Polyol composition, polyurethane resin composition, coating film and leather-like sheet

Abstract

A polyol composition, a polyurethane resin composition, a coating and a leather-like sheet. A carbonate-containing polyol composition is provided, which can reduce the amount of solvent used in the manufacture of coatings and polyurethanes and can obtain polyurethanes with excellent low-temperature flexibility, chemical resistance (such as oleic acid resistance) and wear resistance. A carbonate-containing polyol composition, having a number average molecular weight of 300 to 10,000, containing a structural unit (I): -(R 11 ‑O‑CO‑O) n11 -The repeating unit shown in the figure, and the structural unit (II): selected from -(R 21 ‑O) n21 ‑The repeating unit shown and ‑(R 31 ‑CO‑O) n31 ‑, wherein the content of the structural unit (II) is 1% by mass or more and 99% by mass or less relative to the total mass of the structural unit (I) and the structural unit (II).

Description

Technical Field

[0001] The present invention relates to a polyol composition, a polyurethane resin composition, a coating film and a leather-like sheet. Background Art

[0002] In the past, polyurethane resins were used in a wide range of areas 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 durability of polyurethane resins such as heat resistance, weather resistance, hydrolysis resistance, solvent resistance, sunscreen resistance, and damage resistance have been increasing. On the other hand, in Europe, China, etc., for the purpose of reducing environmental burden, the transfer to materials that can achieve VOC reduction is being promoted.

[0003] According to Non-Patent Document 1, polyether polyols, which are usually used as polyol components, have low viscosity. Therefore, polyurethanes using polyether polyols have excellent flexibility and hydrolysis resistance, but poor heat resistance and weather resistance. In addition, polyurethanes using polyester polyols have improved heat resistance and weather resistance, but poor hydrolysis resistance. In contrast, polyurethanes using polycarbonate polyols have 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: "Collection of Examples of Material Selection, Structural Control and Modification of Polyurethanes" Items 51 to 62, published by the Institute of Technical Information, Inc., first edition published in December 2014 Summary of the invention

[0011] Problem that the invention aims to solve

[0012] However, the viscosity of the polycarbonate polyol alone is higher than that of other polyols, and therefore, in order to facilitate the handling of the polycarbonate polyol, an operation of lowering the viscosity using an organic solvent is generally performed.

[0013] For example, when polycarbonate polyol is used in the production of coatings and polyurethanes, a large amount of solvent is required. The polyurethane resin obtained using the polycarbonate diol described in Patent Documents 1 and 2 still has room for improvement in applications requiring strict physical properties such as low-temperature flexibility and durability.

[0014] Therefore, the present invention is carried out in view of the above-mentioned situation, and its purpose is to provide a polyol composition containing a carbonate group that can reduce the amount of solvent used when manufacturing coatings and polyurethanes, and can obtain polyurethanes with excellent low-temperature flexibility, chemical resistance (such as oleic acid resistance) and wear resistance.

[0015] Solutions for solving problems

[0016] As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by using a polyol composition containing carbonate groups at a specific ratio and having a specific structure, thereby completing the present invention.

[0017] That is, the present invention includes the following aspects.

[0018] [1] A carbonate group-containing polyol composition having a number average molecular weight of 300 to 10,000,

[0019] It contains a structural unit (I): a repeating unit represented by the following formula (A), and a structural unit (II): at least one selected from the group consisting of a repeating unit represented by the following formula (B) and a repeating unit represented by the following formula (C),

[0020] The content of the structural unit (II) is 1% by mass or more and 99% by mass or less relative to the total mass of the structural unit (I) and the structural unit (II).

[0021] -(R 11 -O-CO-O) n11 -···(A)

[0022] (In formula (A), R 11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 15 carbon atoms. 11 They are optionally the same as or different from each other.

[0023] n11 is an arbitrary integer. )

[0024] -(R 21 -O)n21 -···(B)

[0025] (In formula (B), R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. 21 They are optionally the same or different from each other. n21 is any integer greater than 2.)

[0026] -(R 31 -CO-O) n31 -···(C)

[0027] (In formula (C), R 31 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. 31 They are optionally the same or different from each other. n31 is an arbitrary integer.)

[0028] [2] The carbonate group-containing polyol composition according to [1], wherein

[0029] The content of the structural unit (II) is 40% by mass or more and 95% by mass or less relative to the total mass of the structural unit (I) and the structural unit (II).

[0030] [3] The carbonate group-containing polyol composition according to [1] or [2], wherein

[0031] The structural unit (II) is a repeating unit represented by the above formula (B).

[0032] [4] A polyurethane resin composition comprising the carbonate group-containing polyol composition according to any one of [1] to [3], a compound having a plurality of isocyanate groups, and at least one chain extender selected from the group consisting of a polyol and a polyamine.

[0033] [5] A coating formed from the polyurethane resin composition according to [4].

[0034] [6] A leather-like sheet having the coating described in [5].

[0035] Effects of the Invention

[0036] According to the present invention, the amount of solvent used can be reduced when producing coating materials and polyurethanes, and polyurethanes having excellent low-temperature flexibility, chemical resistance, and abrasion resistance can be provided. DETAILED DESCRIPTION

[0037] Hereinafter, a method for implementing the present invention (hereinafter referred to as "this embodiment") will be described. The following this embodiment is an example for illustrating the present invention and does not mean that the present invention is limited to the following contents. The present invention can be implemented by appropriately modifying it within the scope of its purpose.

[0038] <Carbonate Group-Containing Polyol Composition>

[0039] The carbonate-group-containing polyol composition of the present embodiment has a number average molecular weight of 300 to 10,000, and contains the following structural unit (I) and the following structural unit (II), wherein the content of the aforementioned structural unit (II) is 1% by mass or more and 99% by mass or less relative to the total mass of the aforementioned structural unit (I) and the aforementioned structural unit (II).

[0040] · Structural unit (I): a repeating unit represented by the following formula (A).

[0041] -(R 11 -O-CO-O) n11 -···(A)

[0042] (In formula (A), R 11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 15 carbon atoms. 11 They are optionally the same as or different from each other.

[0043] n11 is an arbitrary integer. )

[0044] Structural unit (II): at least one selected from the group consisting of a repeating unit represented by the following formula (B) and a repeating unit represented by the following formula (C).

[0045] -(R 21 -O) n21 -···(B)

[0046] (In formula (B), R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. 21 They are optionally the same or different from each other. n21 is any integer greater than 2.)

[0047] -(R 31 -CO-O) n31 -···(C)

[0048] (In formula (C), R 31 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. 31They are optionally the same or different from each other. n31 is an arbitrary integer.)

[0049] The carbonate group-containing polyol composition of the present embodiment has such a configuration, so that the amount of solvent used can be reduced when producing a coating or polyurethane, and a polyurethane having excellent low-temperature flexibility, chemical resistance, and abrasion resistance can be provided.

[0050] In the polyol composition containing carbonate group of the present embodiment, the aforementioned structural unit (II) is preferably the repeating unit shown in the above-mentioned formula (B) or the repeating unit shown in the above-mentioned formula (C). In the polyol composition containing carbonate group of the present embodiment, if the aforementioned structural unit (II) is the repeating unit shown in the above-mentioned formula (B) or the repeating unit shown in the above-mentioned formula (C), there is the following tendency: the amount of solvent can be further reduced when manufacturing coating, polyurethane, and polyurethane with better low-temperature flexibility, chemical resistance and wear resistance can be provided.

[0051] In the polyol composition containing carbonate group of the present embodiment, the aforementioned structural unit (II) is more preferably the repeating unit shown in the above-mentioned formula (B). In the polyol composition containing carbonate group of the present embodiment, if the aforementioned structural unit (II) is the repeating unit shown in the above-mentioned formula (B), there is the following tendency: the consumption of solvent can be further reduced when manufacturing coating, polyurethane, and low temperature flexibility, chemical resistance and abrasion resistance can be provided. More excellent polyurethane.

[0052] In addition, in this embodiment, the structural unit (I) and the structural unit (II) can be confirmed by the method described in the examples described later.

[0053] In the carbonate group-containing polyol composition of the present embodiment, the terminal structure 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 carbonate groups, or a terminal structure in which both terminals are bonded to hydroxyl groups.

[0054] In the carbonate group-containing polyol composition of the present embodiment, the terminal structure 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.

[0055] Next, the details of the repeating unit represented by the above formula (A) are described below.

[0056] (R 11 )

[0057] In the above formula (A), R 11is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 15 carbon atoms. 11 They are optionally the same as or different from each other.

[0058] As R 11 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.

[0059] 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.

[0060] As R 11 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.

[0061] 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.

[0062] As R 11 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.

[0063] As R 11 Specific examples of the divalent cyclic aliphatic hydrocarbon group in are not particularly limited, and examples thereof include cyclobutylene, cyclopentylene, cyclohexylene, and cycloheptylene.

[0064] 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.

[0065] As R 11 Specific examples of the divalent aromatic hydrocarbon group in are not particularly limited, and examples thereof include phenylene and naphthylene.

[0066] Among them, as R 11, 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 which is a butylene group or a hexylene group.

[0067] In addition, it is preferred that at least a portion of the carbonate group-containing polyol composition of the present embodiment has R 11 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 carbonate group-containing polyol composition that is liquid at room temperature tends to be obtained.

[0068] It should be noted that in the present embodiment, R 11 The composition of can be determined by the following method.

[0069] First, weigh 1 g of the sample into a 100 ml eggplant flask, and 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 above mixture to room temperature, add 1 to 2 drops of phenolphthalein as an indicator to the above mixture, and neutralize it with hydrochloric acid. Thereafter, cool the above mixture in a refrigerator for 3 hours, remove the precipitated salt by filtration, and then 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 the R in the repeating unit represented by the above formula (A) in the polyol composition containing a carbonate group. 11 composition.

[0070] (n11)

[0071] In the above formula (A), n11 represents a carbonate structure (-R 11 n11 is an arbitrary integer, but the average value of n11 in the entire polyol composition containing carbonate groups of the present embodiment is preferably in the range of more than 1 and less than 50, more preferably in the range of more than 2 and less than 50, further preferably in the range of more than 2 and less than 30, and particularly preferably in the range of more than 3 and less than 20.

[0072] n11 can be determined by, if necessary, subjecting the carbonate group-containing polyol composition to alkali decomposition to extract a raw material diol component, and subjecting the component to GC-MS measurement, LC-MS measurement, NMR measurement, and GPC measurement.

[0073] Next, the details of the repeating unit represented by the above formula (B) are described below.

[0074] (R 21 )

[0075] In the above formula (B), R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or an aromatic hydrocarbon group having 2 to 20 carbon atoms. 21 They are optionally the same as or different from each other.

[0076] As R 21 The divalent straight-chain aliphatic hydrocarbon group in has a carbon number of 2 or more and 20 or less, preferably 2 or more and 12 or less, and more preferably 3 or more and 6 or less. 21 When the carbon number of the divalent linear aliphatic hydrocarbon group in the polyol is 3 or more, there is a tendency to provide a polyurethane having better low-temperature flexibility, chemical resistance, and abrasion resistance.

[0077] As R 21 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.

[0078] As R 21 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.

[0079] As R 21 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.

[0080] As R 21 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.

[0081] As R 21 Specific examples of the divalent cyclic aliphatic hydrocarbon group in are not particularly limited, and examples thereof include cyclobutylene, cyclopentylene, cyclohexylene, and cycloheptylene.

[0082] 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.

[0083] As R 21Specific examples of the divalent aromatic hydrocarbon group in are not particularly limited, and examples thereof include phenylene and naphthylene.

[0084] Among them, as R 21 , preferably a divalent straight-chain, branched or cyclic aliphatic hydrocarbon group (i.e., an alkylene group) having 2 to 20 carbon atoms, more preferably 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. In particular, if R 21 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.

[0085] (n21)

[0086] In the above formula (B), n21 represents a structure (-R 21 In the above formula (B), n21 is an arbitrary integer, and the average value of n21 in the entire polyol composition containing carbonate groups of the present embodiment is more than 11, preferably in the range of more than 12 and less than 70, more preferably in the range of more than 12 and less than 60, and particularly preferably in the range of more than 15 and less than 50.

[0087] By making the n21 average value in the whole polyol composition that contains carbonate group of present embodiment be more than the above-mentioned lower limit, thereby there is the tendency that can obtain the polyurethane that flexibility and low temperature flexibility are more excellent.In addition, by making the n21 average value in the whole polyol composition that contains carbonate group of present embodiment be below the above-mentioned upper limit, thereby there is the tendency that the viscosity of the polyol composition that contains carbonate group becomes lower viscosity.

[0088] The above n21 can be determined by, if necessary, subjecting the carbonate group-containing polyol composition to alkali decomposition to extract a raw material diol component, and subjecting the component to GC-MS measurement, LC-MS measurement, NMR measurement, and GPC measurement.

[0089] Among them, the repeating unit represented by the above formula (B) is preferably a polyoxyalkylene structure.

[0090] Specific examples of preferred oxyalkylene groups included in the above formula (B) 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 the above formula (B) the above structure, there is a tendency that the polyol composition containing a carbonate group is liquid at room temperature due to the introduction of a side chain methyl group, and has excellent workability, and the obtained polyurethane is rich in flexibility and low temperature characteristics.

[0091] Next, the details of the repeating unit represented by the above formula (C) are described below.

[0092] (R 31 )

[0093] In the above formula (C), R 31 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or an aromatic hydrocarbon group having 2 to 20 carbon atoms. 31 They are optionally the same as or different from each other.

[0094] As R 31 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.

[0095] As R 31 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.

[0096] As R 31 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.

[0097] As R 31 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.

[0098] As R 31 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.

[0099] As R 31Specific examples of the divalent cyclic aliphatic hydrocarbon group in are not particularly limited, and examples thereof include cyclobutylene, cyclopentylene, cyclohexylene, and cycloheptylene.

[0100] As R 31 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.

[0101] As R 31 Specific examples of the divalent aromatic hydrocarbon group in are not particularly limited, and examples thereof include phenylene and naphthylene.

[0102] Among them, as R 31 , preferably a divalent straight-chain, branched or cyclic aliphatic hydrocarbon group (i.e., an alkylene group) having 2 to 20 carbon atoms, more preferably 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. In particular, if R 31 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.

[0103] (n31)

[0104] In the above formula (C), n31 represents a structure (-R 31 In the above formula (C), n31 is an arbitrary integer, and the average value of n31 in the entire polyol composition containing carbonate groups of the present embodiment is more than 2, preferably in the range of more than 2 and less than 50, more preferably in the range of more than 3 and less than 30, and particularly preferably in the range of more than 4 and less than 25.

[0105] By making the average value of n31 in the whole polyol composition containing carbonate group of present embodiment be more than the above-mentioned lower limit, thereby there is the tendency that can obtain the polyurethane of flexibility and low temperature flexibility more excellent.In addition, by making the average value of n31 in the whole polyol composition containing carbonate group of present embodiment be below the above-mentioned upper limit, thereby there is the tendency that the viscosity of the polyol composition containing carbonate group becomes lower viscosity.

[0106] The above n31 can be determined by, if necessary, subjecting the carbonate group-containing polyol composition to alkali decomposition to extract a raw material diol component, and subjecting the component to GC-MS measurement, LC-MS measurement, NMR measurement, and GPC measurement.

[0107] The method for obtaining the carbonate group-containing polyol composition according to the present embodiment is not particularly limited, and examples thereof include the following methods (i) to (iii).

[0108] (i) A method of conducting an ester exchange reaction using a compound having a repeating unit represented by the above formula (A) and one or more selected from the group consisting of a compound having a repeating unit represented by the above formula (B) and a compound having a repeating unit represented by the above formula (C).

[0109] (ii) A method of obtaining a carbonate group-containing polyol composition having a predetermined molecular weight by mixing a carbonate compound described later, a polyol raw material satisfying structural unit (I), and one or more selected from the group consisting of a compound having a repeating unit represented by the above formula (B) and a compound having a repeating unit represented by the above formula (C), reacting the mixture at 100 to 200° C. in the presence of an ester exchange catalyst under normal pressure or reduced pressure, and removing the generated alcohol derived from the carbonate raw material.

[0110] (iii) A method of mixing a compound having a repeating unit represented by the above formula (A) with one or more selected from the group consisting of a compound having a repeating unit represented by the above formula (B) and a compound having a repeating unit represented by the above formula (C).

[0111] When the polyol composition containing carbonate groups of the present embodiment is obtained through synthesis reaction, a catalyst is usually added to implement. The catalyst used in the present embodiment can be freely selected from common transesterification catalysts. As transesterification catalysts, there are no particular restrictions, and metals, salts, alkoxides, and organic compounds such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, and cerium can be used. Particularly preferred are compounds of titanium, magnesium, tin, and lead. In addition, the amount of the catalyst is usually 0.00001 to 0.1 mass % relative to the mass of the polyol containing carbonate groups.

[0112] In the carbonate-containing polyol composition of the present embodiment, relative to the total mass of the aforementioned structural unit (I) and the aforementioned structural unit (II), the content of the aforementioned structural unit (II) is 1% by mass or more and 99% by mass or less, preferably 40% by mass or more and 95% by mass or less, more preferably 45% by mass to 90% by mass, and further preferably 50 to 85% by mass. The lower limit of the content of the structural unit (II) is particularly preferably 52% by mass or more.

[0113] When the content of the structural unit (II) relative to the total mass of the structural unit (I) and the structural unit (II) is greater than or equal to the lower limit, the flexibility of the obtained polyurethane is improved. In addition, when the content of the structural unit (II) relative to the total mass of the structural unit (I) and the structural unit (II) is less than or equal to the upper limit, the chemical resistance and abrasion resistance of the obtained polyurethane are improved.

[0114] It should be noted that in the present embodiment, the contents of the structural unit (I) and the structural unit (II) can be measured by the method described in the Examples described below.

[0115] The number average molecular weight of the polyol composition containing carbonate groups of the present embodiment is 300 to 10000, preferably 400 to 5000, and more preferably 450 to 3500. If the number average molecular weight of the polyol composition containing carbonate groups is above the aforementioned lower limit, the flexibility of the obtained polyurethane is improved, and if the number average molecular weight of the polyol composition containing carbonate groups is below the aforementioned upper limit, the wear resistance and chemical resistance of the obtained polyurethane are improved.

[0116] The method for controlling the number average molecular weight of the carbonate group-containing polyol composition of the present embodiment to the aforementioned range is not particularly limited, and examples thereof include a method of using structural units (I) and structural units (II) whose number average molecular weights are controlled to the aforementioned range; a method of using structural units (I) having a number average molecular weight greater than the aforementioned range and structural units (II) having a number average molecular weight less than the aforementioned range; a method of conducting the reaction while confirming the number average molecular weight using the aforementioned method (ii), and stopping the reaction when the number average molecular weight is within the aforementioned range, etc.

[0117] In the present embodiment, the number average molecular weight of the carbonate group-containing polyol composition can be calculated from the hydroxyl value of the carbonate group-containing polyol composition using the method described in Examples below.

[0118] <Structural Unit (I)>

[0119] The structural unit (I) possessed by the polyol composition containing carbonate group of the present embodiment is the repeating unit shown in the above-mentioned formula (A). The structural unit (I) is not particularly limited and can be obtained by, for example, reacting the carbonate compound represented by various polyols such as shown below with ethylene carbonate, dimethyl carbonate, diethyl carbonate, and diphenyl carbonate. The method for reacting these compounds is not particularly limited.

[0120] As an example of a method for reacting these compounds, there is no particular limitation, and for example the following method can be cited: the aforementioned carbonate compound is mixed with the polyol described below, reacted at 100 to 200° C. under normal pressure or reduced pressure and in the presence of an ester exchange catalyst, the alcohol derived from the carbonate compound generated is removed to obtain a low molecular weight polycarbonate polyol, then, heated at 160 to 250° C. under reduced pressure to remove unreacted carbonate compound and polyol, and the low molecular weight polycarbonate polyol is condensed to obtain.

[0121] The polyol raw material for forming the structural unit (I) is not particularly limited, and examples thereof include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,14-tetradecanediol, and diols having no side chains; 2-methyl-1,8-octanediol, Diols having a side chain such as 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethyl-1,3-propanediol; and one or more of cyclic diols such as 1,4-cyclohexanedimethanol and 2-bis(4-hydroxycyclohexyl)propane.

[0122] In addition, a small amount of a compound having three or more hydroxyl groups in one molecule, such as trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, etc., may also be used. If too much of the compound having three or more hydroxyl groups in one molecule is used, it is possible to crosslink and gel during the reaction. Therefore, the total amount of the compound having three or more hydroxyl groups in one molecule relative to the aliphatic and / or alicyclic diol is preferably set to 0.01 to 5% by mass. More preferably, it is 0.01 to 1% by mass.

[0123] As the raw material of the structural unit (I) used in the present embodiment, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol are preferred, and among them, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol are particularly preferred.

[0124] <Structural Unit (II)>

[0125] The structural unit (II) contained in the carbonate group-containing polyol composition of the present embodiment is at least one selected from the group consisting of a repeating unit represented by the above formula (B) and a repeating unit represented by the above formula (C).

[0126] The raw material for forming the repeating unit shown in the above formula (B) is not particularly limited, and examples thereof include polyether polyols. As the polyether polyol, there is no particular limitation as long as it is a polyol having an ether bond in the molecule, and it may contain a carbonate bond and / or an ester bond within the range that does not impair the functions and characteristics of the polyether polyol. As the polyether polyol, it is preferably a polyether polyol obtained, for example, by ring-opening polymerization of a cyclic ether or ring-opening polymerization of an epoxy compound, in which an alkylene group is ether-bonded.

[0127] The number of carbon atoms in the main chain of the polyether polyol is not particularly limited, but from the viewpoint of easy availability, the number of carbon atoms in the main chain is preferably 2 to 4. Furthermore, from the viewpoint of suppressing a decrease in water resistance of the polyurethane due to water absorption, the content of oxygen atoms is preferably small, and the number of carbon atoms in the main chain is more preferably 3 to 4.

[0128] Specific examples of polyether polyols are not particularly limited, and examples thereof include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, and copolymers of two or more thereof; random copolymers and block copolymers of ethylene oxide and propylene oxide, or random copolymers and block copolymers of ethylene oxide and butylene oxide, etc. Among them, polytetramethylene ether glycol, polytetramethylene ether glycol having an alkyl side chain, polypropylene glycol, polyethylene glycol, and copolymers of two or more thereof, etc. are preferred.

[0129] The raw material for forming the repeating unit shown in the above formula (C) is not particularly limited, and polyester polyols can be cited as examples. As polyester polyols, as long as they are polyols having ester bonds in the molecule, there are no particular limitations, and carbonate bonds and / or ether bonds can be contained within the range that does not damage the functions and characteristics of the polyester polyols. As polyester polyols, there are no particular limitations, and polyester polyols, for example, obtained by condensation of carboxylic acids and polyols, polyester polyols obtained by condensation of carboxylic esters and polyols, polyester polyols obtained by condensation of a mixture of carboxylic acids and carboxylic esters and polyols, polyester polyols obtained by ring-opening polymerization of cyclic esters, polyester polyols obtained by condensing hydroxycarboxylic acids to polyols, etc. can be cited.

[0130] Specific examples of the polyester polyols are not particularly limited, and examples thereof include polyethylene adipate diol, polypropylene adipate diol, polybutylene adipate diol, polypentylene adipate diol, polyhexylene adipate diol, polyethylene adipate butylene adipate diol, poly(1,6-hexanediol isophthalate adipate diol), polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol, polybutylene sebacate diol, poly(3-methyl-1,5-pentanediol adipate) diol, poly-γ-butyrolactone diol, poly-δ-valerolactone diol, poly-ε-caprolactone diol, and condensation products of 1,6-hexanediol and dimer acid. Among them, preferred are polyethylene adipate diol, polypropylene adipate diol, polybutylene adipate diol, polypentylene adipate diol, polyhexylene adipate diol, poly(3-methyl-1,5-pentanediol adipate) diol, and poly-ε-caprolactone diol; more preferred are polyhexylene adipate diol, poly(3-methyl-1,5-pentanediol adipate) diol, and poly-ε-caprolactone diol.

[0131] <Purpose>

[0132] The carbonate-containing polyol composition of the present embodiment can be used as a raw material for the polyurethane reacted with polyisocyanates. The polyurethane obtained using the carbonate-containing polyol composition of the present embodiment has excellent chemical resistance, heat resistance, and weather resistance, and therefore, can be widely used in, for example, foam, elastomer, coating, coating agent, adhesive, bonding agent, artificial leather, synthetic leather, water-based polyurethane coating, etc.

[0133] <Polyurethane resin composition>

[0134] The polyurethane resin composition of the present embodiment is obtained by using the carbonate group-containing polyol composition, a compound having a plurality of isocyanate groups, and at least one chain extender selected from the group consisting of polyols and polyamines.

[0135] The method for producing the polyurethane resin composition of the present embodiment uses known polyurethane reaction conditions for producing ordinary polyurethane.

[0136] Specific examples of the method for producing the polyurethane resin composition of the present embodiment are not particularly limited, and examples thereof include a method in which the above-mentioned carbonate group-containing polyol composition, other polyols, polyisocyanate and chain extender are mixed together and reacted (hereinafter sometimes referred to as the "one-step method"); a method in which the above-mentioned carbonate group-containing polyol composition, other polyols and polyisocyanate 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"), etc.

[0137] <Compound Having Isocyanate Group>

[0138] The compound having a plurality of isocyanate groups used in the polyurethane resin composition of the present embodiment is not particularly limited as long as it functions as a curing agent, and an isocyanate compound having two or more isocyanate groups at the terminal is used.

[0139] 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.

[0140] The chain aliphatic diisocyanate is not particularly limited, and examples thereof include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

[0141] The cyclic aliphatic diisocyanate is not particularly limited, and examples thereof include isophorone diisocyanate.

[0142] 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.

[0143] 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.

[0144] As the isocyanate compound, a commercially available product may be used, or the isocyanate compound may be synthesized by a known method.

[0145] The amount 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 polyol (e.g., polycarbonate diol) can be set to, for example, more than 0.2 and less than 5.0, for example, more than 0.4 and 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 to further improve the smoothness of the coating.

[0146] <Chain Extender>

[0147] The chain extender used when producing the polyurethane resin composition of the present embodiment is not particularly limited, and examples thereof include common polyols and polyamines.

[0148] The polyol is not particularly limited, and examples thereof include linear diols, branched diols, cyclic diols, and diols having an aromatic ring.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] The polyamine is not particularly limited, and examples thereof include hydroxyamines and polyamines.

[0154] The hydroxyamines are not particularly limited, and examples thereof include N-methylethanolamine and N-ethylethanolamine.

[0155] 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.

[0156] These chain extenders may be used alone or in combination of two or more.

[0157] <Lamination>

[0158] The coating film of the present embodiment is formed of the above-mentioned polyurethane resin composition. Specifically, the coating film of the present embodiment can be formed by, for example, applying the above-mentioned polyurethane resin composition to a substrate and drying it.

[0159] The aforementioned substrate is not particularly limited, and examples thereof include fibrous substrates formed of nonwoven fabrics, knitted fabrics, woven fabrics, and the like, and resin films. The aforementioned fibrous substrate is not particularly limited, and examples thereof include chemical fibers such as polyester fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, and polylactic acid fibers; cotton, linen, silk, wool, and blended fibers thereof. The aforementioned resin film is not particularly limited, and examples thereof include polyethylene terephthalate films, polycarbonate films, acrylic resin films, COP (cycloolefin polymer) films, and TAC (cellulose triacetate) films.

[0160] The surface of the substrate may be subjected to treatments such as antistatic treatment, mold release treatment, water repellent treatment, water absorption treatment, antibacterial and deodorizing treatment, antibacterial treatment, and ultraviolet light shielding treatment as required.

[0161] The method for coating the polyurethane resin composition on the substrate is not particularly limited, and examples thereof include coating methods using an applicator, a bar coater, a knife coater, a T-die coater, a roll coater, and the like.

[0162] As a method for drying the applied polyurethane resin composition, for example, there is a method of drying it at a temperature of 50 to 140° C. for 30 seconds to 10 minutes.

[0163] The thickness of the coating film of the present embodiment can be appropriately determined according to the intended use, and is, for example, in the range of 0.001 to 10 mm.

[0164] <Leather Sample Sheet>

[0165] The leather-like sheet of the present embodiment has the above-mentioned coating film.

[0166] In order to obtain a leather-like sheet using the above-mentioned coating film, it is preferable that the above-mentioned coating film be used as an adhesive layer, a surface layer, or a surface treatment layer of the leather-like sheet.

[0167] The method for manufacturing the leather-like sheet of the present embodiment is not particularly limited, and examples thereof include a method of laminating the surface treatment layer formed on the release paper with the above-mentioned coating film by a known method. The material forming the above-mentioned surface treatment layer is not particularly limited, and examples thereof include solvent-based urethane resins, water-based urethane resins, and water-based acrylic resins. In addition, the above-mentioned lamination can use a known adhesive as needed.

[0168] As shown above, the polyol composition containing carbonate groups of the present embodiment can provide a polyurethane resin composition excellent in flexibility, chemical resistance and wear resistance. Thereby, this polyurethane resin composition can be suitably used as a material used in the manufacture of leather-like sheets such as synthetic leather and artificial leather, clothing, support pads, polishing pads, etc., and can be particularly suitably used as a material for leather-like sheets.

[0169] Example

[0170] Hereinafter, the present embodiment will be described in more detail using examples etc., but the present embodiment is not limited to these examples at all. The analysis methods and evaluation of physical properties in the following examples and comparative examples were carried out according to the following test methods.

[0171] <Hydroxy Value>

[0172] The hydroxyl value of the carbonate group-containing polyol (composition) is measured by the following method.

[0173] First, using a measuring cylinder, add pyridine to 12.5g of acetic anhydride to make 50mL to prepare an acetylating agent. Next, accurately weigh 2.5g of the sample into a 100mL eggplant-shaped flask. Next, use a full-volume pipette to add 5mL of the acetylating agent and 10mL of toluene to the aforementioned eggplant-shaped flask, install a cooling tube, and stir and heat the solution in the aforementioned eggplant-shaped flask at 100°C for 1 hour. Next, use a full-volume pipette to add 2.5mL of distilled water to the aforementioned eggplant-shaped flask, and then 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 acetylating agent, 10 mL of toluene and 2.5 mL of distilled water were put into 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 polyol (composition) containing a carbonate group was calculated using the following formula (i).

[0174] Hydroxyl value (mg-KOH / g)={(FE)×28.05×f} / G···(i)

[0175] 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.

[0176] <Number Average Molecular Weight (A)>

[0177] The number average molecular weight (A) of the polycarbonate diol obtained in the synthesis examples described below and the carbonate group-containing polyol (composition) obtained in the examples and comparative examples described below was calculated using the following formula (ii) from the hydroxyl value determined by the above method.

[0178] Number average molecular weight (A) = 2 / (H×10 -3 / 56.11)···(ii)

[0179] In addition, in formula (ii), H represents the hydroxyl value (mg-KOH / g) of the carbonate group-containing polyol (composition).

[0180] <Content of Structural Unit (II)>

[0181] The carbonate group-containing polyol composition was subjected to alkali decomposition to extract the raw material component, and the component was subjected to GC-MS measurement, LC-MS measurement, and GPC measurement. In addition, the carbonate group-containing polyol composition was dissolved in CDCl3 and subjected to 400 MHz 1 The content of the structural unit (II) relative to the total mass of the structural unit (I) and the structural unit (II) was determined by H-NMR (AL-400 manufactured by JEOL Ltd.).

[0182] In addition, the structural unit (I) and the structural unit (II) in the carbonate group-containing polyol composition are also confirmed by this measuring method.

[0183] <Determination of Molecular Weight>

[0184] A portion of the polyurethane coating obtained in the application examples and comparative application examples described later was cut out, and an N,N-dimethylformamide solution was prepared in such a manner that the polyurethane concentration reached 0.1% by mass. The number average molecular weight (Mn) converted to standard polystyrene was measured using a GPC apparatus [manufactured by Tosoh Corporation, product name "HLC-8320" (column: Tsk gel SuperHM-H·4 columns), an eluent being a solution obtained by dissolving 2.6 g of lithium bromide in 1 L of dimethylformamide].

[0185] <Low-temperature flexibility of polyurethane coating>

[0186] According to JIS K6250 (2019), short strip test pieces with a width of 10 mm, a length of 100 mm, and a thickness of about 0.1 mm were made from the polyurethane coating obtained in the application examples and comparative application examples described later. For the test pieces produced, a tensile testing machine (manufactured by ORIENTEC, product name "TENSILON, model: RTE-1210") was used, and the distance between the chucks was set to 20 mm. Next, after standing at -20°C for 5 minutes, a tensile test was performed at a tensile speed of 100 mm / min, and the low-temperature flexibility was evaluated according to the stress (100% modulus) when the test piece was elongated 100%, according to the following evaluation criteria.

[0187] (Evaluation Criteria)

[0188] ○: 100% modulus less than 12.0 MPa

[0189] △: 100% modulus is 12.0 MPa or more and less than 18.0 MPa

[0190] ×: 100% modulus is 18.0 MPa or more

[0191] <Chemical resistance of polyurethane coating>

[0192] As chemical resistance, oleic acid resistance was evaluated using oleic acid.

[0193] A cotton ball with a diameter of 10 mm impregnated with oleic acid was placed on the polyurethane coating obtained in the application examples and comparative application examples described below for 1 minute, and the state of the coating was observed after the solvent remaining on the surface was removed. The determination method is as follows.

[0194] ○: Transparent, no dents

[0195] △: Slightly cloudy or slightly concave

[0196] ×: cloudy or sunken

[0197] <Abrasion resistance of polyurethane coating>

[0198] The polyurethane coatings obtained in the application examples and comparative application examples described below were measured for wear resistance using a cone abrasion tester in accordance with the method of JIS K5600-5-8. The wear resistance was evaluated according to the following evaluation criteria based on the mass change (mg) of the polyurethane coating (including the glass plate) before the abrasion test and the mass of the polyurethane coating (including the glass plate) after the abrasion test (500 revolutions).

[0199] (Evaluation Criteria)

[0200] ○: Mass change is less than 1.5 mg

[0201] △: Mass change is 1.5 mg or more and less than 3.0 mg

[0202] ×: Mass change is 3.0 mg or more

[0203] <Low-temperature properties of polyurethane films (glass transition temperature)>

[0204] A test piece with a width of 10 mm, a length of 40 mm, and a thickness of 0.4 mm was cut from the polyurethane film obtained in the application examples and the application comparison examples described later. A viscoelasticity measuring device (manufactured by Hitachi High-Technologies Corporation, [TA7000 series, DMA7100]) was used to set the test piece with a chuck distance of 20 mm, and the viscoelasticity was measured while heating from -100 ° C to 100 ° C at 5 ° C / min. The peak of tan δ was read to determine the glass transition temperature (Tg) of the polyurethane film. The lower the glass transition temperature (Tg), the better the low temperature characteristics were evaluated.

[0205] [Synthesis Example 1] Preparation of Polycarbonate Diol P-1

[0206] Into a 1L glass flask (hereinafter also referred to as "reactor") equipped with a distillation tower filled with a regular packing and a stirring device, 275g of 2-methyl-1,3-propanediol, 212g of 1,4-butanediol and 476g of ethylene carbonate were added, and 0.097g 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 taken out 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-1 (577g) that was liquid at room temperature.

[0207] The hydroxyl value of the obtained polycarbonate diol P-1 was 53.0 mgKOH / g. The number average molecular weight of the obtained polycarbonate diol P-1 was 2,117.

[0208] [Synthesis Example 2] Preparation of Polycarbonate Diol P-2

[0209] Using the same apparatus as in Synthesis Example 1, 536 g of 1,6-hexanediol and 400 g of ethylene carbonate were added, and then 0.048 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 taken out 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-2 (468 g) that was solid at room temperature. The hydroxyl value of the obtained polycarbonate diol P-2 was 55.2 mgKOH / g. In addition, the number average molecular weight of the obtained polycarbonate diol P-2 was 2033.

[0210] [Synthesis Example 3] Preparation of Polycarbonate Diol P-3

[0211] Using the same apparatus as in Synthesis Example 1, 335 g of 1,4-butanediol, 195 g of 1,10-decanediol and 405 g of dimethyl carbonate were added, and then 0.093 g 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 taken out 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-3 (399 g) that was waxy (solid) at room temperature. The hydroxyl value of the obtained polycarbonate diol P-3 was 56.3 mgKOH / g. In addition, the number average molecular weight of the obtained polycarbonate diol P-3 was 1992.

[0212] [Synthesis Example 4] Preparation of Polycarbonate Diol P-4

[0213] Using the same apparatus as in Synthesis Example 1, 270 g of 1,6-hexanediol, 250 g of 1,4-butanediol and 445 g of ethylene carbonate were added, and then 0.112 g of magnesium acetate tetrahydrate 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 taken out while reacting at a reaction temperature of 90 to 160°C for 20 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 8 hours to obtain polycarbonate diol P-4 (462 g) that was liquid at room temperature. The hydroxyl value of the obtained polycarbonate diol P-4 was 55.8 mgKOH / g. In addition, the number average molecular weight of the obtained polycarbonate diol P-4 was 2010.

[0214] [Synthesis Example 5] Preparation of Polycarbonate Diol P-5

[0215] Using the same apparatus as in Synthesis Example 1, 230 g of 1,5-pentanediol, 250 g of 1,6-hexanediol and 400 g of ethylene carbonate were added, and then 0.047 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 taken out 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 55.2 mgKOH / g. In addition, the number average molecular weight of the obtained polycarbonate diol P-5 was 2033.

[0216] [Synthesis Example 6] Preparation of Polycarbonate Diol P-6

[0217] Using the same apparatus as in Synthesis Example 1, 383 g of 1,3-propylene glycol and 444 g of ethylene carbonate were added, and 0.041 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 taken out 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-6 (290 g) which was liquid at room temperature.

[0218] The hydroxyl value of the obtained polycarbonate diol P-6 was 56.2 mgKOH / g. The number average molecular weight of the obtained polycarbonate diol P-6 was 1,996.

[0219] [Synthesis Example 7] Preparation of Polycarbonate Diol P-7

[0220] Using the same apparatus as in Synthesis Example 1, 255 g of 3-methyl-1,5-pentanediol, 254 g of 1,6-hexanediol and 380 g of ethylene carbonate were added, and then 0.047 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 taken out 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 (466 g) that was liquid at room temperature. The hydroxyl value of the obtained polycarbonate diol P-7 was 56.4 mgKOH / g. In addition, the number average molecular weight of the obtained polycarbonate diol P-7 was 1989.

[0221] [Example 1] Preparation of carbonate group-containing polyol composition A-1

[0222] Into a 1L glass flask equipped with a stirring device (hereinafter also referred to as a "reactor"), 270 g of the polycarbonate diol P-1 obtained in Synthesis Example 1 and 230 g of "PTMG850" (trade name, number average molecular weight: about 850) manufactured by Mitsubishi Chemical Corporation 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 in an amount of 1.3 times the mass ratio of the catalyst, and a heating treatment was performed at 115°C as the temperature in the reactor for 3 hours, thereby obtaining a carbonate-containing polyol composition A-1. It should be noted that, with respect to the transesterification reaction, GPC measurement was performed on the reaction solution 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.

[0223] The physical properties of the obtained carbonate group-containing polyol composition A-1 were measured by the above-mentioned methods. The results are shown in Table 1.

[0224] Furthermore, the obtained carbonate group-containing polyol composition A-1 contains a repeating unit represented by the formula (A) and a repeating unit represented by the formula (B).

[0225] [Examples 2 to 13]

[0226] The types and charging amounts of each raw material were changed as described in Table 1 and Table 2, respectively. In addition, all the same conditions and methods as in Example 1 were used to react to obtain carbonate-containing polyol compositions A-2 to A-13 of Examples 2 to 13. The physical properties of the obtained carbonate-containing polyol compositions A-2 to A-13 were measured by the above method. The results are shown in Table 1 and Table 2.

[0227] Furthermore, the obtained carbonate group-containing polyol compositions A-2 to A-13 contain a repeating unit represented by the formula (A) and a repeating unit represented by the formula (B) or (C).

[0228] [Example 14]

[0229] Using the same apparatus as in Example 1, 240 g of the polycarbonate diol P-4 obtained in Synthesis Example 4 and 260 g of "NEWPOL PE-61" (trade name, number average molecular weight: about 2000) manufactured by Sanyo Chemical Industries, Ltd. were charged.

[0230] Next, dibutyl phosphoric acid was added in an amount 1.3 times the mass ratio of the catalyst, and the mixture was heated at 115° C. for 3 hours in the reactor to obtain a carbonate group-containing polyol composition A-15. It should be noted that GPC measurement of the reaction solution over time confirmed that the peak derived from the raw material did not change.

[0231] The physical properties of the obtained carbonate group-containing polyol composition A-14 were measured by the above-mentioned methods. The results are shown in Table 3.

[0232] Furthermore, the obtained carbonate group-containing polyol composition A-14 contains a repeating unit represented by the formula (A) and a repeating unit represented by the formula (B).

[0233] [Example 15]

[0234] Using the same apparatus as in Synthesis Example 1, 115 g of 1,5-pentanediol, 125 g of 1,6-hexanediol, 350 g of "NEWPOL PE-61" (trade name, number average molecular weight: about 2000) manufactured by Sanyo Chemical Industries, Ltd., and 240 g of ethylene carbonate were added, and 0.047 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 taken out while reacting at a reaction temperature of 165° C. for 8 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 3 hours to obtain a carbonate-containing polyol composition P-8 (580 g).

[0235] The hydroxyl value of the obtained carbonate-containing polyol composition P-8 was 55.8 mgKOH / g. In addition, the number average molecular weight of the obtained carbonate-containing polyol composition P-8 was 2011. Next, dibutyl phosphoric acid was added in an amount of 1.3 times the mass ratio relative to titanium tetra-n-butoxide, and a heat treatment was performed for 3 hours at 115° C. as the temperature in the reactor, thereby obtaining a carbonate-containing polyol composition A-15.

[0236] The physical properties of the obtained carbonate group-containing polyol composition A-15 were measured by the above-mentioned methods. The results are shown in Table 3.

[0237] Furthermore, the obtained carbonate group-containing polyol composition A-15 contains a repeating unit represented by the formula (A) and a repeating unit represented by the formula (B).

[0238] [Example 16]

[0239] Using the same apparatus as in Synthesis Example 1, 115 g of 1,5-pentanediol, 125 g of 1,6-hexanediol, and 350 g of "KURARAY POLYOIL P-2010" (trade name, number average molecular weight: about 2000) manufactured by Kuraray Co., Ltd. were added, and 0.059 g of magnesium acetate tetrahydrate was added as a catalyst. The reactor was immersed in an oil bath at 180°C, and a portion of the distillate was taken out while reacting at a reaction temperature of 165°C for 8 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 3 hours to obtain a carbonate-containing polyol composition P-9 (585 g).

[0240] The hydroxyl value of the obtained carbonate-containing polyol composition P-9 was 56.0 mgKOH / g. In addition, the number average molecular weight of the obtained carbonate-containing polyol composition P-9 was 2004. Next, dibutyl phosphoric acid was added in an amount of 1.3 times the mass ratio of magnesium acetate tetrahydrate, and a heat treatment was performed for 3 hours at 115° C. as the temperature in the reactor, thereby obtaining a carbonate-containing polyol composition A-16.

[0241] The physical properties of the obtained carbonate group-containing polyol composition A-16 were measured by the above-mentioned methods. The results are shown in Table 3.

[0242] Furthermore, the obtained carbonate group-containing polyol composition A-16 contains a repeating unit represented by the formula (A) and a repeating unit represented by the formula (B).

[0243] [Examples 17-18]

[0244] The types and feeding amounts of each raw material were changed as described in Table 3, and the reaction was carried out under the same conditions and methods as in Example 1 to obtain carbonate-containing polyol compositions A-17 to A-18 of Examples 17 to 18. The physical properties of the obtained carbonate-containing polyol compositions A-17 to A-18 were measured by the above method. The results are shown in Table 3.

[0245] Furthermore, the obtained carbonate group-containing polyol composition A-17 contains a repeating unit represented by the formula (A) and a repeating unit represented by the formula (B).

[0246] Furthermore, the obtained carbonate group-containing polyol composition A-18 contains a repeating unit represented by the formula (A) and a repeating unit represented by the formula (C).

[0247] [Comparative Examples 1-2]

[0248] The types and feeding amounts of each raw material were changed as described in Table 3, and in addition, all the same conditions and methods as in Example 1 were used to react to obtain polyol compositions B-1 to B-2 containing carbonate groups of Comparative Examples 1 to 2. The physical properties of the obtained polyol compositions B-1 to B-2 containing carbonate groups were measured by the above method, and the results are shown in Table 3.

[0249] [Table 1]

[0250]

[0251] [Table 2]

[0252]

[0253] [Table 3]

[0254]

[0255] It should be noted that the abbreviations in Tables 1 to 3 are as follows.

[0256] PTMG850: PTMG850 (manufactured by Mitsubishi Chemical Corporation, polytetramethylene ether glycol, number average molecular weight: about 850)

[0257] PTMG2000: PTMG2000 (manufactured by Mitsubishi Chemical Corporation, polytetramethylene ether glycol, number average molecular weight: about 2000)

[0258] #102: PRONON #102 (manufactured by NOF Corporation, polypropylene glycol, number average molecular weight: about 1250)

[0259] PE-61: NEWPOL PE-61 (manufactured by Sanyo Chemical Industries, Ltd., polypropylene glycol, number average molecular weight: about 2000)

[0260] P2010: KURARAY POLYOIL P-2010 (manufactured by Kuraray Co., Ltd., poly(3-methyl-1,5-pentanediol adipate diol), number average molecular weight: about 2000)

[0261] N164: NIPPOLAM 164 (manufactured by Tosoh Corporation, polyhexamethylene adipate diol, number average molecular weight: about 1000)

[0262] PCL208: PLACCEL 208 (manufactured by Daicel Corporation, poly-ε-caprolactone diol, number average molecular weight: about 830)

[0263] PCL320: PLACCEL 320 (manufactured by Daicel Corporation, poly-ε-caprolactone triol, number average molecular weight: about 2000)

[0264] [Application Example 1] Synthesis of polyurethane film PA-1

[0265] Into a 500 ml separable flask equipped with a thermocouple and a cooling tube, 40 g of the carbonate-containing polyol composition A-1 synthesized in Example 1, 280 g of N,N-dimethylformamide (DMF) (solid content set to 20% by mass), and 0.32 g of a 1% dibutyltin dilaurate toluene solution (50 ppm relative to the total mass of 4,4'-diphenylmethane diisocyanate (hereinafter also referred to as "MDI") and the carbonate-containing polyol composition were placed, and heated in an oil bath at 40°C. In the flask, while stirring the solution in the flask at 100 rpm under a nitrogen atmosphere, 24.6 g of MDI (3.09 times [mol] relative to OH [mol] of the carbonate-containing polyol composition)) was added dropwise, and the solution in the flask was further 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, 5.4 g of 1,4-butanediol (hereinafter also referred to as "1,4-BDO") in an amount necessary to be calculated from the residual isocyanate was added to the flask in portions.

[0266] 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 79,200.

[0267] Using a 0.8-2.5 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 applied in a manner that the dry film thickness reached 50-400 μm, 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, the polyurethane film PA-1 was obtained by standing at a constant temperature and humidity of 23°C and 55% RH for more than 12 hours. The obtained polyurethane film PA-1 was evaluated for various physical properties by the above method. The evaluation results are shown in Table 4.

[0268] [Application Examples 2 to 18]

[0269] Except for changing the types of each raw material as described in Tables 4 to 6, the reaction was carried out under the same conditions and methods as in Application Example 1 to obtain polyurethane films PA-2 to PA-18. The obtained polyurethane films PA-2 to PA-18 were evaluated for various physical properties using the above methods. The evaluation results are shown in Tables 4 to 6.

[0270] [Application Comparative Examples 1 and 2]

[0271] The reaction was carried out under the same conditions and methods as in Application Example 1 except that the types of the raw materials were changed as described in Table 6, thereby obtaining polyurethane films PB-1 to PB-2. The obtained polyurethane films PB-1 to PB-2 were evaluated for various physical properties using the above methods. The evaluation results are shown in Table 6.

[0272] [Table 4]

[0273]

[0274] [Table 5]

[0275]

[0276] [Table 6]

[0277]

[0278] It should be noted that the abbreviations in Tables 4 to 6 are as follows.

[0279] MDI: 4,4'-diphenylmethane diisocyanate

[0280] Hydrogenated MDI: 4,4'-methylenebiscyclohexyl diisocyanate

[0281] 1,4-BDO: 1,4-Butanediol

[0282] IPDA: Isophorone diamine

[0283] DMF: N,N-dimethylformamide

[0284] DBTL: Dibutyltin dilaurate

[0285] Industrial Applicability

[0286] The polyol composition containing carbonate group of the present invention can reduce the consumption (mixing) of solvent when manufacturing for example coating, polyurethane, and is useful as the raw material of coating, polycarbonate-based polyurethane. In addition, the polyurethane manufactured using the polyol composition containing carbonate group of the present invention has the excellent specialties of low temperature flexibility, durability (chemical resistance and abrasion resistance), and can be suitably utilized in wide fields such as elastic fiber, synthetic or artificial leather, coating, high-performance elastomer.

Claims

1. A carbonate-containing polyol composition having a number average molecular weight of 300 to 10,000, It contains a structural unit (I): a repeating unit represented by the following formula (A), and a structural unit (II): a repeating unit represented by the following formula (B), The content of the structural unit (II) is 45% by mass or more and 90% by mass or less relative to the total mass of the structural unit (I) and the structural unit (II), -(R 11 -O-CO-O) n11 -···(AND) In formula (A), R 11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 15 carbon atoms, and when there are plural R 11 are optionally the same or different from each other; n11 is any integer greater than 2, -(R 21 -O) n21 -···(B) In formula (B), R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, and when there are plural of them, R 21 They are optionally the same as or different from each other; n21 is any integer greater than 11.

2. The carbonate group-containing polyol composition according to claim 1, wherein The number average molecular weight is 400-5000.

3. The carbonate group-containing polyol composition according to claim 1, wherein The number average molecular weight is 450-3500.

4. The carbonate group-containing polyol composition according to claim 1, wherein R in the repeating unit represented by the formula (A) 11 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.

5. The carbonate group-containing polyol composition according to claim 1, wherein The R 11 It is a divalent straight-chain aliphatic hydrocarbon group having 3 to 10 carbon atoms, or a divalent branched-chain aliphatic hydrocarbon group having 3 to 10 carbon atoms.

6. The carbonate group-containing polyol composition according to claim 1, wherein The R 11 It is butylene or hexylene.

7. The carbonate group-containing polyol composition according to claim 1, wherein The R 21 It is a divalent straight-chain aliphatic hydrocarbon group having 2 to 6 carbon atoms or a divalent branched-chain aliphatic hydrocarbon group having 3 to 6 carbon atoms.

8. The carbonate group-containing polyol composition according to claim 1, wherein The R 21 It is a divalent straight-chain aliphatic hydrocarbon group having 2 to 6 carbon atoms and a divalent branched-chain aliphatic hydrocarbon group having 3 to 6 carbon atoms.

9. The carbonate group-containing polyol composition according to claim 1, wherein The R 21 It is a divalent straight-chain aliphatic hydrocarbon group having 3 to 6 carbon atoms or a divalent branched-chain aliphatic hydrocarbon group having 3 to 6 carbon atoms.

10. The carbonate group-containing polyol composition according to claim 1, wherein The R 21 It is a divalent straight-chain aliphatic hydrocarbon group having 3 to 6 carbon atoms and a divalent branched-chain aliphatic hydrocarbon group having 3 to 6 carbon atoms.

11. The carbonate group-containing polyol composition according to claim 1, wherein The average value of n21 is 11 or more and 50 or less.

12. The carbonate group-containing polyol composition according to claim 1, wherein The average value of n21 is 12 or more and 50 or less.

13. The carbonate group-containing polyol composition according to claim 1, wherein The average value of n21 is 15 or more and 50 or less.

14. The carbonate group-containing polyol composition according to claim 1, wherein The content of the structural unit (II) is 45% by mass or more and 85% by mass or less relative to the total mass of the structural unit (I) and the structural unit (II).

15. The carbonate group-containing polyol composition according to claim 1, wherein The content of the structural unit (II) is 50% by mass or more and 90% by mass or less relative to the total mass of the structural unit (I) and the structural unit (II).

16. The carbonate group-containing polyol composition according to claim 1, wherein The content of the structural unit (II) is 50% by mass or more and 85% by mass or less relative to the total mass of the structural unit (I) and the structural unit (II).

17. The carbonate group-containing polyol composition according to claim 1, wherein The content of the structural unit (II) is 52% by mass or more and 80.0% by mass or less relative to the total mass of the structural unit (I) and the structural unit (II).

18. The carbonate group-containing polyol composition according to any one of claims 1 to 17, wherein The structural unit (II) comprises a polyoxyalkylene structure.

19. The carbonate group-containing polyol composition according to any one of claims 1 to 17, wherein The structural unit (II) comprises oxy-1-methylethylene or oxyethylene.

20. A polyurethane resin composition comprising the carbonate group-containing polyol composition according to any one of claims 1 to 19, a compound having a plurality of isocyanate groups, and at least one chain extender selected from the group consisting of polyols and polyamines. 21 . A coating formed from the polyurethane resin composition according to claim 20 .

22. A leather-like sheet having the coating according to claim 21.

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