Polycarbonate polyol composition

Abstract

To provide a polycarbonate polyol composition capable of forming a polyurethane having excellent flexibility and durability (chemical resistance or heat resistance).SOLUTION: There is provided a polycarbonate polyol composition having a hydroxyl value of 14 mg / KOH or more and 376 mg / KOH or less, wherein a polyhydric hydroxy compound obtained by hydrolyzing the composition contains at least one compound represented by following formula (A), HO-R1-OH (A) (in the formula (A), R1 is a specific aliphatic hydrocarbon group or a specific aromatic hydrocarbon group) and at least one compound represented by following formula (B), HO-R2-O-R3-OH (B) (in the formula (B), R2 and R3 each independently are a specific aliphatic hydrocarbon group or a specific aromatic hydrocarbon group) and the amount of the compound represented by the formula (B) is 0.01 to 30.0 mass% based on the total mass of the polyhydric hydroxy compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate polyol composition. [Background technology]

[0002] Conventionally, the main raw materials for the soft segment of polyurethanes produced on an industrial scale can be divided into ether types typified by polytetramethylene glycol, polyester polyol types typified by adipate esters, polylactone types typified by polycaprolactone, and polycarbonate types typified by polycarbonate diol (see, for example, Non-Patent Document 1).

[0003] In general, polyurethane resins using polycarbonate diol as a polyol component are known to have various physical properties superior to polyurethane resins using polyether or polyester. For example, Patent Document 1 discloses a polycarbonate diol with excellent reaction stability, and Patent Document 2 discloses a polycarbonate diol / polyether block copolymer with reduced viscosity. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 3128275 [Patent Document 2] Patent Publication No. 2006-124485 [Non-patent literature]

[0005] [Non-Patent Document 1] "Fundamentals and Applications of Polyurethane" pp. 96-106, edited by Katsuji Matsunaga, CMC Publishing Co., Ltd., published November 2006 Summary of the Invention [Problem to be solved by the invention]

[0006] However, even the polyurethane resins using the polycarbonate diols described in Patent Documents 1 and 2 have room for improvement in applications where strict physical properties such as flexibility and durability are required.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polycarbonate polyol composition capable of forming a polyurethane having excellent flexibility and durability (chemical resistance or heat resistance). [Means for solving the problem]

[0008] As a result of extensive research, the present inventors have found that polyurethanes having an excellent balance between flexibility and durability can be obtained by using polycarbonate polyol compositions which have a predetermined hydroxyl value and which, upon hydrolysis, yield predetermined amounts of predetermined polyhydric hydroxy compounds, and have thus completed the present invention.

[0009] That is, the present invention includes the following aspects. [1] A polycarbonate polyol composition having a hydroxyl value of 14 mg / KOH or more and 376 mg / KOH or less, The polyhydric hydroxy compound obtained by hydrolyzing the polycarbonate polyol composition is At least one compound represented by the following formula (A), HO-R 1 -OH···(A) (In formula (A), R 1 is a divalent linear, branched, or cyclic aliphatic hydrocarbon group which may contain a heteroatom, or a divalent aromatic hydrocarbon group which may contain a heteroatom. At least one compound represented by the following formula (B), HO-R 2 -OR 3 -OH···(B) (In formula (B), R 2 and R 3are each independently a divalent linear, branched, or cyclic aliphatic hydrocarbon group having from 2 to 20 carbon atoms, which may contain a heteroatom, or a divalent aromatic hydrocarbon group, which may contain a heteroatom. Including, the amount of the compound represented by formula (B) is 0.01 to 30.0% by mass based on the total mass of the polyvalent hydroxy compounds; Polycarbonate polyol compositions. [2] The polycarbonate polyol composition according to [1], wherein the polyhydric hydroxy compound obtained by hydrolyzing the polycarbonate polyol composition contains at least two types of compounds represented by the formula (B). [3] The polycarbonate polyol composition according to [1] or [2], wherein the polyhydric hydroxy compound obtained by hydrolyzing the polycarbonate polyol composition contains diethylene glycol (B1). [4] The polycarbonate polyol composition according to any one of [1] to [3], wherein the polyvalent hydroxy compound obtained by hydrolyzing the polycarbonate polyol composition comprises a compound represented by the following formula (B2): HO-R 4 -OR 5 -OH···(B2) (In formula (B2), R 4 and R 5 are each independently a divalent linear, branched, or cyclic aliphatic hydrocarbon group having from 2 to 20 carbon atoms, or a divalent aromatic hydrocarbon group which may contain a heteroatom; R 4 and R 5 At least one of the above is a divalent linear aliphatic hydrocarbon group having 4 to 20 carbon atoms. [5] The polycarbonate polyol composition according to any one of [1] to [4], wherein the hydroxyl value is from 42 mg / KOH to 374 mg / KOH. [6] The polycarbonate polyol composition according to any one of [1] to [5], wherein the amount of the compound represented by formula (B) is 0.01 to 10.0 mass % based on the total mass of the polyvalent hydroxy compounds. [7] The polycarbonate polyol composition according to any one of [3] to [6], wherein the amount of the diethylene glycol (B1) is 0.01 to 5.0 mass % based on the total mass of the polyvalent hydroxy compounds. [8] The polycarbonate polyol composition according to any one of [1] to [7], wherein the polyvalent hydroxy compound obtained by hydrolyzing the polycarbonate polyol composition contains at least two types of compounds represented by the formula (A). [9] the polycarbonate polyol composition contains a metal element derived from a transesterification catalyst, The polycarbonate polyol composition according to any one of [1] to [8], wherein the metal element comprises at least one element selected from the group consisting of Group 1 elements of the long periodic table, Group 2 elements of the long periodic table, Group 4 elements of the long periodic table, and Group 7 elements of the long periodic table.

[10] A polyurethane formed from the polycarbonate polyol composition according to any one of [1] to [9].

[11] A water-based polyurethane formed from the polycarbonate polyol composition according to any one of [1] to [9].

[12]

[10] Synthetic leather containing the polyurethane described in

[10] .

[13]

[11] Synthetic leather containing the water-based polyurethane.

[14]

[10] A paint containing the polyurethane described in

[10] .

[15]

[11] A paint containing the water-based polyurethane.

[16]

[10] An adhesive comprising the polyurethane.

[17]

[11] An adhesive comprising the water-based polyurethane. [Effects of the Invention]

[0010] The polycarbonate polyol composition of the present invention can form a polyurethane having excellent flexibility and durability. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail. Note that the present invention is not limited to the following description, and various modifications can be made within the scope of the gist of the present invention.

[0012] <Polycarbonate polyol composition> The polycarbonate polyol composition of the present embodiment has a hydroxyl value of 14 mg / KOH or more and 376 mg / KOH or less, and the polyhydric hydroxy compound obtained by hydrolyzing the polycarbonate polyol composition is At least one compound represented by the following formula (A), HO-R 1 -OH···(A) (In formula (A), R 1 is a divalent linear, branched, or cyclic aliphatic hydrocarbon group which may contain a heteroatom, or a divalent aromatic hydrocarbon group which may contain a heteroatom. At least one compound represented by the following formula (B), HO-R 2 -OR 3 -OH···(B) (In formula (B), R 2 and R 3 are each independently a divalent linear, branched, or cyclic aliphatic hydrocarbon group having from 2 to 20 carbon atoms, which may contain a heteroatom, or a divalent aromatic hydrocarbon group, which may contain a heteroatom. Including, The polycarbonate polyol composition has a content of the compound represented by the formula (B) of 0.01 to 30.0% by mass based on the total mass of the polyvalent hydroxy compounds.

[0013] <Hydroxyl value> The hydroxyl value of the polycarbonate polyol composition of this embodiment is preferably 14 mg / KOH or more and 376 mg / KOH or less, with the lower limit being more preferably 22 mg / KOH or more, even more preferably 28 mg / KOH or more, particularly preferably 32 mg / KOH or more, even more preferably 37.4 mg / KOH or more, and even particularly preferably 42 mg / KOH or more. The upper limit is more preferably 374 mg / KOH or less. The above lower and upper limits may be combined appropriately to define a numerical range.

[0014] When the hydroxyl value of the polycarbonate polyol composition is equal to or greater than the above lower limit, the thermoplastic polyurethane obtained from the polycarbonate polyol composition tends to have better molding processability, whereas when the hydroxyl value of the polycarbonate polyol composition is equal to or less than the above upper limit, the thermoplastic polyurethane obtained from the polycarbonate polyol composition tends to have better flexibility and low-temperature properties.

[0015] The hydroxyl value can be measured by the method described in the examples below.

[0016] The method for controlling the hydroxyl value is not particularly limited, but examples thereof include adding and / or withdrawing a polyvalent hydroxy compound during the production of a polycarbonate polyol composition, and controlling the condensation reaction by adjusting the reaction temperature or the degree of reduced pressure.

[0017] <Polyhydroxy compound (A)> The polyhydric hydroxy compound (A) obtained by hydrolyzing the polycarbonate polyol composition of the present embodiment is preferably a compound represented by the following general formula (A): The hydrolysis method is as described in the examples below. HO-R1 -OH···(A) (R 1 is a divalent linear, branched, or cyclic aliphatic hydrocarbon group which may contain a heteroatom, or a divalent aromatic hydrocarbon group which may contain a heteroatom.

[0018] R 1 When is a divalent linear aliphatic hydrocarbon group which may contain a heteroatom, it preferably has 1 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and even more preferably 3 to 10 carbon atoms. Specific examples thereof include, but are not limited to, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, oxyethylene, oxytetramethylene, polyoxyethylene, polyoxytetramethylene, fluoroalkyl groups, and perfluoroalkyl groups. Among these, from the viewpoint of versatility, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene groups are preferred, and methylene, ethylene, propylene, and butylene groups are more preferred.

[0019] R 1 When is a divalent branched aliphatic hydrocarbon group which may contain a heteroatom, it preferably has from 2 to 20 carbon atoms, and specific examples thereof include, but are not limited to, an isopropylene group, an isobutylene group, a tert-butylene group, an isopentylene group, a 2,2-dimethyltrimethylene group, an isohexylene group, an isoheptylene group, an isooctylene group, an oxy-1-methylethylene group, an oxy-2,2-dimethyltrimethylene group, a polyoxy-1-methylethylene group, etc. Among these, from the viewpoint of versatility, an isopropylene group, an isobutylene group, an isopentylene group, a 2,2-dimethyltrimethylene group or an isohexylene group, and an oxy-1-methylethylene group are preferred.

[0020] R 1When is a divalent alicyclic hydrocarbon group which may contain a heteroatom, it preferably has 2 to 20 carbon atoms, and specific examples thereof include, but are not limited to, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cycloheptylene group.

[0021] R 1 When is a divalent aromatic hydrocarbon group which may contain a hetero atom, specific examples thereof include, but are not limited to, a phenylene group, a naphthylene group, and the like.

[0022] R 1 Specific examples of the heteroatom in the formula (I) include, but are not limited to, boron, oxygen, nitrogen, phosphorus, sulfur, and the like. The formula (I) may have a five-membered heterocyclic structure such as furan, tetrahydrofuran, oxolane, thiolane, or azolidine, or a six-membered heterocyclic structure such as oxane or pyridine.

[0023] Among them, R 1 As for R 1 Preferably, R is a divalent linear, branched or cyclic aliphatic hydrocarbon group which may contain a heteroatom and has a molecular weight of 10 or more. 1 a divalent linear aliphatic hydrocarbon group which may contain a heteroatom and has a molecular weight of 20 or more; or 1 More preferred is a divalent branched chain aliphatic hydrocarbon group which may contain a heteroatom and has a molecular weight of 20 or more. 1 More preferably, R is a divalent linear aliphatic hydrocarbon group having a molecular weight of 10 or more. 1 It is even more preferable that R is a divalent linear aliphatic hydrocarbon group having a molecular weight of 20 or more. 1 As for R 1 R is preferably a divalent linear, branched or cyclic aliphatic hydrocarbon group which may contain a heteroatom and has an upper limit of the molecular weight of 3,000 or less, 1 a divalent linear aliphatic hydrocarbon group which may contain a heteroatom and has an upper limit of the molecular weight of 2500 or less, or R 1More preferred is a divalent branched chain aliphatic hydrocarbon group which may contain a heteroatom and has an upper limit of the molecular weight of 2500 or less, and R 1 More preferably, R is a divalent linear aliphatic hydrocarbon group having an upper limit of the molecular weight of 2000 or less. 1 More preferably, R is a divalent linear aliphatic hydrocarbon group having an upper limit of molecular weight of 1500 or less. 1 Divalent linear aliphatic hydrocarbon groups having an upper limit of molecular weight of 1,000 or less are particularly preferred.

[0024] The polyhydroxy compound (A) may be one type or multiple types, but from the viewpoint of improving the flexibility of the resulting polyurethane, it is preferable to use multiple types.

[0025] <Polyhydroxy Compound (B)> The polyhydric hydroxy compound (B) obtained by hydrolyzing the polycarbonate polyol composition of this embodiment is a compound represented by the following general formula (B): The hydrolysis method is as described in the examples below. HO-R 2 -OR 3 -OH···(B) (R 2 and R 3 are each independently a divalent linear, branched, or cyclic aliphatic hydrocarbon group having from 2 to 20 carbon atoms, which may have a heteroatom, or a divalent aromatic hydrocarbon group, which may have a heteroatom.

[0026] R 2 and R 3 The divalent linear aliphatic hydrocarbon group in the formula (I) preferably has 2 or more and 15 or less carbon atoms, more preferably 2 or more and 12 or less carbon atoms, and even more preferably 2 or more and 10 or less carbon atoms.

[0027] R 2 and R 3Specific examples of the divalent linear aliphatic hydrocarbon group in the formula (I) are not particularly limited, but include, for example, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptylene group, an octylene group, etc. From the viewpoint of versatility, an ethylene group, a trimethylene group, a butylene group, a pentylene group, a hexylene group, and a decamethylene group are preferred.

[0028] R 2 and R 3 The divalent branched aliphatic hydrocarbon group in the formula (I) preferably has 3 or more and 15 or less carbon atoms, more preferably 3 or more and 12 or less carbon atoms, and even more preferably 3 or more and 10 or less carbon atoms.

[0029] R 2 and R 3 Specific examples of the divalent branched aliphatic hydrocarbon group in the formula (I) are not particularly limited, but include, for example, an isopropylene group, an isobutylene group, a tert-butylene group, an isopentylene group, a 2,2-dimethyltrimethylene group, an isohexylene group, an isoheptylene group, an isooctylene group, etc. Among these, from the viewpoint of versatility, an isobutylene group, an isopentylene group, or an isohexylene group is preferred.

[0030] R 2 and R 3 The divalent alicyclic hydrocarbon group in the formula (I) preferably has 3 or more and 15 or less carbon atoms, more preferably 6 or more and 15 or less carbon atoms, and even more preferably 6 or more and 10 or less carbon atoms.

[0031] R 2 and R 3 Specific examples of the divalent cyclic aliphatic hydrocarbon group in the formula (I) include, but are not limited to, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, etc. Among these, a cyclohexylene group is preferred from the viewpoint of versatility.

[0032] R 2 and R 3The divalent aromatic hydrocarbon group in the formula (I) preferably has 6 or more and 15 or less carbon atoms, more preferably 6 or more and 12 or less carbon atoms, and even more preferably 6 or more and 10 or less carbon atoms.

[0033] R 2 and R 3 Specific examples of the divalent aromatic hydrocarbon group in the formula (I) include, but are not limited to, a phenylene group and a naphthylene group.

[0034] R 2 and R 3 Specific examples of the heteroatom in the formula (I) include, but are not limited to, boron, oxygen, nitrogen, phosphorus, sulfur, and the like. The formula (I) may have a five-membered heterocyclic structure such as furan, tetrahydrofuran, oxolane, thiolane, or azolidine, or a six-membered heterocyclic structure such as oxane or pyridine.

[0035] The polyhydroxy compound (B) may be one type or multiple types, but from the viewpoint of improving the flexibility of the resulting polyurethane, it is preferable to use multiple types, and it is more preferable that one type of the multiple types is diethylene glycol (B1). In addition, one of the multiple types of polyhydroxy compounds (B) is preferably a compound represented by the following formula (B2). HO-R 4 -OR 5 -OH···(B2) (In formula (B2), R 4 and R 5 are each independently a divalent linear, branched, or cyclic aliphatic hydrocarbon group having from 2 to 20 carbon atoms, or a divalent aromatic hydrocarbon group which may contain a heteroatom; R 4 and R 5 At least one of the above is a divalent linear aliphatic hydrocarbon group having 4 to 20 carbon atoms.

[0036] Of all the polyhydric hydroxy compounds obtained by hydrolyzing the polycarbonate polyol of this embodiment, the proportion of the polyhydric hydroxy compound (B) represented by general formula (B) is 0.01 to 30.0 mass%. The lower limit is preferably 0.05 mass% or more, and more preferably 0.1 mass% or more. The upper limit is preferably 28 mass% or less, more preferably 25 mass% or less, particularly preferably 20 mass% or less, even more preferably 15 mass% or less, and even more particularly preferably 10 mass% or less. The above lower and upper limits may be combined appropriately to define a numerical range. When the content is within this range, it becomes possible to improve the balance of physical properties between chemical resistance and flexibility of a polyurethane using the polycarbonate polyol composition.

[0037] The polycarbonate polyol composition of the present embodiment contains a repeating unit -R derived from a polyvalent hydroxy compound represented by formula (B): 2 -OR 3 - may be contained as a repeating unit in the structure of the polycarbonate polyol, and the polyvalent hydroxy compound represented by formula (B) may also be contained as a free compound. Therefore, in the polycarbonate polyol composition of this embodiment, the proportion of the polyvalent hydroxy compound represented by formula (B) also includes the amount of the polyvalent hydroxy compound represented by formula (B) that exists as a free compound.

[0038] The amount of the polyhydroxy compound (B) can be measured by the method described in the Examples below.

[0039] The amount of the polyhydric hydroxy compound (B) can be adjusted, for example, by changing the amount of the component corresponding to the polyhydric hydroxy compound (B) used in the production of the polycarbonate dipolyol composition.

[0040] <Diethylene glycol (B1)> Of the polyhydric hydroxy compounds obtained by hydrolysis of the polycarbonate polyol composition of this embodiment, one is preferably diethylene glycol (B1). Of all the polyhydric hydroxy compounds obtained by hydrolysis of the polycarbonate diol of this embodiment, the proportion of diethylene glycol (B1) is preferably 0.01 to 10.0 mass%, more preferably 0.01 to 8.0 mass%, even more preferably 0.01 to 5.0 mass%, and particularly preferably 0.01 to 3.0 mass%. When the proportion is within the above range, it is possible to synthesize a high-molecular-weight polyurethane, which can have flexible and tough physical properties.

[0041] The amount of diethylene glycol (B1) can be measured by the method described in the Examples below.

[0042] The amount of diethylene glycol (B1) can be adjusted, for example, by changing the amount of the component corresponding to diethylene glycol (B1) used in the production of the polycarbonate dipolyol composition.

[0043] Diethylene glycol (B1) is a diethylene glycol having the formula (B) R 2 and R 3 is a polyvalent hydroxy compound that is a divalent linear hydrocarbon group having two carbon atoms, and is therefore included in the proportion of (B). For example, when the polycarbonate polyol composition of this embodiment is hydrolyzed to obtain a polycarbonate polyol containing 0.1 mass % of diethylene glycol (B1) and R 2 and R 3 is other than a divalent linear hydrocarbon group having two carbon atoms, the content of the above general formula (B) is 5.1% by mass, and the content of (B1) is 0.1% by mass.

[0044] <apha> The Hazen color number (hereinafter also referred to as "APHA") value of the polycarbonate polyol composition of this embodiment (APHA value: according to JIS K0071-1 (2017)) is preferably 100 or less, more preferably 60 or less, and even more preferably 50 or less. The lower the APHA value, the better the color tone of the polycarbonate polyol composition itself and the polyurethane obtained using this polycarbonate polyol composition tend to be. The lower limit of the APHA value is not particularly limited, but is, for example, 0.

[0045] The method for obtaining a polycarbonate polyol composition that satisfies such an APHA value is not particularly limited, but examples include a method of comprehensively controlling the selection of the type and amount of catalyst during production, thermal history, amount of residual monomer, etc. Furthermore, the selection of raw materials is also important, and those containing an antioxidant may be used.

[0046] <Number average molecular weight (Mn)> The lower limit of the number average molecular weight (Mn) of the polycarbonate polyol composition of this embodiment is preferably 260 or more, more preferably 280 or more, even more preferably 300 or more, and even more preferably 500 or more. The upper limit of the number average molecular weight (Mn) of the polycarbonate polyol composition of this embodiment is preferably 8000 or less, more preferably 5000 or less, even more preferably 4000 or less, even more preferably 3500 or less, particularly preferably 3000 or less, and more particularly preferably 2600 or less. The above lower limit and upper limit may be combined appropriately to define a numerical range.

[0047] When the number average molecular weight of the polycarbonate polyol composition is equal to or greater than the above lower limit, the flexibility and low-temperature properties of the thermoplastic polyurethane obtained from the polycarbonate polyol composition tend to be better, whereas when the number average molecular weight of the polycarbonate polyol composition is equal to or less than the above upper limit, the molding processability of the thermoplastic polyurethane obtained from the polycarbonate polyol composition tends to be better.

[0048] In this embodiment, the number average molecular weight (Mn) of the polycarbonate polyol composition can be calculated from the hydroxyl value of the polycarbonate polyol composition using the method described in the examples below.

[0049] The polycarbonate polyol composition of this embodiment preferably has molecular terminals that are primarily hydroxyl groups, with the terminal OH group ratio being 95.0 to 99.9%. A terminal OH group ratio of 99.9% or less can inhibit the formation of fine high-molecular-weight gels, while a terminal OH group ratio of 95.0% or more is preferred because it promotes curing of the coating film and results in excellent coating film appearance. The terminal OH group ratio is more preferably 97.0 to 99.9%, and even more preferably 98.0 to 99.9%.

[0050] <Method for producing polycarbonate polyol composition> The method for producing the polycarbonate polyol composition of the present embodiment is not particularly limited, and known methods can be used. For example, the polycarbonate polyol composition can be obtained by heating at 100 to 250°C under normal pressure or reduced pressure to react a carbonate compound with a polyvalent hydroxy compound in the presence of a transesterification catalyst.

[0051] The carbonate compound used in the production of polycarbonate polyol is not limited to the following, but examples thereof include alkylene carbonate, dialkyl carbonate, diaryl carbonate, and the like.

[0052] Examples of alkylene carbonates include, but are not limited to, ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, and 1,2-pentylene carbonate.

[0053] The dialkyl carbonate is not limited to the following, but examples thereof include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, and the like.

[0054] The diaryl carbonate is not limited to the following, but examples thereof include diphenyl carbonate.

[0055] Among these, the carbonate compound used in the production of polycarbonate diol is preferably an alkylene carbonate, and more preferably ethylene carbonate.

[0056] <Polyhydroxy compounds> The polyvalent hydroxy compound used in the production of the polycarbonate polyol composition is not limited to the following, but examples thereof include linear polyvalent hydroxy compounds, branched polyvalent hydroxy compounds, cyclic polyvalent hydroxy compounds, polyvalent hydroxy compounds having an aromatic ring, and polyvalent hydroxy compounds having a heterocycle containing a heteroatom.

[0057] The linear polyhydric hydroxy compound is not particularly limited, but examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nanodiol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol.

[0058] The branched chain polyhydric hydroxy compound is not particularly limited, but 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.

[0059] The cyclic polyhydric hydroxy compound is not particularly limited, but examples thereof include 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2-bis(4-hydroxycyclohexyl)-propane isosorbide.

[0060] The polyhydric hydroxy compound having an aromatic ring is not particularly limited, but examples thereof include p-xylenediol, p-tetrachloroxylenediol, 1,4-bis(hydroxyethoxy)benzene, and 2,2-bis[(4-hydroxyethoxy)phenyl]propane.

[0061] The polyvalent hydroxy compound having a heterocycle containing a hetero atom is not particularly limited, but examples thereof include 2,5-furandiethanol, 2,5-tetrafurandiethanol, and the like.

[0062] Among these, linear polyhydroxy compounds or branched polyhydroxy compounds having 3 to 10 carbon atoms are preferred, and 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nanodiol, 1,10-decanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol are preferred, with 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol being more preferred.

[0063] As the polyvalent hydroxy compound, the above-mentioned polyvalent hydroxy compound (B) may be used.

[0064] <Transesterification catalyst> The transesterification catalyst is not particularly limited, but examples thereof include alkali metals and alkaline earth metals, as well as alcoholates thereof, hydrides thereof, oxides thereof, amides thereof, hydroxides thereof, and salts thereof.

[0065] The salts of alkali metals and alkaline earth metals are not particularly limited, but examples thereof include carbonates, nitrogen-containing borates, and basic salts with organic acids.

[0066] The alkali metal is not particularly limited, but examples thereof include lithium, sodium, and potassium.

[0067] The alkaline earth metal is not particularly limited, but examples thereof include magnesium, calcium, strontium, and barium.

[0068] Furthermore, the transesterification catalyst using a metal other than an alkali metal or an alkaline earth metal is not particularly limited, but examples thereof include metals other than alkali metals and alkaline earth metals, as well as salts thereof, alcoholates thereof, and organic compounds containing such metals.

[0069] Specific examples of metals other than alkali metals and alkaline earth metals include, but are not limited to, aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, indium, tin, antimony, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth, and ytterbium.

[0070] These transesterification catalysts can be used alone or in combination of two or more.

[0071] Among these, the transesterification catalyst is preferably one or more metals selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, titanium, zirconium, tin, lead, manganese, and ytterbium, or a salt thereof, an alkoxide thereof, or an organic compound containing such a metal; more preferably one or more metals selected from the group consisting of lithium, magnesium, calcium, titanium, manganese, ytterbium, tin, zinc, and zirconium; even more preferably one or more metals selected from the group consisting of lithium, magnesium, calcium, titanium, manganese, and ytterbium; even more preferably one or more metals selected from the group consisting of lithium, magnesium, calcium, titanium, and manganese; particularly preferably one or more metals selected from the group consisting of lithium, magnesium, calcium, titanium, and manganese; more particularly preferably one or more metals selected from the group consisting of lithium, magnesium, titanium, and manganese; and even more particularly preferably one or more metals selected from the group consisting of titanium, magnesium, and manganese.

[0072] Specific examples of preferred transesterification catalysts include, but are not limited to, organic compounds of magnesium, organic compounds of lead, organic compounds of titanium, and organic compounds of manganese.

[0073] The organic compound of magnesium is not particularly limited, but examples thereof include magnesium acetate tetrahydrate and anhydrous magnesium acetate.

[0074] The organic lead compound is not particularly limited, but examples thereof include lead acetate trihydrate, tetraphenyl lead, and lead stearate.

[0075] The organic titanium compound is not particularly limited, but examples thereof include titanium tetra-n-butoxide, titanium tetra-n-propoxide, and titanium tetraisopropoxide.

[0076] The organic manganese compound is not particularly limited, but examples thereof include manganese(II) acetate and manganese(II) acetylacetonate.

[0077] The amount of the transesterification catalyst used is preferably 0.00001% by mass or more and 0.1% by mass or less, and more preferably 0.0001% by mass or more and 0.05% by mass or less, based on the total mass of the raw materials.

[0078] The metal element derived from the transesterification catalyst preferably contains at least one element selected from the group consisting of elements of Group 1 of the long periodic table, elements of Group 2 of the long periodic table, elements of Group 4 of the long periodic table, and elements of Group 7 of the long periodic table, more preferably at least one element selected from lithium, sodium, potassium, magnesium, calcium, strontium, barium, titanium, zirconium, and manganese, particularly preferably at least one element selected from lithium, magnesium, calcium, titanium, and manganese, and even more particularly preferably at least one element selected from lithium, titanium, and manganese. Use of the above metal elements as the transesterification catalyst is preferred because it eliminates the need to set the reaction temperature high or add a large amount of catalyst, and tends to suppress discoloration of the aliphatic polycarbonate and thermal degradation when made into polyurethane.

[0079] These metal elements derived from transesterification catalysts can be used alone or in combination of two or more.

[0080] The total content of metal elements derived from the transesterification catalyst in the polycarbonate polyol composition is preferably 0.1 ppm or more and 50 ppm or less, and more preferably 0.1 ppm or more and 40 ppm or less.

[0081] The polycarbonate polyol composition of the present embodiment may contain a catalyst poison such as a phosphoric acid ester, an acidic phosphoric acid ester, a phosphorous acid ester, or a phosphorus compound added thereto in order to deactivate the transesterification catalyst used in producing the polycarbonate polyol.

[0082] The phosphate ester is not particularly limited, but examples thereof include trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, and cresyl diphenyl phosphate.

[0083] The acidic phosphate ester is not particularly limited, but examples thereof include methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, acetylene glycol acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, dibutyl phosphate, monobutyl phosphate, monoisodecyl phosphate, and bis(2-ethylhexyl) phosphate.

[0084] The phosphite ester is not particularly limited, but examples thereof include triphenyl phosphite, trisnonylphenyl phosphite, tricresyl phosphite, triethyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris(tridecyl) phosphite, trioleyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl (monodecyl) phosphite, trilauryl phosphite, phosphite, diethyl hydrogen phosphite, bis(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyldipropylene glycol diphosphite, bis(decyl)pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, and the like.

[0085] The phosphorus compound is not particularly limited, but examples thereof include phosphoric acid, phosphorous acid, and hypophosphorous acid.

[0086] In the polycarbonate polyol composition of the present embodiment, the proportion of the ether polyhydric hydroxy compound represented by formula (B) can be controlled to 0.01 mass % or more and 30 mass % or less by, for example, charging the ether polyhydric hydroxy compound together with the raw material polyhydric hydroxy compound and carbonate compound to produce a polycarbonate polyol, or by adding the ether polyhydric hydroxy compound to a polycarbonate polyol and introducing an ether structure into the polycarbonate polyol by a transesterification reaction.

[0087] The polycarbonate polyol composition of this embodiment can be used as a raw material for polyurethanes and thermoplastic elastomers, as a constituent material for paints and adhesives, and as a modifier for polyesters and polyimides. The polycarbonate polyol composition of this embodiment can also be used as a raw material for polyurethanes to be reacted with polyisocyanates. The polyurethanes obtained in this manner have excellent chemical resistance, heat resistance, and weather resistance, and can therefore be widely used in foams, elastomers, paints, coatings, pressure-sensitive adhesives, adhesives, artificial leather, synthetic leather, water-based polyurethane paints, and the like.

[0088] [Polyurethane] The polyurethane of this embodiment is formed using the polycarbonate polyol composition described above.

[0089] In the method for producing the polyurethane of this embodiment, known polyurethane-forming reaction conditions for producing ordinary polyurethanes are used.

[0090] For example, the polyurethane of this embodiment can be produced by reacting the above-mentioned polycarbonate polyol composition with a polyisocyanate and a chain extender at a temperature ranging from room temperature to 200°C.

[0091] Alternatively, the polyurethane of the present embodiment can be produced by first reacting the above-mentioned polycarbonate polyol composition with an excess amount of polyisocyanate to produce a prepolymer having an isocyanate group at its terminal, and then using a chain extender to increase the degree of polymerization.

[0092] The isocyanate compound used in producing the polyurethane of this embodiment is not particularly limited as long as it functions as a curing agent, and any compound having two or more isocyanate groups at its terminal can be used.

[0093] Such an isocyanate compound is not particularly limited, but examples thereof include linear aliphatic diisocyanates, cyclic aliphatic diisocyanates, aromatic diisocyanates, isocyanate compounds having three or more isocyanate groups, as well as isocyanurate-modified products and biuret-modified products of these isocyanate compounds.

[0094] The chain aliphatic diisocyanate is not particularly limited, but examples thereof include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

[0095] The cycloaliphatic diisocyanate is not particularly limited, but examples thereof include isophorone diisocyanate.

[0096] The aromatic diisocyanate is not particularly limited, but examples thereof include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and naphthylene diisocyanate.

[0097] The isocyanate compound having three or more isocyanate groups is not particularly limited, but examples thereof include triphenylmethane-4,4'-4''-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatobenzene, and 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate.

[0098] The isocyanate compound may be a commercially available product or may be synthesized by a known method.

[0099] The content of the isocyanate compound may be adjusted appropriately depending on the molar amount of hydroxyl groups in the polyol that is the main component.

[0100] Specifically, the molar ratio (NCO / OH) of the isocyanate groups of the isocyanate compound to the hydroxyl groups of the polycarbonate polyol can be, for example, 0.2 or more and 5.0 or less, for example, 0.4 or more and 3.0 or less, or for example, 0.5 or more and 2.0 or less.

[0101] When the NCO / OH ratio is equal to or greater than the lower limit, a tougher coating film tends to be obtained, whereas when the NCO / OH ratio is equal to or less than the upper limit, the smoothness of the coating film tends to be further improved.

[0102] Furthermore, the chain extender used in producing the polyurethane of the present embodiment is a low-molecular-weight compound having at least two active hydrogens that react with the isocyanate group when producing a prepolymer having an isocyanate group, and typical examples of such a compound include polyols and polyamines.

[0103] The polyol is not particularly limited, but examples thereof include linear diols, branched diols, cyclic diols, and diols having an aromatic ring.

[0104] The linear diol is not particularly limited, but examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nanodiol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol.

[0105] The branched diol is not particularly limited, but 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.

[0106] The cyclic diol is not particularly limited, but examples thereof include 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2-bis(4-hydroxycyclohexyl)-propane.

[0107] The diol having an aromatic ring is not particularly limited, but examples thereof include p-xylene diol, p-tetrachloroxylene diol, 1,4-bis(hydroxyethoxy)benzene, and 2,2-bis[(4-hydroxyethoxy)phenyl]propane.

[0108] The polyamine is not particularly limited, but examples thereof include hydroxyamines and polyamines.

[0109] The hydroxyamines are not particularly limited, but examples thereof include N-methylethanolamine and N-ethylethanolamine.

[0110] The polyamines are not particularly limited, but 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, tolylenediamine, hydrazine, piperazine, and N,N'-diaminopiperazine.

[0111] These chain extenders may be used alone or in combination of two or more.

[0112] [Paint or coating composition] The paint or coating composition of the present embodiment comprises the polycarbonate polyol composition described above.

[0113] As a method for producing a paint or coating composition using the above-mentioned polycarbonate polyol composition, a production method known in the art can be used.For example, a two-component solvent-based coating composition can be produced by mixing the paint base obtained from the above-mentioned polycarbonate polyol composition with a curing agent made of polyisocyanate just before coating; a one-component solvent-based coating composition can be produced by reacting the above-mentioned polycarbonate polyol composition with polyisocyanate and making a urethane prepolymer having an isocyanate terminal group; a one-component solvent-based coating composition can be produced by reacting the above-mentioned polycarbonate polyol composition with an organic polyisocyanate and a chain extender and making a polyurethane resin; or a one-component water-based coating composition can be produced.

[0114] To the paint or coating composition of this embodiment, for example, other additives such as curing accelerators (catalysts), leveling agents, organic solvents, fillers, dispersants, flame retardants, dyes, organic or inorganic pigments, release agents, flow control agents, plasticizers, antioxidants, UV absorbers, light stabilizers, antifoaming agents, colorants, solvents, etc. can be added depending on the intended use. By appropriately incorporating these other additives, paint compositions with different properties, such as soft-feel paints and clear paints, can be obtained.

[0115] The curing accelerator (catalyst) is not particularly limited, but examples thereof include commonly used ones such as monoamines, diamines, other triamines, cyclic amines, alcohol amines, ether amines, and metal catalysts.

[0116] The monoamine is not particularly limited, but examples thereof include triethylamine and N,N-dimethylcyclohexylamine.

[0117] The diamine is not particularly limited, but examples thereof include tetramethylethylenediamine.

[0118] The alcohol amine is not particularly limited, but examples thereof include dimethylethanolamine.

[0119] The metal catalyst is not particularly limited, but examples thereof include potassium acetate, potassium 2-ethylhexanoate, calcium acetate, lead octoate, dibutyltin dilaurate, tin octoate, bismuth neodecanoate, bismuth oxycarbonate, bismuth 2-ethylhexanoate, zinc octoate, zinc neodecanoate, phosphine, and phospholine.

[0120] The leveling agent is not particularly limited, but examples thereof include silicone, aerosil, wax, stearates, and polysiloxanes such as BYK-331 (manufactured by BYK Chemicals).

[0121] The organic solvent is not particularly limited, but examples thereof include amide solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, carbonate ester solvents, and aromatic hydrocarbon solvents.

[0122] The amide solvent is not particularly limited, but examples thereof include dimethylformamide, diethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0123] The sulfoxide solvent is not particularly limited, but examples thereof include dimethyl sulfoxide.

[0124] The ketone solvent is not particularly limited, but examples thereof include methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and the like.

[0125] The ether solvent is not particularly limited, but examples thereof include tetrahydrofuran and dioxane.

[0126] The ester solvent is not particularly limited, but examples thereof include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, and propylene glycol 1-monomethyl ether 2-acetate.

[0127] The carbonate ester solvent is not particularly limited, but examples thereof include dimethyl carbonate, diethyl carbonate, and propylene carbonate.

[0128] The aromatic hydrocarbon solvent is not particularly limited, but examples thereof include toluene and xylene.

[0129] These organic solvents may be used alone or as a mixed solvent of two or more kinds. [Example]

[0130] Hereinafter, the present embodiment will be described in more detail with reference to specific examples and comparative examples, but the present embodiment is not limited to these examples and comparative examples as long as the gist of the present embodiment is not exceeded. In the examples, "parts" and "%" are based on mass unless otherwise specified.

[0131] The physical properties and evaluations in the examples and comparative examples described below were measured and evaluated by the methods shown below.

[0132] [Physical Property 1] Hydroxyl value The hydroxyl value of the polycarbonate polyol composition was measured by the following method. First, an acetylation reagent was prepared by adding pyridine to 12.5 g of acetic anhydride in a volumetric flask to make a 50 mL solution. Next, 2.5 g of sample was precisely weighed into a 100 mL recovery flask. Next, 5 mL of the acetylation reagent and 10 mL of toluene were added to the recovery flask using a volumetric pipette. After a condenser was attached, the solution in the recovery flask was stirred and heated at 100°C for 1 hour. Next, 2.5 mL of distilled water was added to the recovery flask using a volumetric pipette, and the solution in the recovery flask was heated and stirred for an additional 10 minutes. After the solution in the recovery flask was cooled for 2 to 3 minutes, 12.5 mL of ethanol was added to the recovery flask. Next, 2 to 3 drops of phenolphthalein were added to the recovery flask as an indicator, and the recovery flask was titrated with 0.5 mol / L ethanolic potassium hydroxide. Next, 5 mL of the acetylation reagent, 10 mL of toluene, and 2.5 mL of distilled water were placed in a 100 mL recovery flask, and the solution in the recovery flask was heated and stirred for 10 minutes, after which titration was carried out in the same manner (blank test). Based on this result, the hydroxyl value of the polycarbonate polyol composition was calculated using the following formula (i). Hydroxyl value (mg-KOH / g) = {(FE) × 28.05 × f} / G (i) In the formula (i), E represents the titer (mL) of the sample, F represents the titer (mL) of the blank test, G represents the sample weight (g), and f represents the factor of the titrant.

[0133] [Physical properties 2] Number average molecular weight The number average molecular weight of the polycarbonate polyol composition was calculated using the following formula (ii) from the hydroxyl value determined in [Physical Properties 1]. Number average molecular weight=2 / (H×10 -3 / 56.11) ···(ii) In the formula (ii), H represents the hydroxyl value (mg-KOH / g) of the polycarbonate polyol composition.

[0134] [Physical Property 3] Determination of the composition of polycarbonate polyol composition The composition of the polycarbonate polyol composition was determined as follows. First, 1 g of sample was weighed into a 100 ml recovery flask, and 30 g of ethanol and 4 g of potassium hydroxide were added to obtain a mixture. The obtained mixture was heated in a 100°C oil bath for 1 hour. After the mixture was cooled to room temperature, 1 to 2 drops of phenolphthalein were added to the mixture as an indicator, and the mixture was neutralized with hydrochloric acid. Thereafter, the mixture was cooled in a refrigerator for 3 hours, and the precipitated salt was removed by filtration. The filtrate was then analyzed by gas chromatography (hereinafter referred to as GC) under the following analytical conditions. The composition of the polycarbonate polyol composition was determined based on the area value of the polyhydric hydroxy compounds obtained by GC analysis.

[0135] (Analysis conditions) Equipment: Gas chromatograph GC-2014 (Shimadzu Corporation) Column: DB-WAX (J&W, USA) 30 m, film thickness 0.25 μm Detector: Flame ionization detector (FID) Heating profile: Heat from 130℃ to 200℃ at 5℃ / min → Hold at 200℃ for 15 minutes

[0136] [Property 4] Polyhydroxy compounds represented by general formula (B) and their proportions A sample was used to hydrolyze a polycarbonate polyol composition in the same manner as in the method for determining the composition of the polycarbonate polyol composition in [Property 3] above, and GC analysis of the hydrolyzate was carried out under the following analytical conditions. The factors of each component were determined in advance, and the proportion of polyhydroxy compounds represented by the following general formula (B) among all polyhydroxy compounds was calculated based on the area values ​​of the polyhydroxy compounds obtained by GC analysis. HO-R 2 -OR 3 -OH···(B) (R 2 and R 3 are each independently a divalent linear, branched, or cyclic aliphatic hydrocarbon group having from 2 to 20 carbon atoms, which may contain a heteroatom, or a divalent aromatic hydrocarbon group, which may contain a heteroatom.

[0137] (Analysis conditions) Equipment: Gas chromatograph GC-2014 (Shimadzu Corporation) Column: DB-WAX (J&W, USA) 30 m, film thickness 0.25 μm Detector: Flame ionization detector (FID) Heating profile: Heat from 130℃ to 200℃ at 5℃ / min → Hold at 200℃ for 15 minutes

[0138] [Physical Property 5] Diethylene glycol (B1) ratio A sample was used to hydrolyze a polycarbonate polyol composition in the same manner as in the method for determining the composition of the polycarbonate polyol composition in [Property 3] above, and GC analysis of the hydrolyzate was carried out under the following analytical conditions: The factors of each component were determined in advance, and the proportion of diethylene glycol (B1) in all polyhydroxy compounds was calculated based on the area values ​​of the polyhydroxy compounds obtained by GC analysis.

[0139] (Analysis conditions) Equipment: Gas chromatograph GC-2014 (Shimadzu Corporation) Column: DB-WAX (J&W, USA) 30 m, film thickness 0.25 μm Detector: Flame ionization detector (FID) Heating profile: Heat from 130℃ to 200℃ at 5℃ / min → Hold at 200℃ for 15 minutes

[0140] [Rating 1] Flexibility 1. Preparation of polyurethane and preparation of test specimens Using polyurethane test pieces (strip-shaped samples 10 mm wide, 100 mm long, and approximately 100 μm thick) prepared by the methods described in the application examples and application comparative examples described below, tensile tests were carried out at a chuck distance of 50 mm, a tensile speed of 100 mm / min, a temperature of 23°C, and a humidity of 50%.

[0141] 2. Flexibility Assessment The flexibility of the polyurethane was evaluated by the 100% modulus in a tensile test at 23°C.

[0142] (Evaluation criteria) A: 100% modulus is greater than 0.5 MPa and less than 7 MPa B: 100% modulus is 7 MPa or more and less than 25 MPa C: 100% modulus is 25 MPa or more or 0.5 MPa or less

[0143] [Evaluation 2] Chemical resistance 1. Preparation of polyurethane and preparation of test specimens Polyurethane was prepared and test specimens were made in the same manner as in [Evaluation 1] above.

[0144] 2. Chemical resistance evaluation The polyurethane test pieces prepared above were immersed in oleic acid at 80°C for 24 hours, and the chemical resistance of the polyurethane was evaluated in terms of the swelling degree (%), which is the rate of change in weight (W2) after immersion relative to the weight (W1) of the test piece before immersion. Swelling degree (%) = (W2 - W1) / (W1) x 100

[0145] (Evaluation criteria) A: Swelling rate (%) is 0% or more and less than 6% B: Swelling rate (%) is 6% or more but less than 8% C: Swelling rate (%) is 8% or more

[0146] [Evaluation 3] Heat resistance evaluation 1. Preparation of polyurethane and preparation of test specimens Polyurethane was prepared and test specimens were made in the same manner as in [Evaluation 1] above.

[0147] 2. Heat resistance evaluation The polyurethane test pieces prepared above were heated at 120°C for 7 days in a multi-safety dryer, product name "MSO-45TP," manufactured by Futaba Scientific Co., Ltd. After heating, the samples were measured for breaking strength in the same manner as in the evaluation of flexibility in [Evaluation 1] above, and the breaking strength retention (%) was calculated. Retention rate (%) = Breaking strength after heating / Breaking strength before heating × 100

[0148] (Evaluation criteria) A: Strength retention rate is 80% or more B: Strength retention rate is 70% or more but less than 80% C: Strength retention rate is less than 70%

[0149] [Synthesis Example 1] Synthesis of ether polyhydroxy compound EG-1 (HO-C4-O-C4-OH) 4,4'-oxybisbutylen-1-ol With reference to the contents of Patent US2018 / 0125821, an ether polyhydroxy compound represented by the following formula (EG-1) (hereinafter also referred to as "EG-1") was synthesized. [ka]

[0150] A specific synthesis scheme is shown below. [ka]

[0151] [Synthesis Example 2] Synthesis of ether polyhydroxy compound EG-2 2,5'-oxyethylenepentylene-1-ol With reference to the contents of Patent US2018 / 0125821, an ether polyhydroxy compound represented by the following formula (EG-2) (hereinafter also referred to as "EG-2") was synthesized. [ka]

[0152] A specific synthesis scheme is shown below. [ka]

[0153] [Example 1] A 2-liter glass flask (reactor) equipped with a rectification column packed with structured packing and a stirrer was charged with 458 g of 1,5-pentanediol, 500 g of 1,6-hexanediol, 760 g of ethylene carbonate, 1.1 g of EG-2 obtained in Synthesis Example 2, and 0.4 g of diethylene glycol (hereinafter referred to as EG). 0.09 g of titanium tetra-n-butoxide was added as a catalyst to the flask, and the mixture in the flask was stirred and heated. The reaction was carried out at a reactor temperature of 165 to 175°C for 12 hours while a portion of the distillate was withdrawn. Next, the reactor was directly connected to a condenser, and the reaction temperature was raised to 180-190°C. Then, the pressure was gradually reduced, and the diol component in the reactor was distilled off while appropriately sampling and measuring the hydroxyl value of the produced polycarbonate polyol, to obtain Polycarbonate Polyol Composition A-1 (860 g) having a hydroxyl value of 56.2 mgKOH / g. Of the polyvalent hydroxy compounds obtained by hydrolyzing composition A-1, the total amount of compounds represented by formula (B) was 3 mass %, and the amount of diethylene glycol (B1) was 0.1 mass %.

[0154] [Example 2] A 2-L glass flask (reactor) equipped with a rectification column packed with structured packing and a stirrer was charged with 917 g of 1,3-propanediol, 14 g of 1,4-butanediol, 1,073 g of ethylene carbonate, 1.2 g of EG-1 obtained in Synthesis Example 1, and 0.8 g of EG. 0.10 g of titanium tetra-n-butoxide was added as a catalyst to the flask, and the mixture in the flask was stirred and heated. The reaction was carried out for 24 hours at a reactor temperature of 145 to 165°C while a portion of the distillate was withdrawn. The reactor was then directly connected to a condenser, and the reaction temperature was raised to 160 to 180°C. The pressure was gradually reduced, and the diol component in the reactor was distilled off while sampling appropriately and measuring the hydroxyl value of the polycarbonate polyol produced. This yielded Polycarbonate Polyol Composition A-2 (680 g) with a hydroxyl value of 57.1 mgKOH / g. Of the polyvalent hydroxy compounds obtained by hydrolyzing composition A-2, the total amount of compounds represented by formula (B) was 5 mass %, and the amount of diethylene glycol (B1) was 2 mass %.

[0155] [Example 3] A 2-L glass flask (reactor) equipped with a rectification column packed with structured packing and a stirrer was charged with 510 g of 1,4-butanediol, 589 g of 1,5-pentanediol, 1,050 g of ethylene carbonate, 0.8 g of EG-2 obtained in Synthesis Example 2, and 0.3 g of EG. 0.10 g of titanium tetra-n-butoxide was added as a catalyst to the flask, and the mixture in the flask was stirred and heated. The reaction was carried out for 18 hours at a reactor temperature of 155-165°C while a portion of the distillate was withdrawn. The reactor was then directly connected to a condenser, and the reaction temperature was raised to 165-180°C. The pressure was gradually reduced, and the diol component in the reactor was distilled off while sampling appropriately and measuring the hydroxyl value of the polycarbonate polyol produced. This yielded Polycarbonate Polyol Composition A-3 (910 g) with a hydroxyl value of 55.5 mgKOH / g. Of the polyvalent hydroxy compounds obtained by hydrolyzing composition A-3, the total amount of compounds represented by formula (B) was 2.5% by mass, and the amount of diethylene glycol (B1) was 0.01% by mass.

[0156] [Example 4] A 2-L glass flask (reactor) equipped with a rectification column packed with structured packing and a stirrer was charged with 628 g of 1,4-butanediol, 408 g of 1,5-pentanediol, 960 g of ethylene carbonate, 0.4 g of EG-1 obtained in Synthesis Example 1, and 0.5 g of EG. 0.07 g of manganese (II) acetate tetrahydrate and 0.01 g of lithium methoxide were added as catalysts to the flask, and the mixture in the flask was stirred and heated. The reaction was carried out for 6 hours at a reactor temperature of 135 to 150°C while a portion of the distillate was withdrawn. Next, the reactor was directly connected to a condenser, and the reaction temperature was raised to 150-180°C. Then, the pressure was gradually reduced, and the diol component in the reactor was distilled off while appropriately sampling and measuring the hydroxyl value of the produced polycarbonate polyol, to obtain Polycarbonate Polyol Composition A-4 (855 g) with a hydroxyl value of 53.4 mg KOH / g. Of the polyvalent hydroxy compounds obtained by hydrolyzing composition A-4, the total amount of compounds represented by formula (B) was 3.2 mass %, and the amount of diethylene glycol (B1) was 0.05 mass %.

[0157] [Example 5] A 2-liter glass flask (reactor) equipped with a rectification column packed with structured packing and a stirrer was charged with 680 g of 1,5-pentanediol, 515 g of 1,6-hexanediol, 960 g of ethylene carbonate, 2.5 g of EG-1 obtained in Synthesis Example 1, 2.4 g of EG-2 obtained in Synthesis Example 2, and 0.5 g of EG. 0.07 g of manganese (II) acetate tetrahydrate was added as a catalyst to the flask, and the mixture in the flask was stirred and heated. The reaction was carried out for 8 hours at a reactor temperature of 135 to 150°C while a portion of the distillate was withdrawn. Next, the reactor was directly connected to a condenser, and the reaction temperature was raised to 150-180°C. Then, the pressure was gradually reduced, and the diol component in the reactor was distilled off while appropriately sampling and measuring the hydroxyl value of the produced polycarbonate polyol, to obtain Polycarbonate Polyol Composition A-5 (991 g) having a hydroxyl value of 54.6 mg KOH / g. Of the polyvalent hydroxy compounds obtained by hydrolyzing composition A-5, the total amount of compounds represented by formula (B) was 10 mass %, and the amount of diethylene glycol (B1) was 0.1 mass %.

[0158] [Example 6] A 2-L glass flask (reactor) equipped with a rectification column packed with structured packing and a stirrer was charged with 612 g of 1,4-butanediol, 296 g of 1,6-hexanediol, 820 g of ethylene carbonate, 10.0 g of EG-1 obtained in Synthesis Example 1, and 8.5 g of EG. 0.10 g of titanium tetra-n-butoxide was added as a catalyst to the flask, and the mixture in the flask was stirred and heated. The reaction was carried out for 15 hours at a reactor temperature of 140 to 160°C while a portion of the distillate was withdrawn. The reactor was then directly connected to a condenser, and the reaction temperature was raised to 160 to 175°C. The pressure was gradually reduced, and the diol component in the reactor was distilled off while sampling appropriately and measuring the hydroxyl value of the polycarbonate polyol produced. This yielded Polycarbonate Polyol Composition A-6 (790 g) with a hydroxyl value of 57.3 mgKOH / g. Of the polyvalent hydroxy compounds obtained by hydrolyzing composition A-6, the total amount of compounds represented by formula (B) was 10 mass %, and the amount of diethylene glycol (B1) was 5 mass %.

[0159] [Example 7] A 2-L glass flask (reactor) equipped with a rectification column packed with structured packing and a stirrer was charged with 551 g of 1,4-butanediol, 267 g of 1,6-hexanediol, 820 g of ethylene carbonate, and 76 g of EG. 0.10 g of titanium tetra-n-butoxide was added as a catalyst to the flask, and the mixture in the flask was stirred and heated. The reaction was carried out for 18 hours at a reactor temperature of 140 to 160°C while a portion of the distillate was withdrawn. The reactor was then directly connected to a condenser, and the reaction temperature was raised to 160 to 175°C. The pressure was gradually reduced, and the diol component in the reactor was distilled off while sampling appropriately and measuring the hydroxyl value of the produced polycarbonate polyol. This yielded Polycarbonate Polyol Composition A-7 (688 g) with a hydroxyl value of 56.1 mgKOH / g. Of the polyvalent hydroxy compounds obtained by hydrolyzing composition A-7, the total amount of compounds represented by formula (B) was 10 mass %, and the amount of diethylene glycol (B1) was 10 mass %.

[0160] [Example 8] A 2-L glass flask (reactor) equipped with a rectification column packed with structured packing and a stirrer was charged with 787 g of 1,4-butanediol, 167 g of 1,10-decanediol, 940 g of dimethyl carbonate, and 6.0 g of EG-1 obtained in Synthesis Example 1. 0.10 g of titanium tetra-n-butoxide was added as a catalyst to the flask, and the mixture in the flask was stirred and heated. The reaction was carried out for 15 hours at a reactor temperature of 150 to 190°C while a portion of the distillate was withdrawn. The reactor was then directly connected to a condenser, and the reaction temperature was raised to 190 to 195°C. The pressure was gradually reduced, and the diol component in the reactor was distilled off while sampling appropriately and measuring the hydroxyl value of the polycarbonate polyol produced. This yielded Polycarbonate Polyol Composition A-8 (795 g) with a hydroxyl value of 52.8 mgKOH / g. Of the polyvalent hydroxy compounds obtained by hydrolyzing composition A-8, the total amount of compounds represented by formula (B) was 1 mass %, and the amount of diethylene glycol (B1) was 0 mass %.

[0161] [Example 9] A 2-L glass flask (reactor) equipped with a rectification column packed with structured packing and a stirrer was charged with 787 g of 1,4-butanediol, 167 g of 1,10-decanediol, 940 g of dimethyl carbonate, 1.5 g of EG-1 obtained in Synthesis Example 1, and 27 g of EG. 0.10 g of titanium tetra-n-butoxide was added as a catalyst to the flask, and the mixture in the flask was stirred and heated. The reaction was carried out for 15 hours at a reactor temperature of 150 to 190°C while a portion of the distillate was withdrawn. The reactor was then directly connected to a condenser, and the reaction temperature was raised to 190 to 195°C. The pressure was gradually reduced, and the diol component in the reactor was distilled off while sampling appropriately and measuring the hydroxyl value of the produced polycarbonate polyol. This yielded 814 g of polycarbonate polyol composition A-9 with a hydroxyl value of 58.1 mgKOH / g. Of the polyvalent hydroxy compounds obtained by hydrolyzing composition A-9, the total amount of compounds represented by formula (B) was 1 mass %, and the amount of diethylene glycol (B1) was 0.8 mass %.

[0162] [Example 10] A 2-L glass flask (reactor) equipped with a rectification column packed with structured packing and a stirrer was charged with 612 g of 1,4-butanediol, 296 g of 1,6-hexanediol, 820 g of ethylene carbonate, 106 g of EG-1 obtained in Synthesis Example 1, and 74 g of EG. 0.08 g of zinc(II) acetylacetonate was added as a catalyst to the flask, and the mixture in the flask was stirred and heated. The reaction was carried out for 15 hours at a reactor temperature of 140 to 160°C while a portion of the distillate was withdrawn. The reactor was then directly connected to a condenser, and the reaction temperature was raised to 160 to 175°C. The pressure was gradually reduced, and the diol component in the reactor was distilled off while sampling appropriately and measuring the hydroxyl value of the polycarbonate polyol produced. This yielded Polycarbonate Polyol Composition A-10 (778 g) with a hydroxyl value of 59.2 mgKOH / g. Of the polyvalent hydroxy compounds obtained by hydrolyzing composition A-10, the total amount of compounds represented by formula (B) was 30 mass %, and the amount of diethylene glycol (B1) was 10 mass %.

[0163] [Example 11] A 2-liter glass flask (reactor) equipped with a rectification column packed with structured packing and a stirrer was charged with 680 g of 1,5-pentanediol, 515 g of 1,6-hexanediol, 960 g of ethylene carbonate, 4.9 g of 4-oxa-1,7-heptanediol, and 0.5 g of EG. 0.07 g of manganese (II) acetate tetrahydrate was added as a catalyst to the flask, and the mixture in the flask was stirred and heated. The reaction was carried out for 8 hours at a reactor temperature of 135 to 150°C, while a portion of the distillate was withdrawn. Next, the reactor was directly connected to a condenser, and the reaction temperature was raised to 150-180°C. Then, the pressure was gradually reduced, and the diol component in the reactor was distilled off while appropriately sampling and measuring the hydroxyl value of the produced polycarbonate polyol, to obtain Polycarbonate Polyol Composition A-11 (990 g) having a hydroxyl value of 54.6 mg KOH / g. Of the polyvalent hydroxy compounds obtained by hydrolyzing composition A-11, the total amount of compounds represented by formula (B) was 10 mass %, and the amount of diethylene glycol (B1) was 0.1 mass %.

[0164] [Comparative Example 1] A 2-liter glass flask (reactor) equipped with a rectification column packed with structured packing and a stirrer was charged with 458 g of 1,5-pentanediol, 500 g of 1,6-hexanediol, 760 g of ethylene carbonate, 124 g of EG-2 obtained in Synthesis Example 2, and 12 g of diethylene glycol (hereinafter referred to as EG). 0.09 g of titanium tetra-n-butoxide was added as a catalyst to the flask, and the mixture in the flask was stirred and heated. The reaction was carried out at a reactor temperature of 165 to 175°C for 12 hours while a portion of the distillate was withdrawn. Next, the reactor was directly connected to a condenser, and the reaction temperature was raised to 180-190°C. Then, the pressure was gradually reduced, and the diol component in the reactor was distilled off while appropriately sampling and measuring the hydroxyl value of the produced polycarbonate polyol, to obtain a polycarbonate polyol composition B-1 (855 g) having a hydroxyl value of 56.5 mgKOH / g. Of the polyvalent hydroxy compounds obtained by hydrolyzing composition B-1, the total amount of compounds represented by formula (B) was 35 mass %, and the amount of diethylene glycol (B1) was 0.1 mass %.

[0165] Comparative Example 2 A 2-L glass flask (reactor) equipped with a rectification column packed with structured packing and a stirrer was charged with 707 g of 1,4-butanediol, 135 g of 1,10-decanediol, 1,002 g of ethylene carbonate, and 171 g of EG. 0.08 g of magnesium(II) acetylacetonate was added as a catalyst to the flask, and the mixture in the flask was stirred and heated. The reaction was carried out for 12 hours at a reactor temperature of 130 to 160°C while a portion of the distillate was withdrawn. The reactor was then directly connected to a condenser, and the reaction temperature was raised to 160 to 175°C. The pressure was gradually reduced, and the diol component in the reactor was distilled off while sampling appropriately and measuring the hydroxyl value of the produced polycarbonate polyol. This yielded Polycarbonate Polyol Composition B-2 (722 g) with a hydroxyl value of 57.6 mgKOH / g. Of the polyvalent hydroxy compounds obtained by hydrolyzing composition B-2, the total amount of compounds represented by formula (B) was 31 mass %, and the amount of diethylene glycol (B1) was 31 mass %.

[0166] Comparative Example 3 A 1-liter glass flask (reactor) equipped with a stirrer was charged with 580 g of the polycarbonate polyol composition A-1 obtained in Example 1, 139 g of 1,5-pentanediol, and 158 g of 1,6-hexanediol. The contents were then heated with stirring, and the reactor temperature was maintained at approximately 165°C for 6 hours. Regarding the reaction, the reaction solution was subjected to GPC measurement over time, and the progress of the reaction was confirmed by observing the disappearance of peaks derived from the raw materials and the appearance of peaks derived from the product over time. A polycarbonate polyol composition B-3 (878 g) with a hydroxyl value of 380 mgKOH / g was obtained. Of the polyvalent hydroxy compounds obtained by hydrolyzing composition B-3, the total amount of compounds represented by formula (B) was 10 mass %, and the amount of diethylene glycol (B1) was 5 mass %.

[0167] [Application Example 1] Synthesis of polyurethane film PA-1 A 500 mL separable flask equipped with a thermocouple and a condenser was charged with 38 g of polycarbonate polyol composition A-1 and 2.1 mol equivalents of dibutyl phosphate relative to titanium tetra-n-butoxide, followed by heating at 115°C for 3 hours. Subsequently, 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 polycarbonate polyol composition) were added and heated in a 40°C oil bath. While stirring the solution in the flask at 100 rpm under a nitrogen atmosphere, 14.8 g of 4,4'-diphenylmethane diisocyanate (MDI) (3.09 mol times the OH group [mol] of the polycarbonate polyol composition) was added dropwise, and the solution in the flask was further stirred for approximately 1.5 hours. The isocyanate group concentration was analyzed, confirming that the theoretical amount had been consumed, yielding a prepolymer. Next, 3.2 g of 1,4-butanediol (1,4-BD), the required amount calculated based on the residual isocyanate, was added in portions to the flask. After stirring the solution in the flask for approximately 1 hour, approximately 1 g of ethanol was added, and the solution in the flask was stirred for an additional 30 minutes to obtain a polyurethane solution with a number-average molecular weight of 74,000. Using a 0.8 mm thick applicator, the resulting polyurethane solution was applied dropwise to the top of a glass plate (JIS R3202, 2 mm x 100 mm x 150 mm) to a dry film thickness of 50-150 μm. The film was then dried on a hot plate at a surface temperature of 60°C for 2 hours and then in an oven at 80°C for 12 hours. The film was then left to stand at a constant temperature and humidity of 23°C and 55% RH for at least 12 hours to obtain polyurethane film PA-1. The resulting polyurethane film PA-1 was subjected to evaluation of various physical properties using the methods described above.

[0168] [Application Examples 2 to 11, Application Comparative Examples 1 to 3] In the production of the polyurethane film of Application Example 1, the polycarbonate polyol composition used was changed to polycarbonate polyol compositions A-2 to A-11 produced in Examples 2 to 11, or polycarbonate polyol compositions B-1 to B-3 produced in Comparative Examples 1 to 3. The reaction was carried out under the same conditions as in Application Example 1, yielding polyurethane films PA-2 to PA-11 and PB-1 to PB-3. The resulting polyurethane films were evaluated for various physical properties using the methods described above. The results are shown in Table 1.

[0169] [Table 1] < / apha>

Claims

1. A polycarbonate polyol composition having a hydroxyl value of 14 mg / KOH or more and 376 mg / KOH or less, The polyhydric hydroxy compound obtained by hydrolyzing the polycarbonate polyol composition is At least one compound represented by the following formula (A), HO-R 1 -OH・・・(A) (In formula (A), R 1 is a divalent linear, branched, or cyclic aliphatic hydrocarbon group which may contain a heteroatom, or a divalent aromatic hydrocarbon group which may contain a heteroatom. At least one compound represented by the following formula (B), HO-R 2 -O-R 3 -OH・・・(B) (In formula (B), R 2 and R 3 are each independently a divalent linear, branched, or cyclic aliphatic hydrocarbon group having from 2 to 20 carbon atoms, which may contain a heteroatom, or a divalent aromatic hydrocarbon group, which may contain a heteroatom. Including, the amount of the compound represented by formula (B) is 0.01 to 30.0% by mass based on the total mass of the polyvalent hydroxy compound; Polycarbonate polyol compositions.

2. 2. The polycarbonate polyol composition according to claim 1, wherein the polyhydric hydroxy compound obtained by hydrolyzing the polycarbonate polyol composition contains at least two types of compounds represented by formula (B).

3. The polycarbonate polyol composition according to claim 2, wherein the polyhydric hydroxy compound obtained by hydrolyzing the polycarbonate polyol composition contains diethylene glycol (B1).

4. The polycarbonate polyol composition according to claim 3, wherein the polyhydric hydroxy compound obtained by hydrolyzing the polycarbonate polyol composition includes a compound represented by the following formula (B2): HO-R 4 -O-R 5 -OH・・・(B2) (In formula (B2), R 4 and R 5 are each independently a divalent linear, branched or cyclic aliphatic hydrocarbon group having from 2 to 20 carbon atoms, or a divalent aromatic hydrocarbon group which may contain a heteroatom; R 4 and R 5 At least one of the above is a divalent linear aliphatic hydrocarbon group having 4 to 20 carbon atoms.

5. The polycarbonate polyol composition according to claim 3, wherein the hydroxyl value is from 42 mg / KOH to 374 mg / KOH.

6. 3. The polycarbonate polyol composition according to claim 1, wherein the amount of the compound represented by formula (B) is 0.01 to 10.0% by mass, based on the total mass of the polyvalent hydroxy compounds.

7. The polycarbonate polyol composition according to claim 3, wherein the amount of the diethylene glycol (B1) is 0.01 to 5.0 mass % based on the total mass of the polyhydric hydroxy compounds.

8. 3. The polycarbonate polyol composition according to claim 1, wherein the polyhydric hydroxy compound obtained by hydrolyzing the polycarbonate polyol composition contains at least two types of compounds represented by formula (A).

9. the polycarbonate polyol composition contains a metal element derived from a transesterification catalyst, 3. The polycarbonate polyol composition according to claim 1 or 2, wherein the metal element comprises at least one element selected from the group consisting of Group 1 elements of the long periodic table, Group 2 elements of the long periodic table, Group 4 elements of the long periodic table, and Group 7 elements of the long periodic table.

10. A polyurethane formed from the polycarbonate polyol composition of claim 1 or 2.

11. A water-based polyurethane formed from the polycarbonate polyol composition according to claim 1 or 2.

12. A synthetic leather comprising the polyurethane of claim 10.

13. A synthetic leather comprising the water-based polyurethane of claim 11.

14. A paint comprising the polyurethane of claim 10.

15. A paint comprising the water-based polyurethane of claim 11.

16. An adhesive comprising the polyurethane of claim 10.

17. An adhesive comprising the water-based polyurethane of claim 11.

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