Diol-containing compositions, polycarbonate diol compositions and methods for producing the same, and polyurethane

Abstract

The objective is to provide a diol-containing composition that enables the stable production of polycarbonate diol compositions for obtaining polyurethanes suitable for use in paints, coatings, and adhesives. [Solution] A diol-containing composition comprising a diol compound (4) represented by the following general formula (IV) and a tetrahydropyran compound (3-1) represented by the following general formula (III-1). [Formula 1] JPEG2026054816000039.jpg567 (In the above general formula (IV), n is an integer between 3 and 6.) [chemical 2] JPEG2026054816000040.jpg1572 (In the above general formula (III-1), R1 is a C2-C12 alkyl group or hydrogen atom, which may have substituents or heteroatoms.) A polycarbonate diol composition comprising the aforementioned diol-containing composition and a carbonate-based compound as raw materials.

Description

[Technical Field]

[0001] The present invention relates to a diol-containing composition, a polycarbonate diol composition, and a method for producing the same. Furthermore, the present invention relates to polyurethane obtained using the polycarbonate diol composition described above. [Background technology]

[0002] As a polyurethane produced on an industrial scale, a polycarbonate-type polyurethane has been proposed that uses polycarbonate diol as the raw material for the soft segment (Non-Patent Document 1). Polycarbonate-type polyurethane is widely used in applications such as automotive artificial leather, building materials like furniture, water-based paints and coatings for clothing, adhesives, and durable films due to its excellent heat resistance and hydrolysis resistance. In particular, polycarbonate-type polyurethanes with excellent adhesion to substrates and chemical resistance are required for applications such as paints, coatings, and adhesives.

[0003] Polycarbonate diols, which are widely available on the market as raw materials for polycarbonate-type polyurethanes, use dihydroxy compounds as raw materials. These dihydroxy compounds mainly consist of linear aliphatic diols with 3 to 6 carbon atoms, such as 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.

[0004] For example, Patent Document 1 discloses a polycarbonate diol made from 1,6-hexanediol and 1,5-pentanediol, and a polyurethane obtained from the polycarbonate diol. Patent Document 2 discloses a polycarbonate diol made from 1,4-butanediol and 1,5-pentanediol, and a polyurethane obtained from the polycarbonate diol. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2-289616 [Patent Document 2] Japanese Patent Application Publication No. 4-7327 [Non-patent literature]

[0006] [Non-Patent Document 1] "Fundamentals and Applications of Polyurethane," pp. 96-106, supervised by Katsuji Matsunaga, CMC Publishing Co., Ltd., published November 2006. [Overview of the project] [Problems that the invention aims to solve]

[0007] However, the polyurethanes obtained from polycarbonate diols described in Patent Documents 1 and 2 are not sufficiently performant for applications such as paints, coatings, and adhesives. Furthermore, Patent Documents 1 and 2 do not mention anything about obtaining polyurethane suitable for use in paints, coatings, and adhesives by incorporating specific compounds into a diol-containing composition.

[0008] This invention was made in view of the above-mentioned problems. The object of the present invention is to provide a diol-containing composition that enables the stable production of polycarbonate diol compositions for obtaining polyurethanes suitable for use in paints, coatings, and adhesives. Furthermore, the present invention aims to provide a method for producing a polycarbonate diol composition suitable for use in paints, coatings, and adhesives. Furthermore, the present invention aims to provide polyurethane suitable for use in paints, coatings, and adhesives. [Means for solving the problem]

[0009] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by including a specific tetrahydropyran compound in the diol-containing composition used as a raw material for polycarbonate diol.

[0010] The present invention has been achieved based on such findings, and the gist thereof is as follows. [1] A diol-containing composition containing a diol compound (4) represented by the following general formula (IV) and a tetrahydropyran compound (3-1) represented by the following general formula (III-1). [Chemical formula] (In the above general formula (IV), n is an integer of 3 to 6.) [Chemical formula] (In the above general formula (III-1), R 1 is an alkyl group having 2 to 12 carbon atoms which may have a substituent or a hetero atom, or a hydrogen atom.) [2] The diol-containing composition according to [1] above, which is used in the step of producing a polycarbonate diol composition.

[0011] [3] The diol-containing composition according to [1] or [2] above, wherein the tetrahydropyran compound (3-1) is contained in the diol-containing composition at 0.01% by mass or more based on the total mass of the diol-containing composition. [4] The diol-containing composition according to any one of [1] to [3] above, wherein the tetrahydropyran compound (3-1) is contained in the diol-containing composition at 2.00% by mass or less based on the total mass of the diol-containing composition. [5] The diol-containing composition according to any one of [1] to [4] above, wherein the diol compound (4) is contained in the diol-containing composition at 90.00% by mass or more and 99.99% by mass or less based on the total mass of the diol-containing composition. [6] The diol-containing composition according to any one of [1] to [5] above, wherein the diol compound (4) contains 1,5-pentanediol.

[0012] [7] The diol-containing composition according to any one of [1] to [6] above, wherein the tetrahydropyran compound (3-1) contains a tetrahydropyran compound (3-2) represented by the following general formula (III-2). [ka] (In the above general formula (III-2), R 2 (This is an alkyl group having 2 to 12 carbon atoms or a hydrogen atom containing a hydroxyl group terminus, which may have a side chain.) [8] The diol-containing composition according to any one of [1] to [7] above, wherein the tetrahydropyran compound (3-1) contains a tetrahydropyran compound (3-3) represented by the following general formula (III-3). [ka] (In the general formula (III-3) above, m is an integer between 2 and 12.) [9] A polycarbonate diol composition made from a diol-containing composition described in any of [1] to [8] above and a carbonate compound.

[0013]

[10] A method for producing a polycarbonate diol composition, comprising polycondensing a diol-containing composition and a carbonate-based compound by transesterification in the presence of a catalyst to obtain a polycarbonate diol, A method for producing a polycarbonate diol composition, wherein the diol-containing composition contains a diol compound (4) represented by the following general formula (IV) and a tetrahydropyran compound (3-1) represented by the following general formula (III-1). [ka] (In the general formula (IV) above, n is an integer between 3 and 6.) [ka] (In the above general formula (III-1), R 1(This is an alkyl group having 2 to 12 carbon atoms or a hydrogen atom, which may have substituents or heteroatoms.)

[0014]

[11] The method for producing the polycarbonate diol composition according to

[10] , wherein the diol-containing composition contains 0.01% by mass or more of the tetrahydropyran compound (3-1) based on the total mass of the diol-containing composition.

[12] A method for producing a polycarbonate diol composition according to

[10] or

[11] , wherein the diol-containing composition contains 2.00% by mass or less of the tetrahydropyran compound (3-1) based on the total mass of the diol-containing composition.

[13] A method for producing the polycarbonate diol composition according to any one of

[10] to

[12] above, wherein the diol compound (4) contains 1,5-pentanediol.

[0015]

[14] A method for producing the polycarbonate diol composition according to any one of

[10] to

[13] above, wherein the tetrahydropyran compound (3-1) contains a tetrahydropyran compound (3-2) represented by the following general formula (III-2). [ka] (In the above general formula (III-2), R 2 (This is an alkyl group having 2 to 12 carbon atoms or a hydrogen atom containing a hydroxyl group terminus, which may have a side chain.)

[15] A method for producing the polycarbonate diol composition according to any one of

[10] to

[14] above, wherein the tetrahydropyran compound (3-1) contains a tetrahydropyran compound (3-3) represented by the following general formula (III-3). [ka] (In the general formula (III-3) above, m is an integer between 2 and 12.)

[16] A polyurethane made from the polycarbonate diol composition and isocyanate compounds described in [9] above. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide a diol-containing composition that enables the stable production of polycarbonate diol compositions for obtaining polyurethanes suitable for use in paints, coatings, and adhesives. Furthermore, according to the present invention, it is possible to provide a method for stably producing polycarbonate diol compositions for obtaining polyurethanes suitable for use in paints, coatings, and adhesives. Furthermore, according to the present invention, it is possible to provide polyurethane suitable for use in paints, coatings, and adhesives. [Modes for carrying out the invention]

[0017] The embodiments of the present invention will be described in detail below. The present invention is not limited to the embodiments described below, and can be implemented in various ways within the scope of its gist.

[0018] In this specification, "structural unit" refers to a unit derived from a raw material compound used in the production of a polycarbonate diol, formed by the polymerization of the raw material compound, and representing a substructure sandwiched between arbitrary linking groups in the resulting polymer. A structural unit also includes a substructure in which one end of the polymer is a linking group and the other is a polymerization-reactive group. A structural unit may be a unit directly formed by a polymerization reaction, or a part of the unit may be converted to a different structure by processing the resulting polymer. In this specification, "repeating unit" is synonymous with "structural unit."

[0019] In this specification, numerical ranges expressed using "~" mean a range that includes the numbers written before and after "~" as the lower and upper limits, respectively, unless otherwise specified. For example, "A~B" means A or greater and B or less.

[0020] In this specification, "including A or B" means "including A," "including B," and "including A and B," unless otherwise specified.

[0021] In this specification, "mass%" indicates the percentage of a given component contained in 100% of the total amount. In this specification, “mass%” and “weight%”, “mass ppm” and “weight ppm”, and “parts by mass” and “parts by weight” are synonymous. Furthermore, when simply written as “ppm”, it refers to “weight ppm”.

[0022] In this specification, "obtained polyurethane" refers to polyurethane produced using a polycarbonate diol composition made from the diol-containing composition of the present invention as a raw material, and polyurethane produced using a polycarbonate diol composition obtained by the method for producing the polycarbonate diol composition of the present invention.

[0023] In this specification, the diol-containing composition of the present invention, the polycarbonate diol composition of the present invention, the method for producing the polycarbonate diol composition of the present invention, and the polyurethane of the present invention are collectively referred to as "the present invention."

[0024] [Diol-containing composition] The diol-containing composition of the present invention is a diol-containing composition that contains the diol compound (4) and the tetrahydropyran compound (3-1) described later.

[0025] The diol-containing composition of the present invention contains a tetrahydropyran compound (3-1), and a polyurethane produced using the diol-containing composition and a carbonate-based compound as raw materials can be suitably used in paints, coatings, and adhesives. Therefore, the diol-containing composition of the present invention can be suitably used in the process of producing a polycarbonate diol composition.

[0026] Although the diol-containing composition of the present invention may sometimes be referred to as a "diol compound" because it is composed of substantially trace amounts of tetrahydropyran compounds and diol compounds, the diol-containing composition of the present invention is not composed solely of diol compounds and should be referred to as a "diol-containing composition."

[0027] <Diol compounds> The diol compound (4) in the present invention is a compound represented by the following general formula (IV), and is one component of the diol-containing composition of the present invention. [ka] (In the general formula (IV) above, n is an integer between 3 and 6.)

[0028] The diol-containing composition of the present invention, by containing the diol compound (4), provides excellent mechanical properties and chemical resistance to polyurethane obtained using a polycarbonate diol manufactured from the diol-containing composition of the present invention (hereinafter sometimes simply referred to as "obtained polyurethane").

[0029] In the diol-containing composition of the present invention, the diol compound (4) is not particularly limited, and known diol compounds used as raw materials for polycarbonate diols can be appropriately selected and used. Specifically, examples include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. The aforementioned diol compound (4) may be used alone or in combination of two or more types.

[0030] The content ratio of the diol compound (4) in the diol-containing composition of the present invention is not particularly limited, but from the viewpoint of having good handling properties of the obtained polycarbonate diol and good flexibility and low-temperature properties of the obtained polyurethane, it is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 98% by mass or more, and particularly preferably 99% by mass or more, based on 100% of the total mass of the diol-containing composition. On the other hand, the upper limit of the content ratio of the diol compound (4) in the diol-containing composition is not particularly limited, and it can be preferably less than 100% by mass, more preferably 99.99% by mass or less, even more preferably 99.95% by mass or less, and particularly preferably 99.90% by mass or less, based on 100% of the total mass of the diol-containing composition. The above upper and lower limits can be combined in any way. For example, the content of the diol compound (4) in the diol-containing composition of the present invention can be 90% by mass or more and less than 100% by mass, more preferably 95% by mass or more and 99.99% by mass or less, even more preferably 98% by mass or more and 99.95% by mass or less, and particularly preferably 99% by mass or more and 99.90% by mass or less, based on 100% of the total mass of the diol-containing composition.

[0031] The diol compound (4) may optionally contain a compound represented by the following general formula (IV-1), namely 1,5-pentanediol. [ka] The presence of 1,5-pentanediol in the diol compound (4) results in improved mechanical properties and chemical resistance of the resulting polyurethane.

[0032] In such cases, the content of 1,5-pentanediol in the diol compound (4) is not particularly limited, but from the viewpoint of good handling properties of the polycarbonate diol and flexibility and low-temperature properties of the obtained polyurethane, it is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and particularly preferably 70% by mass or more, based on 100% of the total mass of the diol compound. This content can also be 90% by mass or more. On the other hand, the upper limit of the content of 1,5-pentanediol in the diol compound is not particularly limited, and may be 100% by mass based on 100% of the total mass of the diol compound, or preferably less than 100% by mass, more preferably 99% by mass or less, even more preferably 98% by mass or less, and particularly preferably 97% by mass or less. The above upper and lower limits can be combined in any way. For example, the content of 1,5-pentanediol in the diol compound can be 100% by mass, preferably 10% by mass or more and less than 100% by mass, more preferably 30% by mass or more and 99% by mass or less, even more preferably 50% by mass or more and 98% by mass or less, and particularly preferably 70% by mass or more and 97% by mass or less, based on 100% of the total mass of the diol compound.

[0033] In the diol-containing composition of the present invention, a single diol compound (4) derived from fossil fuels can be used as the diol compound (4). A fossil fuel-derived diol compound (4) refers to at least one selected from petroleum-derived diols, coal-derived diols, and natural gas-derived diols.

[0034] Alternatively, the diol-containing composition of the present invention may contain a diol compound (4) derived from bio-based raw materials, from the viewpoint of achieving the Sustainable Development Goals (SDGs). Specifically, either a diol compound (4) derived from bio-based raw materials alone, or a mixture containing a diol compound (4) derived from bio-based raw materials and a diol compound (4) derived from fossil fuels, can be used. Examples of diol compounds derived from biomaterials (4) include diol compounds derived from non-edible biomass and / or non-fossil fuels.

[0035] In this invention, non-edible biomass refers to resources derived from non-edible grasses and trees. Specifically, this includes, but is not limited to, cellulose, hemicellulose, and lignin obtained from woody biomass such as coniferous and broad-leaved trees, as well as bioethanol, biodiesel, and plant-derived waste oil obtained from herbaceous biomass such as corn and sugarcane stalks, soybeans, and rapeseed. In this invention, non-fossil fuels refer to, for example, hydrogen, or organic matter derived from plants and animals that does not originate from fossil fuels or non-edible biomass. Specifically, examples include, but are not limited to, methane and sugar ethanol obtained from firewood, charcoal, dried livestock manure, etc.

[0036] For example, the diol-containing composition can use 1,5-pentanediol derived from fossil fuels alone as the diol compound (4). Fossil fuel-derived 1,5-pentanediol refers to at least one of the following: petroleum-derived 1,5-pentanediol, coal-derived 1,5-pentanediol, and natural gas-derived 1,5-pentanediol.

[0037] Alternatively, the diol-containing composition may contain 1,5-pentanediol derived from bio-based raw materials as the diol compound (4) from the viewpoint of achieving the Sustainable Development Goals (SDGs). Specifically, either 1,5-pentanediol derived from bio-based raw materials alone, or a mixture containing 1,5-pentanediol derived from bio-based raw materials and 1,5-pentanediol derived from fossil fuels, can be used. Examples of 1,5-pentanediol derived from bio-based raw materials include 1,5-pentanediol derived from non-edible biomass and / or non-fossil fuels.

[0038] (Tetrahydropyran compound (3-1)) The tetrahydropyran compound (3-1) in the present invention is a compound represented by the following general formula (III-1), and is a component of the diol-containing composition of the present invention.

[0039] [ka] (In the above general formula (III-1), R 1 (This is an alkyl group having 2 to 12 carbon atoms or a hydrogen atom, which may have substituents or heteroatoms.)

[0040] The tetrahydropyran compound (3-1) in the present invention is not particularly limited, and any known compound containing a terminal structure (2-1) represented by the following general formula (II-1), such as a tetrahydropyranyl group, or a compound obtained by replacing some of the hydroxyl groups in the diol compound (4) with a terminal structure (2-1) such as a tetrahydropyranyl group can be used.

[0041] [ka]

[0042] From the viewpoint of ensuring that the resulting polyurethane can be suitably used in paints, coatings, and adhesives, it is preferable that the tetrahydropyran compound (3-1) contains a tetrahydropyran compound (3-2) represented by the following general formula (III-2).

[0043] [ka] (In the above general formula (III-2), R 2 (This is an alkyl group having 2 to 12 carbon atoms or a hydrogen atom containing a hydroxyl group terminus, which may have a side chain.)

[0044] In the above general formula (III-1), R 1 an alkyl group which may have substituents or heteroatoms and in the general formula (III-2), R 2The number of carbon atoms in the alkyl group containing a hydroxyl group terminus, which may have a side chain, is an integer from 2 to 12, preferably 3 to 10, more preferably 3 to 6, even more preferably 4 to 6, and particularly preferably 5, from the viewpoint of obtaining better mechanical properties and chemical resistance of the resulting polyurethane.

[0045] In the diol-containing composition of the present invention, the tetrahydropyran compound (3-1) preferably contains a tetrahydropyran compound (3-3) represented by the following general formula (III-3), from the viewpoint of enabling the obtained polyurethane to be more suitably used in paints, coatings, and adhesives.

[0046] [ka] (In the general formula (III-3) above, m is an integer between 2 and 12.)

[0047] In the above general formula (III-3), m is an integer from 2 to 12, preferably from 3 to 10, more preferably from 3 to 6, even more preferably from 4 to 6, and particularly preferably from 5, from the viewpoint of obtaining better mechanical properties and chemical resistance of the polyurethane.

[0048] The type of tetrahydropyran compound (3-1) in the present invention is not particularly limited, and examples include compounds having 5 to 11 carbon atoms and having 1 to 2, preferably 1, terminal structures (2-1) such as tetrahydropyranyl groups in the molecule. Specifically, examples include 2-hydroxytetrahydropyran, tetrahydropyranylethylene glycol, 3-(2-oxytetrahydropyran)-1-propanol, 4-(2-oxytetrahydropyran)-1-butanol, 5-(2-oxytetrahydropyran)-1-pentanol, and 6-(2-oxytetrahydropyran)-1-hexanol.

[0049] In the diol-containing composition of the present invention, one specific embodiment of the diol-containing composition is one in which, from the viewpoint of excellent mechanical strength and chemical resistance of the obtained polyurethane, the diol compound (4) contains 1,5-pentanediol and the tetrahydropyran compound (3-1) contains 5-(2-oxytetrahydropyran)-1-pentanol.

[0050] <Percentage of tetrahydropyran compound (3-1) content> The lower limit of the content of the tetrahydropyran compound (3-1) in the diol-containing composition of the present invention is not particularly limited. From the viewpoint of the expectation that the obtained polyurethane can be suitably used in paints, coatings, and adhesives, and further from the viewpoint of economic efficiency in reducing the amount of the tetrahydropyran compound (3-1), it is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more, based on the total mass of the diol-containing composition. On the other hand, the upper limit of the content of the tetrahydropyran compound (3-1) is not particularly limited, and from the viewpoint of maintaining good mechanical properties and chemical resistance of the obtained polyurethane, it is preferably 2.00% by mass or less, more preferably 1.80% by mass or less, even more preferably 1.50% by mass or less, and particularly preferably 1.00% by mass or less, relative to the total mass of the diol-containing composition. The above upper and lower limits can be combined arbitrarily. For example, the content of the tetrahydropyran compound (3-1) contained in the diol-containing composition of the present invention is preferably 0.01% by mass or more and 2.00% by mass or less, more preferably 0.02% by mass or more and 1.80% by mass or less, even more preferably 0.05% by mass or more and 1.50% by mass or less, and particularly preferably 0.10% by mass or more and 1.00% by mass or less, based on the total mass of the diol-containing composition.

[0051] [Method for producing polycarbonate diol composition] The method for producing a polycarbonate diol composition using the diol-containing composition of the present invention is not particularly limited. For example, known methods for producing polycarbonate diols described in Schnell, Polymer Reviews Vol. 9, p9-20 (1994), International Publication No. 2015 / 199070, etc. can be used.

[0052] Alternatively, as a specific embodiment of the method for producing a polycarbonate diol composition using the diol-containing composition of the present invention, a diol-containing composition containing a diol compound (4) represented by the following general formula (IV) and a tetrahydropyran compound (3-1) represented by the following general formula (III-1), and a carbonate-based compound described later are polycondensed by a transesterification reaction in the presence of a catalyst described later to obtain a polycarbonate diol. The method for producing the polycarbonate diol composition of the present invention includes this.

Chemical formula

Chemical formula

[0053] The diol-containing composition in the method for producing the polycarbonate diol composition of the present invention is treated as synonymous with the diol-containing composition of the present invention.

[0054] The diol compound (4) in the method for producing the polycarbonate diol composition of the present invention is treated as synonymous with the diol compound (4) mentioned in the description of the diol-containing composition of the present invention.

[0055] In the method for producing the polycarbonate diol composition of the present invention, the tetrahydropyran compound (3-1) is treated as synonymous with the tetrahydropyran compound (3-1) mentioned in the description of the diol-containing composition of the present invention.

[0056] <Carbonate compounds> The carbonate compounds (sometimes referred to as "carbonate diesters") that can be used in the method for producing the polycarbonate diol composition of the present invention are not particularly limited, as long as they do not impair the effects of the present invention. Examples of usable carbonate compounds include known carbonate compounds used in the synthesis of polycarbonate diols, such as dialkyl carbonates, diaryl carbonates, or alkylene carbonates. A person skilled in the art can appropriately select the carbonate compound to be used depending on the intended use of the polycarbonate diol and the manufacturing conditions. For example, from the viewpoint of reactivity between the diol-containing composition and the carbonate compound, diaryl carbonates are preferred as the carbonate compound, and from the viewpoint of economy, dialkyl carbonates or alkylene carbonates are preferred as the carbonate compound. Specific examples of carbonate compounds include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate, and ethylene carbonate.

[0057] The amount of carbonate compound used is not particularly limited, and for example, the conditions described in International Publication No. 2015 / 199070 can be used by a person skilled in the art, optimized as appropriate according to the known art.

[0058] <Catalyst> In the method for producing the polycarbonate diol composition of the present invention, when obtaining a polycarbonate diol by polycondensation of a diol-containing composition and a carbonate compound by transesterification, a known transesterification catalyst used in the synthesis of polycarbonate diols (hereinafter sometimes referred to as "catalyst") can be used as a catalyst to promote the transesterification reaction. In that case, if an excessive amount of catalyst remains in the resulting polycarbonate diol composition, it may inhibit or excessively accelerate the reaction when using the polycarbonate diol composition to produce polyurethane. The type of catalyst and the amount of catalyst remaining in the polycarbonate diol composition are not particularly limited. As a catalyst, for example, those skilled in the art can use the conditions described in International Publication No. 2015 / 199070, which can be appropriately optimized according to the known art.

[0059] In the method for producing polycarbonate diol of the present invention, it is preferable to use a catalyst containing magnesium atoms or a catalyst containing titanium atoms as the catalyst, and it is more preferable to use a catalyst containing titanium atoms. Catalysts containing magnesium atoms are not particularly limited and include, for example, magnesium hydroxide, magnesium bicarbonate, magnesium carbonate, magnesium acetate, magnesium thearate, and magnesium phenylphosphate. Catalysts containing titanium atoms are not particularly limited and include, for example, titanium alkoxides such as tetraethyl titanate, tetraisopropyl titanate, and tetra-n-butyl titanate; and titanium halides such as titanium tetrachloride. The amount of catalyst containing titanium atoms used can be 50 ppm or less by mass, 35 ppm or less, or 25 ppm or less, relative to the total mass of the diol-containing composition in terms of titanium atoms. However, if the amount of catalyst is too small, a sufficient catalytic effect cannot be obtained, so it is preferable that the amount of catalyst containing titanium atoms used be 1 ppm or more by mass, particularly 2 ppm or more, and especially 3 ppm or more, relative to the total mass of the diol-containing composition in terms of titanium atoms.

[0060] <Catalyst deactivator> As mentioned above, when a catalyst is used during the polymerization reaction, the resulting polycarbonate diol composition usually contains residual catalyst. This residual catalyst can cause an increase in molecular weight or a change in composition when the polycarbonate diol composition is heated, or it may become impossible to control the polyurethaneization reaction. To suppress the effects of this residual catalyst, the catalyst deactivator, such as a phosphorus-based compound, can be added in an amount approximately equivalent to the transesterification catalyst used, as needed, to deactivate the transesterification catalyst. Furthermore, the transesterification catalyst can be efficiently deactivated by heat treatment or other methods after addition. The type and amount of catalyst deactivator used, as well as the heat treatment conditions, are not particularly limited. For example, the conditions described in International Publication No. 2015 / 199070 can be used as catalyst deactivators, and can be appropriately optimized by those skilled in the art according to the known art.

[0061] The amount of the phosphorus-based catalyst deactivator used can be 50 ppm or less by mass, 35 ppm or less, or 25 ppm or less, in terms of phosphorus atoms, relative to the total mass of the polycarbonate diol-containing composition. However, if the amount of catalyst is too small, a sufficient catalytic effect cannot be obtained. Therefore, it is preferable that the amount of catalyst containing phosphorus atoms used be 1 ppm or more by mass, particularly 2 ppm or more, and especially 3 ppm or more, in terms of phosphorus atoms, relative to the total mass of the polycarbonate diol-containing composition.

[0062] <Polycarbonate diol composition> A first embodiment of the polycarbonate diol composition in the present invention is a polycarbonate diol composition obtained by using the diol-containing composition of the present invention and a carbonate-based compound as raw materials.

[0063] Alternatively, a second embodiment of the polycarbonate diol composition in the present invention is a polycarbonate diol composition produced using the method for producing the polycarbonate diol composition of the present invention.

[0064] Alternatively, a third embodiment of the polycarbonate diol composition in the present invention is a polycarbonate diol composition containing the polycarbonate diol described later and the tetrahydropyran compound (3-1).

[0065] In the method for producing the polycarbonate diol composition of the present invention, the tetrahydropyran compound (3-1) is treated as synonymous with the tetrahydropyran compound (3-1) mentioned in the description of the diol-containing composition of the present invention.

[0066] Hereinafter, the polycarbonate diol composition obtained by the method for producing the polycarbonate diol composition of the present invention, and the polycarbonate diol composition of the present invention, will be collectively referred to simply as "the polycarbonate diol composition of the present invention."

[0067] The polycarbonate diol composition of the present invention, by containing a tetrahydropyran compound (3-1), is expected to provide superior performance when the resulting polyurethane is used in paints, coatings, and adhesives.

[0068] (Tetrahydropyran compound (3-1)) The tetrahydropyran compound (3-1) described above is a compound represented by the following general formula (III-1), and is one of the components constituting the polycarbonate diol composition of the present invention.

[0069] [ka] (In the above general formula (III-1), R 1 (This is an alkyl group having 2 to 12 carbon atoms or a hydrogen atom, which may have substituents or heteroatoms.)

[0070] In the polycarbonate diol composition of the present invention, the tetrahydropyran compound (3-1) is treated as synonymous with the tetrahydropyran compound (3-1) mentioned in the description of the diol-containing composition of the present invention.

[0071] In the polycarbonate diol composition of the present invention, the tetrahydropyran compound (3-1) preferably contains a tetrahydropyran compound (3-2) represented by the following general formula (III-2), from the viewpoint of being able to more suitably use the obtained polyurethane in applications such as paints, coatings, and adhesives.

[0072] [ka] (In the above general formula (III-2), R 2 (This is an alkyl group having 2 to 12 carbon atoms or a hydrogen atom containing a hydroxyl group terminus, which may have a side chain.)

[0073] In the polycarbonate diol composition of the present invention, the tetrahydropyran compound (3-2) is treated as synonymous with the tetrahydropyran compound (3-2) mentioned in the description of the diol-containing composition of the present invention.

[0074] In the polycarbonate diol composition of the present invention, the tetrahydropyran compound (3-1) preferably contains a tetrahydropyran compound (3-3) represented by the following general formula (III-3), from the viewpoint that the resulting polyurethane can be suitably used in paints, coatings, and adhesives.

[0075] [ka] (In the general formula (III-3) above, m is an integer between 2 and 12.)

[0076] In the method for producing the polycarbonate diol composition of the present invention, the tetrahydropyran compound (3-3) is treated as synonymous with the tetrahydropyran compound (3-3) mentioned in the description of the diol-containing composition of the present invention.

[0077] <Total content ratio of terminal structures (2-1) in polycarbonate diols and compounds (3-1) in polycarbonate diol compositions> In the polycarbonate diol composition of the present invention, the total content ratio of the terminal structure (2-1) in the polycarbonate diol and the compound (3-1) in the polycarbonate diol composition (hereinafter simply referred to as "total content ratio of terminal structure (2-1) and compound (3-1)") is not particularly limited, but can be the first or second embodiment described below.

[0078] (First embodiment) In the polycarbonate diol composition of the present invention, there is no particular upper limit to the total content ratio of the terminal structure (2-1) and compound (3-1). However, from the viewpoint of being able to suitably use the obtained polyurethane in applications such as paints, coatings, and adhesives, and further from the viewpoint of economic efficiency in reducing the tetrahydropyran compound (3-1), it is preferable that the total content ratio of hydroxyl group terminals in the polycarbonate diol and compound (3-1) be 0.01 mol% or more, more preferably 0.05 mol% or more, even more preferably 0.10 mol% or more, and particularly preferably 0.20 mol% or more, based on 100% of the total molar amount of hydroxyl group terminals in the polycarbonate diol and compound (3-1). On the other hand, the upper limit of the total content ratio of the terminal structure (2-1) and compound (3-1) is not particularly limited. From the viewpoint of maintaining good mechanical properties and chemical resistance of the obtained polyurethane, it is preferably 10.0 mol% or less, more preferably 7.00 mol% or less, even more preferably 5.00 mol% or less, and particularly preferably 2.50 mol% or less, based on 100% of the total molar amount of hydroxyl group terminals in the polycarbonate diol and compound (3-1). The above upper and lower limits can be combined arbitrarily. For example, in the polycarbonate diol composition of the present invention, the total content ratio of the terminal structure (2-1) and compound (3-1) is preferably 0.01 mol% to 10.0 mol%, more preferably 0.05 mol% to 7.00 mol%, even more preferably 0.10 mol% to 5.00 mol%, and particularly preferably 0.20 mol% to 2.50 mol%, based on 100% of the total molar amount of hydroxyl group terminals in the polycarbonate diol and compound (3-1).

[0079] (Second embodiment) In the polycarbonate diol composition of the present invention, the lower limit of the total content ratio of the terminal structure (2-1) and compound (3-1) is not particularly limited. From the viewpoint of the expectation that the obtained polyurethane can be suitably used in paints, coatings, and adhesives, and further from the viewpoint of economic efficiency in reducing the tetrahydropyran compound (3-1), it is preferable that the total content ratio of structural unit (1-1) in the polycarbonate diol be 0.01 mol% or more, more preferably 0.02 mol% or more, even more preferably 0.03 mol% or more, and particularly preferably 0.05 mol% or more, based on 100% of the total molar amount of structural unit (1-1) in the polycarbonate diol. On the other hand, the upper limit of the total content ratio of the terminal structure (2-1) and compound (3-1) is not particularly limited. From the viewpoint of maintaining good mechanical properties and chemical resistance of the obtained polyurethane, it is preferably 2.00 mol% or less, more preferably 1.00 mol% or less, even more preferably 0.50 mol% or less, and particularly preferably 0.30 mol% or less, based on 100% of the total molar amount of structural unit (1-1) in the polycarbonate diol. The above upper and lower limits can be combined arbitrarily. For example, in the polycarbonate diol composition of the present invention, the total content ratio of the terminal structure (2-1) and compound (3-1) is preferably 0.01 mol% to 2.00 mol%, more preferably 0.02 mol% to 1.00 mol%, even more preferably 0.03 mol% to 0.50 mol%, and particularly preferably 0.05 mol% to 0.30 mol%, based on 100% of the total molar amount of structural unit (1-1) in the polycarbonate diol.

[0080] <Formyl group> The polycarbonate diol composition of the present invention may contain a formyl group at the polycarbonate diol terminus. It may also contain a compound containing a formyl group.

[0081] When producing a polycarbonate diol composition using a diol-containing composition containing a tetrahydropyran compound (3-1), the terminal structure (2-1) contained in the tetrahydropyran compound (3-1) may open its ring depending on the method of producing the composition, forming a compound containing a formyl group. Furthermore, if the compound containing a formyl group has a hydroxyl group, it may react with a carbonate-based compound described later to form a formyl group in the polycarbonate diol terminal.

[0082] <Total content of formyl groups in the polycarbonate diol termini and formyl group-containing compounds in the polycarbonate diol composition> In the polycarbonate diol composition of the present invention, the upper limit of the total content ratio of formyl groups in the polycarbonate diol termini and formyl group-containing compounds in the polycarbonate diol composition is not particularly limited. However, from the viewpoint of obtaining a polyurethane with excellent mechanical properties and chemical resistance, and suppressing variations in the mechanical properties, it is preferable that the content be 0.005 mol% or more, more preferably 0.010 mol% or more, even more preferably 0.015 mol% or more, and particularly preferably 0.020 mol% or more, based on 100% of the total molar amount of hydroxyl group termini in the polycarbonate diol and compound (3-1). On the other hand, the upper limit of the total content ratio of formyl groups in the polycarbonate diol terminus and formyl group-containing compounds in the polycarbonate diol composition is not particularly limited. From the viewpoint of maintaining good mechanical properties and chemical resistance of the obtained polyurethane, it is preferably 0.40 mol% or less, more preferably 0.20 mol% or less, even more preferably 0.15 mol% or less, and particularly preferably 0.10 mol% or less, based on 100% of the total molar amount of hydroxyl group terminus in the polycarbonate diol and compound (3-1). The above upper and lower limits can be combined arbitrarily. For example, in the polycarbonate diol composition of the present invention, the total content ratio of the formyl group in the polycarbonate diol terminus and the formyl group-containing compound in the polycarbonate diol composition is preferably 0.005 mol% to 0.40 mol%, more preferably 0.010 mol% to 0.20 mol%, even more preferably 0.015 mol% to 0.15 mol%, and particularly preferably 0.020 mol% to 0.10 mol%, based on 100% of the total molar amount of hydroxyl group terminus in the polycarbonate diol and compound (3-1).

[0083] <Polycarbonate diol> The polycarbonate diol in the present invention is a polycarbonate diol containing the terminal structure (2-1) represented by the following general formula (II-1), and is a component constituting the polycarbonate diol composition of the present invention. [ka]

[0084] The polycarbonate diol, by containing the structural unit (2-1), is expected to enable the resulting polyurethane to be suitably used in applications such as paints, coatings, and adhesives. Details of the aforementioned structural unit (2-1) will be described later.

[0085] Furthermore, the polycarbonate diol may contain structural units (1-1) represented by the following general formula (I-1). [ka] (In the above general formula (I-1), R represents a divalent hydrocarbon group having 3 to 12 carbon atoms, which may have substituents or heteroatoms.)

[0086] It is expected that the presence of the aforementioned structural unit (1-1) in the polycarbonate diol will result in improved mechanical properties and chemical resistance of the resulting polyurethane. Details of the aforementioned structural unit (1-1) will be described later.

[0087] Furthermore, the polycarbonate diol may contain structural units derived from diol compounds other than the diol compound (4) to the extent that it does not impair the effects of the present invention. "Diol compounds other than diol compound (4)" are not particularly limited, but examples include the compounds shown in (i) to (v) below. (i) Linear hydrocarbon diols such as ethylene glycol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, and 1,20-eicosanediol. (ii) Anhydrous sugar alcohols such as isosorbide, isomannide, and isoidette (iii) Oxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol (iv) Branched hydrocarbon diols such as 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, 2-methyl-1,4-butanediol, and 2-methyl-1,8-octanediol (v) Fluorene derivatives having two or more hydroxyl groups in the molecule, such as 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, and 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl)fluorene.

[0088] These compounds can be appropriately selected by those skilled in the art depending on the intended use and manufacturing conditions of the polycarbonate diol. Furthermore, these compounds may be used individually or in combination of two or more.

[0089] (Structural unit (1-1)) The structural unit (1-1) described above is a structural unit represented by the following general formula (I-1) that is included in the structure of the polycarbonate diol in the present invention.

[0090] [ka] (In the above general formula (I-1), R represents a divalent hydrocarbon group having 3 to 12 carbon atoms, which may have substituents or heteroatoms.)

[0091] The lower limit of the content of structural unit (1-1) in the polycarbonate diol is not particularly limited, but from the viewpoint of obtaining good mechanical properties and chemical resistance of the obtained polyurethane, it is preferably 40% by mass or more, more preferably 60% by mass or more, even more preferably 75% by mass or more, and particularly preferably 80% by mass or more, based on 100% of the total mass of the polycarbonate diol. On the other hand, the upper limit of the content of structural unit (1-1) is not particularly limited, and may be 100% by mass of the polycarbonate diol other than structural unit (2-1), or it may be less than 100% by mass. Alternatively, from the viewpoint of maintaining good chemical resistance of the obtained polyurethane, it is more preferably 99% by mass or less, even more preferably 98% by mass or less, and particularly preferably 95% by mass or less, based on 100% of the total mass of the polycarbonate diol. The above upper and lower limits can be combined in any way. For example, the content of the structural unit (1-1) in the polycarbonate diol is preferably 40% by mass or more and less than 100% by mass, more preferably 60% by mass or more and 99% by mass or less, even more preferably 75% by mass or more and 98% by mass or less, and particularly preferably 80% by mass or more and 95% by mass or less, based on 100% of the total mass of the polycarbonate diol.

[0092] In the polycarbonate diol, it is preferable that the structural unit (1-1) includes the structural unit (1-2) represented by the following general formula (I-2), from the viewpoint of improving the mechanical properties and chemical resistance of the resulting polyurethane.

[0093] [ka] (In the general formula (I-2) above, n is an integer between 3 and 12.)

[0094] In the general formula (I-2) above, n is an integer between 3 and 12, preferably between 3 and 10, more preferably between 3 and 6, and even more preferably between 4 and 6, from the viewpoint of obtaining better mechanical properties and chemical resistance of the polyurethane.

[0095] In the polycarbonate diol, the structural unit (1-1) preferably includes the structural unit (1-3) represented by the following formula (I-3), from the viewpoint of improving the mechanical properties and chemical resistance of the obtained polyurethane.

[0096] [ka]

[0097] In the polycarbonate diol, the structural unit (1-1) may include structural units derived from diol compounds derived from bio-based raw materials, from the perspective of achieving the Sustainable Development Goals (SDGs). Details of the diol compounds derived from the bio-based raw materials mentioned above will be discussed later.

[0098] (Terminal structure (2-1)) The terminal structure (2-1) described above is a terminal structure represented by the following general formula (II-1) that is included in the structure of the polycarbonate diol.

[0099] [ka]

[0100] The method for producing a polycarbonate diol containing the structural unit (2-1) according to the present invention is not particularly limited, but examples include a method in which a tetrahydropyran compound (3-1) (e.g., 2-hydroxytetrahydropyran, tetrahydropyranylethylene glycol, 5-(2-oxytetrahydropyran)-1-pentanol), described later, is mixed with the diol-containing composition, which is the raw material, before starting the polymerization of the polycarbonate diol, and then polymerization is started; and a method in which the tetrahydropyran compound (3-1) is added at an appropriate timing after the polymerization of the polycarbonate diol has started, and then heated and stirred. The proportion of the structural unit (2-1) in the polycarbonate diol can be controlled by adjusting the amount of the tetrahydropyran compound (3-1). As for the heating and stirring conditions, for example, stirring can be performed at 120 to 200°C for 1 to 24 hours. Alternatively, as a specific embodiment of the present invention's method for producing a polycarbonate diol containing the structural unit (2-1), the method for producing the polycarbonate diol composition of the present invention, which will be described later, can be cited.

[0101] In the polycarbonate diol, the terminal structure (2-1) preferably includes a terminal structure (2-2) represented by the following general formula (II-2), from the viewpoint of enabling the obtained polyurethane to be suitably used in paints, coatings, and adhesives.

[0102] [ka] (In the general formula (II-2) above, m is an integer between 2 and 12.)

[0103] In the general formula (II-2) above, m is the same as m in formula (III-3) above, and is an integer from 2 to 12, preferably 3 to 10, more preferably 3 to 6, even more preferably 4 to 6, and particularly preferably 5, from the viewpoint of obtaining better mechanical properties and chemical resistance of the polyurethane obtained.

[0104] [Polyurethane] The polyurethane of the present invention is a polyurethane made from the polycarbonate diol composition and isocyanate compounds of the present invention as raw materials. The method for producing the polyurethane of the present invention is not particularly limited. As a method for producing the polyurethane of the present invention, for example, a person skilled in the art can use known polyurethane reaction conditions described in International Publication No. 2015 / 016261, International Publication No. 2018 / 088575, etc., which can be appropriately optimized according to the known art.

[0105] For example, the polyurethane of the present invention can be produced by reacting the polycarbonate diol composition of the present invention with a polyol other than the polycarbonate diol, which is used as needed, a polyisocyanate (described later), and a chain extender (described later) which is used as needed, in a temperature range from room temperature to 200°C.

[0106] When using a chain extender, it may be added from the beginning of the reaction or added midway through the reaction. For example, the polyurethane of the present invention can be produced by first reacting the polycarbonate diol of the present invention with an excess of polyisocyanate to produce a prepolymer having isocyanate groups at the ends, and then adding a chain extender and reacting it with the prepolymer to increase the degree of polymerization of the polymer.

[0107] <Polyisocyanate> As the polyisocyanate used in the production of the polyurethane of the present invention, any known polyisocyanate used in the production of polyurethane can be used. The polyisocyanate is not particularly limited. For example, various aliphatic, alicyclic, or aromatic polyisocyanate compounds described in International Publication No. 2015 / 016261 and International Publication No. 2018 / 088575 can be used.

[0108] Specifically, examples include known aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; known alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 1,3-bis(isocyanate-methyl)cyclohexane; and known aromatic diisocyanates such as xylylene diisocyanate, 4,4'-diphenyl diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and 4,4'-diphenyldimethylmethane diisocyanate. These may be used individually or in combination of two or more.

[0109] Among these, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate are preferred because they offer a favorable balance of the physical properties of the resulting polyurethane and are readily available in large quantities at low cost for industrial use.

[0110] <Chain extender> As the chain extender used in the production of polyurethane according to the present invention, known chain extenders used in the production of polyurethane can be used. The chain extender is not particularly limited. Examples of chain extenders include low molecular weight polyols, amines, and water, as described in International Publication No. 2015 / 016261 and International Publication No. 2018 / 088575.

[0111] Specifically, linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol; branched diols such as 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol; diols with ether groups such as diethylene glycol and propylene glycol; alicyclic diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 1,4-dihydroxyethylcyclohexane; xylylene glycol, 1,4-dihydroxy Examples include diols having aromatic groups such as oxyethylbenzene and 4,4'-methylenebis(hydroxyethylbenzene); polyols such as glycerin, trimethylolpropane, and pentaerythritol; hydroxyamines such as N-methylethanolamine and N-ethylethanolamine; polyamines such as ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, 4,4'-diphenylmethanediamine, xylylenediamine, diphenyldiamine, hydrazine, and piperazine; and water. These chain extenders may be used alone or in combination of two or more.

[0112] Among these, ethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, ethylenediamine, 1,3-diaminopropane, isophoronediamine, and 4,4'-diaminodicyclohexylmethane are preferred due to their desirable balance of the physical properties of the resulting polyurethane and their availability in large quantities at low industrial cost.

[0113] <Chain inhibitors> When producing the polyurethane of the present invention, known chain arresters used in the production of polyurethanes may be used as needed to control the molecular weight of the polyurethane. The chain arrester is not particularly limited. Examples of chain arresters include compounds having one active hydrogen group, as described in International Publication No. 2015 / 016261 and International Publication No. 2018 / 088575.

[0114] Specifically, examples include monohydric alcohols such as methanol, ethanol, propanol, butanol, and hexanol, and secondary amines such as diethylamine, dibutylamine, di-n-propylamine, n-butylamine, monoethanolamine, and diethanolamine. These may be used individually or in combination of two or more.

[0115] <Catalyst> When producing the polyurethane of the present invention, known catalysts used in the production of polyurethane can be used. The catalyst is not particularly limited. As a catalyst, known polymerization catalysts such as tertiary amines and organometallic salts such as tin and titanium, as described in International Publication No. 2015 / 016261 and International Publication No. 2018 / 088575, can be used.

[0116] <Solvent> When producing the polyurethane of the present invention, a solvent may be used as needed. The solvent is not particularly limited, and examples include solvents described in International Publication No. 2015 / 016261 and International Publication No. 2018 / 088575.

[0117] Specifically, examples include dimethylformamide, diethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, methyl isobutyl ketone, dioxane, cyclohexanone, benzene, toluene, and ethyl cellsolve. These may be used individually or in combination of two or more.

[0118] <Amount / How to use> In the polyurethane manufacturing method of the present invention, the amounts and methods of use of the polyisocyanate, chain extender, chain arrester, catalyst, and solvent are not particularly limited, and those skilled in the art can use the conditions described in International Publication No. 2015 / 016261 and International Publication No. 2018 / 088575 by optimizing them as appropriate in accordance with the known art.

[0119] <Weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of polyurethane> The lower limit of the weight-average molecular weight (Mw) of the polyurethane of the present invention is not particularly limited. From the viewpoint of obtaining good mechanical properties and chemical resistance of the obtained polyurethane, the lower limit of the weight-average molecular weight (Mw) is preferably 50,000 or more, more preferably 100,000 or more, and even more preferably 150,000 or more. On the other hand, the upper limit of the weight-average molecular weight (Mw) is not particularly limited. From the viewpoint of maintaining good chemical resistance of the obtained polyurethane, the upper limit of the weight-average molecular weight (Mw) is preferably 500,000 or less, more preferably 300,000 or less, and even more preferably 200,000 or less. The above upper and lower limits can be combined in any way. For example, the weight-average molecular weight (Mw) of the polyurethane of the present invention is preferably 50,000 to 500,000, more preferably 100,000 to 300,000, and even more preferably 150,000 to 200,000.

[0120] The lower limit of the molecular weight distribution (Mw / Mn) of the polyurethane of the present invention is not particularly limited. From the viewpoint of obtaining good mechanical properties and chemical resistance of the obtained polyurethane, the lower limit of the molecular weight distribution (Mw / Mn) is preferably 1.50 or higher, more preferably 2.00 or higher, and even more preferably 2.50 or higher. On the other hand, the upper limit of the molecular weight distribution (Mw / Mn) is not particularly limited. From the viewpoint of maintaining good mechanical properties and chemical resistance of the obtained polyurethane, the upper limit of the molecular weight distribution (Mw / Mn) is preferably 4.00 or lower, more preferably 3.00 or lower, and even more preferably 2.90 or lower. The above upper and lower limits can be combined in any way. For example, the molecular weight distribution (Mw / Mn) of the polyurethane of the present invention is preferably 1.50 or more and 4.00 or less, more preferably 2.00 or more and 3.00 or less, and even more preferably 2.50 or more and 2.90 or less.

[0121] The weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured using gel permeation chromatography (GPC measurement), and the measurement conditions are as described in the examples below.

[0122] <Applications of Polyurethane> The polyurethane of the present invention has excellent mechanical properties and chemical resistance, as well as good heat resistance and weather resistance. For this reason, the polyurethane of the present invention can be widely used in foams, elastomers, elastic fibers, paints, fibers, adhesives, flooring materials, sealants, medical materials, artificial leather, synthetic leather, coatings, active energy ray curable polymer compositions, and the like.

[0123] In particular, when the polyurethane of the present invention is used in applications such as active energy ray curable polymer compositions, artificial leather, synthetic leather, paints and coatings such as water-based polyurethane paints, elastic fibers, adhesives, and glues, the following effects can be obtained. In other words, the polyurethane of the present invention has a good balance of chemical resistance, flexibility, heat resistance, and weather resistance, so it can be given excellent properties such as high durability, sufficient flexibility, and resistance to physical impact in parts that come into contact with human skin or are exposed to cosmetic agents or disinfectant alcohol. Furthermore, the polyurethane of the present invention can be suitably used in automotive applications where heat resistance is required and in outdoor applications where weather resistance is required.

[0124] [Effects (1)] In the polycarbonate diol composition produced using the diol-containing composition of the present invention and a carbonate-based compound as raw materials, the polycarbonate diol contains the terminal structure (2-1), and the resulting polyurethane is expected to be suitably used in applications such as paints, coatings, and adhesives. The reason for this is as follows. In other words, the terminal structure (2-1) contained in the polycarbonate diol is incorporated into the resulting polyurethane molecule by forming terminal structures (2-1) at the molecular ends. Because the terminal structure (2-1) in the polyurethane is highly polar, it is expected to improve adhesion to substrates in applications such as paints, coatings, and adhesives.

[0125] [Effects (2)] The polycarbonate diol composition produced using the diol-containing composition of the present invention and a carbonate-based compound as raw materials contains the tetrahydropyran compound (3-1), and the resulting polyurethane is expected to be suitably used in paints, coatings, and adhesives. The reasons for this are as follows. Specifically, the tetrahydropyran compound (3-1) contained in the polycarbonate diol composition exists as a free substance in the resulting polyurethane-containing composition, or as a terminal structure (2-1) at the molecular ends of the resulting polyurethane. Because the terminal structure (2-1) in the polyurethane is highly polar, it is expected to improve adhesion to the substrate in applications such as paints, coatings, and adhesives. Furthermore, the tetrahydropyran compound (3-1) undergoes ring-opening during polyurethane production, forming a branched structure within the polyurethane molecular structure. This action increases the high molecular weight and crosslinking components of the polyurethane. As a result, the resulting polyurethane is expected to have improved tensile strength and elongation at break, and thus improve the film strength of coatings and other films in applications such as paints, coatings, and adhesives. [Examples]

[0126] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples unless it exceeds the essence of the invention.

[0127] [Raw materials used] The abbreviations for the raw materials used in the examples and comparative examples are as follows: 15PD: 1,5-Pentanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) DPC: Diphenyl carbonate (manufactured by Mitsubishi Chemical Corporation) Titanium-based catalyst: Magnesium acetate tetrahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Tetrahydropyranyl ethylene glycol (manufactured by Sigma-Aldrich) 5-(2-oxytetrahydropyran)-1-pentanol was synthesized according to the synthesis method described in the Supporting Information of Org. Lett., Vol.8, No.6, 2006, pp. 1013-1016.

[0128] [Evaluation Method] The evaluation methods for each physical property are as follows:

[0129] <Total content of terminal structures (2-1) in polycarbonate diol compositions (1)> For the polycarbonate diol compositions obtained in the examples and comparative examples, the total content ratio of the terminal structure (2-1) of the polycarbonate diol and the terminal structure (2-1) of the tetrahydropyran compound (3-1) in the polycarbonate diol composition, relative to 100% of the total molar amount of hydroxyl group terminals in the polycarbonate diol and compound (3-1), was measured according to the following procedure. A polycarbonate diol composition was dissolved in CDCl3, and the nuclear magnetic resonance spectrum was measured using a nuclear magnetic resonance spectrometer (400 MHz, manufactured by JEOL Ltd., model name: ECZ-400) at a measurement temperature of 30°C and with 64 cumulative measurements. 1 1H-NMR measurements were performed. obtained 1Based on the 1H-NMR measurement results, the peaks observed at the following signal positions were identified, and the integral values ​​A and B of each peak were obtained. In this evaluation, the tetrahydropyranyl group corresponds to terminal structure (2-1) in the present invention.

[0130] The integral value of the peak of the 1H proton of the methylene group in the tetrahydropyranyl group in the polycarbonate diol present at δ4.60~4.50 ppm and in compound (3-1) = A The integral value of the peak of the 2H proton of the methylene group adjacent to the hydroxyl group end in the polycarbonate diol present at δ3.70~3.50 ppm and in compound (3-1) = B

[0131] Next, the total content ratio (1) (unit: mol%) of terminal structures (2-1) relative to 100% of the total molar amount of hydroxyl terminals in the polycarbonate diol and compound (3-1) contained in the polycarbonate diol composition was calculated using the following formula.

[0132]

number

[0133] <Total content of terminal structures (2-1) in polycarbonate diol compositions (2)> For the polycarbonate diol compositions obtained in the examples and comparative examples, the total content ratio of the terminal structures (2-1) of the polycarbonate diol and the terminal structures (2-1) of the compound (3-1) in the polycarbonate diol composition, relative to 100% of the total molar amount of structural units (1-1) in the polycarbonate diol, was measured according to the following procedure. A polycarbonate diol composition was dissolved in CDCl3, and the nuclear magnetic resonance spectrum was measured using a nuclear magnetic resonance spectrometer (400 MHz, manufactured by JEOL Ltd., model name: ECZ-400) at a measurement temperature of 30°C and with 64 cumulative measurements. 1 1H-NMR measurements were performed. obtained 1From the 1H-NMR measurement results, the peaks observed at the following signal positions were identified, and the integral values ​​A and C of each peak were obtained. In this evaluation, the tetrahydropyranyl group corresponds to terminal structure (2-1) in the present invention.

[0134] The integral value of the peak of the 1H proton of the methylene group in the tetrahydropyranyl group in the polycarbonate diol present at δ4.60~4.50 ppm and in the compound (3-1) = A The integral value of the 6H proton peaks of the β-methylene and γ-methylene groups in the structure derived from 1,5-pentanediol in polycarbonate diols present at δ1.90~1.30 ppm = C

[0135] Next, the total content ratio (2) (unit: mol%) of terminal structures (2-1) relative to 100% of the total molar amount of structural units (1-1) in the polycarbonate diol composition was calculated using the following formula.

[0136]

number

[0137] <Number-average molecular weight M (PCD) of polycarbonate diols> The polycarbonate diol compositions obtained in the examples and comparative examples were dissolved in CDCl3 and measured using a nuclear magnetic resonance spectroscopy analyzer (400 MHz, manufactured by JEOL Ltd., model name: ECZ-400) at a measurement temperature of 30°C and with 64 cumulative measurements. 1 1H-NMR measurements were performed. obtained 1 Based on the 1H-NMR measurement results, the peaks observed at the following signal positions were identified, and the integral values ​​A to C of each peak were obtained. In this evaluation, the tetrahydropyranyl group corresponds to terminal structure (2-1) in the present invention.

[0138] The methylene group in the tetrahydropyranyl group in the polycarbonate diol present at δ4.60~4.50 ppm and in compound (3-1) 1 The integral of the peak of H protons = A The integral value of the peak of the 2H proton of the methylene group adjacent to the hydroxyl group end in the polycarbonate diol present at δ3.70~3.50 ppm and in compound (3-1) = B The integral value of the 6H proton peaks of the β-methylene and γ-methylene groups of the structural units derived from 1,5-pentanediol in polycarbonate diols present at δ1.90~1.30 ppm = C

[0139] The integral value of the peak originating from the polycarbonate diol terminal structural unit derived from 1,5-pentanediol is "15PD". m ", the integral value of the peak originating from the tetrahydropyranyl group (terminal structure (2-1)) is "THP m " he said. Furthermore, the integral value of the peak originating from the structural unit derived from 1,5-pentanediol in polycarbonate diols other than the polycarbonate diol ends is "15PD o " he said. Based on the number of protons in the structural units derived from 15PD, the integral values ​​of the peaks originating from each of the aforementioned structural units were calculated using the following formula. 15PD m =B÷2 15PD o =(C-15PD m ×4)÷6 THP m =A

[0140] Next, the number-average molecular weight M(PCD) of the polycarbonate diol was calculated using the following formula.

[0141]

number

[0142] In the above formula, M(15PD o) is the molecular weight of the structural unit derived from 15PD in the polycarbonate diol other than the polycarbonate diol terminus (=102), M(THP) is the molecular weight of the structural unit derived from 5-(2-oxytetrahydropyran)-1-pentanol (=187), M(15PD m ) refers to the molecular weight of the structural unit derived from 15PD in the polycarbonate diol terminus (=103), and M (carbonyl group) refers to the molecular weight of the carbonyl group (=28).

[0143] [Production and evaluation of polycarbonate diol compositions]

[0144] [Example 1] In a 1 L glass separable flask equipped with a stirrer, distillate trap, and pressure regulator, 15PD as a diol, 5-(2-oxytetrahydropyran)-1-pentanol as a tetrahydropyran compound (3-1), DPC as a carbonate compound, and a titanium-based catalyst as a transesterification catalyst were added in the amounts shown in Table 1. Next, the atmosphere inside the flask was replaced with a nitrogen atmosphere, and the contents of the flask were heated and stirred until the temperature of the contents reached 160°C, thereby heating and dissolving the contents. At this time, the pressure inside the flask was 101 kPa. Subsequently, the pressure inside the flask was gradually reduced from 101 kPa to 24 kPa over 2 minutes, and the reaction was continued for 90 minutes while removing the generated phenol from the reaction system. Next, the pressure inside the flask was gradually reduced to 9.3 kPa over 90 minutes, and then further gradually reduced to 0.7 kPa over 60 minutes, and the reaction was continued. Subsequently, the contents of the flask were heated to a temperature of 170°C, and the reaction was continued for another 90 minutes while removing the phenol and unreacted diol from the reaction system. After that, the contents were allowed to cool to near room temperature (approximately 25°C) to obtain 117 g of polycarbonate diol composition. The obtained polycarbonate diol compositions were evaluated as described above, and the evaluation results are shown in Table 1.

[0145] [Example 2] In Example 1, the reaction was carried out under the same conditions as in Example 1, except that the amount of tetrahydropyran compound (3-1) was changed as shown in Table 1, to obtain 117 g of polycarbonate diol composition. The evaluation results of the obtained polycarbonate diol composition are shown in Table 1.

[0146] [Example 3] In Example 1, the reaction was carried out under the same conditions as in Example 1, except that the amount of tetrahydropyran compound (3-1) was changed as shown in Table 1, to obtain 117 g of polycarbonate diol composition. The evaluation results of the obtained polycarbonate diol composition are shown in Table 1.

[0147] [Comparative Example 1] In Example 1, the reaction was carried out under the same conditions as in Example 1, except that the tetrahydropyran compound (3-1) was not used, to obtain 115 g of polycarbonate diol composition. The evaluation results of the obtained polycarbonate diol composition are shown in Table 1.

[0148] [Polyurethane manufacturing] Polyurethane can be produced using the polycarbonate diol compositions obtained in the examples and comparative examples by the method described below. (Purification process of polycarbonate diol composition) To deactivate the titanium-based catalyst remaining in the polycarbonate diol compositions obtained in the examples and comparative examples, first, an aqueous phosphoric acid solution is added to the polycarbonate diol composition as a catalyst deactivator, and the mixture is heated at 80-170°C for 10-120 minutes to deactivate the remaining titanium-based catalyst. Next, to remove monomers such as phenol, the polycarbonate diol composition with added phosphoric acid is sent to a thin-film distillation apparatus and thin-film distillation is performed (temperature: 180-190°C, pressure: 40-67 Pa). After that, the contents are allowed to cool to near room temperature (approximately 25°C) to obtain the purified polycarbonate diol composition.

[0149] (Polyurethane synthesis) In a separable flask equipped with a thermocouple and condenser, add the purified polycarbonate diol composition (preheated to 80°C), 14BG as a chain extender, U-830 as a catalyst, and DMF as a reaction solvent. Place the flask in an oil bath set to 55°C and stir at a stirring speed of 60 rpm until homogeneous. The water content of the reaction solution in the flask is measured, and the amount of MDI consumed by the water is calculated. The amount of sample taken is also recorded, and the amount of each raw material is corrected accordingly. To the reaction solution, MDI, weighed to have a predetermined NCO / OH molar ratio, is added in solid form using a funnel, and the mixture is stirred at a stirring speed of 60 rpm until homogeneous. In this specification, the term "NCO / OH molar ratio" refers to the ratio (molar ratio) of the total amount of substance (moles) of MDI to the value obtained by subtracting the total amount of water content (moles) from the total amount of substance (moles) of polycarbonate diol and 14BG when MDI is added. Immediately after adding MDI, an exothermic peak accompanied by a rise in the reaction solution temperature of +10 to +15°C was observed. Five minutes after this exothermic peak subsided, the oil bath temperature was set to 70°C and the temperature was increased. One hour after adding MDI, measure the molecular weight of the polyurethane in the reaction solution to confirm whether it has reached the target molecular weight (MW = range of 170,000 to 180,000). If the target has not been reached, add more MDI with an NCO / OH molar ratio within the specified range, allow the reaction to proceed for at least 30 minutes, and then measure the molecular weight of the polyurethane in the reaction solution. Repeat the addition of MDI and molecular weight measurement until the target Mw is reached. Finally, obtain a polyurethane solution containing polyurethane with Mw in the range of 100,000 to 200,000.

[0150] [Table 1] [Industrial applicability]

[0151] According to the present invention, it is possible to provide a diol-containing composition that enables the stable production of polycarbonate diol compositions for obtaining polyurethanes suitable for use in paints, coatings, and adhesives. Furthermore, according to the present invention, it is possible to provide a method for stably producing polycarbonate diol compositions for obtaining polyurethanes suitable for use in paints, coatings, and adhesives. Furthermore, according to the present invention, it is possible to provide polyurethane suitable for use in paints, coatings, and adhesives. As described above, the present invention discloses an industrially important technology and is a technology with high industrial applicability.

Claims

1. A diol-containing composition comprising a diol compound (4) represented by the following general formula (IV) and a tetrahydropyran compound (3-1) represented by the following general formula (III-1). 【Chemistry 1】 (In the general formula (IV) above, n is an integer between 3 and 6.) 【Chemistry 2】 (In the above general formula (III-1), R １ (This is a C2-C12 alkyl group or hydrogen atom, which may have substituents or heteroatoms.)

2. A diol-containing composition according to claim 1, used in a process for producing a polycarbonate diol composition.

3. The diol-containing composition according to claim 1, wherein the diol-containing composition contains 0.01% by mass or more of the tetrahydropyran compound (3-1) based on the total mass of the diol-containing composition.

4. The diol-containing composition according to claim 1, wherein the diol-containing composition contains 2.00% by mass or less of the tetrahydropyran compound (3-1) based on the total mass of the diol-containing composition.

5. The diol-containing composition according to claim 1, wherein the diol-containing composition contains 90.00% by mass or more and 99.99% by mass or less of the diol compound (4) based on the total mass of the diol-containing composition.

6. The diol-containing composition according to claim 1, wherein the diol compound (4) contains 1,5-pentanediol.

7. The diol-containing composition according to claim 1, wherein the tetrahydropyran compound (3-1) contains a tetrahydropyran compound (3-2) represented by the following general formula (III-2). 【Transformation 3】 (In the above general formula (III-2), R ２ (This is an alkyl group having 2 to 12 carbon atoms or a hydrogen atom containing a hydroxyl group terminus, which may have a side chain.)

8. The diol-containing composition according to claim 1, wherein the tetrahydropyran compound (3-1) contains a tetrahydropyran compound (3-3) represented by the following general formula (III-3). 【Chemistry 4】 (In the general formula (III-3) above, m is an integer between 2 and 12.)

9. A polycarbonate diol composition comprising a diol-containing composition according to any one of claims 1 to 8 and a carbonate-based compound as raw materials.

10. A method for producing a polycarbonate diol composition, comprising polycondensing a diol-containing composition and a carbonate-based compound by transesterification in the presence of a catalyst to obtain a polycarbonate diol, A method for producing a polycarbonate diol composition, wherein the diol-containing composition contains a diol compound (4) represented by the following general formula (IV) and a tetrahydropyran compound (3-1) represented by the following general formula (III-1). 【Transformation 5】 (In the general formula (IV) above, n is an integer between 3 and 6.) 【Transformation 6】 (In the above general formula (III-1), R １ (This is a C2-C12 alkyl group or hydrogen atom, which may have substituents or heteroatoms.)

11. The method for producing a polycarbonate diol composition according to claim 10, wherein the diol-containing composition contains 0.01% by mass or more of the tetrahydropyran compound (3-1) based on the total mass of the diol-containing composition.

12. A method for producing a polycarbonate diol composition according to claim 10, wherein the diol-containing composition contains 2.00% by mass or less of the tetrahydropyran compound (3-1) based on the total mass of the diol-containing composition.

13. A method for producing the polycarbonate diol composition according to claim 10, wherein the diol compound (4) contains 1,5-pentanediol.

14. A method for producing a polycarbonate diol composition according to claim 10, wherein the tetrahydropyran compound (3-1) contains a tetrahydropyran compound (3-2) represented by the following general formula (III-2). 【Transformation 7】 (In the above general formula (III-2), R ２ (This is an alkyl group having 2 to 12 carbon atoms or a hydrogen atom containing a hydroxyl group terminus, which may have a side chain.)

15. A method for producing a polycarbonate diol composition according to claim 10, wherein the tetrahydropyran compound (3-1) contains a tetrahydropyran compound (3-3) represented by the following general formula (III-3). 【Transformation 8】 (In the general formula (III-3) above, m is an integer between 2 and 12.)

16. A polyurethane made from the polycarbonate diol composition and isocyanate compound described in claim 9.

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