction described in "Polymer Reviews Vol. 9, pp. 9-20". In addition, as for the method of introducing the structure of the above formula (2), it is not particularly limited as long as a substance having the above-described structure can be obtained. For example, it can be manufactured by adding a hydroxyl compound containing an unsaturated bond to a polycarbonate diol and performing transesterification by heating.

[0124] The transesterification reaction in the method for producing polycarbonate polyols according to this embodiment can be carried out, for example, in the presence or absence of a catalyst. From the viewpoint of reaction efficiency, synthesis in the presence of a catalyst is preferred. Specific examples of the method for producing polycarbonate polyols according to this embodiment are shown below.

[0125] The following illustrates one method for manufacturing the polycarbonate polyol according to this embodiment. The manufacturing of the polycarbonate polyol according to this embodiment is not particularly limited; for example, the transesterification reaction can be carried out in two stages according to the following steps.

[0126] Specifically, a hydroxyl compound and a carbonate compound are mixed in a molar ratio (hydroxyl compound: carbonate compound), for example, 20:1 to 1:10, and an ester exchange catalyst is added as needed. The first stage reaction is carried out under normal or reduced pressure at 100 to 250°C. For example, when dimethyl carbonate is used as the carbonate compound, the generated methanol can be removed as a mixture with dimethyl carbonate to obtain low molecular weight polycarbonate diol. At this time, the alcohol from the carbonate (carbonate) generated in the reaction is removed by distillation. For example, when diethyl carbonate is used as the carbonate compound, the generated ethanol can be removed as a mixture with diethyl carbonate to obtain low molecular weight polycarbonate diol. Alternatively, for example, when ethylene carbonate is used as the carbonate compound, the generated ethylene glycol can be removed as a mixture with ethylene carbonate to obtain low molecular weight polycarbonate diol. Next, as the second stage of the reaction, the reaction product of the first stage can be heated under reduced pressure at 120~250°C to remove unreacted diols and carbonates, and to condense low molecular weight polycarbonate diols to obtain polycarbonate diols of a specified molecular weight.

[0127] Furthermore, by adding hydroxyl compounds with a different backbone to the obtained polycarbonate diol, and adding an ester exchange catalyst as needed, the reaction can be carried out under normal or reduced pressure at 100–250 °C, thereby further introducing different structures. If necessary, low-boiling-point hydroxyl compounds can be removed by heating under reduced pressure at 120–250 °C, and low molecular weight polycarbonate diols can be condensed to obtain polycarbonate diols of a specified molecular weight.

[0128] (Example of the method for importing the structural unit shown in equation (2))

[0129] The purity and hydroxyl value of the terminal hydroxyl groups of the obtained polycarbonate polyol can be determined. A hydroxyl compound with an unsaturated bond having the skeleton of formula (2) is added to it, and an ester exchange catalyst is added as needed. The reaction is carried out under normal or reduced pressure at 120°C to 180°C by heating and stirring. The preferred reaction temperature is 130°C to 160°C. By heating the temperature above 120°C, the reaction tends to proceed rapidly, the processing time can be shortened, and it becomes economically advantageous. By heating the temperature below 180°C, the reflux of the low-boiling-point monohydric alcohol can be appropriately controlled, and the concentration in the reaction solution can be maintained, thus the reaction tends to proceed rapidly. The heating treatment time varies depending on the reaction temperature and the treatment method, and is usually 15 minutes to 10 hours. Furthermore, the low-boiling-point hydroxyl compound can be removed by heating under reduced pressure at 120 to 180°C after adding a deactivating agent as needed.

[0130] (Removal of residual hydroxyl compounds)

[0131] Furthermore, the residual monohydric alcohol from the reaction of polycarbonate polyol with monohydric alcohol, and the hydroxyl compounds from the raw material of polycarbonate polyol produced as a byproduct of transesterification, are preferably removed by adding a deactivating agent as needed, followed by heating at 120-180°C under reduced pressure. The amount of these residual hydroxyl compounds relative to the polycarbonate polyol is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 6% by mass or less. By keeping the residual hydroxyl compounds within this range, the polyurethane obtained using the polycarbonate polyol tends to exhibit excellent tensile strength, flexibility, chemical resistance, and heat resistance.

[0132] (carbonate compounds)

[0133] The carbonate compounds used as raw materials in the method for manufacturing polycarbonate polyols according to 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, trimethylol carbonate, 1,2-propylene carbonate, 1,2-butyl carbonate, 1,3-butyl carbonate, and 1,2-pentane carbonate. One or more of these compounds may be used alone or in combination. From the viewpoint of ease of acquisition and ease of setting polymerization reaction conditions, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate, and ethylene carbonate are preferably used as raw material carbonates.

[0134] (Transesterification catalyst)

[0135] The transesterification catalyst used in the method for manufacturing polycarbonate polyols according to this embodiment is not particularly limited. Examples include alkali metals such as lithium, sodium, and potassium, and alkaline earth metals such as magnesium, calcium, strontium, and barium, as well as their alkali metal salts, hydrides, oxides, amides, carbonates, hydroxides, nitrogen-containing borates, and further, basic alkali metal salts and alkaline earth metal salts of organic acids. Furthermore, the aforementioned catalyst is not particularly limited. Examples include metals such as aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, indium, tin, antimony, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth, and ytterbium, their metal salts, their metal alkoxides, and organic compounds containing the metal. One or more of these can be used alone or, appropriately, two or more. Among these, the polymerization of polycarbonate polyols proceeds well when one or more catalysts are used, such as those from metals like sodium, potassium, magnesium, titanium, zirconium, tin, lead, ytterbium, their metal salts, their metal alkoxides, or organic compounds containing the metal. The reaction of the resulting polycarbonate polyol with the catalyst also has minimal impact, and is therefore preferred. It is even more preferred to use metals like titanium, ytterbium, tin, zirconium, magnesium, their metal salts, their metal alkoxides, or organic compounds containing the metal as the aforementioned catalyst.

[0136] Here, the polycarbonate polyol may contain a catalyst comprising the aforementioned metal element. The amount of residual catalyst in the polycarbonate polyol is not particularly limited, but based on the content of the metal element (catalyst metal equivalent) measured using ICP (Inductively Coupled Plasma) analysis, the lower limit is preferably 0.00001% by mass or more, more preferably 0.00005% by mass or more, further preferably 0.0001% by mass or more, and particularly preferably 0.0005% by mass or more. Furthermore, the upper limit is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, further preferably 0.03% by mass or less, particularly preferably 0.02% by mass or less, even more preferably 0.015% by mass or less, especially more preferably 0.01% by mass or less, and most preferably 0.005% by mass or less.

[0137] It should be noted that if the transesterification catalyst used in the transesterification reaction is subjected to heat treatment immediately after the production of the polycarbonate polyol, it is not consumed by the transesterification reaction; therefore, its content can be calculated based on the amount of transesterification catalyst used. When using commercially available polycarbonate diols, the amount of metal in the transesterification catalyst contained in the polycarbonate diol can be determined by ICP (Inductively Coupled Plasma) method. Furthermore, for the polycarbonate diol used in its production, catalyst poisons such as neutralizing agents, such as organic acids, can be added to deactivate the transesterification catalyst used during its production.

[0138] (Neutralizing agent)

[0139] Examples of neutralizing agents include inorganic acids such as phosphoric acid and hydrochloric acid, organic acids having sulfonic acid groups or aminosulfonic acid groups, and their esters and acyl halides, but these are not particularly limited. They can be used alone or, appropriately, in combination with two or more. Among these, phosphorus compounds such as phosphoric acid, phosphate esters, phosphorous acid, and phosphite esters are preferred from the viewpoint of ease of operation.

[0140] The ratio of the neutralizing agent to the polycarbonate polyol can be appropriately set without particular limitation, but is preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.1% by mass. When the amount of neutralizing agent added is lower than the lower limit of the above-mentioned preferred numerical range, the turbidity and color index of the obtained polycarbonate polyol tend to increase; when it exceeds the upper limit, the reactivity of the polycarbonate polyol tends to slow down. In addition, the equivalent amount of the neutralizing agent relative to the transesterification catalyst can be appropriately set without particular limitation, but is preferably 0.1 or more and 50 or less, more preferably 0.3 or more and 25 or less, further preferably 0.5 or more and 10 or less, and particularly preferably 0.8 or more and 5 or less. If the amount of neutralizing agent is too small relative to the transesterification catalyst, side reactions such as gelation cannot be sufficiently suppressed; if the amount is too large relative to the transesterification catalyst, the turbidity and color index tend to increase.

[0141] (Number average molecular weight)

[0142] The number-average molecular weight (Mn) of the polycarbonate polyol in this embodiment is not particularly limited, but is preferably 300 or more and 5,000 or less. By setting the number-average molecular weight of the polycarbonate polyol to 300 or more, the resulting polyurethane tends to exhibit better low-temperature properties. By setting the number-average molecular weight of the polycarbonate polyol to 5,000 or less, when used as a component material in coatings, the concentration of solid components in the coating is not limited, and it is also easier to suppress any reduction in the processability of the resulting polyurethane. In a preferred embodiment, the number-average molecular weight of the polycarbonate polyol can be 450 or more, 500 or more, 3,000 or less, 2,500 or less, or 2,000 or less. Furthermore, a number of 1,500 or less is extremely preferred from the viewpoint of viscosity and solvent solubility of the resulting polycarbonate polyol. On the other hand, from the viewpoint of the elongation and flexibility of the obtained polyurethane, the number average molecular weight of the polycarbonate polyol is preferably 1,000 or more and 5,000 or less, more preferably 2,000 or more and 4,500 or less. It should be noted that in this embodiment, the number average molecular weight (Mn) can be measured by the method described in the examples described later.

[0143] (Melt viscosity at 50°C)

[0144] The melt viscosity of the polycarbonate polyol in this embodiment at 50°C is not particularly limited, but is preferably 500 to 200,000 mPa·s, more preferably 1,000 to 180,000 mPa·s, and even more preferably 1,500 to 165,000 mPa·s. By setting the melt viscosity at 50°C to 500 mPa·s or higher, there is a tendency to improve the stress, elongation at break, and chemical resistance of the obtained polyurethane. By setting the melt viscosity at 50°C to 180,000 mPa·s or lower, the wettability (contact efficiency) of the obtained composition with the substrate is improved, and therefore there is a tendency to easily exhibit high adhesive strength. In addition, when used as a sealant raw material, the composition is also filled into fine parts, and can exhibit high insulation reliability.

[0145] In this embodiment, the method for controlling the melt viscosity of the polycarbonate polyol at 50°C within the aforementioned range is not particularly limited; for example, methods such as adjusting the aromatic concentration and number-average molecular weight can be used. For instance, if the raw material ratio is adjusted to increase the aromatic concentration, the melt viscosity of the polycarbonate polyol tends to increase. Similarly, if the manufacturing conditions are adjusted to increase the number-average molecular weight, the melt viscosity tends to increase. It should be noted that in this embodiment, the melt viscosity can be measured using the method described in the examples described later.

[0146] (Hydroxy value)

[0147] The hydroxyl value (OH value) of the polycarbonate polyol in this embodiment is not particularly limited, but the lower limit is preferably 20 mg KOH / g or more, more preferably 30 mg KOH / g or more, further preferably 50 mg KOH / g or more, even more preferably 60 mg KOH / g or more, particularly preferably 70 mg KOH / g or more, and most preferably 74 mg KOH / g or more. Furthermore, the upper limit of the hydroxyl value (OH value) of the polycarbonate polyol in this embodiment is not particularly limited, but it is preferably 700 mg KOH / g or less, more preferably 500 mg KOH / g or less, further preferably 400 mg KOH / g or less, even more preferably 350 mg KOH / g or less, particularly preferably 300 mg KOH / g or less, and most preferably 230 mg KOH / g or less. By keeping the hydroxyl value (OH value) of the polycarbonate polyol within the aforementioned preferred range, there is a tendency to easily obtain a polycarbonate polyol with low viscosity, excellent workability, and excellent compatibility with inactive organic solvents. In addition, by using such a polycarbonate polyol, there is a tendency to improve the stress, elongation at break, and chemical resistance of the obtained polyurethane.

[0148] In this embodiment, the method for controlling the hydroxyl value of the polycarbonate polyol within the aforementioned range is not particularly limited. For example, a method that controls the hydroxyl value by adding and / or removing alcohol compounds during the manufacture of the polycarbonate polyol can be cited. It should be noted that in this embodiment, the hydroxyl value can be calculated using the method described in the examples described later.

[0149] (Compositional analysis method)

[0150] In this embodiment, the content of each structure of the polycarbonate polyol can be analyzed by hydrolyzing the polycarbonate polyol and quantifying it using gas chromatography. More specifically, the analysis can be performed using the methods described in the examples.

[0151] [Polyurethane]

[0152] The polyurethane of this embodiment is a polymer of the aforementioned polycarbonate polyol and isocyanate compound. In the method for manufacturing polyurethane using the polycarbonate polyol of this embodiment, there are no particular limitations; generally, a curing agent such as an isocyanate compound (e.g., a polyisocyanate) and a chain extender as needed are used. In the method for manufacturing polyurethane using the polycarbonate polyol of this embodiment, a mixture in which each component is mixed in one step can be used as a curable composition (hereinafter referred to as the "one-step method"). Alternatively, an isocyanate-terminated prepolymer composition obtained by reacting the polycarbonate polyol of this embodiment with an isocyanate compound in advance can be prepared, and a mixture of this isocyanate-terminated prepolymer composition and a chain extender can be used as a curable composition (hereinafter referred to as the "prepolymer method"). Here, one or more prepolymers can be used. Furthermore, a coating composition obtained by mixing the polycarbonate polyol of this embodiment, an isocyanate compound, and other polyols and organic solvents as needed can be used to manufacture a polyurethane coating.

[0153] (Isocyanate compounds)

[0154] There are no particular limitations on the isocyanate compound, but polyisocyanates are preferred. Generally, polyisocyanates with an average number of functional groups of 2 to 6 per molecule can be used. Examples of polyisocyanates include, for example, 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), polymethylene polyphenyl polyisocyanate (PMDI), and other aromatic diisocyanates; phenyl dimethylene diisocyanate (XDI), phenyl diisocyanate, and other aromatic aliphatic diisocyanates; 4,4'-methylene dicyclohexyl diisocyanate (hydrogenated (also known as hydrogenated) MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), cyclohexane diisocyanate (hydrogenated XDI), and other aliphatic diisocyanates; etc., but are not particularly limited to these. As a polyisocyanate, for example, a so-called capped isocyanate can be formed by capping the isocyanate group with a known capping agent such as butanol, 2-ethylhexanol, methyl ethyl ketone oxime, lactams, phenols, imidazoles, or active methylene compounds.

[0155] As a polyisocyanate, a polyisocyanate having an average of 2.1 or more isocyanate groups per molecule can also be used. Among the polyisocyanates having an average of 2.1 or more isocyanate groups per molecule, 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 adduct types can also be used. In addition, commercially available isocyanates include, for example, 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 Durnate products manufactured by Asahi Kasei Corporation, namely Durnate 24A-100, Durnate 22A-75PX, Durnate 18H-70B, Durnate 21S-75E, Durnate THA-100, Durnate TPA-100, Durnate TKA-100, Durnate TLA-100, Durnate TUL-100, Durnate MFA-75X, Durnate TSA-100, Durnate TSS-100, Durnate TSE-100, Durnate D-101, Durnate D-201, and Durnate... Duranate ME20-B80S, Duranate WB40-100, Duranate WB40-80D, Duranate WT20-100, Duranate WT30-100, etc.

[0156] Among these, aromatic polyisocyanates such as MDI are preferred as polyisocyanates. Using aromatic polyisocyanates tends to readily yield polyurethanes with excellent mechanical properties. Furthermore, if aliphatic polyisocyanates such as hydrogenated MDI are used in the curing composition, synthetic leather with excellent weather resistance can be easily obtained from this curing composition. Therefore, aliphatic polyisocyanates are suitable for use in curing compositions for synthetic leather, such as those for the outer layer.

[0157] (Chain extender)

[0158] When manufacturing polyurethane using the polycarbonate polyol of this embodiment, a chain extender can be used as needed. The chain extender can improve the abrasion resistance and strength of the obtained polyurethane; however, it may sometimes reduce the flexibility of the obtained polyurethane, so it can 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; etc. 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.

[0159] The amount of chain extender added can be appropriately set according to the desired performance and is not particularly limited. Relative to the total amount of polycarbonate polyol and isocyanate compound in this embodiment, it 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 15% by mass or less. Furthermore, by using a polyol as a chain extender, the crosslinking density of the obtained polyurethane can be increased, and there is a tendency to improve strength, abrasion resistance, and chemical resistance.

[0160] The amounts of polycarbonate polyol, isocyanate compound, and chain extender in this embodiment can be appropriately set according to the desired performance and are not particularly limited. When expressed as [isocyanate equivalent of the isocyanate compound] / [total hydroxyl equivalent of the polycarbonate polyol and chain extender in this embodiment], it is preferably 0.7 to 1.3, more preferably 0.8 to 1.2, and even more preferably 0.9 to 1.1. By making this ratio 0.7 or more and 1.3 or less, the molecular weight of the obtained polyurethane can be moderately controlled, and it tends to have excellent mechanical properties such as strength, elongation, and abrasion resistance.

[0161] When manufacturing polyurethane using the polycarbonate polyol of this embodiment, a non-reactive organic solvent can be used as needed to adjust the workability during polyurethane manufacturing. The content of the non-reactive 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 a non-reactive organic solvent is effective in reducing the viscosity of the curable composition, improving its workability, and further improving the appearance of the resulting polyurethane.

[0162] (Non-reactive organic solvent)

[0163] There are no particular limitations on inactive organic solvents as long as they are substantially inactive for polyisocyanates, but preferably they do not contain active hydrogen. Examples of inactive organic solvents include hydrocarbons such as pentane, hexane, heptane, octane, decane, petroleum ether, petroleum benzine, ligroin, petroleum spirit, 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. Further examples of inactive organic solvents include methyl ethyl ketone (also referred to as MEK), acetone, N,N-dimethylformamide (DMF), ethyl acetate, butyl acetate, toluene, and xylene, either alone or in mixtures.

[0164] It should be noted that, in this specification, "active hydrogen" refers to hydrogen atoms bonded to oxygen, sulfur, nitrogen, silicon, etc., as well as hydrogen atoms in terminal methylene groups. Additionally, "active hydrogen" refers to hydrogen contained in groups such as -OH, -C(=O)OH, -C(=O)H, -SH, -SO3H, -SO2H, -SOH, -NH2, -NH-, -SiH, and -C≡CH.

[0165] When manufacturing polyurethane using the polycarbonate polyol of this embodiment, polyols other than the polycarbonate polyol of this embodiment can be used as needed. There are no particular limitations on the polyols other than the polycarbonate polyol of this embodiment; examples include other polycarbonate polyols, polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, polyacrylic acid polyols, and oil-modified polyols. The amount of polyols other than the polycarbonate polyol of this embodiment added is not particularly limited, but it 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 the polycarbonate polyol of this embodiment and the polyols other than the polycarbonate polyol of this embodiment.

[0166] Examples of polyol compounds with ester structures include polyester polyols. There are no particular limitations on the diols used as raw materials for polyester polyols; examples include ethylene glycol, diethylene 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, and 1,15-pentadecanediol, which are diols without side chains; 2-methyl-1,8-octanediol, 2-ethyl-1,6-hexanediol, and 2-methyl-1... Diols with side chains, such as 3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethyl-1,3-propanediol; cyclic diols, such as 1,4-cyclohexanediol, 2-bis(4-hydroxycyclohexyl)-propane, and 1,4-cyclohexanediol, are preferred examples. Examples of preferred diols include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol. One or more of these can be used as raw materials for polyester polyols.

[0167] There are no particular limitations on the dicarboxylic acids used as raw materials for polyester polyols. Examples include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, and sebacic acid; and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. More preferably, examples include succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid. One or more of these can be used as raw materials for polyester polyols.

[0168] Cyclic ester compounds can be used as raw materials for polyester polyols and subjected to ring-opening polymerization. There are no particular limitations on the cyclic ester compounds; examples include cyclic ester compounds with 3 to 12 carbon atoms such as β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone, γ-valerolactone, α-methyl-ε-caprolactone, β-methyl-ε-caprolactone, γ-methyl-ε-caprolactone, β,δ-dimethyl-ε-caprolactone, 3,3,5-trimethyl-ε-caprolactone, and heptanolactone (7-heptanolactone). Among these, ε-caprolactone is preferred. One or more cyclic ester compounds can be used as raw materials for polyester polyols.

[0169] Examples of polyol compounds having an ether structure include polyether polyols. There are no particular limitations on polyether polyols; examples include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, and propylene oxide-ethylene oxide copolymers.

[0170] In the polyol composition, the molar ratio of the aforementioned polycarbonate polyol to the polyol compound having the aforementioned ester and ether structures (polycarbonate structure: ester structure and / or ether structure) is not particularly limited, but is preferably in the range of 20:80 to 80:20, more preferably in the range of 30:70 to 75:35, more preferably in the range of 40:60 to 75:35, and even more preferably in the range of 45:55 to 70:30. By making the molar ratio of polycarbonate structure: ester structure and / or ether structure 20:80 or higher, the polyol composition tends to have low melt viscosity and excellent workability. By making the molar ratio of polycarbonate structure: ester structure and / or ether structure 80:20 or lower, the polyurethane obtained from this polyol composition exhibits improved resin properties such as chemical resistance, which is therefore ideal. In particular, by having an ether structure in the aforementioned ratio, the polyol composition has low melt viscosity and excellent workability, resulting in a polyurethane with excellent softness (high elongation, low stress) and resistance to damp heat, which is therefore especially preferred. Furthermore, by having an ester structure in the aforementioned ratio, the polyol composition exhibits low melt viscosity and excellent workability, resulting in polyurethane with excellent heat resistance and chemical resistance, thus making it particularly preferred. In one embodiment, the molar ratio of the polycarbonate polyol to the ester and / or ether structures contained in the aforementioned polycarbonate polyol and the polyol compound having the aforementioned ester and ether structures is preferably in the range of 30:70 to 75:25.

[0171] Carbonate repeating structures: The molar ratios of the components in ester and ether repeating structures can be based on [the following description]. 13 The integral ratio calculated by C-NMR determination is derived from the carbon molar ratio of each structure. Furthermore, polycarbonate polyol compositions can be separated into individual components using methods such as liquid chromatography, taking advantage of differences in molecular weight and polarity. In addition to the analytical methods mentioned above, identification can also be performed using NMR, IR, TOF-SIMS, etc., as needed.

[0172] <Other Additives>

[0173] When manufacturing polyurethane using the polycarbonate polyol composition of this embodiment, curing accelerators (catalysts), fillers, flame retardants, dyes, organic or inorganic pigments, release agents, flow modifiers, plasticizers, oxidation inhibitors, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, defoamers, leveling agents, thixotropic agents, colorants, foaming agents, etc., can be added according to various applications.

[0174] As curing accelerators, there are no particular limitations; examples include amines and metal catalysts. As amine-based accelerators, there are no particular limitations; examples include monoamines such as triethylamine and N,N-dimethylcyclohexylamine, diamines such as tetramethylethylenediamine, as well as triamines, cyclic amines, dimethylethanolamine, and other alkanolamines and ether amines. As metal catalysts, 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. They can be used alone or in combination of two or more.

[0175] As fillers and pigments, there are no particular limitations. Examples include woven 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. They can be used alone or in combination with two or more.

[0176] There are no particular limitations on matting agents; for example, organic micropowders and inorganic micropowders can be used. They can be used alone or in combination of two or more.

[0177] As a leveling agent, there are no particular limitations; for example, silicone, Aerosil, wax, stearate, and polysiloxanes such as BYK-331 (manufactured by BYK-Chemie GmbH) can be used. They can be used alone or in combination of two or more.

[0178] As a thixotropic agent, any thixotropic agent that has been used in the thermosetting resin composition of solder paste can be used. Specifically, there are no particular limitations on the thixotropic agent; examples include castor oil, hydrogenated castor oil, and sorbitol-based thixotropic agents. They can be used alone or in combination of two or more.

[0179] As fillers and pigments, there are no particular limitations; examples include woven fabrics, glass fibers, carbon fibers, polyamide fibers, mica, kaolin, bentonite, metal powders, azo pigments, carbon black, clay, silica, talc, gypsum, alumina white, and barium carbonate. They can be used individually or in combination with two or more.

[0180] 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-Chemie GmbH).

[0181] When manufacturing polyurethane using polycarbonate polyols or the like described in this embodiment, antioxidants, light stabilizers, heat stabilizers, and flame retardants are preferably used as additives. There are no particular limitations on antioxidants; for example, phosphorus compounds such as aliphatic, aromatic, or alkyl-substituted aromatic esters of phosphoric acid or phosphorous acid, hypophosphite derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkyl pentaerythritol diphosphite, and dialkyl bisphenol A diphosphite can be used; sulfur-containing compounds such as phenolic derivatives, especially hindered phenolic compounds, thioethers, dithioesters, mercaptobenzimidazoles, mesolepisyl thiourea, and thiodipropionates can be used; and tin compounds such as tin maleate and dibutyltin monoxide can be used. These can be used alone or in combination of two or more.

[0182] [Curing composition (polycarbonate polyol composition)]

[0183] The polycarbonate polyol composition of this embodiment can be a curable composition, which can be cured to form polyurethane.

[0184] The polycarbonate polyol composition of this embodiment can be manufactured using conventional industrial manufacturing methods.

[0185] The polycarbonate polyol composition of this embodiment can be manufactured, for example, by a method (hereinafter referred to as the "one-step method") of mixing a polycarbonate polyol with a desired inactive organic solvent and additives and reacting the mixture. Alternatively, the polycarbonate polyol composition of this embodiment can be manufactured, for example, by a method (hereinafter referred to as the "prepolymer method") of pre-preparing isocyanate-terminated prepolymers or hydroxyl-terminated prepolymers derived from polycarbonate polyols, mixing these prepolymers with isocyanates and / or polyols, and a desired inactive organic solvent and additives, and reacting the mixture. Here, one or more prepolymers may be used.

[0186] Applications of polyurethane

[0187] The polyurethane manufactured by the above method is suitable for the following applications.

[0188] [Adhesive]

[0189] The adhesive 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.

[0190] [coating]

[0191] The coating of this embodiment contains the aforementioned polyurethane. Because it contains the aforementioned polyurethane, the coating of this embodiment tends to have excellent adhesion and scratch resistance.

[0192] [Sealing material]

[0193] The sealing material of this embodiment includes the polyurethane described above. Because it includes the polyurethane, the sealing material of this embodiment tends to exhibit excellent dimensional stability and durability.

[0194] [Manufacturing of polyurethane coatings]

[0195] By mixing the polycarbonate polyol of this embodiment with a curing agent such as an isocyanate compound to prepare a coating composition (curing composition) (mixing step), applying the obtained coating composition (curing composition) (coating step), and then drying the coated coating composition (drying step), a polyurethane coating film can be obtained. By using the polycarbonate polyol of this embodiment, a polyurethane coating film with excellent chemical resistance, scratch resistance, and mechanical strength can be obtained.

[0196] (Mixed process)

[0197] The mixing process is the process of mixing polycarbonate polyols and curing agents, as well as non-reactive organic solvents, curing accelerators, other polyols and / or other additives as needed, to obtain a coating composition.

[0198] The solvent content in the coating composition can be appropriately set according to the desired performance, without particular limitation, relative to the total mass of the coating composition. For example, it can be set to 10% by mass or more and 90% by mass or less, 15% by mass or more and 70% by mass or less, or 20% by mass or more and 50% by mass or less.

[0199] As for the mixing method, there are no particular limitations. For example, the following method can be used: use a mixer or similar device to mix at a speed of 50 rpm or higher and 1000 rpm or lower for 5 minutes or more and 60 minutes or less, and then use a vacuum degassing device to perform degassing.

[0200] (Coating process)

[0201] In the method for manufacturing a polyurethane coating film according to this embodiment, the coating process is the process of coating the aforementioned coating composition.

[0202] There are no particular limitations on the coating method for the coating composition. For example, the following method can be used: after mixing the components just before coating, the mixture is applied to the substrate by spraying, rolling, brushing, etc. Alternatively, the following method can be used: premix the substances except for the hardener, add the hardener just before coating, mix it evenly, and then apply the coating.

[0203] (Drying process)

[0204] In the polyurethane coating manufacturing method of this embodiment, the drying step is a step of drying the coated coating composition to obtain the coating film.

[0205] The drying time in the drying process can be appropriately set according to the desired performance and is not particularly limited. Preferably, it is 5 to 55 minutes after coating, more preferably 10 to 50 minutes after coating, even more preferably 15 to 45 minutes after coating, and particularly preferably 20 to 30 minutes after coating. When the drying time is within the aforementioned preferred range, there is a tendency to obtain a coating film with better physical properties.

[0206] The drying temperature in the drying process can be set appropriately according to the desired performance, without particular limitation. It is preferably 40℃~200℃, more preferably 50℃~175℃, further preferably 60℃~150℃, particularly preferably 60℃~120℃, and most preferably 60℃~100℃.

[0207] There are no particular limitations on the drying method used in the drying process; for example, natural drying, forced drying, and heat drying can be cited.

[0208] The thickness of the polyurethane coating in this embodiment can be appropriately set according to the desired performance, without particular limitation. It is preferably 1μm to 100μm, more preferably 2μm to 90μm, further preferably 3μm to 80μm, particularly preferably 5μm to 50μm, and most preferably 10μm to 50μm.

[0209] [Other uses]

[0210] The polycarbonate polyol of this embodiment is suitable for the following applications.

[0211] [Aqueous Dispersion Composition]

[0212] Using the polycarbonate polyol of this embodiment, an aqueous dispersion composition can be obtained.

[0213] Waterborne polyurethane

[0214] Aqueous polyurethane can be obtained using the polycarbonate polyol of this embodiment.

[0215] [film]

[0216] The films obtained using the polycarbonate polyols of this embodiment exhibit excellent durability.

[0217] [Artificial leather, synthetic leather]

[0218] The artificial leather and synthetic leather obtained using the polycarbonate polyols of this embodiment exhibit excellent durability. Here, in this specification, "artificial leather" refers to leather with a non-woven fabric base, and "synthetic leather" refers to leather with a knitted / woven fabric base.

[0219] (Manufacturing methods for artificial leather and synthetic leather)

[0220] The method for manufacturing polyurethane using the polycarbonate polyol of this embodiment can be applied to manufacture artificial leather and even synthetic leather. There are no particular limitations on the method for manufacturing artificial leather and even synthetic leather using the polycarbonate polyol of this embodiment. Examples include: a wet method where the polyurethane manufactured using the polycarbonate polyol composition of this embodiment is coated or impregnated onto a substrate (base fabric) and then wet-cured; a dry method where the polyurethane manufactured using the polycarbonate polyol of this embodiment is coated onto release paper or a substrate (base fabric) and then dried; etc. Furthermore, as a method for manufacturing artificial leather and even synthetic leather, a transfer coating method (a type of dry method) can also be used: after coating the polyurethane manufactured using the polycarbonate polyol composition of this embodiment onto release paper to form a skin material, the polyurethane manufactured using the polycarbonate polyol of this embodiment is used as an adhesive layer on it, and then it is bonded to a substrate (base fabric) and the release paper is removed. That is, the polycarbonate polyol and curing composition of this embodiment can be used as adhesive layers for artificial leather and even synthetic leather. For polycarbonate polyols and the like in this embodiment, a dry method (transfer coating method) is suitable to suppress the amount of inactive organic solvent used.

[0221] As can be seen from the above, a preferred embodiment of the polycarbonate polyol, etc., in this embodiment is an adhesive composition. Furthermore, a preferred embodiment of the polycarbonate polyol, etc., in this embodiment is a water-based polyurethane. Moreover, a preferred embodiment of the polycarbonate polyol composition in this embodiment is a water-dispersible composition.

[0222] Polyurethane manufactured using the polycarbonate polyols of this embodiment can be used as a lamination melt adhesive, surface protectant, etc., for various films. Furthermore, aqueous polyurethanes manufactured using the polycarbonate polyols of this embodiment can be used not only for artificial leather and synthetic leather as described above, but also as coatings, coating agents, and various other materials. Moreover, artificial leather and synthetic leather obtained using the polycarbonate polyols of this embodiment can be used for automotive interior materials such as car seats, furniture such as sofas, clothing, shoes, bags, and other miscellaneous products.

[0223] It should be noted that this disclosure also provides a method for manufacturing the polycarbonate polyol of this embodiment. That is, the method for manufacturing the polycarbonate polyol of this embodiment includes the following steps: adding a hydroxyl compound containing unsaturated bonds having a structural unit shown in the aforementioned formula (2) to a polyol having a repeating structural unit shown in the aforementioned formula (1), and reacting it by heating and stirring at atmospheric pressure or reduced pressure at 120°C to 180°C.

[0224] Example

[0225] The present invention will be further described in detail below with examples and comparative examples, but the present invention is not limited to these examples as long as it does not depart from its spirit. It should be noted that, unless otherwise specified, "%" refers to "mass %", "ppb" refers to "mass ppb", and "ppm" refers to "mass ppm". Furthermore, in the following examples and comparative examples, the methods for analyzing and evaluating the physical properties of each component are as described below. Regarding the analytical peripheral equipment, equipment with equivalent performance can be used.

[0226] Number-average molecular weight of polycarbonate polyols

[0227] The number-average molecular weight (Mn) of polycarbonate polyols was determined by gel permeation chromatography (GPC) analysis using a standard curve prepared with standard polystyrene of known molecular weight (GPC apparatus and analytical conditions described below).

[0228] The polycarbonate polyols obtained in the examples and comparative examples described below were used as samples. They were prepared with tetrahydrofuran (hereinafter also referred to as "THF") at a concentration of 0.5% by mass, and the number-average molecular weight (Mn) of the polycarbonate polyols, converted to standard polystyrene, was determined using the GPC apparatus described below.

[0229] (GPC apparatus and analytical conditions)

[0230] GPC device: HLC-8320 manufactured by Tosoh Corporation

[0231] Column: TSKgel G4000H 1 column

[0232] G3000H 1 piece

[0233] G2000H 2 sticks

[0234] Eluent: Tetrahydrofuran (THF)

[0235] Flow rate: 1.0 mL / min

[0236] Column temperature: 40℃

[0237] RI detector: RI (built into device HLC-8320)

[0238] Standard curve: Standard polystyrene (manufactured by Tosoh Corporation)

[0239] F-20 (molecular weight: 1.90 × 10⁻⁶) 5 )

[0240] F-10 (Molecular weight: 9.64 × 10⁻⁶) 4 )

[0241] F-4 (molecular weight: 3.79 × 10⁻⁴) 4 )

[0242] F-2 (molecular weight: 1.81 × 10⁻⁶) 4 )

[0243] F-1 (molecular weight: 1.02 × 10⁻⁶) 4 )

[0244] • A-5000 (Molecular weight: 5.97×10⁻⁶) 3 )

[0245] A-2500 (Molecular weight: 2.63 × 10⁻⁶) 3 )

[0246] A-500

[0247] ·A-1000

[0248] <Molar ratio of the sum of repeating carbonate structures: ester repeating structures and ether repeating structures>

[0249] Carbonate repeating structures, ester repeating structures, and ether repeating structures are based on 1 H-NMR and 13 Identification was performed using C-NMR. The following apparatus was used for NMR-based measurements. 13 In C-NMR, the repeating structure of the carbonate group is represented by a peak around 150–155 ppm (-O-). C =OO-, derived from carbonate group), the ester repeating structure uses a peak around 165~180ppm (- C =OO-, derived from ester group), the repeating structure of the ether uses a peak around 50~90ppm (- C -O- C - (derived from ether groups), the molar ratio of repeating structural units is calculated from the ratio of their signal intensities. It should be noted that when there are two or more C elements corresponding to a specific peak, the molar ratio of repeating structural units is calculated by dividing the signal intensity by the number of C elements. The apparatus and measurement conditions are performed according to the following settings.

[0250] 1 H-NMR

[0251] Device: JEOL-ECZ500 (SC) (product name)

[0252] Solvent: Deuterated chloroform (containing 1 vol% tetramethylsilane)

[0253] Total number of times: 120

[0254] Sample concentration: 10 wt / vol%

[0255] Chemical shift reference: Tetramethylsilane is set to 0.0 ppm.

[0256] 13 C-NMR

[0257] Device: JEOL-ECZ500 (SC) (product name)

[0258] Solvent: Deuterated chloroform (containing 1 vol% tetramethylsilane)

[0259] Total number of times: 5120

[0260] Sample concentration: 30 wt / vol%

[0261] Chemical shift standard: Deuterated chloroform is set at 77.0 ppm.

[0262] Hydroxyl value of polycarbonate polyols

[0263] The hydroxyl values ​​of the polycarbonate polyols obtained in the examples and comparative examples described later were determined by the following methods.

[0264] First, using a volumetric flask, add pyridine to 12.5 g of acetic anhydride to make 50 mL to prepare an acetylation reagent. Next, accurately weigh 2.5 g of the sample in a 100-mL eggplant-shaped flask. Next, use a full-volume pipette to add 5 mL of the acetylation reagent and 10 mL of toluene to the aforementioned eggplant-shaped flask, then install a condenser, and stir and heat the solution in the aforementioned eggplant-shaped flask at 100 °C for 1 hour. Next, use a full-volume pipette to add 2.5 mL of distilled water to the aforementioned eggplant-shaped flask, and further heat and stir the solution in the aforementioned eggplant-shaped flask for 10 minutes. After cooling the solution in the aforementioned eggplant-shaped flask for 2 - 3 minutes, add 12.5 mL of ethanol to the aforementioned eggplant-shaped flask. Next, put 2 - 3 drops of phenolphthalein as an indicator in the aforementioned eggplant-shaped flask, and titrate with 0.5 mol / L alcoholic potassium hydroxide. Next, put 5 mL of the acetylation reagent, 10 mL of toluene, and 2.5 mL of distilled water into a 100-mL eggplant-shaped flask, heat and stir the solution in the aforementioned eggplant-shaped flask for 10 minutes, and then perform titration in the same way (blank test). Based on this result, calculate the hydroxyl value of the polycarbonate polyol using the following formula (i). It should be noted that in formula (i), E represents the titration volume (mL) of the sample, F represents the titration volume (mL) of the blank test, G represents the sample mass (g), and f represents the factor of the titrant.

[0265] Hydroxyl value (mgKOH / g) = {(F - E) × 28.05 × f} / G... (i)

[0266] <Viscosity>

[0267] For the polycarbonate group-containing polyol obtained in the following Examples and Comparative Examples, use an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., TVE-22HT, cone plate: No. 6) to measure the melt viscosity of the polycarbonate group-containing polyol at 23 °C.

[0268] <a. Analysis of all hydroxy compounds constituting the polycarbonate polyol>

[0269] Measure the proportion of the structural units of the polycarbonate polyol obtained in the following Examples and Comparative Examples as follows.

[0270] Add 1 g of polycarbonate polyol to a 100 mL eggplant-shaped flask, add 0.1 g of diethylene glycol diethyl ether as an internal standard, further add 30 g of ethanol and 4 g of potassium hydroxide, and carry out a hydrolysis reaction at 100 °C for 1 hour. After cooling to room temperature, add 2 - 3 drops of phenolphthalein as an indicator to the aforementioned eggplant-shaped flask and neutralize with hydrochloric acid. After cooling the aforementioned eggplant-shaped flask in a refrigerator for 1 hour, remove the precipitated salt by filtration to obtain a composition analysis solution. Analyze the hydroxyl compound components contained in the polycarbonate polyol in the obtained composition analysis solution by gas chromatography (GC). For the concentration of each hydroxyl compound, a standard curve is prepared in advance from each hydroxyl compound known as a reference substance, and the mass% is calculated from the area ratio obtained by gas chromatography (GC). The analysis is carried out as follows: Use a gas chromatograph GC-14B (manufactured by Shimadzu Corporation) equipped with DB-WAX (manufactured by J&W) as a column, and use a flame ionization detector (FID) as a detector. It should be noted that the temperature rising curve of the column is set to a curve that maintains at 60 °C for 5 minutes and then rises to 250 °C at a rate of 10 °C / minute.

[0271] <b. Analysis of residual hydroxyl compounds in polycarbonate polyol>

[0272] Dissolve 1 g of polycarbonate polyol and 0.1 g of diethylene glycol diethyl ether as an internal standard in 10 g of acetone, and measure the content of residual hydroxyl compounds under the same conditions as the aforementioned GC analysis.

[0273] <Calculation of the ratio of each structural unit>

[0274] From the above hydroxyl value, the results of the analysis in a above and the analysis in b above, calculate the terminal hydroxyl purity as follows.

[0275] 1. Content of the structural unit shown in equation (2)

[0276] The value obtained by dividing the mass of the hydroxyl compound having the structure of formula (2) measured in a above by the mass of the polycarbonate polyol (excluding the residual hydroxyl compound measured in b above) is used as the content of the structural unit shown in formula (2).

[0277] 2. The mass ratio of the structure shown in equation (2) to the sum of the structure shown in equation (2) and the structure of R4.

[0278] The value obtained by dividing the mass of the hydroxyl compound having the structure of formula (2) measured in a above by the sum of the mass of the hydroxyl compound having the structure of formula (2) measured in a above and the mass of the hydroxyl compound having the structure of R4 measured in b above is used as the mass ratio of the structure shown in the aforementioned formula (2) to the sum of the structure shown in formula (2) and the structure of R4.

[0279] 3. Purity of terminal hydroxyl groups

[0280] Calculate the purity of the terminal hydroxyl groups using the following formula.

[0281] [1] Purity of terminal hydroxyl groups = [[2] Amount of terminal hydroxyl groups in polycarbonate polyol] / [[3] Amount of terminal groups in polycarbonate polyol]

[0282] [2] The amount of terminal hydroxyl groups in polycarbonate polyols = [[4] Total hydroxyl group amount] - [[5] The amount of hydroxyl groups in residual hydroxyl compounds]

[0283] [4] Total hydroxyl content: The amount of hydroxyl content calculated from the hydroxyl value (the total amount of terminal hydroxyl groups in polycarbonate polyols and the amount of hydroxyl groups in residual hydroxyl compounds).

[0284] [5] Residual hydroxyl content: The total hydroxyl content of each free hydroxyl compound measured in b above.

[0285] [3] The amount of terminal groups in polycarbonate polyols = [[2] The amount of terminal hydroxyl groups in polycarbonate polyols] + [[6] The amount of monohydroxyl groups in the backbone of polycarbonate polyols]

[0286] [6] The amount of monohydroxyl groups in the backbone of polycarbonate polyols = [[7] Total amount of monohydroxyl groups] - [[8] Free amount of monohydroxyl groups]

[0287] [7] Total amount of monohydroxyl groups: The total amount of hydroxyl groups of all monohydroxy compounds measured in a above.

[0288] [8] Amount of free monohydroxyl groups: The amount of hydroxyl groups of all free monohydroxyl compounds measured in b above.

[0289] <Confirmation of the properties of polycarbonate diol>

[0290] Polycarbonate diol heated to 60°C was placed into transparent sample vials, and its state after cooling to room temperature (23°C) was observed visually. The state of the transparent vial that is slightly fluid when tilted is described as "liquid". The state of the vial that is opaque or does not change even when tilted, as well as both, is described as "solid".

[0291] Thermal stability

[0292] The coloration of the polycarbonate polyols obtained in the examples and comparative examples described below upon heating was evaluated using the following methods.

[0293] Add 50g of carbonate-containing polyol to a 100cc eggplant-shaped flask, add a stir bar, and heat for one week under a nitrogen atmosphere in an oil bath at 150°C. Evaluate the colorability based on the change in APHA before and after heating, according to the following criteria.

[0294] (Evaluation Criteria)

[0295] ◎ (Excellent): The increase in APHA after heating is less than 5.

[0296] 〇 (Good): The increase in APHA after heating is above 5 and less than 10.

[0297] △ (Poor): The increase in APHA after heating is above 10 but less than 20.

[0298] × (Bad): The APHA level rises above 20 after heating.

[0299] (APHA value)

[0300] The determination was performed according to JIS K0071-1 (1998), by comparing the solution with a standard solution placed in a colorimetric tube. The reagent used was a 1000° (1 mg Pt / mL) colorimetric standard solution (Kishida Chemical Co., Ltd.). Furthermore, solutions were prepared and determined at 5-fold intervals up to APHA50.

[0301] <Reactivity Assessment>

[0302] 60g of polycarbonate polyol was added to a 200mL wide-mouth glass bottle, and after thorough nitrogen purging, it was heated in an oil bath set to 80°C. Then, MDI heated at 80°C was added at an NCO / OH ratio of 1.2. The viscosity rise behavior was confirmed using a stirrer with a torque monitor, and the viscosity rise rate (= torque value after 30 minutes / initial torque value) was calculated and determined according to the following evaluation criteria.

[0303] (Evaluation Criteria)

[0304] ◎ (Excellent): Viscosity increase rate less than 2

[0305] 〇 (Good): Viscosity increase rate is 2 or higher but less than 3.

[0306] △ (Poor): Viscosity increase rate is 3 or higher but less than 5.

[0307] × (Bad): Viscosity increase rate of 5 or higher or cannot be evaluated.

[0308] [Example 1] Synthesis of polycarbonate polyol P-1

[0309] In a 3L glass flask (hereinafter referred to as the "reactor") equipped with a distillation column filled with a regularly packed material and a stirring device, 731g (7.03mol) of 1,5-pentanediol, 830g (7.03mol) of 1,6-hexanediol, and 1239g (12.8mol) of ethylene carbonate (EC) were added. Then, 0.1393g of tetrabutoxide titanium as a catalyst was added to the reactor. Under atmospheric pressure, the temperature was increased from 90°C to 185°C while distilling to remove low-boiling components, and the reaction was carried out for 25 hours. Next, the reactor was directly connected to a condenser, and the pressure was gradually reduced, and the reaction was continued for another 5 hours. Afterward, atmospheric pressure was established under nitrogen, and the temperature was lowered to 150°C. Then, 1.73g (0.0376mol) of ethanol and 0.00377g (0.0376mmol) of 4-hexen-1-ol were added, and the mixture was stirred for 3 hours. Next, the temperature was lowered to 100°C, and 0.103 g (0.891 mmol) of 85% phosphoric acid aqueous solution was added. After stirring for 5 hours, the temperature was raised to 170°C, and the pressure was slowly reduced to remove low-boiling components, yielding 1820 g of polycarbonate polyol P-1, which was liquid at 23°C. Various properties of the obtained polycarbonate polyol P-1 were determined using the above method. The hydroxyl value of the obtained polycarbonate polyol P-1 was 56.2 mg KOH / g. Furthermore, the number-average molecular weight of the obtained polycarbonate polyol P-1 was 1996. The purity of the terminal hydroxyl groups of the obtained polycarbonate polyol P-1 was 96%, and the ratio of 2-hexen-1-ol in the terminal monohydric alcohol backbone (=M2 / (M1+M2)) was 0.001. The results are shown in Tables 2 and 3.

[0310] [Examples 2-9, Comparative Examples 1-5]

[0311] The raw material polyols used in Example 1 were changed to the types and amounts of raw material polyols listed in Table 2. Except for this, polycarbonate polyols P-2 to P-9 and B-1 to B-5 were obtained using the same method as in Example 1. Various physical properties of the obtained polycarbonate polyols P-2 to P-9 and B-1 to B-5 were measured using the above method. The results are shown in Tables 2 and 3. It should be noted that the abbreviations in Tables 2 and 3 are as follows.

[0312] (A): Aliphatic hydroxyl compounds (aliphatic diols) of formula (1)

[0313] HDO: 1,6-Hexanediol

[0314] PDO: 1,5-Pentanediol

[0315] BDO: 1,4-Butanediol

[0316] PnDO: 1,3-Propanediol

[0317] (B): Catalyst

[0318] Ti: Tetra-n-Butoxide Titanium

[0319] (C): Neutralizing agent

[0320] Phosphoric acid

[0321] TEP: Triethyl Phosphate

[0322] (M1): Monohydric alcohol

[0323] MeOH: Methanol

[0324] IPA: Isopropanol

[0325] 2EHOH: 2-Ethylhexanol

[0326] (M2): Compounds containing unsaturated bonds

[0327] [Table 1]

[0328]

[0329] [Table 2]

[0330]

[0331] [Table 3]

[0332]

[0333] [Application Examples 1-9 and Comparative Application Examples 1-5] Evaluation of Carbamates

[0334] [Manufacturing of polyurethane]

[0335] Polyurethane films were manufactured using polycarbonate polyols P-1~P-9 and B-1~B-5 obtained in the Examples and Comparative Examples, as described below. 38 g of polycarbonate polyol, 224 g of dimethylformamide (hereinafter sometimes abbreviated as DMF), and 0.26 g of a 1% dibutyltin dilaurate toluene solution (total mass of MDI and polycarbonate polyol being 50 ppm) were placed in a 500 mL detachable flask equipped with a thermocouple and a condenser, and 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 polycarbonate polyol) was added dropwise, and the solution was further stirred for approximately 1.5 hours. The isocyanate group concentration was analyzed, confirming that the theoretical amount had been consumed, and a prepolymer was obtained. Next, the required amount of 1,4-butanediol (1,4-BD) (3.2 g), calculated based on the residual isocyanate, was added in portions to the flask. 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.

[0336] Next, using a 0.8 mm thick applicator, the obtained polyurethane solution was dropped onto a glass plate (JIS R3202, 2 mm × 100 mm × 150 mm) to coat the film to a 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. After further standing at a constant temperature and humidity of 23 °C and 55% RH for at least 12 hours, polyurethane films of Application Examples 1–9 and Comparative Examples 1–5 were obtained. The obtained polyurethane films were evaluated for various physical properties using the methods described below. The evaluation results are shown in Table 4.

[0337] Tensile Test

[0338] According to JIS K6301 (2010), a tensile testing machine (manufactured by Orientec Co., Ltd., product name "Tensilon, Model RTE-1210") was used to conduct tensile tests on test pieces of polyurethane coatings with a width of 10 mm, a length of 100 mm, and a thickness of about 0.5 mm, at a chuck spacing of 20 mm, a tensile speed of 100 mm / min, and a temperature of 23°C (relative humidity of 55%). The strength at the point of break and the elongation at the point of break were determined.

[0339] (Evaluation Criteria)

[0340] • Fracture strength

[0341] ◎ (Excellent): Those with a fracture strength of 50 MPa or higher.

[0342] ○ (Good): The fracture strength is above 30 MPa and below 50 MPa.

[0343] △ (Poor): The fracture strength is above 20MPa but less than 30MPa.

[0344] × (Bad): Those with a fracture point strength less than 20MPa or cannot be evaluated.

[0345] Elongation at break

[0346] ◎ (Excellent): Elongation at break is over 700%.

[0347] ○ (Good): Elongation at break is 400% or more but less than 700%

[0348] △ (Poor): Elongation at break is 200% or more but less than 400%.

[0349] × (Bad): Elongation at break less than 200% or cannot be evaluated.

[0350] <Evaluation of Chemical Resistance>

[0351] Test pieces of 3cm × 3cm were cut from the polyurethane coating. After the mass of the test pieces was determined using a precision balance, they were placed in a 250mL glass bottle containing 50mL of oleic acid as the test solvent and left to stand in a constant temperature bath at 80℃ under a nitrogen atmosphere for 16 hours. After the test, the test pieces were removed, and the surface and back were gently wiped with a paper wiper. The mass was then determined using a precision balance, and the rate of change in mass from the beginning of the test (increase rate: oleic acid resistance swelling rate) was calculated. The results were evaluated according to the following criteria.

[0352] (Evaluation Criteria)

[0353] ◎ (Excellent): Those with a quality increase rate of less than 4%

[0354] ○ (Good): Quality increase rate of 4% or more but less than 6%

[0355] △ (Poor): Those with a quality increase rate of 6% or more but less than 20%

[0356] × (Bad): Quality improvement rate of 20% or higher or cannot be evaluated.

[0357] <Number-average molecular weight of polyurethane>

[0358] A portion of the above polyurethane film was cut off, and an N,N-dimethylacetamide solution was prepared with a polyurethane concentration of 0.1% by mass. The number-average molecular weight (Mn) converted to standard polystyrene was determined using a GPC apparatus [manufactured by Tosoh Corporation, product name "HLC-8320" (column: Tskgel SuperHM-H·4 columns), and the eluent was a solution made by dissolving 2.6 g of lithium bromide in 1 L of dimethylacetamide].

[0359] [Table 4]

[0360]

[0361] [Application Examples 10-18, Comparative Application Examples 6-10] Coating Evaluation

[0362] Using polycarbonate polyols P-1 to P-9 and B-1 to B-5 obtained in the Examples and Comparative Examples as the main agent, and Durnate TPA-100 (manufactured by Asahi Kasei Corporation, NCO%=23.1) as the curing agent, the main agent and curing agent were measured in a plastic container such that the ratio of the molar number of hydroxyl (OH) groups in the polycarbonate polyol to the molar number of isocyanate groups (NCO) groups in the curing agent (hereinafter also referred to as "NCO / OH ratio") was 1.1. Dibutyltin dilaurate was added as a catalyst at a total mass of 100 ppm relative to the main agent and curing agent. Butyl acetate was added as a solvent such that the solid content of the final coating composition was 42% by mass, and the mixture was stirred until homogeneous to obtain coating composition 1. Using the obtained coating compositions 1, each was coated onto a polycarbonate sheet (“TAKIRON PC-1600” (trade name), 2mm × 70mm × 150mm) with a dried film thickness of 40μm. The coating compositions 1 coated on the polycarbonate sheet were baked at 60°C for 30 minutes to dry, and then cured at room temperature for 24 hours to obtain polyurethane coating films. Various physical properties of the obtained polyurethane coating films were evaluated using methods described later. The evaluation results are shown in Table 5.

[0363] <Weathering Resistance Test>

[0364] Using a super xenon lamp weathering tester (irradiance: 60W / m²) 2 As conditions for the weather resistance test, the temperature of the black panel under light exposure was set to 65°C and the humidity to 50%. After 102 minutes, water was sprayed while maintaining a humidity of 95% for 18 minutes, and this cycle was repeated. Gloss (gloss retention) and tinting (tinting resistance) were evaluated before the start of the weather resistance test and 2000 hours later.

[0365] <Gloss retention>

[0366] The gloss (45° reflectance of light) was measured using a gloss meter before and after the lightfastness test. The gloss retention rate was calculated as a percentage obtained by dividing the gloss after 2000 hours by the gloss before the start of the weatherfastness test. Based on the calculated gloss retention rate, the weatherfastness was evaluated according to the following evaluation criteria.

[0367] (Evaluation Criteria)

[0368] ○ (Excellent): Gloss retention rate of over 90%

[0369] △ (Good): Gloss retention rate is 80% or higher but less than 90%.

[0370] <Colorfastness>

[0371] In addition, L was measured before and after the lightfastness test using a colorimeter. a b (CIE1976), based on the color difference (ΔE) calculated by the following color difference formula, the colorfastness is evaluated according to the following criteria.

[0372] ΔE={(ΔL) ) 2 +(Δa ) 2 +(Δb ) 2} 1 / 2

[0373] (ΔL) , Δa Δb For L a b (The difference between the measured values ​​before and 2000 hours after the start of the respective weather resistance tests)

[0374] (Evaluation Criteria)

[0375] ◎ (Excellent): ΔE is less than 2

[0376] ○ (Good): ΔE is 2 or more and less than 5

[0377] △ (Poor): ΔE is 5 or more but less than 10

[0378] × (Bad): ΔE is 10 or higher

[0379] [Table 5]

[0380]

[0381] [Application Example 19] Preparation of polyol composition Q-1

[0382] 50g of the polycarbonate polyol P-3 obtained in Example 3 was weighed and mixed with 50g of a Resonac-made polyester polyol (Teslac, 2460, molecular weight 2000, liquid polyol) to obtain a polyol composition (Q-1). The physical property results of Q-1 are recorded in Table 6. Based on... 13 The integral ratio of the repeating carbonate structure to the repeating ester structure was calculated by C-NMR determination, and the result was that the repeating carbonate structure to repeating ester structure was 44:56 (molar ratio).

[0383] [Application Example 20] Preparation of polyol composition Q-2

[0384] The polyester polyol used in Application Example 19 was changed to a polyester polyol manufactured by Kuraray (Kuraray Polyol, P-2010, molecular weight 2000, liquid polyol). Otherwise, the polyol composition (Q-2) was obtained using the same method as in Application Example 1. The physical property test results of Q-2 are recorded in Table 6. Based on... 13 The integral ratio of the carbonate repeating structure to the ester repeating structure was calculated by C-NMR determination, and the result was carbonate repeating structure: ester repeating structure = 48:52 (molar ratio).

[0385] [Application Example 21] Manufacturing of polyol composition Q-3

[0386] 20g of polycarbonate polyol P-3 obtained in Example 3 and 30g of polycarbonate polyol P-5 obtained in Example 5 were weighed and mixed with 50g of Resonac-made polyester polyol (Teslac, 2460, molecular weight 2000, liquid polyol) to obtain polyol composition (Q-3). The physical property test results of Q-3 are recorded in Table 6. Based on the results obtained by... 13 The integral ratio of the carbonate repeating structure to the ester repeating structure was calculated by C-NMR determination, and the result was carbonate repeating structure: ester repeating structure = 42:58 (molar ratio).

[0387] [Application Example 22] Manufacturing of polyol composition Q-4

[0388] The polyester polyol used in Application Example 21 was changed to a polyester polyol manufactured by Kuraray (Kuraray Polyol, P-2010, molecular weight 2000, liquid polyol). Otherwise, the polyol composition (Q-4) was obtained using the same method as in Application Example 1. The physical property test results for Q-4 are recorded in Table 6. The physical property test results for Q-3 are recorded in Table 6. Based on... 13The integral ratio of the carbonate repeating structure to the ester repeating structure was calculated by C-NMR determination, and the result was carbonate repeating structure: ester repeating structure = 47:53 (molar ratio).

[0389] [Application Example 23] Manufacturing of polyol composition Q-5

[0390] 70g of the polycarbonate polyol P-3 obtained in Example 3 was weighed and mixed with 30g of a Resonac-made polyester polyol (Teslac, 2460, molecular weight 2000, liquid polyol) to obtain a polyol composition (Q-5). The physical property results of Q-5 are recorded in Table 6. Based on... 13 The integral ratio of the repeating carbonate structure to the repeating ester structure, calculated by C-NMR, yielded a ratio of 64:36 (molar ratio).

[0391] [Application Example 24] Preparation of polyol composition Q-6

[0392] The polyester polyol used in Application Example 23 was changed to a polyester polyol manufactured by Kuraray (Kuraray Polyol, P-2010, molecular weight 2000, liquid polyol). Otherwise, the polyol composition (Q-6) was obtained using the same method as in Application Example 1. The physical property test results of Q-6 are recorded in Table 6. Based on the... 13 The integral ratio of the repeating carbonate structure to the repeating ester structure, calculated by C-NMR, yielded a result of 68:32 (molar ratio).

[0393] [Application Example 25] Manufacturing of polyol composition Q-7

[0394] Weigh 70g of the polycarbonate polyol P-3 obtained in Example 3 and mix it with 30g of polytetramethylene ether glycol (PTMG2000) manufactured by Mitsubishi Chemical to obtain a polyol composition (Q-7). Based on the... 13 The integral ratio of the carbonate repeating structure to the ether repeating structure was calculated by C-NMR determination, and the result was carbonate repeating structure: ether repeating structure = 63:27 (molar ratio).

[0395] [Table 6]

[0396]

[0397] [Application Examples 26-32] Evaluation of carbamates in polyol compositions

[0398] The polycarbonate polyol used in Application Example 1 was replaced with polyol compositions Q-1 to 7 obtained in Application Examples 19 to 25. Otherwise, polyurethane films were obtained using the same method as in Application Example 1. Each polyurethane film was evaluated for various physical properties using the aforementioned method. The evaluation results are shown in Table 7.

[0399] [Table 7]

[0400]

[0401] [Application Examples 33-39] Evaluation of Coating Films of Polyol Compositions

[0402] The polycarbonate polyol used in Application Example 10 was replaced with polyol compositions Q-1 to 7 obtained in Application Examples 19 to 25. Otherwise, polyurethane coatings were obtained using the same method as in Application Example 10. Each polyurethane coating was evaluated for various physical properties using the aforementioned method. The evaluation results are shown in Table 8.

[0403] [Table 8]

[0404]

[0405] Industrial availability

[0406] The polycarbonate polyol of the present invention has excellent heat resistance and weather resistance. For example, it can provide polyurethane that is coloring caused by heat during the manufacture of polyurethane and that coloring is suppressed over time. Therefore, it can be widely and effectively used as a constituent material for, for example, coatings, coating compositions, adhesives, adhesive compositions, sealants, water-based polyurethanes, water-dispersible compositions, polyurethanes for synthetic leather, synthetic leather, etc.

Claims

1. A polycarbonate polyol, characterized in that, It has a repeating structural unit as shown in equation (1) and a structural unit as shown in equation (2). In equation (1), R1 is any divalent aliphatic hydrocarbon group. In equation (2), R2 is any monovalent aliphatic hydrocarbon group and R3 is any divalent aliphatic hydrocarbon group.

2. The polycarbonate polyol according to claim 1, wherein, The content of the structural unit shown in formula (2) is 0.001ppm to 30,000ppm.

3. The polycarbonate polyol according to claim 1, wherein, The content of the structural unit shown in formula (2) is 5ppm to 170ppm.

4. The polycarbonate polyol according to claim 1, having a structural unit of formula (11) formed by bonding the repeating structural unit of formula (1) with the structural unit of formula (2), In equation (11), R1 is any divalent aliphatic hydrocarbon group, R2 is any monovalent aliphatic hydrocarbon group, and R3 is any divalent aliphatic hydrocarbon group.

5. The polycarbonate polyol according to claim 1, further comprising the structural unit shown in formula (3) below, In formula (3), R5 is any divalent aliphatic hydrocarbon group, and R4 is an aliphatic hydrocarbon group with 1 to 12 carbon atoms.

6. The polycarbonate polyol according to claim 5, wherein, The mass ratio of the structural unit shown in Equation (2) to the sum of the structural unit shown in Equation (2) and R4 in Equation (3) is 0.000001~0.

20.

7. The polycarbonate polyol according to claim 1, wherein the purity of its terminal hydroxyl groups is 90 mol% to 98 mol%.

8. The polycarbonate polyol according to claim 1, wherein, The repeating structural unit shown in Equation (1) includes two or more repeating structural units shown in Equation (1) with different R1.

9. The polycarbonate polyol according to claim 1, wherein, The repeating structural unit shown in formula (1) contains two or more aliphatic structures with 2 to 20 carbon atoms, different from R1.

10. The polycarbonate polyol according to claim 9, wherein, In the formula (1), the ratio of the two aliphatic hydrocarbon groups in R1 is 0.1 to 0.

9.

11. The polycarbonate polyol according to claim 1, wherein, The repeating structural unit shown in formula (1) includes an aliphatic structure with 5 carbon atoms in R1 and an aliphatic structure with 6 carbon atoms in R1. The content of the structural unit shown in formula (2) is 5ppm to 170ppm.

12. The polycarbonate polyol according to claim 1, wherein the number average molecular weight is 300 or more and 5000 or less.

13. The polycarbonate polyol according to claim 1, wherein the hydroxyl value is 20 mg KOH / g to 700 mg KOH / g.

14. The polycarbonate polyol according to claim 1, wherein, The structural unit shown in formula (2) is derived from the structure of unsaturated monohydroxy alcohols with 4 to 9 carbon atoms.

15. A polyol composition comprising: the polycarbonate polyol of claim 1 and a polyol compound having an ester structure and / or an ether structure.

16. The polyol composition according to claim 15, wherein, The total molar ratio of the polycarbonate polyol to the polyol compound having an ester structure and / or an ether structure, comprising the polycarbonate structure, ester structure, and ether structure, is in the range of 20:80 to 80:

20.

17. The polyol composition according to claim 15, wherein, The total molar ratio of the polycarbonate polyol to the polyol compound having an ester structure and / or an ether structure, comprising the polycarbonate structure, ester structure, and ether structure, is in the range of 30:70 to 75:

25.

18. A polyurethane comprising a polycarbonate polyol as described in any one of claims 1 to 14 or a polyol composition as described in any one of claims 15 to 17 and an isocyanate compound.

19. An adhesive comprising the polyurethane of claim 18.

20. A coating comprising the polyurethane of claim 18.

21. A sealing material comprising the polyurethane of claim 18.

22. A waterborne polyurethane obtained using any one of the polycarbonate polyols of claims 1 to 14 or any one of the polyol compositions of claims 15 to 17.

23. An aqueous dispersion composition obtained using any one of the polycarbonate polyols according to claims 1 to 14 or any one of the polyol compositions according to claims 15 to 17.

24. A synthetic leather obtained using any one of the polycarbonate polyols according to claims 1 to 14 or any one of the polyol compositions according to claims 15 to 17.

25. An automotive interior material comprising the synthetic leather of claim 24.

26. A method for manufacturing the polycarbonate polyol according to claim 1, comprising: In a polyol having repeating structural units as shown in formula (1), a hydroxyl compound containing unsaturated bonds having structural units as shown in formula (2) is added. The reaction is carried out under normal or reduced pressure at 120°C to 180°C by heating and stirring.

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