Polymer, and polyurethane including structure derived from said polymer

Abstract

A polymer, and a polyurethane including a structure derived from said polymer, said polymer being a reaction product of a diol component (A) that includes at least one type of diol selected from the group consisting of a diol (a1) represented by general formula (I) and a diol (a2) represented by general formula (II), and a component (B) that is at least one type of substance selected from the group consisting of a dicarboxylic acid (b1) and a carbonic acid ester (b2) (where each symbol in each general formula is as defined in the description).

Description

Polyurethanes containing polymers and structures derived from said polymers

[0001] This invention relates to polyurethanes comprising polymers and structures derived from said polymers.

[0002] Polyurethanes containing structures derived from polyols and polyisocyanates have been known conventionally. For example, Patent Document 1 discloses a polyurethane obtained by crosslinking at least a portion of the unsaturated bonds of an unsaturated bond-containing polyurethane obtained by a polymerization reaction using a polyol (a), a polyisocyanate compound (b), and a chain extender (c) containing an unsaturated bond-containing polyol (i-1) and / or an unsaturated bond-containing polyamine (ii-1) as raw materials.

[0003] Japanese Patent Publication No. 2013-10920

[0004] Polyurethane is used in a variety of applications, and therefore requires a variety of properties. Among these, flexibility and strength are particularly important, but these are often conflicting, making it difficult to achieve both simultaneously. Therefore, the present invention aims to provide a novel polymer that can provide a polyurethane that achieves both good flexibility and excellent strength.

[0005] As a result of diligent research, the inventors have found that the above problems can be solved by creating a polymer that satisfies specific requirements. That is, the present invention encompasses the following invention: [1] A polymer which is a reaction product of a diol component (A) comprising at least one selected from the group consisting of a diol (a1) represented by the following general formula (I) and a diol (a2) represented by the following general formula, and a component (B) which is at least one selected from the group consisting of dicarboxylic acid (b1) and carbonate ester (b2). (In general formula (I), R １ and R ２ Each of these independently represents a hydrocarbon group having 1 to 10 carbon atoms, and R ３ R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. In general formula (II), R ４ R represents a hydrocarbon group having 1 to 10 carbon atoms. ５ R represents a single bond or a hydrocarbon group having 1 to 9 carbon atoms.６ represents a hydrocarbon group having 1 to 5 carbon atoms.) [2] The total content of at least one selected from the group consisting of the diol (a1) and the diol (a2) is 0.01 to 3.5 mol% in 100 mol% of the diol component (A). The polymer according to [1] above. [3] In the general formula (I), R １ and R ２ each independently represents a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ３ represents a hydrogen atom, a methyl group or an ethyl group. The polymer according to [1] or [2] above. [4] In the general formula (II), R ４ represents a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ５ represents a single bond or a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R ６ represents a methyl group or an ethyl group; the polymer according to any one of [1] to [3] above. [5] The polymer according to any one of [1] to [4] above, wherein the diol component (A) contains a diol (a3) represented by the following general formula (III). (In the general formula (III), R ７ and R ８ each independently represents a hydrocarbon group having 1 to 10 carbon atoms, and R ９ represents a hydrocarbon group having 1 to 5 carbon atoms.) [6] In the general formula (III), R ７ and R ８ each independently represents a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R ９ represents a saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms; the polymer according to [5] above. [7] The polymer according to [5] or [6] above, wherein the content of the diol (a3) is 20 mol% or more and 99.99 mol% or less in 100 mol% of the diol component (A). [8] The polymer according to any one of [1] to [7] above, wherein the dicarboxylic acid (b1) contains a dicarboxylic acid (b1-1) represented by the following general formula (IV). (In the general formula (IV), R １０ represents a hydrocarbon group having 1 to 12 carbon atoms.) [9] In the general formula (IV), R １０The polymer according to [8], wherein is a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, a saturated alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms.

[10] The polymer according to [8] or [9], wherein the content of the dicarboxylic acid (b1-1) is 80 to 100 mol% in 100 mol% of the dicarboxylic acid (b1).

[11] The polymer according to any one of [1] to

[10] , wherein the content of the dicarboxylic acid (b1) is 80 to 100 mol% in 100 mol% of the component (B).

[12] The polymer according to any one of [1] to

[10] , wherein the content of the carbonate ester (b2) is 50 to 100 mol% in 100 mol% of the component (B).

[13] The polymer according to any one of [1] to

[12] , wherein the content of structural units derived from components (A) and (B) is 80 to 100 mol% of the total structural units in the polymer.

[14] The polymer according to any one of [1] to

[13] , wherein the polymer is a polymeric polyol.

[15] A polyurethane comprising a structure derived from the polymer according to any one of [1] to

[14] .

[16] The polyurethane according to

[15] , wherein it is thermoplastic.

[0006] According to the present invention, it is possible to provide a novel polymer that can provide polyurethane that is capable of achieving both good flexibility and excellent strength.

[0007] The following description is based on examples of embodiments of the present invention (hereinafter also referred to as "one aspect of the present invention"). However, the embodiments shown below are illustrative examples for realizing the technical concept of the present invention, and the present invention is not limited to the following description. Embodiments in which any of the matters described herein are arbitrarily selected or arbitrarily combined are also included in the present invention. In this specification, preferred forms of embodiments are shown, but combinations of two or more individual preferred forms are also preferred forms. Preferred provisions can be arbitrarily selected, and for example, a combination of preferred provisions can be said to be more preferred. In this specification, unless otherwise specified, the description of a numerical range as "XX to YY" means "XX or more and YY or less" (XX represents the lower limit and YY represents the upper limit). For example, when the numerical range is simply described as "10 to 90", it represents a range of 10 or more and 90 or less. In this specification, the lower limit and upper limit values ​​described in stages for numerical ranges (content of each component, content of each structural unit, values ​​calculated from them, and each physical property, etc.) can be combined independently. For example, from the description "preferably 10 to 90, more preferably 30 to 60" for the same item, the "preferred lower limit (10)" and the "more preferred upper limit (60)" can be combined to arrive at "10 to 60". Regarding the numerical range, for example, based on the description "preferably 10 to 90, more preferably 30 to 60", the upper limit can not be specifically specified, and only the lower limit can be specified as "10 or more" or "30 or more". Similarly, the lower limit can not be specifically specified, and only the upper limit can be specified as "90 or less" or "60 or less". The same applies when the upper limit of the numerical range is "less than" and when the lower limit is "greater than". As before, for example, from the descriptions "preferably 10 or more, more preferably 30 or more" and "preferably 90 or less, more preferably 60 or less" for the same item, the "preferred lower limit (10)" and the "more preferred upper limit (60)" can be combined to arrive at "10 or more and 60 or less". As described above, the lower limit can be specified as "10 or more" or "30 or more," and similarly, the upper limit can be specified as "90 or less" or "60 or less."The same applies when the terms "greater than or equal to" and "less than or equal to" in the above description are replaced with "greater than" and "less than," respectively. That is, for example, based on the description "preferably more than 10 and less than 90, more preferably 30 or more and 60 or less," the upper and lower limits can be combined to become "more than 10 and 60 or less" and "30 or more and less than 90." In this specification, unless otherwise specified, the terms "flexibility," "strength," and "elongation at break" refer to the "flexibility," "strength," and "elongation at break" imparted to polyurethanes and the like produced using a polymer that is one aspect of the present invention, and each is specifically evaluated by the method described in the examples.

[0008] [Polymer] A polymer according to one aspect of the present invention is a polymer (hereinafter also simply referred to as "polymer") which is a reaction product of a diol component (A) (hereinafter also simply referred to as "component (A)") which includes at least one selected from the group consisting of a diol (a1) represented by the following general formula (I) and a diol (a2) represented by the following general formula (II), and a component (B) (hereinafter also simply referred to as "component (B)") which is at least one selected from the group consisting of dicarboxylic acid (b1) and carbonate ester (b2).

[0009] (In general formula (I), R １ and R ２ Each of these independently represents a hydrocarbon group having 1 to 10 carbon atoms, and R ３ R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. In general formula (II), R ４ R represents a hydrocarbon group having 1 to 10 carbon atoms. ５ R represents a single bond or a hydrocarbon group having 1 to 9 carbon atoms. ６ (where represents a hydrocarbon group having 1 to 5 carbon atoms.) The polymer according to one aspect of the present invention will be described below. In this specification, unless otherwise specified, "the polymer" refers to the polymer according to one aspect of the present invention.

[0010] <Component (A)> Component (A) comprises at least one selected from the group consisting of diol (a1) represented by the following general formula (I) (hereinafter also simply referred to as "diol (a1)") and diol (a2) represented by the following general formula (II) (hereinafter also simply referred to as "diol (a2)").

[0011] (Diol (a1)) The diol (a1) is represented by the following general formula (I).

[0012] In general formula (I), R １ and R ２ Each of these independently represents a hydrocarbon group having 1 to 10 carbon atoms, preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, even more preferably a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms, even more preferably a methylene group or an ethylene group, and even more preferably an ethylene group. In general formula (I), R ３ R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms, even more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom. ３ The hydrocarbon group having 1 to 4 carbon atoms in relation to this preferably does not contain reactive double or triple bonds.

[0013] As mentioned above, R １ , R ２ and R ３ Each of the provisions that is preferred can be arbitrarily selected and combined. １ , R ２ and R ３ R may be the same or different. For example, in one embodiment of the present invention, in general formula (I), R １ and R ２ Each of these independently represents a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ３ R more preferably represents a hydrogen atom, a methyl group, or an ethyl group; １ and R ２Each of these independently represents a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R ３ R more preferably represents a hydrogen atom, a methyl group, or an ethyl group; １ and R ２ Each of these independently represents either a methylene group or an ethylene group, R ３ It is more preferable that R represents a hydrogen atom; １ and R ２ Each of these independently represents an ethylene group, and R ３ It is even more preferable that this represents a hydrogen atom.

[0014] Examples of the diol (a1) include at least one selected from the group consisting of 2-methylidene-1,3-propanediol, 2-methylidene-1,4-butanediol, 3-methylidene-1,5-pentanediol, 2-methylidene-1,3-propanediol, 2-methylidene-1,4-butanediol, 3-ethylidene-1,5-pentanediol, 2-ethylidene-1,3-propanediol, 2-ethylidene-1,4-butanediol, and 3-ethylidene-1,5-pentanediol. Among these, at least one selected from the group consisting of 2-methylidene-1,4-butanediol, 3-ethylidene-1,5-pentanediol, and 3-methylidene-1,5-pentanediol is preferred for the diol (a1). Of the diol (a1), 3-methylidene-1,5-pentanediol is more preferred from the viewpoint of suppressing hydrolysis and suppressing crystallinity. The diol (a1) may be used alone or in combination of two or more types.

[0015] (Diol (a2)) The diol (a2) is represented by the following general formula (II).

[0016] In general formula (II), R ４ R represents a hydrocarbon group having 1 to 10 carbon atoms, preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, even more preferably a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms, and even more preferably a methylene group or an ethylene group. In general formula (II), R ５R represents a single bond or a hydrocarbon group having 1 to 9 carbon atoms, preferably a single bond or a saturated aliphatic hydrocarbon group having 1 to 9 carbon atoms, more preferably a single bond or a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms, and even more preferably a methylene group or an ethylene group. Here, R ５ When represents a single bond, of the two carbon atoms represented in general formula (II), R ５ The carbon atom bonded to it is R ５ This indicates that it is directly bonded to the hydroxyl group that is bonded to it. In general formula (II), R ６ R represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms, more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, even more preferably a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms, even more preferably a methyl group or an ethyl group, and even more preferably a methyl group. ６ The hydrocarbon group having 1 to 5 carbon atoms in relation to this preferably does not contain a double bond or a triple bond.

[0017] As mentioned above, R ４ , R ５ and R ６ Each of the preferred ranges can be arbitrarily selected and combined. ４ , R ５ and R ６ They may be the same or they may be different. For example, in one embodiment of the present invention, in general formula (II), R ４ R represents a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms. ５ R represents a single bond or a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms. ６ R more preferably represents a methyl group or an ethyl group; ４ R represents a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms. ５ R represents a single bond or a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms. ６ R more preferably represents a methyl group or an ethyl group; ４ R represents a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms. ５ R represents a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms. ６ R more preferably represents a methyl group or an ethyl group;４ represents a methylene group or an ethylene group, R ５ represents a methylene group or an ethylene group, R ６ R more preferably represents a methyl group or an ethyl group; ４ represents a methylene group or an ethylene group, R ５ represents a methylene group or an ethylene group, R ６ It is even more preferable that represents a methyl group.

[0018] Examples of the diol (a2) include at least one selected from the group consisting of 2-methyl-1-propene-1,3-diol, 2-methyl-2-butene-1,4-diol, 2-methyl-2-pentene-1,5-diol, 3-methyl-2-pentene-1,5-diol, 2-ethyl-1-propene-1,3-diol, 2-ethyl-2-butene-1,4-diol, 2-ethyl-2-pentene-1,5-diol, and 3-ethyl-2-pentene-1,5-diol. From the viewpoint of suppressing hydrolysis and crystallinity, at least one diol (a2) selected from the group consisting of 2-methyl-2-pentene-1,5-diol and 3-methyl-2-pentene-1,5-diol is more preferred. The diol (a2) may be used alone or in combination of two or more.

[0019] From the viewpoint of making it easier to obtain the effects of the present invention, the total content of at least one selected from the group consisting of diol (a1) and diol (a2) is preferably 0.01 to 3.5 mol%, more preferably 0.03 to 3.0 mol%, even more preferably 0.05 to 3.0 mol%, even more preferably 0.08 to 2.9 mol%, even more preferably 0.12 to 2.8 mol%, and even more preferably 0.16 to 2.8 mol% of 100 mol% of component (A). From the viewpoint of making it easier to obtain a polymer that can provide polyurethane with an excellent balance of good flexibility and excellent strength, and from the viewpoint of preventing particulate defects from occurring in molded articles such as polyurethane films obtained, the total content of at least one selected from the group consisting of diol (a1) and diol (a2) is preferably 0.01 to 2.9 mol%, more preferably 0.05 to 2.8 mol%, even more preferably 0.05 to 2.6 mol%, even more preferably 0.07 to 2.5 mol%, even more preferably 0.08 to 2.5 mol%, even more preferably 0.12 to 2.5 mol%, even more preferably 0.16 to 2.5 mol%, and even more preferably 0.20 to 2.0 mol% of 100 mol% of component (A).

[0020] (Diol (a3)) The component (A) preferably contains a diol (a3) ​​represented by the following general formula (III) (hereinafter also simply referred to as "diol (a3)").

[0021]

[0022] In general formula (III), R ７ and R ８ Each of these independently represents a hydrocarbon group having 1 to 10 carbon atoms, preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, even more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, even more preferably a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms, even more preferably a methylene group or an ethylene group, and even more preferably an ethylene group. In general formula (III), R ９represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms, more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, still more preferably a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms, even more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R ９ The hydrocarbon group having 1 to 5 carbon atoms according to ９ preferably does not contain a double bond or a triple bond.

[0023] As described above, R ７ , R ８ and R ９ The provisions that each of them is preferable can be arbitrarily selected and combined. R ７ , R ８ and R ９ may be the same or different. For example, in one embodiment of the present invention, in the general formula (III), R ７ and R ８ each independently represents a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R ９ more preferably represents a saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms; R ７ and R ８ each independently represents a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ９ more preferably represents a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms; R ７ and R ８ each independently represents a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R ９ more preferably represents a methyl group or an ethyl group; R ７ and R ８ each independently represents a methylene group or an ethylene group, and R ９ more preferably represents a methyl group or an ethyl group; R ７ and R ８ each independently represents an ethylene group, and R ９ more preferably represents a methyl group.

[0024] Preferred examples of the diol (a3) ​​include, for example, at least one selected from the group consisting of 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 2-methyl-1,9-nonanediol, and 2,8-dimethyl-1,9-nonanediol.

[0025] As for the diol (a3), from the viewpoint of high reactivity with polyisocyanate, at least one selected from the group consisting of branched aliphatic diols in which both hydroxyl groups are primary hydroxyl groups is preferred; from the viewpoint of both hydroxyl groups having the same reactivity as polyisocyanate and being able to give a homogeneous polyurethane, at least one selected from the group consisting of branched aliphatic diols having mirror symmetry is more preferred; from the viewpoint of availability, at least one selected from the group consisting of 2-methyl-1,3-propanediol and 3-methyl-1,5-pentanediol is even more preferred; and from the viewpoint of the resulting polymer having low viscosity, 3-methyl-1,5-pentanediol is even more preferred.

[0026] Examples of branched aliphatic diols in which both hydroxyl groups are primary hydroxyl groups include at least one selected from the group consisting of 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 2-methyl-1,9-nonanediol, and 2,8-dimethyl-1,9-nonanediol. These may be used individually or in combination of two or more. Examples of the enantiomer-symmetry branched aliphatic diol include at least one selected from the group consisting of 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, and 2,4-diethyl-1,5-pentanediol. These may be used individually or in combination of two or more. The diol (a3) ​​may be used individually or in combination of two or more.

[0027] From the viewpoint of making it easier to obtain the effects of the present invention, the content of the diol (a3) ​​is preferably 20 to 99.99 mol%, more preferably 50 to 99.99 mol%, even more preferably 80 to 99.99 mol%, even more preferably 90 to 99.99 mol%, even more preferably 95 to 99.99 mol%, even more preferably 96.5 to 99.99 mol%, even more preferably 97.0 to 99.99 mol%, even more preferably 97.2 to 99.99 mol%, even more preferably 97.2 to 99.97 mol%, and even more preferably 97.2 to 99.95 mol%. In one embodiment of the present invention, the content of the diol (a3) ​​may be, for example, 97.0 to 99.97 mol%, 97.0 to 99.95 mol%, 97.1 to 99.99 mol%, 97.1 to 99.92 mol%, 97.2 to 99.88 mol%, 97.2 to 99.84 mol%, 97.4 to 99.95 mol%, 97.5 to 99.93 mol%, 97.5 to 99.92 mol%, 97.5 to 99.88 mol%, 97.5 to 99.84 mol%, or 98.0 to 99.80 mol% of 100 mol% of component (A).

[0028] From the viewpoint of making it easier to obtain the effects of the present invention, the total content of the diols (a1), (a2), and (a3) ​​is preferably 20 to 100 mol%, more preferably 50 to 100 mol%, even more preferably 80 to 100 mol%, even more preferably 90 to 100 mol%, even more preferably 95 to 100 mol%, even more preferably 98 to 100 mol%, even more preferably 99 to 100 mol%, and may also be 100 mol%.

[0029] (Other Diols) The above component (A) may also contain other diols other than the above diol (a1), the above diol (a2), and the above diol (a3). The aforementioned other diols include, for example, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 1,4-pentanediol, 2-ethyl-2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, etc., as well as branched aliphatic diols other than the aforementioned diols (a1), diol (a2), and diol (a3). Examples of other diols include: linear aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol; alicyclic diols such as cyclohexanedimethanol and cyclohexanediol; aromatic diols such as bisphenols, catechol, resorcinol, and hydroquinone; and diols with a number average molecular weight of 300 to 3,000 obtained by polymerizing cyclic monomers using polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polycaprolactone polyol as initiators. Among these other diols, branched aliphatic diols other than the aforementioned diol (a1), diol (a2), and diol (a3) ​​are preferred. The aforementioned other diols may be used individually or in combination of two or more types.

[0030] Preferably, component (A) does not substantially contain diols that introduce double or triple bonds into the side chains of the molecular structure of the resulting polymer. The term "diol that introduces double or triple bonds into the side chains of the molecular structure of the resulting polymer" refers to a diol that, after polymerization, introduces double or triple bonds such as vinyl groups into locations other than the main chain of the molecular structure of the resulting polymer. In this specification, the term "main chain of the molecular structure of the polymer" refers to the longest chain-like structure portion (the chain-like structure portion formed by the bonding of the most atoms) in the molecular structure constituting the polymer. For example, if the polymer is obtained by polymerization of the diol (a1) represented by the general formula (I), then R １ and R ２ The carbon atom located between them becomes the carbon atom that constitutes the main chain of the polymer. And the carbon atom that is directly bonded to that carbon atom (R ３ Double bonds connecting carbon atoms (which are bonded to each other) are also double bonds included in the "main chain" of the molecular structure of the resulting polymer. On the other hand, for example, diols such as 1-butene-3,4-diol, in which carbon atoms other than carbon atoms between two hydroxyl groups form a double bond, can be cited as an example of a "diol that introduces a double or triple bond into the side chain portion of the molecular structure of the resulting polymer."

[0031] The phrase "substantially free of diols that introduce double or triple bonds into the side chains of the molecular structure of the resulting polymer" specifically means that, in 100 mol% of component (A), the content of diols that introduce double or triple bonds into the side chains of the resulting polymer is less than 1 mol%, preferably 0.5 mol% or less, more preferably 0.1 mol% or less, even more preferably 0.05 mol% or less, and even more preferably 0.01 mol% or less. In one embodiment of the present invention, the content of diols that introduce double or triple bonds into the side chains of the resulting polymer in 100 mol% of component (A) may be 0 mol%. In other words, in one embodiment of the present invention, the content of the diol that introduces a double bond or triple bond to the side chain of the obtained polymer is preferably 0 mol% or more and less than 1 mol%, more preferably 0 to 0.5 mol%, even more preferably 0 to 0.1 mol%, even more preferably 0 to 0.05 mol%, even more preferably 0 to 0.01 mol%, and may also be 0 mol%.

[0032] Preferably, component (A) does not substantially contain any other diols, specifically monosubstituted olefin diols. For example, the aforementioned 1-butene-3,4-diol is an example of a "monosubstituted olefin diol". Specifically, "substantially free of monosubstituted olefin diols" means that the content of the monosubstituted olefin diol in 100 mol% of component (A) is less than 1 mol%, preferably 0.5 mol% or less, more preferably 0.1 mol% or less, even more preferably 0.05 mol% or less, and even more preferably 0.01 mol% or less. In one embodiment of the present invention, the content of the monosubstituted olefin diol in 100 mol% of component (A) may be 0 mol%. In other words, in one embodiment of the present invention, the content of the monosubstituted olefin diol is preferably 0 mol% or more and less than 1 mol% of 100 mol% of component (A), more preferably 0 to 0.5 mol%, even more preferably 0 to 0.1 mol%, even more preferably 0 to 0.05 mol%, even more preferably 0 to 0.01 mol%, and may also be 0 mol%.

[0033] <Component (B)> Component (B) is at least one selected from the group consisting of dicarboxylic acid (b1) and carbonate ester (b2).

[0034] (Dicarboxylic acid (b1)) The dicarboxylic acid (b1) is not particularly limited as long as it can polymerize with component (A) and the effects of the present invention are achieved, but it is preferable that it includes a dicarboxylic acid (b1-1) represented by the following general formula (IV) (hereinafter also simply referred to as "dicarboxylic acid (b1-1)").

[0035] In general formula (IV), R １０ This represents a hydrocarbon group having 1 to 12 carbon atoms, and from the viewpoint of easily improving the heat resistance and low-temperature properties of the resulting polyurethane, it is preferably a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, a saturated alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a saturated aliphatic hydrocarbon group having 2 to 9 carbon atoms, a saturated alicyclic hydrocarbon group having 4 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, even more preferably a saturated aliphatic hydrocarbon group having 4 to 8 carbon atoms, a saturated alicyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a saturated aliphatic hydrocarbon group having 4 to 8 carbon atoms. The dicarboxylic acid (b1) may be used alone or in combination of two or more types.

[0036] For example, succinic acid (R １０ (2 carbon atoms), glutaric acid (R １０ (3 carbon atoms), adipic acid (R １０ (4 carbon atoms), pimelic acid (R １０ (5 carbon atoms), suberic acid (R １０ (6 carbon atoms), azelaic acid (R １０ (7 carbon atoms), sebacic acid (R １０ (8 carbon atoms), undecane dioic acid (R １０ (of which there are 9 carbon atoms), dodecane dioic acid (R １０ Saturated aliphatic dicarboxylic acids such as those with 10 carbon atoms; 1,1-cyclohexanedicarboxylic acid (R １０ (6 carbon atoms), 1,2-cyclohexanedicarboxylic acid (R １０(6 carbon atoms), 1,3-cyclohexanedicarboxylic acid (R １０ (6 carbon atoms), 1,4-cyclohexanedicarboxylic acid (R carbon atoms) １０ 6) Saturated alicyclic dicarboxylic acids such as; phthalic acid (R １０ (6 carbon atoms), isophthalic acid (R １０ (6 carbon atoms), terephthalic acid (R １０ (6 carbon atoms), 2,6-naphthalenedicarboxylic acid (R １０ Aromatic dicarboxylic acids such as those with 10 carbon atoms; and so on. Dicarboxylic acids (b1-1) include succinic acid (R １０ (2 carbon atoms), adipic acid (R １０ (4 carbon atoms), azelaic acid (R １０ (7 carbon atoms), sebacic acid (R １０ (8 carbon atoms), 1,4-cyclohexanedicarboxylic acid (R carbon atoms) １０ 6) Phthalates (R １０ (6 carbon atoms), isophthalic acid (R １０ (6 carbon atoms) and terephthalic acid (R １０ At least one selected from the group consisting of (6 carbon atoms) is preferred, at least one selected from the group consisting of adipic acid, azelaic acid, sebacic acid and 1,4-cyclohexanedicarboxylic acid is more preferred, and at least one selected from the group consisting of adipic acid, azelaic acid and sebacic acid is even more preferred. The dicarboxylic acid (b1-1) may be used alone or in combination of two or more.

[0037] From the viewpoint of making it easier to obtain the effects of the present invention, the content of the dicarboxylic acid (b1-1) is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, even more preferably 95 to 100 mol%, and may be 100 mol%, out of 100 mol% of the dicarboxylic acid (b1).

[0038] In one embodiment of the polymer, when component (B) mainly contains the dicarboxylic acid (b1), from the viewpoint of making it easier to obtain the effects of the present invention, the content of the dicarboxylic acid (b1) is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, even more preferably 95 to 100 mol%, and may be 100 mol%, of 100 mol% of component (B).

[0039] (Carbonate ester (b2)) The carbonate ester (b2) is preferably a carbonic acid diester in which two hydrogen atoms of carbonic acid are substituted. Examples of the carbonic acid diester include at least one selected from the group consisting of alkylene carbonates, dialkyl carbonates, and diaryl carbonates. Examples of the alkylene carbonate include at least one selected from the group consisting of ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 5-methyl-1,3-dioxan-2-one, 1,2-butylene carbonate, 1,3-butylene carbonate, and 1,2-pentylene carbonate. Examples of the dialkyl carbonate include at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, and di-n-butyl carbonate. Examples of the diaryl carbonate include at least one selected from the group consisting of diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, and m-cresyl carbonate. Among these diester carbonates, dialkyl carbonates are more preferred, and at least one selected from the group consisting of dimethyl carbonate and diethyl carbonate is even more preferred. The diester carbonate (b2) may be used alone or in combination of two or more.

[0040] In one embodiment of the polymer, when component (B) mainly contains the carbonate ester (b2), from the viewpoint of making it easier to obtain the effects of the present invention, the content of the carbonate ester (b2) is preferably 50 to 100 mol%, more preferably 80 to 100 mol%, even more preferably 90 to 100 mol%, and may be 100 mol%, of 100 mol% of component (B).

[0041] In one embodiment of the polymer, if component (B) consists of both the dicarboxylic acid (b1) and the carbonate ester (b2), the molar ratio of the content of the dicarboxylic acid (b1) to the content of the carbonate ester (b2) may be, for example, 95:5 to 5:95, 90:10 to 10:90, 80:20 to 20:80, 70:30 to 30:70, 60:40 to 40:60, or 50:50, in 100 mol% of component (B), where the content of dicarboxylic acid (b1) (mol%) : content of carbonate ester (b2) (mol%) = 95:5 to 5:95, 90:10 to 10:90, 80:20 to 20:80, 70:30 to 30:70, 60:40 to 40:60, or 50:50.

[0042] Since the polymer is a reaction product of at least component (A) and component (B), the polymer in one aspect of the present invention can be said to be a polymer containing structural units derived from component (A) and structural units derived from component (B). In one aspect of the present invention, the polymer contains structural units derived from component (A) in an amount of preferably 50 to 72 mol%, more preferably 51 to 67 mol%, and even more preferably 52 to 64 mol%, of the total 100 mol% of structural units derived from components (A) and (B). In one aspect of the present invention, the polymer contains structural units derived from component (B) in an amount of preferably 28 to 50 mol%, more preferably 33 to 49 mol%, and even more preferably 36 to 48 mol%, of the total 100 mol% of structural units derived from components (A) and (B). The polymer contains structural units derived from components (A) and (B) in an amount of 80 to 100 mol%, more preferably 85 to 100 mol%, even more preferably 90 to 100 mol%, even more preferably 95 to 100 mol%, and even more preferably 99 to 100 mol%, out of 100 mol% of the total structural units in the polymer, and may also be 100 mol%.

[0043] <Other Components> The polymer may be a polymer obtained by reacting components (A) and (B) with other components other than components (A) and (B), as long as the effects of the present invention are achieved. The other components are components that can react with component (A) (except for component (B)), components that can react with component (B) (except for component (A)), or components that can react with the structure obtained by the reaction of components (A) and (B) (except for components (A) and (B)), and are not particularly limited as long as the effects of the present invention are achieved. Examples of the other components include monoalcohols; polyols having three or more hydroxyl groups; monocarboxylic acids; polycarboxylic acids having three or more carboxyl groups; polycaprolactones; compounds that can form carbonates such as haloformates and carbonyl halides; and the like.

[0044] Examples of the monoalcohol include at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-butanol, and 2-butanol. The polyol having three or more hydroxyl groups can be any alcohol having three or more hydroxyl groups, and the number of hydroxyl groups per molecule of the alcohol having three or more hydroxyl groups is preferably 3 to 10, more preferably 3 to 5, even more preferably 3 or 4, and even more preferably 3, from the viewpoint of the viscosity of the resulting polymer. Examples of the polyol having three or more hydroxyl groups include at least one selected from the group consisting of linear aliphatic polyols, branched aliphatic polyols, alicyclic polyols, and aromatic polyols. Specific examples of the polyol having three or more hydroxyl groups include at least one selected from the group consisting of trimethylolpropane, trimethylolethane, glycerin, and pentaerythritol. From the viewpoint of reactivity and availability, the polyol having three or more hydroxyl groups preferably includes trimethylolpropane.

[0045] Examples of the monocarboxylic acid include at least one selected from the group consisting of formic acid, acetic acid, propionic acid, and butanoic acid. The polycarboxylic acid having three or more carboxyl groups may be any carboxylic acid having three or more carboxyl groups, and the number of carboxyl groups per molecule of the polycarboxylic acid having three or more carboxyl groups is preferably 3 to 10, more preferably 3 to 5, even more preferably 3 or 4, and even more preferably 3, from the viewpoint of the viscosity of the resulting polymer. Examples of the polycarboxylic acid having three or more carboxyl groups include at least one selected from the group consisting of linear aliphatic polycarboxylic acid, branched aliphatic polycarboxylic acid, alicyclic polycarboxylic acid, and aromatic polycarboxylic acid.

[0046] The other components mentioned above may be used individually or in combination of two or more.

[0047] The content of structural units derived from the other components in the polymer is preferably 0 to 20 mol%, more preferably 0 to 15 mol%, even more preferably 0 to 10 mol%, even more preferably 0 to 5 mol%, and even more preferably 0 to 1 mol%, out of 100 mol% of the total structural units in the polymer, and may also be 0 mol%.

[0048] The polymer preferably contains substantially no structural units derived from polyisocyanate. Specifically, "substantially no structural units derived from polyisocyanate" means that, of 100 mol% of the total structural units in the polymer, the structural units derived from polyisocyanate are 5 mol% or less, preferably 1 mol% or less, more preferably 0.1 mol% or less, even more preferably 0.05 mol% or less, and even more preferably 0.01 mol% or less. In one embodiment of the polymer of the present invention, the structural units derived from polyisocyanate may be 0 mol% of the total structural units in the polymer. In other words, in one embodiment of the polymer of the present invention, the content of structural units derived from polyisocyanate is preferably 0 to 5 mol%, more preferably 0 to 1 mol%, even more preferably 0 to 0.1 mol%, even more preferably 0 to 0.05 mol%, even more preferably 0 to 0.01 mol%, and may also be 0 mol%.

[0049] Preferably, the polymer substantially does not contain double or triple bonds in the side chains of its molecular structure. Specifically, "the polymer substantially does not contain double or triple bonds in the side chains of its molecular structure" means that, out of 100 mol% of the total structural units in the polymer, the structural units derived from the component that introduces double or triple bonds into the side chains of the polymer are less than 0.5 mol%, preferably 0.1 mol% or less, more preferably 0.05 mol% or less, even more preferably 0.01 mol% or less, and even more preferably 0.005 mol% or less. In one embodiment of the polymer of the present invention, out of 100 mol% of the total structural units in the polymer, the structural units derived from the component that introduces double or triple bonds into the side chains of the polymer may be 0 mol%. In other words, in a polymer according to one aspect of the present invention, the structural units derived from a component that introduces a double bond or triple bond to the side chain of the polymer are preferably 0 mol% or more and less than 0.5 mol%, more preferably 0 to 0.1 mol%, even more preferably 0 to 0.05 mol%, even more preferably 0 to 0.01 mol%, even more preferably 0 to 0.005 mol% or less, and may even be 0 mol%.

[0050] Preferably, the polymer contains substantially no structural units derived from a monosubstituted olefin diol. Specifically, "substantially no structural units derived from a monosubstituted olefin diol" means that, of 100 mol% of the total structural units in the polymer, the structural units derived from the monosubstituted olefin diol are less than 0.5 mol%, preferably 0.1 mol% or less, more preferably 0.05 mol% or less, even more preferably 0.01 mol% or less, and even more preferably 0.005 mol% or less. In one embodiment of the polymer of the present invention, of 100 mol% of the total structural units in the polymer, the structural units derived from the monosubstituted olefin diol may be 0 mol%. In other words, in one embodiment of the polymer of the present invention, the structural units derived from the diol, which is the monosubstituted olefin, are preferably 0 mol% or more and less than 0.5 mol%, more preferably 0 to 0.1 mol%, even more preferably 0 to 0.05 mol%, even more preferably 0 to 0.01 mol%, even more preferably 0 to 0.005 mol% or less, and may even be 0 mol%.

[0051] The polymer is preferably at least one selected from the group consisting of polyester, polycarbonate, and high-molecular-weight polyols, and more preferably a high-molecular-weight polyol. Here, in this specification, "high-molecular-weight polyol" refers to a polyol with a number-average molecular weight (Mn) of 300 or more. The high-molecular-weight polyol is preferably at least one selected from the group consisting of polyester polyols and polycarbonate polyols. The polyester and polycarbonate can be modified by, for example, reacting the terminal portion of the molecular structure that does not have hydroxyl groups with a polyol such as a diol component (preferably component (A)) to produce a high-molecular-weight polyol. Therefore, the polyester and polycarbonate are polymers that can provide polyurethane that can achieve both good flexibility and excellent strength. The polymer can also be used for purposes other than as a raw material for polyurethane.

[0052] When the polymer is used as a raw material for polyurethane, as described later, it is preferable from the viewpoint of mechanical properties of the resulting polyurethane if the number average molecular weight (Mn) of the polymer is 300 or more. On the other hand, it is preferable from the viewpoint of ease of preparation when synthesizing polyurethane if the number average molecular weight (Mn) of the polymer is 10,000 or less. For similar reasons, the number average molecular weight (Mn) of the polymer is preferably 300 to 10,000, more preferably 400 to 8,000, and even more preferably 500 to 3,000. The number average molecular weight (Mn) of the polymer is the value measured by the method described in the examples.

[0053] From the viewpoint of superior low-temperature properties, the glass transition temperature (Tg) of the polymer is preferably 0°C or lower, more preferably -10°C or lower, even more preferably -20°C or lower, even more preferably -30°C or lower, even more preferably -40°C or lower, and even more preferably -50°C or lower. On the other hand, there is no particular limit to the lower limit of the glass transition temperature (Tg), and a lower value is preferable, but it is preferably -100°C. In one embodiment of the present invention, when the polymer is the polyester or the polyester polyol, from the viewpoint of superior low-temperature properties, as described above, a lower value is preferable and there is no particular limit to the lower limit of the glass transition temperature (Tg). For example, in one embodiment of the present invention, the glass transition temperature (Tg) of the polyester or the polyester polyol is preferably -100°C to -30°C, more preferably -100°C to -40°C, and even more preferably -100°C to -50°C. In one embodiment of the present invention, when the polymer is the polycarbonate or the polycarbonate polyol, from the viewpoint of superior low-temperature properties, a lower lower limit of the glass transition temperature (Tg) is preferable and there are no particular restrictions. For example, the glass transition temperature (Tg) of the polycarbonate or the polycarbonate polyol is preferably -100°C to 0°C, more preferably -100°C to -10°C, even more preferably -100°C to -20°C, and even more preferably -100°C to -30°C.

[0054] <Method for producing polymers> There are no particular limitations on the method for producing the polymers. For example, when the dicarboxylic acid (b1) is used as component (B), the polymer can be produced by reacting component (A) and the dicarboxylic acid (b1) in the same manner as known methods for polymerizing polyesters or polyester polyols. For example, the polymer can be produced by charging component (A), the dicarboxylic acid (b1), and any other component as needed in a predetermined ratio, carrying out an esterification or transesterification reaction, and further polycondensing the resulting reaction product at high temperature and under vacuum in the presence of a polycondensation catalyst. In this case, known catalysts can be used as the polycondensation catalyst, and examples include titanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, and tetrabutoxytitanium; tin compounds such as di-n-butyltin oxide, di-n-butyltin dilaurate, and dibutyltin diacetate; and combinations of acetates of magnesium, calcium, zinc, etc. with antimony oxide or the titanium compounds. These polycondensation catalysts are preferably present in an amount of 5 to 500 ppm by mass relative to the total amount of component (A) and the dicarboxylic acid (b1) (or, if other components are included, the total amount of component (A), the dicarboxylic acid (b1), and the other components).

[0055] For example, when the carbonate ester (b2) is used as component (B), it can be produced by reacting component (A) and the carbonate ester (b2) in a manner similar to known methods for polymerizing polycarbonate or polycarbonate polyols. For example, there are no particular restrictions on the specific method for producing the polycarbonate polyol. The component (A) and the carbonate ester (b2) may be reacted in one step with any other components as needed to obtain the desired polycarbonate polyol, or a low molecular weight polycarbonate polyol may be obtained first, and then further polymerized to a higher degree to obtain the desired polycarbonate polyol. A more specific method for the latter production method is, for example, the following method. Specifically, first, the polyol component (former) described in component (A) and other components used as needed, and the carbonate ester (b2) (latter) are mixed in a molar ratio of former / latter = 20 / 1 to 1 / 10, and the first step of the reaction is carried out at 100 to 250°C under normal or reduced pressure to obtain a reaction product containing a low molecular weight polycarbonate polyol. Here, if, for example, at least one selected from dimethyl carbonate and diethyl carbonate is used as the carbonate ester (b2), at least one selected from the resulting methanol and ethanol can be removed as dimethyl carbonate, diethyl carbonate, or a mixture of dimethyl carbonate and diethyl carbonate to obtain a low molecular weight polycarbonate polyol. Similarly, if, for example, ethylene carbonate is used as the carbonate ester (b2), the resulting ethylene glycol can be removed as a mixture with ethylene carbonate to obtain a low molecular weight polycarbonate polyol. Next, in the second reaction stage, the reaction product from the first stage is heated under reduced pressure at 160 to 250°C to remove unreacted polyol components and carbonate esters, and to condense low molecular weight polycarbonate polyols, thereby obtaining a target polycarbonate polyol having a predetermined molecular weight.

[0056] In the production of polycarbonate polyols, a catalyst may be added to accelerate the reaction. There are no particular restrictions on the type of catalyst, but examples include alkali metal or alkaline earth metal compounds such as alkali metal or alkaline earth metal alcoholates, hydrides, oxides, amides, carbonates, hydroxides, nitrogen-containing borates, and organic acid salts. Examples of alkali metals include lithium, sodium, and potassium, and examples of alkaline earth metals include magnesium, calcium, strontium, and barium. Other catalysts other than alkali metal or alkaline earth metal compounds may also be used as the catalyst. Other catalysts include, for example, elemental metals other than alkali metals and alkaline earth metals such as aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, indium, tin, antimony, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth, and ytterbium, as well as inorganic salts and organic compounds. Examples of metal organic compounds include metal alkoxides and organic acid salts. In the production of the polycarbonate polyol, one type of catalyst may be used alone, or two or more types may be used in combination.

[0057] When a polycarbonate polyol is produced using the catalyst described above, some of the catalyst may remain in the resulting polycarbonate polyol. The amount of the catalyst in the polycarbonate polyol is preferably 0.0001 to 0.05% by mass, and more preferably 0.0005 to 0.02% by mass, based on the mass of the polycarbonate polyol, as measured by ICP (inductively coupled plasma) emission spectrometry.

[0058] The catalyst used in the production of polycarbonate polyols may be treated with a phosphorus compound. Examples of the phosphorus compounds include phosphoric acid triesters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, and cresyl-diphenyl phosphate; acidic phosphates such as methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, dibutyl phosphate, monobutyl phosphate, monoisodecyl phosphate, and bis(2-ethylhexyl) phosphate; and triphenyl phosphate. Trisnonylphenyl phosphite, tricresyl phosphite, triethyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris(tridecyl) phosphite, trioleyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl(monodecyl) phosphite, trilauryl phosphite, diethylhydrogen phosphite, bis(2-ethylhexyl) Examples include phosphorous acid esters such as hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyldipropylene glycol diphosphite, bis(decyl)pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, and tris(2,4-di-tert-butylphenyl) phosphite; phosphoric acid; phosphorous acid; hypophosphorous acid. These phosphorus compounds may be used individually or in combination of two or more.

[0059] In cases where treatment with a phosphorus compound as described above is performed, the resulting polycarbonate polyol may contain residual phosphorus compounds. The content of the phosphorus compound in the polycarbonate polyol is preferably 0.0001 to 0.05% by mass, and more preferably 0.0005 to 0.02% by mass, based on the mass of the polycarbonate polyol, as measured by ICP emission spectrometry for the phosphorus element (P).

[0060] [Polyurethane] A polyurethane according to one aspect of the present invention includes a structure derived from the polymer, preferably a structure derived from the polymer polyol, more preferably a structure derived from at least one selected from the group consisting of polyester polyol and polycarbonate polyol, and even more preferably a structure derived from polyester polyol. The polyurethane may be thermosetting or thermoplastic. In one aspect of the present invention, the polyurethane is preferably thermoplastic. That is, the polyurethane is preferably thermoplastic polyurethane (hereinafter also abbreviated as "TPU").

[0061] The polyurethane comprises at least structural units (P) derived from the polymer and structural units (I) derived from the polyisocyanate, and may, for example, be a polyurethane comprising structural units (P) derived from the polymer, structural units (I) derived from the polyisocyanate, and structural units (C) derived from a chain extender. In one embodiment of the present invention, when the polyurethane is TPU, it is preferable that the polyurethane comprises structural units (P) derived from the polymer, structural units (I) derived from the polyisocyanate, and structural units (C) derived from a chain extender.

[0062] <Structural Unit (P)> The structural unit (P) is derived from the polymer and mainly constitutes a soft segment in the polyurethane. The polymer is the same as that described above in the section on the polymer, which is one aspect of the present invention, and the preferred embodiment is also the same. Therefore, a detailed explanation is omitted here. The polymer that constitutes the structural unit (P) may be used alone or in combination of two or more types.

[0063] <Structural Unit (I)> The structural unit (I) is derived from polyisocyanate and mainly constitutes a hard segment in the polyurethane. When the polyurethane contains structural unit (C) described later, it is preferable that the structural unit (I) together with structural unit (C) constitute a hard segment.

[0064] (Polyisocyanate) As the polyisocyanate, a polyisocyanate commonly used in the production of polyurethane can be used. From the viewpoint of the melt viscosity of the resulting polyurethane, the number of isocyanate groups per molecule of the polyisocyanate is preferably 2 to 10, more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 to 3, and even more preferably 2. That is, the polyisocyanate is more preferably diisocyanate or triisocyanate, and even more preferably diisocyanate. As the diisocyanate, an organic diisocyanate is preferred.

[0065] Examples of the polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, isophorone diisocyanate, isopropylidene bis(4-cyclohexyl isocyanate), and 1 ,3-bis(isocyanatomethyl)cyclohexane, cyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, cyclo Aliphatic or alicyclic diisocyanates such as lohexylene diisocyanate, methylcyclohexylene diisocyanate, and bis(2-isocyanatoethyl)-4-cyclohexene; 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (abbreviation: MDI), 2,4-tollylene diisocyanate, 2,6-tollylene diisocyanate, m-phenylene diisocyanate, and p-phenylene diisocyanate. Examples include aromatic diisocyanates such as m-xylylene diisocyanate, p-xylylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, chlorophenylene-2,4-diisocyanate, and tetramethylxylylene diisocyanate. These may be used individually or in combination of two or more.Among these, from the viewpoint of availability, at least one selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,5-naphthylene diisocyanate, m-xylylene diisocyanate, and 4,4'-diphenylmethane diisocyanate (MDI) is preferred, and from the viewpoint of good reactivity, at least one selected from the group consisting of 1,5-naphthylene diisocyanate, m-xylylene diisocyanate, and 4,4'-diphenylmethane diisocyanate (MDI) is more preferred, and 4,4'-diphenylmethane diisocyanate (MDI) is even more preferred.

[0066] <Structural Unit (C)> The structural unit (C) is derived from a chain extender, which is an optional component. There are no particular restrictions, but generally, in polyurethane, units consisting of isocyanate and a chain extender are said to be the main components of the hard segment. Therefore, the structural unit (C) mainly forms the hard segment together with the structural unit (I) in the polyurethane.

[0067] (Chain extender) Any of the chain extenders conventionally used in the production of ordinary polyurethanes may be used as the chain extender that constitutes the structural unit (C) above. Specifically, it is preferable to use a low molecular weight compound having two or more active hydrogen atoms in the molecule that can react with an isocyanate group, and it is more preferable to use a compound having two or more active hydrogen atoms in the molecule that can react with an isocyanate group and a molecular weight of less than 500. The molecular weight is even more preferably less than 450, even more preferably less than 400, and even more preferably less than 300.

[0068] Examples of the chain elongators include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and neopenediol. Diols such as thyl glycol, 1,6-hexanediol, 2,5-dimethyl-2,5-hexanediol, 3-methyl-1,5-pentanediol, 1,4-bis(β-hydroxyethoxy)benzene, 1,4-cyclohexanediol, cyclohexanedimethanol (e.g., 1,4-cyclohexanedimethanol, etc.), bis(β-hydroxyethyl) terephthalate, 1,9-nonanediol, m-xylylene glycol, p-xylylene glycol, triethylene glycol, etc.Ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 3-methylpentamethylenediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-diaminopropane, 1,3-diaminopropane Ropane, hydrazine, xylylenediamine, isophoronediamine, piperazine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, tolylenediamine, xylenediamine, dihydrazide adipate, dihydrazide isophthalate, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-methylene-bis(2-chloroaniline), 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl sulfide, 2,6-diaminotoluene, 2,4-diaminochlorobenzene, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 3,3'-diaminobenzophenone, Diamines such as 3,4-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diaminobibenzyl, 2,2'-diamino-1,1'-binaphthalene, 1,3-bis(4-aminophenoxy)alkane, 1,4-bis(4-aminophenoxy)alkane, 1,5-bis(4-aminophenoxy)alkane, 1,n-bis(4-aminophenoxy)alkanes (where n is 3 to 10), 1,2-bis[2-(4-aminophenoxy)ethoxy]ethane, 9,9-bis(4-aminophenyl)fluorene, and 4,4'-diaminobenzanilide;These are some examples. These may be used individually or in combination of two or more types.

[0069] Among the above, diols are preferred as the chain extender, and diols with a molecular weight of less than 500 are more preferred. The molecular weight of the diol is more preferably less than 450, even more preferably less than 400, and even more preferably less than 300. The diols having a molecular weight of less than 500 are preferably, from the viewpoint of availability and reactivity, at least one selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and 3-methyl-1,5-pentanediol; more preferably, at least one selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 3-methyl-1,5-pentanediol; even more preferably, at least one selected from the group consisting of ethylene glycol, 1,3-propanediol, and 1,4-butanediol; and even more preferably, at least one selected from the group consisting of ethylene glycol and 1,4-butanediol. Here, the molecular weight of the chain extender refers to the value obtained by summing the atomic weights of the elements constituting the compound. For example, if the chain extender is the diol, it can also be calculated as the sum of the atomic weights of each element constituting the molecular formula representing the diol. The molecular weight of the chain extender can also be measured, for example, using gas chromatography-mass spectrometry (GC-MS).

[0070] <Other structural units (U)> The polyurethane may further contain other structural units (U) in addition to the structural units (P), structural units (I), and structural units (C) described above, as long as they do not interfere with the objectives and effects of the present invention. Examples of other structural units (U) include structural units derived from polyethers and structural units derived from polyureas.

[0071] Unless it precludes achieving the objectives and effects of the present invention, the raw materials constituting the polyurethane structural units (P), (I), and (C), as well as other structural units (U), may each be manufactured from petroleum-derived raw materials or from plant-derived raw materials. Furthermore, these raw materials may each be manufactured using mass balance-type raw materials.

[0072] <Content of each structural unit> (Content of structural unit (P)) The polyurethane preferably contains 14 to 98% by mass of the structural unit (P) out of 100% by mass of all structural units in the polyurethane. A content of 14% by mass or more of the structural unit (P) is preferable because it facilitates the synthesis of polyurethane within a suitable hardness range. On the other hand, a content of 98% by mass or less of the structural unit (P) is preferable because it facilitates the synthesis of polyurethane with good mechanical properties. From a similar viewpoint, the content of the structural unit (P) is more preferably 20 to 97% by mass, even more preferably 40 to 95% by mass, and even more preferably 63 to 93% by mass out of 100% by mass of all structural units in the polyurethane.

[0073] (Content of structural unit (I)) The polyurethane preferably contains 2 to 86% by mass of structural unit (I) out of 100% by mass of all structural units in the polyurethane. A content of structural unit (I) of 2% by mass or more is preferable because it facilitates the synthesis of polyurethane within a suitable hardness range. On the other hand, a content of structural unit (I) of 86% by mass or less is preferable because it facilitates the synthesis of polyurethane with good mechanical properties. From a similar viewpoint, the content of structural unit (I) is more preferably 3 to 80% by mass, even more preferably 5 to 60% by mass, and even more preferably 7 to 37% by mass out of 100% by mass of all structural units in the polyurethane.

[0074] (Content of structural unit (C)) The content of the structural unit (C) is preferably 0 to 12% by mass, more preferably 0 to 11% by mass, even more preferably 0 to 10% by mass, and even more preferably 0 to 9% by mass, out of 100% by mass of the total structural units in the polyurethane. In one embodiment of the present invention, when the polyurethane contains the structural unit (C), the content of the structural unit (C) is preferably 1 to 12% by mass, more preferably 1 to 11% by mass, even more preferably 1 to 10% by mass, even more preferably 2 to 9% by mass, and even more preferably 2 to 8% by mass, out of 100% by mass of the total structural units in the polyurethane.

[0075] (Total content of structural units (P), structural units (I), and structural units (C)) The total content of structural units (P), structural units (I), and structural units (C) which may be included as needed, in 100% by mass of all structural units in the polyurethane is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 75 to 100% by mass, even more preferably 80 to 100% by mass, even more preferably 86 to 100% by mass, even more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, and may also be 100% by mass. Here, regarding the content of structural units (P) and structural units (I) as described above, and structural units (C) which may be included as needed, each can take on the respective content described above independently. However, it is naturally understood that when combining the selected content, there are no combinations in which the total content of structural units (P) and structural units (I) and structural units (C) exceeds 100% by mass of the total structural units in the polyurethane. That is, the total content of structural units (P) and structural units (I) and structural units (C) which may be included as needed is at most 100% by mass of the total structural units in the polyurethane. Similarly, if the polyurethane further contains the other structural units (U), the total content of structural units (P) and structural units (I) and structural units (C) and structural units (U) which may be included as needed is at most 100% by mass of the total structural units in the polyurethane.

[0076] In this specification, the content of each structural unit can be calculated from the blending amount of the raw material compound that forms each structural unit. １ It can also be determined by measurement using H-NMR. In this case, if necessary, １３ After identifying each structural unit that makes up polyurethane using analyses such as C-NMR and GC-MS, the content of each structural unit is determined. １ It can also be determined by measurement using H-NMR.

[0077] <Method for Producing Polyurethane> There are no particular limitations on the method for producing polyurethane. It can be produced by reacting the polymer, polyisocyanate, and, if necessary, a chain extender, using known urethane reaction techniques. For example, it can be obtained by polymerization using a known prepolymer method or a one-shot method for urethane reaction. For example, when using a chain extender, the desired polyurethane may be produced by reacting all the components used in the reaction together, or the polymer and polyisocyanate may be reacted first under conditions where the molar equivalent of polyisocyanate is in excess to produce a urethane prepolymer having isocyanate ends, and then the desired polyurethane may be produced by reacting this urethane prepolymer having isocyanate ends with a chain extender to increase its molecular weight.

[0078] There are no particular restrictions on the reaction temperature in the urethane formation reaction for producing the polyurethane, but a temperature of -20 to 200°C is preferably used, more preferably 0 to 150°C, and even more preferably 20 to 110°C.

[0079] (Catalyst) The urethane reaction may use a catalyst. In the prepolymer method described above, it is also preferable to use a catalyst when reacting a chain extender with a urethane prepolymer having isocyanate ends. As the catalyst, a urethane reaction catalyst that has been conventionally used in the production of polyurethane can be used. Examples of the urethane reaction catalyst include organotin compounds, organozinc compounds, organolead compounds, organobismuth compounds, organotitanium compounds, organozirconium compounds, and amine compounds. Among these, from the viewpoint of reactivity, at least one selected from the group consisting of amine compounds, organotin compounds, and organobismuth compounds is preferred, at least one selected from the group consisting of amine compounds and organotin compounds is more preferred, and from the viewpoint of ease of handling, amine compounds are even more preferred. Examples of organotin compounds include trimethylsuturate and dibutylsuturate. As the amine compound, a tertiary amine compound is preferred. Examples of tertiary amine compounds include at least one selected from the group consisting of triethylamine, triethylenediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, bis(2-dimethylaminoethyl) ether, N,N,N',N'',N''-pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N,N-dimethylethanolamine, 1-methylimidazole, 1,2-dimethylimidazole, N,N'-dimethylpiperazine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]undecene-7, 1,5-diazabicyclo[4,3,0]nonene-5, 1,8-diazabicyclo[5,4,0]decene-7, and 1,4-diazabicyclo[3,3,3]octene-4. These may be used individually or in combination of two or more types.

[0080] When using the catalyst, the amount of catalyst used is preferably 0.1 to 1,000 ppm by mass, more preferably 1 to 800 ppm by mass, and even more preferably 10 to 500 ppm by mass, relative to the total amount of the polymer, polyisocyanate, and chain extender, from the viewpoint of ensuring an appropriate polymerization reaction rate.

[0081] (Glass transition temperature) The glass transition temperature (Tg) of the polyurethane is preferably 10°C or lower, more preferably -10°C or lower, and even more preferably -30°C or lower, from the viewpoint of superior low-temperature characteristics. On the other hand, there is no particular limit to the lower limit of the glass transition temperature (Tg), the lower the better, and preferably -100°C. In one embodiment of the present invention, the glass transition temperature (Tg) of the polyurethane is preferably -100 to 10°C, more preferably -100 to -10°C, and even more preferably -100 to -30°C. The value of the glass transition temperature (Tg) of the polyurethane is specifically the value measured by the method described in the examples.

[0082] (Weight-average molecular weight) When the polyurethane is TPU, the weight-average molecular weight (Mw) of the TPU is preferably 10,000 to 500,000, more preferably 20,000 to 250,000, and even more preferably 50,000 to 200,000. A weight-average molecular weight (Mw) of 10,000 or more is preferable from the viewpoint of obtaining better mechanical performance and durability, and a weight-average molecular weight (Mw) of 500,000 or less is preferable from the viewpoint of obtaining better moldability. The weight-average molecular weight (Mw) of the TPU can be determined by gel permeation chromatography (GPC) on a standard poly(methyl methacrylate) basis. For example, it can be measured by the method shown below. <GPC Measurement Conditions> Apparatus: Tosoh Corporation GPC apparatus "HLC-8220" Separation column: Tosoh Corporation "TSKgel AWM-M (column diameter = 6.0 mm, column length = 15 cm)" (two columns connected in series) Eluent: N,N-dimethylformamide with 10 mM lithium bromide dissolved in it Eluent flow rate: 1.0 mL / min Column temperature: 40°C Detection method: Differential refractive index (RI) Injection volume: 10 μL Concentration: 1 mg / 1 mL (TPU / N,N-dimethylformamide) Standard: Poly(methyl methacrylate)

[0083] [Polyurethane Composition] In one aspect of the present invention, a polyurethane composition containing the polyurethane is provided. The polyurethane may contain other components as needed. That is, in one aspect of the present invention, a polyurethane composition containing the polyurethane and other components is provided. As described above, the polyurethane composition may contain thermosetting polyurethane, thermoplastic polyurethane, or both. The content of the polyurethane in the polyurethane composition can be adjusted as appropriate depending on the application in which the polyurethane composition is used. In one aspect of the polyurethane composition, the content of the polyurethane is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on 100% by mass of the polyurethane composition. On the other hand, the upper limit of the content of the polyurethane in the polyurethane composition is not particularly limited, but may be, for example, 99.99% by mass. The polyurethane content is preferably 50 to 99.99% by mass, more preferably 80 to 99.98% by mass, even more preferably 90 to 99.97% by mass, and even more preferably 95 to 99.95% by mass, based on 100% by mass of the polyurethane composition.

[0084] Other components include additives such as plasticizers, crosslinking agents, fillers, crosslinking accelerators, crosslinking aids, softeners, tackifiers, anti-aging agents, foaming agents, processing aids, adhesion enhancers, inorganic fillers, organic fillers, nucleating agents, heat stabilizers, weather stabilizers, antistatic agents, colorants, lubricants, flame retardants, flame retardant aids (such as antimony oxide), blooming inhibitors, mold release agents, thickeners, antioxidants, conductive agents, and hydrolysis inhibitors (such as carbodiimide). In addition, other components may include polymers other than polyurethane, which are one embodiment of the present invention. Polymers other than polyurethane may include, for example, at least one selected from the group consisting of polyurethanes other than polyurethane, polyvinyl chloride, polymethacrylate esters, and thermoplastic polyester elastomers. In the polyurethane composition, the other components may be used individually or in combination of two or more. In the polyurethane composition, the total content of the other components is preferably 50% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on 100% by mass of the polyurethane composition. On the other hand, the lower limit of the total content of the other components in the polyurethane composition is not particularly limited, but for example, it may be 0.01% by mass, based on 100% by mass of the polyurethane composition. In the polyurethane composition, the total content of the other components is preferably 0.01 to 50% by mass, more preferably 0.02 to 20% by mass, even more preferably 0.03 to 10% by mass, and even more preferably 0.05 to 5% by mass, based on 100% by mass of the polyurethane composition.

[0085] The other components may be appropriately blended, for example, during or after the polymerization of the polyurethane. The other components may also be pre-blended with the raw material components (for example, the polymer) before the polymerization of the polyurethane.

[0086] One aspect of the present invention, the polyurethane composition, can be used, for example, as a coating agent. The application of the coating agent is not particularly limited, but examples include at least one selected from the group consisting of electronic equipment components, clothing, furniture components, home appliance components, daily necessities, and automobile components. The coating agent can be used by mixing a coating agent resin containing at least the polyurethane with other components such as the crosslinking agent as needed. For example, the coating agent can be applied to a substrate using known techniques such as spray coating, knife coating, wire bar coating, doctor blade coating, reverse roll coating, and calender coating to form a coating film made of the coating agent.

[0087] The aforementioned substrate is not particularly limited and includes substrates that include at least one selected from the group consisting of metals, inorganic materials, and resins. For example, substrates molded from materials such as metals such as stainless steel, phosphated steel, zinc steel, iron, copper, aluminum, and brass; inorganic materials such as glass; polyester resins such as polyethylene terephthalate resin, polyethylene naphthalate resin, and polybutylene phthalate resin; polycarbonate resin; polystyrene resin; acrylic resin; AS resin; ABS resin; polycarbonate-ABS resin; 6-nylon resin; 6,6-nylon resin; MXD6 nylon resin; polyvinyl chloride resin; polyvinyl alcohol resin; polyurethane resin; phenolic resin; melamine resin; polyacetal resin; polyolefin resins such as polyethylene and polypropylene; chlorinated polyolefin resin; polyamide resin; polyether ether ketone resin; polyphenylene sulfide resin; NBR resin; chloroprene resin; SBR resin; SEBS resin; and other resins. The substrate may be a fiber, and at least one selected from the group consisting of organic fibers, inorganic fibers, and carbon fibers can be used. Examples of such fibers include organic fibers containing at least one selected from the group consisting of polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyethylene resin, polypropylene resin, polystyrene resin, 6-nylon resin, 6,6-nylon resin, acrylic resin, polyvinyl alcohol resin, cellulose, polylactic acid, cotton, and wool as the most abundant component; inorganic fibers such as glass wool; and carbon fibers. From the viewpoint of improving adhesion with the coating agent, a pre-treated substrate can also be used. For example, a substrate whose surface has been pre-treated by corona discharge treatment, flame treatment, ultraviolet irradiation treatment, ozone treatment, etc. can also be used.

[0088] [Molded Article] In one aspect of the present invention, the polyurethane can be used as a molded article. In other words, a molded article according to one aspect of the present invention includes the polyurethane. It is preferable that a molded article according to one aspect of the present invention includes the TPU, as it is possible to use a molding method that takes advantage of the property that the polyurethane becomes flexible when heated to a certain temperature and solidifies when cooled, making it easier to process. The molded article can be used as, for example, at least one selected from the group consisting of automobile parts, industrial parts, films, sheets, daily necessities, medical products, building materials, and sporting goods. Examples of the molded products include automotive parts such as bumpers, side moldings, taillight seals, snow chains, ball joint seals, constant velocity joint boots, bellows, spring cover materials, ABS cables, ABS cable plugs, instrument panel surfaces, gear knobs, console boxes, door seal covers, sheet materials, knobs, etc.; industrial parts such as belts, tubes, hoses, wire insulation materials, cable insulation materials, fire hoses, gears, casters, packing materials, and wind turbines for wind power generation; films and sheets such as various types of sheets, air mats, synthetic leather, and protective films; daily necessities such as shoe soles, shoe cushioning materials, watch bands, camera grips, animal ear tags, smartphone cases, tablet cases, keyboard protective covers, and decorative items; medical products such as heart valves, bypass devices, artificial heart chambers, dialysis tubes, thin films, connectors, catheters, medical tubes, and pacemaker insulators; building materials such as interior and exterior materials; and sports equipment such as skis and rackets. Because the aforementioned TPU also exhibits excellent low-temperature properties, it can be suitably used in applications where thermoplastic polyurethane is used in low-temperature environments, or in applications in cold regions. For example, it can be used in transport belts for handling food at low temperatures.

[0089] There are no particular limitations on the molding method for the molded article. For example, a molding method in which the polyurethane or polyurethane composition is cut or shaved directly immediately after polymerization; casting or dipping in which the polyurethane or polyurethane composition is dissolved in a solvent to form a homogeneous solution and then formed into a sheet or film; and various molding methods such as extrusion molding, injection molding, calendering, casting, blow molding, inflation molding, foam molding, rotational molding, and slush molding in which the polyurethane or polyurethane composition is heated and kneaded before molding. The molded article may be formed solely from the polyurethane or polyurethane composition, or it may be a composite molded article of the polyurethane or polyurethane composition and other materials (for example, a laminated structure of the polyurethane or polyurethane composition and other materials). There are no particular limitations on the composite molded article, but it may be molded by insert molding, co-extrusion molding, etc.

[0090] The polyurethane, polyurethane composition, or molded article immediately after polymerization may be used as is for various purposes. For example, if necessary, it may be used after undergoing an annealing process to improve or stabilize its physical properties by promoting phase separation. The time required for the annealing process is not particularly limited as long as the above objective is achieved. When TPU is used as the polyurethane, the time required for the annealing process is preferably 10 minutes or more, more preferably 1 hour or more, even more preferably 2 hours or more, and even more preferably 3 hours or more, from the viewpoint of facilitating the achievement of the above objective. From the viewpoint of productivity, the time required for the annealing process is preferably 3 months or less, more preferably 1 month or less, even more preferably 1 week or less, and even more preferably 1 day or less. In one embodiment of the annealing process, the time required for the annealing process is preferably 10 minutes or more and 3 months or less, more preferably 1 hour or more and 1 month or less, even more preferably 2 hours or more and 1 day or less, and even more preferably 3 hours or more and 1 day or less. In the annealing process, the higher the temperature during the annealing process, the easier it is to achieve the above objective. Therefore, the temperature in the annealing process is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. On the other hand, from the viewpoint of suppressing thermal deformation of the obtained molded article, the temperature is preferably 150°C or lower, more preferably 140°C or lower, and even more preferably 130°C or lower. In one embodiment of the annealing process, the temperature in the annealing process is preferably 30 to 150°C, more preferably 40 to 140°C, and even more preferably 50 to 130°C. The temperature may be changed during the annealing process. When the temperature is changed during the annealing process, from the viewpoint of suppressing thermal deformation of the obtained molded article, it is preferable to have a shorter exposure time to higher temperatures.

[0091] The embodiments of this model will be described in more detail below with reference to examples, but the embodiments are not limited to these examples.

[0092] <Preparation of 3-methyl-1,5-pentanediols> The 3-methyl-1,5-pentanediols used in the examples and comparative examples were prepared by the following method. The gas chromatography analysis shown in the following production examples was evaluated using the following method.

[0093] <Composition Ratio: Gas Chromatography (GC) Analysis> Analysis of each component was performed using a gas chromatograph GC2014 (Shimadzu Corporation: FID detector) and a capillary column (Agilent Technologies, Inc.: DB-1701, length 50 m, inner diameter 0.32 mm, film thickness 1.0 μm) under the following conditions: Column temperature: Increased from 70°C to 250°C at a heating rate of 5°C / min FID temperature: 250°C Injection port temperature: 250°C Carrier gas: Helium Makeup gas: Helium Injection volume: 0.2 μL Split ratio: 50

[0094] [Production Example 1] Isobutene and formaldehyde were reacted by the following procedure to produce 3-methyl-3-buten-1-ol, a γ,δ-unsaturated alcohol. In the process, a mixture of the target product, 3-methylidene-1,5-pentanediol, 3-methyl-2-penten-1,5-diol, and 2-methyl-2-penten-1,5-diol (hereinafter also referred to as "MPEDs"), was obtained. Unless otherwise specified, the pressure throughout the entire process in Production Example 1 was 200 kg / cm². ２Each operation was performed while maintaining a pressure of 19.6 MPa. A 50 wt% formaldehyde aqueous solution (hereinafter also referred to as "raw material solution 1A") was delivered at a rate of 94.0 mL / hr to a stainless steel reaction tube (preheating tube 1) with an inner diameter of 16 mm and a length of 80 mm (volume of 16.1 mL) heated to 80°C to preheat the raw material solution 1A. A mixed solution of 55.8 wt% isobutene and 44.2 wt% tert-butyl alcohol (hereinafter also referred to as "raw material solution 2A") was delivered at a rate of 1,109.2 mL / hr to a stainless steel reaction tube (preheating tube 2) with an inner diameter of 16 mm and a length of 1,000 mm (volume of 201.1 mL) heated to 25°C. Here, the amount of isobutene used per 1 mol of formaldehyde was adjusted to 5 mol, and the amount of tert-butyl alcohol used per 1 mol of formaldehyde was adjusted to 3 mol. After the raw material liquids 1A and 2A were combined and brought into contact at the outlets of both preheating tubes, the resulting mixture was immediately sent to a stainless steel reaction tube (referred to as the "reactor" in Production Example 1) with an inner diameter of 16 mm and a length of 500 mm (volume of 100.5 mL) heated to 280°C, where the isobutene and formaldehyde were reacted to obtain a reaction solution. The average residence time of the mixture in the reactor was 5 minutes. The outlet of the reactor was connected to a cooling tube with an inner diameter of 16 mm and a length of 1,000 mm, and the outlet pressure of the cooling tube was set to 200 kg / cm². ２The pressure was maintained at 19.6 MPa, and the reaction solution was discharged from the outlet of the condenser. GC analysis of the obtained reaction solution under the above conditions showed a formaldehyde conversion rate of 88.3%. The obtained reaction solution was distilled using a distillation column with a length of 6,000 mm, a diameter of 150 A, and 20 theoretical plates, under conditions of a top pressure of 1 kPaA and reflux ratio of 20, yielding 640.9 g of a mixture of 3-methylidene-1,5-pentanediol, 3-methyl-2-pentene-1,5-diol, and 2-methyl-2-pentene-1,5-diol (MPEDs) as a fraction with a boiling point of 133-135°C. The yield of the resulting mixture was 1.9%. The content of each compound in the mixture, calculated by GC analysis under the aforementioned conditions, was 57.36 wt% for 3-methylidene-1,5-pentanediol, 31.88 wt% for 3-methyl-2-pentene-1,5-diol, and 2.95 wt% for 2-methyl-2-pentene-1,5-diol. The remainder was a reaction by-product.

[0095] [Production Example 2] 640.1 g of the mixture obtained in Production Example 1 (containing 57.36 wt% 3-methylidene-1,5-pentanediol, 31.88 wt% 3-methyl-2-pentene-1,5-diol, and 2.95 wt% 2-methyl-2-pentene-1,5-diol, totaling 5.08 mol) was placed in an autoclave and placed under a nitrogen atmosphere. Then, 12.0 g (2 wt%) of Raney nickel ("Metalist® MC804", manufactured by Evonik Japan Co., Ltd.) was added, and the internal temperature of the autoclave was set to 120°C. Subsequently, hydrogen was introduced into the autoclave, the internal pressure of the autoclave was set to 2.0 MPaG, and the mixture was stirred at 1,000 rpm for 18 hours to react with hydrogen. After that, it was cooled to room temperature to obtain the reaction mixture. Raney nickel was removed from the reaction mixture by filtration to obtain the reaction solution. GC analysis of the obtained reaction solution under the aforementioned conditions revealed that the hydrogen conversion rate of 3-methylidene-1,5-pentanediol and 3-methyl-2-pentene-1,5-diol contained in the starting materials was 99.8%, and the selectivity for 3-methyl-1,5-pentanediol (also referred to as "MPD" herein) was 93.8%. The remainder were reaction by-products. The obtained reaction solution was then distilled using a distillation column with a column length of 1,000 mm, a column diameter of 25 A, and 20 theoretical plates under conditions of a top pressure of 1 kPa A and a reflux ratio of 20, yielding 347.8 g of a fraction with a boiling point of 139-140°C as the product. GC analysis under the aforementioned conditions revealed that the content of each compound in the obtained product was 99.88 wt% for 3-methyl-1,5-pentanediol, 0.07 wt% for 3-methylidene-1,5-pentanediol, 0.04 wt% for 3-methyl-2-pentene-1,5-diol, and 0.01 wt% for 2-methyl-2-pentene-1,5-diol. The remainder was reaction by-products.

[0096] [Production Example 3] 2-propanol (1,047 mL, 823 g) and 40 g of Raney nickel ("Metalist® MC804", manufactured by Evonik Japan Co., Ltd.) as a hydrogenation catalyst were placed in an autoclave. 0.66 g of 30% by mass sodium hydroxide aqueous solution was added, and hydrogen was introduced to achieve a reaction temperature of 120°C and a reaction pressure of 0.8 MPaG. One hour after the reaction temperature reached 120°C, 2,000 mL of 2-hydroxy-4-methyltetrahydropyran containing 1.31 g of 30% by mass sodium hydroxide aqueous solution was supplied to the autoclave over 4 hours, and the mixture was stirred for 4 hours to react 2-hydroxy-4-methyltetrahydropyran with hydrogen. During this reaction, the 2-hydroxy-4-methyltetrahydropyran was completely consumed. Subsequently, simple distillation was performed to obtain 2,376 mL of a reaction solution containing 3-methyl-1,5-pentanediol (62.1 wt%), 2-propanol (32.1 wt%), and β-methyl-5-valerolactone (1.1 wt%). The obtained reaction solution was distilled using a distillation column with a column length of 1,000 mm, a column diameter of 25 A, and 20 theoretical plates, at a reflux ratio of 6.0 and a top pressure of 1 kPaA, to obtain 3-methyl-1,5-pentanediol as a fraction with a boiling point of 139-140°C. GC analysis under the above conditions showed that the content of 3-methyl-1,5-pentanediol was 99.9 wt%, and the content of other components was less than 0.1 wt%.

[0097] <Production of High-Molecular-Weight Polyols> [Synthesis Comparative Example 1] 131.0 g of 3-methyl-1,5-pentanediol obtained in Production Example 3 and 120.5 g of adipic acid were placed in a 300 mL four-necked flask equipped with a thermometer, Liebig condenser, and nitrogen inlet tube. The mixture was heated at 200°C under atmospheric pressure and a nitrogen stream while stirring, and the esterification reaction was carried out while continuously distilling off the water produced. When the amount of water distilled off decreased, 150 μL of tetraisopropyl titanate (also known as tetraisopropoxytitanium) was added, and the reaction was continued until the acid value of the high-molecular-weight polyol in the reaction solution was 0.5 mg KOH / g or less. Thereafter, the vacuum was gradually increased using a vacuum pump, and 3-methyl-1,5-pentanediol (MPD) was distilled off until the number-average molecular weight (Mn) was around 2,000, completing the reaction. The number-average molecular weight (Mn) of the obtained polyester polyol CA was 1,997. The acid value of the polymer polyol in the reaction solution was measured by the following method: (1) Approximately 5 g of polymer polyol (sample) was accurately weighed into a 100 mL Erlenmeyer flask. (2) 20 mL of acetone was added to dissolve the polymer polyol. (3) 2 to 3 drops of phenolphthalein (alcohol solution) were added, and the mixture was titrated with 0.1 mol / L (N / 10) potassium hydroxide solution (ethanol solution), with the endpoint being the point where a faint pink color persisted for 20 seconds. (4) For the blank, 20 mL of acetone was taken into a 100 mL Erlenmeyer flask, and phenolphthalein (alcohol solution) was used as an indicator, and the mixture was titrated with 0.1 mol / L (N / 10) potassium hydroxide solution (ethanol solution). The acid value was calculated using the following formula. Oxidation (mg KOH / g) = (X - Y) × f × 5.6¹ / S X: Titration volume of sample (mL) Y: Titration volume of blank (mL) f: Accurate concentration (factor) of 0.1 mol / L (N / 10) potassium hydroxide solution (mol / L) S: Sample volume (g)

[0098] [Synthesis Examples 1-5, 7 and 8] Polyester polyols A-E, G and H were obtained in the same manner as in Comparative Example 1, except that instead of MPD, a diol component was used which was a mixture of MPD obtained in Production Example 3 and a mixture obtained in Production Example 1 (MPEDs) in the amounts shown in Table 1 below.

[0099] [Synthesis Example 6] Polyester polyol F was obtained in the same manner as in Comparative Synthesis Example 1, except that the product obtained in Production Example 2 was used instead of MPD.

[0100]

[0101] [Synthesis Example 9] 131.0 g of the diol component, obtained by mixing the MPD obtained in Production Example 3 and the mixture (MPEDs) obtained in Production Example 1 in the same ratio as in Synthesis Example 3, and 119.0 g of diethyl carbonate were placed in a 300 mL four-necked flask equipped with a thermometer, condenser, and nitrogen inlet tube. The mixture was heated at 200°C under atmospheric pressure and a nitrogen stream while stirring, and the transesterification reaction was carried out while continuously distilling off the generated ethanol from the reaction system. When the amount of ethanol distilled off decreased, 150 μL of tetraisopropyl titanate was added, and the reaction was continued until the acid value of the polymer polyol in the reaction solution was 0.5 mg KOH / g or less. Thereafter, the vacuum was gradually increased using a vacuum pump, and the reaction was completed by distilling off the MPD until the number average molecular weight (Mn) was around 2,000. The number average molecular weight (Mn) of the obtained polycarbonate polyol I was 2002. The acid value of the polymer polyol in the reaction solution was measured using the same method as in Comparative Example 1 of Synthesis.

[0102] [Comparative Synthesis Example 2] Polycarbonate polyol CI was obtained in the same manner as in Synthesis Example 9, except that the MPD obtained in Production Example 3 was used instead of the diol component obtained by mixing the MPD obtained in Production Example 3 and the mixture (MPEDs) obtained in Production Example 1 in the same ratio as in Synthesis Example 3.

[0103] [Synthesis Comparative Example 3] Polyester polyol CB was obtained in the same manner as in Synthesis Example 3, except that 1-butene-3,4-diol (hereinafter also referred to as "3,4-BEG") was used instead of MPEDs. The obtained polyester polyol CB was subjected to GC analysis as described later. When the ratio of MPD to 3,4-BEG was analyzed, 3,4-BEG was not detected. Unlike MPEDs, which are made of polysubstituted olefins, 3,4-BEG is a monosubstituted olefin and therefore highly reactive. It is presumed that the double bond site reacted and disappeared at the high temperature under the polyol synthesis conditions.

[0104] The properties of the polyester polyols and polycarbonate polyols obtained in the synthesis examples and comparative examples were evaluated using the following method. The results are shown in Table 2 below.

[0105] <Number-average molecular weight (Mn)> The number-average molecular weight (Mn) of the polyester polyol and polycarbonate polyol obtained in the synthesis examples and comparative examples was determined by the following calculation based on the hydroxyl value of the polyester polyol and polycarbonate polyol: Number-average molecular weight (Mn) of polyester polyol and polycarbonate polyol = Molecular weight of KOH (56.1) × Number of functional groups × 1,000 / Hydroxyl value (mgKOH / g) The hydroxyl value was measured in accordance with Method B (phthalation method) described in JIS K1557-1:2007.

[0106] <Glass Transition Temperature (Tg) of Polyester Polyols and Polycarbonate Polyols> The glass transition temperature (Tg) of the polyester polyols and polycarbonate polyols obtained in the synthesis examples and comparative examples was measured using a differential scanning calorimeter (DSC). A Waters "DSC250" differential scanning calorimeter (DSC) was used. 2 mg of each polyester polyol or polycarbonate polyol was used as the measurement sample. The measurement conditions were as follows: the temperature was raised from 23°C to 180°C at a rate of 10°C / min, held at 180°C for 5 minutes, and then cooled to -120°C at a rate of 10°C / min. After that, it was held at -120°C for 5 minutes, and then raised to 180°C at a rate of 10°C / min. The glass transition temperature (Tg) was determined during the second heating process.

[0107] <Gas Chromatography (GC) Analysis of Polyester Polyols and Polycarbonate Polyols> A mixture of 2 g of the polyester polyol or polycarbonate polyol obtained in the synthesis example and 25 mL of 0.1 N potassium hydroxide methanol solution was added to a 50 mL three-necked flask equipped with a Liebig condenser and heated at 50°C for 6 hours. The weight ratio of MPD to MPEDs in the polyester polyol was confirmed in the same manner as the GC analysis described above in the section on the production example of 3-methyl-1,5-pentanediols. From the weight ratio, the molar ratio of MPD to MPEDs in the polyester polyol or polycarbonate polyol was also calculated.

[0108]

[0109] <Production of Polyurethane> [Production Example P1] 120 g of polyester polyol A obtained in Synthesis Example 1 was fixed, and each component was placed in a 1 L separable flask equipped with a nitrogen inlet tube and a thermometer so that the molar ratio of polyester polyol A, 1,4-butanediol, and 4,4'-diphenylmethanediisocyanate was polyester polyol A:1,4-butanediol:4,4'-diphenylmethanediisocyanate = 1:2:3 (68% by mass of polyester polyol A, 6% by mass of 1,4-butanediol, and 26% by mass of 4,4'-diphenylmethanediisocyanate in 100% by mass) to form a mixed solution (70 wt% of the mixed solution contained in dehydrated dimethylformamide). Specifically, 120 g (60 mmol) of polyester polyol A, 10.8 g (120 mmol) of 1,4-butanediol, 45.0 g (180 mmol) of 4,4'-diphenylmethane diisocyanate, and 410 g of dehydrated dimethylformamide (enough to make up 70 wt% of the mixed solution) were added to a 1 L separable flask equipped with a nitrogen inlet tube and a thermometer to obtain a mixed solution. The obtained mixed solution was heated at 80°C for 6 hours to react polyester polyol A, 1,4-butanediol, and 4,4'-diphenylmethane diisocyanate to produce a thermoplastic polyurethane, thereby obtaining polyurethane solution A.

[0110] [Manufacturing Examples P2 to P8 and Manufacturing Comparative Example CP1] Polyurethane solutions B to H and polyurethane solution CA were obtained in the same manner as in Manufacturing Example P1, except that polyester polyols B to H from Synthesis Examples 2 to 8 or polyester polyol CA from Synthesis Comparative Example 1 were used instead of polyester polyol A.

[0111] [Manufacturing Example P9 and Manufacturing Comparative Example CP2] Polyurethane solution I and polyurethane solution CI were obtained in the same manner as in Manufacturing Example P1, except that polycarbonate polyol I from Synthesis Example 9 or polycarbonate polyol CI from Synthesis Comparative Example 2 were used instead of polyester polyol A.

[0112] [Example 1] 100 g of polyurethane solution A was placed in a flask, 0.1 g of dilauroyl peroxide (manufactured by Nippon Oil & Fats Co., Ltd., trade name "Perloyl® L") was added, and the mixture was stirred at 23°C for 1 hour to obtain a polyurethane solution containing 0.1% by mass of peroxide. Next, this polyurethane solution containing 0.1% by mass of peroxide was coated onto a polypropylene sheet using a bar coater, dried in an oven (ESPEC "SPH-202") at 60°C for 24 hours, and then dried at 100°C for 7 hours to obtain a 100 μm thick polyurethane film F1 formed from thermoplastic polyurethane. The obtained polyurethane film F1 had a molar ratio of structural units (P) derived from polyester polyol A, structural units (C) derived from 1,4-butanediol, and structural units (I) derived from 4,4'-diphenylmethanediisocyanate, calculated from the blending amounts of the raw material compounds of the thermoplastic polyurethane, where structural units (P):structural units (C):structural units (I) = 1:2:3. Furthermore, the obtained polyurethane film F1 had the following mass percentages of structural units (P) derived from polyester polyol A, structural units (C) derived from 1,4-butanediol, and structural units (I) derived from 4,4'-diphenylmethanediisocyanate, calculated from the blending amounts of the raw materials for thermoplastic polyurethane: structural unit (P) 68% by mass, structural unit (C) 6% by mass, and structural unit (I) 26% by mass.

[0113] [Examples 2-4] Polyurethane films F2-F4 were obtained in the same manner as in Example 1, except that polyurethane solutions B-D obtained in manufacturing examples P2-P4 were used instead of polyurethane solution A. All of the obtained polyurethane films F2-F4 had a thickness of 100 μm. The obtained polyurethane films F2-F4 had a molar ratio of structural units (P) derived from polyester polyols B-D, structural units (C) derived from 1,4-butanediol, and structural units (I) derived from 4,4'-diphenylmethanediisocyanate, calculated from the blending amounts of the raw material compounds of thermoplastic polyurethane, which was structural units (P):structural units (C):structural units (I) = 1:2:3. Furthermore, in the obtained polyurethane films F2 to F4, the mass percentages of structural units (P) derived from polyester polyols B to D, structural units (C) derived from 1,4-butanediol, and structural units (I) derived from 4,4'-diphenylmethanediisocyanate, calculated from the blending amounts of the raw materials for thermoplastic polyurethane, were 68% by mass for structural unit (P), 6% by mass for structural unit (C), and 26% by mass for structural unit (I).

[0114] [Example 5] Polyurethane film F5 was obtained in the same manner as in Example 1, except that polyurethane solution D obtained in Manufacturing Example P4 was used instead of polyurethane solution A, and dilauroyl peroxide was not added and stirring was not performed. The obtained polyurethane film F5 had a thickness of 100 μm. The obtained polyurethane film F5 had a molar ratio of structural units (P) derived from polyester polyol D, structural units (C) derived from 1,4-butanediol, and structural units (I) derived from 4,4'-diphenylmethanediisocyanate, which was calculated from the blending amounts of the raw material compounds of thermoplastic polyurethane, with structural units (P):structural units (C):structural units (I) = 1:2:3. Furthermore, the obtained polyurethane film F5 had the following mass percentages per 100% by mass of structural units (P) derived from polyester polyol D, structural units (C) derived from 1,4-butanediol, and structural units (I) derived from 4,4'-diphenylmethanediisocyanate, calculated from the blending amounts of the raw materials for thermoplastic polyurethane: structural unit (P) 68% by mass, structural unit (C) 6% by mass, and structural unit (I) 26% by mass.

[0115] [Examples 6-9] Polyurethane films F6-F9 were obtained in the same manner as in Example 1, except that polyurethane solutions E-H obtained in manufacturing examples P5-P8 were used instead of polyurethane solution A. All of the obtained polyurethane films F6-F9 had a thickness of 100 μm. The obtained polyurethane films F6-F9 had a molar ratio of structural units (P) derived from polyester polyols E-H, structural units (C) derived from 1,4-butanediol, and structural units (I) derived from 4,4'-diphenylmethanediisocyanate, calculated from the blending amounts of the raw material compounds of thermoplastic polyurethane, which was structural units (P):structural units (C):structural units (I) = 1:2:3. Furthermore, in the obtained polyurethane films F6 to F9, the mass percentages of structural units (P) derived from polyester polyols E to H, structural units (C) derived from 1,4-butanediol, and structural units (I) derived from 4,4'-diphenylmethanediisocyanate, calculated from the blending amounts of the raw materials for thermoplastic polyurethane, were 68% by mass for structural unit (P), 6% by mass for structural unit (C), and 26% by mass for structural unit (I) per 100% by mass.

[0116] [Example 10] A polyurethane film F10 was obtained in the same manner as in Example 1, except that polyurethane solution I obtained in Manufacturing Example P9 was used instead of polyurethane solution A. The obtained polyurethane film F10 had a thickness of 100 μm. The obtained polyurethane film F10 had a molar ratio of structural units (P) derived from polycarbonate polyol I, structural units (C) derived from 1,4-butanediol, and structural units (I) derived from 4,4'-diphenylmethane diisocyanate, calculated from the blending amounts of the raw material compounds for thermoplastic polyurethane, which was structural units (P):structural units (C):structural units (I) = 1:2:3. Furthermore, the obtained polyurethane film F10 had the following mass percentages per 100 mass of structural units (P) derived from polycarbonate polyol I, structural units (C) derived from 1,4-butanediol, and structural units (I) derived from 4,4'-diphenylmethane diisocyanate, calculated from the blending amounts of the raw materials for thermoplastic polyurethane: structural unit (P) 68% by mass, structural unit (C) 6% by mass, and structural unit (I) 26% by mass.

[0117] [Comparative Example 1] Polyurethane film CF1 was obtained in the same manner as in Example 1, except that polyurethane solution CA obtained in manufacturing comparative example CP1 was used instead of polyurethane solution A, and the addition and stirring of dilauroyl peroxide and drying at 100°C for 7 hours were omitted. The obtained polyurethane film CF1 had a molar ratio of structural units (P) derived from polyester polyol CA, structural units (C) derived from 1,4-butanediol, and structural units (I) derived from 4,4'-diphenylmethanediisocyanate, calculated from the blending amounts of thermoplastic polyurethane raw material compounds, where structural units (P):structural units (C):structural units (I) = 1:2:3. Furthermore, the obtained polyurethane film CF1 had the following mass percentages per 100% by mass of structural units (P) derived from polyester polyol CA, structural units (C) derived from 1,4-butanediol, and structural units (I) derived from 4,4'-diphenylmethanediisocyanate, calculated from the blending amounts of the raw materials for thermoplastic polyurethane: structural unit (P) 68% by mass, structural unit (C) 6% by mass, and structural unit (I) 26% by mass.

[0118] [Comparative Example 2] Polyurethane film CF2 was obtained in the same manner as in Example 1, except that polyurethane solution CI obtained in manufacturing comparative example CP2 was used instead of polyurethane solution A, and the addition and stirring of dilauroyl peroxide and drying at 100°C for 7 hours were omitted. The obtained polyurethane film CF2 had a molar ratio of structural units (P) derived from polycarbonate polyol CI, structural units (C) derived from 1,4-butanediol, and structural units (I) derived from 4,4'-diphenylmethane diisocyanate, calculated from the blending amounts of the raw material compounds for thermoplastic polyurethane, where structural units (P):structural units (C):structural units (I) = 1:2:3. Furthermore, the mass percentages of structural units (P) derived from polycarbonate polyol CI, structural units (C) derived from 1,4-butanediol, and structural units (I) derived from 4,4'-diphenylmethane diisocyanate, calculated from the blending amounts of the raw material compounds for thermoplastic polyurethane, were 68% by mass for structural unit (P), 6% by mass for structural unit (C), and 26% by mass for structural unit (I) per 100% by mass.

[0119] The properties of the polyurethane films formed from the thermoplastic polyurethanes obtained in the examples and comparative examples were evaluated using the following method. The results are shown in Table 3 below.

[0120] <Thickness> Using the polyurethane films obtained in the examples and comparative examples, dumbbell-shaped No. 4 test specimens were prepared in accordance with JIS K 6251:2004. The thickness of these test specimens was measured using a test specimen thickness gauge (SDA-25 model, manufactured by Polymer Instruments Co., Ltd.).

[0121] <100% Modulus (M100)> Dumbbell-shaped No. 4 test specimens were prepared from each polyurethane film obtained in the examples and comparative examples in accordance with JIS K 6251:2004. The 100% modulus of these test specimens was measured using a tensile testing machine (Instron "5566" model). The gauge length was set to 20 mm, the tensile speed was 500 mm / min, and the test was conducted at 23°C.

[0122] <Elongation at Break> Using the polyurethane films obtained in the examples and comparative examples, dumbbell-shaped test specimens of type 4 were prepared in accordance with JIS K 6251:2004. The elongation at break of these test specimens was measured in accordance with JIS K 6251:2004.

[0123] <Evaluation of particulate defects> Each polyurethane film obtained in the examples and comparative examples was visually inspected, and those with particulate defects were classified as "NG" and those without were classified as "OK".

[0124] <Glass transition temperature (Tg) of polyurethane film> The glass transition temperature of the polyurethane film was determined in the same manner as the glass transition temperature of polyester polyol, except that 2 mg of each polyurethane film obtained in the examples and comparative examples was weighed and used as the measurement sample.

[0125]

[0126] From the results in Table 3, the thermoplastic polyurethanes of Examples 1 to 9 obtained using polyester polyols A to H of Synthesis Examples 1 to 8 exhibited good elongation at break and M100 values, and were confirmed to achieve both good flexibility and excellent strength compared to the thermoplastic polyurethane of Comparative Example 1 obtained using polyester polyol CA of Synthesis Comparative Example 1. Although the thermoplastic polyurethane of Comparative Example 1 exhibited good elongation at break, its M100 value was inferior to that of the thermoplastic polyurethanes of Examples 1 to 9, and it was confirmed that it could not achieve both good flexibility and excellent strength. The thermoplastic polyurethane of Example 10 obtained using polycarbonate polyol I of Synthesis Example 9 exhibited good elongation at break and M100 values, and was confirmed to achieve both good flexibility and excellent strength compared to the thermoplastic polyurethane of Comparative Example 2 obtained using polycarbonate polyol CI of Synthesis Comparative Example 2. Although the thermoplastic polyurethane of Comparative Example 2 exhibited good elongation at break, its M100 value was inferior to that of the thermoplastic polyurethane of Example 10, and it was confirmed that it could not achieve both good flexibility and excellent strength. In other words, it was confirmed that by using a polymer according to one aspect of the present invention, it is possible to provide a polyurethane that can achieve both good flexibility and excellent strength. Furthermore, it was confirmed that thermoplastic polyurethanes obtained using polyester polyols A to D and F to H of Examples 1 to 5 and 7 to 9, and polycarbonate polyol I of Example 10, in which the total content of at least one selected from the group consisting of diol (a1) and diol (a2) in 100 mol% of the diol component (A) used in the production of polyester polyols A to D and F to H and polycarbonate polyol I is 2.5 mol% or less, show no particulate defects in the polyurethane film and yield a better appearance. This is thought to be because the number of reaction sites with the crosslinking agent is adjusted to an appropriate number, thereby suppressing the occurrence of particulate defects.

Claims

1. A polymer obtained by the reaction of a diol component (A) comprising at least one selected from the group consisting of a diol (a1) represented by the following general formula (I) and a diol (a2) represented by the following general formula, and a component (B) which is at least one selected from the group consisting of dicarboxylic acid (b1) and carbonate ester (b2). (In general formula (I), R １ and R ２ Each of these independently represents a hydrocarbon group having 1 to 10 carbon atoms, and R ３ R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. In general formula (II), R ４ R represents a hydrocarbon group with 1 to 10 carbon atoms. ５ R represents a single bond or a hydrocarbon group having 1 to 9 carbon atoms. ６ (This represents a hydrocarbon group with 1 to 5 carbon atoms.) 2. The polymer according to claim 1, wherein the total content of at least one selected from the group consisting of the diol (a1) and the diol (a2) is 0.01 to 3.5 mol% of 100 mol% of the diol component (A).

3. In the general formula (I), R １ and R ２ each independently represents a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ３ represents a hydrogen atom, a methyl group or an ethyl group. The polymer according to claim 1 or 2.

4. In the above general formula (II), R ４ R represents a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms. ５ R represents a single bond or a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms. ６ The polymer according to any one of claims 1 to 3, wherein represents a methyl group or an ethyl group.

5. The polymer according to any one of claims 1 to 4, wherein the diol component (A) comprises a diol (a3) ​​represented by the following general formula (III). (In general formula (III), R ７ and R ８ Each of these independently represents a hydrocarbon group having 1 to 10 carbon atoms, and R ９ (This represents a hydrocarbon group with 1 to 5 carbon atoms.) 6. In the above general formula (III), R ７ and R ８ Each of these independently represents a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R ９ The polymer according to claim 5, wherein represents a saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms.

7. The polymer according to claim 5 or 6, wherein the content of the diol (a3) ​​is 20 mol% or more and 99.99 mol% or less in 100 mol% of the diol component (A).

8. The polymer according to any one of claims 1 to 7, wherein the dicarboxylic acid (b1) comprises a dicarboxylic acid (b1-1) represented by the following general formula (IV). (In general formula (IV), R １０ (This represents a hydrocarbon group with 1 to 12 carbon atoms.) 9. In the above general formula (IV), R １０ The polymer according to claim 8, wherein is a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, a saturated alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms.

10. The polymer according to claim 8 or 9, wherein the content of the dicarboxylic acid (b1-1) is 80 to 100 mol% of 100 mol% of the dicarboxylic acid (b1).

11. The polymer according to any one of claims 1 to 10, wherein the content of the dicarboxylic acid (b1) is 80 to 100 mol% of 100 mol% of component (B).

12. The polymer according to any one of claims 1 to 10, wherein the content of the carbonate ester (b2) is 50 to 100 mol% of 100 mol% of component (B).

13. The polymer according to any one of claims 1 to 12, wherein the content of structural units derived from components (A) and (B) is 80 to 100 mol% of the total structural units in the polymer.

14. The polymer according to any one of claims 1 to 13, wherein the polymer is a polymeric polyol.

15. A polyurethane comprising a structure derived from the polymer described in any one of claims 1 to 14.

16. The polyurethane according to claim 15, wherein it is thermoplastic.

Images