Polycarbonate diol composition and coating composition using the same

Abstract

A polycarbonate diol composition comprises a polycarbonate diol represented by a specific formula and a diol component represented by a specific formula, wherein 90 mol% or more of the total amount of terminal groups are hydroxyl groups, the hydroxyl value is 10 to 400 mgKOH / g, and the proportion of the polycarbonate diol is 80 mass% or more and 99.90 mass% or less, and the proportion of the diol component is 0.10 mass% or more and 20 mass% or less, relative to 100 mass% of the total of the carbonate diol and the diol component.

Description

Technical Field

[0001] The present invention relates to a polycarbonate diol composition and a coating composition using the same. Background Art

[0002] Conventionally, there has been proposed a technique for using, for example, polycarbonate diol, which can impart excellent flexibility, weather resistance, hydrolysis resistance, oil resistance, and chemical resistance, as a main agent of a urethane coating composition.

[0003] As such a polycarbonate diol, a polycarbonate diol that is liquid at room temperature and that uses two or more diols is generally used from the viewpoint of handling properties and compatibility with solvents. For example, Patent Document 1 discloses a polycarbonate diol using 1,5-pentanediol and 1,6-hexanediol as diol components. In addition, for example, Patent Document 2 discloses a polycarbonate diol using 1,4-butanediol and 1,6-hexanediol.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2001 / 090213

[0007] Patent Document 2: International Publication No. 2009 / 063767 Summary of the invention

[0008] Problem that the invention aims to solve

[0009] However, even polycarbonate diols that are liquid at room temperature may become cloudy or crystallized when stored at low temperatures, and coating compositions using these polycarbonate diols may generate turbidity and sediments when stored at low temperatures. In addition, polycarbonate diols generally have poor compatibility with acrylic polyols, and therefore cannot be used in combination with acrylic polyols. Furthermore, even the polycarbonate diols described in Patent Documents 1 and 2 above have room for improvement in these aspects.

[0010] Therefore, an object of the present invention is to provide a polycarbonate diol composition having excellent stability during low-temperature storage and excellent compatibility with acrylic polyol.

[0011] Solutions for solving problems

[0012] The present inventors have conducted intensive studies to solve the above problems and have found that the use of a polycarbonate polyol composition having a specific structure has excellent stability during low-temperature storage, compatibility with acrylic polyol, and adhesion after a durability test, thereby completing the present invention.

[0013] That is, the configuration of the present invention is as follows.

[0014] [1] A polycarbonate diol composition comprising a polycarbonate diol represented by the following formula (A) and a diol component represented by the following formula (B),

[0015] More than 90 mol% of the total amount of terminal groups of the polycarbonate diol composition are hydroxyl groups.

[0016] The hydroxyl value of the polycarbonate diol composition is 10 to 400 mgKOH / g.

[0017] The ratio of the polycarbonate diol is 80% by mass or more and 99.90% by mass or less, and the ratio of the diol component is 0.10% by mass or more and 20% by mass or less, relative to 100% by mass of the total of the carbonate diol and the diol component.

[0018]

[0019] (In formula (A), R1 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 15 carbon atoms. A plurality of R1s present may be the same or different. a is a number of 1 to 50.)

[0020] HO-R2-OH…(B)

[0021] (In formula (B), R2 is a divalent linear or branched aliphatic hydrocarbon group having 2 or more and 5 or less carbon atoms.)

[0022] [2] The polycarbonate diol composition according to [1], wherein, in the molecular weight calculation result of the polycarbonate diol composition measured by gel permeation chromatography (GPC), the area ratio (%) of the number average molecular weight of 500 or less is 1% to 30%.

[0023] [3] The polycarbonate diol composition according to any one of [1] or [2], wherein the ratio of the diol component represented by formula (B) in the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition is 5 mol% or more and 100 mol% or less.

[0024] [4] The polycarbonate diol composition according to any one of [1] to [3], wherein the polycarbonate diol composition has an appearance of a transparent liquid when stored at 5°C for one week.

[0025] [5] A coating composition comprising the polycarbonate diol composition according to any one of [1] to [4].

[0026] [6] A coating film obtained from the coating composition described in [5].

[0027] [7] A polyurethane obtained using the polycarbonate diol composition according to any one of [1] to [4].

[0028] [8] An aqueous polyurethane obtained using the polycarbonate diol composition according to any one of [1] to [4].

[0029] [9] An artificial leather obtained using the polyurethane described in [7] or the water-based polyurethane described in [8].

[0030]

[10] A synthetic leather obtained using the polyurethane described in [7] or the water-based polyurethane described in [8].

[0031]

[11] A coating material using the polyurethane described in [7] or the water-based polyurethane described in [8].

[0032]

[12] A coating agent obtained using the polyurethane described in [7] or the water-based polyurethane described in [8].

[0033]

[13] A polycarbonate diol composition comprising a polycarbonate diol represented by the following formula (AA) and a diol component represented by the following formula (BB),

[0034] More than 90 mol% of the total amount of terminal groups of the polycarbonate diol composition are hydroxyl groups.

[0035] The hydroxyl value of the polycarbonate diol composition is 10 to 400 mgKOH / g.

[0036] The ratio of the polycarbonate diol is 80% by mass or more and 99.90% by mass or less, and the ratio of the diol component is 0.10% by mass or more and 20% by mass or less, relative to 100% by mass of the total of the carbonate diol and the diol component.

[0037]

[0038] (In formula (AA), R11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group which may contain a heteroatom, or a divalent aromatic hydrocarbon group which may contain a heteroatom. A plurality of R11s which exist may be the same or different from each other. aa is a number which is greater than or equal to 1 and less than or equal to 50.)

[0039] HO-R22-OH…(RR)

[0040] (In formula (BB), R22 is a divalent linear or branched aliphatic hydrocarbon group having 2 to 5 carbon atoms, which may contain a heteroatom.)

[0041]

[14] The polycarbonate diol composition according to

[13] , wherein, in the molecular weight calculation result of the polycarbonate diol composition measured by gel permeation chromatography (GPC), the area ratio (%) of the number average molecular weight of 500 or less is 1% to 30%.

[0042]

[15] The polycarbonate diol composition according to

[13] or

[14] , wherein the proportion of the diol component represented by formula (BB) in the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition is 5 mol% or more and 100 mol% or less.

[0043]

[16] The polycarbonate diol composition according to any one of

[13] to

[15] , wherein the polycarbonate diol composition has an appearance of a transparent liquid when stored at 5°C for one week.

[0044]

[17] A coating composition comprising the polycarbonate diol composition according to any one of

[13] to

[16] .

[0045]

[18] A coating film obtained from the coating composition described in

[17] .

[0046]

[19] A polyurethane obtained using the polycarbonate diol composition according to any one of

[13] to

[16] .

[0047]

[20] An aqueous polyurethane obtained using the polycarbonate diol composition according to any one of

[13] to

[16] .

[0048]

[21] An artificial leather obtained using the polyurethane described in

[19] or the water-based polyurethane described in

[20] .

[0049]

[22] A synthetic leather obtained using the polyurethane described in

[19] or the water-based polyurethane described in

[20] .

[0050]

[23] A coating obtained using the polyurethane described in

[19] or the water-based polyurethane described in

[20] .

[0051]

[24] A coating agent obtained using the polyurethane described in

[19] or the water-based polyurethane described in

[20] .

[0052] Effects of the Invention

[0053] According to the present invention, it is possible to provide a polycarbonate diol composition which is excellent in stability during low-temperature storage, compatibility with acrylic polyol, and adhesion after a durability test. DETAILED DESCRIPTION

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

[0055] [Polycarbonate diol composition]

[0056] The polycarbonate diol composition of the present embodiment includes the polycarbonate diol composition of the first embodiment and the polycarbonate diol composition of the second embodiment.

[0057] [First polycarbonate diol composition]

[0058] The polycarbonate diol composition of the first embodiment contains polycarbonate diol. The polycarbonate diol composition of the first embodiment contains a polycarbonate diol represented by the following formula (A) and a diol component represented by the following formula (B), 90 mol% or more of the total amount of terminal groups are hydroxyl groups, the hydroxyl value is 10 to 400 mgKOH / g, and relative to 100 mass% of the total of the carbonate diol and the diol component, the proportion of the polycarbonate diol is 80 mass% or more and 99.90 mass% or less, and the proportion of the diol component is 0.10 mass% or more and 20 mass% or less.

[0059]

[0060] (In formula (A), R1 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 15 carbon atoms. A plurality of R1s present may be the same or different. a is a number of 1 to 50.)

[0061] HO-R2-OH…(B)

[0062] (In formula (B), R2 is a divalent linear or branched aliphatic hydrocarbon group having 2 to 5 carbon atoms.)

[0063] Regarding the ratio of the carbonate diol (A) to the diol component (B) in the polycarbonate diol composition of the first embodiment, relative to the total of 100 mass% of the carbonate diol and the diol component, the ratio of the polycarbonate diol is 80 mass% or more and 99.90 mass% or less, and the ratio of the diol component is 0.10 mass% or more and 20 mass% or less; preferably, the ratio of the polycarbonate diol is 90 mass% or more and 99.90 mass% or less, and the ratio of the diol component is 0.10 mass% or more and 10 mass% or less; more preferably, the ratio of the polycarbonate diol is 93 mass% or more and 99.90 mass% or less. % or less, and the proportion of the above-mentioned diol component is from 0.10 mass % to 7 mass % or less; it is further preferred that the proportion of the above-mentioned polycarbonate diol is from 95 mass % to 99.90 mass % or less, and the proportion of the above-mentioned diol component is from 0.10 mass % to 5 mass % or less; it is still further preferred that the proportion of the above-mentioned polycarbonate diol is from 97 mass % to 99.85 mass % or less, and the proportion of the above-mentioned diol component is from 0.15 mass % to 3 mass %, and it is particularly preferred that the proportion of the above-mentioned polycarbonate diol is from 97 mass % to 99.8 mass % or less, and the proportion of the above-mentioned diol component is from 0.2 mass % to 3 mass %.

[0064] When the ratio of the carbonate diol (A) to the diol component (B) is within the above range, the coating composition using the polycarbonate diol composition tends to be excellent in leveling property and adhesion.

[0065] The ratio of the carbonate diol (A) to the diol component (B) in the polycarbonate diol composition can be calculated from the area ratio (%) measured by gel permeation chromatography (hereinafter also referred to as "GPC"). GPC measurement can be performed by the method described in the examples below.

[0066] In the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition of the first embodiment, the ratio of the diol component represented by the above formula (B) is preferably 5 mol% or more and 100 mol% or less, more preferably 20 mol% or more and 90 mol% or less, further preferably 30 mol% or more and 70 mol% or less, further preferably 35 mol% or more and 65 mol% or less, and particularly preferably 45 mol% or more and 55 mol% or less. By making the ratio of the diol component represented by the above formula (B) in the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition within the above range, the polycarbonate diol composition of the first embodiment tends to have excellent transparent liquid properties when stored at 5°C and compatibility with acrylic polyol. The method for obtaining a polycarbonate diol composition in which the ratio of the diol component represented by formula (B) during hydrolysis is within the above range is not particularly limited, and examples thereof include: a method of producing the polycarbonate diol composition by adjusting the ratio of the diol component represented by formula (B) to other diol components; a method of adding the diol component represented by formula (B) and other diol components to the obtained polycarbonate diol composition, etc. The hydrolysis of the polycarbonate diol composition can be carried out using the method described in the Examples described below.

[0067] [Polycarbonate diol composition of the second embodiment]

[0068] The polycarbonate diol composition of the second embodiment will be described below. The polycarbonate diol composition of the second embodiment is a generalized polycarbonate diol composition of the first embodiment described above.

[0069] That is, the polycarbonate diol composition of the second embodiment contains:

[0070] A polycarbonate diol represented by the following formula (AA) and a diol component represented by the following formula (BB),

[0071] More than 90 mol% of the total amount of terminal groups of the polycarbonate diol composition are hydroxyl groups.

[0072] The hydroxyl value of the polycarbonate diol composition is 10 to 400 mgKOH / g.

[0073] The ratio of the polycarbonate diol is 80% by mass or more and 99.90% by mass or less, and the ratio of the diol component is 0.10% by mass or more and 20% by mass or less, relative to 100% by mass of the total of the carbonate diol and the diol component.

[0074]

[0075] (In formula (AA), R11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group which may contain a heteroatom, or a divalent aromatic hydrocarbon group which may contain a heteroatom. A plurality of R11s which exist may be the same or different from each other. aa is a number which is greater than or equal to 1 and less than or equal to 50.)

[0076] HO-R22-OH…(BB)

[0077] (In formula (BB), R22 is a divalent linear or branched aliphatic hydrocarbon group having 2 to 5 carbon atoms, which may contain a heteroatom.)

[0078] Regarding the ratio of the carbonate diol (AA) to the diol component (BB) in the polycarbonate diol composition of the second embodiment, relative to the total of 100 mass% of the carbonate diol and the diol component, the ratio of the polycarbonate diol is 80 mass% or more and 99.90 mass% or less, and the ratio of the diol component is 0.10 mass% or more and 20 mass% or less; preferably, the ratio of the polycarbonate diol is 90 mass% or more and 99.90 mass% or less, and the ratio of the diol component is 0.10 mass% or more and 10 mass% or less; more preferably, the ratio of the polycarbonate diol is 93 mass% or more and 99.90 mass% or less. Preferably, the proportion of the above-mentioned diol component is from 0.10 mass % to 7 mass %; more preferably, the proportion of the above-mentioned polycarbonate diol is from 95 mass % to 99.90 mass %, and the proportion of the above-mentioned diol component is from 0.10 mass % to 5 mass %; further preferably, the proportion of the above-mentioned polycarbonate diol is from 97 mass % to 99.85 mass %, and the proportion of the above-mentioned diol component is from 0.15 mass % to 3 mass %; particularly preferably, the proportion of the above-mentioned polycarbonate diol is from 97 mass % to 99.8 mass %, and the proportion of the above-mentioned diol component is from 0.2 mass % to 3 mass %.

[0079] When the ratio of the carbonate diol (AA) to the diol component (BB) is within the above range, the coating composition using the polycarbonate diol composition tends to be excellent in leveling property and adhesion.

[0080] The ratio of carbonate diol (AA) to diol component (BB) in the polycarbonate diol composition can be calculated from the area ratio (%) measured by gel permeation chromatography (hereinafter also referred to as "GPC"). GPC measurement can be performed by the method described in the examples below.

[0081] In the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition of the second embodiment, the ratio of the diol component represented by the above formula (BB) is preferably 5 mol% or more and 100 mol% or less, more preferably 20 mol% or more and 90 mol% or less, further preferably 30 mol% or more and 70 mol% or less, further preferably 35 mol% or more and 65 mol% or less, and particularly preferably 45 mol% or more and 55 mol% or less. By making the ratio of the diol component represented by the above formula (BB) in the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition within the above range, the polycarbonate diol composition of the second embodiment tends to have excellent transparent liquid properties and compatibility with acrylic polyol when stored at 5°C. The method for obtaining a polycarbonate diol composition in which the ratio of the diol component represented by formula (BB) during hydrolysis is within the above range is not particularly limited, and examples thereof include: a method of producing the polycarbonate diol composition by adjusting the ratio of the diol component represented by formula (BB) to other diol components; a method of adding the diol component represented by formula (BB) and other diol components to the obtained polycarbonate diol composition, etc. The hydrolysis of the polycarbonate diol composition can be carried out using the method described in the Examples described below.

[0082] The hydroxyl value of the polycarbonate diol composition of the present embodiment is 10 to 400 mgKOH / g, preferably 20 to 300 mgKOH / g, and more preferably 30 to 250 mgKOH / g. By making the hydroxyl value greater than the above lower limit, the flexibility and low temperature properties of the thermoplastic urethane obtained from the polycarbonate diol composition tend to be better. On the other hand, by making the hydroxyl value less than the above upper limit, the molding processability of the thermoplastic urethane obtained from the polycarbonate diol composition tends to be better. The hydroxyl value can be calculated using the method described in the examples described later.

[0083] In the polycarbonate diol composition of the present embodiment, 90 mol% or more of the total terminal groups are hydroxyl groups, preferably 90 mol% or more and 100 mol% or less of the total terminal groups are hydroxyl groups, and more preferably 95 mol% or more and 100 mol% or less of the total terminal groups are hydroxyl groups.

[0084] In the polycarbonate diol composition of the present embodiment, when the ratio of the hydroxyl group in the total amount of terminal groups is within the above range, the drying property, adhesion, and chemical resistance of a coating film using the polycarbonate diol composition tend to be improved.

[0085] The method for obtaining a polycarbonate diol composition in which the ratio of hydroxyl groups in the total amount of terminal groups is within the above range is not particularly limited, and examples thereof include: a method of using high-purity raw materials when producing the polycarbonate diol composition; a method of setting the reaction temperature to 200° C. or less to suppress dehydration of terminal hydroxyl groups when producing the polycarbonate diol composition, etc.

[0086] In the polycarbonate diol composition of the present embodiment, examples of terminal groups other than a hydroxyl group include an alkyl group, a vinyl group, and an aryl group.

[0087] It should be noted that, in the present embodiment, the ratio of the hydroxyl group in the total amount of the terminal groups can be measured using the method described in the Examples described later.

[0088] In the molecular weight calculation result calculated by GPC measurement of the polycarbonate diol composition of the present embodiment, the area ratio (%) of the number average molecular weight of 500 or less is preferably 1% or more and 30% or less, more preferably 1% or more and 25% or less, further preferably 1% or more and 20% or less, and particularly preferably 1.0% or more and 15% or less. By making the area ratio (%) of the number average molecular weight of 500 or less within the above range, the coating composition using the polycarbonate diol composition of the present embodiment tends to have excellent stability when stored at 5°C, and the polycarbonate diol composition of the present embodiment tends to have excellent compatibility with polyester polyols, acrylic polyols, polyether polyols, polyolefin polyols, fluorine-containing polyols and other polyols and additives such as leveling agents described in Japanese Patent Application Laid-Open No. 2018-012769. The method for obtaining the polycarbonate diol composition having the area ratio (%) of the number average molecular weight of 500 or less in the above range is not particularly limited, and examples thereof include a method of adding a polyol or diol having a number average molecular weight of 500 or less. The area ratio (%) of the polycarbonate diol composition obtained by GPC measurement can be calculated using the method described in the Examples described below.

[0089] The polycarbonate diol composition of the present embodiment preferably has a transparent liquid appearance when stored for one week at 5° C. A coating composition using such a polycarbonate diol composition can suppress generation of turbidity and sediment during low-temperature storage and tends to have better stability during low-temperature storage.

[0090] The method for obtaining a polycarbonate diol composition having a transparent liquid appearance when stored at 5°C for one week is not particularly limited, and examples thereof include: a method of using two or more diols to produce the polycarbonate diol composition; a method of using one or more diols that are liquid at 23°C to produce the polycarbonate diol composition, etc.

[0091] (R1)

[0092] In formula (A), R1 is a divalent aliphatic or alicyclic hydrocarbon group having 2 to 15 carbon atoms. A plurality of R1 groups may be the same or different from each other.

[0093] The divalent straight-chain aliphatic hydrocarbon group in R1 has a carbon number of 2 or more and 15 or less, preferably 3 or more and 12 or less, and more preferably 3 or more and 10 or less.

[0094] Specific examples of the divalent straight-chain aliphatic hydrocarbon group having 2 or more and 15 or less carbon atoms in R1 are not particularly limited, and examples thereof include ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene. Among them, propylene, butylene, pentylene, hexylene, nonylene, and decylene are preferred from the viewpoint of versatility.

[0095] The divalent branched aliphatic hydrocarbon group in R1 has 3 or more and 15 or less, preferably 3 or more and 12 or less, and more preferably 3 or more and 10 or less carbon atoms.

[0096] The divalent branched aliphatic hydrocarbon group in R1 is not particularly limited, and examples thereof include isopropylene, isobutylene, tert-butylene, isopentylene, 2,2-dimethyltrimethylene, isohexylene, isoheptylene, isooctylene, etc. Among them, isopropylene, isobutylene, isopentylene, 2,2-dimethyltrimethylene, or isohexylene is preferred from the viewpoint of versatility.

[0097] The divalent cyclic aliphatic hydrocarbon group in R1 has 3 or more and 15 or less, preferably 6 or more and 15 or less, and more preferably 6 or more and 10 or less carbon atoms.

[0098] The divalent cyclic aliphatic hydrocarbon group in R1 is not particularly limited, and examples thereof include cyclobutylene, cyclopentylene, cyclohexylene, and cycloheptylene.

[0099] The divalent aromatic hydrocarbon group in R1 has a carbon number of 6 or more and 15 or less, preferably 6 or more and 12 or less, and more preferably 6 or more and 10 or less.

[0100] The divalent aromatic hydrocarbon group in R1 is not particularly limited, and examples thereof include a phenylene group and a naphthylene group.

[0101] Among them, as R1, a divalent straight-chain, branched or cyclic aliphatic hydrocarbon group (i.e., an alkylene group) having a carbon number of 2 to 15 is preferred, a divalent straight-chain aliphatic hydrocarbon group having a carbon number of 3 to 12 is more preferred, or a divalent branched aliphatic hydrocarbon group having a carbon number of 3 to 15 is more preferred, and a divalent straight-chain aliphatic hydrocarbon group having a carbon number of 3 to 10 is further preferred.

[0102] (R11)

[0103] In formula (AA), R11 is a divalent aliphatic or alicyclic hydrocarbon group which may contain a heteroatom. A plurality of R11 groups may be the same or different from each other.

[0104] As the divalent straight-chain aliphatic hydrocarbon group which may contain a hetero atom in R11, the molecular weight of R11 is preferably 20 or more and 3000 or less, more preferably 30 or more and 2500 or less, and further preferably 40 or more and 2200 or less.

[0105] For example, R11 is ethylene (-CH 2 -CH 2 -), the molecular weight of R11 is (12+1×2)+(12+1×2)=28.

[0106] Specific examples of the divalent straight-chain aliphatic hydrocarbon group optionally containing a heteroatom in R11 are not particularly limited, and examples thereof include ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, oxyethylene, oxytetramethylene, etc. Among them, propylene, butylene, pentylene, hexylene, nonylene, decylene, oxyethylene, oxy1-methylethylene, oxytetramethylene, polyoxyethylene, polyoxy1-methylethylene, and polyoxytetramethylene are preferred from the viewpoint of versatility.

[0107] As the divalent branched aliphatic hydrocarbon group which may contain a hetero atom in R11, the molecular weight of the R11 substituent is preferably 20 or more and 3000 or less, more preferably 30 or more and 2500 or less, and further preferably 40 or more and 2200 or less.

[0108] The divalent branched aliphatic hydrocarbon group optionally containing a hetero atom in R11 is not particularly limited, and examples thereof include isopropylene, isobutylene, tert-butylene, isopentylene, 2,2-dimethyltrimethylene, isohexylene, isoheptylene, isooctylene, oxy-1-methylethylene, oxy-2,2-dimethyltrimethylene, etc. Among them, isopropylene, isobutylene, isopentylene, 2,2-dimethyltrimethylene or isohexylene, oxy-1-methylethylene, and polyoxy-1-methylethylene are preferred from the viewpoint of versatility.

[0109] As the divalent cyclic aliphatic hydrocarbon group which may contain a hetero atom in R11, the molecular weight of the R11 substituent is preferably 20 or more and 3000 or less, more preferably 30 or more and 2500 or less, and further preferably 40 or more and 2200 or less.

[0110] The divalent cyclic aliphatic hydrocarbon group which may contain a hetero atom in R11 is not particularly limited, and examples thereof include cyclobutylene, cyclopentylene, cyclohexylene, and cycloheptylene.

[0111] As the divalent aromatic hydrocarbon group which may contain a hetero atom in R11, the molecular weight of the R11 substituent is preferably 20 or more and 3000 or less, more preferably 30 or more and 2500 or less, and further preferably 40 or more and 2200 or less.

[0112] The divalent aromatic hydrocarbon group which may contain a hetero atom in R11 is not particularly limited, and examples thereof include a phenylene group and a naphthylene group.

[0113] Among them, as R11, preferably, the molecular weight of the R11 substituent is 20 to 3000, which is a divalent straight-chain, branched or cyclic aliphatic hydrocarbon group optionally containing a hetero atom, more preferably, the molecular weight of the R11 substituent is 30 to 2500, which is a divalent straight-chain aliphatic hydrocarbon group optionally containing a hetero atom, or the molecular weight of the R11 substituent is 30 to 2500, which is a divalent branched aliphatic hydrocarbon group optionally containing a hetero atom, and further preferably, the molecular weight of the R11 substituent is 40 to 2200, which is a divalent straight-chain aliphatic hydrocarbon group optionally containing a hetero atom.

[0114] (R2)

[0115] In formula (B), R2 is a divalent linear or branched aliphatic hydrocarbon group having 2 to 5 carbon atoms.

[0116] Specific examples of the divalent straight-chain hydrocarbon group having 2 or more and 5 or less carbon atoms in R2 are not particularly limited, and examples thereof include ethylene, propylene, butylene, pentylene, etc. Among them, propylene, butylene, and pentylene are preferred from the viewpoint of versatility.

[0117] Specific examples of the divalent branched hydrocarbon group having 2 to 5 carbon atoms in R2 are not particularly limited, and examples thereof include isopropylene, isobutylene, isopentylene, and 2,2-dimethyltrimethylene.

[0118] As a method for controlling the ratio of the polycarbonate diol (A) to the diol component (B) in the polycarbonate diol composition of the present embodiment, for example, a method of allowing the diol component (B) to remain during the process of producing the polycarbonate diol (A) may be used, and another method of adding the diol component (B) to the polycarbonate diol (A) may be used.

[0119] Specific examples of the diol component (B) used in the present embodiment are not particularly limited as long as they are diols having a carbon number of 2 or more and 5 or less, and examples thereof include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, etc. Among them, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 2-methyl-1,3-propanediol are preferred from the viewpoint of being liquid at 23° C. and from the viewpoint of versatility, and ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,5-pentanediol are particularly preferred.

[0120] (R22)

[0121] In the formula (BB), R22 is a divalent linear or branched aliphatic hydrocarbon group having 2 to 5 carbon atoms which may contain a heteroatom.

[0122] Specific examples of the divalent straight-chain hydrocarbon group having 2 or more and 5 or less carbon atoms which may contain heteroatoms in R22 are not particularly limited, and examples thereof include ethylene, propylene, butylene, pentylene, oxyethylene, etc. Among them, propylene, butylene, pentylene, and oxyethylene are preferred from the viewpoint of versatility.

[0123] Specific examples of the divalent branched hydrocarbon group having 2 to 5 carbon atoms which may contain a hetero atom in R22 are not particularly limited, and examples thereof include isopropylene, isobutylene, isopentylene, 2,2-dimethyltrimethylene, and oxy-1-methylethylene.

[0124] As a method for controlling the ratio of the polycarbonate diol (AA) to the diol component (BB) in the polycarbonate diol composition of the present embodiment, for example, a method of allowing the diol component (BB) to remain during the process of producing the polycarbonate diol (AA) may be used, and another method of adding the diol component (BB) to the polycarbonate diol (AA) may be used.

[0125] Specific examples of the diol component (BB) used in the present embodiment are not particularly limited as long as they are diols having a carbon number of 2 or more and 5 or less and optionally containing heteroatoms, and examples thereof include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol, etc. Among them, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, and diethylene glycol are preferred from the viewpoint of being liquid at 23° C. and from the viewpoint of versatility, and ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,5-pentanediol are particularly preferred.

[0126] As a method for controlling the hydroxyl value of the polycarbonate diol composition, it is preferable to select a polycarbonate diol (A) or a polycarbonate diol (AA) having an appropriate hydroxyl value as a raw material.

[0127] [Method for producing polycarbonate diol (A)]

[0128] The method for producing the polycarbonate diol (A) used in the first embodiment is not particularly limited, and a known method can be adopted. For example, the polycarbonate diol (A) can be obtained by reacting a carbonate compound and a diol compound in the presence of an ester exchange catalyst.

[0129] (Carbonate compound)

[0130] The carbonate compound used for producing the polycarbonate diol (A) used in the first embodiment is not limited to the following compounds, and examples thereof include alkylene carbonates, dialkyl carbonates, and diaryl carbonates.

[0131] The alkylene carbonate is not particularly limited, and examples thereof include ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, and 1,2-pentylene carbonate.

[0132] The dialkyl carbonate is not particularly limited, and examples thereof include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate.

[0133] The diaryl carbonate is not particularly limited, and examples thereof include diphenyl carbonate.

[0134] Among them, as the carbonate compound used for producing the polycarbonate diol, alkylene carbonate is preferred, and dimethyl carbonate and ethylene carbonate are more preferred.

[0135] (Diol compound)

[0136] The diol compound used for producing the polycarbonate diol (A) is not limited to the following compounds, and examples thereof include linear diols, branched diols, cyclic diols, and diols having an aromatic ring.

[0137] The linear diol is not particularly limited, and examples thereof include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol.

[0138] The branched diol is not particularly limited, and examples thereof include 2-methyl-1,8-octanediol, neopentyl glycol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, and 2,4-diethyl-1,5-pentanediol.

[0139] The cyclic diol is not particularly limited, and examples thereof include 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2-bis(4-hydroxycyclohexyl)propane.

[0140] [Method for producing polycarbonate diol (AA)]

[0141] The method for producing the polycarbonate diol (AA) used in the second embodiment is not particularly limited, and a known method can be adopted. For example, the polycarbonate diol (AA) can be obtained by reacting a carbonate compound and a diol compound in the presence of an ester exchange catalyst.

[0142] (Carbonate compound)

[0143] The carbonate compound used for producing the polycarbonate diol (AA) used in the second embodiment is not limited to the following compounds, and examples thereof include alkylene carbonates, dialkyl carbonates, and diaryl carbonates.

[0144] The alkylene carbonate is not particularly limited, and examples thereof include ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, and 1,2-pentylene carbonate.

[0145] The dialkyl carbonate is not particularly limited, and examples thereof include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate.

[0146] The diaryl carbonate is not particularly limited, and examples thereof include diphenyl carbonate.

[0147] Among them, as the carbonate compound used for producing the polycarbonate diol, alkylene carbonate is preferred, and dimethyl carbonate and ethylene carbonate are more preferred.

[0148] (Diol compound)

[0149] The diol compound used for producing the polycarbonate diol (AA) is not limited to the following compounds, and examples thereof include linear diols, branched diols, cyclic diols, and diols having an aromatic ring.

[0150] The linear diol is not particularly limited, and examples thereof include ethylene glycol, 1,3-propylene glycol, 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 polyethylene glycol.

[0151] The branched diol is not particularly limited, and examples thereof include 2-methyl-1,8-octanediol, neopentyl glycol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, and polypropylene glycol.

[0152] The cyclic diol is not particularly limited, and examples thereof include 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-bis(4-hydroxycyclohexyl)propane, and isosorbide.

[0153] [Production Conditions of Polycarbonate Diol (A) or Polycarbonate Diol (AA)]

[0154] When producing the polycarbonate diol (A) or the polycarbonate diol (AA) used in the present embodiment, a transesterification catalyst may be used.

[0155] The transesterification catalyst is not particularly limited, and examples thereof include alkali metals and alkaline earth metals, alkoxides thereof, hydrides thereof, oxides thereof, amides thereof, hydroxides thereof, and salts thereof.

[0156] The salt of an alkali metal or an alkaline earth metal is not particularly limited, and examples thereof include carbonates, nitrogen-containing borates, and basic salts with organic acids.

[0157] The alkali metal is not particularly limited, and examples thereof include lithium, sodium, and potassium.

[0158] The alkaline earth metal is not particularly limited, and examples thereof include magnesium, calcium, strontium, and barium.

[0159] The transesterification catalyst using a metal other than an alkali metal and an alkaline earth metal is not particularly limited, and examples thereof include metals other than an alkali metal and an alkaline earth metal, and salts thereof, alkoxides thereof, and organic compounds containing the metal.

[0160] Specific examples of metals other than alkali metals and alkaline earth metals include, but are not particularly 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.

[0161] These transesterification catalysts may be used alone or in combination of two or more.

[0162] Among them, the ester exchange reaction catalyst is preferably one or more metals selected from the group consisting of sodium, potassium, magnesium, potassium, titanium, zirconium, tin, lead and ytterbium, or salts thereof, alkoxides thereof or organic compounds containing these metals, from the viewpoint that the ester exchange reaction to obtain the polycarbonate diol proceeds more smoothly and the influence on the urethane reaction when the obtained polycarbonate diol is used is less.

[0163] Furthermore, as the transesterification catalyst, at least one metal selected from the group consisting of magnesium, titanium, ytterbium, tin and zirconium is more preferred.

[0164] Specific examples of preferred transesterification catalysts include organic lead compounds and organic titanium compounds.

[0165] The organic lead compound is not particularly limited, and examples thereof include lead acetate trihydrate, tetraphenyl lead, and lead stearate.

[0166] The organic titanium compound is not particularly limited, and examples thereof include titanium tetra-n-butoxide, titanium tetra-n-propoxide, and titanium tetraisopropoxide.

[0167] The amount of the transesterification reaction catalyst used is preferably 0.00001% by mass or more and 0.1% by mass or less, and more preferably 0.0001% by mass or more and 0.05% by mass or less, based on the total mass of the raw materials.

[0168] The transesterification catalyst used in the transesterification reaction is not consumed by the transesterification reaction when the polycarbonate diol is heated after the polycarbonate diol is produced, so it can be calculated based on the amount of the transesterification catalyst used. When commercially available polycarbonate diol is used, the amount of metal in the transesterification catalyst contained in the polycarbonate diol can be determined by measuring the amount of metal in the transesterification catalyst by ICP (Inductively Coupled Plasma).

[0169] The polycarbonate diol (A) used in the present embodiment can also be produced by a transesterification reaction between a polycarbonate diol and a diol compound, or a transesterification reaction between two or more polycarbonate diols.

[0170] When the polycarbonate diol as a raw material contains a catalyst poison of the transesterification reaction catalyst used in its production, the transesterification reaction generally tends to be difficult to proceed. Therefore, when producing the polycarbonate diol, a necessary amount of the transesterification reaction catalyst may be newly added.

[0171] On the other hand, when the polycarbonate diol as a raw material does not contain a catalyst poison of the transesterification reaction catalyst, there is a tendency that the transesterification reaction in the present embodiment is easy to proceed. However, when it is desired to further reduce the reaction temperature in the production process of the polycarbonate diol, when it is desired to further shorten the reaction time, etc., a necessary amount of transesterification reaction catalyst may be added again. In this case, the same catalyst as the transesterification reaction catalyst used in the production of the polycarbonate diol as a raw material may be used.

[0172] Specifically, the transesterification reaction can be carried out by mixing the raw materials and stirring them under heating.

[0173] The temperature of the transesterification reaction is not particularly limited, but is preferably 120°C or higher and 250°C or lower, and more preferably 140°C or higher and 200°C or lower.

[0174] By setting the reaction temperature to be equal to or higher than the above lower limit, the transesterification reaction can be carried out in a shorter time, and the economic efficiency is excellent. By setting the reaction temperature to be equal to or lower than the above upper limit, the coloration of the obtained polycarbonate diol can be more effectively prevented.

[0175] The reaction pressure of transesterification reaction is not particularly limited, and is preferably above normal pressure and below 1MPa. By setting the reaction pressure to the above range, the reaction can be more easily implemented. In addition, when using auxiliary raw materials, considering their vapor pressures, etc., the transesterification reaction can be more efficiently promoted by a certain degree of pressurization.

[0176] 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 gradually becomes smaller over time, and this can be confirmed by the disappearance of the peak.

[0177] In the method for producing polycarbonate diol, a step of dehydrating the raw materials used may be performed as a pretreatment before the above-mentioned transesterification reaction.

[0178] In the method for producing a polycarbonate diol, after the above-mentioned transesterification reaction, a step of adding the above-mentioned catalyst poison to the transesterification reaction catalyst may be performed as a post-treatment.

[0179] [Coating composition]

[0180] The coating composition of the present embodiment contains the above-mentioned polycarbonate diol composition. The coating composition of the present embodiment contains the above-mentioned polycarbonate diol composition, and thus has excellent stability during low-temperature storage.

[0181] The coating composition of the present embodiment may contain a curing agent composition. Examples of the curing agent composition include a curing agent composition containing a polyisocyanate.

[0182] As a method for manufacturing the coating composition of this embodiment, a manufacturing method known in the industry can be used. For example, a two-component solvent-based coating composition can be manufactured by mixing a coating main agent composition obtained from the above-mentioned polycarbonate diol composition and a curing agent composition containing a polyisocyanate immediately before coating; a one-component solvent-based coating composition containing a urethane prepolymer having a terminal isocyanate group obtained by reacting the above-mentioned polycarbonate diol composition and a polyisocyanate; and a one-component solvent-based coating composition containing a polyurethane resin obtained by reacting the above-mentioned polycarbonate diol composition, an organic polyisocyanate, and a chain extender.

[0183] In the coating composition of the present embodiment, for example, other additives such as curing accelerator (catalyst), matting agent, anti-settling agent, leveling agent, filler, dispersant, flame retardant, dye, organic or inorganic pigment, release agent, fluidity regulator, plasticizer, antioxidant, ultraviolet absorber, light stabilizer, defoamer, colorant, solvent, etc. can be added according to various uses. By appropriately containing these other additives, coating compositions with different properties such as soft-touch coatings and clear coatings can be obtained.

[0184] [Coating]

[0185] The coating film of the present embodiment is obtained from the above-mentioned coating composition. The coating film of the present embodiment is obtained from the above-mentioned coating composition, and thus has excellent adhesion after a durability test.

[0186] The method for producing the coating film of the present embodiment is not particularly limited, and a known production method can be used.

[0187] [Polyurethane]

[0188] The polyurethane of the present embodiment is obtained by using the above-mentioned polycarbonate diol composition. The polyurethane of the present embodiment is obtained by using the above-mentioned polycarbonate diol composition, and thus has excellent adhesion after a durability test.

[0189] The water-based polyurethane of the present embodiment is obtained by using the above-mentioned polycarbonate diol composition. The water-based polyurethane of the present embodiment is obtained by using the above-mentioned polycarbonate diol composition, and thus has excellent adhesion after a durability test.

[0190] There are no particular limitations on the method for obtaining the polyurethane of the present embodiment, and examples thereof include: a prepolymer method (two-stage method) in which a prepolymer having an NCO group at the end is synthesized using the above-mentioned polycarbonate diol composition and isocyanate compound, and then a polyol and / or polyamine is added to extend the chain; and a one-step method (one-stage method) in which the above-mentioned polycarbonate diol composition, isocyanate compound and polyol and / or polyamine are simultaneously polymerized.

[0191] In addition, the method for obtaining the aqueous polyurethane according to the present embodiment is not particularly limited, and examples thereof include the method described in Examples of JP-A-2017-71685.

[0192] [leather]

[0193] The artificial leather of the present embodiment is obtained by using the above-mentioned polyurethane or water-based polyurethane. The artificial leather of the present embodiment is obtained by using the above-mentioned polyurethane or water-based polyurethane, and thus has excellent adhesion after a durability test.

[0194] The synthetic leather of the present embodiment is obtained by using the above-mentioned polyurethane or water-based polyurethane. The synthetic leather of the present embodiment is obtained by using the above-mentioned polyurethane or water-based polyurethane, and thus has excellent adhesion after a durability test.

[0195] [coating]

[0196] The coating material of the present embodiment is obtained by using the above-mentioned polyurethane or water-based polyurethane. The coating material of the present embodiment is obtained by using the above-mentioned polyurethane or water-based polyurethane, and thus has excellent adhesion after a durability test.

[0197] [Coating agent]

[0198] The coating agent of the present embodiment is obtained by using the above-mentioned polyurethane or water-based polyurethane. The coating agent of the present embodiment is obtained by using the above-mentioned polyurethane or water-based polyurethane, and thus has excellent adhesion after a durability test.

[0199] Example

[0200] The present embodiment is further specifically described below by giving specific examples and comparative examples, but the present embodiment is not limited to these examples and comparative examples unless exceeding the gist thereof. In the present examples, "parts" and "%" are based on mass unless otherwise specified.

[0201] The physical properties and evaluations in the Examples and Comparative Examples described below were measured and evaluated by the methods described below.

[0202] [Hydroxy value]

[0203] The hydroxyl value of the polycarbonate diol or the polycarbonate diol composition is measured by the following method.

[0204] First, using a volumetric flask, add pyridine to 12.5g of acetic anhydride and make it 50mL to prepare an acetylating agent. Next, accurately weigh 1.0-10.0g of the sample into a 100mL eggplant flask. Next, add 5mL of the acetylating agent and 10mL of toluene to the above eggplant flask with a full-volume pipette, install a condenser, and stir and heat the solution in the above eggplant flask at 100°C for 1 hour. Next, add 2.5mL of distilled water to the above eggplant flask with a full-volume pipette, and further heat and stir the solution in the above eggplant flask for 10 minutes. After cooling the solution in the above eggplant flask for 2-3 minutes, add 12.5mL of ethanol to the above eggplant flask. Next, add 2-3 drops of phenolphthalein as an indicator to the above eggplant flask, and titrate with 0.5mol / L of alcoholic potassium hydroxide. Next, 5 mL of the acetylating agent, 10 mL of toluene and 2.5 mL of distilled water were placed in a 100 mL eggplant flask, the solution in the eggplant flask was heated and stirred for 10 minutes, and then titrated in the same manner (blank test). Based on the result, the hydroxyl value was calculated using the following formula (i).

[0205] Hydroxyl value (mg-KOH / g)={(FE)×28.05×f} / G···(i)

[0206] It should be noted that, in formula (i), E represents the titration amount of the sample (mL), F represents the titration amount of the blank test (mL), G represents the mass of the sample (g), and f represents the factor of the titration solution.

[0207] [GPC measurement]

[0208] The GPC measurement of the polycarbonate diol or the polycarbonate diol composition is carried out by the following method.

[0209] The concentration of each polycarbonate diol or polycarbonate diol composition was adjusted to 0.5% by mass with tetrahydrofuran (hereinafter referred to as THF), and the number average molecular weight converted by standard polystyrene was measured using the following GPC device. Then, the ratio of carbonate diol (hereinafter also referred to as "(A)") and diol component (hereinafter also referred to as "B") and the area ratio % of number average molecular weight below 500 were obtained from the GPC measurement result.

[0210] GPC equipment: HLC-8320 manufactured by Tosoh Corporation

[0211] Chromatographic column: TSKgel G4000H 1 piece

[0212] G3000H 1 piece

[0213] G2000H 2

[0214] Eluent: Tetrahydrofuran (THF)

[0215] Flow rate: 1.0mL / min

[0216] Column temperature: 40°C

[0217] RI detector: RI (built-in device HLC-8320)

[0218] Standard curve: Standard polystyrene (manufactured by Tosoh Corporation)

[0219] ·F-20 (molecular weight: 1.90×10 5 )

[0220] ·F-10 (molecular weight: 9.64×10 4 )

[0221] ·F-4 (molecular weight: 3.79×10 4 )

[0222] ·F-2 (molecular weight: 1.81×10 4 )

[0223] ·F-1(molecular weight: 1.02×10 4 )

[0224] ·A-5000 (molecular weight: 5.97×10 3 )

[0225] ·A-2500 (molecular weight: 2.63×10 3 )

[0226] A-500

[0227] A-1000

[0228] In addition, the molecular weight of 2-10mer is calculated from A-500 and A-1000.

[0229] Dimer (molecular weight: 266)

[0230] Trimer (molecular weight: 370)

[0231] 4-mer (molecular weight: 474)

[0232] Pentamer (molecular weight: 578)

[0233] Hexamer (molecular weight: 682)

[0234] 7-mer (molecular weight: 786)

[0235] 8-mer (molecular weight: 890)

[0236] 9-mer (molecular weight: 994)

[0237] 10-mer (molecular weight: 1098)

[0238] Standard curve type: cubic polynomial

[0239] [hydrolysis]

[0240] The hydrolysis of the polycarbonate diol or the polycarbonate diol composition is carried out by the following method.

[0241] Take 1g of sample to a 100mL eggplant flask, add 30g of ethanol and 4g of potassium hydroxide, and react at 100°C for 1 hour. After cooling to room temperature, 2 to 3 drops of phenolphthalein as an indicator are added to the above-mentioned eggplant flask and neutralized with hydrochloric acid. After cooling the above-mentioned eggplant flask in a refrigerator for 1 hour, the precipitated salt is removed by filtration and analyzed by gas chromatography. Regarding the concentration of each dihydroxy compound, a standard curve is prepared in advance from each known dihydroxy compound as a standard substance, and the mass % is calculated by the area ratio obtained by gas chromatography (GC). A gas chromatograph GC-14B (manufactured by Shimadzu Corporation) with DB-WAX (manufactured by J&W) as a chromatographic column and a hydrogen flame ionization detector (FID) is used as a detector for analysis. It should be noted that the temperature rise curve of the chromatographic column is: after keeping at 60°C for 5 minutes, the temperature is increased to 250°C at 10°C / minute.

[0242] For example, when the dihydroxy compounds as a result of hydrolyzing a polycarbonate diol composition are 1,6-hexanediol (0.3 mol), 1,5-pentanediol (0.2 mol), 1,4-butanediol (0.1 mol), and 1,3-propylene glycol (0.05 mol), the ratio of the dihydroxy compound represented by the above formula (B) in the dihydroxy compounds obtained by hydrolyzing the polycarbonate diol composition is (0.2+0.1+0.05)÷(0.3+0.2+0.1+0.05)=53.8 mol%.

[0243] [Ratio of hydroxyl groups in the total amount of terminal groups]

[0244] The ratio of the hydroxyl group in the total amount of terminal groups of the polycarbonate diol composition is measured by the method for measuring the terminal primary OH ratio described in Japanese Patent No. 3874664. Specifically, the measurement is performed as follows.

[0245] 70 g to 100 g of a polycarbonate diol composition is weighed into a 300 cc eggplant flask, and the polycarbonate diol composition is heated in a heating bath of about 180° C. under a pressure of 0.1 kPa or less with stirring using a rotary evaporator connected to a trap bulb for fraction recovery. A fraction corresponding to 1 to 2% by mass of the polycarbonate diol composition, i.e., about 1 g (0.7 to 2 g) of the fraction is obtained in the trap bulb, which is recovered using about 100 g (95 to 105 g) of ethanol as a solvent (in addition, a solvent such as tetrahydrofuran, acetone, methanol, etc. may also be used), and the recovered solution is subjected to GC analysis, and the peak area value of the obtained chromatogram is calculated by the following formula.

[0246] Terminal hydroxyl group ratio (mol %)=(total of peak areas of diols having a terminal hydroxyl group)÷(total of peak areas of alcohols including diols (excluding ethanol when ethanol is used as a solvent))×100.

[0247] It should be noted that the conditions for GC analysis are as follows.

[0248] The analysis conditions of the gas chromatography were as follows: column: DB-WAX (manufactured by J&W Company, USA), 30 m, film thickness: 0.25 μm, temperature rising conditions: 60° C. to 250° C., detector: FID (flame ionization detector).

[0249] [Low-temperature storage of polycarbonate diol composition]

[0250] The appearance of the polycarbonate diol or the polycarbonate diol composition after storage at 5° C. for one week was evaluated using a small environmental tester (ESPEC SU-241). The evaluation results are shown by the following symbols.

[0251] ○: Transparent liquid

[0252] △: cloudy or waxy

[0253] ×: Cured

[0254] [Evaluation of low temperature storage performance]

[0255] The main agent composition was stored at 5°C for 1 week using a small environmental tester (ESPEC SU-241). After standing for 1 day in an atmosphere of 23°C and 50% RH, the main agent composition and the curing agent composition were mixed in such a manner that the ratio of the number of moles of hydroxyl groups (OH groups) contained in the main agent composition to the number of moles of isocyanate groups (NCO groups) contained in the curing agent (hereinafter also referred to as "NCO / OH ratio") was 1.1 to obtain a coating composition. The obtained coating composition was applied to an acrylonitrile-butadiene-styrene copolymer (hereinafter also referred to as "ABS") resin plate with a thickness of 40 μm. The surface of the cured coating film was confirmed and evaluated. The judgment is shown by the following symbols. It should be noted that as the curing agent composition, a polyisocyanate (manufactured by Asahi Kasei Corporation, "TPA-100" (trade name), NCO content 23.1%) was used.

[0256] ○: No pitting or whitening of the coating film, and the coating feels smooth.

[0257] △: There are tiny pits or the texture is slightly rough.

[0258] ×: There are pitting and the hand feels rough.

[0259] [Durability test]

[0260] The main agent composition and TPA-100 were mixed in a manner such that the NCO / OH ratio was 1.1 to obtain a coating composition. The obtained coating composition was applied to three resin plates (ABS resin, polycarbonate resin (PC resin), polymethyl methacrylate (hereinafter also referred to as "PMMA") resin) at a thickness of 40 μm. DPWL-5R manufactured by Suga Test Instruments Co., Ltd. (blackboard temperature 60°C, irradiance 30 w / m 2 , cycle conditions: irradiation and 60°C for 4 hours, humidity and 40°C for 4 hours, ultraviolet fluorescent lamp: SUGA-FS-40) The obtained coating film was subjected to a 250-hour durability test.

[0261] [Adhesion Evaluation]

[0262] The adhesion of the coating after the durability test was evaluated as follows. Based on the cross-cut method of JIS K5600-5-6:1999, a cutter was used to form 100 1 mm × 1 mm grids on the coating. Then, a transparent tape was attached to the surface of the coating with the cuts, and the tape was peeled off and the number of remaining grids was measured. The adhesion was evaluated based on the measured number of grids based on the following evaluation criteria.

[0263] (Evaluation Criteria)

[0264] ○: The number of grids is 90 or more

[0265] △: The number of grids is 80 or more and less than 90

[0266] ×: The number of grids is less than 80 and cannot be evaluated

[0267] [Compatibility]

[0268] To 20 g of acrylic polyol ("Setalux 1152" (trade name) manufactured by Allnex (hydroxyl value 138.6 mgKOH / g resin, solid content 61 mass %)), 20 g of polycarbonate diol or polycarbonate diol composition was added in a manner of 0.2 g at a time, and the maximum amount of polycarbonate diol or polycarbonate diol composition added that can be uniformly compatible when mixed at 60° C. was determined. The compatibility ratio was calculated by the following formula (ii).

[0269] Compatibility ratio (%) = (PCD / 20) × 100 (ii)

[0270] In addition, in formula (ii), PCD represents the maximum addition amount (g) of polycarbonate diol or polycarbonate diol composition.

[0271] <Synthesis of polycarbonate diol and polycarbonate diol composition>

[0272] [Comparative Example 1: Synthesis of polycarbonate diol composition (A-1)]

[0273] After adding 550 g of 2-methyl-1,3-propanediol, 423 g of 1,4-butanediol and 952 g of ethylene carbonate to a 3 L glass flask (reactor) equipped with a distillation column filled with regular packing and a stirring device, 0.195 g of titanium tetra-n-butoxide as a catalyst was added. While taking out a portion of the distillate, the reaction was carried out at a reaction temperature of 150 to 165°C for 25 hours. Next, the reactor was directly connected to the condenser, the reaction temperature was increased to 170 to 180°C, and the pressure was gradually reduced. While appropriately sampling and measuring the hydroxyl value of the generated polycarbonate diol, the diol component in the reactor was distilled off, thereby obtaining a polycarbonate diol composition A-1 (576 g) having a hydroxyl value of 56.2 mgKOH / g. The obtained polycarbonate diol composition was evaluated based on the above method. The evaluation results are recorded in Table 1. In the obtained polycarbonate diol composition, 96 mol% of the total amount of terminal groups were hydroxyl groups.

[0274] [Example 1: Synthesis of polycarbonate diol composition (B-1)]

[0275] After adding 550 g of 2-methyl-1,3-propanediol, 423 g of 1,4-butanediol and 952 g of ethylene carbonate to a 3 L glass flask (reactor) equipped with a distillation column filled with regular packing and a stirring device, 0.197 g of titanium tetra-n-butoxide as a catalyst was added. The reaction was carried out at a reaction temperature of 150 to 165°C for 25 hours while taking out a portion of the distillate. Next, the reactor was directly connected to a condenser, the reaction temperature was raised to 170 to 180°C, and then the pressure was gradually reduced. While appropriately sampling and measuring the hydroxyl value of the generated polycarbonate diol, the diol component in the reactor was distilled off, thereby obtaining a polycarbonate diol (570 g) having a hydroxyl value of 53.0 mgKOH / g. The obtained polycarbonate diol (300 g) was transferred to a 0.5 L glass flask (reactor) equipped with a stirring device, 0.39 g of 2-methyl-1,3-propanediol and 0.39 g of 1,4-butanediol were added, and stirred at 115° C. for 1 hour to obtain a polycarbonate diol composition B-1 (hydroxyl value: 56.1 mgKOH / g). The obtained polycarbonate diol composition was evaluated based on the above method. The evaluation results are recorded in Table 1. In the obtained polycarbonate diol composition, 96 mol% of the total amount of terminal groups were hydroxyl groups.

[0276] [Comparative Example 2: Synthesis of polycarbonate diol (A-2)]

[0277] After adding 330 g of 1,4-butanediol, 130 g of 1,6-hexanediol and 416 g of ethylene carbonate to a 1L glass flask (reactor) equipped with a distillation tower filled with regular packing and a stirring device, 0.095 g of titanium tetra-n-butoxide as a catalyst was added. While taking out a portion of the distillate, the reaction was carried out at a reaction temperature of 155 to 165°C for 18 hours. Next, the reactor was directly connected to the condenser, and the reaction temperature was increased to 165 to 180°C, and the pressure was gradually reduced. While appropriately sampling and measuring the hydroxyl value of the generated polycarbonate diol, the diol component in the reactor was distilled off, thereby obtaining a polycarbonate diol composition A-2 (325 g) having a hydroxyl value of 56.9 mgKOH / g. The obtained polycarbonate diol composition was evaluated based on the above method. The evaluation results are recorded in Table 1. In the obtained polycarbonate diol composition, 97 mol% of the total amount of terminal groups were hydroxyl groups.

[0278] [Example 2: Synthesis of polycarbonate diol composition (B-2)]

[0279] After adding 330 g of 1,4-butanediol, 130 g of 1,6-hexanediol and 416 g of ethylene carbonate to a 1L glass flask (reactor) equipped with a distillation column filled with regular packing and a stirring device, 0.093 g of titanium tetra-n-butoxide as a catalyst was added. The reaction was carried out at a reaction temperature of 155 to 165°C for 18 hours while taking out a portion of the distillate. Next, the reactor was directly connected to a condenser, the reaction temperature was raised to 165 to 180°C, and the pressure was gradually reduced. While appropriately sampling and measuring the hydroxyl value of the generated polycarbonate diol, the diol component in the reactor was distilled off, thereby obtaining a polycarbonate diol (316 g) having a hydroxyl value of 51.9 mgKOH / g. The obtained polycarbonate diol (200 g) was transferred to a 0.5 L glass flask (reactor) equipped with a stirring device, 0.48 g of 1,4-butanediol and 0.30 g of 1,6-hexanediol were added, and stirred at 115° C. for 1 hour to obtain a polycarbonate diol composition B-2 (hydroxyl value: 56.3 mgKOH / g). The obtained polycarbonate diol composition was evaluated based on the above method. The evaluation results are recorded in Table 1. In the obtained polycarbonate diol composition, 98 mol% of the total amount of terminal groups were hydroxyl groups.

[0280] [Comparative Example 3: Synthesis of polycarbonate diol (A-3)]

[0281] After adding 702 g of 1,4-butanediol, 708 g of 1,6-hexanediol and 1188 g of ethylene carbonate to a 3 L glass flask (reactor) equipped with a distillation tower filled with regular packing and a stirring device, 0.276 g of titanium tetra-n-butoxide as a catalyst was added. While taking out a portion of the distillate, the reaction was carried out at a reaction temperature of 150 to 165°C for 20 hours. Next, the reactor was directly connected to the condenser, the reaction temperature was increased to 170 to 180°C, and the pressure was gradually reduced. While appropriately sampling and measuring the hydroxyl value of the generated polycarbonate diol, the diol component in the reactor was distilled off, thereby obtaining a polycarbonate diol composition A-3 (1196 g) having a hydroxyl value of 51.6 mgKOH / g. The obtained polycarbonate diol composition was evaluated based on the above method. The evaluation results are recorded in Table 1. In the obtained polycarbonate diol composition, 98 mol% of the total amount of terminal groups were hydroxyl groups.

[0282] [Example 3: Synthesis of polycarbonate diol composition (B-3)]

[0283] In a 0.5L glass flask (reactor) equipped with a stirring device, 0.38g of 1,4-butanediol and 0.50g of 1,6-hexanediol were added to the polycarbonate diol A-3 (200g) obtained in Comparative Example 3, and stirred at 115°C for 1 hour to obtain a polycarbonate diol composition B-3 (hydroxyl value: 56.3mgKOH / g). The obtained polycarbonate diol composition was evaluated based on the above method. The evaluation results are recorded in Table 1. In the obtained polycarbonate diol composition, 98 mol% of the total amount of terminal groups were hydroxyl groups.

[0284] [Example 4: Synthesis of polycarbonate diol composition (B-4)]

[0285] In a 0.5L glass flask (reactor) equipped with a stirring device, 17.5g of 1,4-butanediol and 23.1g of 1,6-hexanediol were added to the polycarbonate diol A-3 (200g) obtained in Comparative Example 3, and stirred at 115°C for 1 hour to obtain a polycarbonate diol composition B-4 (hydroxyl value: 225.0mgKOH / g). The obtained polycarbonate diol composition was evaluated based on the above method. The evaluation results are recorded in Table 1. In the obtained polycarbonate diol composition, 99 mol% of the total amount of terminal groups were hydroxyl groups.

[0286] [Example 5: Synthesis of polycarbonate diol composition (B-5)]

[0287] In a 0.5L glass flask (reactor) equipped with a stirring device, 9.00 g of the polycarbonate diol composition B-4 obtained in Example 4 was added to the polycarbonate diol A-3 (200 g) obtained in Comparative Example 3, and stirred at 115°C for 1 hour to obtain a polycarbonate diol composition B-5 (hydroxyl value: 59.0 mgKOH / g). The obtained polycarbonate diol composition was evaluated based on the above method. The evaluation results are recorded in Table 1. In the obtained polycarbonate diol composition, 98 mol% of the total amount of terminal groups were hydroxyl groups.

[0288] [Example 6: Synthesis of polycarbonate diol composition (B-6)]

[0289] In a 0.5 L glass flask (reactor) equipped with a stirring device, 21.0 g of the polycarbonate diol composition B-4 obtained in Example 4 was added to the polycarbonate diol A-3 (200 g) obtained in Comparative Example 3, and stirred at 115° C. for 1 hour to obtain a polycarbonate diol composition B-6 (hydroxyl value: 68.2 mgKOH / g). The obtained polycarbonate diol composition was evaluated based on the above method. The evaluation results are recorded in Table 1. In the obtained polycarbonate diol composition, 98 mol% of the total amount of terminal groups were hydroxyl groups.

[0290] [Example 7: Synthesis of polycarbonate diol composition (B-7)]

[0291] In a 0.3 L glass flask (reactor) equipped with a stirring device, 19.6 g of 1,4-butanediol, 25.6 g of 1,6-hexanediol, and 110.9 g of the polycarbonate diol composition B-4 obtained in Example 4 were added to the polycarbonate diol A-3 (100 g) obtained in Comparative Example 3, and stirred at 165° C. for 3 hours to obtain a polycarbonate diol composition (hydroxyl value: 289.5 mgKOH / g).

[0292] The obtained polycarbonate diol composition was evaluated based on the above method. The evaluation results are shown in Table 1. In the obtained polycarbonate diol composition, 98 mol% of the total amount of terminal groups were hydroxyl groups.

[0293] [Example 8: Synthesis of polycarbonate diol composition (B-8)]

[0294] In a 0.3 L glass flask (reactor) equipped with a stirring device, 38.6 g of polyether diol (manufactured by Sanyo Chemical Industries, Ltd., "NEWPOL PE-61" (trade name), number average molecular weight: about 2000, PEG / PPG=5 / 30 copolymer) was added to the polycarbonate diol A-3 (90 g) obtained in Comparative Example 3, and the mixture was stirred at 165°C for 10 hours to obtain a polycarbonate diol composition (hydroxyl value: 55.7 mgKOH / g).

[0295] The obtained polycarbonate diol composition was evaluated based on the above method. The evaluation results are shown in Table 1. In the obtained polycarbonate diol composition, 95 mol% of the total amount of terminal groups were hydroxyl groups.

[0296] [Table 1]

[0297]

[0298] <Preparation of main agent composition>

[0299] [Example 9]

[0300] In a 0.5L plastic container, 100g of the polycarbonate diol composition B-1 obtained in Example 1 as a main agent, 12.0g of "ACEMATT TS 100" (trade name) manufactured by Evonik as a matting agent, 0.01g of dibutyltin dilaurate as a catalyst, 1.2g of "DISPARLON AQ-002" (trade name) manufactured by Kusumoto Chemicals Co., Ltd. as an anti-settling agent, and 218g of butyl acetate as a solvent were added, and stirred with a stirrer until uniform to obtain a main agent composition BR-1. The obtained main agent composition was evaluated based on the above method. The evaluation results are recorded in Table 2.

[0301] [Examples 10 to 11 and 16]

[0302] As the main agent, polycarbonate diol compositions B-2 to B-3 and B-8 were used instead of polycarbonate diol composition B-1, and the main agent compositions BR-2 to BR-3 and BR-8 were obtained by the same method as in Example 9. The obtained main agent compositions were evaluated based on the above method. The evaluation results are recorded in Table 2.

[0303] [Example 12]

[0304] In a 0.5L plastic container, 65g of the polycarbonate diol composition B-4 obtained in Example 4 as a main agent, 11.7g of "ACEMATT TS 100" (trade name) manufactured by Evonik as a matting agent, 0.01g of dibutyltin dilaurate as a catalyst, 1.2g of "DISPARLON AQ-002" (trade name) manufactured by Kusumoto Chemicals Co., Ltd. as an anti-settling agent, and 212g of butyl acetate as a solvent were added, and stirred with a stirrer until uniform to obtain a main agent composition BR-4. The obtained main agent composition was evaluated based on the above method. The evaluation results are recorded in Table 2.

[0305] [Example 13]

[0306] In a 0.5L plastic container, 100g of the polycarbonate diol composition B-5 obtained in Example 5 as a main agent, 12.0g of "ACEMATT TS 100" (trade name) manufactured by Evonik as a matting agent, 0.01g of dibutyltin dilaurate as a catalyst, 1.2g of "DISPARLON AQ-002" (trade name) manufactured by Kusumoto Chemicals Co., Ltd. as an anti-settling agent, and 219g of butyl acetate as a solvent were added, and stirred with a stirrer until uniform to obtain a main agent composition BR-5. The obtained main agent composition was evaluated based on the above method. The evaluation results are recorded in Table 2.

[0307] [Example 14]

[0308] In a 0.5L plastic container, 100g of the polycarbonate diol composition B-6 obtained in Example 6 as a main agent, 12.4g of "ACEMATT TS 100" (trade name) manufactured by Evonik as a matting agent, 0.01g of dibutyltin dilaurate as a catalyst, 1.2g of "DISPARLON AQ-002" (trade name) manufactured by Kusumoto Chemicals Co., Ltd. as an anti-settling agent, and 225g of butyl acetate as a solvent were added, and stirred with a stirrer until uniform to obtain a main agent composition BR-6. The obtained main agent composition was evaluated based on the above method. The evaluation results are recorded in Table 2.

[0309] [Example 15]

[0310] In a 0.5L plastic container, 100g of the polycarbonate diol composition B-7 obtained in Example 7 as a main agent, 12.4g of "ACEMATT TS 100" (trade name) manufactured by Evonik as a matting agent, 0.01g of dibutyltin dilaurate as a catalyst, 1.2g of "DISPARLON AQ-002" (trade name) manufactured by Kusumoto Chemicals Co., Ltd. as an anti-settling agent, and 215g of butyl acetate as a solvent were added, and stirred with a stirrer until uniform to obtain a main agent composition BR-7. The obtained main agent composition was evaluated based on the above method. The evaluation results are recorded in Table 2.

[0311] [Comparative Example 4]

[0312] In a 0.5L plastic container, 100 g of the polycarbonate diol composition A-1 obtained in Comparative Example 1 as a main agent, 12.0 g of "ACEMATT TS 100" (trade name) manufactured by Evonik as a matting agent, 0.01 g of dibutyltin dilaurate as a catalyst, 1.2 g of "DISPARLON AQ-002" (trade name) manufactured by Kusumoto Chemicals as an anti-settling agent, and 218 g of butyl acetate as a solvent were added, and stirred with a stirrer until uniform to obtain a main agent composition AR-1. The obtained main agent composition was evaluated based on the above method. The evaluation results are recorded in Table 2.

[0313] [Comparative Examples 5-6]

[0314] Main agent compositions AR-2 and AR-3 were obtained by the same method as in Comparative Example 4 except that polycarbonate diol compositions A-2 and A-3 were used instead of polycarbonate diol composition A-1 as the main agent. The obtained main agent compositions were evaluated according to the above method. The evaluation results are shown in Table 2.

[0315] [Table 2]

[0316]

[0317] From the results of Tables 1 and 2, it can be seen that the polycarbonate diol composition containing a polycarbonate diol represented by a specific formula (A) or (AA) and a diol component represented by a specific formula (B) or (BB) at a specific ratio, 90 mol% or more of the total amount of terminal groups being hydroxyl groups and having a hydroxyl value of 10 to 400 mgKOH / g has excellent compatibility with acrylic polyols, and when used as a coating composition, has excellent stability during low-temperature storage, and the coating film obtained from the coating composition has excellent adhesion after a durability test. In particular, it was found that when the ratio of the dihydroxy compound represented by the specific formula (B) or (BB) in the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition is 50 mol%, the compatibility with acrylic polyols is further excellent.

[0318] This application is based on the Japanese patent application (Japanese Patent Application No. 2019-206617) filed on November 15, 2019, the contents of which are incorporated herein by reference.

[0319] Industrial Applicability

[0320] The present invention can be preferably used in a wide range of fields such as coatings for automobiles, buses, trains, construction machinery, agricultural machinery, floors / walls / roofs of buildings, metal products, mortar and concrete products, wood products, plastic products, calcium silicate boards, gypsum boards and other ceramic building materials.

Claims

1. A polycarbonate diol composition comprising a polycarbonate diol represented by the following formula (A) and a diol component represented by the following formula (B), More than 90 mol% of the total amount of terminal groups of the polycarbonate diol composition are hydroxyl groups, The polycarbonate diol composition has a hydroxyl value of 10 to 400 mgKOH / g, With respect to 100 mass % of the total of the carbonate diol and the diol component, the ratio of the polycarbonate diol is 80 mass % or more and 99.90 mass % or less, and the ratio of the diol component is 0.10 mass % or more and 20 mass % or less, In the molecular weight calculation result of the polycarbonate diol composition measured by gel permeation chromatography (GPC), the area ratio (%) of the polycarbonate diol having a number average molecular weight of 500 or less is 1% or more and 30% or less, In formula (A), R1 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 15 carbon atoms, and a plurality of R1s present may be the same or different from each other, and a is a number of 1 to 50. HO-R2-OH…(B) In formula (B), R2 is a divalent linear or branched aliphatic hydrocarbon group having 2 or more and 5 or less carbon atoms, in, In the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition, the ratio of the diol component represented by formula (B) is 5 mol% or more and 100 mol% or less.

2. The polycarbonate diol composition according to claim 1, wherein The ratio of the polycarbonate diol is 95% by mass or more and 99.90% by mass or less, and the ratio of the diol component is 0.10% by mass or more and 5% by mass or less.

3. The polycarbonate diol composition according to claim 1, wherein The ratio of the polycarbonate diol is 97% by mass or more and 99.8% by mass or less, and the ratio of the diol component is 0.2% by mass or more and 3% by mass or less.

4. The polycarbonate diol composition according to any one of claims 1 to 3, wherein The hydroxyl value is 20 to 300 mgKOH / g.

5. The polycarbonate diol composition according to any one of claims 1 to 3, wherein The hydroxyl value is 30 to 250 mgKOH / g.

6. The polycarbonate diol composition according to any one of claims 1 to 3, wherein 95 mol % or more and 100 mol % or less of the total amount of the terminal groups are hydroxyl groups.

7. The polycarbonate diol composition according to any one of claims 1 to 3, wherein R1 is a divalent linear aliphatic hydrocarbon group having 3 to 12 carbon atoms or a divalent branched aliphatic hydrocarbon group having 3 to 15 carbon atoms.

8. The polycarbonate diol composition according to any one of claims 1 to 3, wherein In the molecular weight calculation result calculated by gel permeation chromatography (GPC) measurement of the polycarbonate diol composition, the area ratio (%) of the number average molecular weight of 500 or less is 1% to 20%.

9. The polycarbonate diol composition according to any one of claims 1 to 3, wherein In the molecular weight calculation result of the polycarbonate diol composition calculated by gel permeation chromatography (GPC), the area ratio (%) of the number average molecular weight of 500 or less is 1% to 15%.

10. The polycarbonate diol composition according to any one of claims 1 to 3, wherein In the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition, the ratio of the diol component represented by formula (B) is 20 mol% or more and 90 mol% or less.

11. The polycarbonate diol composition according to any one of claims 1 to 3, wherein In the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition, the ratio of the diol component represented by formula (B) is 30 mol% or more and 70 mol% or less.

12. The polycarbonate diol composition according to any one of claims 1 to 3, wherein In the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition, the ratio of the diol component represented by formula (B) is 35 mol% or more and 65 mol% or less.

13. The polycarbonate diol composition according to any one of claims 1 to 3, wherein In the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition, the ratio of the diol component represented by formula (B) is 45 mol% or more and 55 mol% or less.

14. The polycarbonate diol composition according to any one of claims 1 to 3, wherein When the polycarbonate diol composition was stored at 5° C. for one week, it had a transparent liquid appearance. 15 . A coating composition comprising the polycarbonate diol composition according to claim 1 .

16. A coating film obtained from the coating composition according to claim 15. 17 . A polyurethane obtained by using the polycarbonate diol composition according to claim 1 . 18 . A water-based polyurethane obtained by using the polycarbonate diol composition according to claim 1 .

19. Artificial leather obtained by using the polyurethane according to claim 17 or the water-based polyurethane according to claim 18.

20. A synthetic leather obtained by using the polyurethane according to claim 17 or the water-based polyurethane according to claim 18.

21. A coating obtained by using the polyurethane according to claim 17 or the water-based polyurethane according to claim 18.

22. A coating agent obtained by using the polyurethane according to claim 17 or the water-based polyurethane according to claim 18.

23. A method for storing a polycarbonate diol composition, wherein the polycarbonate diol composition comprises a polycarbonate diol represented by the following formula (A) and a diol component represented by the following formula (B), More than 90 mol% of the total amount of terminal groups of the polycarbonate diol composition are hydroxyl groups, The polycarbonate diol composition has a hydroxyl value of 10 to 400 mgKOH / g, With respect to 100 mass % of the total of the carbonate diol and the diol component, the ratio of the polycarbonate diol is 80 mass % or more and 99.90 mass % or less, and the ratio of the diol component is 0.10 mass % or more and 20 mass % or less, In the molecular weight calculation result of the polycarbonate diol composition measured by gel permeation chromatography (GPC), the area ratio (%) of the polycarbonate diol having a number average molecular weight of 500 or less is 1% or more and 30% or less, In formula (A), R1 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 15 carbon atoms, and a plurality of R1s present may be the same or different from each other, and a is a number of 1 to 50. HO-R2-OH…(B) In formula (B), R2 is a divalent linear or branched aliphatic hydrocarbon group having 2 or more and 5 or less carbon atoms, in, In the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition, the ratio of the diol component represented by formula (B) is 5 mol% or more and 100 mol% or less.

24. A polycarbonate diol composition comprising a polycarbonate diol represented by the following formula (AA) and a diol component represented by the following formula (BB), More than 90 mol% of the total amount of terminal groups of the polycarbonate diol composition are hydroxyl groups, The polycarbonate diol composition has a hydroxyl value of 10 to 400 mgKOH / g, With respect to 100 mass % of the total of the carbonate diol and the diol component, the ratio of the polycarbonate diol is 80 mass % or more and 99.90 mass % or less, and the ratio of the diol component is 0.10 mass % or more and 20 mass % or less, In the molecular weight calculation result of the polycarbonate diol composition measured by gel permeation chromatography (GPC), the area ratio (%) of the polycarbonate diol having a number average molecular weight of 500 or less is 1% or more and 30% or less, In the formula (AA), R11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group which may contain a heteroatom, or a divalent aromatic hydrocarbon group which may contain a heteroatom, and a plurality of R11s which exist may be the same or different from each other, and aa is a number which is greater than or equal to 1 and less than or equal to 50. HO-R22-OH…(BB) In formula (BB), R22 is a divalent linear or branched aliphatic hydrocarbon group having 2 to 5 carbon atoms which may contain a heteroatom, in, In the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition, the ratio of the diol component represented by the formula (BB) is 5 mol% or more and 100 mol% or less.

25. The polycarbonate diol composition according to claim 24, wherein The ratio of the polycarbonate diol is 95% by mass or more and 99.90% by mass or less, and the ratio of the diol component is 0.10% by mass or more and 5% by mass or less.

26. The polycarbonate diol composition according to claim 24, wherein The ratio of the polycarbonate diol is 97% by mass or more and 99.8% by mass or less, and the ratio of the diol component is 0.2% by mass or more and 3% by mass or less.

27. The polycarbonate diol composition according to any one of claims 24 to 26, wherein The hydroxyl value is 20 to 300 mgKOH / g.

28. The polycarbonate diol composition according to any one of claims 24 to 26, wherein The hydroxyl value is 30 to 250 mgKOH / g.

29. The polycarbonate diol composition according to any one of claims 24 to 26, wherein 95 mol % or more and 100 mol % or less of the total amount of the terminal groups are hydroxyl groups.

30. The polycarbonate diol composition according to any one of claims 24 to 26, wherein R11 is a divalent linear aliphatic hydrocarbon group which may contain a heteroatom and has a molecular weight of 30 to 2500 as the R11 substituent, or a divalent branched aliphatic hydrocarbon group which may contain a heteroatom and has a molecular weight of 30 to 2500 as the R11 substituent.

31. The polycarbonate diol composition according to any one of claims 24 to 26, wherein In the molecular weight calculation result calculated by gel permeation chromatography (GPC) measurement of the polycarbonate diol composition, the area ratio (%) of the number average molecular weight of 500 or less is 1% to 20%.

32. The polycarbonate diol composition according to any one of claims 24 to 26, wherein In the molecular weight calculation result of the polycarbonate diol composition calculated by gel permeation chromatography (GPC), the area ratio (%) of the number average molecular weight of 500 or less is 1% to 15%.

33. The polycarbonate diol composition according to any one of claims 24 to 26, wherein In the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition, the ratio of the diol component represented by the formula (BB) is 20 mol% or more and 90 mol% or less.

34. The polycarbonate diol composition according to any one of claims 24 to 26, wherein In the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition, the ratio of the diol component represented by formula (BB) is 30 mol% or more and 70 mol% or less.

35. The polycarbonate diol composition according to any one of claims 24 to 26, wherein In the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition, the ratio of the diol component represented by the formula (BB) is 35 mol% or more and 65 mol% or less.

36. The polycarbonate diol composition according to any one of claims 24 to 26, wherein In the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition, the ratio of the diol component represented by the formula (BB) is 45 mol% or more and 55 mol% or less.

37. The polycarbonate diol composition according to any one of claims 24 to 26, wherein When the polycarbonate diol composition was stored at 5° C. for one week, it had a transparent liquid appearance.

38. A coating composition comprising the polycarbonate diol composition according to any one of claims 24 to 37.

39. A coating film obtained from the coating composition according to claim 38. 40 . A polyurethane obtained by using the polycarbonate diol composition according to claim 24 .

41. A water-based polyurethane obtained by using the polycarbonate diol composition according to any one of claims 24 to 37.

42. Artificial leather obtained by using the polyurethane according to claim 40 or the water-based polyurethane according to claim 41.

43. A synthetic leather obtained by using the polyurethane according to claim 40 or the water-based polyurethane according to claim 41.

44. A coating obtained by using the polyurethane according to claim 40 or the water-based polyurethane according to claim 41.

45. A coating agent obtained by using the polyurethane according to claim 40 or the water-based polyurethane according to claim 41.

46. ​​A method for storing a polycarbonate diol composition, wherein the polycarbonate diol composition comprises a polycarbonate diol represented by the following formula (AA) and a diol component represented by the following formula (BB), More than 90 mol% of the total amount of terminal groups of the polycarbonate diol composition are hydroxyl groups, The polycarbonate diol composition has a hydroxyl value of 10 to 400 mgKOH / g, With respect to 100 mass % of the total of the carbonate diol and the diol component, the ratio of the polycarbonate diol is 80 mass % or more and 99.90 mass % or less, and the ratio of the diol component is 0.10 mass % or more and 20 mass % or less, In the molecular weight calculation result of the polycarbonate diol composition measured by gel permeation chromatography (GPC), the area ratio (%) of the polycarbonate diol having a number average molecular weight of 500 or less is 1% or more and 30% or less, In the formula (AA), R11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group which may contain a heteroatom, or a divalent aromatic hydrocarbon group which may contain a heteroatom, and a plurality of R11s which exist may be the same or different from each other, and aa is a number which is greater than or equal to 1 and less than or equal to 50. HO-R22-OH…(BB) In formula (BB), R22 is a divalent linear or branched aliphatic hydrocarbon group having 2 to 5 carbon atoms which may contain a heteroatom, in, In the dihydroxy compound obtained by hydrolyzing the polycarbonate diol composition, the ratio of the diol component represented by the formula (BB) is 5 mol% or more and 100 mol% or less.

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