Polycarbonate diol composition

Abstract

A polycarbonate diol composition comprising a repeating structural unit represented by the following general formula (I) and further comprising at least one repeating structural unit selected from the group consisting of repeating structural units represented by the following general formulas (II) to (IV), wherein the polycarbonate diol composition satisfies specific conditions.

Description

[0001] This application is a divisional application of the application with an application date of April 20, 2022, an application number of 202280029570.6, and an invention title of "Polycarbonate Diol Composition". Technical Field

[0002] The present invention relates to a polycarbonate diol composition. Background Art

[0003] In the past, polyurethane resins have been used in a wide range of fields such as synthetic leather, artificial leather, adhesives, furniture coatings, and automotive coatings. Among the raw materials of polyurethane resins, polyethers, polyesters, and polycarbonates are used as the polyol components that react with isocyanates. However, in recent years, there has been an increasing demand for the tolerance of polyurethane resins in terms of heat resistance, weather resistance, hydrolysis resistance, solvent resistance, sunscreen resistance, scratch resistance, etc.

[0004] According to Non-Patent Document 1, generally, as the polyol component, polyether polyols have a low viscosity. Therefore, polyurethanes using polyether polyols are excellent in flexibility and hydrolysis resistance but poor in heat resistance and weather resistance. In addition, polyurethanes using polyester polyols have improved heat resistance and weather resistance but poor hydrolysis resistance. In contrast, polyurethanes using polycarbonate polyols exhibit the best durability grade in terms of durability such as heat resistance, chemical resistance, and hydrolysis resistance, but there is still room for improvement in terms of high viscosity and processability.

[0005] To solve the above problems, various studies have been proposed to introduce ether bonds and ester bonds into polycarbonate polyols. For example, Patent Document 1 describes a manufacturing method for synthesizing copolycarbonate diols by transesterification of polycarbonate diols, and Patent Document 2 describes a polyester polyol having a specific structure. In addition, Patent Document 3 discloses a coating composition obtained using a specific polycarbonate diol composition.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent Laid-Open No. 3-252420

[0009] Patent Document 2: Japanese Patent Laid-Open No. 2019-151813

[0010] Patent Document 3: International Publication No. 2019 / 131617

[0011] Non-Patent Documents

[0012] Non-Patent Document 1: "Collection of Examples of Material Selection, Structure Control, and Modification of Polyurethanes", Items 51 to 62, published by Technical Information Association, Inc., first edition released in December 2014 Summary of the Invention

[0013] Problems to be Solved by the Invention

[0014] However, in the technologies described in Patent Documents 1 and 2, there is room for improvement in the hue of the copolycarbonate diol, and there are still problems in terms of compatibility with other polyols and solvents. In addition, in the technology described in Patent Document 3, in the manufacturing method of the polycarbonate diol composition, GPC measurement is used to confirm the progress and completion of the reaction, but there is still room for further improvement in terms of quality stability.

[0015] Therefore, the present invention has been made in view of the above circumstances, and an object thereof is to provide a polycarbonate diol composition having excellent quality stability, little coloring, and excellent compatibility with other polyols or solvents.

[0016] Solutions to the Problems

[0017] The present inventors repeatedly conducted in-depth research and found that a polycarbonate diol composition having a specific structure solves the above problems by satisfying specific conditions, thereby completing the present invention.

[0018] That is, the present invention has the following gist.

[0019] [1] A polycarbonate diol composition comprising a repeating structural unit represented by the following general formula (I), and further comprising at least one repeating structural unit selected from the group consisting of a repeating structural unit represented by the following general formula (II), a repeating structural unit represented by the following general formula (III), and a repeating structural unit represented by the following general formula (IV), and the polycarbonate diol composition satisfies the following formula (Formula 1).

[0020]

[0021] (In general formula (I), R 11 is a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 15 or less carbon atoms, and may optionally have a hetero atom. When there are a plurality of R 11 may be the same or different from each other.)

[0022]

[0023] (In general formula (II), R 21 is a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms. When there are a plurality of R21 Each may be the same as or different from each other. n21 is an arbitrary integer.)

[0024]

[0025] (In general formula (III), R 31 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms. When there are a plurality of R's 31 each may be the same as or different from each other.)

[0026]

[0027] (In general formula (IV), R 41 and R 42 are each independently a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms. When there are a plurality of R's 41 and R 42 each may be the same as or different from each other.)

[0028] xy ≥ 3.7 × α (α = 22.4 × Mn -0.41 )... (Formula 1)

[0029] (In (Formula 1), x is the ratio of the content (mass %) of the repeating structural unit represented by the general formula (I) to the total mass (mass %) of the repeating structural units represented by the general formulas (I) to (IV), y is the titration amount (mL) in the cloud point titration method of the polycarbonate diol composition, and Mn is the number average molecular weight of the polycarbonate diol composition.)

[0030] [2] A polycarbonate diol composition comprising a repeating structural unit represented by the following general formula (I), further comprising at least 1 repeating structural unit selected from the group consisting of a repeating structural unit represented by the following general formula (II), a repeating structural unit represented by the following general formula (III), and a repeating structural unit represented by the following general formula (IV), the content of the repeating structural unit represented by the general formula (I) is 40 mass % or more with respect to the total mass of the repeating structural units represented by the general formulas (I) to (IV), and the titration amount of the polycarbonate diol composition in the cloud point titration method is 4.0 mL or more and 9.5 mL or less.

[0031]

[0032] (In general formula (I), R 11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 15 or less carbon atoms, optionally having a hetero atom. When there are a plurality of R's 11 each may be the same as or different from each other.)

[0033]

[0034] (In general formula (II), R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms. When there are a plurality of Rs 21 may be the same or different from each other. n21 is an arbitrary integer.)

[0035]

[0036] (In general formula (III), R 31 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms. When there are a plurality of Rs 31 may be the same or different from each other.)

[0037]

[0038] (In general formula (IV), R 41 and R 42 are each independently a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms. When there are a plurality of Rs 41 and R 42 may be the same or different from each other.)

[0039] [3] The polycarbonate diol composition according to [1], wherein the content of the repeating structural unit represented by the general formula (I) is 5% by mass or more and 95% by mass or less with respect to the total mass of the repeating structural units represented by the general formulas (I) to (IV).

[0040] [4] The polycarbonate diol composition according to any one of [1] to [3], wherein the content of the repeating structural unit represented by the general formula (I) is 40% by mass or more and 90% by mass or less with respect to the total mass of the repeating structural units represented by the general formulas (I) to (IV).

[0041] [5] The polycarbonate diol composition according to any one of [1] to [4], having an acid value of 0.001 mg-KOH / g or more and 0.8 mg-KOH / g or less.

[0042] [6] The polycarbonate diol composition according to any one of [1] to [5], having a peroxide content of 10 meq / kg or less.

[0043] [7] The polycarbonate diol composition according to any one of [1] to [6], wherein the Hazen color number value (APHA value) based on JIS K0071-1 (2017) is 100 or less.

[0044] [8] The polycarbonate diol composition according to any one of [1] to [7], wherein, among the repeating structural units represented by the general formulas (II) to (IV), the average value of the number of repetitions n21 of the repeating structural unit represented by the general formula (II) is 15 or more.

[0045] [9] The polycarbonate diol composition according to any one of [1] to [8], wherein, among the repeating structural units represented by the general formulas (II) to (IV), at least the repeating structural unit represented by the general formula (II) or (IV) is included.

[0046]

[10] The polycarbonate diol composition according to any one of [1] to [9], wherein, among the repeating structural units represented by the general formulas (II) to (IV), at least the repeating structural unit represented by the general formula (II) is included.

[0047]

[11] A polyurethane formed by using the polycarbonate diol composition according to any one of [1] to

[10] .

[0048]

[12] The polyurethane according to

[11] , wherein, for the stress at 100% elongation of the polyurethane based on the tensile test, ΔM calculated by the following formula (B) is 1.0 or more and 19.0 or less.

[0049] ΔM = M1 - M2…(B)

[0050] (In formula (B), M1 is the stress at 100% elongation of the tensile test under the condition of -20°C, and M2 represents the stress at 100% elongation of the tensile test under the condition of 23°C.)

[0051]

[13] A synthetic leather containing the polyurethane according to

[11] or

[12] .

[0052] Effects of the Invention

[0053] The polycarbonate diol composition of the present invention has excellent quality stability, less coloring, and excellent compatibility with solvents and other polyols. Detailed Description of the Invention

[0054] Hereinafter, the mode for implementing the present invention (hereinafter referred to as "the present embodiment") will be described in detail. It should be noted that the present invention is not limited to the following description, and various modifications can be made within the scope of its gist.

[0055] [Polycarbonate diol composition]

[0056] The first polycarbonate diol composition of the present embodiment contains a repeating structural unit represented by the following general formula (I) (hereinafter also abbreviated as "structural unit (I)"), and further contains at least one repeating structural unit selected from the group consisting of a repeating structural unit represented by the following general formula (II) (hereinafter also abbreviated as "structural unit (II)"), a repeating structural unit represented by the following general formula (III) (hereinafter also abbreviated as "structural unit (III)"), and a repeating structural unit represented by the following general formula (IV) (hereinafter also abbreviated as "structural unit (IV)"), and the first polycarbonate diol composition satisfies the following formula (Formula 1).

[0057]

[0058] (In general formula (I), R 11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 15 or less carbon atoms, and may optionally have a hetero atom. When there are a plurality of R 11 may be the same or different from each other.)

[0059]

[0060] (In general formula (II), R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms. When there are a plurality of R 21 may be the same or different from each other. n21 is an arbitrary integer.)

[0061]

[0062] (In general formula (III), R 31 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms. When there are a plurality of R 31 may be the same or different from each other.)

[0063]

[0064] (In general formula (IV), R 41 and R 42 are each independently a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms. When there are a plurality of R 41 and R 42 may be the same or different from each other.)

[0065] xy≥3.7×α (α = 22.4×Mn -0.41)…(Formula 1)

[0066] (In Formula (1), x is the ratio of the content (mass %) of the repeating structural unit represented by the aforementioned general formula (I) to the total mass (mass %) of the repeating structural units represented by the aforementioned general formulas (I) to (IV), y is the titration volume (mL) in the cloud point titration method of the polycarbonate diol composition, and Mn is the number average molecular weight of the polycarbonate diol composition.)

[0067] By having such characteristics, the polycarbonate diol composition of the present embodiment has excellent quality stability and excellent compatibility with solvents and other polyols.

[0068] In addition, the second polycarbonate diol composition of the present embodiment contains a repeating structural unit represented by the following general formula (I) (hereinafter also abbreviated as "structural unit (I)"), and also contains at least one repeating structural unit selected from the group consisting of a repeating structural unit represented by the following general formula (II) (hereinafter also abbreviated as "structural unit (II)"), a repeating structural unit represented by the following general formula (III) (hereinafter also abbreviated as "structural unit (III)"), and a repeating structural unit represented by the following general formula (IV) (hereinafter also abbreviated as "structural unit (IV)"). The content of the repeating structural unit represented by the aforementioned general formula (I) is 40 mass % or more with respect to the total mass of the repeating structural units represented by the aforementioned general formulas (I) to (IV), and the titration volume of the polycarbonate diol composition in the cloud point titration method is 4.0 mL or more and 9.5 mL or less.

[0069]

[0070] (In general formula (I), R 11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 15 or less carbon atoms, and may optionally have a hetero atom. When there are a plurality of R 11 they may be the same or different from each other.)

[0071]

[0072] (In general formula (II), R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms. When there are a plurality of R 21 they may be the same or different from each other. n21 is an arbitrary integer.)

[0073]

[0074] (In general formula (III), R 31is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. When there are a plurality of Rs 31 may be the same or different from each other. )

[0075]

[0076] (In general formula (IV), R 41 and R 42 are each independently a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. When there are a plurality of Rs 41 and R 42 may be the same or different from each other. )

[0077] By having such characteristics, the polycarbonate diol composition of the present embodiment has excellent compatibility with solvents and other polyols.

[0078] The method for producing the polycarbonate diol composition of the present embodiment is not particularly limited, and it may be a copolymer of structural unit (I) and at least one structural unit selected from structural units (II) to (IV), or may exist independently.

[0079] [Structural unit (I)]

[0080] In the polycarbonate diol composition of the present embodiment, the details of structural unit (I) are described below.

[0081] (R 11 )

[0082] In general formula (I), R 11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 15 carbon atoms, and may optionally have a heteroatom. When there are a plurality of Rs 11 may be the same or different from each other.

[0083] As the divalent linear aliphatic hydrocarbon group in R 11 , the number of carbon atoms is 2 or more and 15 or less, preferably 3 or more and 12 or less, more preferably 3 or more and 10 or less.

[0084] As specific examples of the divalent linear aliphatic hydrocarbon group in R 11 , there is no particular limitation, and examples thereof include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, etc. From the viewpoint of versatility, trimethylene, butylene, pentylene, hexylene, and decamethylene are preferred.

[0085] As R 11The divalent branched aliphatic hydrocarbon group therein has 3 or more and 15 or less carbon atoms, preferably 3 or more and 12 or less carbon atoms, more preferably 3 or more and 10 or less carbon atoms.

[0086] As R 11 Specific examples of the divalent branched aliphatic hydrocarbon group in

[0087] As R 11 The divalent cyclic aliphatic hydrocarbon group therein has 3 or more and 15 or less carbon atoms, preferably 6 or more and 15 or less carbon atoms, more preferably 6 or more and 10 or less carbon atoms.

[0088] As R 11 Specific examples of the divalent cyclic aliphatic hydrocarbon group in

[0089] As R 11 The divalent aromatic hydrocarbon group therein has 6 or more and 15 or less carbon atoms, preferably 6 or more and 12 or less carbon atoms, more preferably 6 or more and 10 or less carbon atoms.

[0090] As R 11 Specific examples of the divalent aromatic hydrocarbon group in

[0091] As R 11 Specific examples of the heteroatom in

[0092] Among them, as R 11 is preferably a divalent straight-chain aliphatic hydrocarbon group having 3 or more and 10 or less carbon atoms, or a divalent branched aliphatic hydrocarbon group having 3 or more and 10 or less carbon atoms, more preferably a divalent straight-chain aliphatic hydrocarbon group having 4 or more and 6 or less carbon atoms, and further preferably a divalent straight-chain aliphatic hydrocarbon group of butylene, pentylene and hexylene.

[0093] In addition, in the polycarbonate diol composition of the present embodiment, with respect to at least a part of the aforementioned polycarbonate diol, R in the general formula (I) 11Preferably, it is at least two or more selected from the group consisting of linear and branched aliphatic hydrocarbon groups having 2 or more and 15 or less carbon atoms. In this case, there is a tendency to obtain a liquid polycarbonate diol composition at room temperature.

[0094] In addition, in the polycarbonate diol composition of the present embodiment, when a molecule having a structural unit represented by the general formula (I) is included, the two terminals of the molecule are preferably hydroxyl groups.

[0095] In the polycarbonate diol composition of the present embodiment, the molecule having a polycarbonate structure preferably has hydroxyl groups at both terminals. That is, the molecule having a polycarbonate structure included in the polycarbonate diol composition of the present embodiment is preferably a polycarbonate diol. Due to impurities in various raw materials used to manufacture the polycarbonate diol composition, end structures by-produced during the manufacture of the polycarbonate diol composition, etc., or in order to control the urethanization reaction rate and state in the use of the polycarbonate diol composition, sometimes a part of the terminal hydroxyl groups is converted into an alkyl group, an aryl group, etc. that do not react with an isocyanate group. In the present embodiment, such a situation is also taken into account, and strictly speaking, the terminal groups of the above polycarbonate diol also include the case where 100 mol% of both terminals are not hydroxyl groups. From this viewpoint, the proportion of hydroxyl groups relative to the total molar amount of the terminal groups is preferably 90 mol% or more, more preferably 95 mol% or more, and further preferably 98 mol% or more.

[0096] In the present embodiment, the two-terminal structure of the polycarbonate diol included in the polycarbonate diol composition can be confirmed by, for example, the method for measuring the primary terminal OH ratio described in Japanese Patent No. 3874664 (Reference 1). Among them, as the solvent for the recovered fraction, in addition to ethanol, solvents such as tetrahydrofuran, acetone, and methanol can also be used.

[0097] [Structural unit (II)]

[0098] Next, the details of the structural unit (II) will be described below.

[0099] (R 21 )

[0100] In the general formula (II), R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or an aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms. When there are a plurality of R 21 they may be the same or different from each other optionally.

[0101] As the divalent linear aliphatic hydrocarbon group in R 21 , the number of carbon atoms is 2 or more and 20 or less, preferably 2 or more and 12 or less, and more preferably 2 or more and 6 or less.

[0102] As R 21 Specific examples of the divalent linear aliphatic hydrocarbon group in are not particularly limited, and examples thereof include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, etc.

[0103] As R 21 In the divalent branched aliphatic hydrocarbon group, the number of carbon atoms is 3 or more and 20 or less, preferably 3 or more and 12 or less, and more preferably 3 or more and 6 or less.

[0104] As R 21 Specific examples of the divalent branched aliphatic hydrocarbon group in are not particularly limited, and examples thereof include isopropylidene, isobutylidene, tert-butylidene, isopentylidene, 2,2-dimethyltrimethylene, isohexylidene, isooctylidene, etc.

[0105] As R 21 In the divalent cyclic aliphatic hydrocarbon group, the number of carbon atoms is 6 or more and 20 or less, preferably 6 or more and 12 or less, and more preferably 6 or more and 8 or less.

[0106] As R 21 Specific examples of the divalent cyclic aliphatic hydrocarbon group in are not particularly limited, and examples thereof include cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, etc.

[0107] As R 21 In the divalent aromatic hydrocarbon group, the number of carbon atoms is 6 or more and 15 or less, preferably 6 or more and 12 or less, and more preferably 6 or more and 10 or less.

[0108] As R 21 Specific examples of the divalent aromatic hydrocarbon group in are not particularly limited, and examples thereof include phenylene, naphthylene, etc.

[0109] Among them, as R 21 , it is preferably a divalent linear, branched or cyclic aliphatic hydrocarbon group (i.e., alkylene group) having 2 or more and 20 or less carbon atoms, and more preferably a divalent linear aliphatic hydrocarbon group having 2 or more and 6 or less carbon atoms and / or a divalent branched aliphatic hydrocarbon group having 3 or more and 6 or less carbon atoms.

[0110] (n21)

[0111] In the general formula (II), n21 represents the structure (-R 21-O-) repetition number. In the general formula (II), n21 is an arbitrary integer. The average value of n21 in the entire polycarbonate diol composition of the present embodiment is preferably 12 or more, more preferably in the range of 12 or more and 70 or less, further preferably in the range of 12 or more and 60 or less, still more preferably 15 or more, and particularly preferably in the range of 15 or more and 50 or less.

[0112] By making the average value of n21 in the entire polycarbonate diol composition of the present embodiment be above the above lower limit value, there is a tendency to obtain a polyurethane with more excellent flexibility and low-temperature flexibility. In addition, by making the average value of n21 in the entire polycarbonate diol composition of the present embodiment be below the above upper limit value, there is a tendency for the viscosity of the polycarbonate diol composition to become lower.

[0113] The above n21 can be obtained as follows: The polycarbonate diol composition is subjected to alkali decomposition to extract the raw material diol component, and GC-MS measurement, LC-MS measurement, and gel permeation chromatography (GPC) measurement are performed on this component. Specifically, it can be obtained by the method described in the examples below.

[0114] Among them, as the structural unit (II), a polyoxyalkylene structure is preferred.

[0115] Specific examples of the preferred oxyalkylene contained in the structural unit (II) are not particularly limited, and examples thereof include oxyethylene, oxy-1-methylethylene, oxytetramethylene, oxy-2,2-dimethyltrimethylene, etc. Among them, a structure containing oxy-1-methylethylene is preferred, and oxy-1-methylethylene and oxyethylene are particularly preferred.

[0116] [Structural unit (III)]

[0117] Next, the details of the structural unit (III) will be described below.

[0118] (R 31 )

[0119] In the general formula (III), R 31 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms. When there are a plurality of R 31 they may be the same or different from each other optionally.

[0120] As R in the general formula (III) 31, without particular limitation, examples of which include linear or branched alkylene groups having 2 to 20 carbon atoms. Specifically, without particular limitation, examples include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, propylene, isobutylene, 2-methyltetramethylene, 2-methylpentamethylene, 3-methylpentamethylene, isononamethylene, 2-methylnonamethylene, etc. In addition, as R in the general formula (III) 31 , without particular limitation, examples of which include substituted or unsubstituted cycloalkylene groups having 3 to 20 carbon atoms. Specifically, without particular limitation, examples include cyclopentylene, cyclohexylene, 1,2-dimethylenecyclopentyl, 1,3-dimethylenecyclopentyl, 1,2-dimethylenecyclohexyl, 1,3-dimethylenecyclohexyl, 1,4-dimethylenecyclohexyl, 4,4'-methylenedicyclohexyl, 2,2-dicyclohexylpropyl, etc. In addition, as R in the general formula (III) 31 , without particular limitation, examples of which include substituted or unsubstituted arylene groups having 6 to 20 carbon atoms. Specifically, without particular limitation, examples include phenylene, 1,2-dimethylenephenyl, 1,3-dimethylenephenyl, 1,4-dimethylenephenyl, naphthylene, 4,4'-methylenediphenylene, 2,2-diphenylpropyl, etc.

[0121] Among them, from the viewpoints of improving the stain resistance and solvent resistance when producing polyurethane and the ease of obtaining the cyclic ester compound as a raw material, R 31 is preferably pentamethylene.

[0122] [Structural unit (IV)]

[0123] Next, the details of the structural unit (IV) will be described below.

[0124] (R 41 )

[0125] In the general formula (IV), each R 41 is independently a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms. When there are a plurality of Rs, the Rs 41 may be the same or different from each other optionally.

[0126] As R in the general formula (IV) 41, without particular limitation, examples of which include linear or branched alkylene groups having 2 to 20 carbon atoms. Specifically, without particular limitation, examples include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, propylene, isobutylene, 2-methyltetramethylene, 2-methylpentamethylene, 3-methylpentamethylene, isononamethylene, 2-methylnonamethylene, etc. In addition, as R in the general formula (IV) 41 , without particular limitation, examples of which include substituted or unsubstituted cycloalkylene groups having 3 to 20 carbon atoms. Specifically, without particular limitation, examples include cyclopentylene, cyclohexylene, 1,2-dimethylenecyclopentyl, 1,3-dimethylenecyclopentyl, 1,2-dimethylenecyclohexyl, 1,3-dimethylenecyclohexyl, 1,4-dimethylenecyclohexyl, 4,4'-methylenedicyclohexyl, 2,2-dicyclohexylpropyl, etc. In addition, as R in the general formula (IV) 41 , without particular limitation, examples of which include substituted or unsubstituted arylene groups having 6 to 20 carbon atoms. Specifically, without particular limitation, examples include phenylene, 1,2-dimethylenephenyl, 1,3-dimethylenephenyl, 1,4-dimethylenephenyl, naphthylene, 4,4'-methylenediphenylene, 2,2-diphenylpropyl, etc.

[0127] (R 42 )

[0128] In the general formula (IV), R 42 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms. When there are multiple R 42 they may be the same or different from each other optionally.

[0129] As R in the general formula (IV) 42 , without particular limitation, examples of which include linear or branched alkylene groups having 2 to 20 carbon atoms. Specifically, without particular limitation, examples include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, propylene, isobutylene, 2-methyltetramethylene, 2-methylpentamethylene, 3-methylpentamethylene, isononamethylene, 2-methylnonamethylene, etc. In addition, as R in the general formula (IV) 42, without particular limitation, examples of which include substituted or unsubstituted subcycloalkyl groups having 3 to 20 carbon atoms. Specifically, without particular limitation, examples include subcyclopentyl, subcyclohexyl, 1,2-dimethylenecyclopentyl, 1,3-dimethylenecyclopentyl, 1,2-dimethylenecyclohexyl, 1,3-dimethylenecyclohexyl, 1,4-dimethylenecyclohexyl, 4,4'-methylenedicyclohexyl, 2,2-dicyclohexylpropyl, and the like. In addition, as R in the general formula (IV) 42 , without particular limitation, examples of which include substituted or unsubstituted arylene groups having 6 to 20 carbon atoms. Specifically, without particular limitation, examples include phenylene, 1,2-dimethylenephenylene, 1,3-dimethylenephenylene, 1,4-dimethylenephenylene, naphthylene, 4,4'-methylenediphenylene, 2,2-diphenylpropyl, and the like.

[0130] [Structural unit (II) - Structural unit (IV)]

[0131] The polycarbonate diol composition of the present embodiment contains at least one repeating structural unit selected from the group consisting of a repeating structural unit represented by the following general formula (II), a repeating structural unit represented by the following general formula (III), and a repeating structural unit represented by the following general formula (IV).

[0132]

[0133] (In the general formula (II), R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms. When there are a plurality of R 21 they may be the same or different from each other. n21 is an arbitrary integer.)

[0134]

[0135] (In the general formula (III), R 31 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms. When there are a plurality of R 31 they may be the same or different from each other.)

[0136]

[0137] (In the general formula (IV), R 41 and R 42 are each independently a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms. When there are a plurality of R 41 and R 42 they may be the same or different from each other.)

[0138] In the polycarbonate diol composition of this embodiment, the terminal structure of structural units (II) to (IV) may be a terminal structure in which one terminal is bonded to a carbonate group and the other terminal is bonded to a hydroxyl group, or may be a terminal structure in which both terminals are bonded to a carbonate group, or may be a terminal structure in which both terminals are bonded to a hydroxyl group.

[0139] In addition, in the polycarbonate diol composition of this embodiment, the terminal structure of structural units (II) to (IV) may be a mixture of a terminal structure in which one terminal is bonded to a carbonate group and the other terminal is bonded to a hydroxyl group, a terminal structure in which both terminals are bonded to a carbonate group, and a terminal structure in which both terminals are bonded to a hydroxyl group.

[0140] Among them, in the polycarbonate diol composition of this embodiment, from the viewpoints of flexibility, low-temperature characteristics, and heat and humidity resistance, among structural units (II) to (IV), it is preferable to contain structural unit (II) or (IV), and more preferably to contain structural unit (II).

[0141] [Cloud point titration]

[0142] The titration amount of the second polycarbonate diol composition of this embodiment in the cloud point titration method is 4.0 mL or more and 9.5 mL or less, preferably 4.0 mL or more and 8.5 mL or less.

[0143] In this embodiment, the titration amount in the cloud point titration method means: First, dissolve the polycarbonate diol composition in butyl acetate as a good solvent, titrate the resulting solution with hexane as a poor solvent, and the titration amount when cloudiness starts to occur. In addition, when it is insoluble in butyl acetate, it can be dissolved in acetone. Specifically, it can be obtained by the method described in the following examples.

[0144] In this cloud point titration, the solubility in the solvent shows differences due to the type, molecular weight, and structure of the polyol. Generally speaking, the smaller the molecular weight, the higher the solubility in the solvent. In addition, the solubility also varies depending on the functional groups contained. Therefore, in the case of blending two or more polyols and in the case of reacting them to change the structure, there are differences in solubility.

[0145] The titration amount of the second polycarbonate diol composition of this embodiment in the cloud point titration method is 4.0 mL or more and 9.5 mL or less, preferably 4.0 mL or more and 8.5 mL or less, more preferably 4.0 mL or more and 7.6 mL or less, and further preferably 4.1 mL or more and 7.4 mL or less.

[0146] By making the titration amount in the cloud point titration method be not less than the above lower limit value, the compatibility of the polycarbonate diol composition with the solvent and the compatibility with the raw materials in the synthesis of polyurethane are improved. In addition, by making the titration amount in the cloud point titration method be not more than the above upper limit value, a polyurethane with excellent balance of low-temperature flexibility, chemical resistance, and durability such as heat and humidity resistance can be obtained. Therefore, it is preferred.

[0147] For the polycarbonate diol composition, there is no particular limitation on the method for controlling the titration amount in the cloud point titration method to the aforementioned range. Examples thereof include a method of adjusting the feeding ratio of the structural unit (I) to the structural units (II) to (IV). In addition, in the method for producing the polycarbonate diol used in the present embodiment described later, a method of adjusting the reaction time and a method of appropriately adjusting the oxygen concentration during mixing and stirring can also be cited.

[0148] In addition, if this cloud point titration method is used, the progress of the transesterification reaction can be evaluated. Therefore, by setting the target value of the titration amount in the cloud point titration method, there is a tendency to reduce the deviation of the transesterification reaction caused by the production batch and obtain a polycarbonate diol composition with excellent quality stabilization.

[0149] [Relational expression (Equation 1)]

[0150] The first polycarbonate diol composition of the present embodiment satisfies the following formula (Equation 1).

[0151] xy≥3.7×α (α = 22.4×Mn -0.41 )…(Equation 1)

[0152] (In (Equation 1), x is the ratio of the content (mass %) of the repeating structural unit represented by the aforementioned general formula (I) to the total mass (mass %) of the repeating structural units represented by the aforementioned general formulas (I) to (IV), y is the titration amount (mL) of the polycarbonate diol composition in the cloud point titration method, and Mn is the number average molecular weight of the polycarbonate diol composition.)

[0153] Here, the number average molecular weight can be calculated based on the hydroxyl value of the polycarbonate diol composition using the method described in the examples below.

[0154] Regarding cloud point titration, generally, compounds with a small molecular weight have high solubility in the solvent. Therefore, there is a tendency for the titration amount of the poor solvent to be high. α is a factor that offsets the difference caused by the molecular weight.

[0155] Generally, polycarbonate diol has low solubility in solvents. Therefore, if x increases, there is a tendency for y to decrease. It is speculated that the more randomly the repeating structural units represented by the aforementioned general formulas (I) to (IV) and the repeating structural unit represented by the aforementioned general formula (I) exist, the larger the titration amount in the cloud point titration. In addition, as a method for obtaining the polycarbonate diol composition satisfying the above formula (Formula 1), there is no particular limitation, and examples thereof include a method of appropriately setting the reaction time until the modification is sufficiently carried out.

[0156] [Content of structural unit (I)]

[0157] In the polycarbonate diol composition of the present embodiment, the content of the structural unit (I) is preferably 5% by mass or more and 95% by mass or less, more preferably 20% by mass or more and 90% by mass or less, and still more preferably 40% by mass or more and 90% by mass or less, relative to the total mass of the structural units (I) to (IV). By making the content of the structural unit (I) not less than the above lower limit value, a polyurethane having more excellent durability such as chemical resistance and heat and humidity resistance can be obtained, which is preferable. In addition, by making the content of the structural unit (I) not more than the above upper limit value, the viscosity of the polycarbonate diol composition tends to decrease. It should be noted that the content of the structural unit (I) can be measured by the method described in the examples below.

[0158] [Number average molecular weight]

[0159] The number average molecular weight of the polycarbonate diol composition of the present embodiment is preferably 250 or more and 10000 or less, more preferably 400 or more and 8000 or less, still more preferably 500 or more and 5000 or less, and particularly preferably 500 or more and 3000 or less. By making the number average molecular weight of the polycarbonate diol composition of the present embodiment not more than the above upper limit value, the viscosity decreases and the processability during the production of polyurethane improves. In addition, by making the number average molecular weight not less than the above lower limit value, the polyurethane produced using the polycarbonate diol composition of the present embodiment tends to have excellent softness.

[0160] As a method for controlling the number average molecular weight of the polycarbonate diol composition of the present embodiment to the aforementioned range, there is no particular limitation, and examples thereof include a method of using the structural unit (I) whose number average molecular weight is controlled to the aforementioned range and at least one structural unit selected from the structural units (II) to (IV) whose number average molecular weight is controlled to the aforementioned range; a method of using the structural unit (I) whose number average molecular weight is greater than the aforementioned range and at least one structural unit selected from the structural units (II) to (IV) whose number average molecular weight is less than the aforementioned range; a method of reacting while confirming the number average molecular weight and stopping the reaction at the time point when it reaches the aforementioned range, and the like.

[0161] In this embodiment, the number-average molecular weight of the polycarbonate diol composition can be measured by the method described in the examples below.

[0162] [Acid value]

[0163] The acid value of the polycarbonate diol composition of this embodiment is preferably 0.001 mg-KOH / g or more and 0.8 mg-KOH / g or less, more preferably 0.005 mg-KOH / g or more and 0.6 mg-KOH / g or less, and still more preferably 0.01 mg-KOH / g or more and 0.6 mg-KOH / g or less. Since it is difficult to completely remove acidic compounds from raw materials, catalysts, additives, etc., it is preferable from the aspect of the productivity of the polycarbonate diol composition by making the acid value above the above lower limit value. In addition, by making the acid value below the above upper limit value, there is a tendency that coloring can be reduced.

[0164] As a method for controlling the acid value of the polycarbonate diol composition to the aforementioned range, there is no particular limitation, and examples thereof include a method of adjusting the acid value of the raw materials when manufacturing the polycarbonate diol composition, and a method of appropriately selecting and adding a catalyst poison for deactivating the catalyst.

[0165] In this embodiment, the acid value of the polycarbonate diol composition can be measured by the method described in the examples below.

[0166] [Peroxide value]

[0167] The peroxide content (hereinafter also referred to as "peroxide value") of the polycarbonate diol composition of this embodiment is preferably 10 meq / kg or less, more preferably 3 meq / kg or less. If the peroxide value of the polycarbonate diol composition of this embodiment is 10 meq / kg or less, there is a tendency that coloring is suppressed. The lower limit of the peroxide value of the polycarbonate diol composition of this embodiment is not particularly limited, for example, it is 0.01 meq / kg. It should be noted that as the method for measuring the aforementioned peroxide value, examples include: a method of reacting potassium iodide with oxidized oil under acidic conditions and obtaining the iodine liberated by titration with sodium thiosulfate by titration method. For example, a peroxide value test paper (trade name: "POV test paper", manufactured by Shibata Chemical Co., Ltd.) can be used for simple measurement. Specifically, it can be measured by the method described in the examples below.

[0168] As a method for controlling the peroxide value of the polycarbonate diol composition to the aforementioned range, there is no particular limitation, and examples thereof include a method of setting the reaction temperature to 200°C or lower in order to reduce oxidative cracking caused by thermal decomposition; a method of setting the oxygen concentration to 0.5% or lower when manufacturing the polycarbonate diol composition; a method of setting the nitrogen flow rate during manufacturing to 0.1 L / min or more and 50 L / min or less, and the above methods can also be combined.

[0169] [APHA]

[0170] The Hazen color number (hereinafter also referred to as "APHA") value of the polycarbonate diol composition of the present embodiment (APHA value: based on JIS K0071-1 (2017)) is preferably 100 or less, more preferably 60 or less, and still more preferably 50 or less. The lower the APHA value, the better the hue of the polycarbonate diol composition itself and the hue of the polyurethane obtained using the polycarbonate diol composition. The lower limit of the APHA value is not particularly limited and is, for example, 0.

[0171] A polycarbonate diol composition satisfying such an APHA value can be manufactured by setting the APHA of the raw materials used to 100 or less, and in the manufacturing method of the polycarbonate diol used in the present embodiment described later, it becomes more effective by setting the oxygen concentration during mixing and stirring to 0.5% or less.

[0172] It should be noted that in the present embodiment, the APHA value can be measured by the method described in the examples below.

[0173] <Manufacturing method of polycarbonate diol composition>

[0174] Regarding the manufacturing method of the polycarbonate diol composition of the present embodiment, there is no particular limitation as long as the above characteristics can be satisfied, and examples thereof include the following methods: a method of transesterification using a polycarbonate diol represented by the following general formula (I-1) (hereinafter sometimes referred to as "polycarbonate diol (I-1)") and at least one selected from the group consisting of an ether diol represented by the following general formula (II-1) (hereinafter sometimes referred to as "ether diol (II-1)"), a polycaprolactone diol (III-1) represented by the following general formula (III-1) (hereinafter sometimes referred to as "lactone diol (III-1)"), and a polyester diol represented by the following general formula (IV-1) (hereinafter sometimes referred to as "ester diol (IV-1)"); a method of reacting the polycarbonate diol (I-1) with a cyclic ester compound.

[0175]

[0176] (In the general formula (I-1), R 111 and R 112Are the same as the above R 11 respectively. n11 is an arbitrary integer.)

[0177]

[0178] (In general formula (II-1), R 211 is the same as the above R 21 respectively. n211 is the same as the above n21.)

[0179]

[0180] (In general formula (III-1), R 311 is the same as the above R 31 respectively. n311 is an arbitrary integer)

[0181]

[0182] (In general formula (IV-1), R 411 and R 421 are the same as the above R 41 and R 42 respectively. n411 is an arbitrary integer.)

[0183] [Polycarbonate diol (I-1)]

[0184] As the polycarbonate diol (I-1) for manufacturing the polycarbonate diol composition of the present embodiment, it only needs to have the structure shown in the above general formula (I-1). As the manufacturing method of the polycarbonate diol (I-1), there is no particular limitation, and a known method can also be adopted. For example, by reacting a carbonate compound with a diol compound in the presence of a transesterification catalyst, the polycarbonate diol (I-1) can be obtained.

[0185] (Carbonate compound)

[0186] As the carbonate compound for manufacturing the polycarbonate diol (I-1), it is not limited to the following compounds, and examples thereof include alkylene carbonates, dialkyl carbonates, diaryl carbonates, etc.

[0187] As the alkylene carbonate, there is no particular limitation, and examples thereof include ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 1,2-pentylene carbonate, etc.

[0188] As the dialkyl carbonate, there is no particular limitation, and examples thereof include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, etc.

[0189] As the diaryl carbonate, there is no particular limitation, and examples thereof include diphenyl carbonate, etc.

[0190] Among them, as the carbonate compound for producing the polycarbonate diol (I-1), ethylene carbonate, dimethyl carbonate, diethyl carbonate, and diphenyl carbonate are preferred, and ethylene carbonate is more preferred.

[0191] (Diol compound)

[0192] The diol compound for producing the polycarbonate diol (I-1) is not limited to the following compounds, and examples thereof include linear diols, branched diols, cyclic diols, and diols having an aromatic ring.

[0193] As the linear diol, there is no particular limitation, and examples thereof 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, etc.

[0194] As the branched diol, there is no particular limitation, and examples thereof include 2-methyl-1,8-octanediol, neopentyl glycol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, etc.

[0195] As the cyclic diol, there is no particular limitation, and examples thereof include 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-bis(4-hydroxycyclohexyl)propane, etc.

[0196] As the diol having an aromatic ring, there is no particular limitation, and examples thereof include terephthalyl alcohol, tetrachloroterephthalyl alcohol, 1,4-bis(hydroxyethoxy)benzene, 2,2-bis[(4-hydroxyethoxy)phenyl]propane, etc.

[0197] Among them, a linear diol or a branched diol having 3 or more and 10 or less carbon atoms is preferred, and 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol or 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol are preferred, and 1,4-butanediol, 1,5-pentanediol or 1,6-hexanediol are more preferred.

[0198] [Manufacturing conditions of polycarbonate diol composition and polycarbonate diol (I-1)]

[0199] When producing the polycarbonate diol (I-1) as a raw material, a transesterification catalyst can be used. As the catalyst, it can be selected from common transesterification catalysts.

[0200] As the transesterification catalyst, there is no particular limitation, and examples thereof include alkali metals and alkaline earth metals, as well as their alcoholates, their hydrides, their oxides, their amides, their hydroxides and their salts, etc.

[0201] As the salts of alkali metals and alkaline earth metals, there is no particular limitation, and examples thereof include carbonates, nitrogen-containing borates, basic salts formed with organic acids, etc.

[0202] As the alkali metal, there is no particular limitation, and examples thereof include lithium, sodium, potassium, etc.

[0203] As the alkaline earth metal, there is no particular limitation, and examples thereof include magnesium, calcium, strontium, barium, etc.

[0204] In addition, as the transesterification catalyst using metals other than alkali metals and alkaline earth metals, there is no particular limitation, and examples thereof include metals other than alkali metals and alkaline earth metals, as well as their salts, their alcoholates and organic compounds containing the metal, etc.

[0205] As specific examples of metals other than alkali metals and alkaline earth metals, there is no particular limitation, and examples thereof include 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, ytterbium, etc.

[0206] These transesterification catalysts can be used alone, or two or more of them can be used in combination.

[0207] Among them, as the transesterification catalyst, from the aspect of more favorably performing the transesterification reaction for obtaining polycarbonate diol and having a smaller impact on the urethane reaction when using the obtained polycarbonate diol, it is preferably one or more metals selected from the group consisting of sodium, potassium, magnesium, potassium, titanium, zirconium, tin, lead and ytterbium; or their salts, their alcoholates or organic compounds containing these metals.

[0208] In addition, as the transesterification catalyst, it is more preferably one or more metals selected from the group consisting of magnesium, titanium, ytterbium, tin and zirconium.

[0209] As specific examples of the preferred transesterification catalyst, there is no particular limitation, and examples thereof include organic compounds of magnesium, organic compounds of lead, organic compounds of titanium, etc.

[0210] As the organic compound of magnesium, there is no particular limitation, and examples thereof include magnesium acetate tetrahydrate, magnesium acetate anhydrous, etc.

[0211] As the organic compound of lead, there is no particular limitation, and examples thereof include lead acetate trihydrate, tetraphenyllead, lead stearate, etc.

[0212] The organotitanium compounds are not particularly limited, and examples thereof include titanium tetra-n-butoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, etc.

[0213] The amount of the transesterification catalyst used is preferably 0.00001% by mass or more and 0.1% by mass or less, more preferably 0.0001% by mass or more and 0.05% by mass or less, based on the total mass of the raw materials.

[0214] In the case of performing a heat treatment after manufacturing the polycarbonate diol, the transesterification catalyst used in the transesterification reaction is not consumed by the transesterification reaction. Therefore, it can be calculated based on the amount of the transesterification catalyst used. In the case of using a commercially available polycarbonate diol, etc., the amount of the metal of the transesterification catalyst contained in the polycarbonate diol is determined by ICP (Inductively Coupled Plasma emission spectrometry) and obtained.

[0215] In the polycarbonate diol (I-1) for manufacturing the polycarbonate diol composition of the present embodiment, in order to deactivate the transesterification catalyst used during its manufacture, a catalyst poison such as a phosphate compound may be added.

[0216] When the polycarbonate diol (I-1) as a raw material contains a catalyst poison of the transesterification catalyst used during its manufacture, etc., there is usually a tendency that the ether diol (II-1) and the ester diol (IV-1) do not easily undergo a transesterification reaction with the polycarbonate diol (I-1). Therefore, when manufacturing the polycarbonate diol composition of the present embodiment, a necessary amount of the above-mentioned transesterification catalyst may be added again.

[0217] On the other hand, when the polycarbonate diol (I-1) as a raw material does not contain a catalyst poison of the transesterification catalyst, there is usually a tendency that the transesterification reaction in the present embodiment easily proceeds. However, in the case of wanting to further lower the reaction temperature in the manufacturing process of the polycarbonate diol composition of the present embodiment, the case of wanting to further shorten the reaction time, etc., a necessary amount of the transesterification catalyst may also be added again. In this case, the same catalyst as the transesterification catalyst used in the manufacture of the polycarbonate diol (I-1) as a raw material can be used.

[0218] In addition, the polycarbonate diol (I-1) for manufacturing the polycarbonate diol composition of the present embodiment may be a homopolymer polycarbonate diol obtained from one diol compound, or a copolymer polycarbonate diol obtained from two or more diol compounds.

[0219] Any of the above-exemplified polycarbonate diols (I-1) can be used to obtain a polycarbonate diol composition through a transesterification reaction.

[0220] However, for example, a homopolymer polycarbonate diol obtained using 1,6 - hexanediol which is widely used in the market is usually a solid at normal temperature. Therefore, there is a tendency that the polycarbonate diol composition obtained by the transesterification reaction with this homopolymer polycarbonate diol is also a solid at normal temperature.

[0221] On the other hand, for example, a copolymer polycarbonate diol obtained using any two of 1,4 - butanediol, 1,5 - pentanediol, and 1,6 - hexanediol is a liquid at normal temperature. Therefore, there is a tendency that the polycarbonate diol composition obtained by the transesterification reaction with this copolymer polycarbonate diol is also a liquid at normal temperature.

[0222] (n11)

[0223] In the general formula (I - 1), n11 represents the number of repetitions of the carbonate structure (-R 111 -O-CO-O-). n11 is an arbitrary integer, and the average value of n11 is preferably in the range of 1 or more and 50 or less, more preferably in the range of 2 or more and 50 or less, further preferably in the range of 3 or more and 30 or less, and particularly preferably in the range of 4 or more and 20 or less.

[0224] The number - average molecular weight of the polycarbonate diol (I - 1) used for manufacturing the polycarbonate diol composition of the present embodiment is not particularly limited, and is preferably 500 or more and 5000 or less, more preferably 1000 or more and 3000 or less.

[0225] By making the number - average molecular weight of the polycarbonate diol (I - 1) be above the above - mentioned lower limit value, there is a tendency that the performance expected for the polycarbonate diol composition is further improved. On the other hand, by making the number - average molecular weight of the polycarbonate diol (I - 1) be below the above - mentioned upper limit value, it is preferable in terms of the processability during the manufacture of the polycarbonate diol composition.

[0226] [ether diol (II - 1)]

[0227] As the ether diol (II-1) for producing the polycarbonate diol composition of the present embodiment, it is sufficient if it has the structure represented by the above general formula (II-1). Among them, as the ether diol (II-1), a polyoxyalkylene diol having primary hydroxyl groups at both ends is preferred. Regarding the ether diol (II-1), products of various molecular weights are commercially available, and such commercially available products can also be used. There is no particular limitation on the commercially available product of the ether diol (II-1), and examples thereof include "NEWPOL" series, "PrimPol" series, "SANNIX" series manufactured by Sanyo Chemical Industries, Ltd.; "PLONON" series manufactured by Nippon Oil Corporation; "PREMINOL", "EXCENOL" series manufactured by AGC Inc.; polyoxyalkylene diols such as "PTMG" series manufactured by Mitsubishi Chemical Corporation; polyether diols such as PTXG manufactured by Asahi Kasei Corporation, etc.

[0228] There is no particular limitation on the number average molecular weight of the ether diol (II-1), and it is preferably 400 or more and 3000 or less, more preferably 600 or more and 2500 or less. By making the number average molecular weight of the ether diol (II-1) used in the production be above the above lower limit value, there is a tendency for the flexibility to be further improved when used for polyurethane, and by making the number average molecular weight of the ether diol (II-1) be below the above upper limit value, there is a tendency to further suppress the crystallinity of the polycarbonate diol composition of the present embodiment.

[0229] [Polycaprolactone diol (III-1) and cyclic ester compound]

[0230] As the polycaprolactone diol (III-1) for producing the polycarbonate diol composition of the present embodiment, it is sufficient if it has the structure represented by the above general formula (III-1). Among them, regarding the polycaprolactone diol (III-1), products of various molecular weights are commercially available, and such commercially available products can also be used. There is no particular limitation on the commercially available product, and examples thereof include "Placcel" series manufactured by Daicel Chemical Industries, Ltd., "Polylite" series manufactured by DIC Corporation, etc.

[0231] (n311)

[0232] In the general formula (III-1), n311 represents the repetition number of the structure (-R 311 -O-CO-). In the general formula (III-1), n311 is an arbitrary integer, and the average value of n311 is 1 or more, preferably in the range of 1 or more and 50 or less, more preferably in the range of 1 or more and 30 or less, and particularly preferably in the range of 1 or more and 20 or less.

[0233] The number average molecular weight of the polycaprolactone diol (III-1) is not particularly limited, preferably 400 or more and 3000 or less, more preferably 600 or more and 2000 or less. By making the number average molecular weight of the lactone diol (III-1) used in the production at least the above lower limit value, there is a tendency for the softness of the polyurethane obtained from the polycarbonate diol composition of the present embodiment to be further improved. By making the number average molecular weight of the lactone diol (III-1) at most the above upper limit value, there is a tendency for the polycarbonate diol composition of the present embodiment to have a lower viscosity.

[0234] In addition, the cyclic ester compound can be ring-opening polymerized.

[0235] The cyclic ester compound is not particularly limited, and examples thereof include cyclic ester compounds having 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, heptalactone (7-heptalactone). It is particularly preferred to use ε-caprolactone which provides the structural unit (III) in the aforementioned formula (III) in which R 31 is a linear alkylene group having 5 carbon atoms.

[0236] [Ester diol (IV-1)]

[0237] As the ester diol (IV-1) used for producing the polycarbonate diol composition of the present embodiment, it is sufficient if it has the structure represented by the above general formula (IV-1). Among them, products with various molecular weights of the ester diol (IV-1) are already on the market, and such commercially available products can also be used. Commercially available products of the ether diol (II-1) are not particularly limited, and examples thereof include the "Polylite" series manufactured by DIC Corporation; the "KURARAY POLYOL" series manufactured by Kuraray Co., Ltd.; the "NIPPOLAN" series manufactured by Tosoh Corporation; the "ADEKA NEWACE" series manufactured by ADEKA Corporation, etc.

[0238] (n411)

[0239] In the general formula (IV-1), n411 represents the number of repetitions of the structure (-CO-R 411 -CO-O-R 421 -O-). In the general formula (IV-1), n411 is an arbitrary integer, and the average value of n411 is 1 or more, preferably in the range of 1 or more and 50 or less, more preferably in the range of 2 or more and 30 or less, and particularly preferably in the range of 4 or more and 20 or less.

[0240] The number average molecular weight of the ester diol (IV-1) is not particularly limited, preferably 400 or more and 3000 or less, more preferably 600 or more and 2000 or less. By making the number average molecular weight of the ester diol (IV-1) used in the production the above lower limit or more, there is a tendency for the softness of the polyurethane obtained from the polycarbonate diol composition of the present embodiment to be further improved. By making the number average molecular weight of the ester diol (IV-1) the above upper limit or less, there is a tendency for the polycarbonate diol composition of the present embodiment to become lower in viscosity.

[0241] The method for producing the polycarbonate diol composition of the present embodiment is not particularly limited. Preferably, the polycarbonate diol (I-1) is mixed with at least one compound selected from the group consisting of an ether diol (II-1), an ester diol (IV-1), and a cyclic ester compound, and the mixture is heated and stirred for production.

[0242] The temperature during the reaction is not particularly limited, preferably 120°C or more and 200°C or less, more preferably 140°C or more and 180°C or less.

[0243] By setting the reaction temperature to the above lower limit or more, the transesterification reaction can be carried out in a shorter time, and there is a tendency for excellent economy. By setting the reaction temperature to the above upper limit or less, there is a tendency that the acid value of the obtained polycarbonate diol composition can be controlled within a specific range, or coloring can be more effectively prevented.

[0244] In addition, during production, it is preferable to set the oxygen concentration to 0.5% or less. As a method for setting the oxygen concentration to 0.5% or less, there is no particular limitation, and examples include: after replacing with nitrogen at 1.5 times or more of the reaction apparatus and reacting while flowing nitrogen; after reducing the pressure to 0.1 kPa·s or less, performing nitrogen replacement and reacting under slightly reduced pressure. By setting the oxygen concentration to 0.5% or less, there is a tendency to suppress the generation of peroxides and prevent coloring of the obtained polycarbonate diol composition.

[0245] In addition, in order to set the oxygen concentration to 0.5% or less, it is preferable to flow nitrogen at a nitrogen flow rate of 0.1 L / min or more and 50 L / min or less, more preferably 0.2 L / min or more and 30 L / min or less. By making the nitrogen flow rate the above lower limit or more, the mixing of oxygen can be prevented, so it is preferable. In addition, by making the nitrogen flow rate the above upper limit or less, there is a tendency to prevent the volatilization of the raw material diol and make the hydroxyl value of the obtained polycarbonate diol composition constant.

[0246] [Use]

[0247] The polycarbonate diol composition of the present embodiment can be used as a raw material for polyurethanes that react with polyisocyanates. The polyurethanes produced using the polycarbonate diol composition of the present embodiment exhibit excellent chemical resistance, heat resistance, and weather resistance. Therefore, they can be widely used in foams, elastomers, coatings, coating agents, adhesives, binders, artificial leather, synthetic leather, aqueous polyurethane coatings, and the like. Furthermore, they can be used as modifiers for polyesters, polyimides, and the like.

[0248] [Polyurethane]

[0249] The polyurethane of the present embodiment is produced using the above polycarbonate diol composition.

[0250] [Stress at 100% elongation]

[0251] Regarding the polyurethane of the present embodiment, for the stress at 100% elongation based on a tensile test, ΔM calculated using the following formula (B) is preferably 1.0 or more and 19.0 or less, more preferably 3.5 or more and 18.5 or less, and even more preferably 5.0 or more and 17.0 or less.

[0252] ΔM = M1 - M2…(B)

[0253] (In formula (B), M1 is the stress at 100% elongation in a tensile test under the condition of -20°C, and M2 represents the stress at 100% elongation in a tensile test under the condition of 23°C.)

[0254] By making ΔM of the polyurethane of the present embodiment equal to or greater than the above lower limit value, there is a tendency for an excellent balance between flexibility and durability. In addition, by making ΔM of the polyurethane of the present embodiment equal to or less than the above upper limit value, the difference in elastic modulus caused by temperature is small. Therefore, there is a tendency for excellent mechanical properties at low temperatures.

[0255] The method for producing the polyurethane of the present embodiment can use the well-known polyurethane-forming reaction conditions commonly used for producing polyurethanes, and can be carried out in the absence or presence of a solvent.

[0256] As an example, without particular limitation, the following methods can be mentioned: a method of mixing and reacting the above polycarbonate diol composition, other polyols, polyisocyanates, and chain extenders together (hereinafter sometimes referred to as the "one-step method"); a method of first reacting the above polycarbonate diol composition, other polyols, and polyisocyanates to prepare a prepolymer with isocyanate groups at both ends, and then reacting the prepolymer with a chain extender (hereinafter sometimes referred to as the "prepolymer method"), and the like.

[0257] The isocyanate compound contained in the polyurethane of the present embodiment is not particularly limited as long as it functions as a curing agent, and a compound having two or more isocyanate groups at the terminal is used.

[0258] As such an isocyanate compound, there is no particular limitation, and examples thereof include chain aliphatic diisocyanates, cycloaliphatic diisocyanates, aromatic diisocyanates, isocyanate compounds having three or more isocyanate groups, and isocyanurate-modified products and biuret-modified products of these isocyanate compounds.

[0259] As the chain aliphatic diisocyanate, there is no particular limitation, and examples thereof include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

[0260] As the cycloaliphatic diisocyanate, there is no particular limitation, and examples thereof include isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and the like.

[0261] As the aromatic diisocyanate, there is no particular limitation, and examples thereof include toluene diisocyanate, 4,4'-diphenylmethane diisocyanate (hereinafter sometimes abbreviated as "MDI"), xylylene diisocyanate, and naphthalene diisocyanate.

[0262] As the isocyanate compound having three or more isocyanate groups, there is no particular limitation, and examples thereof include triphenylmethane-4,4'-4”-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, and 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate.

[0263] The isocyanate compound can be a commercially available product or can be synthesized by a known method.

[0264] The content of the isocyanate compound can be appropriately adjusted according to the molar amount of the hydroxyl group of the polyol as the main component. Specifically, the molar ratio (NCO / OH) of the isocyanate group of the isocyanate compound to the hydroxyl group of the polycarbonate diol can be, for example, 0.2 or more and 5.0 or less, for example, 0.4 or more and 3.0 or less, for example, 0.5 or more and 2.0 or less. If the NCO / OH is at or above the above lower limit value, there is a tendency to obtain a tougher coating film. On the other hand, if the NCO / OH is at or below the above upper limit value, there is a tendency to further improve the smoothness of the coating film.

[0265] In addition, the chain extender used in the production of the polyurethane of the present embodiment is not particularly limited, and examples thereof include ordinary polyols and polyamines.

[0266] As the polyol, there is no particular limitation, and examples thereof include linear diols, branched diols, cyclic diols, diols having an aromatic ring, etc.

[0267] As the linear diol, there is no particular limitation, and examples thereof include ethylene glycol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc.

[0268] As the branched diol, there is no particular limitation, and examples thereof include 2-methyl-1,8-octanediol, neopentyl glycol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, etc.

[0269] As the cyclic diol, there is no particular limitation, and examples thereof include 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-bis(4-hydroxycyclohexyl)-propane, etc.

[0270] As the diol having an aromatic ring, there is no particular limitation, and examples thereof include terephthalyl alcohol, tetrachloroterephthalyl alcohol, 1,4-bis(hydroxyethoxy)benzene, 2,2-bis〔(4-hydroxyethoxy)phenyl〕propane, etc.

[0271] As the polyamine, there is no particular limitation, and examples thereof include hydroxylamines, polyamines, etc.

[0272] As the hydroxylamines, there is no particular limitation, and examples thereof include N-methylethanolamine, N-ethylethanolamine, etc.

[0273] As the polyamines, there is no particular limitation, and examples thereof include ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropyl ethylenediamine, di-2-hydroxypropyl ethylenediamine, 4,4'-diphenylmethanediamine, methylenebis(orthochloroaniline), xylylenediamine, diphenyldiamine, toluenediamine, hydrazine, piperazine, N,N'-diaminopiperazine, etc.

[0274] These chain extenders can be used alone or in combination of two or more.

[0275] [Synthetic leather]

[0276] The synthetic leather of this embodiment contains the above polyurethane.

[0277] The synthetic leather of the present embodiment is not particularly limited, and examples thereof include synthetic leather having a base fabric, an adhesive layer, an intermediate layer, and a skin layer laminated in this order. In such synthetic leather, at least one selected from the group consisting of the base fabric, the adhesive layer, the intermediate layer, and the skin layer preferably contains the above polyurethane.

[0278] As the base fabric (base material), various substances can be used and there is no particular limitation. Examples thereof include fibrous base materials. As the fibrous base material, there is no particular limitation, and examples thereof include a fiber aggregate obtained by forming fibers into a non-woven fabric, a woven fabric, a mesh fabric, etc.; or a base material obtained by binding the fibers of the fiber aggregate with an elastic polymer. As the fibers used in the fiber aggregate, there is no particular limitation, and examples thereof include natural fibers such as cotton, hemp, and wool; regenerated or semi-synthetic fibers such as rayon and acetate; synthetic fibers such as polyamide, polyester, polyacrylonitrile, polyvinyl alcohol, and polyolefin. These fibers can be single-spun fibers or mixed-spun fibers. As other base materials, there is no particular limitation, and examples thereof include paper, release paper, plastic films of polyester and polyolefin, metal plates such as aluminum, and glass plates.

[0279] In the synthetic leather of the present embodiment, the above polyurethane is preferably used for the adhesive layer, the intermediate layer, and the skin layer. In addition, when forming each layer, a crosslinking agent, other resins, an antioxidant, an ultraviolet absorber, a hydrolysis inhibitor, a pigment, a dye, a colorant, a flame retardant, an organic solvent, etc. can be added as needed.

[0280] The manufacturing method of the synthetic leather of the present embodiment is not particularly limited as long as the above polyurethane is used, and a known manufacturing method of synthetic leather can be used.

[0281] [Coating or coating agent composition]

[0282] The coating or coating agent composition (coating) of the present embodiment is made using the above polycarbonate diol composition.

[0283] As a method of manufacturing a coating or coating agent composition (coating) using the above polycarbonate diol composition, a manufacturing method well-known in the industry can be used. Compositions such as the following can be manufactured: a two-component solvent-based coating composition in which a coating main agent obtained from the above polycarbonate diol composition and a curing agent containing a polyisocyanate are mixed immediately before coating; a one-component solvent-based coating composition containing a urethane prepolymer having an isocyanate terminal group obtained by reacting the above polycarbonate diol with a polyisocyanate; a one-component solvent-based coating composition containing a polyurethane resin obtained by reacting the above polycarbonate diol, an organic polyisocyanate, and a chain extender.

[0284] In the coating or coating agent composition (coating) of the present embodiment, for example, a curing accelerator (catalyst), a leveling agent, a filler, a dispersant, a flame retardant, a dye, an organic or inorganic pigment, a release agent, a fluidity regulator, a plasticizer, an antioxidant, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a colorant, a solvent, and other additives can be added according to various uses. By appropriately containing these other additives, coating compositions with different properties such as a soft-feel coating and a transparent coating can be obtained.

[0285] As the curing accelerator (catalyst), there is no particular limitation, and examples thereof include commonly used substances such as monoamines, diamines, and triamines, cyclic amines, alkanolamines, etheramines, and metal catalysts.

[0286] As the monoamine, there is no particular limitation, and examples thereof include triethylamine, N,N-dimethylcyclohexylamine, etc. As the diamine, there is no particular limitation, and examples thereof include tetramethylethylenediamine, etc.

[0287] As the alkanolamine, there is no particular limitation, and examples thereof include dimethylethanolamine, etc.

[0288] As the metal catalyst, there is no particular limitation, and examples thereof include potassium acetate, potassium 2-ethylhexanoate, calcium acetate, lead octoate, dibutyltin dilaurate, tin octoate, bismuth neodecanoate, bismuthyl carbonate, bismuth 2-ethylhexanoate, zinc octoate, zinc neodecanoate, phosphine, phosphorine, etc.

[0289] As specific examples of the organic solvent, there is no particular limitation, and examples thereof include amide solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, carbonate solvents, aromatic hydrocarbon solvents, etc.

[0290] These organic solvents can be used alone or in the form of a mixed solvent of two or more kinds.

[0291] Examples

[0292] Hereinafter, specific examples and comparative examples are listed to more specifically illustrate the present embodiment. However, the present embodiment is not limited to these examples and comparative examples as long as it does not exceed its gist. In the present examples, unless otherwise specified, "parts" and "%" are based on a mass basis.

[0293] The physical properties and evaluations in the following-described examples and comparative examples were measured and evaluated by the methods shown below.

[0294] [Physical Property 1] Hydroxyl value

[0295] The hydroxyl value of the polycarbonate diol (composition) was measured by the following method.

[0296] First, using a volumetric flask, pyridine was added to 12.5 g of acetic anhydride to make 50 mL, and an acetylation reagent was prepared. Next, 2.5 g of the sample was precisely weighed into a 100 mL eggplant-shaped flask. Then, 5 mL of the acetylation reagent and 10 mL of toluene were added to the aforementioned eggplant-shaped flask using a full-volume pipette, and then a condenser was installed. The solution in the eggplant-shaped flask was stirred and heated at 100 °C for 1 hour. Next, 2.5 mL of distilled water was added to the aforementioned eggplant-shaped flask using a full-volume pipette, and then the solution in the aforementioned eggplant-shaped flask was further heated and stirred for 10 minutes. After the solution in the aforementioned eggplant-shaped flask was cooled for 2 - 3 minutes, 12.5 mL of ethanol was added to the aforementioned eggplant-shaped flask. Then, 2 - 3 drops of phenolphthalein were added to the aforementioned eggplant-shaped flask as an indicator, and titration was performed with 0.5 mol / L alcoholic potassium hydroxide. Next, 5 mL of the acetylation reagent, 10 mL of toluene, and 2.5 mL of distilled water were added to a 100 mL eggplant-shaped flask. After the solution in the aforementioned eggplant-shaped flask was heated and stirred for 10 minutes, titration was performed in the same manner (blank test). Based on this result, the hydroxyl value of the polycarbonate diol (composition) was calculated by the following formula (i).

[0297] Hydroxyl value (mg-KOH / g) = {(F - E) × 28.05 × f} / G ··· (i)

[0298] 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.

[0299] [Physical property 2] Number-average molecular weight (A)

[0300] The number-average molecular weight (A) of the polycarbonate diol (composition) was calculated using the following formula (ii) and the hydroxyl value obtained in [Physical property 1].

[0301] Number-average molecular weight (A) = 2 / (H × 10 -3 / 56.11) … (ii)

[0302] It should be noted that in formula (ii), H represents the hydroxyl value (mg-KOH / g) of the polycarbonate diol (composition).

[0303] It should be noted that in the following Examples and Comparative Examples, the number-average molecular weight Mn of the polycarbonate diol composition applied in the following formula 1 was set as the number-average molecular weight (A) calculated using the above formula (ii).

[0304] xy ≥ 3.7 × α (α = 22.4 × Mn -0.41 ) … (Formula 1)

[0305] (In formula (1), x is the ratio of the content (mass %) of the repeating structural unit represented by the aforementioned general formula (I) to the total mass (mass %) of the repeating structural units represented by the aforementioned general formulas (I) to (IV), y is the titration amount (mL) in the cloud point titration method of the polycarbonate diol composition, and Mn is the number average molecular weight of the polycarbonate diol composition.)

[0306] [Physical Property 3] Molecular Weight (B)

[0307] Cut a part of the polyurethane film obtained in the following application examples and application comparative examples, and prepare an N,N-dimethylformamide solution so that the concentration of polyurethane becomes 0.1 mass %. Use a GPC device [manufactured by Tosoh Corporation, product name "HLC-8320" (column: Tskgel SuperHM-H · 4 pieces)], and use a solution obtained by dissolving 2.6 g of lithium bromide in 1 L of dimethylformamide as the eluent to measure the number average molecular weight (Mn) and weight average molecular weight (Mw) of the polyurethane in terms of standard polystyrene conversion. In addition, calculate the molecular weight distribution (Mw / Mn) based on their measurement results.)

[0308] [Physical Property 4] Hazen Color Number (APHA)

[0309] In accordance with JIS K0071-1 (2017), compare with the standard solution placed in the colorimetric tube to measure the APHA of the polycarbonate diol composition obtained in the following examples and comparative examples. Use the chromaticity standard solution 1000 degrees (Fuji Film Wako Pure Chemical Industries, Ltd.) as the reagent. In addition, prepare solutions with a scale of 5 until the APHA reaches 30 and make a judgment. In the case of a slightly turbid liquid, heat it at 60 °C to dissolve it and then measure it.)

[0310] [Physical Property 5] Cloud Point Titration

[0311] Under the condition of 25 °C, dissolve 0.5 g of the polycarbonate diol composition obtained in the following examples and comparative examples in 8.8 g of butyl acetate, and while stirring the resulting solution, slowly dropwise add hexane little by little, and find the titration amount at the start of cloudiness, and calculate the cloud point titration using the following formula (iii).

[0312] Cloud Point Titration = 0.5 × I × 56.1 / (J × K) … (iii)

[0313] It should be noted that in the following formula (iii), I represents the titration amount (mL) obtained as above, J represents the mass (g) of the weighed sample, and K represents the hydroxyl value (mg-KOH / g) of the polycarbonate diol composition.)

[0314] [Physical Property 6] Acid Value

[0315] Except for changing the solvent to toluene / ethanol (2 / 1), the acid value of the polycarbonate diol compositions obtained in the following Examples and Comparative Examples was determined using the method based on JIS K 0070-1992.

[0316] [Physical Property 7] Content of Structural Unit (I) in Polycarbonate Diol Composition

[0317] Measure 1 g of the sample of the polycarbonate diol composition obtained in the following Examples and Comparative Examples into a 100 mL eggplant-shaped flask, add 30 g of methanol and 8 g of 28% sodium methoxide methanol solution, and react at 100 °C for 1 hour. After cooling the reaction solution to room temperature, add 2 - 3 drops of phenolphthalein to the indicator and neutralize with hydrochloric acid. After cooling in the refrigerator for 1 hour, filter with a filter and analyze using a gas chromatograph (GC). In the GC analysis, as the column, use a gas chromatograph GC-14B (manufactured by Shimadzu Corporation, Japan) equipped with DB-WAX (manufactured by J&W Company, USA), use diethylene glycol diethyl ester as the internal standard, and perform quantitative analysis of each component using a flame ionization detector (FID) as the detector. It should be noted that in the temperature rising curve of the column, after maintaining at 60 °C for 5 minutes, raise the temperature to 250 °C at a rate of 10 °C / min.

[0318] Based on each alcohol component and the methyl ester component from the dibasic acid detected by the above analysis results, the composition of the polycarbonate diol composition was determined.

[0319] In the case where the methyl ester component from the dibasic acid is not detected, regarding the composition of the polyester polycarbonate polyol containing the dibasic acid, the number of moles of the diols constituting the carbonate skeleton was determined by using the value obtained by subtracting the diol having the same number of moles as the number of moles of the methyl ester from the dibasic acid (when using multiple diols, according to the ratio of the diols determined by gas chromatography, the composition of the diols in the carbonate skeleton and the diols in the ester skeleton were set to be the same for calculation).

[0320] [Physical Property 8] Peroxide Value (POV)

[0321] Immerse the sample of the polycarbonate diol composition obtained in the following Examples and Comparative Examples in the test section of a POV test paper (manufactured by Shibata Scientific Co., Ltd.), leave it for 3 minutes and wash with pure water. Compare the POV test paper of this sample with the standard color sample, and judge the peroxide value (POV) in the sample as follows.

[0322] [Judgment Criteria]

[0323] It is marked as 〇 when it is detected as 0 meq / kg or more and 3 meq / kg or less in the standard color sample.

[0324] When it is more than 3 meq / kg and less than or equal to 10 meq / kg, which is equivalent to 10 of the standard color sample, it is denoted as △.

[0325] When it is more than 10 meq / kg and less than or equal to 40 meq / kg, which is equivalent to 30 of the standard color sample, it is denoted as ×.

[0326] [Physical Property 9] Quality Stability

[0327] The polycarbonate diol compositions obtained in the following Examples and Comparative Examples were stored at 25 °C for 6 months, and the quality stability was evaluated as follows based on the appearance change compared to just after manufacturing.

[0328] [Evaluation Criteria]

[0329] 〇: No appearance change compared to just after manufacturing

[0330] ×: There is an appearance change compared to just after manufacturing (such as two-layer separation, turbidity, precipitation, etc.)

[0331] [Evaluation 1] Compatibility Evaluation (Polyol)

[0332] The compatibility of the polycarbonate diol compositions obtained in the following Examples and Comparative Examples was evaluated as follows. As an example of the polyol, polyester polyol (manufactured by Showa Denko Materials Co., Ltd., "TESLAC 2460" (trade name), number average molecular weight: about 2000) was used. This polyester polyol and the polycarbonate diol composition were successively mixed and stirred at a mass ratio of 7:3, and the compatibility was evaluated as follows based on the appearance of the resulting solution.

[0333] [Evaluation Criteria]

[0334] 〇: Transparent

[0335] △: Slightly turbid or slightly two-layer separated

[0336] ×: Turbid

[0337] [Evaluation 2] Compatibility Evaluation (Solvent)

[0338] The compatibility of the polycarbonate diol compositions obtained in the following Examples and Comparative Examples was evaluated as follows. As an example of the solvent, methyl isobutyl ketone (hereinafter also denoted as "MIBK") was used. The polycarbonate diol composition was compounded into methyl isobutyl ketone so that the solid content became 75%, mixed and stirred at 25 °C, and after standing for 30 minutes, the compatibility was evaluated as follows based on the appearance of the resulting solution.

[0339] [Evaluation Criteria]

[0340] 〇: Transparent

[0341] △: Slightly turbid

[0342] ×: Turbid

[0343] [Evaluation 3] Tensile test at room temperature

[0344] According to JIS K6250 (2019), short strip test pieces with a width of 10 mm, a length of 100 mm, and a thickness of approximately 0.1 mm are made from the polyurethane films obtained in the application examples and application comparative examples described below. For the test pieces thus made, using a tensile testing machine (manufactured by ORIENTEC Co., Ltd., product name "TENSILON, RTE-1210 type"), under the conditions that the distance between the clamps is 20 mm and the tensile speed is 100 mm / minute, a tensile test is carried out at a temperature of 23°C (relative humidity 55%), and the stress (100% modulus) when the test piece elongates by 100% is measured. The lower the 100% modulus, the more excellent the softness at room temperature is evaluated.

[0345] [Evaluation 4] Tensile test at low temperature

[0346] According to JIS K6250 (2019), short strip test pieces with a width of 10 mm, a length of 100 mm, and a thickness of approximately 0.1 mm are made from the polyurethane films obtained in the application examples and application comparative examples described below. In a tensile testing machine (manufactured by ORIENTEC Co., Ltd., product name "TENSILON, RTE-1210 type") equipped with a constant temperature bath (manufactured by ORIENTEC Co., Ltd., "TLF-R3T-E-W type"), the test pieces thus made are set under the condition that the distance between the clamps is 20 mm. Then, after leaving the test pieces standing at -20°C for 5 minutes, a tensile test of the test pieces is carried out under the condition that the tensile speed is 100 mm / minute, and the stress (100% modulus) when the test piece elongates by 100% is measured. The lower the 100% modulus, the more excellent the softness is evaluated.

[0347] [Evaluation 5] Stress at 100% elongation (hereinafter sometimes referred to as "ΔM")

[0348] Based on the 100% modulus (stress at 100% elongation) obtained in the aforementioned [Evaluation 1] and [Evaluation 2], ΔM is calculated using the following formula (B).

[0349] ΔM = M1 - M2...(B)

[0350] (In formula (B), M1 is the stress at 100% elongation under the condition of -20°C obtained in [Evaluation 2], and M2 is the stress at 100% elongation under the condition of 23°C obtained in [Evaluation 1].)

[0351] [Evaluation 6] Evaluation of moisture and heat resistance

[0352] Short strip samples with a width of 10 mm, a length of 100 mm, and a thickness of about 100 μm were made from the polyurethane films obtained in the following application examples and application comparative examples. For the samples made, using a thermo-hygrostat manufactured by ESPEC Corporation, product name "PL-1J", heating was carried out for 10 days under the conditions of a temperature of 85 °C and a humidity of 85%. For the heated samples, the breaking strength was measured in the same manner as in the above <Normal Temperature Tensile Test>, and the retention rate (%) of the breaking strength was calculated from the following formula (C).

[0353] Retention rate = Breaking strength after heating / Breaking strength before heating × 100…(C)

[0354] [Evaluation 7] ΔAPHA of the polyurethane solution

[0355] The polyurethane solutions obtained in the following application examples and application comparative examples were stored using a small environmental test machine at 40 °C, and the change over time (ΔAPHA (after 3 months of storage - just after preparation)) of the APHA of the polyurethane solution just after preparation and the APHA of the polyurethane solution after 3 months of storage at 40 °C was measured.

[0356] It should be noted that the abbreviations in the table and the main text are as follows.

[0357] A-1: Polyoxytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG2000" (trade name), number average molecular weight: about 2000, in the general formula (II-1), R 211 : Tetramethylene, n211: about 28)

[0358] A-2: Polyoxytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG1000" (trade name), number average molecular weight: about 1000, in the general formula (II-1), R 211 : Tetramethylene, n211: about 14)

[0359] A-3: Polyoxyethylene polyoxypropylene glycol (manufactured by Sanyo Chemical Industries, Ltd., "NEWPOL PE-61" (trade name), number average molecular weight: about 2000, in the general formula (II-1), R 211 : Isopropylidene and methylene, n211: about 35)

[0360] A-4: Polyoxyethylene polyoxypropylene glycol (manufactured by Sanyo Chemical Industries, Ltd., "NEWPOL PE-62" (trade name), number average molecular weight: about 2400, in the general formula (II-1), R 211 : Isopropylidene and methylene, n211: about 44)

[0361] A-5: Copolymer of tetrahydrofuran and neopentyl glycol (manufactured by Asahi Kasei Corporation, "PTXG" (trade name), number average molecular weight: about 1800, in general formula (II-1), R 211 : 2,2-dimethyltrimethylene and tetramethylene, n211: about 23)

[0362] B-1: Polycaprolactone polyol (manufactured by Daicel Chemical Industries, Ltd., "Placcel 220" (trade name), number average molecular weight: about 2000, in general formula (III-1), R 311 : Pentamethylene, n311: about 18)

[0363] B-2: Polyester polyol (manufactured by DIC Corporation, "OD-X-2692" (trade name), number average molecular weight: about 2000, in general formula (IV-1), R 411 : Tetramethylene, R 421 : Isobutylene, n411: about 10)

[0364] B-3: Polyester polyol (manufactured by Kuraray Co., Ltd., "P-2020" (trade name), number average molecular weight: about 2000, in general formula (IV-1), R 411 : Phenylene, R 421 : 3-methylpentamethylene, n411: about 8)

[0365] [Synthesis Example 1] Production of polycarbonate diol P-1

[0366] Into a 1 L glass flask (hereinafter also referred to as "reactor") equipped with a rectification column filled with regular packing and a stirring device, 230 g of 1,5-pentanediol, 250 g of 1,6-hexanediol, and 400 g of ethylene carbonate were charged, and then 0.0468 g of tetra-n-butyl titanate was charged as a catalyst. The reactor was immersed in an oil bath at 180 °C, and while extracting a part of the distillate, the reaction was carried out at a reaction temperature of 165 °C for 12 hours. Then, the reactor was directly connected to a condenser, the temperature of the oil bath was raised to 180 °C, and the pressure was gradually reduced, and the reaction was further carried out for 3 hours to obtain polycarbonate diol P-1 (466 g) which was liquid at room temperature. The hydroxyl value of the obtained polycarbonate diol P-1 was 55.2 mg-KOH / g. In addition, the number average molecular weight of the obtained polycarbonate diol P-1 was 2033.

[0367] [Synthesis Example 2] Production of polycarbonate diol P-2

[0368] Into a 1-L glass flask (hereinafter also referred to as "reactor") equipped with a rectifying column filled with regular packing and a stirring device, 270 g of 1,6-hexanediol, 250 g of 1,4-butanediol, and 445 g of ethylene carbonate were charged, and then 0.0960 g of tetrabutyl titanate was charged as a catalyst. The reactor was immersed in an oil bath at 140 to 160 °C, and while a part of the distillate was withdrawn, the reaction was carried out at a reaction temperature of 90 to 160 °C for 20 hours. Then, the reactor was directly connected to a condenser, the temperature of the oil bath was raised to 180 °C, and the pressure was slowly reduced, and the reaction was further carried out for 8 hours to obtain a polycarbonate diol P-2 (462 g) that was liquid at room temperature. The hydroxyl value of the obtained polycarbonate diol P-2 was 56.1 mg-KOH / g. In addition, the number-average molecular weight of the obtained polycarbonate diol P-2 was 2000.

[0369] [Synthesis Example 3] Production of polycarbonate diol P-3

[0370] Into a 1-L glass flask (hereinafter also referred to as "reactor") equipped with a rectifying column filled with regular packing and a stirring device, 230 g of 1,5-pentanediol, 250 g of 1,6-hexanediol, and 400 g of ethylene carbonate were charged, and then 0.0468 g of tetrabutyl titanate was charged as a catalyst. The reactor was immersed in an oil bath at 180 °C, and while a part of the distillate was withdrawn, the reaction was carried out at a reaction temperature of 165 °C for 12 hours. Then, the reactor was directly connected to a condenser, the temperature of the oil bath was raised to 165 °C, and the pressure was slowly reduced, and the reaction was further carried out for 3 hours to obtain a polycarbonate diol P-3 (478 g) that was liquid at room temperature. The hydroxyl value of the obtained polycarbonate diol P-3 was 112.0 mg-KOH / g. In addition, the number-average molecular weight of the obtained polycarbonate diol P-3 was 1002.

[0371] [Example 1] Production of polycarbonate diol composition SA-1

[0372] Into a 1 L glass flask equipped with a stirring device (hereinafter also referred to as "reactor"), 90 parts by mass (360 g) of the polycarbonate diol P-2 obtained in Synthesis Example 2 and 10 parts by mass (40 g) of polytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG2000" (trade name), number average molecular weight: about 2000) were charged. Then, the pressure in the reactor was reduced to 0.1 kPa·s or less using a vacuum pump, and the mixture was stirred at 120 °C for 10 minutes. Thereafter, nitrogen replacement was carried out, and it was confirmed that the oxygen concentration was 0.5% or less. While maintaining the nitrogen flow rate at 1 L / min, the mixture was heated and stirred at a reactor internal temperature of about 145 °C for 12 hours. For the reaction solution, cloud point titration was carried out over time. After confirming that the cloud point titration amount did not change, dibutyl phosphoric acid was added in such a manner that the mass ratio to titanium tetrabutoxide was 1.3 times, and the mixture was heat-treated at a reactor internal temperature of 110 °C for 3 hours, thereby obtaining a polycarbonate diol composition SA-1. The physical properties of the obtained polycarbonate diol composition SA-1 were measured by the above method. The results are shown in Table 1. The hydroxyl value of the obtained polycarbonate diol composition SA-1 was 56.6 mg-KOH / g. In addition, the number average molecular weight of the obtained polycarbonate diol composition SA-1 was 1982.

[0373] In addition, the obtained polycarbonate diol composition SA-1 contains a repeating structural unit represented by the following formula (A1) and a repeating structural unit represented by the following formula (B1).

[0374]

[0375] (In general formula (A1), R 11 is an aliphatic hydrocarbon group having 4 or 6 carbon atoms.)

[0376]

[0377] (In general formula (B1), R 21 is tetramethylene, and the average value of n21 is about 28.)

[0378] [Examples 2 to 13]

[0379] As described in Tables 1 and 2 respectively, the types and charging amounts of the respective raw materials were changed. Except for this, the reactions were all carried out under the same conditions and methods as in Example 1 to obtain polycarbonate diol compositions SA-2 to SA-13 of Examples 2 to 13. Regular quantification during cloud point titration of the obtained polycarbonate diol compositions SA-2 to SA-13 was carried out, and the physical properties were measured by the above method. The results are shown in Tables 1 and 2.

[0380] In addition, the obtained polycarbonate diol compositions SA-2 to SA-13 contain repeating structural units represented by the following formulas (A2) to (A13) and repeating structural units represented by the following formulas (B2) to (B13) in this order.

[0381]

[0382] (In general formula (A2), R 11 is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.)

[0383]

[0384] (In general formula (B2), R 21 is tetramethylene, and the average value of n21 is about 28.)

[0385]

[0386] (In general formula (A3), R 11 is an aliphatic hydrocarbon group having 4 or 6 carbon atoms.)

[0387]

[0388] (In general formula (B3), R 21 is isopropylidene and methylene, and the average value of n21 is about 35.)

[0389]

[0390] (In general formula (A4), R 11 is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.)

[0391]

[0392] (In general formula (B4), R 21 is tetramethylene, and the average value of n21 is about 28.)

[0393]

[0394] (In general formula (A5), R 11 is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.)

[0395]

[0396] (In general formula (B5), R 21 is 2,2-dimethyltrimethylene and tetramethylene, and the average value of n21 is about 23.)

[0397]

[0398] (In general formula (A6), R 11 is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.)

[0399]

[0400] (In general formula (B6), R 21 is 2,2-dimethyltrimethylene and tetramethylene, and the average value of n21 is about 23.)

[0401]

[0402] (In general formula (A7), R 11 is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.)

[0403]

[0404] (In general formula (B7), R 21 is tetramethylene, and the average value of n21 is about 14.)

[0405]

[0406] (In general formula (A8), R 11 is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.)

[0407]

[0408] (In general formula (B8), R 21 is isopropylidene and methylene, and the average value of n21 is about 44.)

[0409]

[0410] (In general formula (A9), R 11 is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.)

[0411]

[0412] (In general formula (B9), R 21 is isopropylidene and methylene, and the average value of n21 is about 35.)

[0413]

[0414] (In general formula (A10), R 11 is an aliphatic hydrocarbon group having 4 or 6 carbon atoms.)

[0415]

[0416] (In general formula (B10), R 31 is pentamethylene.)

[0417]

[0418] (In general formula (A11), R 11 is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.)

[0419]

[0420] (In general formula (B11), R 41 is tetramethylene, and R 42 is isobutylene.)

[0421]

[0422] (In general formula (A12), R 11 is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.)

[0423]

[0424] (In general formula (B12), R 41 is phenylene, and R 42 is 3-methylpentamethylene.)

[0425]

[0426] (In general formula (A3), R 11 is an aliphatic hydrocarbon group having 4 or 6 carbon atoms.)

[0427]

[0428] (In general formula (B3), R 21 is isopropylidene and methylene, and the average value of n21 is about 35.)

[0429] [Comparative Example 1] Preparation of Polycarbonate Diol Composition SB-1

[0430] Into a 1 L glass flask equipped with a stirring device (hereinafter also referred to as "reactor"), 25 parts by mass (100 g) of the polycarbonate diol P-1 obtained in Synthesis Example 1 and 75 parts by mass (300 g) of polytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG2000" (trade name), number average molecular weight: about 2000) were charged. Under an air atmosphere, the temperature inside the reactor was heated to about 145 °C and maintained for 10 hours while stirring. Then, dibutyl phosphate was added in a mass ratio of 1.3 times that of titanium tetrabutoxide, and heat treatment was carried out at a reactor internal temperature of 110 °C for 3 hours to obtain a polycarbonate diol composition SB-1. The physical properties of the obtained polycarbonate diol composition SB-1 were measured by the above method. The results are shown in Table 3. The hydroxyl value of the obtained polycarbonate diol composition SB-1 was 56.2 mg-KOH / g, and the number average molecular weight was 1996.

[0431] [Comparative Example 2] Preparation of Polycarbonate Diol Composition SB-2

[0432] The types and charging amounts of the respective raw materials were changed as described in Table 2, and the reaction was carried out under the same conditions and methods as in Comparative Example 1 except for this, to obtain a polycarbonate diol composition SB-2 of Comparative Example 2. The physical properties of the obtained polycarbonate diol composition SB-2 were measured by the above method. The results are shown in Table 3.

[0433] [Comparative Example 3] Preparation of Polycarbonate Diol Composition SB-3

[0434] 400 g of the polycarbonate diol P-2 obtained in Synthesis Example 2 was added to a 1 L glass flask equipped with a stirring device (hereinafter also referred to as "reactor"), and dibutyl phosphate was added in a mass ratio of 1.3 times that of titanium tetrabutoxide, and heat treatment was carried out at a reactor internal temperature of 110 °C for 3 hours to obtain a polycarbonate diol composition SB-3. The physical properties of the obtained polycarbonate diol composition SB-3 were measured by the above method. The results are shown in Table 3. The hydroxyl value of the obtained polycarbonate diol composition SB-3 was 56.1 mg-KOH / g, and the number average molecular weight was 2000.

[0435] [Comparative Example 4] Preparation of Polycarbonate Diol Composition SB-4

[0436] Into a 1-L glass flask equipped with a stirring device (hereinafter also referred to as "reactor"), 90 parts by mass (360 g) of the polycarbonate diol P-2 obtained in Synthesis Example 2 and 10 parts by mass (40 g) of polytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG2000" (trade name), number average molecular weight: about 2000) were charged. Next, the inside of the reactor was evacuated to 0.1 kPa·s or less using a vacuum pump, stirred at 120 °C for 10 minutes, and then purged with nitrogen, and the oxygen concentration was confirmed to be 0.5% or less. While maintaining the nitrogen flow rate at 1 L / min, the reaction mixture was heated and stirred at an internal temperature of the reactor of about 145 °C for 6 hours. The reaction solution was subjected to GPC measurement over time, and the disappearance of the peak derived from the raw material and the generation of the peak derived from the product were confirmed over time to confirm the progress of the reaction. Thereafter, dibutyl phosphoric acid was added in an amount 1.3 times the mass ratio with respect to titanium tetrabutoxide, and heat-treated at an internal temperature of the reactor of 110 °C for 3 hours to obtain a polycarbonate diol composition SB-4. Each physical property of the obtained polycarbonate diol composition SB-4 was measured by the above method. The results are shown in Table 3. The hydroxyl value of the obtained polycarbonate diol composition SB-4 was 56.2 mg-KOH / g. In addition, the number average molecular weight of the obtained polycarbonate diol composition SB-4 was 1996.

[0437] [Table 1]

[0438]

[0439] [Table 2]

[0440]

[0441] [Table 3]

[0442]

[0443] [Application Example 1] Synthesis of Polyurethane Film PA-1

[0444] Into a 500 mL separable flask equipped with a thermocouple and a cooling tube, 138 g of polycarbonate diol composition SA-1, 224 g of dimethylformamide (hereinafter sometimes abbreviated as DMF), and 0.26 g of a 1% dibutyltin dilaurate toluene solution (50 ppm based on the total mass of MDI and the polycarbonate diol composition) were charged, and heated with 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 [mol] relative to the OH [mol] of the polycarbonate diol composition) was added dropwise into the flask. Furthermore, the solution in the flask was stirred for about 1.5 hours. The isocyanate group concentration was analyzed, and it was confirmed that the theoretical amount was consumed to obtain a prepolymer. Next, 3.2 g of 1,4-butanediol (1,4-BD), which is the necessary amount calculated from the residual isocyanate, was added to the flask in portions. After stirring the solution in the flask for about 1 hour, about 1 g of ethanol was added, and further, the solution in the flask was stirred for 30 minutes to obtain a polyurethane solution with a number average molecular weight of 74,000.

[0445] Using a 0.8 mm thick applicator, the obtained polyurethane solution was dropped onto the upper part of a glass plate (JIS R3202, 2 mm × 100 mm × 150 mm) and coated so that the dry film thickness reached 50 to 150 μm, and dried on a heating plate with a surface temperature of 60 °C for 2 hours, and then dried in an oven at 80 °C for 12 hours. Furthermore, it was left standing for 12 hours or more at 23 °C and 55% RH in a constant temperature and humidity environment to obtain a polyurethane film PA-1. The obtained polyurethane film PA-1 was subjected to evaluation of various physical properties using the above method. The evaluation results are shown in Table 4.

[0446] [Application Examples 2 to 13]

[0447] In the production of the polyurethane film in Application Example 1, the polycarbonate diol composition used was changed to the polycarbonate diol compositions SA-2 to SA-13 produced in Examples 2 to 12. Except for this, the reaction was carried out under the same conditions as in Application Example 1 to obtain polyurethane films PA-2 to PA-13. The obtained polyurethane films PA-2 to PA-13 were subjected to evaluation of various physical properties using the above method. The evaluation results are shown in Tables 4 and 5.

[0448] [Application Comparative Examples 1 to 4]

[0449] In the production of the polyurethane film of Application Example 1, the polycarbonate diol composition etc. used were changed to the polycarbonate diol compositions etc. SB-1 to SB-4 produced in Comparative Examples 1 to 3, and the reaction was carried out under the same conditions as in Application Example 1 to obtain polyurethane films PB-1 to PB-4. For the obtained polyurethane films PB-1 to PB-4, various physical properties were evaluated using the above method. The evaluation results are shown in Table 6.

[0450] [Table 4]

[0451] Application Example 1 Application Example 2 Application Example 3 Application Example 4 Application Example 5 Application Example 6 Polyurethane Film PA-1 PA-2 PA-3 PA-4 PA-5 PA-6 Number-average Molecular Weight Mn 74000 68000 68000 71000 81000 79000 Mw / Mn 3.3 3.4 3.3 3.6 3.5 3.2 ΔM {M1(-20°C) - M2(23°C)} 18.2 10.8 10.2 9.9 9.7 9.9 M2(23°C) [MPa] 4.9 4.5 3.2 2.9 3.8 3.2 M1(-20°C) [MPa] 23.1 15.3 13.4 12.8 13.5 13.1 Damp Heat Resistance Test - Retention Rate [%] 77.9 55.1 60.7 57.5 62.5 60.5 ΔAPHA of Polyurethane Solution 20 10 10 10 10 10

[0452] [Table 5]

[0453] Application Example 7 Application Example 8 Application Example 9 Application Example 10 Application Example 11 Application Example 12 Application Example 13 Polyurethane Film PA-7 PA-8 PA-9 PA-10 PA-11 PA-12 PA-13 Number-average Molecular Weight Mn 66000 69000 78000 72000 75000 65000 67000 Mw / Mn 3.3 3.5 3.4 4.1 4.3 4.4 3.6 ΔM {M1(-20°C) - M2(23°C)} 17.1 10.1 10.3 13.3 12.9 19.2 8.4 M2(23°C) [MPa] 5.5 3.6 2.9 4.1 3.9 4.2 2.7 M1(-20°C) [MPa] 22.6 13.7 13.2 17.4 16.8 23.4 11.1 Damp Heat Resistance Test - Retention Rate [%] 75.3 61.2 57.2 54.2 51.6 48.8 43.6 ΔAPHA of Polyurethane Solution 20 10 20 20 30 30 30

[0454] [Table 6]

[0455] Application Comparative Example 1 Application Comparative Example 2 Application Comparative Example 3 Application Comparative Example 4 Polyurethane Film PB-1 PB-2 PB-3 PB-4 Number-average Molecular Weight Mn 69000 59000 85000 67000 Mw / Mn 3.7 3.8 3.5 3.8 ΔM {M1(-20°C) - M2(23°C)} 4.9 4.8 22.3 19.4 M2(23°C) [MPa] 4.3 3.8 5.7 4.8 M1(-20°C) [MPa] 9.2 8.6 28.1 24.2 Damp Heat Resistance Test - Retention Rate [%] 38.1 30.5 92.1 76.6 ΔAPHA of Polyurethane Solution 100 60 10 40

[0456] From the results shown in Tables 1 to 3, it can be seen that: a polycarbonate diol composition containing the repeating structural unit (I), further containing at least one repeating structural unit selected from the group consisting of the repeating structural units (II) to (IV), and satisfying specific conditions has excellent compatibility with polyols and solvents compared to a polycarbonate diol composition that does not satisfy the specific conditions. It can also be seen that: by controlling the acid value and / or peroxide value of the polycarbonate diol composition, APHA can be further reduced and coloring can be further reduced.

[0457] In addition, from the results shown in Tables 4 to 6, it can be seen that: the polyurethanes obtained from the polycarbonate diol compositions of the examples have excellent softness and mechanical properties at low temperatures, and also have an excellent balance with durability such as heat and humidity resistance. It can also be confirmed that: the change over time of APHA of the polyurethane solution obtained from the polycarbonate diol composition of the example is also good.

[0458] This application is based on the Japanese patent application filed on April 21, 2021 (Japanese Patent Application No. 2021-072116), and its content is incorporated herein by reference.

[0459] Industrial Applicability

[0460] The polycarbonate diol composition of the present embodiment can be highly solidified when producing coatings and polyurethanes, for example, and is useful as a raw material for coatings and polycarbonate-based polyurethanes. In addition, the polyurethane produced using the polycarbonate diol composition of the present embodiment has a stable hue, and has the characteristics of excellent low-temperature softness and durability, and can be suitably used in a wide range of fields such as elastic fibers, synthetic or artificial leather, coatings, and high-performance elastomers.

Claims

1. A polycarbonate diol composition comprising a repeating structural unit represented by the following general formula (I), and further comprising at least one repeating structural unit selected from the group consisting of a repeating structural unit represented by the following general formula (II), a repeating structural unit represented by the following general formula (III), and a repeating structural unit represented by the following general formula (IV), wherein the polycarbonate diol composition satisfies the following formula 1, the acid value is 0.001 mg-KOH / g or more and 0.8 mg-KOH / g or less, and the peroxide content is 10 meq / kg or less: In general formula (I), R 11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 15 or less carbon atoms, and when there are a plurality of Rs 11 may be the same as or different from each other In general formula (II), R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, and when there are a plurality of Rs 21 may be the same or different from each other; n21 is an arbitrary integer, In general formula (III), R 31 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, and when there are a plurality of Rs 31 may be the same as or different from each other In general formula (IV), R 41 and R 42 each independently represents a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. When there are a plurality of R 41 and R 42 may be the same or different from each other optionally, xy ≥ 3.7×α (α = 22.4×Mn -0.41 )…(Equation 1) (In formula 1), x is the ratio of the content of the repeating structural unit represented by the general formula (I) in mass % to the total mass of the repeating structural units represented by the general formulas (I) to (IV) in mass %, y is the titration volume in mL in the cloud point titration method of the polycarbonate diol composition, and Mn is the number average molecular weight of the polycarbonate diol composition.

2. A polycarbonate diol composition comprising a repeating structural unit represented by the following general formula (I), and further comprising at least one repeating structural unit selected from the group consisting of a repeating structural unit represented by the following general formula (II), a repeating structural unit represented by the following general formula (III), and a repeating structural unit represented by the following general formula (IV), wherein the content of the repeating structural unit represented by the general formula (I) is 40 mass % or more relative to the total mass of the repeating structural units represented by the general formulas (I) to (IV), the titration volume of the polycarbonate diol composition in the cloud point titration method is 4.0 mL or more and 9.5 mL or less, the acid value is 0.001 mg-KOH / g or more and 0.8 mg-KOH / g or less, and the peroxide content is 10 meq / kg or less, In general formula (I), R 11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 or more and 15 or less carbon atoms, and when there are a plurality of Rs 11 may be the same as or different from each other In general formula (II), R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, and when there are a plurality of Rs 21 may be the same as or different from each other, and n21 is an arbitrary integer. In general formula (III), R 31 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, and when there are a plurality of Rs 31 may be the same as or different from each other, In general formula (IV), R 41 and R 42 are each independently a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, and when there are a plurality of R 41 and R 42 may be the same or different from each other optionally.

3. The polycarbonate diol composition according to claim 1, wherein the content of the repeating structural unit represented by the general formula (I) is 5 mass % or more and 95 mass % or less relative to the total mass of the repeating structural units represented by the general formulas (I) to (IV).

4. The polycarbonate diol composition according to claim 1 or 2, wherein, the content of the repeating structural unit represented by the general formula (I) is 40 mass % or more and 90 mass % or less relative to the total mass of the repeating structural units represented by the general formulas (I) to (IV).

5. The polycarbonate diol composition according to claim 1 or 2, wherein, The Hazen color number value (APHA value) based on JIS K0071-1 (2017) is 100 or less.

6. The polycarbonate diol composition according to claim 1 or 2, wherein Among the repeating structural units represented by the general formulas (II) to (IV), the average value of the repeat number n21 of the repeating structural unit represented by the general formula (II) is 15 or more.

7. The polycarbonate diol composition according to claim 1 or 2, wherein Among the repeating structural units represented by the general formulas (II) to (IV), at least the repeating structural unit represented by the general formula (II) or (IV) is included.

8. The polycarbonate diol composition according to claim 1 or 2, wherein Among the repeating structural units represented by the general formulas (II) to (IV), at least the repeating structural unit represented by the general formula (II) is included.

9. A polyurethane formed by using the polycarbonate diol composition according to claim 1 or 2.

10. The polyurethane according to claim 9, wherein, Regarding the stress at 100% elongation of the polyurethane based on the tensile test, ΔM calculated by the following formula (B) is 1.0 or more and 19.0 or less, ΔM = M1 - M2... (B) In formula (B), M1 is the stress at 100% elongation in a tensile test conducted at -20°C, and M2 represents the stress at 100% elongation in a tensile test conducted at 23°C.

11. A synthetic leather comprising the polyurethane according to claim 9.

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