Polyoxyalkylene polycarbonate diol and its manufacturing method, polyurethane resin precursor, polyurethane resin, polyurethane resin composition, and articles

Abstract

To provide polyoxyalkylene polycarbonate diol which can obtain a polyurethane resin that achieves both strength and flexibility.SOLUTION: Polyoxyalkylene polycarbonate diol has a structural unit derived from polyether polycarbonate diol represented by the following formula (1), and a structural unit derived from cyclic ether having 2 or 3 carbon atoms, and has a number average molecular weight of 500-15,000. In the formula (1), R represents a divalent hydrocarbon group having 4 to 10 carbon atoms; m is a number of 1-20; and n is a number of 2-30. In the formula (1), a plurality of R may be the same number or different numbers; and a plurality of n may be the same number or different numbers.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to polyoxyalkylene polycarbonate diol, a method for producing the same, a polyurethane resin precursor, a polyurethane resin, a polyurethane resin composition, and an article. In particular, the present invention relates to a polyoxyalkylene polycarbonate diol capable of obtaining a polyurethane resin having both strength and flexibility, a method for producing the same, a polyurethane resin precursor obtained from the polyoxyalkylene polycarbonate diol, a polyurethane resin obtained from the polyurethane resin precursor, a polyurethane resin composition containing the polyurethane resin, and an article provided with the polyurethane resin.

Background Art

[0002] Generally, polyurethane resins are widely used in paints, adhesives, binders, coating agents, automotive parts, synthetic leather, artificial leather, elastomers, elastic fibers, flooring materials, printing ink binders, and the like. Among polyurethane resins, as a method for obtaining an elastomer, a polyether polycarbonate diol (hereinafter, also referred to as "PEPCD") obtained by reacting polytetramethylene ether glycol (hereinafter, also referred to as "PTMG") with a carbonate compound is reacted with a polyether polyol, a polyisocyanate, or the like. This is known (see, for example, Patent Documents 1 and 2).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, the polyurethane resins described in these patent documents 1 and 2 did not achieve both strength and flexibility.

[0005] In view of the above problems, the present invention aims to provide a polyoxyalkylene polycarbonate diol capable of producing a polyurethane resin that achieves both strength and flexibility, a method for producing the same, a polyurethane resin precursor obtained from the polyoxyalkylene polycarbonate diol, a polyurethane resin obtained from the polyurethane resin precursor, a polyurethane resin composition containing the polyurethane resin, and an article comprising the polyurethane resin. [Means for solving the problem]

[0006] The present inventors conducted diligent studies to solve the above problems and found that the above problems can be solved if the polyoxyalkylene polycarbonate diol has constituent units derived from a specific PEPCD and constituent units derived from a specific cyclic ether, and its number-average molecular weight (hereinafter sometimes referred to as "Mn") is within a predetermined range, thereby completing the present invention. In other words, the present invention is as follows. [1] A polyoxyalkylene polycarbonate diol having a constituent unit derived from a polyether polycarbonate diol represented by the following formula (1) and a constituent unit derived from a cyclic ether having 2 or 3 carbon atoms, and having a number average molecular weight of 500 to 15000. [ka] ...(1) (In formula (1) above, R represents a divalent hydrocarbon group having 4 to 10 carbon atoms, m is a number from 1 to 20, and n is a number from 2 to 30. Note that in formula (1), multiple Rs may be the same or different, and multiple ns may be the same or different.) [2] The polyoxyalkylene polycarbonate diol according to [1] above, wherein the number average molecular weight of the polyether polycarbonate diol is 250 to 5000. [3] The polyoxyalkylene polycarbonate diol according to [1] or [2] above, wherein the molar ratio of constituent units derived from the cyclic ether to constituent units derived from the polyether polycarbonate diol (cyclic ether / polyether polycarbonate diol) is 4 / 1 to 250 / 1. [4] A polyoxyalkylene polycarbonate diol as described in any of [1] to [3] above, represented by the following formula (2). [ka] ...(2) (In formula (2) above, R represents a divalent hydrocarbon group having 4 to 10 carbon atoms, R' represents a divalent hydrocarbon group having 2 or 3 carbon atoms, l is a number from 1 to 250, m is a number from 1 to 20, and n is a number from 2 to 30. Note that in formula (2), multiple Rs may be the same or different, multiple R's may be the same or different, two ls may be the same or different, and multiple ns may be the same or different.) [5] The polyoxyalkylene polycarbonate diol described in [4] above, wherein R' in formula (2) above contains a branched hydrocarbon group R'. [6] The polyoxyalkylene polycarbonate diol described in [4] above, wherein all R' in formula (2) above are branched hydrocarbon groups. [7] A polyurethane resin precursor obtained by reacting a polyoxyalkylene polycarbonate diol described in any of [1] to [6] above with a polyisocyanate compound. [8] A polyurethane resin obtained by reacting the polyurethane resin precursor described in [7] above with a chain extender. [9] A polyurethane resin composition comprising the polyurethane resin described in [8] above.

[10] An article comprising the polyurethane resin described in [8] above.

[11] A method for producing a polyoxyalkylene polycarbonate diol, comprising polymerizing a polyether polycarbonate diol represented by the following formula (1) with a cyclic ether having 2 or 3 carbon atoms in the presence of a ring-opening polymerization catalyst to obtain a polyoxyalkylene polycarbonate diol having a number average molecular weight of 500 to 15000. [ka] ...(1) (In formula (1) above, R represents a divalent hydrocarbon group having 4 to 10 carbon atoms, m is a number from 1 to 20, and n is a number from 2 to 30. Note that in formula (1), multiple Rs may be the same or different, and multiple ns may be the same or different.)

[12] The method for producing a polyoxyalkylene polycarbonate diol according to

[11] above, wherein the ring-opening polymerization catalyst is a complex metal cyanide catalyst.

[13] A method for producing a polyoxyalkylene polycarbonate diol according to

[11] or

[12] above, wherein the polyether polycarbonate diol represented by formula (1) is reacted with a polyoxyalkylene glycol and a carbonate compound in the presence of a transesterification catalyst.

[14] The method for producing a polyoxyalkylene polycarbonate diol according to

[13] above, wherein the polyoxyalkylene glycol is at least one selected from the group consisting of polytetramethylene ether glycol, copolymer polytetramethylene ether glycol of 3-methyltetrahydrofuran and tetrahydrofuran, and copolymer polyether polyol of neopentyl glycol and tetrahydrofuran. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a polyoxyalkylene polycarbonate diol capable of obtaining a polyurethane resin having both strength and flexibility, a method for producing the same, a polyurethane resin precursor obtained from the polyoxyalkylene polycarbonate diol, a polyurethane resin obtained from the polyurethane resin precursor, a polyurethane resin composition containing the polyurethane resin, and an article provided with the polyurethane resin.

Embodiments for Carrying Out the Invention

[0008] Hereinafter, the present invention will be described in detail. In this specification, those that are described as preferable can be arbitrarily adopted, and a combination of preferable ones can be said to be more preferable. Further, in this specification, the description of "XX to YY" means "XX or more and YY or less". Further, in this specification, for a preferable numerical range (for example, a range such as a content), the lower limit value and the upper limit value described stepwise can be combined independently of each other. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", it is also possible to combine the "preferred lower limit value (10)" and the "more preferred upper limit value (60)" to obtain "10 to 60". Also, in the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. Further, in this specification, the "unit" constituting the polymer means an atomic group formed by polymerization of monomers. Further, in this specification, the Mn and weight average molecular weight (hereinafter sometimes referred to as "Mw") of PEPCD or polyoxyalkylene polycarbonate diol are the molecular weights in terms of polypropylene glycol measured by creating a calibration curve using polypropylene glycol having a known molecular weight in terms of hydroxyl group using gel permeation chromatography (GPC) by the method described in the examples. In addition, in this specification, the Mn and Mw of the polyurethane resin are the polystyrene equivalent molecular weights measured by creating a calibration curve using gel permeation chromatography (GPC) by the method described in the examples and using a standard polystyrene sample with a known molecular weight. In addition, in this specification, the molecular weight distribution is a value calculated from the above Mw and Mn, and is the ratio of Mw to Mn (hereinafter sometimes referred to as "Mw / Mn").

[0009] (Polyoxyalkylene polycarbonate diol) The polyoxyalkylene polycarbonate diol of the present invention has a structural unit derived from PEPCD represented by the following formula (1) and a structural unit derived from a cyclic ether having 2 or 3 carbon atoms, and is a polyoxyalkylene polycarbonate diol having an Mn of 500 to 15000. [Chemical formula] ···(1) In the above formula (1), R represents a divalent hydrocarbon group having 4 to 10 carbon atoms, m is a number from 1 to 20, and n is a number from 2 to 30. In the formula (1), a plurality of Rs may be the same or different, and a plurality of ns may be the same number or different numbers.

[0010] Since the polyoxyalkylene polycarbonate diol has a structural unit derived from the above specific PEPCD and a structural unit derived from the above specific cyclic ether, and the Mn is within the above predetermined range, it becomes possible to obtain a polyurethane resin that achieves both strength and flexibility. Although the reason why the problems can be solved by the present invention is unclear, it is presumed that the presence of carbonate groups derived from PEPCD makes it possible to obtain a high-strength polyurethane resin, and the presence of a structure derived from a cyclic ether at both ends of PEPCD makes it possible to obtain a highly flexible polyurethane resin.

[0011] In formula (1) above, R is not particularly limited as long as it is a divalent hydrocarbon group having 4 to 10 carbon atoms, but is preferably a linear or branched alkylene group having 4 to 6 carbon atoms, more preferably an n-butylene group (4 carbon atoms) or a 2-methylbutylene group (5 carbon atoms), and is particularly preferably an n-butylene group. That is, it is preferable that RO- in formula (1) is derived from PTMG from the viewpoint of industrial availability and superior physical properties of the resulting polyurethane resin. In formula (1) above, the multiple Rs may be the same or different, but from the viewpoint of industrial availability, it is preferable that they be the same.

[0012] In formula (1) above, there are no particular restrictions on m as long as it is a number between 1 and 20, but it is preferably a number between 2 and 10, and more preferably a number between 2 and 7. If m is greater than or equal to the lower limit, the durability of the resulting polyurethane resin can be improved, and if m is less than or equal to the upper limit, the viscosity of PEPCD can be suppressed, improving the handling properties during polyurethaneization.

[0013] In formula (1) above, n is not particularly limited as long as it is a number between 2 and 30, but is preferably a number between 3 and 25, and more preferably a number between 3 and 20. If n is greater than or equal to the lower limit, the flexibility of the resulting polyurethane resin can be improved, and if n is less than or equal to the upper limit, the viscosity and crystallinity of PEPCD can be suppressed, thereby improving handling. Note that the multiple values ​​of n may be the same or different, but from the viewpoint of the industrial availability of PEPCD represented by formula (1), it is preferable that they be the same.

[0014] The Mn of the polyoxyalkylene polycarbonate diol is not particularly limited as long as it is between 500 and 15000, but is preferably 1000 or more, more preferably 1250 or more, even more preferably 1500 or more, and also preferably 12000 or less, more preferably 10000 or less, even more preferably 9000 or less, even more preferably 8000 or less, and especially preferably 3000 or less. Here, "Mn of polyoxyalkylene polycarbonate diol" is typically the polypropylene glycol-equivalent molecular weight measured by creating a calibration curve using polypropylene glycol with a known hydroxyl group-equivalent molecular weight by using gel permeation chromatography (GPC) as described in the examples. If the Mn content of the polyoxyalkylene polycarbonate diol is above the lower limit, the flexibility of the polyurethane resin obtained using the polyoxyalkylene polycarbonate diol will be better, and if it is below the upper limit, the mechanical strength of the polyurethane resin obtained using the polyoxyalkylene polycarbonate diol will be better.

[0015] There are no particular restrictions on the Mw / Mn ratio of the polyoxyalkylene polycarbonate diol, but it is preferably 1.00 to 3.00, more preferably 1.01 to 2.50, even more preferably 1.02 to 2.20, even more preferably 1.03 to 2.00, and most preferably 1.05 to 1.60. When the Mw / Mn ratio of the polyoxyalkylene polycarbonate diol is above the lower limit, the tensile properties and mechanical strength of the polyurethane resin obtained using the polyoxyalkylene polycarbonate diol are improved. When it is below the upper limit, the polyoxyalkylene polycarbonate diol tends to have low viscosity and is easy to handle.

[0016] The viscosity of polyoxyalkylene polycarbonate diol at 25°C is not particularly limited, but is preferably 100 to 100,000 mPa·s, more preferably 300 to 80,000 mPa·s, even more preferably 400 to 60,000 mPa·s, and most preferably 500 to 7,000 mPa·s. If the viscosity of the polyoxyalkylene polycarbonate diol at 25°C is above the lower limit, the tensile properties and mechanical strength of the polyurethane resin obtained using the polyoxyalkylene polycarbonate diol will be better. If it is below the upper limit, the miscibility with the diisocyanate compound will be better, and it will react more easily with the diisocyanate compound. Furthermore, handling properties can be improved. The "viscosity" here is measured using the same method as in the examples.

[0017] The total content of constituent units derived from a specific PEPCD and constituent units derived from a specific cyclic ether in the polyoxyalkylene polycarbonate diol is not particularly limited, but is preferably 80% by mass or more, more preferably 90% by mass or more, particularly preferably 95% by mass or more, and may be 100% by mass (the polyoxyalkylene polycarbonate diol may consist only of constituent units derived from a specific PEPCD and constituent units derived from a specific cyclic ether). In polyoxyalkylene polycarbonate diols, there are no particular restrictions on the molar ratio of constituent units derived from a specific cyclic ether to constituent units derived from a specific PEPCD (cyclic ether / PEPCD), but it is preferably 4 / 1 or more, more preferably 8 / 1 or more, particularly preferably 16 / 1 or more, and also preferably 250 / 1 or less, more preferably 180 / 1 or less, even more preferably 130 / 1 or less, even more preferably 120 / 1 or less, and particularly preferably 70 / 1 or less. When the above molar ratio (cyclic ether / PEPCD) is above the above lower limit, the flexibility of the polyurethane resin obtained using the polyoxyalkylene polycarbonate diol is improved, and when it is below the above upper limit, the tensile properties and mechanical strength of the polyurethane resin obtained using the polyoxyalkylene polycarbonate diol are improved.

[0018] The hydroxyl value (OHV) of polyoxyalkylene polycarbonate diol is not particularly limited, but is preferably 7 mg KOH / g or more, more preferably 10 mg KOH / g or more, more preferably 225 mg KOH / g or less, more preferably 125 mg KOH / g or less, and even more preferably 80 mg KOH / g or less. If the hydroxyl value of the polyoxyalkylene polycarbonate diol is above the lower limit, the mechanical strength of the polyurethane resin obtained using the polyoxyalkylene polycarbonate diol will be better, and if the hydroxyl value of the polyoxyalkylene polycarbonate diol is below the upper limit, the flexibility of the polyurethane resin obtained using the polyoxyalkylene polycarbonate diol will be better. The hydroxyl value of polyoxyalkylene polycarbonate diol is measured by the method described in the examples below.

[0019] The polyoxyalkylene polycarbonate diol of the present invention is not particularly limited as long as it is a polyoxyalkylene polycarbonate diol having constituent units derived from a specific PEPCD and constituent units derived from a specific cyclic ether, and having Mn within a predetermined range, but it is preferably a polyoxyalkylene polycarbonate diol represented by the following formula (2). [ka] ...(2) In equation (2) above, R, m, and n are the same as R, m, and n in equation (1) above, and the preferred values ​​are also the same. In formula (2) above, R' is a divalent hydrocarbon group having 2 or 3 carbon atoms (ethylene group, n-propylene group, or isopropylene group), and preferably a branched hydrocarbon group having 3 carbon atoms (isopropylene group). In formula (2) above, it is preferable that R' is a branched hydrocarbon group such as a branched hydrocarbon group having 3 carbon atoms (isopropylene group), and it is more preferable that all R' are branched hydrocarbon groups such as branched hydrocarbon groups having 3 carbon atoms (isopropylene group). Here, the multiple R' may be the same or may be different.

[0020] In formula (2) above, l is a number between 1 and 250, preferably between 2 and 125, and more preferably between 6 and 80. Here, the two ls may be the same number or different numbers. When l is greater than or equal to the lower limit, the flexibility of the polyurethane resin obtained using the polyoxyalkylene polycarbonate diol is improved, and when l is less than or equal to the upper limit, the mechanical strength of the polyurethane resin obtained using the polyoxyalkylene polycarbonate diol is improved.

[0021] Furthermore, the part represented by (2-A) below in formula (2) is block unit A as a constituent unit derived from PEPCD, and the "-(R'-O)" that is attached to both ends of block unit A l The portion represented by "-" is block unit B, which is a constituent unit derived from a cyclic ether. That is, the polyoxyalkylene polycarbonate diol represented by formula (2) above is a block copolymer having block unit A and block unit B arranged outside block unit A. Because the polyoxyalkylene polycarbonate diol represented by formula (2) above is a block copolymer, the crystallinity of the polyoxyalkylene polycarbonate diol is increased, resulting in better mechanical strength of the polyurethane resin obtained using the polyoxyalkylene polycarbonate diol. [ka] ...(2-A)

[0022] For detailed analysis of polyoxyalkylene polycarbonate diol, the polyoxyalkylene polycarbonate diol is placed in a pressure-resistant container coated with polytetrafluoroethylene along with a 20% by mass sodium hydroxide solution and heated at 190°C for 19 hours. Then, it is extracted with a hexane / water (50 / 50 by mass ratio) mixture, allowed to stand to separate, and the hexane layer is separated. The hexane is then removed from this hexane layer, and the resulting component is dissolved in tetrahydrofuran to obtain a measurement solution. This solution is then measured using a preparative GPC (LC-Force, YMC Co., Ltd. product name), and the measurement solution corresponding to each peak is separated. After separating the measurement solution corresponding to each peak, drying it to remove tetrahydrofuran, 1 Analysis is performed using 1H-NMR. This identifies which of the peaks originates from the polyoxyalkylene glycol and which from the cyclic ether in the polyether polycarbonate diol, and the content ratio of each component is determined by GPC.

[0023] (Method for producing polyoxyalkylene polycarbonate diol) The present invention provides a method for producing polyoxyalkylene polycarbonate diol by polymerizing a specific PEPCD with a specific cyclic ether in the presence of a ring-opening polymerization catalyst such as a complex metal cyanide catalyst.

[0024] <Polyether polycarbonate diol (PEPCD)> The PEPCD used in the production of the polyoxyalkylene polycarbonate diol of the present invention, and which constitutes the constituent unit of the polyoxyalkylene polycarbonate diol, is a specific PEPCD represented by the following formula (1). [ka] ...(1)

[0025] The Mn of PEPCD is not particularly limited, but is preferably 250 or more, more preferably 500 or more, and especially preferably 750 or more, and also preferably 5000 or less, more preferably 3500 or less, and especially preferably 2500 or less. If the Mn of PEPCD is above the lower limit, the mechanical strength of the resulting polyurethane resin will be better, and if the Mn of PEPCD is below the upper limit, the viscosity of the polyoxyalkylene polycarbonate diol will not increase, improving the handling properties during polyurethane formation. The Mn of PEPCD is measured by the method described in the examples below. As PEPCD, for example, NT1002 (Mitsubishi Chemical Corporation product name, transparent viscous liquid, Mn: 1000, glass transition temperature -78°C, R: n-butylene group, n: 3.2, m: 2.7), NT2002 (Mitsubishi Chemical Corporation product name, transparent viscous liquid, Mn: 2000, glass transition temperature -71°C, R: n-butylene group, n: 3.2, m: 6.3), and NT2006 (Mitsubishi Chemical Corporation product name, transparent viscous liquid, Mn: 2000, glass transition temperature -84°C, R: n-butylene group, n: 8.8, m: 2.0) can also be used. Note that n and m are values ​​calculated from the theoretical structure.

[0026] <<Preparation of Polyether Polycarbonate Diol (PEPCD)>> PEPCD, represented by formula (1), can be prepared by polymerizing polyoxyalkylene glycol and a carbonate compound according to a conventional method in the presence of a transesterification catalyst.

[0027] There are no particular restrictions on the polyoxyalkylene glycol used in the preparation of PEPCD. Examples include polyethylene glycol, polypropylene glycol, PTMG, copolymer polytetramethylene ether glycol of 3-methyltetrahydrofuran and tetrahydrofuran, copolymer polyether polyol of neopentyl glycol and tetrahydrofuran, copolymer polyether polyol of ethylene oxide and tetrahydrofuran, copolymer polyether glycol of propylene oxide and tetrahydrofuran, and others. These may be used individually or in combination of two or more. Among these, PTMG, copolymer polytetramethylene ether glycol of 3-methyltetrahydrofuran and tetrahydrofuran, and copolymer polyether polyol of neopentyl glycol and tetrahydrofuran are preferred, with PTMG being more preferred, from the viewpoint of achieving higher mechanical strength in the resulting polyurethane resin.

[0028] The Mn value obtained from the hydroxyl value of the polyoxyalkylene glycol used in the preparation of PEPCD is not particularly limited, but is preferably 100 or more, more preferably 150 or more, particularly preferably 200 or more, and also preferably 2000 or less, more preferably 1500 or less, particularly preferably 1000 or less. If the Mn of the polyoxyalkylene glycol is above the lower limit, the mechanical strength of the resulting polyurethane resin will be better. If it is below the upper limit, the viscosity and crystallinity of the resulting polyoxyalkylene polycarbonate diol will be suppressed, improving handling. The Mn of the polyoxyalkylene glycol can be measured in the same way as the method for measuring the Mn of PEPCD or polyoxyalkylene polycarbonate diol.

[0029] There are no particular restrictions on the carbonate compounds that can be used in the preparation of PEPCD, and examples include dialkyl carbonates, diaryl carbonates, alkylene carbonates, etc. These may be used individually or in combination of two or more. Among these, dialkyl carbonates and alkylene carbonates are preferred from the viewpoint of having better reactivity.

[0030] There are no particular limitations on specific examples of carbonate compounds, but examples include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate, ethylene carbonate, etc. Dimethyl carbonate and ethylene carbonate are preferred, and ethylene carbonate is even more preferred.

[0031] When preparing PEPCD, a transesterification catalyst may be used as needed to promote polymerization. Any compound generally known to have transesterification ability can be used as a transesterification catalyst without restriction.

[0032] There are no particular restrictions on the transesterification catalysts, and examples include compounds of Group 1 metals (excluding hydrogen) of the long-period periodic table (hereinafter simply referred to as "periodic table") such as lithium, sodium, potassium, rubidium, and cesium; compounds of Group 2 metals of the periodic table such as magnesium, calcium, strontium, and barium; compounds of Group 4 metals of the periodic table such as titanium and zirconium; compounds of Group 5 metals of the periodic table such as hafnium; compounds of Group 9 metals of the periodic table such as cobalt; compounds of Group 12 metals of the periodic table such as zinc; compounds of Group 13 metals of the periodic table such as aluminum; compounds of Group 14 metals of the periodic table such as germanium, tin, and lead; compounds of Group 15 metals of the periodic table such as antimony and bismuth; and compounds of lanthanide metals such as lanthanum, cerium, europium, and ytterbium. These may be used individually or in combination of two or more. Among these, compounds of Group 1 metals (excluding hydrogen) and Group 2 metals are preferred, and compounds of Group 2 metals are more preferred, from the viewpoint of increasing the transesterification reaction rate.

[0033] These metal compounds are mainly used as hydroxides or salts. Examples of salts used include halide salts such as chlorides, bromides, and iodides; carboxylate salts such as acetates, formates, and benzoates; inorganic salts such as carbonates and nitrates; sulfonates such as methanesulfonic acid, toluenesulfonic acid, and trifluoromethanesulfonic acid; phosphorus-containing salts such as phosphates, hydrogen phosphates, and dihydrogen phosphates; and acetylacetonate salts. Catalyst metals can also be used as alkoxides such as methoxides and ethoxides.

[0034] Details regarding the preparation of PEPCD are described, for example, in paragraphs 0038 to 0070 of Japanese Patent Publication No. 2020-125428.

[0035] <cyclic ether> The cyclic ether used in the production of the polyoxyalkylene polycarbonate diol of the present invention, which constitutes the constituent unit of the polyoxyalkylene polycarbonate diol, is a cyclic ether having 2 or 3 carbon atoms. Examples of cyclic ethers having 2 or 3 carbon atoms include ethylene oxide (hereinafter sometimes referred to as "EO") and propylene oxide (hereinafter sometimes referred to as "PO"). These may be used individually or in combination of two or more. Among these, EO and PO are preferred, and from the viewpoint of ease of reaction with polyether polycarbonate diol, it is preferable to include PO, and more preferably PO.

[0036] The reaction between cyclic ether and PEPCD involves the ring-opening addition polymerization of the cyclic ether to the hydroxyl groups (active hydrogen-containing groups) of PEPCD, using PEPCD as an initiator, in the presence of a ring-opening polymerization catalyst. This yields a polyoxyalkylene polycarbonate diol having polyoxyalkylene chains composed of oxyalkylene units, with hydroxyl groups at the ends.

[0037] When two or more cyclic ethers are reacted with PEPCD, the ring-opening addition polymerization may be random polymerization, block polymerization, or a combination of random polymerization and block polymerization.

[0038] There are no particular restrictions on the polymerization temperature for the ring-opening polymerization reaction of cyclic ethers, but it is preferably 30 to 180°C, more preferably 70 to 160°C, and most preferably 90 to 140°C. If the polymerization temperature is above the lower limit, the ring-opening polymerization of the cyclic ether can be reliably initiated, and if it is below the upper limit, the decrease in polymerization activity of the ring-opening polymerization catalyst can be suppressed.

[0039] There are no particular restrictions on the polymerization time for the ring-opening polymerization reaction of cyclic ethers, but it is preferably 2 to 18 hours, more preferably 3 to 14 hours, and most preferably 4 to 10 hours. If the polymerization time is above the lower limit, the reaction performs well, and if it is below the upper limit, it is economically efficient.

[0040] There are no particular restrictions on the amount of cyclic ether to be added, but it is preferably 25 to 1500 parts by mass, more preferably 50 to 1200 parts by mass, and most preferably 100 to 700 parts by mass per 100 parts by mass of PEPCD. If the amount of cyclic ether added is within the above preferred range, the tensile properties and mechanical strength of the polyurethane resin obtained using the cyclic ether can be further improved. When EO and PO are used as cyclic ethers, the ratio of the mass of EO to the total mass of EO and PO is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less, from the viewpoint of further improving the tensile properties of the polyurethane resin. Below the above upper limit, the storage modulus at low temperatures tends to be better.

[0041] The ring-opening polymerization reaction of cyclic ethers is preferably carried out under good stirring conditions. When using a general stirring method with a stirring blade, it is preferable to make the rotation speed of the stirring blade as fast as possible, within a range where a large amount of gas from the gas phase is not incorporated into the reaction solution and the stirring efficiency does not decrease. Also, from the viewpoint of narrowing the Mw / Mn ratio of the resulting polymer, it is preferable to make the supply rate of the cyclic ether into the reaction vessel as slow as possible, but this will reduce the production efficiency, so it is preferable to determine the supply rate of the cyclic ether by weighing these factors.

[0042] A reaction solvent may be used in the ring-opening polymerization reaction of cyclic ethers. There are no particular restrictions on the reaction solvent, and examples include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated solvents such as chloroform and dichloromethane; and ethers such as tetrahydrofuran and dioxane. These may be used individually or in combination of two or more. Among these, hexane and tetrahydrofuran are preferred from the viewpoint of having low boiling points and being easy to remove after the reaction is complete. There are no particular restrictions on the amount of reaction solvent used; any desired amount can be used.

[0043] <Ring-opening polymerization catalyst> There are no particular restrictions on the ring-opening addition polymerization catalyst, and suitable examples include complex metal cyanide catalysts (hereinafter sometimes referred to as "DMC catalysts"), alkali catalysts such as sodium hydroxide, potassium hydroxide, and cesium hydroxide, Ziegranata catalysts consisting of organoaluminum compounds and transition metal compounds, metal porphyrin catalysts as complexes obtained by reacting porphyrins, phosphazene catalysts, imino group-containing phosphazenium salts, tris(pentafluorophenyl)borane, catalysts consisting of metal salen complexes, and catalysts consisting of reduced Robson's type macrocyclic ligands. These may be used individually or in combination of two or more. When a DMC catalyst is used as a ring-opening addition polymerization catalyst, polyoxyalkylene polycarbonate diols with a narrow Mw / Mn range and lower viscosity can be obtained. There are no particular restrictions on the DMC catalyst. Examples include zinc hexacyanocobaltate complexes with t-butyl alcohol as the ligand (hereinafter sometimes referred to as "TBA-DMC catalysts"), zinc hexacyanocobaltate complexes with ethylene glycol dimethyl ether (sometimes referred to as "grime") as the ligand, and zinc hexacyanocobaltate complexes with diethylene glycol dimethyl ether (sometimes referred to as "digrim") as the ligand. These may be used individually or in combination of two or more. Among these, the TBA-DMC catalyst is preferred because it exhibits higher activity during polymerization and allows for a narrower Mw / Mn ratio for the polyoxyalkylene polycarbonate diol, thus enabling lower viscosity.

[0044] The amount of ring-opening addition polymerization catalyst added is not particularly limited as long as it is the amount necessary for the ring-opening polymerization of the cyclic ether, but a small amount is preferred, preferably 0.003 to 0.10 parts by mass, more preferably 0.005 to 0.08 parts by mass, and even more preferably 0.005 to 0.06 parts by mass per 100 parts by mass of the initiator PEPCD. The amount of ring-opening addition polymerization catalyst added is preferably 0.003 to 0.03 parts by mass, more preferably 0.004 to 0.025 parts by mass, and particularly preferably 0.005 to 0.02 parts by mass per 100 parts by mass of polyoxyalkylene polycarbonate diol. The less ring-opening addition polymerization catalyst is added in the ring-opening polymerization reaction of cyclic ethers, the less ring-opening addition polymerization catalyst can be contained in the resulting polyoxyalkylene polycarbonate diol. This reduces the influence of the ring-opening addition polymerization catalyst on the reactivity between the polyoxyalkylene polycarbonate diol and the diisocyanate compound, and also reduces costs.

[0045] Ring-opening addition polymerization using a ring-opening addition polymerization catalyst can employ the manufacturing conditions described in, for example, International Publication No. 2003 / 062301, International Publication No. 2004 / 067633, Japanese Patent Publication No. 2004-269776, Japanese Patent Publication No. 2005-15786, International Publication No. 2013 / 065802, and Japanese Patent Publication No. 2015-010162.

[0046] The polyoxyalkylene polycarbonate diol of the present invention can also be used as a raw material for polyhydroxyurethane resin. For example, epoxy groups are attached to the ends of the polyoxyalkylene polycarbonate diol of the present invention in the same manner as described in paragraphs 0026 to 0034 of Japanese Patent No. 3114304 and Example 1 of Japanese Patent Publication No. 7-116171. Next, the epoxy groups at the ends of the polyoxyalkylene polycarbonate diol of the present invention are reacted with carbon dioxide in the same manner as described in paragraphs 0034 to 0043 of Japanese Patent No. 5277233 to obtain a cyclic carbonate compound. Furthermore, a polyhydroxyurethane resin can be obtained by reacting the cyclic carbonate group of the cyclic carbonate compound with an amine compound in the same manner as described in paragraphs 0044 to 0050 of Japanese Patent No. 5277233.

[0047] (Polyurethane resin precursor) The polyurethane resin precursor of the present invention is obtained by reacting the polyoxyalkylene polycarbonate diol of the present invention with a polyisocyanate compound. As polyurethane resin precursors, different polyurethane resin precursors with different terminal groups can be obtained by varying the reaction ratio of polyoxyalkylene polycarbonate diol and polyisocyanate compound. Examples of polyurethane resin precursors include polyurethane resin precursor polymers with isocyanate groups as terminal groups and polyurethane resin precursor polymers with hydroxyl groups as terminal groups. From the viewpoint of easily obtaining polyurethane resin by reaction with a chain extender, polyurethane resin precursors with isocyanate groups as terminal groups are preferred. A polyurethane resin precursor with a hydroxyl group at its terminal end can be cured by reaction with a polyisocyanate compound, as described later. Polyurethane resin precursors with isocyanate groups at the end can be cured by reaction with moisture in the air to obtain a cured product, or they can be reacted with a chain extender (described later) to obtain a cured product (polyurethane resin described later).

[0048] <Polyisocyanate compounds> There are no particular restrictions on polyisocyanate compounds as long as they are compounds having multiple isocyanate groups in one molecule. Examples include aromatic polyisocyanate compounds such as 4,4'-diphenylmethane diisocyanate (hereinafter sometimes referred to as "MDI"), naphthalene-1,5-diisocyanate, polyphenylene polymethylene diisocyanate, 2,4-tole diisocyanate, and 2,6-tole diisocyanate; aralkyl polyisocyanate compounds such as tetramethylxylylene diisocyanate and xylylene diisocyanate; aliphatic polyisocyanate compounds such as hexamethylene diisocyanate; and alicyclic polyisocyanate compounds such as isophorone diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate). Examples include: socyanate compounds; urethane modified compounds obtained from polyisocyanate compounds; biuret modified compounds obtained from polyisocyanate compounds; allophanate modified compounds obtained from polyisocyanate compounds; carbodiimide modified compounds obtained from polyisocyanate compounds; isocyanurate modified compounds obtained from polyisocyanate compounds; polyisocyanate compounds modified with hydrophilic groups such as polyethylene oxide, carboxyl groups, or sulfonic acid groups to become self-emulsifying ("self-emulsifying polyisocyanate compounds"); compounds emulsified with surfactants to make them water-dispersible ("forced-emulsifying polyisocyanate compounds"); water-dispersible polyisocyanates; deblocked forms of blocked isocyanates; and the like. These may be used individually or in combination of two or more. Among these, aromatic polyisocyanate compounds are preferred from the viewpoint of reactivity with polyoxyalkylene polycarbonate diols, 4,4'-diphenylmethane diisocyanate is more preferred, and aliphatic polyisocyanate compounds and alicyclic polyisocyanate compounds are preferred from the viewpoint of easily suppressing yellowing over time, hexamethylene diisocyanate and isophorone diisocyanate are more preferred.

[0049] The index for isocyanate groups, which is the ratio of isocyanate groups of the polyisocyanate compound to the hydroxyl groups of the polyoxyalkylene polycarbonate diol ((number of isocyanate groups in the polyisocyanate compound) / (number of hydroxyl groups in the polyoxyalkylene polycarbonate diol) × 100), is not particularly limited. However, if it is less than 100, the terminal groups of the polyurethane resin precursor obtained by the reaction of the polyoxyalkylene polycarbonate diol and the polyisocyanate compound tend to be hydroxyl groups, and if it is greater than 100, the terminal groups of the polyurethane resin precursor tend to be isocyanate groups. A polyurethane resin precursor with isocyanate groups as terminal groups is preferred, and the index for obtaining this is preferably 150 to 300, more preferably 180 to 280. Furthermore, when obtaining a polyurethane resin precursor with isocyanate groups at the end, it is preferable to use an excess amount of the polyisocyanate compound to react with the polyoxyalkylene polycarbonate diol. By using an excess amount of the polyisocyanate compound, a polyurethane resin precursor with isocyanate groups at both ends can be obtained.

[0050] There are no particular restrictions on the molecular weight of the polyisocyanate compound, but it is preferably 120 to 400, more preferably 130 to 390, and most preferably 140 to 380. If the molecular weight of the polyisocyanate compound is above the lower limit, the reactivity with polyoxyalkylene polycarbonate diol is improved, resulting in better tensile properties and mechanical strength of the polyurethane resin obtained using the polyisocyanate compound. Conversely, if the molecular weight is below the upper limit, the tensile properties and mechanical strength of the polyurethane resin obtained using the polyisocyanate compound are also improved.

[0051] A reaction catalyst may be used when reacting a polyoxyalkylene polycarbonate diol with a polyisocyanate compound. When a reaction catalyst is used when reacting a polyoxyalkylene polycarbonate diol with a polyisocyanate compound, there are no particular restrictions on the reaction catalyst, and examples of known urethane reaction catalysts include organotin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and 2-ethylhexanoate tin; iron compounds such as iron acetylacetonate and ferric chloride; and tertiary amine catalysts such as triethylamine and triethylenediamine. These may be used individually or in combination of two or more. Among these, organotin compounds are preferred from the viewpoint of having better reactivity. When a reaction catalyst is used when reacting a polyoxyalkylene polycarbonate diol with a diisocyanate compound, there are no particular restrictions on the amount of the reaction catalyst added, but it is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 0.1 parts by mass, and most preferably 0.01 to 0.05 parts by mass per 100 parts by mass of polyoxyalkylene polycarbonate diol. When the amount of reaction catalyst added is above the lower limit, the reactivity is superior, and when it is below the upper limit, the storage stability is superior.

[0052] There are no particular restrictions on the temperature when reacting the polyoxyalkylene polycarbonate diol with the polyisocyanate compound, but it is preferably 15 to 120°C, more preferably 30 to 100°C, and most preferably 50 to 90°C. When reacting polyoxyalkylene polycarbonate diol with a polyisocyanate compound, if the temperature is above the lower limit, the reaction is more likely to start reliably, and if the temperature is below the upper limit, the reaction is easier to control.

[0053] There are no particular restrictions on the reaction time when reacting polyoxyalkylene polycarbonate diol with a polyisocyanate compound, but it is preferably 0.1 to 100 hours, more preferably 1 to 10 hours, and most preferably 2 to 6 hours. If the reaction time is above the lower limit, the reaction performance is better, and if it is below the upper limit, the cost-effectiveness is better.

[0054] A solvent may be used when reacting polyoxyalkylene polycarbonate diol with a polyisocyanate compound. There are no particular restrictions on the solvent, but examples of reaction-inert solvents include ethers such as tetrahydrofuran and dioxane; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; secondary alcohols such as isopropyl alcohol; and aromatic hydrocarbons such as toluene and xylene. These may be used individually or in combination of two or more.

[0055] Specific methods for the reaction between polyoxyalkylene polycarbonate diols and polyisocyanate compounds include, for example, the method described in International Publication No. 2006 / 043569.

[0056] Polyurethane resin precursors can be widely used in foams, elastomers, paints, elastic fibers, adhesives, binders, active energy ray curable resin compositions, medical materials, sealants, synthetic leather, artificial leather, coatings, flooring materials, and the like. For example, the elastomer can be used in the applications described in paragraphs 0114 to 0117 of Japanese Patent Publication No. 2017-133024, the paint can be used in the applications described in paragraphs 0118 and 0119 of Japanese Patent Publication No. 2017-133024, the elastic fiber can be used in the applications described in paragraphs 0125 to 0127 of Japanese Patent Publication No. 2017-133024. Furthermore, the adhesive can be used in the applications described in paragraphs 0120 to 0123 of Japanese Patent Publication No. 2017-133024, the binder can be used in the applications described in paragraph 0124 of Japanese Patent Publication No. 2017-133024, and the active energy ray curable resin composition can be used in the applications described in paragraphs 0130 to 0135 of Japanese Patent Publication No. 2017-133024. The medical material can be used for the purposes described in paragraph 0129 of Japanese Patent Publication No. 2017-133024, and the sealant can be used for the purposes described in paragraph 0128 of Japanese Patent Publication No. 2017-133024. The components of the aforementioned paint other than the polyurethane resin precursor can be the same as those used in the paint composition for clear coat and the colored paint composition described later, and the components of the aforementioned adhesive other than the polyurethane resin precursor can be the same as those used in the adhesive composition described later.

[0057] (Polyurethane resin) The polyurethane resin of the present invention is obtained by reacting the polyurethane resin precursor of the present invention with a chain extender. That is, the polyurethane resin of the present invention has units based on the polyoxyalkylene polycarbonate diol of the present invention, units based on a polyisocyanate compound, and units based on a chain extender.

[0058] The proportion of each unit in polyurethane resin can be determined, for example, as follows: The polyurethane resin is placed in a pressure vessel coated with polytetrafluoroethylene along with pyridine and distilled water, and heated at 130°C for 15 hours. Afterward, the pyridine is removed by distillation to obtain a solution dissolved in tetrahydrofuran. This solution is used as the measurement solution, and it is measured using the preparative GPC method described above. For the obtained peaks, the measurement solution corresponding to each peak is separated. For each of the measurement solutions corresponding to the separated peaks, remove the tetrahydrofuran by drying under reduced pressure at 80°C for 1 hour, and then for each of the remaining liquids, 1 The analysis is performed using 1H-NMR. This allows us to identify which of the peaks represents units based on polyoxyalkylene polycarbonate diol, units based on polyisocyanate compounds, and units based on chain extenders. Furthermore, the content ratio of each component is determined by GPC.

[0059] There are no particular restrictions on the Mn of the polyurethane resin, but it is preferably greater than 10,000, more preferably 20,000 to 120,000, even more preferably 30,000 to 110,000, and particularly preferably 40,000 to 100,000. When the Mn content of the polyurethane resin is above the lower limit, the elongation properties are improved, and when it is below the upper limit, the tensile properties are improved. The manganese content (Mn) in the polyurethane resin is measured by the method described in the examples below.

[0060] There are no particular restrictions on the glass transition temperature (Tg) of the polyurethane resin, but it is preferably -60 to 0°C, more preferably -55 to -10°C, and most preferably -50 to -25°C. When the glass transition temperature (Tg) of the polyurethane resin is within the above preferred range, it exhibits superior low-temperature properties. The glass transition temperature (Tg) of the polyurethane resin is measured by the method described in the examples below.

[0061] There are no particular restrictions on the temperature at which the polyurethane resin begins to flow, but it is preferably 100 to 210°C, more preferably 110 to 200°C, even more preferably 120 to 190°C, and most preferably 125 to 180°C. If the flow initiation temperature of the polyurethane resin is above the lower limit, it exhibits superior heat resistance; if it is below the upper limit, it exhibits superior injection moldability. There are no particular limitations on the method for obtaining the polyurethane resin of the present invention. Examples include a method in which polyoxyalkylene polycarbonate diol, a polyisocyanate compound, a chain extender described later, and other components described later as needed are charged together and reacted, and a method in which components other than the polyisocyanate compound and components containing the polyisocyanate compound are prepared separately, mixed, and reacted.

[0062] <Chain extender> The chain extender is preferably at least one selected from the group consisting of polyols and polyamines, and has at least two active hydrogen atoms that react with the isocyanate group.

[0063] There are no particular restrictions on specific examples of chain extenders, but for example, linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol; 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, and 2,4-heptanediol. Branched-chain diols such as 1,4-dimethylolhexane, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, dimergol, neopentyl glycol; ether-group-containing diols such as diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol Diols having an alicyclic structure such as 1,4-dihydroxycyclohexane and 1,4-dihydroxyethylcyclohexane; diols having aromatic groups such as xylylene glycol, 1,4-dihydroxyethylbenzene and 4,4'-methylenebis(hydroxyethylbenzene); polyols such as glycerin, trimethylolpropane and pentaerythritol; hydroxyamines such as N-methylethanolamine and N-ethylethanolamine; ethylenediamine, 1,3-diaminopropane, hexamethylenediamine and triethylenetetramine Polyamines such as 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;These are some examples. These may be used individually or in combination of two or more.

[0064] Among these, ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol are preferred, with 1,4-butanediol being more preferred, due to their superior flexibility and elastic recovery properties in the resulting polyurethane resin, and their availability in large quantities at low industrial cost.

[0065] There are no particular restrictions on the molecular weight of the chain extender, but it is preferably between 60 and 1000, and more preferably between 60 and less than 300. If the molecular weight of the chain extender is within the above preferred range, the tensile properties and mechanical strength of the resulting polyurethane resin can be further improved.

[0066] (Polyurethane resin composition) The polyurethane resin composition of the present invention comprises the polyurethane resin of the present invention and optionally contains other components.

[0067] <Other ingredients> Other components include, for example, polyols other than the polyoxyalkylene polycarbonate diol of the present invention (also referred to as "other polyols"), polyoxyalkylene monools, polycarbonate monools, stabilizers, fillers (reinforcers), pigments (inorganic pigments, organic pigments), flame retardants, mold release agents, and antifungal agents.

[0068] <Other polyols> Other polyols are not particularly limited and include, for example, polyoxyalkylene diols, polyoxyalkylene triols, polyoxyalkylene tetraols, polyester polyols, polyether polyester polyols, and polycarbonate diols. These may be used individually or in combination of two or more. <Stabilizer> There are no particular restrictions on the stabilizers used; examples include antioxidants, UV absorbers and other anti-aging agents, and light stabilizers. These may be used individually or in combination of two or more. Examples of anti-aging agents include hindered phenol compounds such as butylhydroxytoluene (BHT); benzotriazole and hindered amine compounds; butylhydroxyanisole (BHA); diphenylamine; phenylenediamine; triphenyl phosphite; and others. These may be used individually or in combination of two or more.

[0069] <Fillers (reinforcers)> There are no particular restrictions on the fillers (reinforcements), and examples include carbon black, aluminum hydroxide, calcium carbonate, titanium dioxide, silica, glass, bone meal, wood flour, and fiber flakes. These may be used individually or in combination of two or more.

[0070] <Pigments> There are no particular restrictions on the inorganic pigments used; examples include titanium dioxide, zinc oxide, ultramarine, red iron oxide, lithopon, lead, cadmium, iron, cobalt, aluminum, hydrochloride salts, sulfates, etc. These may be used individually or in combination of two or more. There are no particular restrictions on the organic pigments used; examples include azo pigments and copper phthalocyanine pigments. These may be used individually or in combination of two or more.

[0071] <Flame retardant> There are no particular restrictions on the flame retardants used; examples include chloroalkyl phosphates, dimethylmethylphosphonates, ammonium polyphosphates, and organobromine compounds. These may be used individually or in combination of two or more.

[0072] <Release agent> There are no particular restrictions on the release agent; examples include waxes, soaps, and silicone oils. These may be used individually or in combination of two or more.

[0073] <Antifungal agent> There are no particular restrictions on the antifungal agents used; examples include pentachlorophenol, pentachlorophenol laurate, and bis(tri-n-butyltin) oxide. These may be used individually or in combination of two or more.

[0074] The polyurethane resin composition of the present invention contains a polyurethane resin that achieves both strength and flexibility, and is therefore suitable for use in paint compositions, adhesive compositions, printing ink compositions, adhesive compositions, porous films formed on nonwoven fabrics of artificial leather, tire compositions, elastomers, elastic fibers, binders, active energy ray curable resin compositions, medical materials, sealants, coatings, foams, flooring materials, and the like. In particular, when the polyurethane resin composition of the present invention is applied to a tire composition, it is possible to obtain a tire with excellent handling stability on icy roads and the like.

[0075] Furthermore, the elastomer can be used in the applications described in paragraphs 0114 to 0117 of Japanese Patent Publication No. 2017-133024, and the elastic fiber can be used in the applications described in paragraphs 0125 to 0127 of Japanese Patent Publication No. 2017-133024. The binder can be used in the applications described in paragraph 0124 of Japanese Patent Publication No. 2017-133024, and the active energy ray curable resin composition can be used in the applications described in paragraphs 0130 to 0135 of Japanese Patent Publication No. 2017-133024. The medical material can be used in the applications described in paragraph 0129 of Japanese Patent Publication No. 2017-133024, and the sealant can be used in the applications described in paragraph 0128 of Japanese Patent Publication No. 2017-133024.

[0076] Furthermore, the polyurethane resin composition of the present invention may contain a solvent. The solvent may be water or an organic solvent, or both. When the polyurethane resin composition of the present invention contains water as a solvent, it may be an aqueous solution in which the polyurethane resin is dissolved in water, or an aqueous dispersion in which the polyurethane resin is dispersed in water. The aqueous dispersion may be a dispersion in which the polyurethane resin is dispersed in water by a surfactant, or a self-emulsifying dispersion in which the polyurethane resin is dispersed in water. The dispersion in which polyurethane resin is dispersed in water with a surfactant may be, for example, a dispersion obtained by forcibly emulsifying a polyurethane resin precursor obtained by reacting a polyoxyalkylene polycarbonate diol with a polyisocyanate compound in the presence of a surfactant and water by methods such as high-speed stirring, ultrasonic or high-pressure emulsification, and then reacting it with a chain extender. The surfactant is not particularly limited, but it is preferable to use a nonionic surfactant, and polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, polyoxyalkylene monoalkaplyl ether, polyoxyethylene distyrylphenyl ether, polyoxyethylene propylene distyrylphenyl ether, polyoxyethylene tristyrylphenyl ether, polyoxyethylene propylene tristyrylphenyl ether, and pluronic-type nonionic surfactants are more preferable. A self-emulsifying dispersion in which the polyurethane resin itself is dispersed in water may be a dispersion obtained by dispersing a polyurethane resin precursor, which is obtained by reacting a polyoxyalkylene polycarbonate diol, a polyisocyanate compound, and a compound that exhibits ionic activity in water, in water, and then further reacting it with a chain extender. Examples of compounds that exhibit ionic properties in water include compounds having a sulfo group, compounds having a carboxyl group, compounds having an amino group, compounds having a phosphate structure, and compounds having a quaternary ammonium salt structure. Specifically, examples of compounds that exhibit ionic properties in water include 2-oxyethanesulfonic acid, phenolsulfonic acid, 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2-(2-aminoethylamino)ethanesulfonic acid, ethylenediaminepropylsulfonic acid, ethylenediaminebutylsulfonic acid, 1,2- or 1,3-propylenediamine-β-ethylsulfonic acid, 2-(3-aminopropylamino)-ethanesulfonic acid, 2, Examples include compounds having a sulfo group, such as 4-diaminobenzenesulfonic acid; dihydroxycarboxylic acids such as 2,2-dimethylol lactic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid; compounds having a sulfo group and a carbonyl group, such as sulfobenzoic acid, sulfosuccinic acid, and 5-sulfoisophthalic acid; and compounds having a sulfo group and an amino group, such as sulfanilic acid and 1,3-phenylenediamine-4,6-disulfonic acid. As a method for obtaining a dispersion in which polyurethane resin is dispersed in water with an emulsifier, and a self-emulsifying dispersion in which the polyurethane resin itself is dispersed in water, for example, the methods described in Japanese Patent Publication No. 2001-354742 and Japanese Patent Publication No. 2019-112564 can be used. When the polyurethane resin composition of the present invention contains water as a solvent, the composition can be used in paints, ink binders, coatings, adhesives, artificial leather, synthetic leather, and the like. The polyurethane resin composition of the present invention may contain a polyurethane resin solution in which the polyurethane resin of the present invention is dissolved in an organic solvent, or it may be the polyurethane resin solution itself. The polyurethane resin solution may be obtained by reacting the polyurethane resin precursor of the present invention with the chain extender in an organic solvent as described above, or by adding an organic solvent to a polyurethane resin that does not contain an organic solvent, or by reacting the polyurethane resin precursor of the present invention with the chain extender in an organic solvent and then adding an organic solvent. There are no particular restrictions on the organic solvent, and examples include dimethylformamide, dimethylacetamide, dimethyl sulfoxide, methyl ethyl ketone, cyclohexanone, ethyl acetate, isopropyl alcohol, toluene, methanol, and ethanol. These may be used individually or in combination of two or more. Polyurethane resin solutions can be used as components in solvent-based two-component paints, moisture-curing one-component paints, blocked isocyanate-based solvent paints, alkyd resin paints, urethane-modified synthetic resin paints, and UV-curing paints. In the case of a paint composition, it may be a paint composition for clear coat that does not contain pigments, or it may be a colored paint composition that contains pigments.

[0077] Other components of the clear coat coating composition besides the polyurethane resin of the present invention include known substances such as organic solvents, reactive diluents, transparent pigments, fillers, dyes, nanoparticles, light stabilizers, antioxidants, degassing agents, emulsifiers, slip additives, polymerization inhibitors, adhesion promoters, flow regulators, film-forming aids, thickeners, slack regulators, flame retardants, corrosion inhibitors, catalysts, waxes, drying agents, biocides, and matting agents. The clear coat coating composition preferably contains 1 to 80% by mass of the polyurethane resin of the present invention. In addition, other components of the colored paint composition besides the polyurethane resin of the present invention include organic solvents, pigments, dyes, and the same as those described above. A colored paint composition containing a pigment preferably contains 1 to 80% by mass of the polyurethane resin of the present invention.

[0078] Components other than the polyurethane resin of the present invention in the adhesive composition include various additives such as organic solvents, catalysts, reaction accelerators, internal release agents, fillers, reinforcing agents, dyes, pigments, colorants, flame retardants, ultraviolet absorbers, antioxidants, hydrolysis resistance improvers, antifungal agents, and stabilizers; various fibers such as glass fibers and polyester fibers; inorganic components such as talc and silica; and various coupling agents. The adhesive composition preferably contains 1 to 80% by mass of the polyurethane resin of the present invention. Other components in the printing ink composition besides the polyurethane resin of the present invention include organic solvents, colorants, and other additives. The printing ink composition preferably contains 1 to 80% by mass of the polyurethane resin of the present invention.

[0079] In addition to the polyurethane resin of the present invention, components other than the polyurethane resin of the present invention in the composition for forming the surface layer of synthetic leather and artificial leather, and in the porous film formed on the nonwoven fabric of artificial leather, include organic solvents, resins other than the polyurethane resin of the present invention, colorants, and other additives. The composition for forming the surface layer of synthetic leather and artificial leather preferably contains 1 to 80% by mass of the polyurethane resin of the present invention.

[0080] Components other than the polyurethane resin of the present invention in the adhesive composition include pigments, solvents, resins other than the polyurethane resin of the present invention, anti-blocking agents, dispersion stabilizers, viscosity modifiers, leveling agents, gelation inhibitors, light stabilizers, antioxidants, ultraviolet absorbers, heat resistance improvers, fillers, plasticizers, lubricants, antistatic agents, reinforcing materials, catalysts, auxiliary agents, and other additives. There are no particular restrictions on the solvent, as long as it is suitable for the properties of the resulting polyurethane resin; both aqueous and organic solvents can be used. The adhesive composition preferably contains 1 to 80% by mass of the polyurethane resin of the present invention. The above adhesive composition can be used for forming the surface layer of synthetic leather and artificial leather, for bonding between layers, in food packaging, shoes, footwear, binders, decorative paper, wood, structural members, and automobile components. Furthermore, the above adhesive composition can also be used as a component of low-temperature adhesives and hot-melt adhesives. The above adhesive composition may contain a solvent as needed.

[0081] Other components of the present invention in the tire composition include catalysts, fillers, flame retardants, colorants such as pigments or dyes, antistatic agents, reinforcing fibers, antioxidants, and other additives. Furthermore, the tire composition may optionally contain rubber, elastomers, thermoplastic resins, fillers such as silica, calcium carbonate, and clay, anti-aging agents, oils, plasticizers, colorants, weather-resistant agents, and the like. The tire composition preferably contains 1 to 80% by mass of the polyurethane resin of the present invention. The above tire composition is used in tires and tire components. Specifically, it is used in pneumatic tires and non-pneumatic tires or parts thereof. Examples of tire components include, but are not limited to, run-flat tire supports, airless tire supports, and tire skeletons.

[0082] (Goods) The article of the present invention is an article comprising the polyurethane resin of the present invention. The article of the present invention may be composed entirely of the polyurethane resin composition of the present invention, or a portion of it may be composed of the polyurethane resin composition of the present invention. There are no particular limitations on the embodiments in which a part of an article is composed of the polyurethane resin composition of the present invention, but examples include an embodiment having a layer of the polyurethane resin composition on the surface or inside, or an embodiment having a layer impregnated with the polyurethane resin composition on the surface or inside.

[0083] Articles that can be obtained using the polyurethane resin composition of the present invention include, for example, painted articles, laminates, printed materials, synthetic leather, artificial leather, tires, and tire parts. A painted article is an article on which a coating composition, which is the polyurethane resin composition of the present invention, is applied to the surface of the object to be painted. There are no particular limitations on the object to be painted, but examples include leather, textiles, vinyl chloride, acrylic resin, polystyrene, polypropylene, polyester, polyurethane and other resins, metals, glass, paper, wood, cement, and rubber. Methods for applying a paint composition to the surface of an object to be painted include, for example, the roll coating method, the spray coating method, the dip coating method, the spin coating method, the curtain coating method, and the die coating method.

[0084] Laminates containing the polyurethane resin composition of the present invention include articles having an adhesive composition, which is the polyurethane resin composition of the present invention, between layers. Specific materials that constitute the laminate with the adhesive composition between layers include, for example, plastics such as polyethylene terephthalate, polyethylene naphthalate, acrylic, polycarbonate, nylon, polyolefin, polyamide, polyvinyl chloride, and polyimide, as well as paper, metal foil, and glass. Methods for applying the adhesive composition between each layer of a laminate include, for example, roll coating, die coating, screen printing, gravure coating, spin coating, and dispenser coating. Using the above methods, the adhesive composition is applied to one side of a material such as plastic, paper, metal foil, or glass, and then other materials such as plastic, paper, metal foil, or glass are laminated on top of the applied adhesive composition under atmospheric pressure or reduced pressure. Alternatively, the laminate can be obtained by directly filling the spaces between layers of plastic, paper, metal foil, or glass with the adhesive composition using a dispenser.

[0085] The printed material is one in which a printing ink composition, which is a polyurethane resin composition of the present invention, is applied to one or both sides of the substrate to be printed. Printed materials are obtained by applying a printing ink composition to a substrate to be printed using methods such as gravure coating, roll coating, die coating, curtain coating, or spin coating, and then forming a coating film by heating or vacuum drying as necessary. Examples of substrates for printing include polyethylene terephthalate, nylon, polyolefins such as polyethylene and polypropylene, plastic films such as polystyrene, vinyl chloride, acrylic, and cellophane, metal films such as aluminum foil, rubber, and elastomers.

[0086] Synthetic leather and artificial leather are obtained by a wet solidification method, which involves applying or impregnating the surface of a fibrous base material or nonwoven fabric with the polyurethane resin composition of the present invention, and passing it through a water tank, or by a dry solidification method, which involves passing it through a heated oven, etc. The polyurethane resin composition may be uniformly applied to a substrate, dried, and then peeled off the substrate to form a film. Alternatively, it may be injected into a mold to form a film. The film-formed articles can be used, for example, as stretchable films for disposable diapers and dustproofing, as well as for general-purpose conveyor belts, various keyboard sheets, laminates, laminated glass interlayers, adhesives, cushioning materials, and multilayer actuator components.

[0087] The polyurethane resin composition of the present invention, when it does not contain an organic solvent, can be molded into a film or any other shape by heating it to melt or soften it and then inserting it into a mold. There are no particular restrictions on the uses of articles formed into film form. Examples include: disposable diapers, stretchable films used for dust protection, general-purpose conveyor belts, various keyboard sheets, laminates, laminated glass interlayers, adhesives, cushioning materials, and multilayer actuator components.

[0088] The physical properties of the article of the present invention when it is a film will be described below. There are no particular restrictions on the film's breaking strength Tmax, but it is preferably 20 to 100 MPa, more preferably 24 to 70 MPa, and even more preferably 28 to 50 MPa. There are no particular restrictions on the film's elongation at break E, but it is preferably 900-1500%, more preferably 900-1300%, and most preferably 900-1100%. There are no particular restrictions on the glass transition temperature (Tg) of the film, but it is preferably -100 to 10°C, more preferably -70 to 0°C, and even more preferably -50 to -10°C. There are no particular restrictions on the storage modulus E' (-20°C) of the film, but it is preferably 0.1 to 1000 MPa, more preferably 0.5 to 100 MPa, and most preferably 1.0 to 25 MPa. The "breaking strength Tmax," "breaking elongation E," "glass transition temperature Tg," and "storage modulus E'" in this example are measured using the same method as in the example. [Examples]

[0089] The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the following examples.

[0090] (Evaluation test) <Hydroxyl Value (OHV)> The hydroxyl values ​​(OHV) of the polyoxyalkylene polycarbonate diols ("PEPCD+PO" or "PEPCD+PO / EO") obtained in Synthesis Examples 1-7 described below, the PEPCD used in Example 3, the polypropylene glycol (PPG) used in Example 4, or the PTMG used in Example 5 were calculated using an acetylation reagent in accordance with JIS K 1557 (2007). The measured results are shown in Table 1.

[0091] <Molecular weight> The Mn and Mw of the polyoxyalkylene polycarbonate diols ("PEPCD+PO" or "PEPCD+PO / EO") obtained in Synthesis Examples 1-7 described below, the PEPCD used in Example 3 described below, the polypropylene glycol (PPG) used in Example 4 described below, or the PTMG used in Example 5 described below were measured by gel permeation chromatography (GPC). The measurement results are shown in Table 1. Tetrahydrofuran was used as the solvent, and the calibration curve was created using polypropylene glycol with a known hydroxyl value-based molecular weight. In other words, the molecular weight was determined as polypropylene glycol-based molecular weight. Furthermore, "hydroxyl value-based molecular weight" refers to the molecular weight calculated using the hydroxyl value, which is calculated based on JIS K 1557 (2007), for oxyalkylene polymers containing repeating units based on alkylene oxide monomers, and applied to the formula "[56,100 / (hydroxyl value)] × 2 (number of hydroxyl groups in the oxyalkylene polymer)".

[0092] Furthermore, the Mn content of the polyurethane resins obtained in each of the examples described below was measured by GPC. The measurement results are shown in Table 2. Tetrahydrofuran was used as the solvent, and the calibration curve was created using polystyrene with a known molecular weight. In other words, the molecular weight was determined as polystyrene-equivalent molecular weight.

[0093] <Viscosity> The viscosity (in mPa·s) at 25°C of the polyoxyalkylene polycarbonate diols ("PEPCD+PO" or "PEPCD+PO / EO") obtained in Synthesis Examples 1-7 described below, the PEPCD used in Example 3 described below, the polypropylene glycol (PPG) used in Example 4 described below, or the mixture of PEPCD and polypropylene glycol (PPG) used in Example 6 described below was measured using an E-type viscometer (product name: VISCOMETER TV-22, manufactured by Toki Sangyo Co., Ltd.). The measurement results are shown in Table 1.

[0094] <Hard segment content> The hard segment content shown in Table 2 is the value (mass %) obtained by calculating using the following formula (3) in each example. (Mass of polyisocyanate compound + Mass of chain extender) / (Mass of polyisocyanate compound + Mass of chain extender + Q) × 100 ... (3) However, Q represents the mass of the polyoxyalkylene polycarbonate diol (「PEPCD+PO」 or 「PEPCD+PO / EO」) used in Example 1 or 2 described below, the mass of PEPCD used in Example 3 described below, the mass of polypropylene glycol (PPG) used in Example 4 described below, the mass of PTMG used in Example 5 described below, or the mass of the mixture of PEPCD and polypropylene glycol (PPG) used in Example 6 described below.

[0095] <NCO unit content> The NCO unit content shown in Table 2 is the value (% by mass) obtained by calculation using the following formula (4) in each example. (Mass of polyisocyanate compound) / (Mass of polyisocyanate compound + Mass of chain extender + Q) × 100 ··· (4) However, Q is the same as in the above formula (3).

[0096] <Tensile test> The film of the polyurethane resin obtained in each example described below was punched out with a dumbbell-shaped mold (dumbbell No. 3) to obtain test pieces. Using these test pieces, a tensile test (product name: Tensilon VTM, manufactured by Toyobo Co., Ltd.) was conducted at a tensile speed of 300 mm / min, and the tensile properties of the breaking strength (Tmax, unit: MPa) and elongation at break (E, unit: %) were measured in accordance with the test method of JIS K6251:2017. The measurement results are shown in Table 2. If the breaking strength (Tmax) is in the range of 20 MPa or more, the toughness of the film is exhibited. If it is in the range of 24 MPa or more, the toughness of the film is good and the strength of the film is good. If the elongation at break (E) is in the range of 900% or more, the flexibility of the film is good.

[0097] <Heat resistance> After storing the above dumbbell-shaped test pieces in an oven at 100 °C for one week, a tensile test was conducted and the breaking strength was measured. The retention rate was calculated by comparing with the breaking strength before the heat resistance test. The results are shown in Table 2. If the retention rate is 80% or more, it is good.

[0098] <Hydrolysis resistance> The dumbbell-shaped test specimens described above were immersed in 80°C hot water for one week, and then a tensile test was performed to measure their breaking strength. The retention rate was calculated by comparing it with the breaking strength before the hydrolysis resistance test. The results are shown in Table 2. A retention rate of 80% or higher is considered good.

[0099] <Storage modulus and glass transition temperature> The polyurethane resin films obtained in the examples described below were prepared as test samples measuring 5 mm × 10 mm. The storage modulus E' (MPa) and glass transition temperature Tg (°C) at -20°C were measured for the obtained test samples under the following conditions. The measurement results are shown in Table 2. Measuring device: Dynamic viscoelasticity measuring device (product name: DMA242E Artemis, manufactured by NETZSCH) Mode: Tensile mode Temperature range: -100 to 120°C Heating rate: 3°C / min Measurement frequency: 1Hz

[0100] <Synthesis of polyoxyalkylene polycarbonate diol ("PEPCD+PO" or "PEPCD+PO / EO")> The following synthesis examples 1 and 2 are used in the examples 1 and 2.

[0101] (Synthesis Example 1) PEPCD (product name: NT1002, manufactured by Mitsubishi Chemical Corporation, transparent viscous liquid, Mn: 1000, glass transition temperature -78°C, R: n-butylene group, n: 3.2, m: 2.7), represented by the above formula (1), was used as an initiator. To 100 parts by mass of this initiator, 0.02 parts by mass of a zinc hexacyanocobaltate complex (TBA-DMC catalyst) with t-butyl alcohol as a ligand was used as a ring-opening polymerization catalyst to perform ring-opening addition polymerization on 100 parts by mass of PO as a cyclic ether at 130°C for 4 hours to obtain 200 parts by mass of polyoxyalkylene polycarbonate diol (a1) represented by the above formula (2) (R: n-butylene group, n: 3.2, m: 2.7, R': isopropylene group, l: 8.6). The obtained polyoxyalkylene polycarbonate diol (a1) was a transparent liquid. The Mn of the PO moiety in polyoxyalkylene polycarbonate diol (a1), calculated from the amount of PO used (100 parts by mass), was 1000. Furthermore, the molar ratio of constituent units derived from PO to constituent units derived from PEPCD (PO / PEPCD) in the obtained polyoxyalkylene polycarbonate diol (a1) was 17 / 1. Note that n, m, and l are theoretically calculated values. Furthermore, l was calculated assuming that PO was uniformly added to both ends (assuming that the l values ​​at both ends are equal). The following examples also used the same assumption. However, in synthesis example 2, it was assumed that PO and EO were uniformly added to both ends.

[0102] (Synthesis Example 2) Except for using 50 parts by mass of PO and 50 parts by mass of EO as the cyclic ether instead of 100 parts by mass of PO, 200 parts by mass of polyoxyalkylene polycarbonate diol (a2) (R: n-butylene group, n: 3.2, m: 2.7, R': isopropylene group, ethylene group, l: 10.0) represented by formula (2) above was obtained in the same manner as in Synthesis Example 1. The obtained polyoxyalkylene polycarbonate diol (a2) was a transparent liquid. The Mn of the PO moiety and the Mn of the EO moiety in polyoxyalkylene polycarbonate diol (a2), calculated from the amount of PO charged (50 parts by mass) and the amount of EO charged (50 parts by mass), were 500. Furthermore, the molar ratio of constituent units derived from PO and EO to constituent units derived from PEPCD in the obtained polyoxyalkylene polycarbonate diol (a2) ([PO+EO] / PEPCD) was 20 / 1.

[0103] (Synthesis Example 3) Using 100 parts by mass of the same initiator as in Synthesis Example 1, 0.05 parts by mass of TBA-DMC catalyst was used as a ring-opening polymerization catalyst. 400 parts by mass of PO as a cyclic ether were subjected to ring-opening addition polymerization at 130°C for 4 hours to obtain 500 parts by mass of polyoxyalkylene polycarbonate diol (a3) ​​represented by the above formula (2) (R: n-butylene group, n: 3.2, m: 2.7, R': isopropylene group, l: 34.5). The obtained polyoxyalkylene polycarbonate diol (a3) ​​was a transparent liquid. The Mn of the PO moiety in polyoxyalkylene polycarbonate diol (a3), calculated from the amount of PO used (400 parts by mass), was 4000. Furthermore, the molar ratio of constituent units derived from PO to constituent units derived from PEPCD (PO / PEPCD) in the obtained polyoxyalkylene polycarbonate diol (a3) ​​was 69 / 1.

[0104] (Synthesis Example 4) Using 100 parts by mass of the same initiator as in Synthesis Example 1, 0.08 parts by mass of TBA-DMC catalyst was used as a ring-opening polymerization catalyst. 700 parts by mass of PO as a cyclic ether were subjected to ring-opening addition polymerization at 130°C for 6 hours to obtain 800 parts by mass of polyoxyalkylene polycarbonate diol (a4) represented by the above formula (2) (R: n-butylene group, n: 3.2, m: 2.7, R': isopropylene group, l: 60.3). The obtained polyoxyalkylene polycarbonate diol (a4) was a transparent liquid. The Mn of the PO moiety in polyoxyalkylene polycarbonate diol (a4), calculated from the amount of PO used (700 parts by mass), was 7000. Furthermore, the molar ratio of constituent units derived from PO to constituent units derived from PEPCD (PO / PEPCD) in the obtained polyoxyalkylene polycarbonate diol (a4) was 121 / 1.

[0105] (Synthesis Example 5) PEPCD (product name: NT2006, manufactured by Mitsubishi Chemical Corporation, transparent viscous liquid, Mn: 2000, glass transition temperature -84°C, R: n-butylene group, n: 8.8, m: 2.0), represented by the above formula (1), was used as an initiator. Using 0.015 parts by mass of TBA-DMC catalyst as a ring-opening polymerization catalyst with 100 parts by mass of this initiator, 50 parts by mass of PO as a cyclic ether were subjected to ring-opening addition polymerization at 130°C for 3 hours to obtain 150 parts by mass of polyoxyalkylene polycarbonate diol (a5) represented by the above formula (2) (R: n-butylene group, n: 8.8, m: 2.0, R': isopropylene group, l: 8.6). The obtained polyoxyalkylene polycarbonate diol (a5) was a transparent liquid. The Mn of the PO moiety in polyoxyalkylene polycarbonate diol (a5), calculated from the amount of PO used (50 parts by mass), was 1000. Furthermore, the molar ratio of constituent units derived from PO to constituent units derived from PEPCD (PO / PEPCD) in the obtained polyoxyalkylene polycarbonate diol (a5) was 17 / 1.

[0106] (Synthesis Example 6) Using 100 parts by mass of the same initiator as in Synthesis Example 5, 0.025 parts by mass of TBA-DMC catalyst was used as a ring-opening polymerization catalyst. 150 parts by mass of PO as a cyclic ether were subjected to ring-opening addition polymerization at 130°C for 6 hours to obtain 250 parts by mass of polyoxyalkylene polycarbonate diol (a6) represented by the above formula (2) (R: n-butylene group, n: 8.8, m: 2.0, R': isopropylene group, l: 25.9). The obtained polyoxyalkylene polycarbonate diol (a6) was a transparent liquid. The Mn of the PO moiety in polyoxyalkylene polycarbonate diol (a6), calculated from the amount of PO used (150 parts by mass), was 3000. Furthermore, the molar ratio of constituent units derived from PO to constituent units derived from PEPCD (PO / PEPCD) in the obtained polyoxyalkylene polycarbonate diol (a6) was 52 / 1.

[0107] (Synthesis Example 7) Using 100 parts by mass of the same initiator as in Synthesis Example 5, 0.04 parts by mass of TBA-DMC catalyst was used as a ring-opening polymerization catalyst. 300 parts by mass of PO as a cyclic ether were subjected to ring-opening addition polymerization at 130°C for 8 hours to obtain 400 parts by mass of polyoxyalkylene polycarbonate diol (a7) represented by the above formula (2) (R: n-butylene group, n: 8.8, m: 2.0, R': isopropylene group, l: 51.7). The obtained polyoxyalkylene polycarbonate diol (a7) was a transparent liquid. The Mn of the PO moiety in polyoxyalkylene polycarbonate diol (a7), calculated from the amount of PO used (300 parts by mass), was 6000. Furthermore, the molar ratio of constituent units derived from PO to constituent units derived from PEPCD (PO / PEPCD) in the obtained polyoxyalkylene polycarbonate diol (a7) was 10³ / 1.

[0108] Similar to the polyoxyalkylene polycarbonate diols ("PEPCD+PO" or "PEPCD+PO / EO") obtained in Synthesis Examples 1-7, the PEPCD (product name: NT2002, manufactured by Mitsubishi Chemical Corporation, viscous liquid, glass transition temperature -71°C) used in Comparative Example 3, the polypropylene glycol (PPG) (product name: EL2020, manufactured by AGC Corporation, liquid) used in Comparative Example 4, and the P used in Comparative Example 5 The hydroxyl value (OHV) (mg-KOH / g), Mn, Mw / Mn, and viscosity (mPa·s) were measured for TMG (Sigma-Aldrich, solid), a mixture (mass ratio 1:1) of PEPCD (product name: NT2002, Mitsubishi Chemical Corporation, viscous liquid, glass transition temperature -71°C) used in Comparative Example 6, and polypropylene glycol (PPG) (product name: EL2020, AGC, liquid). The measurement results are shown in Table 1.

[0109] [Table 1]

[0110] <Synthesis of polyurethane resin> In the following examples, Examples 1 and 2 are examples of actual cases, and Examples 3 to 6 are comparative examples.

[0111] (Example 1) In a reaction vessel, 266 g of polyoxyalkylene polycarbonate diol (a1) obtained in Synthesis Example 1, 73.7 g of 4,4'-diphenylmethane diisocyanate (hereinafter sometimes referred to as "MDI") (isocyanate group index: 218), and 3.5 g of antioxidant (Irganox 1010) were mixed and heated to 80°C for 5 hours to obtain a polyurethane resin precursor. The amount of NCO (mass%) relative to the polyurethane resin precursor was calculated according to Method A of JIS K 1603-1:2007, and the reaction endpoint was determined when the theoretical amount was reached. The same procedure was followed in the following examples. Next, 14.9 g of 1,4-butanediol as a chain extender was added to the obtained polyurethane resin precursor, and the resulting mixture was transferred to a stainless steel palette and reacted at 130°C for 4 hours to obtain polyurethane resin (A1) with a hard segment content of 25% by mass.

[0112] The obtained polyurethane resin (A1) was dissolved in tetrahydrofuran, filtered using a hydrophilic polytetrafluoroethylene filter (product name: Millex-LH filter, manufactured by Merck Millipore, pore size: 0.45 μm, filter diameter: 25 mm), and the amount of Mn was measured by GPC. Furthermore, the obtained polyurethane resin (A1) was molded using a hydraulic molding machine at a temperature of 180°C to obtain a film with a thickness of approximately 250 μm.

[0113] (Example 2) In a reaction vessel, 266 g of polyoxyalkylene polycarbonate diol (a2) obtained in Synthesis Example 2, 73.4 g of MDI (isocyanate group index: 226), and 3.5 g of antioxidant (Irganox 1010) were mixed and heated to 80°C for 3 hours to obtain a polyurethane resin precursor. Next, 15.3 g of 1,4-butanediol as a chain extender was added to the obtained polyurethane resin precursor, and the resulting mixture was transferred to a stainless steel pallet and reacted at 130°C for 4 hours to obtain polyurethane resin (A2) with a hard segment content of 25% by mass.

[0114] The Mn content of the obtained polyurethane resin (A2) was measured in the same manner as in Example 1. Furthermore, the obtained polyurethane resin (A2) was molded under the same conditions as in Example 1 to obtain a film with a thickness of approximately 250 μm.

[0115] (Example 3) In a reaction vessel, 266 g of PEPCD (product name: NT2002, manufactured by Mitsubishi Chemical Corporation, viscous liquid, glass transition temperature -71°C), 73.9 g of MDI (isocyanate group index: 215), and 3.5 g of antioxidant (Irganox 1010) were mixed and heated to 80°C for 3 hours to obtain a polyurethane resin precursor. Next, 14.8 g of 1,4-butanediol as a chain extender was added to the obtained polyurethane resin precursor, and the resulting mixture was transferred to a stainless steel palette and reacted at 130°C for 4 hours to obtain polyurethane resin (A3) with a hard segment content of 25% by mass.

[0116] The Mn content of the obtained polyurethane resin (A3) was measured in the same manner as in Example 1. Furthermore, the obtained polyurethane resin (A3) was molded under the same conditions as in Example 1 to obtain a film with a thickness of approximately 250 μm.

[0117] (Example 4) In a reaction vessel, 266 g of polypropylene glycol (PPG) (product name: EL2020, manufactured by AGC Inc.), 73.4 g of MDI (isocyanate group index: 225), and 3.5 g of antioxidant (Irganox 1010) were mixed and heated to 80°C for 6.5 hours to obtain a polyurethane resin precursor. Next, 15.2 g of 1,4-butanediol as a chain extender was added to the obtained polyurethane resin precursor, and the resulting mixture was transferred to a stainless steel palette and reacted at 130°C for 4 hours to obtain polyurethane resin (A4) with a hard segment content of 25% by mass.

[0118] The Mn content of the obtained polyurethane resin (A4) was measured in the same manner as in Example 1. Furthermore, the obtained polyurethane resin (A4) was molded under the same conditions as in Example 1 to obtain a film with a thickness of approximately 250 μm.

[0119] (Example 5) In a reaction vessel, 266 g of PTMG (manufactured by Sigma-Aldrich), 73.3 g of MDI (isocyanate group index: 228), and 3.5 g of antioxidant (Irganox 1010) were mixed and heated to 80°C for 3 hours to obtain a polyurethane resin precursor. Next, 15.4 g of 1,4-butanediol as a chain extender was added to the obtained polyurethane resin precursor, and the resulting mixture was transferred to a stainless steel palette and reacted at 130°C for 4 hours to obtain polyurethane resin (A5) with a hard segment content of 25% by mass.

[0120] The Mn content of the obtained polyurethane resin (A5) was measured in the same manner as in Example 1. Furthermore, the obtained polyurethane resin (A5) was molded under the same conditions as in Example 1 to obtain a film with a thickness of approximately 250 μm.

[0121] (Example 6) In a reaction vessel, 266 g of a mixture (mass ratio 1:1) of PEPCD (product name: NT2002, manufactured by Mitsubishi Chemical Corporation, viscous liquid, glass transition temperature -71°C) and polypropylene glycol (PPG) (product name: EL2020, manufactured by AGC Inc., liquid), 73.7 g of MDI (isocyanate group index: 218), and 3.5 g of antioxidant (Irganox1010) were mixed and heated to 80°C for 8 hours to obtain a polyurethane resin precursor. Next, 14.9 g of 1,4-butanediol as a chain extender was added to the obtained polyurethane resin precursor, and the resulting mixture was transferred to a stainless steel palette and reacted at 130°C for 4 hours to obtain polyurethane resin (A6) with a hard segment content of 25% by mass.

[0122] The Mn content of the obtained polyurethane resin (A6) was measured in the same manner as in Example 1. Furthermore, the obtained polyurethane resin (A6) was molded under the same conditions as in Example 1 to obtain a film with a thickness of approximately 250 μm.

[0123] For Examples 1 to 6, the hard segment content (mass%), NCO unit content (mass%), and Mn of the obtained polyurethane resin, as well as the tensile properties (breaking strength Tmax (MPa), elongation at break E (%)), heat resistance, hydrolysis resistance, glass transition temperature Tg (°C), and storage modulus E' (MPa) of the obtained film, were measured or evaluated, and the measurement and evaluation results are shown in Table 2.

[0124] [Table 2]

[0125] As shown in Table 2, in Examples 1 and 2, good results were obtained in terms of tensile properties (strength and flexibility), heat resistance, glass transition temperature Tg, and storage modulus E'. Furthermore, both tensile properties and heat resistance were good in Examples 1 and 2. Furthermore, Example 1 showed better hydrolysis resistance than Example 2. In contrast, in Example 3, the elongation at break E (%) was small, and sufficient tensile properties were not obtained. Also, in Example 4, the breaking strength Tmax (MPa) was small, and sufficient tensile properties were not obtained. Furthermore, in Example 5, the elongation at break E (%) was small, and sufficient tensile properties were not obtained. In addition, in Example 6, the breaking strength Tmax (MPa) was small, and sufficient tensile properties were not obtained. [Industrial applicability]

[0126] The polyoxyalkylene polycarbonate diol of the present invention can react with a polyisocyanate compound and a chain extender to form a polyurethane resin that exhibits both strength and flexibility. The polyurethane resin composition of the present invention, which contains the polyurethane resin of the present invention, is suitable for use in paint compositions, adhesive compositions, printing ink compositions, compositions for forming the surface layer of synthetic leather and artificial leather, adhesive compositions for interlayers, porous films formed on nonwoven fabrics of artificial leather, tire compositions, elastomers, elastic fibers, binders, active energy ray curable resin compositions, medical materials, sealants, coatings, foams, flooring materials, and the like.

Claims

1. It has a constituent unit derived from a polyether polycarbonate diol represented by the following formula (1), and a constituent unit derived from a cyclic ether having 2 or 3 carbon atoms, and has a number-average molecular weight of 1,000 to 15,000. The polyoxyalkylene polycarbonate diol has a number-average molecular weight of 1,000 to 5,000. 【Chemistry 1】 ・・・（１） (In formula (1) above, R represents a divalent hydrocarbon group having 4 to 10 carbon atoms, m is a number from 1 to 20, and n is a number from 2 to 30. In formula (1), multiple Rs may be the same or different, and multiple ns may be the same or different.)

2. The polyoxyalkylene polycarbonate diol according to claim 1, wherein the molar ratio of constituent units derived from the cyclic ether to constituent units derived from the polyether polycarbonate diol (cyclic ether / polyether polycarbonate diol) is 4 / 1 to 250 / 1.

3. The polyoxyalkylene polycarbonate diol according to claim 1, represented by the following formula (2). 【Chemistry 2】 ・・・（２） (In formula (2) above, R represents a divalent hydrocarbon group having 4 to 10 carbon atoms, R' represents a divalent hydrocarbon group having 2 or 3 carbon atoms, l is a number from 1 to 250, m is a number from 1 to 20, and n is a number from 2 to 30. In formula (2), multiple Rs may be the same or different, multiple R's may be the same or different, two ls may be the same or different, and multiple ns may be the same or different.)

4. The polyoxyalkylene polycarbonate diol according to claim 3, wherein R' in formula (2) comprises a branched hydrocarbon group.

5. The polyoxyalkylene polycarbonate diol according to claim 3, wherein all R' in formula (2) are branched hydrocarbon groups.

6. A polyurethane resin precursor obtained by reacting a polyoxyalkylene polycarbonate diol according to any one of claims 1 to 5 with a polyisocyanate compound.

7. A polyurethane resin obtained by reacting a polyurethane resin precursor according to claim 6 with a chain extender.

8. A polyurethane resin composition comprising the polyurethane resin described in Claim 7.

9. An article comprising the polyurethane resin described in Claim 7.

10. A method for producing a polyoxyalkylene polycarbonate diol, comprising polymerizing a polyether polycarbonate diol having a number average molecular weight of 1,000 to 5,000 represented by the following formula (1) with a cyclic ether having 2 or 3 carbon atoms in the presence of a ring-opening polymerization catalyst to obtain a polyoxyalkylene polycarbonate diol having a number average molecular weight of 1,000 to 15,000. 【Transformation 3】 ・・・（１） (In formula (1) above, R represents a divalent hydrocarbon group having 4 to 10 carbon atoms, m is a number from 1 to 20, and n is a number from 2 to 30. In formula (1), multiple Rs may be the same or different, and multiple ns may be the same or different.)

11. The method for producing a polyoxyalkylene polycarbonate diol according to claim 10, wherein the polyether polycarbonate diol is obtained by reacting a polyoxyalkylene glycol with a carbonate compound in the presence of a transesterification catalyst.

12. The method for producing a polyoxyalkylene polycarbonate diol according to claim 10 or 11, wherein the amount of the ring-opening polymerization catalyst added is 0.003 to 0.10 parts by mass per 100 parts by mass of the polyether polycarbonate diol.

13. A method for producing a polyoxyalkylene polycarbonate diol according to claim 10 or 11, wherein the ring-opening polymerization catalyst is a complex metal cyanide catalyst.

14. The method for producing a polyoxyalkylene polycarbonate diol according to claim 11, wherein the polyoxyalkylene glycol is at least one selected from the group consisting of polytetramethylene ether glycol, copolymer polytetramethylene ether glycol of 3-methyltetrahydrofuran and tetrahydrofuran, and copolymer polyether polyol of neopentyl glycol and tetrahydrofuran.

Images