Polycarbonate diol composition

Abstract

To provide a polycarbonate diol composition that has excellent stability of quality, is less colored, and has excellent compatibility with other polyols, solvents and the like.SOLUTION: A polycarbonate diol composition comprises a repeating structural unit represented by the general formula (I) in the figure, and at least one further repeating structural unit selected from the group consisting of repeating structural units represented by the general formulas (II) to (IV) in the figure, and satisfies specific conditions.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a polycarbonate diol composition. [Background technology]

[0002] Traditionally, polyurethane resins have been used in a wide range of applications, including synthetic leather, artificial leather, adhesives, furniture coatings, and automotive coatings. Among the raw materials for polyurethane resins, polyethers, polyesters, and polycarbonates are used as polyol components that react with isocyanates. However, in recent years, there has been a growing demand for greater resistance in polyurethane resins, including heat resistance, weather resistance, hydrolysis resistance, solvent resistance, sun protection resistance, and scratch resistance.

[0003] According to Non-Patent Document 1, polyether polyols generally have low viscosity as a polyol component. Therefore, polyurethanes using polyether polyols are said to have excellent flexibility and hydrolysis resistance, but poor heat resistance and weather resistance. Polyurethanes using polyester polyols have improved heat resistance and weather resistance, but poor hydrolysis resistance. In contrast, polyurethanes using polycarbonate polyols are considered to be the best durability grade in terms of durability such as heat resistance, chemical resistance and hydrolysis resistance, but their high viscosity leaves room for improvement in handling.

[0004] To address the above issues, various methods have been proposed to introduce ether or ester bonds into polycarbonate polyols. For example, Patent Document 1 describes a manufacturing method for synthesizing copolymerized polycarbonate diols by transesterifying polycarbonate diols, and Patent Document 2 describes polyester polyols having a specific structure. Furthermore, Patent Document 3 discloses a paint composition using a specific polycarbonate diol composition. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 3-252420 [Patent Document 2] Japanese Patent Publication No. 2019-151813 [Patent Document 3] International Publication No. 2019 / 131617 [Non-patent literature]

[0006] [Non-Patent Document 1] "Case Studies on Material Selection, Structural Control, and Modification of Polyurethane," Sections 51-62, published by the Japan Technical Information Association, December 2014, 1st edition. [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] However, the technologies described in Patent Documents 1 and 2 use copolymerized polycarbonate diol Ru and However, compatibility with other polyols and solvents remains a challenge. Furthermore, in the technology described in Patent Document 3, the progress and completion of the reaction are confirmed by GPC measurement in the method for producing the polycarbonate diol composition, but there is still room for further improvement in terms of quality stability.

[0008] Therefore, the present invention has been made in view of the above circumstances, and is excellent in quality stability. , others The objective is to provide a polycarbonate diol composition that exhibits excellent compatibility with polyols, solvents, and the like. [Means for solving the problem]

[0009] As a result of diligent research, the inventors of the present invention discovered that a polycarbonate diol composition having a specific structure can solve the above problem by satisfying specific conditions, leading to the present invention.

[0010] In other words, the gist of this invention is as follows: [1] A polycarbonate diol composition comprising a repeating structural unit represented by the following general formula (I), 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 satisfying the following formula (Formula 1). [Chemical Formula] (In general formula (I), R 11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 15 carbon atoms, or an aromatic hydrocarbon group, and may have a heteroatom. When a plurality of R 11 are present, they may be the same as or different from each other.) [Chemical Formula] (In general formula (II), R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. When a plurality of R 21 are present, they may be the same as or different from each other. n21 is any integer.) [Chemical Formula] (In general formula (III), R 31 is a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. When a plurality of R 31 are present, they may be the same as or different from each other.) [Chemical Formula] (In general formula (IV), R 41 and R 42 are each independently a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. When a plurality of R 41 and R 42 are present, they may be the same as or different from each other.) xy ≥ 3.7 × α (α = 22.4 × Mn) -0.41 )...(Formula 1) (In formula 1, x is the ratio (mass%) of the content (mass%) of the repeating structural unit represented by general formula (I) to the total mass (mass%) of the repeating structural units represented by general formulas (I) to (IV), y is the titration volume (mL) of the polycarbonate diol composition by the turbidity titration method, 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 general formula (I) is 40% by mass or more relative to the total mass of the repeating structural units represented by general formulas (I) to (IV), and the titration volume by the turbidity titration method is 4.0 mL or more and 9.5 mL or less. [ka] (In general formula (I), R 11 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 15 carbon atoms, or an aromatic hydrocarbon group, which may have heteroatoms. 11 They may be the same or they may be different. [ka] (In general formula (II), R 21 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. 21 n21 may be the same as or different from each other. [ka] (In general formula (III), R31 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. 31 They may be the same or they may be different. [ka] (In general formula (IV), R 41 and R 42 Each of these is independently a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. 41 and R 42 They may be the same or they may be different. [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, relative to the total mass of the repeating structural units represented by the general formulas (I) to (IV). [4] A 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, relative to the total mass of the repeating structural units represented by the general formulas (I) to (IV). [5] A polycarbonate diol composition according to any one of [1] to [4], wherein the acid value is 0.001 mg-KOH / g or more and 0.8 mg-KOH / g or less. [6] A polycarbonate diol composition according to any one of [1] to [5], wherein the peroxide content is 10 meq / kg or less. [ 7 ] Among the repeating structural units represented by the general formulas (II) to (IV) above, the average number of repetitions n21 of the repeating structural unit represented by the general formula (II) is 15 or more, [1] to [ 6 A polycarbonate diol composition as described in any of the following: [ 8 ] Among the repeating structural units represented by the general formulas (II) to (IV) above, [1] to [ ] include at least a repeating structural unit represented by general formula (II) or (IV). 7 A polycarbonate diol composition as described in any of the following: [ 9 ] Among the repeating structural units represented by the above general formulas (II) to (IV), [1] to [ ] include at least the repeating structural unit represented by general formula (II). 8 A polycarbonate diol composition as described in any of the following: [ 10 ] [1]~[ 9 A polyurethane comprising a polycarbonate diol composition as described in any of the following. [ 11 ] The ΔM calculated by the following formula (B) for the 100% elongation stress of the aforementioned polyurethane in the tensile test is between 1.0 and 19.0, 10 Polyurethane as described in [ ]. ΔM = M1 - M2 ···(B) (In equation (B), M1 represents the 100% elongation stress in the tensile test under -20°C conditions, and M2 represents the 100% elongation stress in the tensile test under 23°C conditions.) [ 12 ] [ 10 ] or [ 11 Synthetic leather containing polyurethane as described in [ ]. [Effects of the Invention]

[0011] The polycarbonate diol composition of the present invention has excellent quality stability. , melt It exhibits excellent compatibility with other polyols and other agents. [Modes for carrying out the invention]

[0012] The embodiments for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail below. However, the present invention is not limited to the following description and can be implemented in various ways within the scope of its gist.

[0013] [Polycarbonate diol composition] The first polycarbonate diol composition of this embodiment contains a repeating structural unit represented by the following general formula (I) (hereinafter also simply referred to 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 simply referred to as "structural unit (II)"), a repeating structural unit represented by the following general formula (III) (hereinafter also simply referred to as "structural unit (III)"), and a repeating structural unit represented by the following general formula (IV) (hereinafter also simply referred to as "structural unit (IV)"), and satisfies the following formula (Formula 1). [ka] ...(I) (In general formula (I), R 11 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 15 carbon atoms, or an aromatic hydrocarbon group, which may have heteroatoms. 11 They may be the same or they may be different. [ka] ...(II) (In general formula (II), R 21 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. 21 n21 may be the same as or different from each other. [ka] ...(III) (In general formula (III), R 31 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. 31 They may be the same or they may be different. [ka] ...(IV) (In general formula (IV), R 41 and R 42 Each of these is independently a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. 41 and R 42 They may be the same or they may be different. xy ≥ 3.7 × α (α = 22.4 × Mn) -0.41 )...(Formula 1) (In formula 1, x is the ratio (mass%) of the content (mass%) of the repeating structural unit represented by general formula (I) to the total mass (mass%) of the repeating structural units represented by general formulas (I) to (IV), y is the titration volume (mL) of the polycarbonate diol composition by the turbidity titration method, and Mn is the number-average molecular weight of the polycarbonate diol composition.)

[0014] The polycarbonate diol composition of this embodiment, having these characteristics, exhibits excellent quality stability and excellent compatibility with solvents and other polyols.

[0015] Furthermore, the second polycarbonate diol composition of this embodiment contains a repeating structural unit represented by the following general formula (I) (hereinafter also simply referred to 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 simply referred to as "structural unit (II)"), a repeating structural unit represented by the following general formula (III) (hereinafter also simply referred to as "structural unit (III)"), and a repeating structural unit represented by the following general formula (IV) (hereinafter also simply referred to as "structural unit (IV)"), wherein the content of the repeating structural unit represented by general formula (I) is 40% by mass or more relative to the total mass of the repeating structural units represented by general formulas (I) to (IV), and the titration volume by the turbidity titration method is 4.0 mL or more and 9.5 mL or less. [ka] ...(I) (In general formula (I), R 11 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 15 carbon atoms, or an aromatic hydrocarbon group, which may have heteroatoms. 11 They may be the same or they may be different. [ka] ...(II) (In general formula (II), R 21 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. 21 n21 may be the same as or different from each other. [ka] ...(III) (In general formula (III), R 31 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. 31 They may be the same or they may be different. [ka] ...(IV) (In general formula (IV), R 41 and R 42 Each of these is independently a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. 41 and R 42 They may be the same or they may be different.

[0016] The polycarbonate diol composition of this embodiment, having these characteristics, exhibits excellent compatibility with solvents and other polyols.

[0017] The polycarbonate diol composition of this embodiment is not particularly limited in its manufacturing method and may be a copolymer of structural unit (I) and at least one of structural units (II) to (IV), or each may exist independently.

[0018] [Structural Unit (I)] In this actual form of polycarbonate diol composition, the details of structural unit (I) are described below.

[0019] (R 11 ) In general formula (I), R 11 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 15 carbon atoms, and may have heteroatoms. 11 These may be identical or different from one another.

[0020] R 11 The divalent linear aliphatic hydrocarbon group in this compound preferably has 2 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and more preferably 3 to 10 carbon atoms.

[0021] R 11 Specific examples of divalent linear aliphatic hydrocarbon groups in this context are not particularly limited, but include, for example, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptylene, and octylene groups. From the viewpoint of versatility, trimethylene, butylene, pentylene, hexylene, and decamethylene groups are preferred.

[0022] R 11 The divalent branched aliphatic hydrocarbon group in this compound has 3 to 15 carbon atoms, preferably 3 to 12, and more preferably 3 to 10.

[0023] R 11Specific examples of divalent branched-chain aliphatic hydrocarbon groups in this context are not particularly limited, but include, for example, isopropylene, isobutylene, tert-butylene, isopentylene, 2,2-dimethyltrimethylene, isohexylene, isoheptylene, and isooctylene. Among these, isobutylene, isopentylene, or isohexylene are preferred from the viewpoint of versatility.

[0024] R 11 The divalent cyclic aliphatic hydrocarbon group in this product preferably has 3 to 15 carbon atoms, more preferably 6 to 15 carbon atoms, and more preferably 6 to 10 carbon atoms.

[0025] R 11 Specific examples of divalent cyclic aliphatic hydrocarbon groups in this context are not particularly limited, but include, for example, cyclobutylene, cyclopentylene, cyclohexylene, and cycloheptylene groups. Among these, cyclohexylene is preferred from the viewpoint of versatility.

[0026] R 11 The divalent aromatic hydrocarbon group in this compound has 6 to 15 carbon atoms, preferably 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms.

[0027] R 11 Specific examples of divalent aromatic hydrocarbon groups in this context are not limited to, but include, for example, phenylene groups and naphthylene groups.

[0028] R 11 Specific examples of heteroatoms in this compound are not limited to, but include, for example, boron, oxygen, nitrogen, phosphorus, sulfur, etc., and may have five-membered heterocyclic structures such as oxolane, thiolane, and azolidine, or six-membered heterocyclic structures such as oxane and pyridine.

[0029] Among them, R 11Preferably, the group is a divalent linear aliphatic hydrocarbon group having 3 to 10 carbon atoms, or a divalent branched aliphatic hydrocarbon group having 3 to 10 carbon atoms; more preferably, a divalent linear aliphatic hydrocarbon group having 4 to 6 carbon atoms; and even more preferably, a divalent linear aliphatic hydrocarbon group of butylene, pentylene, and hexylene.

[0030] Furthermore, in the polycarbonate diol composition of this embodiment, at least a portion of the polycarbonate diol is R in general formula (I). 11 Preferably, the group consists of at least two divalent linear and branched aliphatic hydrocarbon groups having 2 to 15 carbon atoms. In this case, a polycarbonate diol composition that is liquid at room temperature tends to be obtained.

[0031] Furthermore, if the polycarbonate diol composition of this embodiment contains a molecule having a structural unit represented by general formula (I), it is preferable that both ends of the molecule are hydroxyl groups.

[0032] In this embodiment, the molecules having a polycarbonate structure contained in the polycarbonate diol composition preferably have hydroxyl groups at both ends. That is, the molecules having a polycarbonate structure contained in the polycarbonate diol composition in this embodiment preferably are polycarbonate diols. Due to impurities in the various raw materials used in the production of the polycarbonate diol composition, or by-products of the terminal structure during the production of the polycarbonate diol composition, or for the purpose of controlling the urethane reaction rate and state in the intended use of the polycarbonate diol composition, some of the terminal hydroxyl groups may be converted to alkyl groups or aryl groups that do not react with isocyanate groups. In this embodiment, such cases are also taken into consideration, and the terminal groups of the polycarbonate diol include cases where not exactly 100 mol% of both ends are hydroxyl groups. From this viewpoint, the ratio of hydroxyl groups to the total molar amount of terminal groups is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 98 mol% or more.

[0033] In this embodiment, the terminal structures of the polycarbonate diol contained in the polycarbonate diol composition can be confirmed, for example, in accordance with the method for measuring the primary terminal OH ratio described in Japanese Patent No. 3874664 (Reference 1). However, in addition to ethanol, solvents such as tetrahydrofuran, acetone, and methanol can be used as the solvent for recovering the fraction.

[0034] [Structural Units (II)] Next, the details of structural unit (II) will be explained below.

[0035] (R 21 ) In general formula (II), R 21 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. 21 These may be identical or different from one another.

[0036] R 21 The divalent linear aliphatic hydrocarbon group in this compound has 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms.

[0037] R 21 Specific examples of divalent linear aliphatic hydrocarbon groups in this context are not particularly limited, but include, for example, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptylene, and octylene groups.

[0038] R 21 The divalent branched aliphatic hydrocarbon group in this compound has 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.

[0039] R 21Specific examples of divalent branched-chain alfalfa hydrocarbon groups in this context are not particularly limited, but include, for example, isopropylene, isobutylene, tert-butylene, isopentylene, 2,2-dimethyltrimethylene, isohexylene, isoheptylene, isooctylene, and so on.

[0040] R 21 The divalent cyclic aliphatic hydrocarbon group in this compound has 6 to 20 carbon atoms, preferably 6 to 12, and more preferably 6 to 8 carbon atoms.

[0041] R 21 Specific examples of divalent cyclic aliphatic hydrocarbon groups in this context are not limited to, but include, for example, cyclobutylene, cyclopentylene, cyclohexylene, and cycloheptylene groups.

[0042] R 21 The divalent aromatic hydrocarbon group in this compound has 6 to 15 carbon atoms, preferably 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms.

[0043] R 21 Specific examples of divalent aromatic hydrocarbon groups in this context are not limited to, but include, for example, phenylene groups and naphthylene groups.

[0044] Among them, R 21 Preferably, the group is a divalent linear, branched, or cyclic aliphatic hydrocarbon group (i.e., alkylene group) having 2 to 20 carbon atoms, and more preferably, a divalent linear aliphatic hydrocarbon group having 2 to 6 carbon atoms, and / or a divalent branched aliphatic hydrocarbon group having 3 to 6 carbon atoms.

[0045] (n21) In general formula (II), n21 is structure (-R 21This represents the number of repetitions of -O-). In general formula (II), n21 is any integer, but the average value of n21 in the entire polycarbonate diol composition of this embodiment is preferably 12 or more, more preferably in the range of 12 to 70, even more preferably in the range of 12 to 60, even more preferably 15 or more, and particularly preferably in the range of 15 to 50.

[0046] In this embodiment, if the average value of n21 in the entire polycarbonate diol composition is above the lower limit, a polyurethane with even greater flexibility and low-temperature flexibility tends to be obtained. Also, if the average value of n21 in the entire polycarbonate diol composition in this embodiment is below the upper limit, the viscosity of the polycarbonate diol composition tends to be lower.

[0047] The above n21 can be determined by alkaline decomposition of the polycarbonate diol composition to extract the raw material diol component, and then performing GC-MS, LC-MS, and gel permeation chromatography (GPC) measurements on the component. Specifically, it can be determined by the method described in the examples below.

[0048] Among these, the polyoxyalkylene structure is preferred as the structural unit (II).

[0049] Specific examples of preferred oxyalkylene groups included in structural unit (II) are not particularly limited, but include, for example, oxyethylene group, oxy-1-methylethylene group, oxytetramethylene group, and oxy-2,2-dimethyltrimethylene group. Among these, structures containing an oxy-1-methylethylene group are preferred, and oxy-1-methylethylene group and oxyethylene group are particularly preferred.

[0050] [Structural Unit (III)] Next, the details of structural unit (III) will be explained below.

[0051] (R 31 ) In general formula (III), R 31 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. 31 These may be identical or different from one another.

[0052] R in general formula (III) 31 Examples include linear or branched alkylene groups having 2 to 20 carbon atoms, although these are not particularly limited. Specifically, examples include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, propylene, isobutylene, 2-methyltetramethylene, 2-methylpentamethylene, 3-methylpentamethylene, isononamethylene, 2-methylnonamethylene, etc. Also, R in general formula (III) 31 Examples include, but are not particularly limited, substituted or unsubstituted cycloalkylene groups having 3 to 20 carbon atoms. Specifically, but are not particularly limited, examples include cyclopentylene group, cyclohexylene group, 1,2-dimethylenecyclopentane group, 1,3-dimethylenecyclopentane group, 1,2-dimethylenecyclohexane group, 1,3-dimethylenecyclohexane group, 1,4-dimethylenecyclohexane group, 4,4'-methylenedicyclohexylene group, 2,2-dicyclohexylenepropane group, etc. Also, R in general formula (III) 31 Examples include, but are not limited to, substituted or unsubstituted arylene groups having 6 to 20 carbon atoms. Specifically, but are not limited to, examples include phenylene groups, 1,2-dimethylenebenzene groups, 1,3-dimethylenebenzene groups, 1,4-dimethylenebenzene groups, naphthylene groups, 4,4'-methylenediphenylene groups, 2,2-diphenylenepropane groups, etc.

[0053] In particular, from the viewpoint of improving stain resistance and solvent resistance when made into polyurethane, and the ease of obtaining the cyclic ester compound used as a raw material, R 31 A pentamethylene group is preferred.

[0054] [Structural Units (IV)] Next, the details of structural unit (IV) will be explained below.

[0055] (R 41 ) In general formula (IV), R 41 Each of these is independently a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. 41 These may be identical or different from one another.

[0056] R in general formula (IV) 41 Examples include linear or branched alkylene groups having 2 to 20 carbon atoms, although these are not particularly limited. Specifically, examples include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, propylene, isobutylene, 2-methyltetramethylene, 2-methylpentamethylene, 3-methylpentamethylene, isononamethylene, 2-methylnonamethylene, etc. Also, R in general formula (IV) 41 Examples include, but are not particularly limited, substituted or unsubstituted cycloalkylene groups having 3 to 20 carbon atoms. Specifically, but are not particularly limited, examples include cyclopentylene group, cyclohexylene group, 1,2-dimethylenecyclopentane group, 1,3-dimethylenecyclopentane group, 1,2-dimethylenecyclohexane group, 1,3-dimethylenecyclohexane group, 1,4-dimethylenecyclohexane group, 4,4'-methylenedicyclohexylene group, 2,2-dicyclohexylenepropane group, etc. Also, R in general formula (IV) 41Examples include, but are not limited to, substituted or unsubstituted arylene groups having 6 to 20 carbon atoms. Specifically, but are not limited to, examples include phenylene groups, 1,2-dimethylenebenzene groups, 1,3-dimethylenebenzene groups, 1,4-dimethylenebenzene groups, naphthylene groups, 4,4'-methylenediphenylene groups, 2,2-diphenylenepropane groups, etc.

[0057] (R 42 ) In general formula (IV), R 42 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. 42 These may be identical or different from one another.

[0058] R in general formula (IV) 42 Examples include linear or branched alkylene groups having 2 to 20 carbon atoms, although these are not particularly limited. Specifically, examples include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, propylene, isobutylene, 2-methyltetramethylene, 2-methylpentamethylene, 3-methylpentamethylene, isononamethylene, 2-methylnonamethylene, etc. Also, R in general formula (IV) 42 Examples include, but are not particularly limited, substituted or unsubstituted cycloalkylene groups having 3 to 20 carbon atoms. Specifically, but are not particularly limited, examples include cyclopentylene group, cyclohexylene group, 1,2-dimethylenecyclopentane group, 1,3-dimethylenecyclopentane group, 1,2-dimethylenecyclohexane group, 1,3-dimethylenecyclohexane group, 1,4-dimethylenecyclohexane group, 4,4'-methylenedicyclohexylene group, 2,2-dicyclohexylenepropane group, etc. Also, R in general formula (IV) 42Although not particularly limited, examples include substituted or unsubstituted arylene groups having 6 to 20 carbon atoms. Specific examples include, but are not limited to, a phenylene group, a 1,2-dimethylene benzene group, a 1,3-dimethylene benzene group, a 1,4-dimethylene benzene group, a naphthylene group, a 4,4'-methylenediphenylene group, and a 2,2-diphenylene propane group.

[0059] [Structural units (II) to (IV)] The polycarbonate diol composition of the present embodiment includes 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).

Chemical Formula

Chemical Formula

Chemical Formula

[0060] In the polycarbonate diol composition of this embodiment, the terminal structures of structural units (II) to (IV) may be terminal structures in which one end is bonded to a carbonate group and the other end is bonded to a hydroxyl group, or terminal structures in which both ends are bonded to a carbonate group, or terminal structures in which both ends are bonded to a hydroxyl group.

[0061] Furthermore, in the polycarbonate diol composition of this embodiment, the terminal structures of structural units (II) to (IV) may be a mixture of terminal structures in which one terminal is bonded to a carbonate group and the other terminal is bonded to a hydroxyl group, terminal structures in which both terminals are bonded to a carbonate group, and terminal structures in which both terminals are bonded to a hydroxyl group.

[0062] In particular, the polycarbonate diol composition of this embodiment preferably contains structural unit (II) or (IV) among structural units (II) to (IV), and more preferably contains structural unit (II), from the viewpoint of flexibility, low-temperature properties, and resistance to humid heat.

[0063] [Cloudy point titration] The second polycarbonate diol composition of this embodiment has a titration volume of 4.0 mL or more and 9.5 mL or less by turbidity titration, and preferably 4.0 mL or more and 8.5 mL or less.

[0064] In this embodiment, the titration volume in the turbidity titration method is determined by dissolving the polycarbonate diol composition in butyl acetate, a good solvent, and then titrating the resulting solution with hexane, a poor solvent, at the point when the solution begins to become cloudy. If the solution is insoluble in butyl acetate, it may be dissolved in acetone. Specifically, the titration volume can be determined by the method described in the examples below.

[0065] This turbidity titration evaluates solubility in a solvent, and differences appear depending on the type, molecular weight, and structure of the polyol. Generally, the smaller the molecular weight, the higher the solubility in the solvent, and solubility also differs depending on the functional groups it contains. Therefore, for polyols, there will be differences in solubility when two or more polyols are blended and when the structure has changed due to reaction.

[0066] The second polycarbonate diol composition of this embodiment has a titration volume of 4.0 mL to 9.5 mL by turbidity titration, preferably 4.0 mL to 8.5 mL, more preferably 4.0 mL to 7.6 mL, and even more preferably 4.1 mL to 7.4 mL.

[0067] When the titration volume in the turbidity titration method is above the lower limit, the compatibility of the polycarbonate diol composition with solvents and raw materials for polyurethane synthesis is improved. Conversely, when the titration volume in the turbidity titration method is below the upper limit, a polyurethane with an excellent balance of low-temperature flexibility and durability such as chemical resistance and heat and humidity resistance is obtained, which is preferable.

[0068] In a polycarbonate diol composition, the method for controlling the titration volume in the turbidity titration method to the above range is not particularly limited, but for example, one method is to adjust the charging ratio of structural unit (I) and structural units (II) to (IV), and also, as used in the embodiment described later... In the method for producing polycarbonate diol, methods for adjusting the reaction time and methods for appropriately adjusting the oxygen concentration during mixing and stirring are also mentioned.

[0069] Furthermore, since the progress of the transesterification reaction can be evaluated using this turbidity titration method, setting a target value for the titration volume using the turbidity titration method tends to reduce variations in the transesterification reaction between manufacturing lots, resulting in polycarbonate diol compositions with excellent quality stability.

[0070] [Relational Expression (Formula 1)] The first polycarbonate diol composition of the present embodiment satisfies the following formula (Formula 1). xy≧3.7×α (α=22.4×Mn -0.41 ) ···(Formula 1) (In Formula (1), x is the content (mass%) of the repeating structural unit represented by the general formula (I), relative to the total mass (mass%) of the repeating structural units represented by general formulas (I) to (IV); y is the titer (mL) obtained by the cloud point titration method for the polycarbonate diol composition; and Mn is the number average molecular weight of the polycarbonate diol composition)

[0071] Here, the number average molecular weight can be calculated from the hydroxyl value of the polycarbonate diol composition using the method described in the Examples mentioned later.

[0072] In cloud point titration, since compounds with lower molecular weight generally have higher solubility in solvents, the titer of the poor solvent tends to be higher. α is a factor that offsets differences caused by molecular weight.

[0073] In general, polycarbonate diol has low solubility in solvents, so as x increases, y tends to decrease. It is inferred that the more randomly the repeating structural units represented by general formulas (I) to (IV) and the repeating structural unit represented by general formula (I) are distributed, the higher the titer obtained in cloud point titration. Further, the method for obtaining a polycarbonate diol composition that satisfies the above formula (Formula 1) is not particularly limited, and examples thereof include a method of appropriately setting the reaction time until modification proceeds sufficiently.

[0074] [Content of Structural Unit (I)] In the polycarbonate diol composition of this embodiment, the content of structural unit (I) is preferably 5% to 95% by mass, more preferably 20% to 90% by mass, and even more preferably 40% to 90% by mass, relative to the total mass of structural units (I) to (IV). A content of structural unit (I) above the lower limit is preferable because it yields a polyurethane with superior durability, such as chemical resistance and heat and humidity resistance. Furthermore, a content of structural unit (I) below the upper limit tends to result in a lower viscosity of the polycarbonate diol composition. The content of structural unit (I) can be measured by the method described in the examples below.

[0075] [Number average molecular weight] The number average molecular weight of the polycarbonate diol composition of this embodiment is preferably 250 to 10,000, more preferably 400 to 8,000, even more preferably 500 to 5,000, and particularly preferably 500 to 3,000. The polycarbonate diol composition of this embodiment, when its number average molecular weight is below the upper limit, tends to have lower viscosity and improved handling properties during polyurethane production. Furthermore, when its number average molecular weight is above the lower limit, the polyurethane produced using the polycarbonate diol composition of this embodiment tends to have superior flexibility.

[0076] The method for controlling the number-average molecular weight of the polycarbonate diol composition of this embodiment to the aforementioned range is not particularly limited, but examples include using a structural unit (I) whose number-average molecular weight is controlled to the aforementioned range and at least one structural unit from structural units (II) to (IV) whose number-average molecular weight is controlled to the aforementioned range; using a structural unit (I) whose number-average molecular weight is greater than the aforementioned range and at least one structural unit from structural units (II) to (IV) whose number-average molecular weight is smaller than the aforementioned range; and carrying out the reaction while checking the number-average molecular weight and stopping the reaction when it reaches the aforementioned range.

[0077] In this embodiment, the number-average molecular weight of the polycarbonate diol composition can be measured by the method described in the examples below.

[0078] [Acid value] 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 even more preferably 0.01 mg-KOH / g or more and 0.6 mg-KOH / g or less. Since it is difficult to remove all acidic compounds derived from raw materials, catalysts, additives, etc., an acid value of above the lower limit is preferable in terms of productivity of the polycarbonate diol composition, and an acid value of below the upper limit tends to reduce the occurrence of discoloration.

[0079] The method for controlling the acid value of the polycarbonate diol composition to the above range is not particularly limited, but examples include adjusting the raw material acid value during the production of the polycarbonate diol composition, and appropriately selecting the addition of a catalyst poison to deactivate the catalyst.

[0080] In this embodiment, the acid value of the polycarbonate diol composition can be measured by the method described in the examples below.

[0081] [Peroxide value] 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, and more preferably 3 meq / kg or less. When the peroxide value of the polycarbonate diol composition of this embodiment is 10 meq / kg or less, discoloration tends to be suppressed. The lower limit of the peroxide value of the polycarbonate diol composition of this embodiment is not particularly limited, but for example, it is 0.01 meq / kg. As for the method of measuring the peroxide value, there is the sodium thiosulfate titration method, in which oxidized oil and fat are reacted with potassium iodide in an acid and the liberated iodine is determined by titration, but for example, it can be measured simply using peroxide value measuring test paper (product name: "POV test paper", manufactured by Shibata Chemical Co., Ltd.). Specifically, it can be measured by the method described in the examples below.

[0082] There are no particular limitations on the method for controlling the peroxide value of the polycarbonate diol composition to the above range, but examples include lowering the reaction temperature to 200°C or below to reduce oxidative cleavage due to thermal decomposition, lowering the oxygen concentration to 0.5% or below during the production of the polycarbonate diol composition, or lowering the nitrogen flow rate during production to 0.1 L / min or more and 50 L / min or less. The above methods may also be combined.

[0086] <Method for producing polycarbonate diol composition> There are no particular restrictions on the method for producing the polycarbonate diol composition of this embodiment as long as the above characteristics are satisfied. For example, one method is to carry out a transesterification reaction 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)"), or a method is to react polycarbonate diol (I-1) with a cyclic ester compound. [ka] ...(I-1) (In general formula (I-1), R 111 and R 112 These are the R values ​​mentioned above. 11 This is equivalent to the above. n11 is any integer. [ka] ...(II-1) (In general formula (II-1), R 211 The above R 21 It is the same as above. n211 is the same as n21 above. [ka] ...(III-1) (In general formula (III-1), R 311 The above R 31 This is the same as n311 being any integer. [ka] ...(IV-1) (In general formula (IV-1), R 411 and R421 These are the R values ​​mentioned above. 41 and R 42 This is the same as (n411 is any integer).

[0087] [Polycarbonate diol (I-1)] The polycarbonate diol (I-1) used in the production of the polycarbonate diol composition of this embodiment may be any polycarbonate diol (I-1) having the structure represented by the general formula (I-1) described above. The method for producing polycarbonate diol (I-1) is not particularly limited, and known methods can be employed. For example, polycarbonate diol (I-1) can be obtained by reacting a carbonate compound with a diol compound in the presence of a transesterification catalyst.

[0088] (Carbonate compounds) The carbonate compounds used in the production of polycarbonate diol (I-1) are not limited to the following, but examples include alkylene carbonates, dialkyl carbonates, diaryl carbonates, etc.

[0089] The alkylene carbonate is not particularly limited, but examples include ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, and 1,2-pentylene carbonate.

[0090] The dialkyl carbonate is not particularly limited, but examples include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate.

[0091] The diaryl carbonate is not particularly limited, but examples include diphenyl carbonate.

[0092] Among these, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and diphenyl carbonate are preferred as carbonate compounds used in the production of polycarbonate diol (I-1), with ethylene carbonate being more preferred.

[0093] (Diol compounds) The diol compounds used in the production of polycarbonate diol (I-1) are not limited to the following, but examples include linear diols, branched diols, cyclic diols, and diols having aromatic rings.

[0094] The linear diols are not particularly limited, but examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nanodiol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol.

[0095] The branched-chain diols are not particularly limited, but examples 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, and 2,4-diethyl-1,5-pentanediol.

[0096] Examples of cyclic diols are not particularly limited, but include 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2-bis(4-hydroxycyclohexyl)-propane.

[0097] Diols having an aromatic ring are not particularly limited, but examples include p-xylenediol, p-tetrachloroxylenediol, 1,4-bis(hydroxyethoxy)benzene, and 2,2-bis[(4-hydroxyethoxy)phenyl]propane.

[0098] Among these, linear or branched diols having 3 to 10 carbon atoms are preferred, with 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol or 1,6-hexanediol, 1,9-nanodiol, 1,10-decanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol being preferred, and 1,4-butanediol, 1,5-pentanediol or 1,6-hexanediol being more preferred.

[0099] [Production conditions for polycarbonate diol composition and polycarbonate diol (I-1)] A transesterification catalyst can be used in the production of the raw material, polycarbonate diol (I-1). The catalyst can be selected from conventional transesterification catalysts.

[0100] The catalysts for transesterification reactions are not particularly limited, but examples include alkali metals and alkaline earth metals, as well as their alcoholates, hydrides, oxides, amides, hydroxides, and salts.

[0101] The alkali metal and alkaline earth metal salts are not particularly limited, but examples include carbonates, nitrogen-containing borates, and basic salts with organic acids.

[0102] Alkali metals are not particularly limited, but examples include lithium, sodium, and potassium.

[0103] Alkaline earth metals are not particularly limited, but examples include magnesium, calcium, strontium, and barium.

[0104] Furthermore, while not particularly limited, transesterification catalysts using metals other than alkali metals and alkaline earth metals include, for example, metals other than alkali metals and alkaline earth metals, as well as their salts, their alcoholates, and organic compounds containing such metals.

[0105] Specific examples of metals other than alkali metals and alkaline earth metals are not limited to, but include, for example, aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, indium, tin, antimony, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth, and ytterbium.

[0106] These transesterification catalysts can be used individually or in combination of two or more.

[0107] In particular, as a transesterification catalyst, one or more metals selected from the group consisting of sodium, potassium, magnesium, titanium, zirconium, tin, lead, and ytterbium, or their salts, their alkoxides, or organic compounds containing these metals are preferred, because they allow the transesterification reaction to obtain polycarbonate diols to proceed more smoothly and have less influence on the urethane reaction when the resulting polycarbonate diol is used.

[0108] Furthermore, one or more metals selected from the group consisting of magnesium, titanium, ytterbium, tin, and zirconium are more preferred as the transesterification catalyst.

[0109] Specific examples of preferred transesterification catalysts, though not limited to those mentioned above, include, for example, organic compounds of magnesium, organic compounds of lead, and organic compounds of titanium.

[0110] Examples of magnesium organic compounds include magnesium tetrahydrate and magnesium anhydride.

[0111] Organic compounds of lead are not particularly limited, but examples include lead acetate trihydrate, tetraphenyl lead, and lead stearate.

[0112] The organic compounds of titanium are not particularly limited, but examples include titanium tetra-n-butoxide, titanium tetra-n-propoxide, and titanium tetraisopropoxide.

[0113] The amount of transesterification catalyst used is preferably 0.00001% by mass or more and 0.1% by mass or less, and more preferably 0.0001% by mass or more and 0.05% by mass or less, relative to the total mass of the raw materials.

[0114] If the transesterification catalyst used in the transesterification reaction is subjected to heat treatment immediately following the production of the polycarbonate diol, it is not consumed in the transesterification reaction and can therefore be calculated based on the amount of transesterification catalyst used. When using commercially available polycarbonate diols, the amount of metal in the transesterification catalyst contained in the polycarbonate diol can be determined by measuring it using ICP (Inductively Coupled Plasma).

[0115] The polycarbonate diol (I-1) used in the production of the polycarbonate diol composition of this embodiment may have a catalyst poison such as a phosphate ester compound added to it in order to deactivate the transesterification reaction catalyst used during its production.

[0116] If the raw material, polycarbonate diol (I-1), contains catalyst poisons from the transesterification reaction catalyst used during its production, the transesterification reaction between ether diol (II-1) or ester diol (IV-1) and polycarbonate diol (I-1) tends to be less likely to proceed. Therefore, in the production of the polycarbonate diol composition of this embodiment, the necessary amount of the transesterification reaction catalyst described above can be added.

[0117] On the other hand, if the raw material polycarbonate diol (I-1) does not contain the catalyst poison of the transesterification reaction catalyst, the transesterification reaction in this embodiment tends to proceed easily. However, if it is desired to further lower the reaction temperature or shorten the reaction time in the manufacturing process of the polycarbonate diol composition of this embodiment, the required amount of transesterification reaction catalyst can be added. In that case, the same type of transesterification reaction catalyst used in the production of the raw material polycarbonate diol (I-1) can be used.

[0118] Furthermore, the polycarbonate diol (I-1) used in the production of the polycarbonate diol composition of this embodiment may be a homopolycarbonate diol obtained from one type of diol compound, or a copolymerized polycarbonate diol obtained from two or more types of diol compounds.

[0119] A polycarbonate diol composition can be obtained by transesterification using any of the polycarbonate diols (I-1) exemplified above.

[0120] However, homopolycarbonate diols obtained using, for example, 1,6-hexanediol, which is widely used in the market, are usually solid at room temperature. Therefore, polycarbonate diol compositions obtained by transesterification reactions with such homopolycarbonate diols also tend to be solid at room temperature.

[0121] On the other hand, copolymerized polycarbonate diols obtained using, for example, any two of 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are liquid at room temperature. Therefore, polycarbonate diol compositions obtained by transesterification reactions with these copolymerized polycarbonate diols also tend to be liquid at room temperature.

[0122] (n11) In general formula (I-1), n11 is a carbonate structure (-R 111 This represents the number of repetitions of -O-CO-O-). n11 is any integer, but the mean of n11 is preferably in the range of 1 to 50, more preferably in the range of 2 to 50, even more preferably in the range of 3 to 30, and particularly preferably in the range of 4 to 20.

[0123] The number-average molecular weight of the polycarbonate diol (I-1) used in the production of the polycarbonate diol composition of this embodiment is not particularly limited, but is preferably 500 to 5000, and more preferably 1000 to 3000.

[0124] When the number-average molecular weight of polycarbonate diol (I-1) is above the lower limit, the expected performance of the polycarbonate diol composition tends to improve. On the other hand, when the number-average molecular weight of polycarbonate diol (I-1) is below the upper limit, it is preferable in terms of handling during the production of the polycarbonate diol composition.

[0125] [Etherdiol (II-1)] The etherdiol (II-1) used in the production of the polycarbonate diol composition of this embodiment may be any etherdiol (II-1) having the structure represented by the general formula (II-1) described above. Among these, polyoxyalkylenediol having primary hydroxyl groups at both ends is preferred as the etherdiol (II-1). Etherdiol (II-1) is commercially available in various molecular weights, and such commercially available products can also be used. Commercially available etherdiol (II-1) products are not particularly limited, but examples include the "Newpol" series, "Primepol" series, and "Sannix" series from Sanyo Chemical Industries, Ltd., the "Pronon" series from NOF Corporation, the "Preminol" and "Exenol" series from AGC Inc., the "PTMG" series from Mitsubishi Chemical Corporation, and polyether glycols such as PTXG from Asahi Kasei Corporation.

[0126] The number-average molecular weight of etherdiol(II-1) is not particularly limited, but is preferably 400 to 3000, and more preferably 600 to 2500. When the number-average molecular weight of the etherdiol(II-1) used in production is above the lower limit, the flexibility tends to be further improved when used in polyurethane, and when the number-average molecular weight of etherdiol(II-1) is below the upper limit, the crystallinity of the polycarbonate diol composition of this embodiment tends to be further suppressed.

[0127] [Polycaprolactone diol (III-1) and cyclic ester compounds] The polycaprolactone diol (III-1) used in the production of the polycarbonate diol composition of this embodiment can be any polycaprolactone diol (III-1) having the structure represented by the general formula (III-1) described above. In particular, polycaprolactone diol (III-1) is commercially available in various molecular weights, and such commercially available products can also be used. There are no particular limitations on commercially available products, but examples include the "Plaxel" series from Daicel Organic Synthesis Company, Ltd. and the "Polylite" series from DIC Corporation.

[0128] (n311) In general formula (III-1), n311 is structure (-R 311 This represents the number of repetitions of -O-CO-). In general formula (III-1), n311 is any integer, but the average value of n311 is 1 or greater, preferably in the range of 1 to 50, more preferably in the range of 1 to 30, and particularly preferably in the range of 1 to 20.

[0129] The number-average molecular weight of polycaprolactone diol (III-1) is not particularly limited, but is preferably 400 to 3000, and more preferably 600 to 2000. When the number-average molecular weight of lactone diol (III-1) used in production is above the lower limit, the flexibility of the polyurethane obtained from the polycarbonate diol composition of this embodiment tends to be further improved, and when the number-average molecular weight of lactone diol (III-1) is below the upper limit, the polycarbonate diol composition of this embodiment tends to have a lower viscosity.

[0130] Alternatively, cyclic ester compounds may be subjected to ring-opening polymerization.

[0131] The cyclic ester compounds are not particularly limited, but examples 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-trimethylε-caprolactone, and enantractone (7-heptalidone). In particular, R in formula (III) 31 It is preferable to use ε-caprolactone, which gives structural unit (III) a linear alkylene group having 5 carbon atoms.

[0132] [Esterdiol (IV-1)] The ester diol (IV-1) used in the production of the polycarbonate diol composition of this embodiment can be any ester diol (IV-1) having the structure represented by the general formula (IV-1) described above. Among these, ester diol (IV-1) products of various molecular weights are commercially available, and such commercially available products can also be used. Commercially available ether diol (II-1) products are not particularly limited, but examples include the "Polylight" series from DIC Corporation, the "Kuraray Polyol" series from Kuraray Co., Ltd., the "Nipporan" series from Tosoh Corporation, and the "ADEKA New Ace" series from ADEKA Corporation.

[0133] (n411) In general formula (IV-1), n411 is structure (-CO-R 411 -CO-OR 421 This represents the number of repetitions of -O-). In general formula (IV-1), n411 is any integer, but the mean value of n411 is 1 or greater, preferably in the range of 1 to 50, more preferably in the range of 2 to 30, and particularly preferably in the range of 4 to 20.

[0134] The number-average molecular weight of ester diol (IV-1) is not particularly limited, but is preferably 400 to 3000, and more preferably 600 to 2000. When the number-average molecular weight of the ester diol (IV-1) used in production is above the lower limit, the flexibility of the polyurethane obtained from the polycarbonate diol composition of this embodiment tends to be further improved, and when the number-average molecular weight of ester diol (IV-1) is below the upper limit, the polycarbonate diol composition of this embodiment tends to have a lower viscosity.

[0135] The method for producing the polycarbonate diol composition of this embodiment is not particularly limited, but it is preferable to produce it by mixing polycarbonate diol (I-1) with at least one compound selected from the group consisting of ether diol (II-1), ester diol (IV-1), and cyclic ester compounds, and stirring while heating.

[0136] The reaction temperature is not particularly limited, but is preferably between 120°C and 200°C, and more preferably between 140°C and 180°C.

[0137] By setting the reaction temperature above the lower limit, the transesterification reaction can be carried out in a shorter time, which tends to be more economical. By setting the reaction temperature below the upper limit, the acid value of the resulting polycarbonate diol composition can be controlled within a specific range, and discoloration can be prevented more effectively.

[0138] Furthermore, it is preferable to keep the oxygen concentration below 0.5% during manufacturing. There are no particular limitations on how to keep the oxygen concentration below 0.5%, but examples include replacing the reactor with nitrogen at a rate of 1.5 times or more and then carrying out the reaction while flowing nitrogen, or reducing the pressure to below 0.1 kPa.s, then replacing with nitrogen and carrying out the reaction under slight reduced pressure. Keeping the oxygen concentration below 0.5% tends to suppress the formation of peroxides and prevent discoloration of the resulting polycarbonate diol composition.

[0139] Furthermore, in order to reduce 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, and more preferably at a nitrogen flow rate of 0.2 L / min or more and 30 L / min or less. It is preferable that the nitrogen flow rate is above the lower limit above because it is possible to prevent the incorporation of oxygen, and it is preferable that the nitrogen flow rate is below the upper limit above because it is possible to prevent the volatilization of the raw material diol, and the hydroxyl value of the resulting polycarbonate diol composition tends to be kept constant.

[0140] [Application] The polycarbonate diol composition of this embodiment can be used as a raw material for polyurethane to be reacted with polyisocyanate. Polyurethane produced using the polycarbonate diol composition of this embodiment exhibits excellent chemical resistance, heat resistance, and weather resistance, and can therefore be widely used in foams, elastomers, paints, coatings, adhesives, artificial leather, synthetic leather, water-based polyurethane paints, and the like. Furthermore, it can be used as a modifier for polyesters and polyimides.

[0141] [Polyurethane] The polyurethane in this embodiment is made using the polycarbonate diol composition described above.

[0142] [Δ100% Elongation Stress] In this embodiment, the polyurethane has a ΔM of 1.0 to 19.0, calculated by the following formula (B) for 100% elongation stress in a tensile test, more preferably 3.5 to 18.5, and even more preferably 5.0 to 17.0. ΔM = M1 - M2 ···(B) (In equation (B), M1 represents the 100% elongation stress in the tensile test under -20°C conditions, and M2 represents the 100% elongation stress in the tensile test under 23°C conditions.)

[0143] The polyurethane of this embodiment tends to have an excellent balance of flexibility and durability because ΔM is above the lower limit value. Furthermore, because ΔM is below the upper limit value, the polyurethane of this embodiment tends to have excellent mechanical properties at low temperatures due to the small difference in elastic modulus with temperature.

[0144] The method for producing polyurethane in this embodiment uses known polyurethaneization reaction conditions that are typically used for producing polyurethane, and can be carried out either without a solvent or in the presence of a solvent.

[0145] Examples include, but are not limited to, a method in which the above-mentioned polycarbonate diol composition, other polyols, polyisocyanates, and chain extenders are mixed together and reacted (hereinafter sometimes referred to as the "one-shot method"), or a method in which the above-mentioned polycarbonate diol composition, other polyols, and polyisocyanates are first reacted to prepare a prepolymer of isocyanate groups at both ends, and then the prepolymer is reacted with a chain extender (hereinafter sometimes referred to as the "prepolymer method").

[0146] The isocyanate compound contained in the polyurethane of this embodiment is not particularly limited as long as it acts as a curing agent, and one having two or more isocyanate groups at its terminal end is used.

[0147] Such isocyanate compounds are not particularly limited, but examples include linear aliphatic diisocyanates, cyclic aliphatic diisocyanates, aromatic diisocyanates, and isocyanate compounds having three or more isocyanate groups, as well as isocyanurate-modified and biuret-modified products of these isocyanate compounds.

[0148] The chain-like aliphatic diisocyanates are not particularly limited, but examples include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

[0149] Examples of cyclic aliphatic diisocyanates are not particularly limited, but include isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.

[0150] Aromatic diisocyanates are not particularly limited, but examples include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (hereinafter sometimes abbreviated as "MDI"), xylylene diisocyanate, and naphthylene diisocyanate.

[0151] The isocyanate compounds having three or more isocyanate groups are not particularly limited, but examples include triphenylmethane-4,4'-4''-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoene, and 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate.

[0152] The isocyanate compound may be a commercially available product or may be synthesized using known methods.

[0153] The content of the isocyanate compound can be adjusted as appropriate according to the molar amount of hydroxyl groups in the polyol, which is the main component. Specifically, the molar ratio of isocyanate groups of the isocyanate compound to hydroxyl groups of the polycarbonate diol (NCO / OH) can be, for example, 0.2 to 5.0, 0.4 to 3.0, or 0.5 to 2.0. When NCO / OH is above the lower limit, a tougher coating film tends to be obtained. On the other hand, when NCO / OH is below the upper limit, the smoothness of the coating film tends to improve.

[0154] Furthermore, the chain extender used in the production of the polyurethane in this embodiment is not particularly limited, but examples include polyols and polyamines.

[0155] The polyol is not particularly limited, but examples include linear diols, branched diols, cyclic diols, and diols having aromatic rings.

[0156] The linear diols are not particularly limited, but examples include ethylene glycol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nanonediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol.

[0157] The branched-chain diols are not particularly limited, but examples 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, and 2,4-diethyl-1,5-pentanediol.

[0158] Examples of cyclic diols are not particularly limited, but include 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2-bis(4-hydroxycyclohexyl)-propane.

[0159] Diols having an aromatic ring are not particularly limited, but examples include p-xylenediol, p-tetrachloroxylenediol, 1,4-bis(hydroxyethoxy)benzene, and 2,2-bis[(4-hydroxyethoxy)phenyl]propane.

[0160] Polyamines are not particularly limited, but examples include hydroxyamines and other polyamines.

[0161] Examples of hydroxyamines include N-methylethanolamine and N-ethylethanolamine, although these are not particularly limited.

[0162] Polyamines are not particularly limited, but examples include ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4,4'-diphenylmethanediamine, methylenebis(o-chloroaniline), xylylenediamine, diphenyldiamine, tolylenediamine, hydrazine, piperazine, and N,N'-diaminopiperazine.

[0163] These chain extenders may be used individually or in combination of two or more.

[0164] [Synthetic leather] The synthetic leather of this embodiment includes the polyurethane described above.

[0165] The synthetic leather of this embodiment is not particularly limited, but examples include synthetic leather in which a base fabric, adhesive layer, intermediate layer, and surface layer are sequentially laminated. In such synthetic leather, it is preferable that at least one selected from the group consisting of the base fabric, adhesive layer, intermediate layer, and surface layer contains the above-mentioned polyurethane.

[0166] Various materials can be used as the base fabric (substrate), and are not particularly limited, but examples include fibrous substrates. Fibrous substrates are not particularly limited, but examples include fiber aggregates in which fibers are formed into nonwoven fabrics, woven fabrics, mesh fabrics, etc., or fiber aggregates in which each fiber is bonded with an elastic polymer. The fibers used in these fiber aggregates are not particularly limited, but examples include natural fibers such as cotton, linen, and wool, recycled or semi-synthetic fibers such as rayon and acetate, and synthetic fibers such as polyamide, polyester, polyacrylonitrile, polyvinyl alcohol, and polyolefin. These fibers may be single-spun fibers or mixed-spun fibers. Other substrates are not particularly limited, but examples include paper, release paper, plastic films of polyester or polyolefin, metal plates such as aluminum, and glass plates.

[0167] In the synthetic leather of this embodiment, it is preferable to use the above-mentioned polyurethane in the adhesive layer, intermediate layer, and surface layer. Furthermore, when forming each layer, crosslinking agents, other resins, antioxidants, UV absorbers, hydrolysis inhibitors, pigments, dyes, colorants, flame retardants, organic solvents, etc., can be added as needed.

[0168] The method for manufacturing synthetic leather in this embodiment is not particularly limited as long as the above-mentioned polyurethane is used, and known methods for manufacturing synthetic leather can be used.

[0169] [Paint or coating composition] The paint or coating composition (paint) of this embodiment is made using the polycarbonate diol composition described above.

[0170] As a method for producing a paint or coating agent composition (paint) using the above polycarbonate diol composition, production methods known in the art are used. For example, a two-component solvent-based coating composition in which a paint base material obtained from the above polycarbonate diol composition and a curing agent composed of polyisocyanate are mixed immediately before coating; a one-component solvent-based coating composition composed of a urethane prepolymer having isocyanate terminal groups obtained by reacting the above polycarbonate diol with polyisocyanate; and a one-component solvent-based coating composition composed of a polyurethane resin obtained by reacting the above polycarbonate diol, organic polyisocyanate and a chain extender can be produced.

[0171] The paint or coating agent composition (paint) of the present embodiment may, for example, have other additives such as curing accelerators (catalysts), leveling agents, fillers, dispersants, flame retardants, dyes, organic or inorganic pigments, release agents, fluidity regulators, plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, defoamers, colorants, and solvents added thereto according to various applications. By appropriately containing these other additives, paint compositions having different properties such as soft-feel paints and clear paints can be obtained.

[0172] The curing accelerator (catalyst) is not particularly limited, and examples thereof include commonly used ones such as monoamines, diamines, triamines, cyclic amines, alcohol amines, ether amines, and metal catalysts.

[0173] The monoamine is not particularly limited, and examples thereof include triethylamine and N,N-dimethylcyclohexylamine. The diamine is not particularly limited, and examples thereof include tetramethylethylenediamine.

[0174] The alcohol amine is not particularly limited, and examples thereof include dimethylethanolamine.

[0175] The metal catalyst is not particularly limited, but examples include potassium acetate, potassium 2-ethylhexanoate, calcium acetate, lead octoate, dibutyltin dilaurate, tin octoate, bismuth neodecanoate, bismuth oxycarbonate, bismuth 2-ethylhexanoate, zinc octoate, zinc neodecanoate, phosphine, phospholine, and the like.

[0176] Specific examples of organic solvents are not limited to amide solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, carbonate ester solvents, aromatic hydrocarbon solvents, etc.

[0177] These organic solvents may be used individually or as a mixture of two or more solvents. [Examples]

[0178] The embodiment will be described in more detail below with reference to specific examples and comparative examples, but the embodiment is not limited in any way by these examples and comparative examples unless it exceeds the essence of the embodiment. In this embodiment, unless otherwise specified, "parts" and "%" are based on mass.

[0179] The physical properties and evaluations in the examples and comparative examples described later were measured and evaluated by the methods shown below.

[0180] [Physical property 1] Hydroxyl value The hydroxyl value of the polycarbonate diol (composition) was measured by the following method. First, using a volumetric flask, pyridine was added to 12.5 g of acetic anhydride to make 50 mL to prepare the acetylation reagent. Next, 2.5 g of the sample was accurately weighed into a 100 mL round-bottom flask. Then, 5 mL of the acetylation reagent and 10 mL of toluene were added to the round-bottom flask using a volumetric pipette, and a condenser was attached. The solution in the round-bottom flask was heated and stirred at 100°C for 1 hour. Next, 2.5 mL of distilled water was added to the round-bottom flask using a volumetric pipette, and the solution in the round-bottom flask was heated and stirred for a further 10 minutes. After cooling the solution in the round-bottom flask for 2-3 minutes, 12.5 mL of ethanol was added to the round-bottom flask. Next, 2-3 drops of phenolphthalein were added to the round-bottom flask as an indicator, and the solution was titrated with 0.5 mol / L ethanolic potassium hydroxide. Next, 5 mL of acetylation reagent, 10 mL of toluene, and 2.5 mL of distilled water were placed in a 100 mL round-bottom flask, and the solution in the flask was heated and stirred for 10 minutes, after which titration was performed in the same manner (blank test). Based on these results, the hydroxyl value of the polycarbonate diol (composition) was calculated using the following formula (i). Hydroxyl value (mg-KOH / g) = {(FE) × 28.05 × f} / G ... (i) In formula (i), E represents the titration volume of the sample (mL), F represents the titration volume of the blank (mL), G represents the sample mass (g), and f represents the titrant factor.

[0181] [Physical properties 2] Number average molecular weight (A) The number-average molecular weight (A) of the polycarbonate diol (composition) was calculated from the hydroxyl value obtained in [Physical Properties 1] using the following formula (ii). Number average molecular weight (A)=2 / (H×10 -3 / 56.11) ···(ii) In formula (ii), H represents the hydroxyl value (mg-KOH / g) of the polycarbonate diol (composition). In the examples and comparative examples described later, the number-average molecular weight Mn of the polycarbonate diol composition applied to Formula 1 below was the number-average molecular weight (A) calculated using the above formula (ii). xy ≥ 3.7 × α (α = 22.4 × Mn)-0.41 )...(Formula 1) (In formula 1, x is the ratio (mass%) of the content (mass%) of the repeating structural unit represented by general formula (I) to the total mass (mass%) of the repeating structural units represented by general formulas (I) to (IV), y is the titration volume (mL) of the polycarbonate diol composition by the turbidity titration method, and Mn is the number-average molecular weight of the polycarbonate diol composition.)

[0182] [Physical property 3] Molecular weight (B) A portion of the polyurethane film obtained in the application examples and comparative examples described later was cut, and an N,N-dimethylformamide solution was prepared to a polyurethane concentration of 0.1% by mass. The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the polyurethane, in terms of standard polystyrene, were measured using a GPC apparatus [Tosoh Corporation, product name "HLC-8320" (column: Tskgel SuperHM-H, 4 columns), with a solution of 2.6 g of lithium bromide dissolved in 1 L of dimethylformamide as the eluent]. The molecular weight distribution (Mw / Mn) was also calculated from these measurement results.

[0184] [Physical property 5] Turbidity point titration Under 25°C conditions, 0.5 g of the polycarbonate diol composition obtained in the examples and comparative examples described below was dissolved in 8.8 g of butyl acetate. Hexane was added dropwise to the resulting solution while stirring, and the titration volume at which the solution began to become cloudy was determined. The turbidity titration was then calculated using the following formula (iii). Turbid point titration=0.5×I×56.1 / (J×K)···(iii) In formula (iii) below, I represents the titration volume (mL) obtained above, J represents the weighed sample mass (g), and K represents the hydroxyl value (mg-KOH / g) of the polycarbonate diol composition.

[0185] [Physical Properties 6] Acid Value The acid value of the polycarbonate diol compositions obtained in the examples and comparative examples described below was determined using a method in accordance with JIS K 0070-1992, except that the solvent was changed to toluene / ethanol (2 / 1).

[0186] [Physical Properties 7] Structural Unit (I) Content in Polycarbonate Diol Compositions 1 g of the polycarbonate diol composition sample obtained in the examples and comparative examples described below was placed in a 100 mL round-bottom flask, and 30 g of methanol and 8 g of 28% sodium methoxide methanol solution were added. The reaction was carried out at 100°C for 1 hour. After the reaction solution was cooled to room temperature, 2-3 drops of phenolphthalein were added as an indicator and neutralized with hydrochloric acid. After cooling in the refrigerator for 1 hour, the solution was filtered and analyzed using gas chromatography (GC). For the GC analysis, a gas chromatography GC-14B (Shimadzu Corporation, Japan) equipped with a DB-WAX column (J&W, USA) was used, with diethylene glycol diethyl ester as the internal standard and a flame ionization detector (FID) as the detector to quantitatively analyze each component. The column heating profile was maintained at 60°C for 5 minutes, then heated to 250°C at a rate of 10°C / min. Based on the above analysis results, the composition of the polycarbonate diol composition was determined from the detected alcohol components and the methyl ester components derived from the dibasic acid. If methyl ester components derived from dibasic acids were not detected, the composition of the polyester polycarbonate polyol containing dibasic acids was determined by subtracting the same number of molars of diols from the methyl ester derived from the dibasic acid (if multiple diols were used, the composition of diols in the carbonate skeleton and the ester skeleton were assumed to be the same based on the ratio of diols determined by gas chromatography).

[0187] [Physical Properties 8] Peroxide Value (POV) Samples of the polycarbonate diol compositions obtained in the examples and comparative examples described below were immersed in the test area of ​​POV test paper (Shibata Scientific Co., Ltd.), left for 3 minutes, and then washed with pure water. The POV test paper of the sample was compared with a standard color chart, and the peroxide value (POV) of the sample was determined as follows. [Judgment criteria] A value of 0 meq / kg or more and 3 meq / kg or less, detected as 0 in the standard color sample, is rated ○. A value of more than 3 meq / kg and 10 meq / kg or less, equivalent to 10 of the standard color sample, is rated △. A value of more than 10 meq / kg and 40 meq / kg or less, equivalent to 30 of the standard color sample, is rated ×.

[0188] [Physical Property 9] Quality Stability The polycarbonate diol compositions obtained in the Examples and Comparative Examples described below were stored at 25°C for 6 months, and quality stability was evaluated as follows based on changes in appearance compared to immediately after production. [Evaluation Criteria] ○: No change in appearance from immediately after production ×: There is a change in appearance compared to immediately after production (for example, two-layer separation, cloudiness, precipitation, etc.)

[0189] [Evaluation 1] Compatibility Evaluation (Polyol) The compatibility of the polycarbonate diol compositions obtained in the Examples and Comparative Examples described below was evaluated as follows. As an example of a polyol, polyester polyol (manufactured by Showa Denko Materials Co., Ltd., "Tesslac 2460" (trade name), number average molecular weight: approx. 2000) was used. The polyester polyol and the polycarbonate diol composition were sequentially mixed and stirred at a mass ratio of 7:3, and compatibility was evaluated as follows based on the appearance of the resulting solution. [Evaluation Criteria] ○: Transparent △: Slightly cloudy or slightly separated into two layers ×: Cloudy

[0190] [Evaluation 2] Compatibility Evaluation (Solvent) The compatibility of the polycarbonate diol compositions obtained in the Examples and Comparative Examples described below was evaluated as follows. As an example of a solvent, methyl isobutyl ketone (hereinafter also referred to as "MIBK") was used. The polycarbonate diol composition was blended into methyl isobutyl ketone to obtain a solid content of 75%, mixed and stirred at 25°C, allowed to stand for 30 minutes, and compatibility was evaluated as follows based on the appearance of the resulting solution. [Evaluation Criteria] ○: Transparent △: Slightly cloudy ×: It is cloudy / milky.

[0191] [Evaluation 3] Room temperature tensile test In accordance with JIS K6250 (2019), strip-shaped test pieces measuring 10 mm in width, 100 mm in length, and approximately 0.1 mm in thickness were prepared from the polyurethane films obtained in the application examples and comparative application examples described below. Tensile tests were performed on the prepared test pieces using a tensile testing machine (Orientec Co., Ltd., product name "Tensilon, model RTE-1210") at a chuck distance of 20 mm, a tensile speed of 100 mm / min, and a temperature of 23°C (relative humidity 55%). The stress (100% modulus) at which the test piece was 100% elongated was measured. A lower 100% modulus was considered to indicate better flexibility at room temperature.

[0192] [Evaluation 4] Low-temperature tensile test In accordance with JIS K6250 (2019), strip-shaped test specimens measuring 10 mm in width, 100 mm in length, and approximately 0.1 mm in thickness were prepared from the polyurethane films obtained in the application examples and comparative application examples described below. The prepared test specimens were placed in a tensile testing machine (Orientec Co., Ltd., product name "Tensilon, model RTE-1210") equipped with a constant temperature chamber (Orientec Co., Ltd., "Model TLF-R3T-EW") with a chuck distance of 20 mm. Subsequently, the test specimens were left to stand at -20°C for 5 minutes, and then a tensile test was performed on the test specimens at a tensile speed of 100 mm / min. The stress (100% modulus) at which the test specimen was 100% elongated was measured. A lower 100% modulus was considered to indicate better flexibility at low temperatures.

[0193] [Evaluation 5] Stress at Δ100% extension (hereinafter sometimes referred to as "ΔM") The aforementioned [evaluation] 3 ] and [evaluation 4 From the 100% modulus (stress at 100% tensile stress) obtained by [ ], ΔM was calculated using the following equation (B). ΔM = M1 - M2 ···(B) (In formula (B), M1 is [evaluation 4 This is the stress at 100% elongation under -20°C conditions, obtained by [Evaluation], and M2 is [Evaluation]3 This is the stress at 100% elongation under 23°C conditions, as determined by [the formula / method used].

[0194] [Evaluation 6] Evaluation of moisture and heat resistance From the polyurethane films obtained in the application examples and comparative application examples described below, strip-shaped samples measuring 10 mm in width, 100 mm in length, and approximately 100 μm in thickness were prepared. The prepared samples were heated for 10 days under conditions of 85°C and 85% humidity in an ESPEC Corporation constant temperature and humidity chamber, product name "PL-1J". After heating, the breaking strength of the samples was measured in the same manner as in the <room temperature tensile test> described above, and the retention rate of breaking strength (%) was calculated from the following formula (C). Retention rate = Breaking strength after heating / Breaking strength before heating × 100 ... (C)

[0196] The abbreviations used in the table and text are as follows: A-1: Polyoxytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG2000" (product name), number average molecular weight: approximately 2000, in general formula (II-1), R 211 : Tetramethylene group, n211: approximately 28) A-2: Polyoxytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG1000" (product name), number average molecular weight: approximately 1000, in general formula (II-1), R 211 : Tetramethylene group, n211: approximately 14) A-3: Polyoxyethylene polyoxypropylene glycol (manufactured by Sanyo Chemical Industries, Ltd., "Newpol PE-61" (product name), number average molecular weight: approximately 2000, in general formula (II-1), R 211 : Isopropylene group and ethylene base, n211: approx. 35) A-4: Polyoxyethylene polyoxypropylene glycol (manufactured by Sanyo Chemical Industries, Ltd., "Newpol PE-62" (product name), number average molecular weight: approximately 2400, in general formula (II-1), R 211 : Isopropylene group and ethylene base, n211: approx. 44) A-5: Copolymer of tetrahydrofuran and neopentyl glycol (manufactured by Asahi Kasei Corporation, "PTXG" (product name), number average molecular weight: approximately 1800, in general formula (II-1), R 211 : 2,2-dimethyltrimethylene group and tetramethylene group, n211: approximately 23) B-1: Polycaprolactone polyol (manufactured by Daicel Organic Synthesis Company, Ltd., "Praxel 220" (product name), number average molecular weight: approximately 2000, in general formula (III-1), R 311 :Pentamethylene group, n311:approximately 18) B-2: Polyester polyol (manufactured by DIC Corporation, "OD-X-2692" (product name), number average molecular weight: approximately 2000, in general formula (IV-1), R 411 : Tetramethylene group, R 421 : Isobutylene group, n411: approximately 10) B-3: Polyester polyol (manufactured by Kuraray Co., Ltd., "P-2020" (product name), number average molecular weight: approximately 2000, in general formula (IV-1), R 411 : Phenylene group, R 421 :3-methylpentamethylene group, n411:approximately 8)

[0197] [Synthesis Example 1] Production of Polycarbonate Diol P-1 230 g of 1,5-pentanediol, 250 g of 1,6-hexanediol, and 400 g of ethylene carbonate were charged into a 1 L glass flask (hereinafter also referred to as the "reactor") equipped with a rectification column packed with ordered packing and a stirrer. Then, 0.0468 g of titanium tetra-n-butoxide was added as a catalyst. The reactor was immersed in an oil bath at 180°C, and the reaction was carried out at a reaction temperature of 165°C for 12 hours, while removing a portion of the distillate. Next, the reactor was directly connected to a condenser, the oil bath temperature was raised to 180°C, and the reaction was carried out for a further 3 hours while gradually decreasing the pressure, yielding polycarbonate diol P-1 (466 g), which is liquid at room temperature. The hydroxyl value of the obtained polycarbonate diol P-1 was 55.2 mg-KOH / g. The number-average molecular weight of the obtained polycarbonate diol P-1 was 2033.

[0198] [Synthesis Example 2] Production of Polycarbonate Diol P-2 270 g of 1,6-hexanediol, 250 g of 1,4-butanediol, and 445 g of ethylene carbonate were charged into a 1 L glass flask (hereinafter also referred to as the "reactor") equipped with a rectification column packed with ordered packing and a stirrer. Then, 0.0960 g of titanium tetra-n-butoxide was added as a catalyst. The reactor was immersed in an oil bath at 140-160°C, and the reaction was carried out for 20 hours at a reaction temperature of 90-160°C, while removing a portion of the distillate. Next, the reactor was directly connected to a condenser, the oil bath temperature was raised to 180°C, and the reaction was carried out for a further 8 hours while gradually reducing the pressure, yielding polycarbonate diol P-2 (462 g), which is liquid at room temperature. The hydroxyl value of the obtained polycarbonate diol P-2 was 56.1 mg-KOH / g. Furthermore, the number-average molecular weight of the obtained polycarbonate diol P-2 was 2000.

[0199] [Synthesis Example 3] Production of Polycarbonate Diol P-3 230 g of 1,5-pentanediol, 250 g of 1,6-hexanediol, and 400 g of ethylene carbonate were charged into a 1 L glass flask (hereinafter also referred to as the "reactor") equipped with a rectification column packed with ordered packing and a stirrer. Then, 0.0468 g of titanium tetra-n-butoxide was added as a catalyst. The reactor was immersed in an oil bath at 180°C, and the reaction was carried out at a reaction temperature of 165°C for 12 hours, while removing a portion of the distillate. Next, the reactor was directly connected to a condenser, the oil bath temperature was raised to 165°C, and the reaction was carried out for a further 3 hours while gradually decreasing the pressure, yielding polycarbonate diol P-3 (478 g), which is liquid at room temperature. The hydroxyl value of the obtained polycarbonate diol P-3 was 112.0 mg-KOH / g. The number-average molecular weight of the obtained polycarbonate diol P-3 was 1002.

[0200] [Example 1] Preparation of polycarbonate diol composition SA-1 90 parts by mass (360 g) of polycarbonate diol P-2 obtained in Synthesis Example 2 and 10 parts by mass (40 g) of polyoxytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG2000" (product name), number average molecular weight: approximately 2000) were charged into a 1 L glass flask equipped with a stirring device (hereinafter also referred to as the "reactor"). Next, the reactor was stirred at 120°C for 10 minutes under reduced pressure of 0.1 kPa.s or less using a vacuum pump, and then nitrogen purging was performed to confirm that the oxygen concentration was 0.5% or less. The reactor was heated and stirred at approximately 145°C for 12 hours while maintaining a nitrogen flow rate of 1 L / min. The reaction solution was subjected to turbidity titration over time, and after confirming that there was no change in the turbidity titration volume, dibutyl phosphate was added to titanium tetra-n-butoxide in a mass ratio of 1.3 times, and the mixture was heated at a reactor temperature of 110°C for 3 hours to obtain polycarbonate diol composition SA-1. The physical properties of the obtained polycarbonate diol composition SA-1 were measured by the method described above. The results are shown in Table 1. The hydroxyl value of the obtained polycarbonate diol composition SA-1 was 56.6 mg-KOH / g. The number-average molecular weight of the obtained polycarbonate diol composition SA-1 was 1982. Furthermore, the obtained polycarbonate diol composition SA-1 contained a repeating structural unit represented by the following formula (A1) and a repeating structural unit represented by the following formula (B1). [ka] ...(A 1 ) (In general formula (A1), R 11 (This is an aliphatic hydrocarbon group having 4 or 6 carbon atoms.) [ka] ...(B1) (In general formula (B1), R 21 (This is a tetramethylene group, and the average value of n21 is approximately 28.)

[0201] [Examples 2-13] Except for changing the types and quantities of each raw material as shown in Tables 1 and 2, the reaction was carried out under the same conditions and methods as in Example 1, yielding the polycarbonate diol compositions SA-2 to SA-13 of Examples 2 to 13. Periodic quantitative analysis and various physical properties of the obtained polycarbonate diol compositions SA-2 to SA-13 were measured by turbidity titration using the method described above. The results are shown in Tables 1 and 2. Furthermore, the obtained polycarbonate diol compositions SA-2 to SA-13 contained, in order, repeating structural units represented by the following formulas (A2) to (A13) and repeating structural units represented by the following formulas (B2) to (B13). [ka] ...(A2) (In general formula (A2), R 11 (This is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.) [ka] ...(B2) (In general formula (B2), R 21 (This is a tetramethylene group, and the average value of n21 is approximately 28.) [ka] ...(A3) (In general formula (A3), R 11 (This is an aliphatic hydrocarbon group having 4 or 6 carbon atoms.) [ka] ...(B3) (In general formula (B3), R 21 isopropylene group and ethylene (This is the baseline, and the average value for n21 is approximately 35.) [ka] ...(A4) (In general formula (A4), R 11 (This is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.) [ka] ...(B4) (In general formula (B4), R 21 teeth, Isopropylene group and ethylene group Yes, the average value for n21 is approximately 28. [ka] ...(A5) (In general formula (A5), R 11 (This is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.) [ka] ...(B5) (In general formula (B5), R 21 It contains 2,2-dimethyltrimethylene and tetramethylene groups, and the average value of n21 is approximately 23. [ka] ...(A6) (In general formula (A6), R 11 (This is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.) [ka] ...(B6) (In general formula (B6), R 21 It contains 2,2-dimethyltrimethylene and tetramethylene groups, and the average value of n21 is approximately 23. [ka] ...(A7) (In general formula (A7), R 11 (This is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.) [ka] ...(B7) (In general formula (B7), R 21 It contains a tetramethylene group, and the average value of n21 is approximately 14. [ka] ...(A8) (In general formula (A8), R 11 (This is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.) [ka] ...(B8) (In general formula (B8), R 21 isopropylene group and ethylene (There is a base, and the average value for n21 is approximately 44.) [ka] ...(A9) (In general formula (A9), R 11 (This is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.) [ka] ...(B9) (In general formula (B9), R 21 isopropylene group and ethylene (There is a base, and the average value for n21 is approximately 35.) [ka] ...(A10) (In general formula (A10), R 11 (This is an aliphatic hydrocarbon group having 4 or 6 carbon atoms.) [ka] ...(B10) (In general formula (B10), R 31 (This is a pentamethylene group.) [ka] ...(A11) (In general formula (A11), R 11 (This is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.) [ka] ...(B11) (In general formula (B11), R 41 is a tetramethylene group, and R 42 (This is an isobutylene group.) [ka] ...(A12) (In general formula (A12), R 11 (This is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.) [ka] ...(B12) (In general formula (B12), R 41 is a phenylene group, R 42 (This is a 3-methylpentamethylene group.) [ka] ...(A13) (General formula (A 13 ), R 11 (This is an aliphatic hydrocarbon group having 4 or 6 carbon atoms.) [ka] ...(B13) (General formula (B 13 ), R 21 isopropylene group and ethylene (This is the baseline, and the average value for n21 is approximately 35.)

[0202] [Comparative Example 1] Production of Polycarbonate Diol Composition SB-1 In a 1 L glass flask equipped with a stirring device (hereinafter also referred to as the "reactor"), 25 parts by mass (100 g) of polycarbonate diol P-1 obtained in Synthesis Example 1 and 75 parts by mass (300 g) of polyoxytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG2000" (product name), number average molecular weight: approximately 2000) were charged. Under an air atmosphere, the reactor temperature was heated to approximately 145°C and maintained for 10 hours with stirring. Next, dibutyl phosphate was added in an amount 1.3 times the mass ratio of titanium tetra-n-butoxide, and the mixture was heated at a reactor temperature of 110°C for 3 hours to obtain polycarbonate diol composition SB-1. The physical properties of the obtained polycarbonate diol composition SB-1 were measured by the method described above. The results are shown in Table 3. The obtained polycarbonate diol composition SB-1 had a hydroxyl value of 56.2 mg-KOH / g and a number-average molecular weight of 1996.

[0203] [Comparative Example 2] Production of Polycarbonate Diol Composition SB-2 The reaction was carried out under the same conditions and methods as in Comparative Example 1, except that the types and amounts of each raw material were changed as shown in Table 2, to obtain the polycarbonate diol composition SB-2 of Comparative Example 2. The physical properties of the obtained polycarbonate diol composition SB-2 were measured by the method described above. The results are shown in Table 3.

[0204] [Comparative Example 3] Production of Polycarbonate Diol Composition SB-3 Polycarbonate diol composition SB-3 was obtained by heating a 1 L glass flask equipped with a stirring device (hereinafter also referred to as the "reactor") with 400 g of polycarbonate diol P-2 obtained in Synthesis Example 2 and dibutyl phosphate in an amount 1.3 times the mass ratio of titanium tetra-n-butoxide, and heating at a reactor temperature of 110 °C for 3 hours. The physical properties of the obtained polycarbonate diol composition SB-3 were measured by the method described above. 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.

[0205] [Comparative Example 4] Production of Polycarbonate Diol Composition SB-4 90 parts by mass (360 g) of polycarbonate diol P-2 obtained in Synthesis Example 2 and 10 parts by mass (40 g) of polyoxytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG2000" (product name), number average molecular weight: approximately 2000) were charged into a 1 L glass flask equipped with a stirring device (hereinafter also referred to as the "reactor"). Next, the reactor was stirred at 120°C for 10 minutes under a reduced pressure of 0.1 kPa.s or less using a vacuum pump, and then nitrogen purging was performed to confirm that the oxygen concentration was 0.5% or less. The reactor temperature was heated and stirred at approximately 145°C for 6 hours while maintaining a nitrogen flow rate of 1 L / min. GPC measurements were performed on the reaction solution over time to confirm the progress of the reaction by observing the disappearance of peaks originating from the raw materials and the appearance of peaks originating from the products over time. Subsequently, dibutyl phosphate was added to titanium tetra-n-butoxide in an amount 1.3 times its mass ratio, and the mixture was heated at 110°C for 3 hours to obtain polycarbonate diol composition SB-4. The physical properties of the obtained polycarbonate diol composition SB-4 were measured by the method described above. The results are shown in Table 3. The hydroxyl value of the obtained polycarbonate diol composition SB-4 was 56.2 mg-KOH / g. The number-average molecular weight of the obtained polycarbonate diol composition SB-4 was 1996.

[0206] [Table 1]

[0207] [Table 2]

[0208] [Table 3]

[0209] [Application Example 1] Synthesis of polyurethane film PA-1 In a 500 mL separable flask equipped with a thermocouple and a condenser, 38 g of polycarbonate diol composition SA-1, 224 g of dimethylformamide (hereinafter sometimes abbreviated as DMF), and 0.26 g of 1% dibutyltin dilaurate toluene solution (50 ppm relative to the total mass of MDI and polycarbonate diol composition) were placed and heated in an oil bath at 40°C. While stirring the solution in the flask at 100 rpm under a nitrogen atmosphere, 14.8 g of MDI (3.09 times [mol] relative to the OH [mol] of the polycarbonate diol composition) was added dropwise, and the solution in the flask was stirred for approximately 1.5 hours. The isocyanate group concentration was analyzed to confirm that the theoretical amount had been consumed, and a prepolymer was obtained. Subsequently, 3.2 g of 1,4-butanediol (1,4-BD), the required amount calculated from the remaining isocyanate, was added to the flask in portions. After stirring the solution in the flask for about 1 hour, approximately 1 g of ethanol was added, and the solution in the flask was stirred for another 30 minutes to obtain a polyurethane solution with a number-average molecular weight of 74,000. Using a 0.8 mm thick applicator, the obtained polyurethane solution was dropped onto a glass plate (JIS R3202, 2 mm × 100 mm × 150 mm) to coat it to a dry film thickness of 50 to 150 μm. The plate was then dried on a hot plate at a surface temperature of 60°C for 2 hours, followed by drying in an oven at 80°C for 12 hours. The film was then left to stand for more than 12 hours under constant temperature and humidity conditions of 23°C and 55% RH to obtain polyurethane film PA-1. The obtained polyurethane film PA-1 was subjected to evaluation of various physical properties using the method described above. The evaluation results are shown in Table 4.

[0210] [Application Examples 2-13] In the production of the polyurethane film of Application Example 1, the reaction was carried out under the same conditions as in Application Example 1, except that the polycarbonate diol composition used was changed to the polycarbonate diol compositions SA-2 to SA-13 produced in Examples 2 to 12, and polyurethane films PA-2 to PA-13 were obtained. The obtained polyurethane films PA-2 to PA-13 were subjected to evaluation of various physical properties using the method described above. The evaluation results are shown in Tables 4 and 5.

[0211] [Examples of Applications 1-4] In the production of the polyurethane film of Application Example 1, the reaction was carried out under the same conditions as in Application Example 1, except that the polycarbonate diol compositions used were changed to the polycarbonate diol compositions SB-1 to SB-4 produced in Comparative Examples 1 to 3, and polyurethane films PB-1 to PB-4 were obtained. The obtained polyurethane films PB-1 to PB-4 were subjected to evaluation of various physical properties using the method described above. The evaluation results are shown in Table 6.

[0212] [Table 4]

[0213] [Table 5]

[0214] [Table 6]

[0215] The results shown in Tables 1-3 indicate that polycarbonate diol compositions containing repeating structural unit (I), and further containing at least one repeating structural unit selected from the group consisting of repeating structural units (II) to (IV), and satisfying specific conditions, exhibit superior compatibility with polyols and solvents compared to polycarbonate diol compositions that do not satisfy the specific conditions.

[0216] Furthermore, the results shown in Tables 4-6 indicate that the polyurethane obtained from the polycarbonate diol compositions of the examples exhibits excellent flexibility and mechanical properties at low temperatures, as well as a good balance with durability such as resistance to moisture and heat. [Industrial applicability]

[0218] The polycarbonate diol composition of this embodiment can be made high-solids, for example, during the manufacture of paints and polyurethanes, and is useful as a raw material for paints and polycarbonate-based polyurethanes. Furthermore, the polyurethane produced using the polycarbonate diol composition of this embodiment is , low It possesses excellent flexibility and durability, making it suitable for use in a wide range of fields, including elastic fibers, synthetic or artificial leather, paints, and high-performance elastomers.

Claims

1. A polycarbonate diol composition that includes a repeating structural unit represented by the following general formula (I), and further includes 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 satisfies the following formula (Formula 1). 【Chemistry 1】 (In general formula (I), R 11 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 15 carbon atoms, or an aromatic hydrocarbon group. 11 They may be the same or they may be different. 【Chemistry 2】 (In general formula (II), R 21 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. 21 (These two integers may be identical or different. n²¹ is any integer.) 【Transformation 3】 (In general formula (III), R 31 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. 31 They may be the same or they may be different. 【Chemistry 4】 In the general formula (IV), R 41 and R 42 each independently represent a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. When there are a plurality of R 41 and R 42 may be the same as or different from each other.) xｽ≧3.7×α (α=22.4×Mn -0.41 ) ・・・(Formula 1) (In formula 1, x is the ratio (mass%) of the content (mass%) of the repeating structural unit represented by general formula (I) to (IV) relative to the total mass (mass%) of the repeating structural units represented by general formulas (I) to (IV), y is the titration volume (mL) of the polycarbonate diol composition by the turbidity titration method, 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 general formula (I) is 40% by mass or more relative to the total mass of the repeating structural units represented by general formulas (I) to (IV), and the titration volume by the turbidity titration method is 4.0 mL or more and 9.5 mL or less. 【Transformation 5】 (In general formula (I), R 11 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 15 carbon atoms, or an aromatic hydrocarbon group. 11 They may be the same or they may be different. 【Transformation 6】 (In general formula (II), R 21 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. 21 (These two integers may be identical or different. n²¹ is any integer.) 【Transformation 7】 (In general formula (III), R 31 R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. 31 They may be the same or they may be different. 【Transformation 8】 (In general formula (IV), R 41 and R 42 Each of these is independently a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. 41 and R 42 They may be the same or they may be different.

3. The polycarbonate diol composition according to claim 1, wherein the content of the repeating structural unit represented by general formula (I) is 5% by mass or more and 95% by mass or less, relative to the total mass of the repeating structural units represented by 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 general formula (I) is 40% by mass or more and 90% by mass or less, relative to the total mass of the repeating structural units represented by general formulas (I) to (IV).

5. The polycarbonate diol composition according to claim 1 or 2, wherein the acid value is 0.001 mg-KOH / g or more and 0.8 mg-KOH / g or less.

6. The polycarbonate diol composition according to claim 1 or 2, wherein the peroxide content is 10 meq / kg or less.

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), the average value of the number of repetitions n21 of the repeating structural unit represented by general formula (II) is 15 or more.

8. The polycarbonate diol composition according to claim 1 or 2, comprising at least one repeating structural unit represented by general formula (II) or (IV) among the repeating structural units represented by general formula (II) to (IV).

9. The polycarbonate diol composition according to claim 1 or 2, comprising at least one repeating structural unit represented by general formula (II) among the repeating structural units represented by general formula (II) to (IV).

10. A polyurethane comprising the polycarbonate diol composition described in claim 1 or 2.

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

12. Synthetic leather comprising the polyurethane described in claim 10.

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