Polycarbonate diol composition

Abstract

A polycarbonate diol composition contains a polycarbonate diol having a structure represented by the following general formula (I) and a polycarbonate structure represented by the following general formula (II), wherein the melt viscosity of the polycarbonate diol composition at 50° C. is 1000 to 10000 mPa·s, and the average value of the repetition number n11 in the following general formula (I) is greater than 12.

Description

Technical Field

[0001] The present invention relates to polycarbonate diol compositions. Background Art

[0002] In the past, polyurethane resins were used in a wide range of fields, such as synthetic leather, artificial leather, adhesives, furniture coatings, and automotive coatings. Among the raw materials of polyurethane resins, polyethers, polyesters, and polycarbonates are used as polyol components that react with isocyanates. However, in recent years, the requirements for the resistance of polyurethane resins, such as heat resistance, weather resistance, hydrolysis resistance, solvent resistance, sunscreen resistance, and scratch resistance, have been increasing.

[0003] According to Non-Patent Document 1, generally speaking, as a polyol component, polyether polyol has a low viscosity. Therefore, although polyurethane using polyether polyol has excellent flexibility and hydrolysis resistance, it has poor heat resistance and weather resistance. In addition, although polyurethane using polyester polyol has improved heat resistance and weather resistance, it has poor hydrolysis resistance. In contrast, polyurethane using polycarbonate polyol has the best durability level in terms of durability such as heat resistance, chemical resistance, and hydrolysis resistance.

[0004] For example, Patent Document 1 discloses a method for producing copolymerized polycarbonate diol economically and simply. Also, for example, Patent Document 2 discloses a polycarbonate diol / polyether block copolymer.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 3-252420

[0008] Patent Document 2: Japanese Patent Application Publication No. 2006-124486

[0009] Non-patent literature

[0010] Non-patent document 1: "Polyurethane Material Selection, Structure Control and Modification Case Collection" Items 51 to 62, published by the Technical Information Association, first edition published in December 2014 Summary of the invention

[0011] Problem that the invention aims to solve

[0012] However, polycarbonate polyols have high viscosity and require a large amount of solvent when producing coatings and polyurethanes. Polyurethane resins obtained using polycarbonate diols described in Patent Documents 1 and 2 also have room for improvement in applications requiring strict physical properties such as low-temperature flexibility and durability.

[0013] Therefore, the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polycarbonate diol composition which can reduce the amount of solvent used in the production of coatings and polyurethanes, can obtain a polyurethane having excellent low-temperature flexibility, excellent oleic acid resistance and excellent resistance to moist heat, and can also obtain a coating composition having excellent film-forming properties even at a high solid content concentration.

[0014] Solutions for solving problems

[0015] As a result of intensive studies, the present inventors have found that a polycarbonate diol composition having a specific structure and a melt viscosity at 50° C. within a specific range can reduce the amount of solvent used in the production of coatings and polyurethanes, and can obtain a polyurethane having excellent low-temperature flexibility, excellent oleic acid resistance, and excellent resistance to wet heat, and can also obtain a coating composition having excellent film-forming properties even at a high solid content concentration, thereby completing the present invention.

[0016] That is, the present invention includes the following aspects.

[0017] [1] A polycarbonate diol composition comprising a polycarbonate diol having a structure represented by the following general formula (I) and a polycarbonate structure represented by the following general formula (II),

[0018] The polycarbonate diol composition has a melt viscosity of 1,000 to 10,000 mPa·s at 50° C., and an average value of the repeating number n11 in the following general formula (I) is 12 or more.

[0019]

[0020] (In the general formula (I), R 11 is a divalent linear, branched or cyclic aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms. 11 They can be the same or different. n11 is an arbitrary integer.)

[0021]

[0022] (In the general formula (II), R 21 is a divalent linear, branched or cyclic aliphatic or aromatic hydrocarbon group having 2 to 15 carbon atoms. 21 They are optional and may be the same or different. n21 is an arbitrary integer.)

[0023] [2] The polycarbonate diol composition according to [1], wherein the average value of the repeating number n11 in the general formula (I) is 15 or more.

[0024] [3] The polycarbonate diol composition according to [1] or [2], wherein in at least a portion of the polycarbonate diol, R in the general formula (II) 21 They are at least two or more selected from the group consisting of divalent linear and branched aliphatic hydrocarbon groups having 2 to 15 carbon atoms.

[0025] [4] The polycarbonate diol composition according to any one of [1] to [3], wherein R in the general formula (I) 11 The content of the structure which is a linear and / or branched divalent aliphatic hydrocarbon group having 3 carbon atoms in the structure represented by the above general formula (I) is 60% by mass or more and 95% by mass or less.

[0026] [5] The polycarbonate diol composition according to any one of [1] to [4], wherein the content of the structure represented by the general formula (I) is 5% by mass or more and 40% by mass or less, and the content of the polycarbonate structure represented by the general formula (II) is 60% by mass or more and 95% by mass or less, relative to the total mass of the structure represented by the general formula (I) and the polycarbonate structure represented by the general formula (II).

[0027] [6] The polycarbonate diol composition according to any one of [1] to [5], wherein the glass transition temperature measured by a differential scanning calorimeter is -50°C or lower.

[0028] [7] The polycarbonate diol composition according to any one of [1] to [6], which is liquid and transparent at 23°C.

[0029] [8] The polycarbonate diol composition according to any one of [1] to [7], wherein, in the molecular weight calculation result of the polycarbonate diol composition calculated by gel permeation chromatography, the area ratio (%) of the number average molecular weight (Mn) below 1000 is 7% or less.

[0030] [9] A polyurethane produced using the polycarbonate diol composition according to any one of [1] to [8].

[0031]

[10] A synthetic leather comprising a base fabric, an adhesive layer, an intermediate layer and a surface layer laminated in this order, comprising the polyurethane described in [9].

[0032] Effects of the Invention

[0033] The polycarbonate diol composition of the present invention can reduce the amount of solvent used in producing coatings and polyurethanes, and can obtain polyurethanes having excellent low-temperature flexibility, excellent oleic acid resistance, and excellent moist heat resistance. In addition, it can obtain coating compositions having excellent film-forming properties even at high solid content concentrations. DETAILED DESCRIPTION

[0034] Hereinafter, this specific embodiment (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 various modifications can be made within the scope of the gist thereof.

[0035] [Polycarbonate diol composition]

[0036] The polycarbonate diol composition of the present embodiment contains a polycarbonate diol having a structure represented by the following general formula (I) (hereinafter sometimes referred to as "structure (I)") and a polycarbonate structure represented by the following general formula (II) (hereinafter sometimes referred to as "polycarbonate structure (II)") in the molecular chain, and the average value of the repetition number n11 in the following general formula (I) is greater than 12.

[0037]

[0038] (In the general formula (I), R 11 is a divalent linear, branched or cyclic aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms. 11 They can be the same or different. n11 is an arbitrary integer.)

[0039]

[0040] (In the general formula (II), R 21 is a divalent linear, branched or cyclic aliphatic or aromatic hydrocarbon group having 2 to 15 carbon atoms. 21 They are optional and may be the same or different. n21 is an arbitrary integer.)

[0041] [Structure (I)]

[0042] In the polycarbonate diol composition of the present embodiment, the content of structure (I) is preferably 5 mass % to 40 mass %, more preferably 10 mass % to 35 mass %, based on the total mass of structure (I) and polycarbonate structure (II).

[0043] When the content of structure (I) is greater than or equal to the above lower limit, the viscosity of the polycarbonate diol composition tends to be lowered. In addition, when the content of structure (I) is less than or equal to the above upper limit, a polyurethane having better durability such as chemical resistance and moisture and heat resistance can be obtained, which is preferred.

[0044] In the polycarbonate diol used in the present embodiment, the terminal structure of structure (I) is a terminal structure in which one terminal is bonded to a carbonate group and the other terminal is bonded to a hydroxyl group, a terminal structure in which both terminals are bonded to a carbonate group, or a terminal structure in which both terminals are bonded to a hydroxyl group.

[0045] In the polycarbonate diol used in the present embodiment, the terminal structure of structure (I) may be a mixture of a terminal structure in which one terminal is bonded to a carbonate group and the other terminal is bonded to a hydroxyl group and a terminal structure in which both terminals are bonded to carbonate groups.

[0046] Next, the details of structure (I) are described below.

[0047] (R 11 )

[0048] In the general formula (I), R 11 is a divalent linear, branched or cyclic aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms. 11 Optional same or different.

[0049] As R 11 The divalent straight-chain aliphatic hydrocarbon group in has 2 or more and 20 or less carbon atoms, preferably 2 or more and 12 or less, and more preferably 2 or more and 6 or less carbon atoms.

[0050] As R 11 Specific examples of the divalent straight-chain aliphatic hydrocarbon group in are not particularly limited, and examples thereof include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptylene, and octylene.

[0051] As R 11 The divalent branched aliphatic hydrocarbon group in has 3 or more and 20 or less carbon atoms, preferably 3 or more and 12 or less, and more preferably 3 or more and 6 or less carbon atoms.

[0052] As R 11 Specific examples of the divalent branched aliphatic hydrocarbon group in are not particularly limited, and examples thereof include isopropylene, isobutylene, tert-butylene, isopentylene, 2,2-dimethyltrimethylene, isohexylene, isoheptylene, and isooctylene.

[0053] As R 11 The divalent cyclic aliphatic hydrocarbon group in has 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and more preferably 6 to 8 carbon atoms.

[0054] As R 11Specific examples of the divalent cyclic aliphatic hydrocarbon group in are not particularly limited, and examples thereof include cyclobutylene, cyclopentylene, cyclohexylene, and cycloheptylene.

[0055] As R 11 The divalent aromatic hydrocarbon group in has 6 or more and 15 or less carbon atoms, preferably 6 or more and 12 or less carbon atoms, and more preferably 6 or more and 10 or less carbon atoms.

[0056] As R 11 Specific examples of the divalent aromatic hydrocarbon group in are not particularly limited, and examples thereof include phenylene and naphthylene.

[0057] Among them, as R 11 , preferably a divalent linear, branched or cyclic aliphatic hydrocarbon group (i.e., an alkylene group) having 2 to 20 carbon atoms, more preferably a divalent linear aliphatic hydrocarbon group having 2 to 6 carbon atoms, and / or a divalent branched aliphatic hydrocarbon group having 3 to 6 carbon atoms. In particular, if R 11 When a divalent branched aliphatic hydrocarbon group is contained, there is a tendency to obtain a polyurethane having better low-temperature properties and durability such as chemical resistance and moisture and heat resistance.

[0058] In addition, R in the general formula (I) 11 The content of the structure of the straight-chain and / or branched divalent aliphatic hydrocarbon group having 3 carbon atoms in the structure represented by the general formula (I) is preferably 60% by mass or more and 95% by mass or less, and more preferably 70 to 95% by mass. 11 When the content ratio of the structure which is a linear and / or branched divalent aliphatic hydrocarbon group having 3 carbon atoms is within the above range, there is a tendency that a polyurethane having excellent transparency and further excellent low-temperature characteristics can be obtained.

[0059] It should be noted that, in this embodiment, R in the general formula (I) of the polycarbonate diol 11 The ratio of the structure which is a linear and / or branched divalent aliphatic hydrocarbon group having 3 carbon atoms can be determined by the following method.

[0060] The sample was dissolved in deuterated chloroform (manufactured by Aldrich) to obtain a 3 wt / vol% solution. Tetramethylsilane (TMS) was added to the solution as a chemical shift standard, and the obtained solution was measured using JNM-ECA500 manufactured by JEOL Ltd. 1 In this measurement, the resonance frequency was set to 500 MHz, the number of accumulations was set to 128, and the TMS signal was set to 0 ppm. 1The H-NMR spectrum can be used to determine the ratio of structures belonging to linear and / or branched divalent aliphatic hydrocarbon groups having 3 carbon atoms.

[0061] (n11)

[0062] In the general formula (I), n11 represents a structure (-R 11 In the general formula (I), n11 is an arbitrary integer, but the average value of n11 in the entire polycarbonate diol composition of the present embodiment is 12 or more, preferably in the range of 12 or more and 70 or less, more preferably in the range of 12 or more and 60 or less, and particularly preferably in the range of 15 or more and 50 or less.

[0063] By making the average value of n11 in the entire polycarbonate diol composition of the present embodiment greater than or equal to the above lower limit, a polyurethane having better flexibility and low-temperature flexibility tends to be obtained. In addition, by making the average value of n11 in the entire polycarbonate diol composition of the present embodiment less than or equal to the above upper limit, the viscosity of the polycarbonate diol composition tends to become lower.

[0064] The above n11 can be determined by alkali decomposing the polycarbonate diol composition to extract the raw material diol component and subjecting the component to GC-MS measurement, LC-MS measurement and gel permeation chromatography (GPC) measurement. Specifically, it can be determined by the method described in the examples below.

[0065] Among them, as structure (I), a polyoxyalkylene structure is preferred.

[0066] Specific examples of preferred oxyalkylene groups included in structure (I) are not particularly limited, and examples thereof include oxyethylene, oxy-1-methylethylene, oxytetramethylene, oxy-2,2-dimethyltrimethylene, etc. Among them, a structure containing oxy-1-methylethylene is preferred, and oxy-1-methylethylene and oxyethylene are particularly preferred. By making the preferred oxyalkylene group included in structure (I) the above structure, there is a tendency that the polycarbonate diol composition is liquid at room temperature due to the introduction of a side chain methyl group, and has excellent workability, and the obtained polyurethane has excellent flexibility and low temperature characteristics.

[0067] When the structure (I) contains oxy-1-methylethylene and oxyethylene, it is preferred that the oxy-1-methylethylene is contained in an amount of 60% by mass or more and 95% by mass or less and 5% by mass or more and 40% by mass or less relative to the total mass of the structure (I). When the ratio of oxy-1-methylethylene is equal to or greater than the above lower limit, the low temperature properties of the polyurethane tend to be excellent, and when the ratio is equal to or less than the above upper limit, the breaking strength of the polyurethane film tends to be excellent.

[0068] [Polycarbonate structure (II)]

[0069] In the polycarbonate diol composition of the present embodiment, the content of the polycarbonate structure (II) is preferably 60% by mass or more and 95% by mass or less, and more preferably 65% ​​by mass or more and 90% by mass or less, based on the total mass of the structure (I) and the polycarbonate structure (II).

[0070] By making the content of the polycarbonate structure (II) not less than the above lower limit, a polyurethane having better resistance to moisture and heat, chemical resistance, etc. can be obtained. In addition, by making the content of the polycarbonate structure (II) not more than the above upper limit, the viscosity of the polycarbonate diol composition tends to become lower.

[0071] Next, the details of the polycarbonate structure (II) will be described below.

[0072] (R 21 )

[0073] In the general formula (II), R 21 is a divalent linear, branched or cyclic aliphatic or aromatic hydrocarbon group having 2 to 15 carbon atoms. 21 Optional same or different.

[0074] As R 21 The divalent straight-chain aliphatic hydrocarbon group in has 2 or more and 15 or less carbon atoms, preferably 3 or more and 12 or less carbon atoms, and more preferably 3 or more and 10 or less carbon atoms.

[0075] As R 21 The divalent straight-chain aliphatic hydrocarbon group having 2 or more and 15 or less carbon atoms in the formula (C) may be specifically exemplified by the above R 11 Among them, a butylene group, a pentylene group or a hexylene group is preferred from the viewpoint of versatility.

[0076] As R 21 The divalent branched aliphatic hydrocarbon group in has 3 or more and 15 or less carbon atoms, preferably 3 or more and 12 or less carbon atoms, and more preferably 3 or more and 10 or less carbon atoms.

[0077] As R 21 The divalent branched aliphatic hydrocarbon group having 2 or more and 15 or less carbon atoms in the above R 11 Among them, isopentylene or isohexylene is preferred from the viewpoint of versatility.

[0078] As R 21 The divalent cyclic aliphatic hydrocarbon group in has 3 or more and 15 or less carbon atoms, preferably 6 or more and 15 or less carbon atoms, and more preferably 6 or more and 10 or less carbon atoms.

[0079] As R 21 Specific examples of the divalent cyclic aliphatic hydrocarbon group in the formula (a) include the group consisting of the group R 11 Among them, cyclohexylene is preferred from the viewpoint of versatility.

[0080] As R 21 The divalent aromatic hydrocarbon group in has 6 or more and 15 or less carbon atoms, preferably 6 or more and 12 or less carbon atoms, and more preferably 6 or more and 10 or less carbon atoms.

[0081] As R 21 Specific examples of the divalent aromatic hydrocarbon group in the formula (a) include the group consisting of the group R 11 The same groups as exemplified in .

[0082] Among them, as R 21 , preferably a divalent straight-chain aliphatic hydrocarbon group having 3 to 10 carbon atoms, or a divalent branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, more preferably a divalent straight-chain aliphatic hydrocarbon group having 4 to 6 carbon atoms, further preferably a divalent straight-chain aliphatic hydrocarbon group of butylene and hexylene.

[0083] In the polycarbonate diol composition of the present embodiment, it is preferred that at least a part of the polycarbonate diol has R 21 They are at least two or more selected from the group consisting of divalent linear and branched aliphatic hydrocarbon groups having a carbon number of 2 to 15. In this case, a polycarbonate diol composition that is liquid at room temperature tends to be obtained.

[0084] It should be noted that in this embodiment, R in the general formula (II) of the polycarbonate diol 21 The composition can be determined by the following method.

[0085] First, weigh 1 g of the sample into a 100 ml eggplant flask, add 30 g of ethanol and 4 g of potassium hydroxide to obtain a mixture. Heat the obtained mixture in an oil bath at 100°C for 1 hour. After cooling the mixture to room temperature, add 1 to 2 drops of phenolphthalein as an indicator to the mixture and neutralize it with hydrochloric acid. Thereafter, cool the mixture in a refrigerator for 3 hours, remove the precipitated salt by filtration, and analyze the filtrate by gas chromatography (hereinafter referred to as GC) using the following analysis conditions. Based on the area value of the diol compound obtained by GC analysis, it is possible to determine R in the general formula (II) in the polycarbonate diol. 21 composition.

[0086] (n21)

[0087] In the general formula (II), n21 represents a carbonate structure (-R 21 n21 is an arbitrary integer, and the average value of n21 in the polycarbonate diol composition of the present embodiment as a whole is preferably in the range of 1 to 50, more preferably in the range of 2 to 50, further preferably in the range of 3 to 30, and particularly preferably in the range of 4 to 20.

[0088] n21 can be determined by alkali decomposing the polycarbonate diol composition to extract the raw material diol component, and subjecting the component to GC-MS measurement, LC-MS measurement, and GPC measurement. Specifically, n21 can be determined by the method described in the examples below.

[0089] In the polycarbonate diol composition of the present embodiment, the content of the structure represented by the general formula (I) and the content of the polycarbonate structure (II) can be measured by, for example, the methods described in the following (1) to (4).

[0090] (1) The polycarbonate diol composition is subjected to alkaline hydrolysis in an alcoholic potassium hydroxide solution to regenerate the diol component.

[0091] (2) Use phenolphthalein as an indicator and add hydrochloric acid for neutralization.

[0092] (3) The precipitated salt is collected by filtration, and the filtrate is subjected to gel permeation chromatography (hereinafter sometimes abbreviated as GPC) measurement.

[0093] (4) The concentration of the diol having a structure represented by the general formula (I) and having hydroxyl groups at both ends in the filtrate is determined from a separately prepared standard curve. The mass of the diol having a structure represented by the general formula (I) and having hydroxyl groups at both ends is calculated from the concentration, and the value obtained by dividing the mass of the polycarbonate diol composition used in the alkaline hydrolysis is the content of the diol having a structure represented by the general formula (I) and having hydroxyl groups at both ends.

[0094] In addition, the terminal structure of the structure represented by general formula (I) in the polycarbonate diol composition is: a terminal structure in which one terminal is bonded to a carbonate group (-O-CO-O-) and the other terminal is bonded to a hydroxyl group (-OH), a terminal structure in which both terminals are bonded to a carbonate group (-O-CO-O-), or a terminal structure in which both terminals are bonded to a hydroxyl group (-OH).

[0095] In addition, both terminals of the molecule having the structure represented by the general formula (I) in the polycarbonate diol composition are hydroxyl groups.

[0096] The two ends of the molecule with a polycarbonate structure contained in the polycarbonate diol composition are hydroxyl groups. That is, the molecule with a polycarbonate structure contained in the polycarbonate diol composition is polycarbonate diol. There are also cases where a portion of the terminal hydroxyl groups are converted into alkyl groups, aryl groups, etc. that do not react with isocyanate groups due to impurities in various raw materials used in the manufacture of the polycarbonate diol composition, terminal structures produced as byproducts in the manufacture of the polycarbonate diol composition, or in order to control the urethanization reaction rate and state of the polycarbonate diol composition in its use. This situation is also taken into account in the present embodiment, and also includes the case where the terminal groups of the above-mentioned polycarbonate diol are not strictly 100 mol% of both ends are hydroxyl groups. From this viewpoint, the ratio of hydroxyl groups to the total molar amount of terminal groups is preferably 90 mol% or more, more preferably 95 mol% or more.

[0097] The two terminal structures of the polycarbonate diol contained in the polycarbonate diol composition can be confirmed by the method for measuring the terminal primary OH ratio described in Japanese Patent No. 3874664 (Reference 1). As the solvent for recovering the fraction, tetrahydrofuran, acetone, methanol and the like can be used in addition to ethanol.

[0098] [Melt viscosity at 50°C]

[0099] The melt viscosity at 50° C. of the polycarbonate diol composition of the present embodiment measured with an E-type viscometer (hereinafter referred to as “melt viscosity at 50° C.”) is 1,000 to 10,000 mPa·s, preferably 2,000 to 9,600 mPa·s, and more preferably 2,500 to 9,600 mPa·s.

[0100] By setting the melt viscosity at 50°C to be above the above lower limit, when a coating or polyurethane using the polycarbonate diol composition of the present embodiment is formed into a coating film, there is a tendency to suppress repulsion and surface unevenness, and excellent film-forming properties. By setting the melt viscosity at 50°C to be below the above upper limit, the amount of solvent used in the manufacture of the coating or polyurethane can be reduced. Here, "repulsion" refers to a phenomenon such as water repellency in which the coating is repelled from the surface of the substrate.

[0101] The method for controlling the melt viscosity at 50° C. to the above range is not particularly limited, and it can be achieved by, for example, adjusting the ratio of the structure represented by the general formula (I) and the polycarbonate structure (II) and the number average molecular weight of the polycarbonate diol composition.

[0102] The melt viscosity at 50° C. tends to decrease as the proportion of the structure represented by the general formula (I) increases, and the melt viscosity at 50° C. tends to increase as the proportion of the polycarbonate structure (II) increases.

[0103] When the viscosity is adjusted by the number average molecular weight of the polycarbonate diol composition, the smaller the number average molecular weight of the polycarbonate diol composition, the smaller the melt viscosity at 50°C, and the larger the number average molecular weight of the polycarbonate diol composition, the larger the melt viscosity at 50°C.

[0104] The number average molecular weight of the polycarbonate diol composition used in the present embodiment is preferably 300 or more and 10,000 or less, more preferably 400 or more and 10,000 or less, and further preferably 850 or more and 3,000 or less.

[0105] When the number average molecular weight of the polycarbonate diol composition used in the present embodiment is high, the melt viscosity at 50° C. tends to be high but the flexibility when made into polyurethane tends to be good. On the other hand, when the number average molecular weight of the polycarbonate diol composition used in the present embodiment is low, the melt viscosity at 50° C. tends to be low but the flexibility tends to be poor due to the increase in the amount of urethane bonds.

[0106] In the present embodiment, the number average molecular weight can be calculated from the hydroxyl value of the polycarbonate diol composition using the method described in Examples below.

[0107] [Glass transition temperature (Tg)]

[0108] The polycarbonate diol composition of the present embodiment has a glass transition temperature (Tg) measured by a differential scanning calorimeter (hereinafter sometimes abbreviated as "DSC") of preferably -50°C or less, more preferably -55°C or less, and more preferably -57°C or more. By making the glass transition temperature (Tg) of the polycarbonate diol composition of the present embodiment below the above upper limit, there is a tendency for the flexibility under low temperature conditions when the polyurethane is prepared to be improved. The lower limit of the glass transition temperature (Tg) of the polycarbonate diol composition of the present embodiment is not particularly limited, and for example, -90°C can be cited.

[0109] The method for obtaining a polycarbonate diol composition having a glass transition temperature (Tg) within the above range is not particularly limited, and examples thereof include a method of adjusting the ratio, type, number average molecular weight, and other conditions of the structure represented by the general formula (I) and the polycarbonate structure (II) by comprehensive consideration.

[0110] [Properties]

[0111] The polycarbonate diol composition of the present embodiment is preferably liquid and transparent at 23° C. Since the polycarbonate diol composition of the present embodiment is liquid and transparent at 23° C., which is a normal temperature, when used as a component of a coating, even when used in a clear coating, the composition has little white turbidity, so that there are few restrictions on the application.

[0112] The method for obtaining a polycarbonate diol composition that is liquid and transparent at 23° C. is not particularly limited, and examples thereof include a method of appropriately selecting the type and amount of raw materials of the polycarbonate diol composition.

[0113] The transparency evaluation is not particularly limited, and can be measured, for example, using a turbidity meter based on an integrating sphere photoelectric photometry.

[0114] <Method for producing polycarbonate diol composition>

[0115] The polycarbonate diol composition of the present embodiment can be obtained by using an ether diol represented by the following general formula (I-1) (hereinafter sometimes referred to as “ether diol (I-1)”) and a polycarbonate diol represented by the following general formula (II-1) (hereinafter sometimes referred to as “polycarbonate diol (II-1)”) and performing an ester exchange reaction.

[0116]

[0117] (In the general formula (I-1), R 111 With the above R 11 Same. n111 is the same as n11 above. )

[0118]

[0119] (In the general formula (I-1), R 211 and R 212 Respectively with the above R 21 Same. n211 is the same as n21 above. )

[0120] [Ether diol (I-1)]

[0121] As the ether diol (I-1) used for manufacturing the polycarbonate diol composition of the present embodiment, any ether diol having the structure represented by the above general formula (I-1) can be used. Among them, as ether diol (I-1), polyoxyalkylene glycol having two terminal primary hydroxyl groups is preferred. Ether diol (I-1) is commercially available in products of various molecular weights, and such commercial products can also be used. Commercial products of ether diol (I-1) include, for example, polyoxyalkylene glycols such as the "NEWPOL" series, "PRIMEPOL" series, and "SANNIX" series manufactured by Sanyo Chemical Industries, Ltd.; the "PRONON" series manufactured by NOF Corporation; the "PREMINOL" and "EXCENOL" series manufactured by AGC Corporation; and the "PTMG" series manufactured by Mitsubishi Chemical Corporation.

[0122] The number average molecular weight of the ether diol (I-1) is not particularly limited, but is preferably 400 to 3000, more preferably 600 to 2000. By making the number average molecular weight of the ether diol (I-1) used in the manufacture above the above lower limit, the amount of the raw material ether diol (I-1) can be further reduced. Furthermore, there is a tendency that the moisture heat resistance and chemical resistance of the polyurethane obtained from the polycarbonate diol composition of the present embodiment are further improved. By making the number average molecular weight of the ether diol (I-1) used in the manufacture below the above upper limit, there is a tendency that the crystallinity of the polycarbonate diol composition of the present embodiment is further suppressed.

[0123] [Polycarbonate diol (II-1)]

[0124] As the polycarbonate diol (II-1) used to manufacture the polycarbonate diol composition of the present embodiment, any polycarbonate diol having a structure represented by the above general formula (II-1) can be used. There is no particular limitation on the method for manufacturing the polycarbonate diol (II-1), and a known method can also be used. For example, a carbonate compound and a diol compound are reacted in the presence of an ester exchange catalyst to obtain the polycarbonate diol (II-1).

[0125] (Carbonate Compound)

[0126] The carbonate compound used for producing the polycarbonate diol (II-1) is not limited to the following compounds, and examples thereof include alkylene carbonates, dialkyl carbonates, and diaryl carbonates.

[0127] 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.

[0128] The dialkyl carbonate is not particularly limited, and examples thereof include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate.

[0129] The diaryl carbonate is not particularly limited, and examples thereof include diphenyl carbonate.

[0130] Among them, as the carbonate compound used for producing the polycarbonate diol (II-1), alkylene carbonate is preferred, and ethylene carbonate is more preferred.

[0131] (Diol compound)

[0132] The diol compound used for producing the polycarbonate diol (II-1) is not limited to the following compounds, and examples thereof include linear diols, branched diols, cyclic diols, and diols having an aromatic ring.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] The diol having an aromatic ring is not particularly limited, and examples thereof include terephthalylidene alcohol, tetrachloroterephthalylidene alcohol, 1,4-bis(hydroxyethoxy)benzene, and 2,2-bis[(4-hydroxyethoxy)phenyl]propane.

[0137] Among them, a linear or branched diol having 3 to 10 carbon atoms is preferred, 1,4-butanediol, 1,5-pentanediol, or 1,6-hexanediol is more preferred, and 1,4-butanediol and 1,6-hexanediol are further preferred.

[0138] [Production Conditions of Polycarbonate Diol Composition and Polycarbonate Diol (II-1)]

[0139] When producing the polycarbonate diol (II-1) as a raw material, a transesterification catalyst may be used. The catalyst may be selected from common transesterification catalysts.

[0140] The transesterification catalyst is not particularly limited, and examples thereof include alkali metals and alkaline earth metals, and alkoxides thereof, hydrides thereof, oxides thereof, amides thereof, hydroxides thereof, and salts thereof.

[0141] 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.

[0142] The alkali metal is not particularly limited, and examples thereof include lithium, sodium, and potassium.

[0143] The alkaline earth metal is not particularly limited, and examples thereof include magnesium, calcium, strontium, and barium.

[0144] 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.

[0145] 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.

[0146] These transesterification catalysts may be used alone or in combination of two or more.

[0147] Among them, as the transesterification reaction catalyst, from the viewpoint of more favorable transesterification reaction to obtain polycarbonate diol and less influence on urethane reaction when the obtained polycarbonate diol is used, 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.

[0148] Furthermore, as the transesterification reaction catalyst, at least one metal selected from the group consisting of magnesium, titanium, ytterbium, tin and zirconium is more preferred.

[0149] Specific examples of preferred transesterification catalysts are not particularly limited, and examples thereof include organic compounds of magnesium, organic compounds of lead, and organic compounds of titanium.

[0150] The organic compound of magnesium is not particularly limited, and examples thereof include magnesium acetate tetrahydrate and magnesium acetate anhydrate.

[0151] The organic lead compound is not particularly limited, and examples thereof include lead acetate trihydrate, tetraphenyl lead, and lead stearate.

[0152] The organic titanium compound is not particularly limited, and examples thereof include titanium tetra-n-butoxide, titanium tetra-n-propoxide, and titanium tetraisopropoxide.

[0153] 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.

[0154] In the case where a heat treatment is performed after the production of the polycarbonate diol, the transesterification catalyst used in the transesterification reaction is not consumed by the transesterification reaction, and therefore, the amount of metal contained in the transesterification catalyst can be calculated based on the amount of the transesterification catalyst used. In the case of using commercially available polycarbonate diol, the amount of metal contained in the transesterification catalyst in the polycarbonate diol can be measured by ICP (Inductively Coupled Plasma).

[0155] The polycarbonate diol (II-1) used for producing the polycarbonate diol composition of the present embodiment may contain a catalyst poison such as a phosphoric acid ester compound in order to deactivate the transesterification catalyst used in the production.

[0156] When the polycarbonate diol (II-1) as a raw material contains a catalyst poison of the transesterification reaction catalyst used in its production, there is generally a tendency that the ether diol (I-1) and the polycarbonate diol (II-1) are not likely to undergo a transesterification reaction. Therefore, when producing the polycarbonate diol composition of the present embodiment, a necessary amount of the transesterification reaction catalyst may be newly added.

[0157] On the other hand, when the polycarbonate diol (II-1) 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 usually easy to occur. However, in the case where it is desired to further reduce the reaction temperature in the production process of the polycarbonate diol composition of the present embodiment, in the case where it is desired to further shorten the reaction time, etc., a necessary amount of transesterification reaction catalyst may be newly added. In this case, the same catalyst as the transesterification reaction catalyst used in the production of the polycarbonate diol (II-1) as a raw material may be used.

[0158] The polycarbonate diol (II-1) used for producing the polycarbonate diol composition of the present embodiment may be a homopolycarbonate diol obtained from one diol compound or a copolymer polycarbonate diol obtained from two or more diol compounds.

[0159] The polycarbonate diol composition can be obtained by using any of the polycarbonate diols (II-1) exemplified above and subjecting it to an ester exchange reaction with the ether diol (I-1).

[0160] However, for example, homopolycarbonate diol obtained using 1,6-hexanediol which is widely used in the market is generally solid at room temperature. Therefore, there is a tendency that the polycarbonate diol composition obtained by the transesterification reaction of the homopolycarbonate diol and the ether diol (I-1) is also solid at room temperature.

[0161] On the other hand, for example, a copolymer polycarbonate diol obtained by using any two of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol is liquid at room temperature. Therefore, there is a tendency that the polycarbonate diol composition obtained by the transesterification reaction of the copolymer polycarbonate diol and the ether diol (I-1) is also liquid at room temperature.

[0162] The number average molecular weight of the polycarbonate diol (II-1) used for producing the polycarbonate diol composition of the present embodiment is not particularly limited, but is preferably 500 or more and 5000 or less, and more preferably 1000 or more and 3000 or less.

[0163] By making the number average molecular weight of the polycarbonate diol (II-1) be greater than the above lower limit, there is a tendency that the performance expected of the polycarbonate diol composition is further improved. On the other hand, by making the number average molecular weight of the polycarbonate diol (II-1) be less than the above upper limit, there is a tendency that the viscosity of the polycarbonate diol composition can be more effectively suppressed and the handling properties can be further improved.

[0164] The method for producing the polycarbonate diol composition of the present embodiment is not particularly limited, but the composition is preferably produced by an ester exchange reaction using the ether diol (I-1) and the polycarbonate diol (II-1).

[0165] Specifically, the transesterification reaction can be carried out by mixing the ether diol (I-1) and the polycarbonate diol (II-1), and stirring the mixture while heating.

[0166] The temperature of the transesterification reaction is not particularly limited, but is preferably 120°C or higher and 200°C or lower, and more preferably 140°C or higher and 180°C or lower.

[0167] 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 coloring of the obtained polycarbonate diol composition can be more effectively prevented.

[0168] 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.

[0169] [Area ratio of number average molecular weight 1000 or less (%)]

[0170] For the polycarbonate diol composition used in the present embodiment, in the molecular weight calculation result calculated by GPC measurement, the area ratio (%) of the number average molecular weight below 1000 is preferably 7% or less, and more preferably 6% or less. The lower limit of the area ratio (%) of the number average molecular weight below 1000 is not particularly limited, and is, for example, 0.5%. If the area ratio (%) of the number average molecular weight below 1000 is within the aforementioned range, there is a tendency for the softness of the obtained polyurethane to be further improved. As a method for controlling the number average molecular weight of the polycarbonate diol composition, it is preferred that: for example, in the presence of a small amount of diol as a raw material of the polycarbonate diol (II-1), polycarbonate diol (II-1) and ether diol (I-1) are used to simultaneously carry out ester exchange reaction and depolymerization; in the presence of one or more ether diols (I-1), an ester exchange reaction is carried out, etc.

[0171] 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 ether diol (I-1) gradually decreases over time and disappears, thereby confirming that the structure derived from the ether diol (I-1) is bonded to the end of the raw material polycarbonate diol (II-1) and the inside of the polymer chain.

[0172] In the method for producing the polycarbonate diol composition of the present embodiment, a step of dehydrating the raw materials used may be performed as a pretreatment before the above-mentioned transesterification reaction.

[0173] In the method for producing the polycarbonate diol composition of the present embodiment, after the above-mentioned transesterification reaction, a step of adding the above-mentioned catalyst poison for the transesterification reaction catalyst as a post-treatment may be performed.

[0174] The polycarbonate diol composition of the present embodiment may also contain ether diol (I-1) and polycarbonate diol (II-1) as raw materials. In the polycarbonate diol composition of the present embodiment, the content of these compounds is arbitrary, preferably 1% by mass or more and 99% by mass or less, more preferably 5% by mass or more and 95% by mass or less, and further preferably 10% by mass or more and 80% by mass or less. In addition, the diol compound as the raw material of the polycarbonate diol (II-1) may be further contained within the range that does not impair the effect. The determination method of these compounds can be determined by LC-MS determination.

[0175] [use]

[0176] The polycarbonate diol composition of the present embodiment can be used as a raw material for polyurethane for reacting with polyisocyanate, and the polyurethane has excellent chemical resistance, heat resistance, and weather resistance, and therefore can be widely used in foams, elastomers, coatings, coating agents, adhesives, adhesives, artificial leather, synthetic leather, water-based polyurethane coatings, etc. Furthermore, it can be used for applications such as a modifier for polyesters and polyimides.

[0177] [Polyurethane]

[0178] The polyurethane of the present embodiment is produced using the above-mentioned polycarbonate diol composition.

[0179] The method for producing the polyurethane of the present embodiment can use known polyurethane reaction conditions for generally producing polyurethane.

[0180] Examples thereof include: a method in which the above-mentioned polycarbonate diol composition, other polyols, polyisocyanates and chain extenders are mixed together and reacted (hereinafter sometimes referred to as the "one-step method"); a method in which the above-mentioned polycarbonate diol composition, other polyols and polyisocyanates are first reacted to prepare a prepolymer having isocyanate groups at both ends, and then the prepolymer is reacted with a chain extender (hereinafter sometimes referred to as the "prepolymer method"); and the like.

[0181] The isocyanate compound contained in the polyurethane of the present embodiment is not particularly limited as long as it functions as a curing agent, and a compound having two or more isocyanate groups at the terminal is used.

[0182] Such isocyanate compounds are not particularly limited, and examples thereof include linear aliphatic diisocyanates, cyclic aliphatic diisocyanates, aromatic diisocyanates, isocyanate compounds having three or more isocyanate groups, and isocyanurate-modified products and biuret-modified products of these isocyanate compounds.

[0183] The chain aliphatic diisocyanate is not particularly limited, and examples thereof include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

[0184] The cyclic aliphatic diisocyanate is not particularly limited, and examples thereof include isophorone diisocyanate.

[0185] The aromatic diisocyanate is not particularly limited, and examples thereof include toluene diisocyanate, 4,4′-diphenylmethane diisocyanate (hereinafter sometimes abbreviated as “MDI”), xylylene diisocyanate, and naphthalene diisocyanate.

[0186] The isocyanate compound having three or more isocyanate groups is not particularly limited, and examples thereof include triphenylmethane-4,4'-4"-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, and 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate.

[0187] As the isocyanate compound, a commercially available product may be used, or the isocyanate compound may be synthesized by a known method.

[0188] The content of the isocyanate compound can be appropriately adjusted according to the molar amount of the hydroxyl group of the polyol as the main agent. Specifically, the molar ratio (NCO / OH) of the isocyanate group of the isocyanate compound relative to the hydroxyl group of the polycarbonate diol can be set to, for example, more than 0.2 and less than 5.0, for example, more than 0.4 and less than 3.0, for example, more than 0.5 and less than 2.0. If NCO / OH is above the above lower limit, there is a tendency to obtain a tougher coating. On the other hand, if NCO / OH is below the above upper limit, there is a tendency that the smoothness of the coating is further improved.

[0189] The chain extender used when producing the polyurethane of the present embodiment is not particularly limited, and examples thereof include common polyols and polyamines.

[0190] The polyol is not particularly limited, and examples thereof include linear diols, branched diols, cyclic diols, and diols having an aromatic ring.

[0191] The linear diol is not particularly limited, and examples thereof include ethylene glycol, 1,3-propylene glycol, 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.

[0192] 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.

[0193] 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.

[0194] The diol having an aromatic ring is not particularly limited, and examples thereof include terephthalylidene alcohol, tetrachloroterephthalylidene alcohol, 1,4-bis(hydroxyethoxy)benzene, and 2,2-bis[(4-hydroxyethoxy)phenyl]propane.

[0195] The polyamine is not particularly limited, and examples thereof include hydroxyamines and polyamines.

[0196] The hydroxyamines are not particularly limited, and examples thereof include N-methylethanolamine and N-ethylethanolamine.

[0197] The polyamines are not particularly limited, and examples thereof include ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4′-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4,4′-diphenylmethanediamine, methylenebis(o-chloroaniline), xylylenediamine, diphenyldiamine, toluenediamine, hydrazine, piperazine, and N,N′-diaminopiperazine.

[0198] These chain extenders may be used alone or in combination of two or more.

[0199] The synthetic leather of the present embodiment is a synthetic leather having a base fabric, an adhesive layer, an intermediate layer and an epidermis layer laminated in sequence, and contains the above-mentioned polyurethane. In the synthetic leather of the present embodiment, the above-mentioned polyurethane is preferably contained in the adhesive layer and / or the intermediate layer, and the synthetic leather of the present embodiment is preferably used to reduce the amount of organic solvent used during manufacturing by containing the above-mentioned polyurethane.

[0200] [Paint or coating composition]

[0201] The coating material or coating agent composition (coating material) of the present embodiment is obtained by using the above-mentioned polycarbonate diol composition.

[0202] As a method for producing a coating or coating composition (coating) using the polycarbonate diol composition, a production method known in the industry can be used. For example, the following compositions can be produced: a two-component solvent-based coating composition in which a coating main agent obtained from the polycarbonate diol composition and a curing agent containing a polyisocyanate are mixed immediately before coating; a one-component solvent-based coating composition containing a urethane prepolymer having an isocyanate terminal group obtained by reacting the polycarbonate diol with a polyisocyanate; and a one-component solvent-based coating composition containing a polyurethane resin obtained by reacting the polycarbonate diol, an organic polyisocyanate, and a chain extender.

[0203] In the coating or coating composition (coating) of the present embodiment, for example, curing accelerators (catalysts), leveling agents, fillers, dispersants, flame retardants, dyes, organic or inorganic pigments, mold release agents, fluidity regulators, plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, defoamers, colorants, solvents and other additives may 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.

[0204] The curing accelerator (catalyst) is not particularly limited, and examples thereof include generally used substances such as monoamines, diamines, triamines, cyclic amines, alcoholamines, etheramines, and metal catalysts.

[0205] The monoamine is not particularly limited, and examples thereof include triethylamine, N,N-dimethylcyclohexylamine, etc. The diamine is not particularly limited, and examples thereof include tetramethylethylenediamine, etc.

[0206] The alcoholamine is not particularly limited, and examples thereof include dimethylethanolamine.

[0207] The metal catalyst is not particularly limited, and examples thereof include potassium acetate, potassium 2-ethylhexanoate, calcium acetate, lead octylate, dibutyltin dilaurate, tin octylate, bismuth neodecanoate, bismuth oxycarbonate, bismuth 2-ethylhexanoate, zinc octylate, zinc neodecanoate, phosphine, and phosphorine.

[0208] Specific examples of the organic solvent include, but are not particularly limited to, amide solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, carbonate solvents, and aromatic hydrocarbon solvents.

[0209] These organic solvents may be used alone or in the form of a mixed solvent of two or more.

[0210] Example

[0211] Hereinafter, specific examples and comparative examples are listed to more specifically describe the present embodiment, but the present embodiment is not limited to these examples and comparative examples as long as the gist thereof is not exceeded. In the present examples, "parts" and "%" are based on mass standards unless otherwise specified.

[0212] The physical properties and evaluations in the examples and comparative examples described below were measured and evaluated by the methods shown below.

[0213] [Physical Property 1] Hydroxyl Value

[0214] The hydroxyl value of the polycarbonate diol (composition) is measured by the following method.

[0215] First, using a volumetric flask, add pyridine to 12.5g of acetic anhydride to make 50mL to prepare an acetylation reagent. Next, accurately weigh 2.5g of the sample into a 100mL eggplant-shaped flask. Next, add 5mL of the acetylation reagent and 10mL of toluene to the aforementioned eggplant-shaped flask using a full-volume pipette, install a cooling tube, and stir and heat the solution in the aforementioned eggplant-shaped flask at 100°C for 1 hour. Next, add 2.5mL of distilled water to the aforementioned eggplant-shaped flask using a full-volume pipette, and further heat and stir the solution in the aforementioned eggplant-shaped flask for 10 minutes. After cooling the solution in the aforementioned eggplant-shaped flask for 2 to 3 minutes, add 12.5mL of ethanol to the aforementioned eggplant-shaped flask. Next, add 2 to 3 drops of phenolphthalein as an indicator to the aforementioned eggplant-shaped 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 added to a 100 mL eggplant-shaped flask, and the solution in the eggplant-shaped flask was heated and stirred for 10 minutes, and then titrated in the same manner (blank test). Based on the result, the hydroxyl value of the polycarbonate diol (composition) was calculated by the following formula (i).

[0216] Hydroxyl value (mg-KOH / g)={(FE)×28.05×f} / G···(i)

[0217] 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.

[0218] [Physical Property 2] Number Average Molecular Weight (A)

[0219] The number average molecular weight (A) of the polycarbonate diol (composition) was calculated from the hydroxyl value determined in [Physical Property 1] using the following formula (ii).

[0220] Number average molecular weight (A) = 2 / (H×10 -3 / 56.11)···(ii)

[0221] In addition, in formula (ii), H represents the hydroxyl value (mg-KOH / g) of the polycarbonate diol (composition).

[0222] [Physical Property 3] Number Average Molecular Weight (B) (Measured by Gel Permeation Chromatography (GPC))

[0223] The polycarbonate diol composition was adjusted with tetrahydrofuran (hereinafter referred to as THF) so that the concentration was 0.2 mass % to obtain a sample. The number average molecular weight (B) of the polycarbonate diol composition calculated in terms of standard polystyrene was measured using the following GPC apparatus. Thereafter, the area ratio (%) with a number average molecular weight (Mn) of 1000 or less was obtained from the molecular weight calculation result of the polycarbonate diol composition.

[0224] GPC equipment: HLC-8320 manufactured by Tosoh Corporation

[0225] Column: TSKgel G4000H 1 column

[0226] G3000H 1 piece

[0227] G2000H 2

[0228] Eluent: Tetrahydrofuran (THF)

[0229] Flow rate: 1.0mL / min

[0230] Column temperature: 40°C

[0231] RI detector: RI (built-in HLC-8320)

[0232] [Physical Property 4] Determination of Melt Viscosity

[0233] After the polycarbonate diol composition was preheated to 50°C, the melt viscosity of the polycarbonate diol composition was measured at 50°C using an E-type viscometer (TVE-22HT, cone No. 6, manufactured by Toki Sangyo Co., Ltd.).

[0234] [Physical Property 5] Determination of Glass Transition Temperature (Tg)

[0235] About 10 g of the polycarbonate diol composition was sealed in an aluminum pan, and a differential scanning calorimeter (DSC7000X, manufactured by Hitachi High-Technologies Corporation) was used to perform temperature raising and lowering operations in a nitrogen atmosphere: raising the temperature from 30°C to 100°C at a rate of 20°C per minute, lowering the temperature from 100°C to -100°C at a rate of 5°C per minute, and raising the temperature from -100°C to 100°C at a rate of 5°C per minute. The inflection point at the second temperature increase was determined as the glass transition temperature (Tg).

[0236] [Physical Property 6] Confirmation of Properties of Polycarbonate Diol Composition

[0237] The polycarbonate diol composition heated to 80° C. was placed in a transparent sample bottle, and the state was visually observed until it was cooled to 23° C. When the sample bottle was tilted even slightly, the composition was judged to be in a liquid state as long as there was fluidity.

[0238] [Physical Property 7] Average value of the number of repetitions (n11) of structure (I) in the polycarbonate diol and average value of the number of repetitions (n21) of the polycarbonate structure (II)

[0239] The average values ​​of n11 and n21 were determined by alkali decomposing the polycarbonate diol composition to extract the raw material diol component, and subjecting the component to GC-MS measurement, LC-MS measurement, and gel permeation chromatography (GPC) measurement.

[0240] [Evaluation 1] Glass transition temperature (Tg) of polyurethane

[0241] A test piece with a width of 10 mm, a length of 40 mm, and a thickness of 0.4 mm was cut out from the polyurethane film. A viscoelasticity measuring device (manufactured by Hitachi High-Technologies Corporation, [TA7000 series, DMA7100]) was used to set the test piece so that the distance between the clamps was 20 mm, and the viscoelasticity was measured while heating from -100°C to 100°C at 5°C / min. The peak of tanδ was read from the measurement result to determine the glass transition temperature (Tg) of the polyurethane.

[0242] [Evaluation 2] Room temperature tensile test

[0243] According to JIS K6301 (2010), a short strip test piece with a width of 10 mm, a length of 100 mm, and a thickness of about 0.1 mm was prepared from a polyurethane film. For the prepared test piece, a tensile tester (manufactured by ORIENTEC, product name "TENSILON, RTE-1210 model") was used to perform a tensile test at a temperature of 23°C (relative humidity of 55%) under the conditions of a distance between the clamps of 20 mm and a tensile speed of 100 mm / min, and the stress (100% modulus) when the test piece was elongated by 100% was measured. The lower the 100% modulus, the better the softness was evaluated.

[0244] [Evaluation 3] Low temperature tensile test

[0245] According to JIS K6301 (2010), a short strip test piece with a width of 10 mm, a length of 100 mm, and a thickness of about 0.1 mm was made from a polyurethane film. The test piece was set up with a distance of 20 mm between the clamps in a tensile testing machine (made by ORIENTEC, "TLF-R3T-EW type") with a constant temperature bath (made by ORIENTEC, "TENSILON, RTE-1210 type"). Then, after the test piece was left to stand at -20°C for 5 minutes, a tensile test of the test piece was performed at a tensile speed of 100 mm / min, and the stress (100% modulus) when the test piece was elongated 100% was measured. The lower the 100% modulus, the better the softness was evaluated.

[0246] [Evaluation 4] Chemical resistance test (oleic acid resistance test)

[0247] As chemical resistance, oleic acid resistance was evaluated using olein.

[0248] A 1cm×10cm test piece is cut out from a polyurethane film. After measuring the mass of the test piece using a precision balance, it is placed in a 250mL glass bottle containing 50mL of oleic acid as a test solvent, and allowed to stand in a thermostatic chamber at 80°C and a nitrogen atmosphere for 24 hours. After the test, the test piece is taken out, the front and back of the test piece are gently wiped with a paper wipe, and the mass is measured using a precision balance to calculate the mass change rate (increase rate (swelling rate (%)) compared to before the test. A mass change rate close to 0% indicates good oleic acid resistance.

[0249] [Evaluation 5] Evaluation of moisture and heat resistance

[0250] A short strip sample with a width of 10 mm, a length of 100 mm, and a thickness of about 100 μm was prepared from a polyurethane film. The prepared sample was heated for 10 days at a temperature of 85°C and a humidity of 85% using a thermostat and hygrostat manufactured by ESPEC, product name "PR-1J". The breaking strength of the heated sample was measured in the same manner as in the above-mentioned <Normal Temperature Tensile Test>, and its retention rate (%) was calculated.

[0251] Retention rate = breaking strength after heating / breaking strength before heating × 100

[0252] [Evaluation 6] Evaluation of heat resistance

[0253] A short strip sample with a width of 10 mm, a length of 100 mm, and a thickness of about 100 μm was prepared from a polyurethane film. The prepared sample was heated at 120° C. for 7 days using a multi-safety dryer, product name “MSO-45TP”, manufactured by Futaba Scientific Co., Ltd. The breaking strength of the heated sample was measured in the same manner as in the above-mentioned <Non-Temperature Tensile Test>, and its retention rate (%) was calculated.

[0254] Retention rate = breaking strength after heating / breaking strength before heating × 100

[0255] [Evaluation 7] Evaluation of coating film forming properties

[0256] The necessary number of removable paper adhesive tapes were pasted as spacers on both ends of a glass plate (JIS R3202, 2 mm × 100 mm × 150 mm). Then, each coating composition prepared according to the application example described below was dripped onto the upper part of the aforementioned glass plate, and applied using a glass rod (8 mm in diameter) in such a way that the dry film thickness reached 30 to 40 μm. Then, the coating was cured for 15 minutes in an atmosphere of 23°C and 50% RH. Then, the coating was dried by baking at 140°C for 20 minutes to obtain a coating film.

[0257] <Evaluation Criteria>

[0258] ○: Indicates that the coating surface is smooth

[0259] △: Indicates that streaks, unevenness, and repulsion are slightly observed on the coating surface

[0260] ×: Indicates that a few streaks, bumps, or repulsions are observed on the coating surface.

[0261] It should be noted that the abbreviations in the tables and this article are as follows.

[0262] E-1: polyoxypropylene glycol (manufactured by Sanyo Chemical Industries, Ltd., "NEWPOL PE-61" (trade name), number average molecular weight: about 2000, ratio of the structure belonging to a linear and / or branched divalent aliphatic hydrocarbon group having 3 carbon atoms: 88%)

[0263] E-2: polyoxytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG2000" (trade name), number average molecular weight: about 2000, ratio of the structure belonging to a linear and / or branched divalent aliphatic hydrocarbon group having 3 carbon atoms: 0%)

[0264] E-3: polyoxypropylene glycol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., polypropylene glycol, diol type, 2,000 (trade name), number average molecular weight: about 2,000, ratio of the structure belonging to a linear and / or branched divalent aliphatic hydrocarbon group having 3 carbon atoms: 100%)

[0265] E-4: polyoxytetramethylene glycol (manufactured by BASF, PolyTHF250 (trade name), number average molecular weight: 250, proportion of the structure belonging to a linear and / or branched divalent aliphatic hydrocarbon group having 3 carbon atoms: 0%)

[0266] E-5: polyoxytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG850" (trade name), number average molecular weight: 850, ratio of the structure belonging to a linear and / or branched divalent aliphatic hydrocarbon group having 3 carbon atoms: 0%)

[0267] E-6: polyoxypropylene glycol (manufactured by NOF Corporation, "PRONON #102" (trade name), number average molecular weight: about 1250, ratio of the structure belonging to a linear and / or branched divalent aliphatic hydrocarbon group having 3 carbon atoms: 90%)

[0268] [Synthesis Example 1] Preparation of Polycarbonate Diol P-1

[0269] After adding 230 g of 1,5-pentanediol, 250 g of 1,6-hexanediol and 400 g of ethylene carbonate to a 1L glass flask (hereinafter also referred to as a "reactor") equipped with a distillation tower filled with regular packing and a stirring device, 0.0468 g of titanium tetra-n-butoxide was added as a catalyst. The reactor was immersed in an oil bath at 180°C, and a portion of the distillate was extracted while reacting at a reaction temperature of 165°C for 12 hours. Next, the reactor was directly connected to the condenser, and after the temperature of the oil bath was raised to 180°C, the pressure was slowly reduced, and the reaction was further carried out for 3 hours to obtain polycarbonate diol P-1 (466 g) which was liquid at room temperature. The hydroxyl value of the obtained polycarbonate diol P-1 was 55.2 mgKOH / g. In addition, the number average molecular weight of the obtained polycarbonate diol P-1 was 2033.

[0270] [Synthesis Example 2] Preparation of Polycarbonate Diol P-2

[0271] After 270 g of 1,6-hexanediol, 250 g of 1,4-butanediol and 445 g of ethylene carbonate were added to a 1L glass flask (hereinafter also referred to as a "reactor") equipped with a distillation column filled with a regular packing and a stirring device, 0.0960 g of titanium tetra-n-butoxide was added as a catalyst. The reactor was immersed in an oil bath at 140 to 160°C, and a portion of the distillate was extracted while reacting at a reaction temperature of 90 to 160°C for 20 hours. Next, the reactor was directly connected to a condenser, and after the temperature of the oil bath was raised to 180°C, the pressure was gradually reduced, and the reaction was further carried out for 8 hours to obtain polycarbonate diol P-2 (462 g) that was liquid at room temperature. The hydroxyl value of the obtained polycarbonate diol P-2 was 55.8 mgKOH / g. In addition, the number average molecular weight of the obtained polycarbonate diol P-2 was 2010.

[0272] [Synthesis Example 3] Preparation of Polycarbonate Diol P-3

[0273] Into a 3L glass flask (hereinafter also referred to as "reactor") equipped with a distillation column filled with a regular packing and a stirring device, 550g of 2-methyl-1,3-propanediol, 423g of 1,4-butanediol and 952g of ethylene carbonate were added, and 0.1925g of titanium tetra-n-butoxide was added as a catalyst. The reactor was immersed in an oil bath at 170°C, and a portion of the distillate was extracted while reacting at a reaction temperature of 155°C for 25 hours. Next, the reactor was directly connected to a condenser, and after the temperature of the oil bath was raised to 170°C, the pressure was gradually reduced, and the reaction was further carried out for 5 hours to obtain polycarbonate diol P-3 (577g) that was liquid at room temperature.

[0274] The hydroxyl value of the obtained polycarbonate diol P-3 was 53.0 mgKOH / g. The number average molecular weight of the obtained polycarbonate diol P-3 was 2,117.

[0275] [Synthesis Example 4] Preparation of Polycarbonate Diol P-4

[0276] After adding 383 g of 1,3-propylene glycol and 444 g of ethylene carbonate to a 3L glass flask (hereinafter also referred to as a "reactor") equipped with a distillation column filled with a regular packing and a stirring device, 0.040 g of titanium tetra-n-butoxide was added as a catalyst. The reactor was immersed in an oil bath, and a portion of the distillate was extracted while reacting at a reaction temperature of 160 to 175°C for 18 hours. Next, the reactor was directly connected to a condenser, and after the temperature of the oil bath was raised to 185°C, the pressure was slowly reduced, and the reaction was further carried out for 6 hours to obtain polycarbonate diol P-4 (290 g) which was liquid at room temperature.

[0277] The hydroxyl value of the obtained polycarbonate diol P-4 was 56.2 mgKOH / g. The number average molecular weight of the obtained polycarbonate diol P-4 was 1,996.

[0278] [Synthesis Example 5] Preparation of Polycarbonate Diol P-5

[0279] After adding 255 g of 3-methyl-1,5-pentanediol, 254 g of 1,6-hexanediol and 380 g of ethylene carbonate to a 1L glass flask (hereinafter also referred to as a "reactor") equipped with a distillation tower filled with regular packing and a stirring device, 0.0468 g of titanium tetra-n-butoxide was added as a catalyst. The reactor was immersed in an oil bath at 180°C, and a portion of the distillate was extracted while reacting at a reaction temperature of 165°C for 12 hours. Next, the reactor was directly connected to the condenser, and after the temperature of the oil bath was raised to 180°C, the pressure was slowly reduced, and the reaction was further carried out for 3 hours to obtain polycarbonate diol P-5 (466 g) that was liquid at room temperature. The hydroxyl value of the obtained polycarbonate diol P-5 was 56.4 mgKOH / g. In addition, the number average molecular weight of the obtained polycarbonate diol P-5 was 1989.

[0280] [Synthesis Example 6] Preparation of Polycarbonate Diol P-6

[0281] Into a 1L glass flask (hereinafter also referred to as "reactor") equipped with a distillation column filled with regular packing and a stirring device, 335g of 1,4-butanediol, 195g of 1,10-decanediol and 405g of dimethyl carbonate were added, and 0.0936g of titanium tetra-n-butoxide was added as a catalyst. The reactor was immersed in an oil bath at 170°C, and a portion of the distillate was extracted while reacting at a reaction temperature of 160°C for 10 hours. Next, the reactor was directly connected to the condenser, and after the temperature of the oil bath was raised to 185°C, the pressure was slowly reduced, and the reaction was further carried out for 2 hours to obtain polycarbonate diol P-6 (399g) that was waxy (solid) at room temperature. The hydroxyl value of the obtained polycarbonate diol P-6 was 56.3mgKOH / g. In addition, the number average molecular weight of the obtained polycarbonate diol P-6 was 1992.

[0282] [Synthesis Example 7] Preparation of Polycarbonate Diol P-7

[0283] After adding 536 g of 1,6-hexanediol and 400 g of ethylene carbonate to a 1L glass flask (hereinafter also referred to as a "reactor") equipped with a distillation tower filled with regular packing and a stirring device, 0.0475 g of titanium tetra-n-butoxide was added as a catalyst. The reactor was immersed in an oil bath at 180°C, and a portion of the distillate was extracted while reacting at a reaction temperature of 165°C for 12 hours. Next, the reactor was directly connected to the condenser, and after the temperature of the oil bath was raised to 180°C, the pressure was slowly reduced, and the reaction was further carried out for 3 hours to obtain polycarbonate diol P-7 (468 g) which was solid at room temperature. The hydroxyl value of the obtained polycarbonate diol P-7 was 55.2 mgKOH / g. In addition, the number average molecular weight of the obtained polycarbonate diol P-7 was 2033.

[0284] [Example 1] Preparation of polycarbonate diol composition A-1

[0285] Into a 1L glass flask equipped with a stirring device (hereinafter also referred to as a "reactor"), 90 parts by mass (360 g) of the polycarbonate diol P-1 obtained in Synthesis Example 1 and 10 parts by mass (40 g) of polyoxypropylene glycol E-1 ("NEWPOL PE-61" (trade name), number average molecular weight: about 2000, manufactured by Sanyo Chemical Industries, Ltd.) were added. Then, they were heated while stirring, and the temperature in the reactor was maintained at about 145° C. for 13 hours. Next, dibutyl phosphoric acid was added so that the mass ratio was 1.3 times that of titanium tetra-n-butoxide, and the temperature in the reactor was heated at 115° C. for 3 hours, thereby obtaining a polycarbonate diol composition A-1. It should be noted that, regarding the transesterification reaction, the reaction solution was subjected to gel permeation chromatography (hereinafter sometimes abbreviated as "GPC") measurement over time, and the disappearance of the peak derived from the raw material and the appearance of the peak derived from the product were confirmed over time, thereby confirming the progress of the reaction. Furthermore, the finally obtained polycarbonate diol composition was confirmed to have a structure corresponding to the reaction that occurred almost quantitatively depending on the amount of raw materials charged, as measured over time by GPC.

[0286] The physical properties of the obtained polycarbonate diol composition A-1 were measured by the above method. The results are shown in Table 1. The hydroxyl value of the obtained polycarbonate diol composition A-1 was 55.5 mgKOH / g. In addition, the number average molecular weight of the obtained polycarbonate diol composition A-1 was 2021.

[0287] [Examples 2 to 19]

[0288] Except for changing the types and charging amounts of each raw material as described in Tables 1 and 2, the same conditions and methods as in Example 1 were used to carry out the reaction, thereby obtaining polycarbonate diol compositions A-2 to A-19 of Examples 2 to 19. The physical properties of the obtained polycarbonate diol compositions A-2 to A-19 were measured by the above methods. The results are shown in Tables 1 and 2.

[0289] [Comparative Examples 1 to 4]

[0290] Except that the types and charging amounts of each raw material were changed as described in Table 3, the reaction was carried out under the same conditions and method as in Example 1 to obtain polycarbonate diol compositions B-1 to B-4 of Comparative Examples 1 to 4. The physical properties of the obtained polycarbonate diol compositions B-1 to B-4 were measured by the above methods. The results are shown in Table 3.

[0291] [Table 1]

[0292]

[0293] [Table 2]

[0294]

[0295] [Table 3]

[0296]

[0297] [Application Example 1-1] Synthesis of polyurethane film PA-1

[0298] In a 500 ml separable flask equipped with a thermocouple and a cooling tube, 38 g of polycarbonate diol composition A-1, 224 g of dimethylformamide (hereinafter sometimes abbreviated as DMF), and 0.26 g of a 1% dibutyltin dilaurate toluene solution (50 ppm relative to the total mass of MDI and the polycarbonate diol composition) were added, and heated in an oil bath at 40°C. While stirring the solution in the flask at 100 rpm under a nitrogen atmosphere, 14.8 g of MDI (3.09 times [mol] relative to the OH [mol] of the polycarbonate diol composition) was added dropwise to the flask, and the solution in the flask was stirred for about 1.5 hours. The isocyanate group concentration was analyzed, and it was confirmed that the theoretical amount was consumed, and a prepolymer was obtained. Next, 3.2 g of 1,4-butanediol (1,4-BD) calculated from the residual isocyanate was added to the flask in portions. After stirring the solution in the flask for about 1 hour, about 1 g of ethanol was added, and the solution in the flask was further stirred for 30 minutes to obtain a polyurethane solution having a number average molecular weight of 71,600.

[0299] Using a 0.8 mm thick applicator, on a glass plate (JIS R3202, 2 mm × 100 mm × 150 mm), the obtained polyurethane solution was dripped onto the upper part of the plate, and the coating was carried out in a manner that the dry film thickness reached 50 to 150 μm, and it was dried on a hot plate with a surface temperature of 60°C for 2 hours, and then dried in an oven at 80°C for 12 hours. Furthermore, it was allowed to stand for more than 12 hours at a constant temperature and humidity of 23°C and 55% RH to obtain a polyurethane film PA-1. The obtained polyurethane film PA-1 was evaluated for various physical properties using the above method. The evaluation results are shown in Table 4.

[0300] [Application Examples 2-1 to 19-1]

[0301] In the manufacture of the polyurethane film of Application Example 1-1, except that the polycarbonate diol composition used was changed to the polycarbonate diol compositions A-2 to A-19 manufactured in Examples 2 to 19, the reaction was carried out under the same conditions as in Application Example 1-1 to obtain polyurethane films PA-2 to PA-19. The obtained polyurethane films PA-2 to PA-19 were evaluated for various physical properties by the above-mentioned methods. The evaluation results are shown in Tables 4 and 5.

[0302] [Application Comparative Examples 1-1 to 4-1]

[0303] In the manufacture of the polyurethane film of Application Example 1-1, the polycarbonate diol composition etc. used was changed to the polycarbonate diol compositions etc. B-1 to B-4 manufactured in Comparative Examples 1 to 4, and the reaction was carried out under the same conditions as in Application Example 1-1 to obtain polyurethane films PB-1 to PB-4. The obtained polyurethane films PB-1 to PB-3 were evaluated for various physical properties by the above-mentioned methods. The evaluation results are shown in Tables 4 and 5.

[0304] [Table 4]

[0305]

[0306] ※Mw / Mn: weight average molecular weight / number average molecular weight

[0307] [Table 5]

[0308]

[0309] ※Mw / Mn: weight average molecular weight / number average molecular weight

[0310] [Table 6]

[0311]

[0312] ※Mw / Mn: weight average molecular weight / number average molecular weight

[0313] [Application Example 1-2] Production of coating composition

[0314] 16.8 g of the polycarbonate diol composition A-1 obtained in Example 1, 3.2 g of a polyisocyanate (TKA-100 (trade name), manufactured by Asahi Kasei Corporation, with an NCO content of 21.7%) as a curing agent so that the NCO / OH molar ratio is 1.0, and 8.6 g of butyl acetate as a solvent so that the solid content is 70% were weighed and mixed to obtain a coating composition. A coating film was prepared by the above method for the obtained coating composition, and the film-forming property was evaluated. The evaluation results are shown in Table 7.

[0315] [Application Examples 2-2 to 19-2]

[0316] In the preparation of the coating composition of Application Example 1-2, the polycarbonate diol composition used was changed to the polycarbonate diol composition A-2 to A-19 prepared in Examples 2 to 19. The same conditions as in Application Example 1-2 were used to obtain each coating composition. A coating film was prepared by the above method for each obtained coating composition, and the film-forming property was evaluated. The evaluation results are shown in Tables 7 and 8.

[0317] [Application Comparative Examples 1-2 to 4-2]

[0318] In the preparation of the coating composition of Application Example 1-2, the polycarbonate diol composition etc. used was changed to the polycarbonate diol composition etc. B-1 to B-4 prepared in Comparative Examples 1 to 4, and the same conditions as those of Application Example 1-2 were used to obtain each coating composition. For each obtained coating composition, a coating film was prepared by the above method, and the film-forming property was evaluated. The evaluation results are shown in Table 9.

[0319] [Table 7]

[0320]

[0321] [Table 8]

[0322]

[0323] [Table 9]

[0324]

[0325] From the results shown in Tables 1 to 9, it can be seen that the polycarbonate diol compositions of Examples 1 to 19 containing a polycarbonate diol having a structure represented by the following general formula (I) (structure (I)) and a polycarbonate structure represented by the following general formula (II) (polycarbonate structure (II)), and having a melt viscosity at 50°C of 1000 to 10000 mPa·s, and an average value of the repetition number n11 in the following general formula (I) of 12 or more, can reduce the amount of solvent used in the production of coatings and polyurethanes, and can obtain polyurethanes with excellent low-temperature flexibility, excellent oleic acid resistance and excellent wet heat resistance. In addition, it is possible to obtain coating compositions with excellent film-forming properties even at a high solid content concentration.

[0326]

[0327] (In the general formula (I), R 11 is a divalent linear, branched or cyclic aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms. 11 They can be the same or different. n11 is an arbitrary integer.)

[0328]

[0329] (In general formula (II), R 21 is a divalent linear, branched or cyclic aliphatic or aromatic hydrocarbon group having 2 to 15 carbon atoms. 21 They are optional and may be the same or different. n21 is an arbitrary integer.)

[0330] In particular, it is known that: R in the general formula (I) 11 In the case of a divalent branched aliphatic hydrocarbon group (e.g., isopropylene), a polyurethane having better low-temperature flexibility, better oleic acid resistance, and better resistance to moist heat can be obtained, and a coating composition having better film-forming properties even at a high solid content concentration can be obtained.

[0331] According to the results shown in Tables 1 to 9, the polycarbonate diol compositions (Examples 1 to 19) in which the average value of the repetition number n11 of the structure (I) is 12 to 70 and the average value of the repetition number n21 of the polycarbonate structure (II) is 1 to 50 have better low-temperature flexibility when made into polyurethanes than the polycarbonate diol composition not having the above-mentioned structure (Comparative Example 2).

[0332] In addition, a comparison between Examples 1 to 3 and Examples 4 to 7 shows that the polycarbonate diol composition tends to have a lower melt viscosity at 50° C. as the content of the structure (I) increases, and is suitable for coatings and high-solidification of polyurethanes.

[0333] In addition, from the comparison between Examples 1 to 3 and 15, it was observed that as the content of the structure (I) in the polycarbonate diol composition increased, the flexibility and low-temperature characteristics of the obtained polyurethane improved.

[0334] In addition, from the comparison between Examples 1 to 3 and 15, it was observed that the durability of the polyurethane, such as oleic acid resistance and moist heat resistance, tended to improve as the content of the structure (I) in the polycarbonate diol composition decreased.

[0335] From the above, it was confirmed that the polycarbonate diol composition of the present embodiment has a low viscosity and therefore can provide a polyurethane having excellent durability in terms of oleic acid resistance and moist heat resistance.

[0336] This application is based on the Japanese patent application (Japanese Patent Application No. 2019-188929) filed on October 15, 2019, the contents of which are incorporated herein by reference.

[0337] Industrial Applicability

[0338] The polycarbonate diol composition of the present invention can be highly solidified when manufacturing coatings and polyurethanes, and is useful as a raw material for coatings and polycarbonate-based polyurethanes. In addition, the polyurethane manufactured using the polycarbonate diol composition of the present invention has the advantages of excellent low-temperature flexibility and durability, and can be suitably used in a wide range of fields such as elastic fibers, synthetic or artificial leathers, coatings, and high-performance elastomers.

Claims

1. A polycarbonate diol composition comprising a polycarbonate diol having a structure represented by the following general formula (I) and a polycarbonate structure represented by the following general formula (II), With respect to the total mass of the structure represented by the general formula (I) and the polycarbonate structure represented by the general formula (II), the content of the structure represented by the general formula (I) is 5 mass % or more and 40 mass % or less, and the content of the polycarbonate structure represented by the general formula (II) is 60 mass % or more and 95 mass % or less, The polycarbonate diol composition has a melt viscosity of 1000 to 10000 mPa·s at 50° C., and an average value of the repeating number n11 in the following general formula (I) is 12 or more. In the general formula (I), R 11 is a divalent linear, branched or cyclic aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms, and the presence of a plurality of R 11 Optional same or different; n11 is any integer, In the general formula (II), R 21 is a divalent linear, branched or cyclic aliphatic or aromatic hydrocarbon group having 2 to 15 carbon atoms, and the presence of a plurality of R 21 Optional same or different; n21 is any integer.

2. The polycarbonate diol composition according to claim 1, wherein R 11 It is a divalent straight-chain aliphatic hydrocarbon group having 2 to 6 carbon atoms and / or a divalent branched aliphatic hydrocarbon group having 3 to 6 carbon atoms.

3. The polycarbonate diol composition according to claim 1 or 2, wherein The average value of the number of repetitions n11 in the general formula (I) is in the range of 70 or less.

4. The polycarbonate diol composition according to claim 1 or 2, wherein The structure represented by the general formula (I) is a polyoxyalkylene structure.

5. The polycarbonate diol composition according to claim 1 or 2, wherein The average value of n21 in the general formula (II) is in the range of 1 to 50.

6. The polycarbonate diol composition according to claim 1 or 2, wherein The number average molecular weight of the polycarbonate diol composition is 300 or more and 10,000 or less.

7. The polycarbonate diol composition according to claim 1 or 2, wherein The number average molecular weight of the polycarbonate diol is 500 or more and 5,000 or less.

8. The polycarbonate diol composition according to claim 1 or 2, wherein The average value of the repetition number n11 in the general formula (I) is 15 or more.

9. The polycarbonate diol composition according to claim 1 or 2, wherein The average value of the repetition number n11 in the general formula (I) is 50 or less.

10. The polycarbonate diol composition according to claim 1 or 2, wherein In at least a portion of the polycarbonate diol, R in the general formula (II) 21 They are at least two or more selected from the group consisting of divalent linear and branched aliphatic hydrocarbon groups having 2 to 15 carbon atoms.

11. The polycarbonate diol composition according to claim 1 or 2, wherein In the general formula (I), R 11 The content of the structure which is a linear and / or branched divalent aliphatic hydrocarbon group having 3 carbon atoms in the structure represented by the general formula (I) is 60% by mass or more and 95% by mass or less. 12 . The polycarbonate diol composition according to claim 1 , wherein a content of the structure represented by the general formula (I) is 10% by mass or more and 35% by mass or less.

13. The polycarbonate diol composition according to claim 1 or 2, wherein The glass transition temperature measured by a differential scanning calorimeter is -50°C or lower. 14 . The polycarbonate diol composition according to claim 1 , which is in a liquid and transparent state at 23° C.

15. The polycarbonate diol composition according to claim 1 or 2, wherein In the calculation result of the molecular weight of the polycarbonate diol composition calculated by gel permeation chromatography, the area ratio (%) of the number average molecular weight (Mn) of 1000 or less is 7% or less. 16 . A polyurethane produced by using the polycarbonate diol composition according to claim 1 .

17. A synthetic leather comprising a base fabric, an adhesive layer, an intermediate layer and a surface layer laminated in sequence, comprising the polyurethane according to claim 16.

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