Oxyethylene structure-containing polycarbonate polyol and use thereof

Abstract

The present invention provides an oxyethylene structure-containing polycarbonate polyol which has a hydroxyl value of 10 mgKOH / g to 400 mgKOH / g, while containing a specific amount of a specific structural unit.

Description

[Technical field]

[0001] The present invention relates to an oxyethylene structure-containing polycarbonate polyol and its use. [Background technology]

[0002] Conventionally, polyurethane resins have been used in a wide range of fields, such as synthetic leather, artificial leather, adhesives, furniture paints, and automotive paints. Among the raw materials of polyurethane resins, polyether polyols, polyester polyols, and polycarbonate polyols are used as polyol components to be reacted with isocyanates. In general, polyurethane resins using polycarbonate polyols as polyol components are known to be more excellent in durability, such as moisture and heat resistance, solvent resistance, sunscreen resistance, and scratch resistance, than polyurethane resins using polyether polyols or polyester polyols.

[0003] In recent years, there has been an increasing need for polycarbonate polyols that can be dispersed in water as a sustainable material. For example, Patent Document 1 discloses a polycarbonate diol composition that is excellent in water dilutability. In addition, for example, Patent Document 2 discloses a polycarbonate / polyoxyethylene block polymer for aqueous compositions that is excellent in water dilutability and can be used as an aqueous composition. In addition, for example, Patent Document 3 discloses a polycarbonate diol composition that can form a coating film that is excellent in contamination resistance and chemical resistance. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2014-80530 A [Patent Document 2] International Publication No. 2015 / 170374 [Patent Document 3] JP 2019-210314 A Summary of the Invention [Problem to be solved by the invention]

[0005] Generally, for example, in the case of two-component urethane paint, the base agent and hardener are mixed before painting, but the base agent and hardener are stored separately until painting. Depending on the storage location, they may be stored for long periods of time in an environment where the temperature is above room temperature.

[0006] However, Patent Documents 1, 2, and 3 do not mention the stability of aqueous dispersions of water-dispersible polycarbonate polyols when stored at room temperature or higher, and there is still room for improvement.

[0007] Furthermore, for example, in two-component urethane paints, polyurethanes, and / or water-based polyurethanes, polycarbonate polyols are sometimes used in combination with ether polyols, but due to compatibility issues, the number average molecular weight of the polycarbonate polyols may be limited to 500 or less.

[0008] However, Patent Documents 1, 2 and 3 are silent about the compatibility between water-dispersible polycarbonate polyol and ether polyol, and there is still room for improvement.

[0009] Therefore, an object of the present invention is to provide an oxyethylene structure-containing polycarbonate polyol that is excellent in stability of an aqueous dispersion and / or compatibility with an ether polyol. [Means for solving the problem]

[0010] As a result of intensive research aimed at solving the above problems, the present inventors have discovered that a polycarbonate polyol having a specific structure exhibits excellent stability of an aqueous dispersion and / or compatibility with an ether polyol, and have thus completed the present invention.

[0011] That is, the present invention is configured as follows. [1] An oxyethylene structure-containing polycarbonate polyol having a hydroxyl value of 10 to 400 mgKOH / g, The polymerizable compound includes a structural unit represented by the following formula (A), a structural unit represented by the following formula (B), and a structural unit represented by the following formula (BB), the molar amount of the structural unit represented by the formula (A) is 30 to 90 mol % based on the total molar amount of the structural unit represented by the formula (A) and the structural unit represented by the formula (B); the molar amount of the structural unit represented by the formula (B) is 10 to 70 mol % relative to the total molar amount of the structural unit represented by the formula (A) and the structural unit represented by the formula (B); An oxyethylene structure-containing polycarbonate polyol, in which the value obtained by the following formula (i) is 150.0 to 400.0: [ka] (In formula (A), R is a divalent aliphatic hydrocarbon group which may contain a heteroatom and / or a divalent aromatic hydrocarbon group which may contain a heteroatom; R 1 are each independently hydrogen or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. [ka] [ka]

number

[10] A coating material comprising the oxyethylene structure-containing polycarbonate polyol according to any one of [1] to [9].

[11] The paint according to

[10] , wherein the paint is a water-based paint.

[12] A polyurethane obtained by using the oxyethylene structure-containing polycarbonate polyol according to any one of [1] to [9].

[13] A water-based polyurethane obtained by using the oxyethylene structure-containing polycarbonate polyol according to any one of [1] to [9].

[14]

[12] Artificial leather containing the polyurethane according to the present invention.

[15]

[13] An artificial leather comprising the water-based polyurethane.

[16]

[12] Synthetic leather comprising the polyurethane according to the present invention.

[17]

[13] Synthetic leather comprising the water-based polyurethane.

[18] A paint comprising the polyurethane according to

[12] .

[19] A paint comprising the water-based polyurethane according to

[13] .

[20] A coating film obtained from the coating material described in

[10] . [twenty one] A coating film obtained from the coating material described in

[11] . Effect of the Invention

[0012] According to the present invention, it is possible to provide an oxyethylene structure-containing polycarbonate polyol having excellent stability of an aqueous dispersion and / or excellent compatibility with an ether polyol. [Brief description of the drawings]

[0013] [Figure 1] FIG. 1 shows the NMR spectrum of an oxyethylene structure-containing polycarbonate polyol. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Hereinafter, an embodiment of the present invention (hereinafter, referred to as "the present embodiment") will be described in detail. Note that the present invention is not limited to the following description, and can be modified in various ways within the scope of the gist of the present invention.

[0015] [Oxyethylene structure-containing polycarbonate polyol] The oxyethylene structure-containing polycarbonate polyol of the present embodiment is The hydroxyl value is 10 to 400 mgKOH / g. The polymerizable compound includes a structural unit represented by the following formula (A), a structural unit represented by the following formula (B), and a structural unit represented by the following formula (BB), the molar amount of the structural unit represented by the formula (A) is 30 to 90 mol % based on the total molar amount of the structural unit represented by the formula (A) and the structural unit represented by the formula (B); the molar amount of the structural unit represented by the formula (B) is 10 to 70 mol % relative to the total molar amount of the structural unit represented by the formula (A) and the structural unit represented by the formula (B); The value obtained by the following formula (i) is 150.0 to 400.0. [ka] (In formula (A), R is a divalent aliphatic hydrocarbon group which may contain a heteroatom and / or a divalent aromatic hydrocarbon group which may contain a heteroatom; R 1 are each independently hydrogen or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. [ka] [ka]

number

[0016] The oxyethylene structure-containing polycarbonate polyol of the present embodiment may be a mixture of a plurality of polyols. In this case, it is sufficient that a part of the plurality of polyols has an oxyethylene structure.

[0017] Although formula (B) has a structure identical to a part of formula (BB), formula (B) and formula (BB) are not overlapping but are different from each other. In other words, when a structure in which the terminal carbon of the structure of formula (B) is bonded to a carbonyl group via oxygen is present in an oxyethylene structure-containing polycarbonate polyol, this is judged to be formula (BB) rather than formula (B).

[0018] In addition, when R in formula (A) has a specific structure, formula (B) may have the same structure as a part of formula (A), but formula (B) and formula (A) do not overlap and are different from each other.

[0019] The oxyethylene structure-containing polycarbonate polyol of the present embodiment has the above-mentioned structure, and thus has excellent stability of the aqueous dispersion and compatibility with ether polyols.

[0020] Based on all structural units constituting the oxyethylene structure-containing polycarbonate polyol, the total amount of the structural units represented by Formula (A), Formula (B) and Formula (BB) is preferably 35 to 100 mol%, more preferably 45 to 100 mol%, even more preferably 50 to 100 mol%, even more preferably 55 to 100 mol%, more particularly preferably 60 to 100 mol%, more particularly preferably 70 to 100 mol%, even more particularly preferably 80 to 100 mol%, and most preferably 90 to 100 mol%.

[0021] When the total amount of the structural units represented by Formula (A), Formula (B), and Formula (BB) is within the above range, the stability and durability of the aqueous dispersion tend to be excellent, and the durability of the coating film, polyurethane film, and / or aqueous polyurethane obtained from such an oxyethylene structure-containing polycarbonate polyol tends to be better.

[0022] (Hydroxyl value) The hydroxyl value of the oxyethylene structure-containing polycarbonate polyol of this embodiment has a lower limit of 10 mgKOH / g or more, preferably 15 mgKOH / g or more, more preferably 20 mgKOH / g or more, even more preferably 25 mgKOH / g or more, even more preferably 30 mgKOH / g or more, particularly preferably 35 mgKOH / g or more, and extremely preferably 40 mgKOH / g or more. The upper limit is 400 mgKOH / g or less, preferably 350 mgKOH / g or less, more preferably 300 mgKOH / g or less, even more preferably 275 mgKOH / g or less, even more preferably 250 mgKOH / g or less, particularly preferably 200 mgKOH / g or less, and extremely preferably 150 mgKOH / g or less. The lower limit and upper limit may be appropriately combined to define a numerical range. For example, the hydroxyl value may be in the range of 10 to 400 mgKOH / g, 15 to 350 mgKOH / g, 20 to 300 mgKOH / g, 25 to 275 mgKOH / g, 30 to 250 mgKOH / g, 35 to 200 mgKOH / g, or 40 to 150 mgKOH / g. When the hydroxyl value of the oxyethylene structure-containing polycarbonate polyol is within the above range, the stability of the aqueous dispersion and the compatibility with the ether polyol tend to be excellent, and the drying property of the coating composition obtained from such an oxyethylene structure-containing polycarbonate polyol, as well as the durability of the coating film, polyurethane film, and / or water-based polyurethane tend to be better.

[0023] The method for controlling the hydroxyl value of the oxyethylene structure-containing polycarbonate polyol of the present embodiment within the above range is not particularly limited, but examples thereof include a method in which, during the production of the oxyethylene structure-containing polycarbonate polyol, the raw material polycarbonate polyol and a polyvalent hydroxy compound having a structure represented by formula (B) are charged so that the hydroxyl value falls within the above range, and a method in which, during the production of the oxyethylene structure-containing polycarbonate polyol, a polyvalent hydroxy compound is added and / or withdrawn to control the hydroxyl value.

[0024] In this embodiment, the hydroxyl value can be calculated using the method described in the examples below.

[0025] (R) In the structure represented by formula (A), R is a divalent aliphatic hydrocarbon group which may contain a heteroatom, and / or a divalent aromatic hydrocarbon group which may contain a heteroatom. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The multiple R's may be the same or different.

[0026] When R is a divalent linear aliphatic hydrocarbon group which may contain a heteroatom, the lower limit of the molecular weight of R is preferably 10 or more, and more preferably 20 or more. The upper limit of the molecular weight of R is preferably 3000 or less, more preferably 2500 or less, and even more preferably 2200 or less. The molecular weight of R may be in the range of 10 to 3000, 20 to 2500, or 20 to 2200, for example.

[0027] For example, if R is an ethylene group (-CH2-CH2-), the molecular weight of R is (12+1×2)+(12+1×2)=28.

[0028] When R is a divalent linear aliphatic hydrocarbon group which may contain a heteroatom, specific examples thereof include, but are not limited to, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, oxyethylene, oxytetramethylene, polyoxyethylene, polyoxytetramethylene, fluoroalkyl groups, perfluoroalkyl groups, etc. Among these, from the viewpoint of versatility, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptalene, octylene, nonylene, and decylene groups are preferred, and methylene, ethylene, propylene, and butylene groups are more preferred.

[0029] When R is a divalent branched aliphatic hydrocarbon group which may contain a heteroatom, the lower limit of the molecular weight of R is preferably 10 or more, and more preferably 20 or more. The upper limit of the molecular weight of R is preferably 3000 or less, more preferably 2500 or less, and even more preferably 2200 or less. The molecular weight of R may be in the range of 10 to 3000, 20 to 2500, or 20 to 2200, for example.

[0030] When R is a divalent branched aliphatic hydrocarbon group which may contain a heteroatom, specific examples thereof include, but are not limited to, isopropylene group, isobutylene group, tert-butylene group, isopentylene group, 2,2-dimethyltrimethylene group, isohexylene group, isoheptylene group, isooctylene group, oxy 1-methylethylene group, oxy 2,2-dimethyltrimethylene group, polyoxy 1-methylethylene group, etc. Among them, from the viewpoint of versatility, isopropylene group, isobutylene group, isopentylene group, 2,2-dimethyltrimethylene group or isohexylene group, and oxy 1-methylethylene group are preferred.

[0031] When R is a divalent cyclic aliphatic hydrocarbon group which may contain a heteroatom, the lower limit of the molecular weight of R is preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more. The upper limit of the molecular weight of R is preferably 3000 or less, more preferably 2500 or less, and even more preferably 2200 or less. The molecular weight of R may be in the range of 10 to 3000, 20 to 2500, or 30 to 2200, for example.

[0032] When R is a divalent cyclic aliphatic hydrocarbon group which may contain a heteroatom, specific examples thereof include, but are not limited to, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cycloheptylene group.

[0033] R may be a divalent aromatic hydrocarbon group which may contain a heteroatom. When R is a divalent aromatic hydrocarbon group which may contain a heteroatom, the lower limit of the molecular weight of R is preferably 50 or more, more preferably 60 or more, and even more preferably 70 or more. The upper limit of the molecular weight of R is preferably 3000 or less, more preferably 2500 or less, and even more preferably 2200 or less. The molecular weight of R may be in the range of, for example, 50 to 3000, 60 to 2500, or 70 to 2200.

[0034] Among these, R is preferably a divalent linear, branched or cyclic aliphatic hydrocarbon group which may contain a heteroatom and wherein the lower limit of the molecular weight of R is 10 or more, more preferably a divalent linear aliphatic hydrocarbon group which may contain a heteroatom and wherein the lower limit of the molecular weight of R is 20 or more, or a divalent branched aliphatic hydrocarbon group which may contain a heteroatom and wherein the lower limit of the molecular weight of R is 20 or more, even more preferably a divalent linear aliphatic hydrocarbon group which has a molecular weight of R of 10 or more, and even more preferably a divalent linear aliphatic hydrocarbon group which has a molecular weight of R of 20 or more. Furthermore, R is preferably a divalent linear, branched or cyclic aliphatic hydrocarbon group which may contain a heteroatom and in which the upper limit of the molecular weight of R is 3000 or less, more preferably a divalent linear aliphatic hydrocarbon group which may contain a heteroatom and in which the upper limit of the molecular weight of R is 2500 or less, or a divalent branched aliphatic hydrocarbon group which may contain a heteroatom and in which the upper limit of the molecular weight of R is 2500 or less, even more preferably a divalent linear aliphatic hydrocarbon group which has an upper limit of the molecular weight of R of 2000 or less, even more preferably a divalent linear aliphatic hydrocarbon group which has an upper limit of the molecular weight of R of 1500 or less, and particularly preferably a divalent linear aliphatic hydrocarbon group which has an upper limit of the molecular weight of R of 1000 or less.

[0035] (R 1 ) In the structure represented by formula (A), R 1 is hydrogen or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. The aliphatic hydrocarbon group may be linear, branched, or cyclic. 1 may be the same as or different from each other.

[0036] R 1 Specific examples of the aliphatic hydrocarbon group in include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a tert-butyl group, and an isopentyl group.

[0037] Among them, R 1 is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, or an isobutyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group, even more preferably a hydrogen atom, a methyl group, or an ethyl group, still more preferably a hydrogen atom, a methyl group, or an ethyl group, particularly preferably a hydrogen atom, or a methyl group, and more particularly preferably a hydrogen atom.

[0038] (Formula (i)) The structural unit represented by formula (A) has durability, the structural unit represented by formula (B) has hydrophilicity, and the structure represented by formula (BB) has hydrophilicity and compatibility with ether polyol. On the other hand, the structural unit represented by formula (A) tends to have reduced hydrophobicity and compatibility with ether polyol, the structural unit represented by formula (B) tends to have reduced hydrophilicity due to a change in three-dimensional structure caused by heating, and the structure represented by formula (BB) tends to have lower hydrophilicity than formula (B). Therefore, in order for an oxyethylene structure-containing polycarbonate polyol to have excellent stability in an aqueous dispersion and compatibility with an ether polyol, the structural unit represented by formula (A), the structural unit represented by formula (B), and the structural unit represented by formula (BB) are essential, and further, it is necessary that these structural units are within a certain range, i.e., the range of the value obtained by formula (i) is within the above-mentioned range. For example, when the value obtained by formula (i) is less than the lower limit of the range, the structural unit represented by formula (BB) is small, and in this case, the oxyethylene structure-containing polycarbonate polyol tends to have a low stability of the aqueous dispersion and a low compatibility with ether polyol. When the value obtained by formula (i) exceeds the upper limit of the range, the structural unit represented by formula (B) is small, and in this case, the oxyethylene structure-containing polycarbonate polyol tends to have a low hydrophilicity and a low dispersibility in water. When the value obtained by formula (i) exceeds the upper limit of the range, the structural unit represented by formula (A) is small, and in this case, the oxyethylene structure-containing polycarbonate polyol tends to have a low durability.

number

[0039] In the formula (i), Mn represents the number average molecular weight of the oxyethylene structure-containing polycarbonate polyol, and can be measured by the GPC measurement described in the Examples below.

[0040] The range of the value obtained by formula (i) is 150.0 to 400.0. The lower limit of the value obtained by formula (i) is preferably 155.0 or more, more preferably 160.0 or more, and even more preferably 165.0 or more. The upper limit is preferably 350.0 or less, more preferably 300.0 or less, and even more preferably 275.0 or less. The numerical range may be defined by appropriately combining the lower limit and the upper limit. For example, the range of the value obtained by formula (i) may be 155.0 to 350.0, 160.0 to 300.0, or 165.0 to 275.0. When the value obtained by formula (i) is within the above range, the stability of the aqueous dispersion and the compatibility with the ether polyol tend to be excellent.

[0041] (Number average molecular weight (Mn)) The number average molecular weight (Mn) of the oxyethylene structure-containing polycarbonate polyol of this embodiment is preferably 300 or more, more preferably 400 or more, even more preferably 500 or more, even more preferably 700 or more, particularly preferably 900 or more, and more particularly preferably 1000 or more. The number average molecular weight (Mn) of the oxyethylene structure-containing polycarbonate polyol of this embodiment is preferably 10000 or less, more preferably 8000 or less, even more preferably 5000 or less, even more preferably 4500 or less, particularly preferably 4000 or less, more particularly preferably 3800 or less, extremely preferably 3500 or less, and even more extremely preferably 3200 or less. The lower limit and upper limit may be appropriately combined to define the numerical range. For example, the number average molecular weight of the oxyethylene structure-containing polycarbonate polyol may be in the range of 300 to 10,000, 400 to 8,000, 500 to 5,000, 700 to 4,500, 900 to 4,000, 1,000 to 3,800, 1,000 to 3,500, or 1,000 to 3,200.

[0042] By having the number average molecular weight (Mn) within the above range, the oxyethylene structure-containing polycarbonate polyol of the present embodiment has excellent compatibility with ether polyols, and further, the durability of paints, polyurethanes, and / or water-based polyurethanes using such oxyethylene structure-containing polycarbonate polyols tends to be even more excellent.

[0043] The method for controlling the number average molecular weight (Mn) of the oxyethylene structure-containing polycarbonate polyol of the present embodiment within the above range is not particularly limited, but examples thereof include a method of charging the raw material polycarbonate polyol and a polyvalent hydroxy compound having a structure represented by formula (B) during the production of the oxyethylene structure-containing polycarbonate polyol so that the number average molecular weight (Mn) falls within the above range, and a method of controlling by adding and / or withdrawing a polyvalent hydroxy compound during the production of the oxyethylene structure-containing polycarbonate polyol.

[0044] In the present embodiment, the number average molecular weight (Mn) of the oxyethylene structure-containing polycarbonate polyol can be calculated by GPC measurement described in the examples below.

[0045] (Molecular weight distribution (Mw / Mn)) The molecular weight distribution (Mw / Mn) of the oxyethylene structure-containing polycarbonate polyol of this embodiment is preferably 1.50 or more, more preferably 1.60 or more, even more preferably 1.70 or more, even more preferably 1.80 or more, and particularly preferably 1.90 or more. The upper limit is preferably 5.00 or less, more preferably 4.00 or less, even more preferably 3.50 or less, even more preferably 2.75 or less, and particularly preferably 2.50 or less. The lower limit and the upper limit may be appropriately combined to define a numerical range. For example, the molecular weight distribution range of the oxyethylene structure-containing polycarbonate polyol may be 1.50 to 5.00, 1.60 to 4.00, 1.70 to 3.50, 1.80 to 2.75, or 1.90 to 2.50.

[0046] Since the molecular weight distribution (Mw / Mn) is within the above range, the oxyethylene structure-containing polycarbonate polyol of the present embodiment has excellent stability in an aqueous dispersion and compatibility with ether polyols, and a coating composition using such an oxyethylene structure-containing polycarbonate polyol tends to have even better flexibility and chemical resistance, and a polyurethane and / or a water-based polyurethane using such an oxyethylene structure-containing polycarbonate polyol tends to have even better flexibility and chemical resistance.

[0047] The method for controlling the molecular weight distribution (Mw / Mn) of the oxyethylene structure-containing polycarbonate polyol of the present embodiment within the above range is not particularly limited, and examples thereof include a method of charging the raw material polycarbonate polyol and a polyvalent hydroxy compound having a structure represented by formula (B) during the production of the oxyethylene structure-containing polycarbonate polyol so that the molecular weight distribution (Mw / Mn) falls within the above range, and a method of controlling by adding and / or withdrawing a polyvalent hydroxy compound during the production of the oxyethylene structure-containing polycarbonate polyol.

[0048] In this embodiment, the number average molecular weight (Mn) and weight average molecular weight (Mw) of the oxyethylene structure-containing polycarbonate polyol can be calculated by GPC measurement described in the Examples described later, and the molecular weight distribution (Mw / Mn) can be calculated from the calculated number average molecular weight (Mn) and weight average molecular weight (Mw) according to the following formula (II). Molecular weight distribution (Mw / Mn) = Weight average molecular weight (Mw) / Number average molecular weight (Mn) (II)

[0049] Among the polyhydric hydroxy compounds obtained by hydrolysis of the oxyethylene structure-containing polycarbonate polyol of the present embodiment, the average carbon number of the polyhydric hydroxy compounds excluding the polyhydric hydroxy compounds having an oxyethylene structure is preferably 2.0 or more, more preferably 2.5 or more, even more preferably 3.0 or more, even more preferably 3.2 or more, particularly preferably 3.5 or more, more particularly preferably 3.8 or more, and extremely preferably 4.0 or more. The upper limit is preferably 15.0 or less, more preferably 12.0 or less, even more preferably 10.0 or less, even more preferably 8.0 or less, particularly preferably 6.5 or less, more particularly preferably 6.0 or less, extremely preferably 5.5 or less, and even extremely preferably 5.2 or less. The lower limit and upper limit may be appropriately combined to define the numerical range. For example, the average carbon number of the polyvalent hydroxy compound (excluding polyvalent hydroxy compounds having an oxyethylene structure) may be in the range of 2.0 to 15.0, 2.5 to 12.0, 3.0 to 10.0, 3.2 to 8.0, 3.5 to 6.5, 3.8 to 6.0, 4.0 to 5.5, or 4.0 to 5.2.

[0050] When the average carbon number of the polyhydric hydroxy compound (excluding polyhydric hydroxy compounds having an oxyethylene structure) is within the above range, the oxyethylene structure-containing polycarbonate polyol of the present embodiment has excellent flexibility and durability, and a coating composition using such an oxyethylene structure-containing polycarbonate polyol tends to have an even better balance between flexibility and durability, and a polyurethane and / or a water-based polyurethane using such an oxyethylene structure-containing polycarbonate polyol tends to have even better flexibility and durability.

[0051] From the viewpoint of improving chemical resistance, it is preferable that the polyvalent hydroxy compound (excluding polyvalent hydroxy compounds having an oxyethylene structure) obtained by hydrolyzing the oxyethylene structure-containing polycarbonate polyol of the present embodiment contains at least one selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol, and 1,3-propanediol is particularly preferable. , 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol, more preferably at least one selected from the group consisting of 1,3-propanediol, 2-methyl-1,3-propanediol, and 1,4-butanediol, and even more preferably at least one selected from the group consisting of 1,3-propanediol and 1,4-butanediol.

[0052] Among the polyhydric hydroxy compounds obtained by hydrolysis of the oxyethylene structure-containing polycarbonate polyol of this embodiment, the number average molecular weight of the polyhydric hydroxy compound having an oxyethylene structure is preferably 300 or more, more preferably 400 or more, even more preferably 500 or more, even more preferably 600 or more, particularly preferably 700 or more, more particularly preferably 800 or more, and extremely preferably 900 or more. The upper limit is preferably 3000 or less, more preferably 2800 or less, even more preferably 2500 or less, even more preferably 2200 or less, particularly preferably 2000 or less, more particularly preferably 1800 or less, extremely preferably 1500 or less, and even extremely preferably 1300 or less. The lower limit and upper limit may be appropriately combined to define the numerical range. For example, the number average molecular weight of the polyvalent hydroxy compound having an oxyethylene structure may be in the range of 300 to 3,000, 400 to 2,800, 500 to 2,500, 600 to 2,200, 700 to 2,000, 800 to 1,800, 900 to 1,500, or 900 to 1,300.

[0053] Since the number average molecular weight of the polyvalent hydroxy compound having an oxyethylene structure is within the above range, the oxyethylene structure-containing polycarbonate polyol of the present embodiment has excellent stability in an aqueous dispersion and compatibility with ether polyols, and a coating composition using such an oxyethylene structure-containing polycarbonate polyol tends to have a better balance between flexibility and chemical resistance, and a polyurethane and / or a water-based polyurethane using such an oxyethylene structure-containing polycarbonate polyol tends to have better flexibility and chemical resistance.

[0054] The polyhydric hydroxy compound having an oxyethylene structure is preferably polyethylene glycol.

[0055] The oxyethylene structure-containing polycarbonate polyol of the present embodiment can have a hydrophilic structure other than the oxyethylene structure. The hydrophilic structure is not particularly limited, but examples thereof include nonionic hydrophilic groups, anionic hydrophilic groups, and cationic hydrophilic groups. Among them, from the viewpoint of versatility, nonionic hydrophilic groups and anionic hydrophilic groups are preferred. The nonionic hydrophilic group is not particularly limited, but examples thereof include glycoside groups. The anionic hydrophilic group is not particularly limited, but examples thereof include sulfonic acid groups and carboxyl groups.

[0056] The content of the hydrophilic structure in the oxyethylene structure-containing polycarbonate polyol is not particularly limited to a lower limit, but it is preferable that the hydrophilic structure is contained so that the stability evaluation of the aqueous dispersion described in the Examples described later is △ or ○, and it is more preferable that the hydrophilic structure is contained so that the aqueous dispersibility evaluation described in the Examples described later is ○. The upper limit is preferably 50 mol% or less, more preferably 35 mol% or less, even more preferably 30 mol% or less, even more preferably 25 mol% or less, particularly preferably 20 mol% or less, more particularly preferably 15 mol% or less, and extremely preferably 10 mol% or less.

[0057] When the content of the hydrophilic structure in the oxyethylene structure-containing polycarbonate polyol is within the above range, the oxyethylene structure-containing polycarbonate polyol of the present embodiment tends to be dispersible in water, and the coating composition and polyurethane obtained from such an oxyethylene structure-containing polycarbonate polyol tend to have excellent durability. The oxyethylene structure-containing polycarbonate polyol of the present embodiment is preferably dispersible in water. When the oxyethylene structure-containing polycarbonate polyol of the present embodiment is dispersible in water, the stability of the water-based coating composition and / or the stability of the water-based polyurethane using the oxyethylene structure-containing polycarbonate polyol tends to be improved.

[0058] Whether or not the oxyethylene structure-containing polycarbonate polyol can be dispersed in water can be determined based on the water dispersibility described in the examples below.

[0059] [Method for producing oxyethylene structure-containing polycarbonate polyol] The oxyethylene structure-containing polycarbonate polyol of the present embodiment can be obtained, for example, by reacting a polycarbonate polyol with a polyvalent hydroxy compound having a structure represented by formula (B) in the presence of an ester exchange reaction catalyst described later.

[0060] If too much catalyst remains in the oxyethylene structure-containing polycarbonate polyol, the oxyethylene structure-containing polycarbonate polyol may become cloudy or may be easily colored by heating. In addition, when producing polyurethane, the reaction may be inhibited or the reaction may be excessively promoted. If the amount of catalyst is too small, the reaction tends to proceed slowly, which is not preferable.

[0061] Therefore, the amount of catalyst remaining in the oxyethylene structure-containing polycarbonate polyol is not particularly limited, but the lower limit of the content calculated as catalyst metal is preferably 0.00001 mass% or more, more preferably 0.00005 mass% or more, even more preferably 0.0001 mass% or more, and even more preferably 0.0005 mass% or more. The upper limit is preferably 0.1 mass% or less, more preferably 0.05 mass% or less, even more preferably 0.03 mass% or less, even more preferably 0.02 mass% or less, particularly preferably 0.015 mass% or less, more particularly preferably 0.01 mass% or less, and extremely preferably 0.005 mass% or less.

[0062] The color (APHA) of the raw material used in producing the oxyethylene structure-containing polycarbonate polyol of the present embodiment is preferably 100 or less, more preferably 80 or less, even more preferably 50 or less, even more preferably 30 or less, and particularly preferably 20 or less. When the APHA of the raw material is the above value or less, the APHA of the obtained oxyethylene structure-containing polycarbonate polyol tends to be excellent.

[0063] (Polyhydroxy compound having a structure represented by formula (B)) The polyhydric hydroxy compound having a structure represented by formula (B) used in producing the oxyethylene structure-containing polycarbonate polyol of this embodiment is not particularly limited, but examples thereof include diethylene glycol, triethylene glycol, tetraethylene glycol, heptaethylene glycol, hexaethylene glycol, heptaethylene glycol, and the "Polyethylene Glycol" series manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.

[0064] [Production conditions of oxyethylene structure-containing polycarbonate polyol] In producing the oxyethylene structure-containing polycarbonate polyol of the present embodiment, a transesterification catalyst can be used.

[0065] The transesterification catalyst is not particularly limited, but examples thereof include alkali metals and alkaline earth metals, as well as their alcoholates, hydrides, oxides, amides, hydroxides and salts.

[0066] The salts of alkali metals and alkaline earth metals are not particularly limited, but examples thereof include carbonates, nitrogen-containing borates, and basic salts with organic acids.

[0067] The alkali metal is not particularly limited, but examples thereof include lithium, sodium, and potassium.

[0068] The alkaline earth metal is not particularly limited, but examples thereof include magnesium, calcium, strontium, barium, and the like.

[0069] In addition, the transesterification catalyst using a metal other than an alkali metal or an alkaline earth metal is not particularly limited, but examples thereof include metals other than an alkali metal or an alkaline earth metal, as well as salts thereof, alcoholates thereof, and organic compounds containing the metals.

[0070] Specific examples of metals other than alkali metals and alkaline earth metals include, but are not limited to, 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.

[0071] These transesterification catalysts can be used alone or in combination of two or more.

[0072] Among them, the transesterification catalyst is preferably one or more metals selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, titanium, manganese, zirconium, tin, lead, and ytterbium, or salts thereof, alkoxides thereof, or organic compounds containing these metals, because the transesterification reaction to obtain an oxyethylene structure-containing polycarbonate polyol proceeds more satisfactorily and the effect on the urethane reaction is less when the obtained oxyethylene structure-containing polycarbonate polyol is used. Among them, lithium, magnesium, calcium, titanium, manganese, ytterbium, tin, zirconium, and ytterbium are preferably used. More preferred are one or more metals selected from the group consisting of lead and zirconium, even more preferred are one or more metals selected from the group consisting of lithium, magnesium, calcium, titanium, manganese and ytterbium, even more preferred are one or more metals selected from the group consisting of lithium, magnesium, calcium, titanium and manganese, particularly preferred are one or more metals selected from the group consisting of lithium, titanium and manganese, more particularly preferred are one or more metals selected from the group consisting of lithium, titanium and manganese, and more particularly preferred are one or more metals selected from the group consisting of titanium and manganese.

[0073] Specific examples of preferred transesterification catalysts include organic compounds of titanium, organic compounds of magnesium, organic compounds of zinc, organic compounds of ytterbium, organic compounds of zirconium, and organic compounds of manganese.

[0074] The organic titanium compound is not particularly limited, but examples thereof include titanium tetra-n-butoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, and the like.

[0075] The organic compound of magnesium is not particularly limited, but examples thereof include magnesium acetate, magnesium(II) acetylacetonate, and 2,2,6,6-tetramethyl-3,5-heptanedionatomagnesium(II) dihydrate.

[0076] The organic zinc compound is not particularly limited, but examples thereof include zinc acetate, zinc(II) acetylacetonate, and 2,2,6,6-tetramethyl-3,5-heptanedionatozinc(II).

[0077] The organic compound of ytterbium is not particularly limited, but examples thereof include ytterbium(III) isopropoxide, ytterbium(III) trifluoromethanesulfonate, tris(cyclopentadienyl)ytterbium(III), and ytterbium(III) acetylacetonate hydrate.

[0078] The organic compound of zirconium is not particularly limited, but examples thereof include zirconium(IV) acetylacetonate, zirconium(IV) tetrapropoxide, zirconium(IV) tetrabutoxide, and zirconium(IV) acetylacetonate.

[0079] The organic compound of manganese is not particularly limited, but examples thereof include manganese(II) acetate and manganese(II) acetylacetonate.

[0080] The amount of the transesterification catalyst used is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and more preferably 0.1% by mass or less, more preferably 0.05% by mass or less, even more preferably 0.025% by mass or less, even more preferably 0.015% by mass or less, and particularly preferably 0.01% by mass or less, relative to the total mass of the raw materials.

[0081] Specifically, the transesterification reaction can be carried out by mixing the raw materials and stirring them while heating.

[0082] The temperature of the ester exchange reaction is not particularly limited, but the lower limit is preferably 120° C. or higher, more preferably 140° C. or higher, and the upper limit is preferably 250° C. or lower, more preferably 200° C. or lower.

[0083] By setting the reaction temperature to the above lower limit, the transesterification reaction can be carried out in a shorter time, which is economically advantageous. By setting the reaction temperature to the above upper limit or less, coloration of the resulting oxyethylene structure-containing polycarbonate polyol can be more effectively prevented.

[0084] The reaction pressure of the transesterification reaction is not particularly limited, but is preferably from normal pressure to 1 MPa. By setting the reaction pressure within the above range, the reaction can be carried out more easily. In addition, when using auxiliary raw materials, the transesterification reaction can be promoted more efficiently by applying a certain amount of pressure in consideration of the vapor pressure of these raw materials.

[0085] The progress and completion of the transesterification reaction can be confirmed by NMR measurement described in the Examples below. As the transesterification reaction between the raw material polycarbonate polyol and the polyvalent hydroxy compound having the structure represented by formula (B) progresses, a structure represented by formula (BB) is formed, so the value of formula (i) increases over time, and it can be confirmed whether the value of formula (i) has reached a predetermined range.

[0086] In the method for producing the oxyethylene structure-containing polycarbonate polyol, a step of dehydrating the raw materials to be used may be carried out as a pretreatment prior to the above-mentioned transesterification reaction.

[0087] In the method for producing the oxyethylene structure-containing polycarbonate polyol, after the above-mentioned transesterification reaction, a step of adding the above-mentioned catalyst poison to the transesterification catalyst may be carried out as a post-treatment.

[0088] [Polycarbonate polyol] The polycarbonate polyol used in producing the oxyethylene structure-containing polycarbonate polyol of the present embodiment is not particularly limited, but can be obtained, for example, by the method for producing a polycarbonate polyol described below. In addition, a commercially available product can be used, and is not particularly limited, but examples thereof include the "Duranol (trade name)" series of T6002, T6001, T5652, T5651, T5650J, T5650E, G4672, T4672, T4671, G3452, G3450J, GE502, and GE501 manufactured by Asahi Kasei Corporation.

[0089] [Production method of polycarbonate polyol] The method for producing the polycarbonate polyol used in the production of the oxyethylene structure-containing polycarbonate polyol of the present embodiment is not particularly limited, and a known method can be adopted. For example, a polycarbonate polyol can be obtained by reacting a carbonate compound with a polyhydric hydroxy compound in the presence of an ester exchange catalyst.

[0090] (Carbonate compounds) The carbonate compound used in the production of the polycarbonate polyol is not limited to the following, but examples thereof include alkylene carbonates, dialkyl carbonates, diaryl carbonates, and the like.

[0091] The alkylene carbonate is not particularly limited, but examples thereof include ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, and 1,2-pentylene carbonate.

[0092] The dialkyl carbonate is not particularly limited, but examples thereof include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate.

[0093] The diaryl carbonate is not particularly limited, but examples thereof include diphenyl carbonate.

[0094] Among these, the carbonate compound used in the production of polycarbonate polyol is preferably dimethyl carbonate, diethyl carbonate, ethylene carbonate, or diphenyl carbonate, more preferably dimethyl carbonate, ethylene carbonate, or diphenyl carbonate, even more preferably ethylene carbonate or diphenyl carbonate, and still more preferably ethylene carbonate.

[0095] (Polyhydroxy compounds) The polyhydric hydroxy compound used in the production of the polycarbonate polyol is not limited to the following, but examples thereof include linear polyhydric hydroxy compounds, branched polyhydric hydroxy compounds, cyclic polyhydric hydroxy compounds, and polyhydric hydroxy compounds having an aromatic ring.

[0096] The linear polyhydric hydroxy compound is not particularly limited, but examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycol, and polytetraethylene glycol.

[0097] Examples of branched polyhydric hydroxy compounds include, but are not limited to, 2-methyl-1,8-octanediol, neopentyl glycol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, trimethylolpropane, pentaerythritol, and polypropylene glycol.

[0098] The cyclic polyhydric hydroxy compound is not particularly limited, but examples thereof include 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2-bis(4-hydroxycyclohexyl)-propane isosorbide.

[0099] (Production conditions of polycarbonate polyol) In producing the polycarbonate polyol, a transesterification catalyst can be used.

[0100] The transesterification catalyst is not particularly limited, but examples thereof include alkali metals and alkaline earth metals, as well as their alcoholates, hydrides, oxides, amides, hydroxides and salts.

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

[0102] The alkali metal is not particularly limited, but examples thereof include lithium, sodium, and potassium.

[0103] The alkaline earth metal is not particularly limited, but examples thereof include magnesium, calcium, strontium, barium, and the like.

[0104] In addition, the transesterification catalyst using a metal other than an alkali metal or an alkaline earth metal is not particularly limited, but examples thereof include metals other than an alkali metal or an alkaline earth metal, as well as salts thereof, alcoholates thereof, and organic compounds containing the metals.

[0105] Specific examples of metals other than alkali metals and alkaline earth metals include, but are not limited to, 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 alone or in combination of two or more.

[0107] Among them, as the transesterification reaction catalyst, since the transesterification reaction to obtain a polycarbonate polyol is carried out better, and the influence on the urethane reaction is less when the obtained polycarbonate polyol is used, one or more metals selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, titanium, manganese, zirconium, tin, lead and ytterbium, or salts thereof, alkoxides thereof, or organic compounds containing these metals are preferred, and one or more metals selected from the group consisting of lithium, magnesium, calcium, titanium, manganese, ytterbium, tin, zinc and zirconium are more preferred, one or more metals selected from the group consisting of lithium, magnesium, calcium, titanium, manganese and ytterbium are even more preferred, one or more metals selected from the group consisting of lithium, magnesium, calcium, titanium and manganese are even more preferred, one or more metals selected from the group consisting of lithium, calcium, titanium and manganese are particularly preferred, one or more metals selected from the group consisting of lithium, titanium and manganese are more particularly preferred, and one or more metals selected from the group consisting of titanium and manganese are more particularly preferred.

[0108] Specific examples of preferred transesterification catalysts include organic compounds of titanium, organic compounds of magnesium, organic compounds of zinc, organic compounds of ytterbium, organic compounds of zirconium, and organic compounds of manganese.

[0109] The organic titanium compound is not particularly limited, but examples thereof include titanium tetra-n-butoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, and the like.

[0110] The organic compound of magnesium is not particularly limited, but examples thereof include magnesium acetate, magnesium(II) acetylacetonate, and 2,2,6,6-tetramethyl-3,5-heptanedionatomagnesium(II) dihydrate.

[0111] The organic zinc compound is not particularly limited, but examples thereof include zinc acetate, zinc(II) acetylacetonate, and 2,2,6,6-tetramethyl-3,5-heptanedionatozinc(II).

[0112] The organic compound of ytterbium is not particularly limited, but examples thereof include ytterbium(III) isopropoxide, ytterbium(III) trifluoromethanesulfonate, tris(cyclopentadienyl)ytterbium(III), and ytterbium(III) acetylacetonate hydrate.

[0113] The organic compound of zirconium is not particularly limited, but examples thereof include zirconium(IV) acetylacetonate, zirconium(IV) tetrapropoxide, zirconium(IV) tetrabutoxide, and zirconium(IV) acetylacetonate.

[0114] The organic compound of manganese is not particularly limited, but examples thereof include manganese(II) acetate and manganese(II) acetylacetonate.

[0115] The amount of the transesterification catalyst used is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and more preferably 0.1% by mass or less, more preferably 0.05% by mass or less, even more preferably 0.025% by mass or less, even more preferably 0.015% by mass or less, and particularly preferably 0.01% by mass or less, relative to the total mass of the raw materials.

[0116] When the heat treatment is performed following the production of the polycarbonate polyol, the transesterification catalyst used in the transesterification reaction is not consumed in the transesterification reaction, and therefore the amount of the transesterification catalyst can be calculated based on the amount of the transesterification catalyst used. When a commercially available polycarbonate polyol is used, the amount of metal in the transesterification catalyst contained in the polycarbonate polyol can be determined by measuring it using ICP (Inductively Coupled Plasma) emission spectroscopy.

[0117] The polycarbonate polyol used in the present embodiment can also be produced by a transesterification reaction between a polycarbonate polyol and a diol compound, or between two or more kinds of polycarbonate polyols.

[0118] When the raw material polycarbonate polyol contains a catalyst poison of the transesterification catalyst used in its production, the transesterification reaction usually tends to proceed less easily. Therefore, when producing polycarbonate polyol, a necessary amount of the above-mentioned transesterification catalyst can be newly added.

[0119] On the other hand, when the raw material polycarbonate polyol does not contain the catalytic poison of the transesterification catalyst, the transesterification reaction in this embodiment tends to proceed easily. However, when the reaction temperature in the production process of polycarbonate polyol is to be lowered or the reaction time is to be shortened, a necessary amount of a new transesterification catalyst can be added. In this case, the same transesterification catalyst as that used in the production of the raw material polycarbonate polyol can be used.

[0120] Specifically, the transesterification reaction can be carried out by mixing the raw materials and stirring them while heating.

[0121] The temperature of the ester exchange reaction is not particularly limited, but the lower limit is preferably 120° C. or higher, more preferably 140° C. or higher, and the upper limit is preferably 250° C. or lower, more preferably 200° C. or lower.

[0122] By setting the reaction temperature to the above lower limit or more, the transesterification reaction can be carried out in a shorter time, which is economically advantageous. By setting the reaction temperature to the above upper limit or less, coloration of the resulting polycarbonate polyol can be more effectively prevented.

[0123] The reaction pressure of the transesterification reaction is not particularly limited, but is preferably from normal pressure to 1 MPa. By setting the reaction pressure within the above range, the reaction can be carried out more easily. In addition, when using auxiliary raw materials, the transesterification reaction can be promoted more efficiently by applying a certain amount of pressure in consideration of the vapor pressure of these raw materials.

[0124] The progress and completion of the transesterification reaction can be confirmed by GPC measurement. As the transesterification reaction proceeds, the peak derived from the raw material becomes smaller over time, and can be confirmed by the disappearance of the peak.

[0125] In the method for producing a polycarbonate polyol, a step of dehydrating the raw materials to be used may be carried out as a pretreatment prior to the above-mentioned transesterification reaction.

[0126] In the method for producing a polycarbonate polyol, after the above-mentioned transesterification reaction, a step of adding the above-mentioned catalyst poison to the transesterification catalyst may be carried out as a post-treatment.

[0127] [paint] The coating material of the present embodiment contains the above-mentioned oxyethylene structure-containing polycarbonate polyol. By containing the above-mentioned oxyethylene structure-containing polycarbonate polyol, the coating material of the present embodiment has excellent compatibility with the ether polyol, flexibility, and durability.

[0128] The paint of the present embodiment is preferably a water-based paint. A water-based paint is a paint that contains water as a solvent or dispersion medium as a main component. If the paint of the present embodiment is a water-based paint, it tends to reduce volatile organic compounds (VOCs).

[0129] The coating material of the present embodiment may contain other components in addition to the above-mentioned oxyethylene structure-containing polycarbonate polyol. The other components are not particularly limited, but may include, for example, a curable composition, a polyhydric alcohol compound, a polyester polyol described in JP 2018-012769 A, an acrylic polyol, a polyether polyol, a polyolefin polyol, a fluorine polyol, and other polyols.

[0130] In addition to the above, other additives such as curing accelerators (catalysts), matting agents, anti-settling agents, leveling agents, fillers, dispersants, flame retardants, dyes, organic or inorganic pigments, release agents, flow control agents, plasticizers, antioxidants, UV absorbers, light stabilizers, defoamers, colorants, solvents, etc. can be added to the paint (paint composition) of this embodiment depending on various applications. By appropriately adding these other additives, paint compositions with different properties, such as soft-feel paints and clear paints, can be obtained.

[0131] The coating material of the present embodiment can also be obtained using polyurethane or water-based polyurethane, which will be described later.

[0132] [Polyurethane] The polyurethane of the present embodiment is obtained by using the above-mentioned oxyethylene structure-containing polycarbonate polyol. Since the polyurethane of the present embodiment is obtained by using the above-mentioned oxyethylene structure-containing polycarbonate polyol, it has excellent flexibility and durability.

[0133] In addition, the water-based polyurethane of this embodiment is obtained by using the above-mentioned oxyethylene structure-containing polycarbonate polyol. The water-based polyurethane of this embodiment is obtained by using the above-mentioned oxyethylene structure-containing polycarbonate polyol, and thus has excellent emulsion particle stability, flexibility, and durability. The water-based polyurethane refers to a polyurethane dispersion containing water as a dispersion medium.

[0134] The method for obtaining the polyurethane of the present embodiment is not particularly limited, but examples thereof include a prepolymer method (two-stage method) in which an NCO group-terminated prepolymer is synthesized using the above-mentioned oxyethylene structure-containing polycarbonate polyol and an isocyanate compound, and then a polyhydric alcohol and / or a polyamine is added to proceed with chain extension, and a one-shot method (single-stage method) in which the above-mentioned oxyethylene structure-containing polycarbonate polyol is polymerized simultaneously with an isocyanate compound and a polyhydric alcohol and / or a polyamine.

[0135] The method for obtaining the water-based polyurethane of the present embodiment is not particularly limited, but may be, for example, the method described in the examples of JP-A No. 2017-71685.

[0136] [leather] The artificial leather of the present embodiment is obtained by using the above-mentioned polyurethane or water-based polyurethane. Since the artificial leather of the present embodiment is obtained by using the above-mentioned polyurethane or water-based polyurethane, it has excellent flexibility and durability.

[0137] The synthetic leather of the present embodiment is obtained by using the above-mentioned polyurethane or water-based polyurethane. Since the synthetic leather of the present embodiment is obtained by using the above-mentioned polyurethane or water-based polyurethane, it has excellent flexibility and durability.

[0138] [Paint film] The coating film of the present embodiment is obtained from the above-mentioned coating material. Since the coating film of the present embodiment is obtained from the above-mentioned coating material, it has excellent flexibility, durability, and coating film appearance when used in combination with an ether polyol. EXAMPLES

[0139] Various physical property values, analytical methods, and measurement conditions of the oxyethylene structure-containing polycarbonate polyols obtained in the examples and comparative examples described below are described below. 1 For values ​​that change depending on the object being measured, such as H-NMR chemical shift values, it is desirable to use values ​​appropriate for each object being measured.

[0140] [Hydroxyl value (OHV) measurement] The hydroxyl value was measured by the following method. A volumetric flask was used to prepare an acetylation reagent by adding pyridine to 12.5 g of acetic anhydride to make a total volume of 50 mL. 1.0 to 10.0 g of a sample was precisely weighed and placed in a 100 mL eggplant flask. 5 mL of the acetylation reagent and 10 mL of toluene were added to the eggplant flask using a volumetric pipette to obtain a solution. Then, a cooling tube was attached to the eggplant flask, and the solution was stirred and heated at 100°C for 1 hour. 2.5 mL of distilled water was added to the eggplant flask using a volumetric pipette, and the obtained solution was heated and stirred for another 10 minutes. After cooling the solution for 2 to 3 minutes, 12.5 mL of ethanol was added to the eggplant flask, and 2 to 3 drops of phenolphthalein were added as an indicator, followed by titration with 0.5 mol / L ethanolic potassium hydroxide. 5 mL of the acetylation reagent, 10 mL of toluene, and 2.5 mL of distilled water were placed in a 100 mL eggplant flask, and the solution was heated and stirred for 10 minutes, and then titration was performed on the obtained solution in the same manner (blank test). Based on this result, the hydroxyl value was calculated using the following formula (III). Hydroxyl number (mg-KOH / g) = {(ba) × 28.05 × f} / e (III) a represents the titer of the sample (mL), b represents the titer of the blank test (mL), e represents the sample volume (g), and f represents the factor of the titrant.

[0141] [GPC measurement] The number average molecular weight (Mn) and weight average molecular weight (Mw) of the oxyethylene structure-containing polycarbonate polyol were measured by GPC according to the following method. The oxyethylene structure-containing polycarbonate polyols obtained in the examples and comparative examples described below were used as samples. The concentration of the measurement sample was adjusted to 0.5 mass% with tetrahydrofuran (hereinafter, THF), and the number average molecular weight (Mn) and weight average molecular weight (Mw) were measured in terms of standard polystyrene using the following GPC device. GPC equipment: Tosoh HLC-8320 Analytical column: TSKgel G4000H x 1 G3000H 1pc G2000H 2pcs Guard column: TSKgel guardcolumn H XL -L Reference column: TSKgel SuperH-RC Eluent: Tetrahydrofuran (THF) Flow rate: 1.0mL / min Column temperature: 40℃ RI detector: RI (built into the device HLC-8320) Calibration curve: Standard polystyrene (Tosoh Corporation)

[0142] ·F-40 (molecular weight: 4.27×10 5 ) ·F-20 (molecular weight: 1.90×10 5 ) ·F-10 (molecular weight: 9.64×10 4 ) ·F-4 (molecular weight: 3.79×10 4 ) ·F-2 (molecular weight: 1.81×10 4 ) ·F-1 (molecular weight: 1.02×10 4 ) ·A-5000 (molecular weight: 5.97×10 3 ) ·A-2500 (molecular weight: 2.63×10 3 ) A-500 A-1000

[0143] The molecular weights of dimers to decamers were calculated from A-500 and A-1000. Dimer (molecular weight: 266) Trimer (molecular weight: 370) Tetramer (molecular weight: 474) Pentamer (molecular weight: 578) Hexamer (molecular weight: 682) Heptamer (molecular weight: 786) Octamer (molecular weight: 890) Nonamer (molecular weight: 994) Decamer (molecular weight: 1098) Calibration curve: 3rd order polynomial

[0144] [Hydrolysis] The oxyethylene structure-containing polycarbonate polyols obtained in the examples and comparative examples described below were hydrolyzed by the following method. 1 g of the sample was placed in a 100 mL eggplant flask, and then 30 g of ethanol and 4 g of potassium hydroxide were added and reacted at 100°C for 1 hour. After cooling to room temperature, 2 to 3 drops of phenolphthalein were added to the eggplant flask as an indicator and neutralized with hydrochloric acid. After cooling the eggplant flask in a refrigerator for 1 hour or more, the precipitated salt was removed by filtration to obtain a filtrate.

[0145] [Molar ratio of polyhydroxy compounds after hydrolysis (excluding polyhydroxy compounds having an oxyethylene structure)] The molar ratio of polyhydric hydroxy compounds (excluding polyhydric hydroxy compounds having an oxyethylene structure) after hydrolysis was measured by the following method. The filtrate obtained by hydrolysis was analyzed by gas chromatography. The concentration of each polyvalent hydroxy compound was calculated by creating a calibration curve using each known polyvalent hydroxy compound as a standard substance in advance, and the weight percentage was calculated from the area ratio obtained by gas chromatography (GC). The analysis was performed using a gas chromatograph GC-2014 (manufactured by Shimadzu Corporation) equipped with DB-WAX (manufactured by J&W) as a column, and a flame ionization detector (FID) as a detector. The temperature rise profile of the column was held at 60°C for 5 minutes, and then raised to 250°C at 10°C / min. The molar ratio of the polyvalent hydroxy compound (excluding polyvalent hydroxy compounds having an oxyethylene structure) was calculated from the weight percentage obtained by the gas chromatography and the molecular weight of each polyvalent hydroxy compound.

[0146] [Number average molecular weight of polyhydroxy compound having an oxyethylene structure after hydrolysis] The number average molecular weight of the polyvalent hydroxy compound having an oxyethylene structure after hydrolysis was analyzed by liquid chromatography mass spectrometry (LC-MS) according to the following procedures 1 to 4. 1. Ethanol is removed from the filtrate obtained by hydrolysis. 2. Weigh out 4.5 mg of the above 1, adjust the volume to 10 mL with acetonitrile, filter, and then perform LC-MS measurement using the following equipment and conditions. 3. Based on the results of 2 above, use a polyhydric hydroxy compound having an oxyethylene structure with a molecular weight close to that of 2 above and carry out the same measurement as in 2 above. 4. The above 2 and 3 were compared, and if the analytical results were consistent, the polyvalent hydroxy compound having an oxyethylene structure used in the above 3 was measured by GPC to determine the number average molecular weight of the polyvalent hydroxy compound having an oxyethylene structure after hydrolysis. Equipment:Thermo Fisher Ultimate3000 / LTQ orbitrap XL Column: Waters Xbridge C18 5um, diameter 4.6mm x length 150mm Flow rate: 0.2mL / min Ionization method: ESI-positive Injection volume: 1.0 uL Eluent conditions: [Table 1]

[0147] [Average carbon number] The average carbon number was calculated from the molar ratio of the polyvalent hydroxy compound (excluding polyvalent hydroxy compounds having an oxyethylene structure) after hydrolysis using the following formula (IV). Σ [number of carbon atoms in polyhydroxy compounds (excluding polyhydroxy compounds having an oxyethylene structure) × mole fraction of the polyhydroxy compounds] (IV) For example, if the molar ratio of polyhydroxy compounds (excluding polyhydroxy compounds having an oxyethylene structure) after hydrolysis is 2-methyl-1,3-propanediol (92 mol%) and 1,6-hexanediol (8 mol%), the average carbon number is 4 × 0.92 + 6 × 0.08, or 4.16.

[0148] [NMR measurement] In the formula (i), the molar ratio [BB / A] of the structural unit represented by formula (BB) to the structural unit represented by formula (A), and the molar ratio [B / (A+B)] of the structural unit represented by formula (B) to the structural units represented by formulas (A) and (B) were measured by nuclear magnetic resonance (NMR) as follows. NMR device: JEOL-ECZ500 Observation kernel: 1 H Waiting time: 5sec Total: 128 times Solvent: CDCl3 Measurement temperature: room temperature Chemical shift reference: TMS 0.00 ppm In the above measurement, the integral values ​​of the following signals were divided by the number of hydrogen atoms, and the molar ratios [BB / A] and [B / (A+B)] were calculated from the divided values.

[0149] The specific calculation method is as follows: Structural amount represented by formula (A): integral value around 4.00 to 4.20 ppm (peak of a1 in formula A-1 below) ÷ (number of hydrogen atoms of a1) Structural amount represented by formula (B): integral value around 3.60 to 3.70 ppm (peak of b1 in formula B-1 below) ÷ (number of hydrogen atoms of b1) Structural mass represented by formula (BB): integral value around 4.25 to 4.30 ppm (peak of bb1 in formula BB-1 below) ÷ (number of hydrogen atoms in bb1) [ka] [ka] [ka] The number of hydrogen atoms in a1 was determined by identifying the polyhydroxy compound (excluding polyhydroxy compounds having an oxyethylene structure) after hydrolysis.

[0150] For example, as a result of the molar ratio of polyvalent hydroxy compounds after hydrolysis (excluding polyvalent hydroxy compounds having an oxyethylene structure), when 1,6-hexanediol (100 mol%) is used as the polyvalent hydroxy compound, the number of hydrogen atoms in a1 is 2. Also, for example, as a result of the molar ratio of polyvalent hydroxy compounds after hydrolysis (excluding polyvalent hydroxy compounds having an oxyethylene structure), when 1,2-propanediol (100 mol%) is used as the polyvalent hydroxy compound, the number of hydrogen atoms in a1 is 1.5. Also, for example, as a result of the molar ratio of polyvalent hydroxy compounds after hydrolysis (excluding polyvalent hydroxy compounds having an oxyethylene structure), when 1,6-hexanediol (60 mol%) and 1,2-propanediol (40 mol%) are used as the polyvalent hydroxy compounds, the number of hydrogen atoms in a1 is 2×0.6+1.5×0.4, or 1.8.

[0151] When peaks overlap, the molar ratios were calculated by identifying each peak. For example, the molar ratios [BB / A] and [B / (A+B)] can be calculated by identifying each peak as follows:

[0152] For example, the case where a polycarbonate polyol was measured by NMR to obtain the spectrum shown in Fig. 1 will be described. The number average molecular weight of the polycarbonate polyol was 1283 by GPC measurement. Furthermore, the polyhydric hydroxyl compounds obtained by hydrolyzing the polycarbonate polyol were identified as 1,6-hexanediol, 1,5-pentanediol, and polyethylene glycol (molecular weight approximately 1000) with an average carbon number of 5.5.

[0153] The structural quantity represented by formula (A) is calculated by (a1 integral value) / (number of hydrogen atoms in a1), the structural quantity represented by formula (B), in which the b1 and a5 peaks overlap, is calculated by [(b1+a5) integral value-a6 integral value] / (number of hydrogen atoms in b1), and the structural quantity represented by formula (BB) is calculated by (bb1 integral value) / (number of hydrogen atoms in bb1). Structural mass represented by formula (A) = 151.142 / 2.0 = 75.571 Structural mass represented by formula (B) = [(83.706)-30.306] / 2 = 26.7 Structural mass represented by formula (BB): 4.00 / 2=2.0 Molar ratio [BB / A] = 2.0 / 75.571 = 0.0265 Molar ratio [B / (A+B)]=26.7 / (75.571+26.7)=0.261 Formula (i) = 0.0265 / 0.261 x 1283 = 130.3

[0154] [Hydrophilic structure] The water dispersibility test described below was carried out to confirm whether the sample was dispersible in water. If the evaluation result was ○ or △, it was determined to have a hydrophilic structure. The hydrophilic structure was determined by the following methods 1), 2), and / or 3). 1) Determined from the structure of the raw materials used. 2) Mass spectrometry and FT-IR measurement of the sample. 1H-NMR measurement and / or 13 The hydrophilic structure was identified and confirmed from various spectra obtained by C-NMR. The analytical methods and identification were performed by referring to known methods and / or Spectral Identification Methods for Organic Compounds (7th Edition) (Tokyo Kagaku Dojin Co., Ltd.). 3) Determined by pyrolysis GC / MS and / or derivatization GC / MS. Specific analytical methods are not particularly limited, but examples include the following <pyrolysis GC / MS> and <derivatization GC / MS>.

[0155] <Pyrolysis GC / MS> Equipment: Agilent Technology 6890GC / 5973MSD Column: HP-5MS (L: 30 m, ID: 0.25 mm, Film thickness: 0.25 μm) Carrier: Helium Ionization method: EI Mass range: m / z 10-800 Oven temperature: 40℃(5min hold)→(10℃ / min)→ 320℃(16min hold) Inlet temperature: 320℃ Transfer temperature: 320℃ Split ratio: Split 1 / 50 Sample size: 0.1 mg Pyrolysis temperature: 600℃ Interface temperature: 320℃

[0156] <Derivatized GC / MS> Equipment: Agilent Technology 7890GC / 5977MSD Column: HP-5MS (L: 30 m, ID: 0.25 mm, Film thickness: 0.25 μm) Carrier: Helium Ionization method; EI Mass range: m / z 10-800 Oven temperature: 40℃(5min hold)→(20℃ / min)→320℃(21min hold) Inlet temperature: 320℃ Transfer temperature: 320℃ Split ratio: Split 1 / 10 Injection volume: 2μL Derivatizing agent: BSA (NO-bis(trimethylsilyl)acetamide)

[0157] [Stability of aqueous dispersion (23℃)] Using the oxyethylene structure-containing polycarbonate polyols obtained in the Examples and Comparative Examples described later, and the urethane group-containing polycarbonate polyols obtained in the Application Examples and Comparative Application Examples described later as samples, the aqueous dispersions obtained by carrying out the following steps 1 and 2 were allowed to stand at 23°C and evaluated according to the following criteria. Step 1: A sample and DPM were weighed out into a plastic container so that the solid content of the sample was 80%, and the resulting solution was stirred with a stirrer until it was uniformly dissolved. Step 2: Pure water was weighed out and poured into the plastic container so that the solid content was 20%, and the resulting solution was stirred with a stirrer until uniformly dispersed, to obtain an aqueous dispersion.

[0158] [Evaluation Criteria] ○: Disperses in water for 7 days or more, no sediment remains △: Dispersible in water, no sediment, 1 day or more but less than 7 days ×: Not dispersed in water (sediment is present) or dispersed in water for less than 1 day

[0159] [Stability of aqueous dispersion (40℃)] Using the oxyethylene structure-containing polycarbonate polyols obtained in the Examples and Comparative Examples described later, and the urethane group-containing polycarbonate polyols obtained in the Application Examples and Comparative Application Examples described later as samples, the aqueous dispersions obtained by carrying out the following steps 1 and 2 were allowed to stand at 40°C and evaluated according to the following criteria. Step 1: A sample and DPM were weighed out into a plastic container so that the solid content of the sample was 80%, and the resulting solution was stirred with a stirrer until it was uniformly dissolved. Step 2: Pure water was weighed out and poured into the plastic container so that the solid content was 20%, and the resulting solution was stirred with a stirrer until uniformly dispersed, to obtain an aqueous dispersion.

[0160] [Evaluation Criteria] ○: Disperses in water for 7 days or more, no sediment remains △: Dispersible in water, no sediment, 1 day or more but less than 7 days ×: Not dispersed in water (sediment is present) or dispersed in water for less than 1 day

[0161] [Compatibility with ether polyols] The following steps 1 to 3 were carried out and evaluated using the oxyethylene structure-containing polycarbonate polyols obtained in the examples and comparative examples described later as samples. Step 1: A sample and polytetramethylene glycol (number average molecular weight 2000) were weighed out into a glass container so that the mass ratio was 90 / 10, and the mixture was stirred at 60° C. using a stirrer. Step 2: The contents were transferred from the glass container to a colorless, transparent glass bottle and allowed to stand at 60° C. for at least 24 hours. Step 3: The contents inside the colorless, transparent glass bottle were checked and evaluated according to the following criteria.

[0162] [Evaluation Criteria] ○: Uniformly dissolved △: Dissolved but hazy ×: Cloudy or separated into two layers

[0163] [Method of producing polyurethane coating film (coating film appearance evaluation)] (Paint composition) According to the paint formulation conditions below, the raw materials to be used (main agent, curing agent, catalyst, solvent, leveling agent, matting agent and anti-settling agent) were weighed out into a plastic container and stirred with a stirrer until uniformly dispersed to obtain a paint composition.

[0164] (Raw materials used) Base: The stability of the aqueous dispersion (23°C) or the stability of the aqueous dispersion (40°C) after standing for 7 days Hardener: WT31-100 (manufactured by Asahi Kasei Corporation, NCO%=17.4, solid content 100%) Catalyst: Borchers LH10 (OMG Borchers, 1% aqueous catalyst) Solvent: Pure water Leveling agent: BYK-331 (manufactured by BYK) Matting agent: ACEMATT TS 100 (manufactured by Evonik) Anti-settling agent: Disparlon AQ-002 (Kusumoto Chemicals)

[0165] (Combination conditions) NCO / OH: 1.25 Paint solids: 20% Catalyst: 0.3% based on the total amount of base resin and hardener Leveling agent: 0.3% based on the total amount of base resin and hardener Matting agent: 10% of the total amount of base resin and hardener Anti-settling agent: 0.6% based on the total amount of base resin and hardener

[0166] (Preparation method) A coating composition was prepared according to the following steps 1 to 3. Step 1: The base material and the solvent were weighed out and placed in a plastic container so that the solid content of the coating composition was 20%, and the resulting solution was stirred with a stirrer until uniformly dispersed. Step 2: The catalyst, leveling agent, matting agent and anti-settling agent were weighed out and placed in the plastic container so as to satisfy the above-mentioned blending conditions, and the resulting solution was stirred with a stirrer until uniformly dispersed. Step 3: A curing agent was weighed out and poured into the plastic container so that the NCO / OH ratio was 1.25, and the resulting solution was stirred with a stirrer until uniformly dispersed to obtain a coating composition.

[0167] (coating process) Each of the obtained coating compositions was applied onto a polycarbonate plate ("TAKIRON PC-1600" (trade name), 2 mm x 70 mm x 150 mm) so that the dry film thickness was 40 µm.

[0168] (drying process) The coating composition applied to the polycarbonate plate was baked at 60°C for 2 hours to obtain a polyurethane coating film. The obtained polyurethane coating film was evaluated for various physical properties by the methods described below.

[0169] (Coating appearance) The appearance of the coating film obtained in the above drying step was visually observed. The coating appearance was judged as follows.

[0170] [Judgment method] ○: Smooth, no cracks or bumps △: No cracks, but some small bumps ×: Cracks and bumps

[0171] [Chemical resistance test (sunscreen resistance test)] As chemical resistance, a sunscreen resistance evaluation was carried out using a commercially available sunscreen cream. The coating film obtained by the above-mentioned polyurethane coating film preparation method was aged for one day under an atmosphere of 23°C and 50% RH, and then a sunscreen (Neutrogena Ultra Sheer DRY-TOUCH SUNSCREEN Broad Spectrum SPF 45) was applied to the coating film after the aging at a rate of 0.5 g / 9 cm 2 The coating was applied so that the coating would be uniform in thickness and heated at 55°C for 1 hour. The surface of the coating was then thoroughly washed with a small amount of neutral detergent to remove the sunscreen, and the coating was dried on a horizontal table in an atmosphere of 23°C and 50% RH. The resulting coating was evaluated for chemical resistance according to the following criteria by evaluating its appearance and pencil hardness. Chemical resistance is one of the indicators of durability. Since it is difficult to perform a reproducible evaluation, if the coating appearance obtained by the polyurethane coating method is "x", it is deemed unassessable.

[0172] (Appearance evaluation) After the test, the coating film was visually inspected for any abnormalities such as traces of the sunscreen agent, swelling, peeling, etc., and was evaluated according to the following criteria. ○: No change in the appearance of the coating △: Slight change in coating appearance ×: There is swelling or trace changes in the appearance of the coating film.

[0173] (Pencil hardness test) After the test, the coating film was inspected for scratches caused by a 6B pencil according to the pencil hardness test method of JIS K5600-5-6:1999, and evaluated according to the following criteria. ○: No scratches are observed. △: There are faint scratches. ×: Scratches are clearly visible or coating peeling is observed.

[0174] (Chemical resistance evaluation criteria) ◎: Appearance "Good" and pencil hardness test "Good" 〇: Appearance is 〇 and pencil hardness is △ or appearance is △ and pencil hardness is 〇 △: Appearance "△" and pencil hardness method "△" ×: At least one “×” was judged in appearance and pencil hardness test.

[0175] [Stability of water-based polyurethane (polyurethane dispersion (PUD) film)] (Raw materials used) Oxyethylene structure-containing polycarbonate polyols (hereinafter sometimes abbreviated as "Polyol") obtained in the examples and comparative examples described below ·DMPA (2,2-dimethylolpropionic acid) Methyl ethyl ketone (MEK) ·Dibutyltin dilaurate (DBTDL) ·IPDI (Isophorone diisocyanate) Triethylamine (TEA) ·Pure water Ethylenediamine (EDA)

[0176] (Amount to be prepared) Polyol, IPDI, DMPA, TEA, and EDA were charged in the molar ratios described in the Application Examples and Application Comparative Examples. DBTDL was added so that the total amount of Polyol, IPDI, and DMPA was 100 ppm. If necessary, DBTDL can be diluted with toluene before addition (e.g., 5% DBTDL-toluene solution). MEK was added so that the solid content in the prepolymer process was 65%. However, if the viscosity becomes high in the prepolymer process, MEK may be added appropriately to adjust the solid content. Pure water was added so that the final solid content after the MEK removal process would be 30%. However, if the viscosity increases during the chain extension process, pure water may be added appropriately to adjust the solid content.

[0177] (Prepolymer process) A 1L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube, and a dropping funnel was filled with nitrogen and stirred at 200 rpm for 15 minutes while refluxing at 80°C. IPDI was then filled with a syringe and stirred at 80°C while refluxing until the NCO% reached 3.5±0.3% by mass, to obtain an MEK solution of a urethane prepolymer containing terminal isocyanate groups. The NCO% is the ratio of the mass of the isocyanate group possessed by the polyisocyanate to the total mass of the raw materials used in the prepolymerization process.

[0178] (Neutralization process and emulsification process) The obtained urethane prepolymer solution was cooled to 35°C, and TEA was added while stirring at 500 rpm. Next, while keeping the solution at 35°C and continuing stirring at 500 rpm, pure water was added dropwise at a rate of 10 mL / min to obtain an emulsion liquid (emulsion liquid).

[0179] (chain elongation process) The obtained emulsion was kept at 35° C. and stirred at 500 rpm, while EDA was added to carry out a chain extension reaction.

[0180] (MEK distillation process) After the chain extension reaction, the solution was heated under reduced pressure to distill off methyl ethyl ketone, thereby obtaining an aqueous polyurethane solution.

[0181] (stability) The resulting water-based polyurethane solution was allowed to stand at 23° C. and evaluated according to the following criteria. [Evaluation Criteria] ○: Disperses in water for 7 days or more, no sediment remains △: Dispersible in water, no sediment, 1 day or more but less than 7 days ×: Water-based polyurethane solution cannot be prepared, or sediment occurs within one day.

[0182] [Molecular weight of water-based polyurethane (polyurethane dispersion (PUD) film)] The number average molecular weight (Mn) of the water-based polyurethanes obtained in the application examples and application comparative examples described later was measured by the following method. The concentration of the measurement sample was adjusted to 0.5 mass % with N,N-dimethylformamide (hereinafter, DMF), and the number average molecular weight (Mn) was measured in terms of standard polystyrene using the following GPC apparatus. GPC equipment: Tosoh HLC-8320 Analytical column: TSKgel SuperHM-H x 4 Guard column: TSKgel guardcolumn HH Reference column: TSKgel SuperH-RC x 2 Eluent: N,N-dimethylformamide (DMF) Flow rate: 1.0mL / min Column temperature: 40℃ RI detector: RI (built into the device HLC-8320) Calibration curve: Standard polystyrene (Tosoh Corporation)

[0183] ·F-40 (molecular weight: 4.27×10 5 ) ·F-20 (molecular weight: 1.90×10 5 ) ·F-10 (molecular weight: 9.64×10 4 ) ·F-4 (molecular weight: 3.79×10 4 ) ·F-2 (molecular weight: 1.81×10 4 ) ·F-1 (molecular weight: 1.02×10 4 ) ·A-5000 (molecular weight: 5.97×10 3 ) ·A-2500 (molecular weight: 2.63×10 3 ) ·A-1000 (molecular weight: 1.05×10 3 ) Calibration curve: 3rd order polynomial

[0184] [FT-IR measurement] Using the oxyethylene structure-containing polycarbonate polyols obtained in the examples and comparative examples described later as samples, the infrared absorption spectrum absorbance of the samples was measured by an FT-IR (Fourier transform infrared spectrophotometer) according to the following method. The measurement sample was thinly spread on a rock salt plate (NaCl plate, 35×35×5 mm), and the infrared absorption spectrum absorbance of the sample was measured by FT-IR using the following device and conditions. FI-IR device: FT / IR-4600 type A (JASCO Corporation) Light source: Standard light source Detector: TGS Number of times: 16 Disassembly: 4cm -1 Zero filling: On Apodization: Cosine Gain: Auto(2) Aperture: Auto (7.1mm) Scan speed: Auto (2mm / sec) Filter: Auto (30000Hz) Data type: Evenly spaced data Horizontal axis: Wavenumber (cm -1 ) Vertical axis: Abs Start: 400cm -1 End: 40000cm -1

[0185] [Polymerization Example 1] In a 20L reactor equipped with a rectification column filled with structured packing and a stirrer, 4580g of 1,5-pentanediol, 5000g of 1,6-hexanediol, and 7600g of ethylene carbonate were charged, and then 0.860g of titanium tetra-n-butoxide was added as a catalyst. The temperature in the reactor was 165-175°C, and the reaction was carried out for 12 hours while extracting a part of the distillate. After that, the reactor was directly connected to a condenser, and the temperature in the reactor was raised to 180-190°C, and the pressure was gradually lowered to carry out the reaction, resulting in polycarbonate polyol P-1 (8608g). The obtained polycarbonate polyol P-1 had an average carbon number of 5.5 and a hydroxyl value of 110.0 mgKOH / g.

[0186] [Polymerization Example 2] 497g of 1,4-butanediol, 468g of 1,6-hexanediol, and 840g of ethylene carbonate were charged into a 2L glass flask (reactor) equipped with a rectification column filled with structured packing and a stirrer, and then 0.180g of titanium tetra-n-butoxide was added as a catalyst. The reaction was carried out for 24 hours at a reaction temperature of 145 to 165°C while extracting a portion of the distillate. Next, the reactor was directly connected to a condenser, and the reaction temperature was increased to 165 to 185°C, after which the pressure was gradually reduced and the reaction was further carried out to obtain polycarbonate polyol P-2 (740g). The resulting polycarbonate polyol P-2 had an average carbon number of 5.0 and a hydroxyl value of 56.1 mgKOH / g.

[0187] [Polymerization Example 3] 832g of 1,3-propanediol, 5g of 1,6-hexanediol, and 967g of ethylene carbonate were charged into a 2L glass flask (reactor) equipped with a rectification column filled with structured packing and a stirrer, and then 0.100g of titanium tetra-n-butoxide was added as a catalyst. The reaction was carried out for 24 hours at a reaction temperature of 160-165°C while extracting a portion of the distillate. Next, the reactor was directly connected to a condenser, and the reaction temperature was set to 165-175°C, and the pressure was gradually reduced to further carry out the reaction, to obtain polycarbonate polyol P-3 (559g). The obtained polycarbonate polyol P-3 had an average carbon number of 3.03 and a hydroxyl value of 56.2 mgKOH / g.

[0188] [Polymerization Example 4] 470g of 2-methyl-1,3-propanediol, 578g of 1,10-decanediol, and 751g of ethylene carbonate were charged into a 2L glass flask (reactor) equipped with a rectification column filled with structured packing and a stirrer, and then 0.200g of titanium tetra-n-butoxide was added as a catalyst. The reaction was carried out for 24 hours at a reaction temperature of 145 to 165°C while extracting a portion of the distillate. Next, the reactor was directly connected to a condenser, and the reaction temperature was increased to 165 to 185°C, after which the pressure was gradually reduced and the reaction was further carried out to obtain polycarbonate polyol P-4 (866g). The resulting polycarbonate polyol P-4 had an average carbon number of 7.0 and a hydroxyl value of 56.5 mgKOH / g.

[0189] [Polymerization Example 5] In a 1L glass flask (reactor) equipped with a stirrer, 800 g of the polycarbonate polyol P-1 obtained in Polymerization Example 1, 55 g of 1,5-pentanediol, and 62 g of 1,6-hexanediol were charged. Then, these were heated with stirring, and the temperature in the reactor was maintained at about 165°C for 6 hours. Regarding the reaction, the reaction solution was subjected to GPC measurement over time, and the disappearance of the peak derived from the raw material and the appearance of the peak derived from the product were confirmed over time to confirm the progress of the reaction. The obtained polycarbonate polyol P-5 had an average carbon number of 5.5 and a hydroxyl value of 224.0 mgKOH / g.

[0190] [Comparative Example 1] In a 0.5 L glass flask (reactor) equipped with a stirrer, 360 g of the polycarbonate polyol P-1 obtained in Polymerization Example 1 and 40 g of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 1000" (trade name), number average molecular weight: about 1000) were charged. Then, these were heated with stirring, and transesterification reaction was carried out at a reactor temperature of about 145 ° C. The reaction solution was subjected to GPC measurement over time to confirm the disappearance of the peak derived from the raw material and the appearance of the peak derived from the product, and the progress and completion of the transesterification reaction were judged. Next, 85% phosphoric acid was added in an amount 2.0 times the molar ratio of titanium tetra-n-butoxide, and the mixture was heated at a reactor temperature of 115°C for 3 hours to obtain oxyethylene structure-containing polycarbonate polyol HP-1. The evaluation results of the obtained oxyethylene structure-containing polycarbonate polyol are shown in Table 1.

[0191] [Comparative Example 2] In a 0.5 L glass flask (reactor) equipped with a stirrer, 360 g of the polycarbonate polyol P-2 obtained in Polymerization Example 2 and 40 g of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 1000" (trade name), number average molecular weight: about 1000) were charged. Then, these were heated with stirring, and transesterification reaction was carried out at a reactor temperature of about 145 ° C. The reaction solution was subjected to GPC measurement over time to confirm the disappearance of the peak derived from the raw material and the appearance of the peak derived from the product, and the progress and completion of the transesterification reaction were judged. Next, dibutyl phosphate was added in an amount 2.0 times the molar ratio of titanium tetra-n-butoxide, and the mixture was heated at a reactor temperature of 115°C for 3 hours to obtain oxyethylene structure-containing polycarbonate polyol HP-2. The evaluation results of the obtained oxyethylene structure-containing polycarbonate polyol are shown in Table 1.

[0192] [Comparative Example 3] In a 0.5 L glass flask (reactor) equipped with a stirrer, 270 g of the polycarbonate polyol P-3 obtained in Polymerization Example 3 and 30 g of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 1000" (trade name), number average molecular weight: about 1000) were charged. Then, these were heated with stirring, and transesterification reaction was carried out at a reactor temperature of about 145 ° C. The reaction solution was subjected to GPC measurement over time to confirm the disappearance of the peak derived from the raw material and the appearance of the peak derived from the product, and the progress and completion of the transesterification reaction were judged. Next, dibutyl phosphate was added in an amount 2.0 times the molar ratio of titanium tetra-n-butoxide, and the mixture was heated at a reactor temperature of 115°C for 3 hours to obtain oxyethylene structure-containing polycarbonate polyol HP-3. The evaluation results of the obtained oxyethylene structure-containing polycarbonate polyol are shown in Table 1.

[0193] [Comparative Example 4] In a 0.5 L glass flask (reactor) equipped with a stirrer, 360 g of the polycarbonate polyol P-4 obtained in Polymerization Example 4 and 40 g of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 2000" (trade name), number average molecular weight: about 2000) were charged. Then, these were heated with stirring, and transesterification reaction was carried out at a reactor temperature of about 145 ° C. The reaction solution was subjected to GPC measurement over time to confirm the disappearance of the peak derived from the raw material and the appearance of the peak derived from the product, and the progress and completion of the transesterification reaction were judged. Next, dibutyl phosphate was added in an amount 2.0 times the molar ratio of titanium tetra-n-butoxide, and the mixture was heated at a reactor temperature of 115°C for 3 hours to obtain oxyethylene structure-containing polycarbonate polyol HP-4. The evaluation results of the obtained oxyethylene structure-containing polycarbonate polyol are shown in Table 1.

[0194] [Comparative Example 5] In a 0.5 L glass flask (reactor) equipped with a stirrer, 300 g of the polycarbonate polyol P-1 obtained in Polymerization Example 1 and 100 g of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 1000" (trade name), number average molecular weight: about 1000) were charged. Next, these were heated with stirring, and transesterification reaction was carried out at a reactor temperature of about 145 ° C. The reaction solution was subjected to GPC measurement over time to confirm the disappearance of the peak derived from the raw material and the appearance of the peak derived from the product, and the progress and completion of the transesterification reaction were judged. Next, dibutyl phosphate was added in an amount 2.0 times the molar ratio of titanium tetra-n-butoxide, and the mixture was heated at a reactor temperature of 115°C for 3 hours to obtain oxyethylene structure-containing polycarbonate polyol HP-5. The evaluation results of the obtained oxyethylene structure-containing polycarbonate polyol are shown in Table 1.

[0195] [Comparative Example 6] In a 0.5L glass flask (reactor) equipped with a stirrer, 392 g of the polycarbonate polyol P-1 obtained in Polymerization Example 1 and 8 g of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 1000" (trade name), number average molecular weight: about 1000) were charged. Then, these were heated while stirring, and transesterification reaction was carried out at a reactor temperature of about 145 ° C. In addition, by measuring the reaction solution over time with GPC, the reaction was continued even after the disappearance of the peak derived from the raw material, and by measuring the reaction solution with NMR over time, a structure represented by formula (BB) was formed, so that the value of formula (i) increased over time, but the value of formula (i) became constant before reaching the range of 150.0 to 400.0, so that the progress and completion of the reaction were judged. Next, dibutyl phosphate was added in an amount 2.0 times the molar ratio of titanium tetra-n-butoxide, and the mixture was heated at a reactor temperature of 115°C for 3 hours to obtain oxyethylene structure-containing polycarbonate polyol HP-6. The evaluation results of the obtained oxyethylene structure-containing polycarbonate polyol are shown in Table 1.

[0196] [Comparative Example 7] In a 0.5 L glass flask (reactor) equipped with a stirrer, 160 g of the polycarbonate polyol P-1 obtained in Polymerization Example 1 and 240 g of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 1000" (trade name), number average molecular weight: about 1000) were charged. Then, these were heated with stirring, and transesterification reaction was carried out at a reactor temperature of about 145 ° C. The reaction solution was subjected to GPC measurement over time to confirm the disappearance of the peak derived from the raw material and the appearance of the peak derived from the product, and the progress and completion of the transesterification reaction were judged. Next, dibutyl phosphate was added in an amount 2.0 times the molar ratio of titanium tetra-n-butoxide, and the mixture was heated at a reactor temperature of 115°C for 3 hours to obtain oxyethylene structure-containing polycarbonate polyol HP-7. The evaluation results of the obtained oxyethylene structure-containing polycarbonate polyol are shown in Table 1.

[0197] [Table 2]

[0198] [Example 1] In a 1.0 L glass flask (reactor) equipped with a stirrer, 90 parts by mass (360 g) of the polycarbonate diol P-1 obtained in Polymerization Example 1 and 10 parts by mass (40 g) of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 1000" (trade name), number average molecular weight: about 1000) were charged. Then, these were heated while stirring, and transesterification reaction was carried out at a reactor temperature of about 145 ° C. Note that, by measuring the reaction solution over time with GPC, the reaction was continued even after the disappearance of the peak derived from the raw material, and by measuring the reaction solution over time with NMR, a structure represented by formula (BB) was formed, so that the value of formula (i) increased over time, and the value of formula (i) was confirmed to reach a range of 150.0 to 400.0, and the progress and completion of the transesterification reaction was judged. Next, 85% phosphoric acid was added in an amount 2.0 times the molar ratio of titanium tetra-n-butoxide, and the mixture was heated at a reactor temperature of 115°C for 3 hours to obtain oxyethylene structure-containing polycarbonate polyol JP-1. The evaluation results of the obtained oxyethylene structure-containing polycarbonate polyol are shown in Table 2.

[0199] [Example 2] In a 0.5L glass flask (reactor) equipped with a stirrer, 360 g of the polycarbonate polyol P-2 obtained in Polymerization Example 2 and 40 g of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 1000" (trade name), number average molecular weight: about 1000) were charged. Then, these were heated while stirring, and transesterification reaction was carried out at a reactor temperature of about 145 ° C. In addition, by measuring the reaction solution over time with GPC, the reaction was continued even after the disappearance of the peak derived from the raw material, and by measuring the reaction solution over time with NMR, a structure represented by formula (BB) was formed, so that the value of formula (i) increased over time, and the value of formula (i) was confirmed to reach a range of 150.0 to 400.0, and the progress and completion of the transesterification reaction was judged. Next, dibutyl phosphate was added in an amount 2.0 times the molar ratio of titanium tetra-n-butoxide, and the mixture was heated at a reactor temperature of 115°C for 3 hours to obtain oxyethylene structure-containing polycarbonate polyol JP-2. The evaluation results of the obtained oxyethylene structure-containing polycarbonate polyol are shown in Table 2.

[0200] [Example 3] In a 0.5L glass flask (reactor) equipped with a stirrer, 270 g of the polycarbonate polyol P-3 obtained in Polymerization Example 3 and 30 g of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 1000" (trade name), number average molecular weight: about 1000) were charged. Then, these were heated while stirring, and transesterification reaction was carried out at a reactor temperature of about 145 ° C. In addition, by measuring the reaction solution over time with GPC, the reaction was continued even after the disappearance of the peak derived from the raw material, and by measuring the reaction solution over time with NMR, a structure represented by formula (BB) was formed, so that the value of formula (i) increased over time, and the value of formula (i) was confirmed to reach a range of 150.0 to 400.0, and the progress and completion of the transesterification reaction was judged. Next, dibutyl phosphate was added in an amount 2.0 times the molar ratio of titanium tetra-n-butoxide, and the mixture was heated at a reactor temperature of 115°C for 3 hours to obtain oxyethylene structure-containing polycarbonate polyol JP-3. The evaluation results of the obtained oxyethylene structure-containing polycarbonate polyol are shown in Table 2.

[0201] [Example 4] In a 0.5L glass flask (reactor) equipped with a stirrer, 360 g of the polycarbonate polyol P-4 obtained in Polymerization Example 4 and 40 g of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 2000" (trade name), number average molecular weight: about 2000) were charged. Then, these were heated while stirring, and transesterification reaction was carried out at a reactor temperature of about 145 ° C. In addition, by measuring the reaction solution over time with GPC, the reaction was continued even after the disappearance of the peak derived from the raw material, and by measuring the reaction solution over time with NMR, a structure represented by formula (BB) was formed, so that the value of formula (i) increased over time, and the value of formula (i) was confirmed to reach a range of 150.0 to 400.0, and the progress and completion of the transesterification reaction was judged. Next, dibutyl phosphate was added in an amount 2.0 times the molar ratio of titanium tetra-n-butoxide, and the mixture was heated at a reactor temperature of 115°C for 3 hours to obtain oxyethylene structure-containing polycarbonate polyol JP-4. The evaluation results of the obtained oxyethylene structure-containing polycarbonate polyol are shown in Table 2.

[0202] [Example 5] In a 0.5L glass flask (reactor) equipped with a stirrer, 300 g of the polycarbonate polyol P-1 obtained in Polymerization Example 1 and 100 g of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 1000" (trade name), number average molecular weight: about 1000) were charged. Then, these were heated while stirring, and transesterification reaction was carried out at a reactor temperature of about 145 ° C. In addition, by measuring the reaction solution over time with GPC, the reaction was continued even after the disappearance of the peak derived from the raw material, and by measuring the reaction solution over time with NMR, a structure represented by formula (BB) was formed, so that the value of formula (i) increased over time, and the value of formula (i) was confirmed to reach a range of 150.0 to 400.0, and the progress and completion of the transesterification reaction was judged. Next, dibutyl phosphate was added in an amount 2.0 times the molar ratio of titanium tetra-n-butoxide, and the mixture was heated at a reactor temperature of 115°C for 3 hours to obtain oxyethylene structure-containing polycarbonate polyol JP-5. The evaluation results of the obtained oxyethylene structure-containing polycarbonate polyol are shown in Table 2.

[0203] [Example 6] In a 0.5L glass flask (reactor) equipped with a stirrer, 360 g of the polycarbonate polyol P-5 obtained in Polymerization Example 5 and 40 g of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 600" (trade name), number average molecular weight: about 600) were charged. Then, these were heated while stirring, and transesterification reaction was carried out at a reactor temperature of about 145 ° C. In addition, by measuring the reaction solution over time with GPC, the reaction was continued even after the disappearance of the peak derived from the raw material, and by measuring the reaction solution over time with NMR, a structure represented by formula (BB) was formed, so that the value of formula (i) increased over time, and the value of formula (i) was confirmed to reach a range of 150.0 to 400.0, and the progress and completion of the transesterification reaction was judged. Next, dibutyl phosphate was added in an amount 2.0 times the molar ratio of titanium tetra-n-butoxide, and the mixture was heated at a reactor temperature of 115°C for 3 hours to obtain oxyethylene structure-containing polycarbonate polyol JP-6. The evaluation results of the obtained oxyethylene structure-containing polycarbonate polyol are shown in Table 2.

[0204] [Example 7] In a 0.5L glass flask (reactor) equipped with a stirrer, 252 g of the polycarbonate polyol P-5 obtained in Polymerization Example 5 and 148 g of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polyethylene Glycol 1000" (trade name), number average molecular weight: about 1000) were charged. Then, these were heated while stirring, and transesterification reaction was carried out at a reactor temperature of about 145 ° C. In addition, by measuring the reaction solution over time with GPC, the reaction was continued even after the disappearance of the peak derived from the raw material, and by measuring the reaction solution over time with NMR, a structure represented by formula (BB) was formed, so that the value of formula (i) increased over time, and the value of formula (i) was confirmed to reach a range of 150.0 to 400.0, and the progress and completion of the transesterification reaction was judged. Next, dibutyl phosphate was added in an amount 2.0 times the molar ratio of titanium tetra-n-butoxide, and the mixture was heated at a reactor temperature of 115°C for 3 hours to obtain oxyethylene structure-containing polycarbonate polyol JP-7. The evaluation results of the obtained oxyethylene structure-containing polycarbonate polyol are shown in Table 2.

[0205] [Table 3]

[0206] [Application Example 1, Application Comparative Example 1] Using the oxyethylene structure-containing polycarbonate polyol JP-1 obtained in Example 1 and the oxyethylene structure-containing polycarbonate polyol HP-1 obtained in Comparative Example 1, Polyol, IPDI, DMPA, TEA, and EDA were charged in a molar ratio of Polyol / IPDI / DMPA / TEA / EDA=1.00 / 2.48 / 0.48 / 0.48 / 0.60, and a water-based polyurethane (PUD) was synthesized by the above-mentioned method, and the stability of the obtained water-based polyurethane was evaluated. The evaluation results are shown in Table 3. [Application Example 2, Application Comparative Example 2] Using the oxyethylene structure-containing polycarbonate polyol JP-2 obtained in Example 2 and the oxyethylene structure-containing polycarbonate polyol HP-2 obtained in Comparative Example 2, Polyol, IPDI, DMPA, TEA, and EDA were charged in a molar ratio of Polyol / IPDI / DMPA / TEA / EDA=1.00 / 2.75 / 0.75 / 0.75 / 0.50, and a water-based polyurethane (PUD) was synthesized by the above-mentioned method, and the stability of the obtained water-based polyurethane was evaluated. The evaluation results are shown in Table 3.

[0207] [Table 4]

[0208] [Application Example 3] In a 0.3 L glass flask (reactor) equipped with a stirrer, JP-1 oxyethylene structure-containing polycarbonate polyol obtained in Example 1 and TLA-100 (manufactured by Asahi Kasei Corporation, NCO%=23.3, solid content 100%, non-water-soluble isocyanate polymer having isocyanurate ring as a raw material for forming a cyclic structure) were charged as an isocyanate compound so that NCO / OH=0.20 and the charged amount was 100 g. Next, these were heated with stirring, and the reaction was carried out at a reactor temperature of about 120° C. until the NCO group disappeared, and a urethane group-containing polycarbonate polyol was obtained. The evaluation results are shown in Table 4. The progress of the reaction was confirmed by performing the above-mentioned FT-IR measurement of the reaction solution, and the wave number of 2271 cm originating from the NCO group was obtained. -1 This was confirmed by the disappearance of the infrared absorption spectrum absorbance (Abs) peak in the vicinity.

[0209] [Application comparison example 3] A urethane group-containing polycarbonate polyol was obtained in the same manner as in Application Example 3, except that the oxyethylene structure-containing polycarbonate polyol was the oxyethylene structure-containing polycarbonate polyol HP-1 obtained in Comparative Example 1. The evaluation results are shown in Table 4. The progress of the reaction was confirmed by carrying out the above-mentioned FT-IR measurement of the reaction solution, and the NCO group-derived 2271 cm wavenumber was obtained. -1 This was confirmed by the disappearance of the infrared absorption spectrum absorbance (Abs) peak in the vicinity.

[0210] [Application Example 4] In a 0.3 L glass flask (reactor) equipped with a stirrer, JP-2 oxyethylene structure-containing polycarbonate polyol obtained in Example 2 and TLA-100 (manufactured by Asahi Kasei Corporation, NCO%=23.3, solid content 100%, non-water-soluble isocyanate polymer having isocyanurate ring as a raw material for forming a cyclic structure) were charged as an isocyanate compound so that NCO / OH=0.10 and the charged amount was 100 g. Then, these were heated with stirring, and the reaction was carried out at a reactor temperature of about 120° C. until the NCO group disappeared, and a urethane group-containing polycarbonate polyol was obtained. The evaluation results are shown in Table 4. The progress of the reaction was confirmed by performing the above-mentioned FT-IR measurement on the reaction solution, and the wave number of 2271 cm originating from the NCO group was obtained. -1 This was confirmed by the disappearance of the infrared absorption spectrum absorbance (Abs) peak in the vicinity.

[0211] [Application comparison example 4] A urethane group-containing polycarbonate polyol was obtained in the same manner as in Application Example 4, except that the oxyethylene structure-containing polycarbonate polyol was the oxyethylene structure-containing polycarbonate polyol HP-2 obtained in Comparative Example 2. The evaluation results are shown in Table 4. The progress of the reaction was confirmed by carrying out the above-mentioned FT-IR measurement of the reaction solution, and the NCO group-derived 2271 cm wavenumber was obtained. -1 This was confirmed by the disappearance of the infrared absorption spectrum absorbance (Abs) peak in the vicinity.

[0212] [Table 5]

[0213] From the above, it was confirmed that the oxyethylene structure-containing polycarbonate polyol of this Example has excellent stability of an aqueous dispersion and excellent compatibility with ether polyol, and further, the stability of an aqueous polyurethane obtained using the Examples of this application and / or the stability of an aqueous dispersion of a urethane group-containing polycarbonate polyol are also excellent.

[0214] The oxyethylene structure-containing polycarbonate polyol of the present invention can be suitably used in a wide range of fields, such as automobiles, buses, railway vehicles, construction machinery, agricultural machinery, floors, walls and roofs of buildings, metal products, mortar and concrete products, woodworking products, plastic products, coatings for ceramic building materials such as calcium silicate boards and gypsum boards, and / or polyurethanes.

Claims

1. An oxyethylene structure-containing polycarbonate polyol having a hydroxyl value of 10 to 400 mgKOH / g, The polymerizable compound includes a structural unit represented by the following formula (A), a structural unit represented by the following formula (B), and a structural unit represented by the following formula (BB), the molar amount of the structural unit represented by the formula (A) is 30 to 90 mol % relative to the total molar amount of the structural unit represented by the formula (A) and the structural unit represented by the formula (B); the molar amount of the structural unit represented by the formula (B) is 10 to 70 mol % relative to the total molar amount of the structural unit represented by the formula (A) and the structural unit represented by the formula (B); the total amount of the structural units represented by the formulas (A), (B) and (BB) is 55 to 100 mol % based on all the structural units constituting the oxyethylene structure-containing polycarbonate polyol; An oxyethylene structure-containing polycarbonate polyol, in which the value obtained by the following formula (i) is 150.0 to 400.0: 【number】 (In formula (A), R is a divalent aliphatic hydrocarbon group which may contain a heteroatom and / or a divalent aromatic hydrocarbon group which may contain a heteroatom; R 1 are each independently hydrogen or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. 【number】 【number】 [0010] (In formula (i), A is the molar amount of the structural unit represented by formula (A), B is the molar amount of the structural unit represented by formula (B), BB is the molar amount of the structural unit represented by formula (BB), Mn is the number average molecular weight of the oxyethylene structure-containing polycarbonate polyol.

2. 2. The oxyethylene structure-containing polycarbonate polyol according to claim 1, wherein R is a divalent aliphatic hydrocarbon group which may contain a heteroatom.

3. The oxyethylene structure-containing polycarbonate polyol according to claim 1, wherein the molecular weight distribution (Mw / Mn) is 1.50 to 5.

00.

4. R 1 The oxyethylene structure-containing polycarbonate polyol according to claim 1 , wherein is hydrogen.

5. The polycarbonate polyol containing an oxyethylene structure according to claim 1, wherein the polyhydric hydroxy compound (excluding polyhydric hydroxy compounds having an oxyethylene structure) obtained by hydrolysis of the polycarbonate polyol containing an oxyethylene structure has an average carbon number of 2.0 or more and 15.0 or less.

6. The polyhydric hydroxy compound (excluding polyhydric hydroxy compounds having an oxyethylene structure) obtained by hydrolysis of the oxyethylene structure-containing polycarbonate polyol according to claim 1 includes at least one selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol.

7. The oxyethylene structure-containing polycarbonate polyol according to claim 1, wherein the number average molecular weight of the polyhydric hydroxy compound having an oxyethylene structure obtained by hydrolysis of the oxyethylene structure-containing polycarbonate polyol is 300 to 3,000.

8. The oxyethylene structure-containing polycarbonate polyol according to claim 7, wherein the polyhydric hydroxy compound having an oxyethylene structure is polyethylene glycol.

9. A urethane-modified polycarbonate polyol containing an oxyethylene structure, obtained by using the polycarbonate polyol containing an oxyethylene structure according to claim 1.

10. A coating material comprising the oxyethylene structure-containing polycarbonate polyol according to any one of claims 1 to 9.

11. The paint of claim 10, wherein the paint is a water-based paint.

12. A polyurethane obtained by using the oxyethylene structure-containing polycarbonate polyol according to any one of claims 1 to 9.

13. A water-based polyurethane obtained by using the oxyethylene structure-containing polycarbonate polyol according to any one of claims 1 to 9.

14. An artificial leather comprising the polyurethane of claim 12.

15. An artificial leather comprising the water-based polyurethane according to claim 13.

16. 13. Synthetic leather comprising the polyurethane of claim 12.

17. 14. Synthetic leather comprising the water-based polyurethane of claim 13.

18. A coating composition comprising the polyurethane of claim 12.

19. A paint comprising the water-based polyurethane of claim 13.

20. A coating film obtained from the coating material according to claim 10.

21. A coating film obtained from the coating material according to claim 11.

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