Polycarbonate polyol composition

Abstract

Provided is a polycarbonate polyol composition comprising: a polycarbonate polyol which includes an alkylene ether structure represented by specific formula (I), an alkyl chain structure represented by specific formula (II), and a polycarbonate structure represented by specific formula (III) and in which the average number of hydroxyl groups per molecule is 2.5-5.0; and a transesterification catalyst containing at least one metal selected from the group consisting of the metals in Groups 4, 5, 6, 7, 8, 9, 10, and 11 of the long-form periodic table. The polycarbonate polyol composition is liquid at 23°C and has a viscosity at 50°C of 500-10,000 mPa·s.

Description

Polycarbonate polyol composition

[0001] The present invention relates to a polycarbonate polyol composition, and to a polyurethane resin, a coating composition, an adhesive composition, an aqueous polyurethane dispersion, and a synthetic leather containing the same.

[0002] Conventionally, polyurethane resins have been used in a wide range of applications, such as synthetic leather, artificial leather, adhesives, furniture paints, and automotive paints, and polyethers, polyesters, and polycarbonates are used as polyol components to be reacted with isocyanates. However, in recent years, there has been an increasing demand for polyurethane resins with improved resistance, such as heat resistance, weather resistance, hydrolysis resistance, solvent resistance, sunscreen resistance, and scratch resistance.

[0003] It is generally known that polyurethane resins using polycarbonate polyol as a polyol component are superior to polyurethane resins using polyether or polyester in terms of moist heat resistance, solvent resistance, sunscreen resistance, scratch resistance, etc. For example, Patent Document 1 discloses a polycarbonate diol using 1,5-pentanediol and 1,6-hexanediol as diol components. Furthermore, Patent Documents 2 and 3 disclose polycarbonate polyols in which the number of hydroxyl groups per molecule exceeds two by using a polyhydric alcohol having a specific structure.

[0004] JP-A-2-289616 JP-A-3-220233 International Publication No. 2022 / 080491

[0005] However, the polycarbonate diols and polycarbonate polyols described in Patent Documents 1 to 3 each have problems. For example, the polycarbonate diol described in Patent Document 1 is liquid and therefore easy to handle, and when made into a polyurethane resin, it has excellent flexibility, but since it has two hydroxyl groups per molecule, there is room for improvement in the tack-drying properties when a polyurethane coating film is formed. The polycarbonate polyol described in Patent Document 2 is solid at 25°C, so there is room for improvement in the appearance when made into a coating film, and there is a concern that it may discolor. The polycarbonate polyol described in Patent Document 3, even though it has fluidity at 25°C, may become cloudy, so there is room for improvement in the appearance when made into a polyurethane coating film, and the elongation and stress in a tensile test are insufficient.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid polycarbonate polyol composition that is low in viscosity, low in color, and does not cause turbidity. Another object of the present invention is to provide a polycarbonate polyol composition that, when used as a raw material for a polyurethane resin, can give a polyurethane resin that is excellent in drying properties, appearance, hardness, chemical resistance, and film strength.

[0007] That is, the present invention includes the following aspects: [1] A polycarbonate polyol composition that is liquid at 23°C and has a viscosity at 50°C of 500 mPa·s or more and 10,000 mPa·s or less, comprising: a polycarbonate polyol that contains an alkylene ether structure represented by the following general formula (I), an alkyl chain structure represented by the following general formula (II), and a polycarbonate structure represented by the following general formula (III), and that has an average number of hydroxyl groups per molecule of 2.5 to 5.0; and a transesterification catalyst that contains at least one metal selected from the group consisting of metals of Groups 4, 5, 6, 7, 8, 9, 10, and 11 of the long form periodic table. (In general formula (I), R １１ is a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having from 2 to 20 carbon atoms, R １２is any one of the polycarbonate structure represented by general formula (III), a hydrogen group, or a hydrocarbon residue which may contain an ether group, a carboxyl group, or a carbonate group. １２ is a polycarbonate structure represented by general formula (III). １１ The hydrocarbon group may be of one type or of multiple types. n11 is an integer of 1 or more and 10 or less, and * represents a bond to the alkyl chain structure represented by general formula (II). (In general formula (II), R ２１ , R ２２ , R ２３ and R ２４ is a group selected from the group consisting of an alkylene ether structure represented by general formula (I), a hydrogen group, a hydroxyl group, and a residue bonded via a divalent hydrocarbon group having from 1 to 20 carbon atoms, and the hydrocarbon group is a linear, branched, or cyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and may contain a hydroxyl group, an amino group, a sulfide group, an ether group, a carbonyl group, a carboxyl group, or a carbonate group. ２１ , R ２２ , R ２３ and R ２４ At least one of R is an alkylene ether structure represented by general formula (I). ２１ , R ２２ , R ２３ , R ２４ The hydrocarbon group may be of one type or of multiple types. (In general formula (III), R ３１ R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having from 2 to 15 carbon atoms. ３１ There are at least two types of hydrocarbon groups. n31 is an arbitrary integer. [2] R in the polycarbonate structure represented by the general formula (III) ３１are at least two types of linear or branched hydrocarbon groups having from 3 to 6 carbon atoms. [3] The polycarbonate polyol composition according to [1] or [2], wherein the mass ratio of the polycarbonate structure represented by general formula (III) in the polycarbonate polyol composition is from 60 to 90 mass%. [4] The polycarbonate polyol composition according to any one of [1] to [3], wherein the molar ratio of carbonate groups derived from the polycarbonate structure represented by general formula (III) to quaternary carbon groups derived from the alkyl chain structure represented by general formula (II) (carbonate groups / quaternary carbon groups) is from 10 to 50. [5] The polycarbonate polyol composition according to any one of [1] to [4], which is transparent at 23°C. [6] The polycarbonate polyol composition according to any one of [1] to [5], which has a Hazen color scale (APHA) of 100 or less. [7] The polycarbonate polyol composition according to any one of [1] to [6], further comprising a transesterification catalyst containing at least one metal selected from the group consisting of metals of Group 1 and Group 2 of the long periodic table. [8] The polycarbonate polyol composition according to any one of [1] to [7], wherein the alkyl chain structure represented by general formula (II) is an alkyl chain structure derived from a polyhydric alcohol, and the polyhydric alcohol is at least one selected from the group consisting of trimethylolpropane and pentaerythritol. [9] The polycarbonate polyol composition according to any one of [1] to [7], further comprising a transesterification catalyst containing at least one metal selected from the group consisting of metals of Group 1 and Group 2 of the long periodic table. １１ is a linear, branched, or cyclic aliphatic hydrocarbon group having from 2 to 3 carbon atoms.

[10] The polycarbonate polyol composition according to any one of [1] to [9], having a hydroxyl value of from 50 to 270 mgKOH / g.

[11] The polycarbonate polyol composition according to any one of [1] to

[10] , further comprising a polyoxyethylene structure represented by the following general formula (IV) in the polycarbonate structure represented by general formula (III): (In general formula (IV), n41 is a number of 3 or more and 50 or less.)

[12] A polyurethane resin comprising a reaction product of the polycarbonate polyol composition according to any one of [1] to

[11] and an isocyanate compound.

[13] A coating composition comprising the polycarbonate polyol composition according to any one of [1] to

[11] .

[14] An adhesive composition comprising the polycarbonate polyol composition according to any one of [1] to

[11] .

[15] An aqueous polyurethane dispersion in which a polyurethane resin comprising the polycarbonate polyol composition according to any one of [1] to

[11] is dispersed in water.

[16] Synthetic leather comprising a polyurethane resin comprising the polycarbonate polyol composition according to any one of [1] to

[11] .

[17] A method for producing the polycarbonate polyol composition according to any one of [1] to

[11] , comprising a step of transesterification and / or depolymerization of a polycarbonate polyol precursor derived from the following general formula (III) with an alkylene oxide group-containing alcohol derived from the following general formulas (I) and (II) in the presence of a transesterification catalyst: (In general formula (I), R １１ is a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having from 2 to 20 carbon atoms, R １２ is any one of the polycarbonate structure represented by general formula (III), a hydrogen group, or a hydrocarbon residue which may contain an ether group, a carboxyl group, or a carbonate group. １２ is a polycarbonate structure represented by general formula (III). １１ The hydrocarbon group may be of one type or of multiple types. n11 is an integer of 1 or more and 10 or less, and * represents a bond to the alkyl chain structure represented by general formula (II). (In general formula (II), R ２１ , R ２２ , R ２３ and R ２４is a group selected from the group consisting of an alkylene ether structure represented by general formula (I), a hydrogen group, a hydroxyl group, and a residue bonded via a divalent hydrocarbon group having from 1 to 20 carbon atoms, and the hydrocarbon group is a linear, branched, or cyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and may contain a hydroxyl group, an amino group, a sulfide group, an ether group, a carbonyl group, a carboxyl group, or a carbonate group. ２１ , R ２２ , R ２３ and R ２４ At least one of R is an alkylene ether structure represented by general formula (I). ２１ , R ２２ , R ２３ , R ２４ The hydrocarbon group may be of one type or of multiple types. (In general formula (III), R ３１ R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having from 2 to 15 carbon atoms. ３１ There are at least two types of hydrocarbon groups. n31 is any integer.

[0008] The present invention can provide a liquid polycarbonate polyol composition that is low in viscosity and colorless and does not become cloudy. Furthermore, the present invention can provide a polycarbonate polyol composition that, when used as a raw material for a polyurethane resin, can give a polyurethane resin that is excellent in drying properties, appearance, hardness, chemical resistance, and film strength.

[0009] Hereinafter, embodiments for carrying out the present invention (hereinafter abbreviated as "present embodiments") will be described in detail. The following embodiments are merely examples for explaining the present invention, and the present invention is not limited to these. In other words, the present invention can be carried out with any modifications within the scope of the gist thereof.

[0010] <Polycarbonate Polyol Composition> The polycarbonate polyol composition of the present embodiment comprises a polycarbonate polyol having an alkylene ether structure represented by the following general formula (I) (hereinafter also simply referred to as the "alkylene ether structure"), an alkyl chain structure represented by the following general formula (II) (hereinafter also simply referred to as the "alkyl chain structure"), and a polycarbonate structure represented by the following general formula (III) (hereinafter also simply referred to as the "polycarbonate structure"), and having an average number of hydroxyl groups per molecule of 2.5 to 5.0; and a transesterification catalyst containing at least one metal selected from the group consisting of metals of Groups 4, 5, 6, 7, 8, 9, 10, and 11 of the long form periodic table, and is liquid at 23°C and has a viscosity at 50°C of 500 mPa·s or more and 10,000 mPa·s or less. (In general formula (I), R １１ is a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having from 2 to 20 carbon atoms, R １２ is any one of the polycarbonate structure represented by general formula (III), a hydrogen group, or a hydrocarbon residue which may contain an ether group, a carboxyl group, or a carbonate group. １２ is a polycarbonate structure represented by general formula (III). １１ The hydrocarbon group may be of one type or of multiple types. n11 is an integer of 1 or more and 10 or less, and * represents a bond to the alkyl chain structure represented by general formula (II). (In general formula (II), R ２１ , R ２２ , R ２３ and R ２４ is a group selected from the group consisting of an alkylene ether structure represented by general formula (I), a hydrogen group, a hydroxyl group, and a residue bonded via a divalent hydrocarbon group having from 1 to 20 carbon atoms, and the hydrocarbon group is a linear, branched, or cyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and may contain a hydroxyl group, an amino group, a sulfide group, an ether group, a carbonyl group, a carboxyl group, or a carbonate group. ２１ , R２２ , R ２３ and R ２４ At least one of R is an alkylene ether structure represented by general formula (I). ２１ , R ２２ , R ２３ , R ２４ The hydrocarbon group may be of one type or of multiple types. (In general formula (III), R ３１ R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having from 2 to 15 carbon atoms. ３１ There are at least two types of hydrocarbon groups. n31 is any integer.

[0011] The terminal structure of the polycarbonate polyol composition of this embodiment is a hydroxyl group. This hydroxyl group is present in the R １２ or those derived from the terminal group of the polycarbonate structure represented by general formula (III). Furthermore, the polycarbonate polyol composition of the present embodiment may contain a polycarbonate diol derived from the polycarbonate structure represented by general formula (III) described below.

[0012] <General Formulas (I) and (II)> In the polycarbonate polyol composition of the present embodiment, the content of the structure having the alkylene ether structure and the alkyl chain structure relative to the total mass of the polycarbonate polyol composition is preferably 3% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less. When the content of the structure having the alkylene ether structure and the alkyl chain structure is within this range, a polyurethane resin excellent in chemical resistance and film strength tends to be obtained.

[0013] <Structure of General Formula (I)> The terminal structure of the polycarbonate polyol composition of the present embodiment is an alkylene ether structure represented by general formula (I) in which R １２ a hydroxyl group consisting of a hydrogen atom and the oxygen atom next to it, or R １２Among all the terminal hydroxyl groups, the molar ratio of hydroxyl groups derived from the alkylene ether structure represented by general formula (I) is preferably 0 mol % or more and 50 mol % or less. When the molar ratio of hydroxyl groups is within this range, the polyurethane resin composition comprising the polycarbonate polyol composition of this embodiment tends to have good film strength and chemical resistance.

[0014] <R １１ In the alkylene ether structure represented by the general formula (I), R １１ is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having from 2 to 20 carbon atoms. １１ is preferably a linear, branched or cyclic aliphatic hydrocarbon group having from 2 to 3 carbon atoms. １１ may be present alone or in plural.

[0015] R １１ The divalent linear aliphatic hydrocarbon group having from 2 to 20 carbon atoms in the formula (I) is not particularly limited, but examples thereof include an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptylene group, and an octylene group.

[0016] R １１ Specific examples of the divalent branched aliphatic hydrocarbon group having from 2 to 20 carbon atoms in the formula (I) include, but are not particularly limited to, an isopropylene group, an isobutylene group, a tert-butylene group, an isopentylene group, a 2,2-dimethyltrimethylene group, an isohexylene group, an isoheptylene group, and an isooctylene group.

[0017] R １１ Specific examples of the divalent cyclic aliphatic hydrocarbon group in the formula (I) include, but are not limited to, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cycloheptylene group.

[0018] R １１Specific examples of the divalent aromatic hydrocarbon group in (I) are not particularly limited, but include, for example, a phenylene group and a naphthylene group. Among these, the hydrocarbon group structure is preferably an aliphatic hydrocarbon group in terms of reactivity during production of the polyurethane resin, chemical resistance, and low coloration, and more preferably a linear aliphatic hydrocarbon group. Furthermore, the number of carbon atoms is preferably from 2 to 20, more preferably from 2 to 6, even more preferably from 2 to 4, and particularly preferably from 2 to 3, in terms of achieving both drying properties and chemical resistance and suppressing turbidity.

[0019] <n11> The number of repeating units n11 in the alkylene ether structure represented by the general formula (I) is an integer of 1 or more and 10 or less, but from the viewpoints of drying property, hardness, and chemical resistance, the average number of repeating units in one molecule is more preferably 1 or more and 5 or less.

[0020] <R １２ > R in the alkylene ether structure １２ is any one of the polycarbonate structure represented by general formula (III), a hydrogen group, or a hydrocarbon residue (for example, a linear, branched, or cyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group) which may contain an ether group, a carboxyl group, or a carbonate group. １２ is a polycarbonate structure represented by general formula (III). Among them, R is preferred in terms of being free from turbidity and achieving both film strength and chemical resistance when made into a polyurethane resin. １２ is preferably any one of a hydrogen group and a linear or branched aliphatic hydrocarbon group containing a carbonate bond. １２ It is preferable in terms of suppressing turbidity that both the alkylene ether structure having a hydrogen group bonded thereto and the alkylene ether structure having a linear or branched aliphatic hydrocarbon group containing a carbonate bond bonded thereto are present as the alkylene ether structure.

[0021] <General Formula (II)> The alkyl chain structure represented by the general formula (II) in the polycarbonate polyol composition of this embodiment includes a structure having a quaternary carbon. The presence of this quaternary carbon allows the reaction with isocyanate and crosslinking to proceed sufficiently, and the resulting polyurethane resin tends to have excellent drying properties and chemical resistance. Furthermore, it is preferable that the alkyl chain structure represented by the general formula (II) is an alkyl chain structure derived from a polyhydric alcohol, and that the polyhydric alcohol is at least one selected from the group consisting of trimethylolpropane and pentaerythritol.

[0022] <R ２１ , R ２２ , R ２３ , R ２４ R in the alkyl chain structure represented by the general formula (II) ２１ , R ２２ , R ２３ , R ２４ The alkylene ether structure is preferably bonded to the R ２１ , R ２２ , R ２３ , R ２４ However, in order to maintain a liquid state at 23°C and to achieve both drying and curing properties, it is preferable that the average number of bonds in the alkylene ether structure represented by general formula (I) is 2 or more. ２１ , R ２２ , R ２３ , R ２４ Among the linking groups bonded to the above, other than the alkylene ether structure, a hydrogen group, or a hydroxyl group, amino group, sulfide group, ether group, carbonyl group, carboxyl group, or carbonate group may be bonded via a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having from 1 to 20 carbon atoms. Among these, having a hydroxyl group is preferred in terms of increasing the number of functional groups, and a hydrocarbon group bonded to a hydroxyl group is preferred in terms of maintaining a liquid state at 23°C and reducing the viscosity, with a hydroxyalkyl group having from 1 to 3 carbon atoms being more preferred.

[0023] <General Formula (III)> With respect to the polycarbonate structure represented by general formula (III) bonded in the polycarbonate polyol composition of this embodiment, the content of the polycarbonate structure relative to the total mass of the alkylene ether structure, the alkyl chain structure, and the polycarbonate structure is preferably 60% by mass or more and 100% by mass or less, more preferably 60% by mass or more and 90% by mass or less, and even more preferably 70% by mass or more and 90% by mass or less. When the content of the polycarbonate structure is within this range, a polyurethane resin that achieves both drying properties, film strength, and chemical resistance tends to be obtained. Of all the terminal hydroxyl groups present in the polycarbonate polyol composition of this embodiment, the molar fraction of hydroxyl groups derived from the polycarbonate structure is preferably 50 mol% or more and 100 mol% or less. When the molar fraction of the hydroxyl groups is within this range, the polyurethane resin composition comprising the polycarbonate polyol composition tends to have good film strength and chemical resistance.

[0024] <R ３１ In the polycarbonate structure represented by the general formula (III), R ３１ is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having from 2 to 15 carbon atoms. ３１ It is preferable that there are at least two kinds of hydrocarbon groups. Specific examples of the hydrocarbon group include the above-mentioned R １１ Among these, R ３１ is preferably a divalent linear aliphatic hydrocarbon group having from 3 to 10 carbon atoms, or a divalent branched aliphatic hydrocarbon group having from 3 to 10 carbon atoms, and more preferably a divalent linear aliphatic hydrocarbon group having from 3 to 6 carbon atoms, or a divalent branched aliphatic hydrocarbon group having from 3 to 6 carbon atoms. In particular, R in the polycarbonate structure represented by the general formula (III) ３１ Preferably, the alkyl group is at least two of linear or branched hydrocarbon groups having 3 to 6 carbon atoms.

[0025] For example, a homo-type polycarbonate diol obtained using 1,6-hexanediol is usually solid at room temperature. Therefore, a polycarbonate polyol composition obtained using 1,6-hexanediol also tends to be solid at room temperature. On the other hand, in this embodiment, ３１ is preferable in that it is obtained from two or more diol compounds, and therefore a polycarbonate polyol composition that is liquid at 23°C and not cloudy can be obtained, and is easy to handle.

[0026] In this embodiment, R in the carbonate structure in the polycarbonate polyol composition ３１ The composition of can be determined by the following method. First, 1 g of a sample is weighed out and placed in a 100 mL recovery flask, followed by the addition of 30 g of ethanol and 4 g of potassium hydroxide to obtain a mixture. The obtained mixture is heated in an oil bath at 100°C for 1 hour. After the mixture is cooled to room temperature, 1 to 2 drops of phenolphthalein are added to the mixture as an indicator, and the mixture is neutralized with hydrochloric acid. Thereafter, the mixture is cooled in a refrigerator for 3 hours, and the precipitated salt is removed by filtration. The filtrate is then analyzed by gas chromatography (hereinafter referred to as GC) under the following analytical conditions. Based on the area value of the diol compound obtained by GC analysis, the R in the carbonate structure in the polycarbonate polyol composition is determined. ３１ The composition of the material can be determined.

[0027] <n31> In this embodiment, n31 in the carbonate structure in the polycarbonate polyol composition is any integer, and can be freely changed as long as it is within the range specified by the hydroxyl value and viscosity at 50°C of the polycarbonate polyol composition. ２１ , R ２２ , R ２３ , R ２４ The number of n31 in each carbonate structure may be different as long as it is within the range defined by the viscosity at 50°C.

[0028] In the polycarbonate polyol composition of this embodiment, the molar ratio (carbonate group / quaternary carbon group) of the carbonate groups derived from the polycarbonate structure represented by general formula (III) to the quaternary carbon groups derived from the alkyl chain structure represented by general formula (II) is preferably 10 to 50, more preferably 10 to 40, and even more preferably 15 to 35. When the molar ratio (carbonate group / quaternary carbon group) is within the above range, the polycarbonate polyol composition of this embodiment tends to have good hardness and chemical resistance. In this embodiment, the molar ratio (carbonate group / quaternary carbon group) can be measured by the method described in the Examples below.

[0029] <Polycarbonate Diol> The polycarbonate polyol composition of this embodiment may contain a polycarbonate diol in addition to the structure containing the alkylene ether structure, the alkyl chain structure, and the polycarbonate structure. This polycarbonate diol has a polycarbonate structure represented by general formula (III) as a structural unit, both terminals are hydroxyl groups, and the average number of hydroxyl groups is 2. The polycarbonate diol may be present as a by-product during the production of the polycarbonate polyol composition, or as a residue when the polycarbonate polyol composition is used as a raw material during the production of a polycarbonate polyol precursor described below. The polycarbonate diol may also be added to the produced polycarbonate polyol composition. The presence or absence of the polycarbonate diol can be determined by whether the average number of hydroxyl groups calculated from the hydroxyl value and number average molecular weight described below includes a decimal point to one decimal place.

[0030] <Physical Properties of Polycarbonate Polyol Composition> <Molecular Weight (Number Average Molecular Weight, Weight Average Molecular Weight)> The number average molecular weight of the polycarbonate polyol composition of this embodiment is preferably 500 to 10,000, more preferably 700 to 2,000, in terms of hardness and drying properties. The weight average molecular weight is preferably 1,500 to 8,000, more preferably 2,000 to 6,000, in terms of suppressing turbidity, reducing viscosity, and improving tensile properties as a polyurethane resin. Each average molecular weight can be measured by gel permeation chromatography (hereinafter referred to as GPC). Each average molecular weight of the polycarbonate polyol composition can be controlled, for example, by the molecular weight of each raw material, the reaction temperature, and the reaction time.

[0031] <State and Viscosity> The polycarbonate polyol composition of this embodiment is preferably liquid and low-colored or transparent, i.e., not cloudy, at 23°C. Being liquid and low-colored or transparent at 23°C means that when used as a coating component, the coating film is less likely to become cloudy, and applications are less limited. There are no particular limitations on the method for obtaining a polycarbonate polyol composition that is liquid and low-colored or transparent at 23°C, and examples include a method in which the types and amounts of raw materials are appropriately selected. There are no particular limitations on the evaluation of transparency, and it can be evaluated, for example, by visual observation or turbidity measurement using integrating sphere photoelectric spectrometry. The polycarbonate polyol composition of this embodiment has a viscosity at 50°C of 500 mPa·s to 10,000 mPa·s, preferably 600 mPa·s to 7,000 mPa·s, and more preferably 750 mPa·s to 5,000 mPa·s. In this embodiment, the viscosity of the polycarbonate polyol composition at 50°C can be measured by the method described in the examples below.

[0032] <Hazen color number (APHA value)> The Hazen color number (APHA value: according to JIS K0071-1 (2017)) of the polycarbonate polyol composition of the present embodiment is preferably 100 or less, more preferably 60 or less, and even more preferably 50 or less. The lower the APHA value, the better the color tone of the polycarbonate polyol composition itself and the polyurethane resin obtained using this polycarbonate polyol composition, i.e., the less colored it tends to be. The lower limit of the APHA value is not particularly limited, but is, for example, 0. The method for obtaining a polycarbonate polyol composition that satisfies such an APHA value is not particularly limited, but examples include a method of comprehensively controlling the selection of the type and amount of catalyst during production, the stirring temperature, the amount of residual monomer, etc. Furthermore, the selection of raw materials is also important, and those containing an antioxidant may be used.

[0033] <Hydroxyl value> The hydroxyl value of the polycarbonate polyol composition of this embodiment is preferably 11 mgKOH / g or more and 500 mgKOH / g or less, more preferably 30 mgKOH / g or more and 400 mgKOH / g or less, even more preferably 50 mgKOH / g or more and 270 mgKOH / g or less, and particularly preferably 60 mgKOH / g or more and 270 mgKOH / g or less. By controlling the hydroxyl value to the above lower limit or more, the polycarbonate polyol composition of this embodiment tends to avoid excessively high viscosity and exhibit excellent handleability, and by controlling the hydroxyl value to the above upper limit or less, the chemical resistance tends to be good. The method for controlling the hydroxyl value of the polycarbonate polyol composition within the above range is not particularly limited, but examples include a method of charging a polyvalent hydroxy compound having an alkylene ether structure and an alkyl chain structure during the production of the polycarbonate polyol composition so that the hydroxyl value falls within the above range, and a method of controlling the hydroxyl value by adding and / or withdrawing a polyvalent hydroxy compound having an alkylene ether structure and an alkyl chain structure after the production of the polycarbonate polyol. The hydroxyl value can be measured by the method described in the examples below.

[0034] <Average Number of Hydroxyl Groups> In the polycarbonate polyol composition of this embodiment, the average number of hydroxyl groups per molecule of the polycarbonate polyol is preferably 2.5 or more and 5.0 or less. Furthermore, in terms of achieving both drying properties, hardness, and chemical resistance, the average number of hydroxyl groups per molecule of the polycarbonate polyol is more preferably 2.8 or more and 4.5 or less, and even more preferably 3.0 or more and 4.0 or less. The average number of hydroxyl groups can be determined in the Examples described below. Note that the "polycarbonate polyol" in this embodiment may be a mixture of polycarbonate polyols having different numbers of hydroxyl groups per molecule. In such cases, the average number of hydroxyl groups of the polycarbonate polyols contained in the mixture refers to the above-mentioned "average number of hydroxyl groups." In this embodiment, when the "polycarbonate polyol" is composed of a single polycarbonate polyol, the number of hydroxyl groups of the polycarbonate polyol refers to the "average number of hydroxyl groups."

[0035] <Hydroxyl Group Ratio> Due to impurities in the various raw materials used in the production of the polycarbonate polyol composition, terminal structures produced as by-products during the production of the polycarbonate polyol composition, or for the purpose of controlling the urethane reaction rate and state in the use application of the polycarbonate polyol composition, some of the terminal hydroxyl groups may be converted to alkyl groups, aryl groups, or the like that do not react with isocyanate groups. Taking such cases into consideration, the present embodiment also encompasses cases where the terminal groups of the polycarbonate diol are not strictly 100 mol % hydroxyl groups at both ends. From this perspective, the ratio of hydroxyl groups to the total molar amount of terminal groups is preferably 90 mol % or more, more preferably 95 mol % or more, and even more preferably 98 mol % or more. In this embodiment, the terminal structure of the polycarbonate polyol composition can be confirmed, for example, in accordance with the method for measuring the primary terminal OH ratio described in Japanese Patent No. 3,874,664.

[0036] <Polyoxyethylene Structure> The polycarbonate polyol composition of the present embodiment may further contain a polyoxyethylene structure represented by the following general formula (IV) in the polycarbonate structure represented by general formula (III). Here, the polyoxyethylene structure represented by general formula (IV) may be bonded within the polycarbonate structure represented by general formula (III) or may be bonded to the terminal thereof. (In general formula (IV), n41 is a number of 3 or more and 50 or less.) By containing this polyoxyethylene structure, the polycarbonate polyol composition does not become cloudy, has excellent dispersibility in water and compatibility with organic solvents, and further, when combined with isocyanate to form a polyurethane resin, tends to have good drying properties, hardness, and chemical resistance all at the same time.

[0037] The terminal structure of the polyoxyethylene structure is a terminal structure in which one terminal is bonded to a carbonate group (-O-CO-O-) and the other terminal is bonded to a hydroxyl group (-OH), a terminal structure in which both terminals are bonded to carbonate groups (-O-CO-O-), or a terminal structure in which both terminals are bonded to hydroxyl groups (-OH). When a raw material having the polyoxyethylene structure is used, both terminals are hydroxyl groups.

[0038] In the polycarbonate polyol composition of the present embodiment, the content of the polyoxyethylene structure relative to the total mass of the polycarbonate polyol composition is preferably 3% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and even more preferably 5% by mass or more and 20% by mass or less, from the viewpoint of achieving both chemical resistance and dispersibility in water.

[0039] Of the polyoxyethylene structures, n41 is preferably 3 or more and 50 or less, more preferably 5 or more and 40 or less, and more preferably 10 or more and 40 or less, from the viewpoints of obtaining a clear polycarbonate polyol composition and achieving both chemical resistance and hardness of a polyurethane resin coating film using the polycarbonate polyol composition. The n41 can be determined by alkaline decomposition of the polycarbonate polyol composition to extract a raw material diol component, and subjecting the component to GC-MS measurement, LC-MS measurement, and GPC measurement.

[0040] The polycarbonate polyol composition of this embodiment contains a first transesterification catalyst containing at least one metal selected from the group consisting of metals of Groups 4, 5, 6, 7, 8, 9, 10, and 11 of the long periodic table. Among these, the metal contained in the transesterification catalyst is more preferably one or more metals selected from the group consisting of lithium, magnesium, calcium, titanium, manganese, ytterbium, tin, zinc, and zirconium, because these metals allow the transesterification reaction and / or depolymerization reaction to obtain the polycarbonate polyol to proceed more smoothly, and result in less coloration and suppressed turbidity of the composition. One or more metals selected from the group consisting of lithium, magnesium, calcium, titanium, manganese, and ytterbium are even more preferred, and one or more metals selected from the group consisting of magnesium, titanium, zirconium, tin, lead, and manganese are particularly preferred, with one or more metals selected from the group consisting of titanium and manganese being extremely preferred.

[0041] The polycarbonate polyol composition of this embodiment may further contain a second transesterification catalyst containing at least one metal selected from the group consisting of metals of Groups 1 and 2 of the long periodic table. The metal contained in the transesterification catalyst is not particularly limited, but examples include lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, and radium. Among these, lithium, sodium, potassium, magnesium, and calcium are preferred, as they allow for better transesterification and / or depolymerization reactions to obtain the polycarbonate polyol composition.

[0042] In the polycarbonate polyol composition of the present embodiment, the total content of the transesterification catalyst is preferably 0.00001 to 0.2 mass%, more preferably 0.0001 to 0.1 mass%, and even more preferably 0.0001 to 0.05 mass%.

[0043] <Polyurethane Resin> The polyurethane resin of this embodiment contains the polycarbonate polyol composition. The polyurethane resin composition may further contain an isocyanate compound described below. Furthermore, the polyurethane resin of this embodiment preferably contains a reaction product of the polycarbonate polyol composition and the isocyanate compound.

[0044] <Isocyanate Compound> The isocyanate compound contained in the polyurethane resin of this embodiment is not particularly limited as long as it functions as a curing agent, and one having two or more isocyanate groups at its terminal is used. Examples of such isocyanate compounds include, but are not limited to, linear aliphatic diisocyanates, cyclic aliphatic diisocyanates, aromatic diisocyanates, isocyanate compounds having three or more isocyanate groups, and isocyanurate-modified products, biuret-modified products, and urethane-modified products of these isocyanate compounds.

[0045] The chain aliphatic diisocyanate is not particularly limited, but examples thereof include hexamethylene diisocyanate (hereinafter sometimes abbreviated as "HDI"), tetramethylene diisocyanate, pentamethylene diisocyanate trimethylhexamethylene diisocyanate, and the like.

[0046] The cycloaliphatic diisocyanate is not particularly limited, but examples thereof include isophorone diisocyanate (hereinafter sometimes abbreviated as "IPDI"), 1,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.

[0047] The aromatic diisocyanate is not particularly limited, but examples thereof include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (hereinafter sometimes abbreviated as "MDI"), xylylene diisocyanate, and naphthylene diisocyanate.

[0048] The isocyanate compound having three or more isocyanate groups is not particularly limited, and examples thereof include triphenylmethane-4,4'-4''-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate, 1,3,6-triisocyanatohexane, 1,8-diisocyanato-4-isocyanatomethyloctane, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

[0049] The isocyanate compound may be, for example, an aliphatic or alicyclic diisocyanate such as HDI or IPDI, or a polyisocyanate derived from an isocyanate compound having three or more isocyanate groups, and having an isocyanurate bond, a carbodiimide bond, a biuret bond, a urethane bond, or the like. Furthermore, so-called blocked isocyanate compounds obtained by blocking these polyisocyanates with a blocking agent such as butanol, 2-ethylhexanol, or other lower alcohols, methyl ethyl ketoxime, lactams, phenols, pyrazoles, imidazoles, or active methylene compounds may also be used. Commercially available isocyanate compounds may be used, or they may be synthesized using known methods.

[0050] The commercially available isocyanate compound is not particularly limited, but examples thereof include Desmodur 44M and 44V70L (both manufactured by Sumika Covestro Urethane Co., Ltd.), Desmodur HL BA, which is a copolymer of TDI and HDI (manufactured by Sumika Covestro Urethane Co., Ltd.), Duranate (manufactured by Asahi Kasei Corporation) 24A-100, 22A-75P, TPA-100, TKA-100, TMA-100, P301-75E, D101, D201, 21S-75E, MFA-75B, MHG-80B, TUL-100, TLA-100, TSA-100, TSS-100, TSE-100, E402-80B ... 05-70B, AE700-100, A201H, 17B-60P, TPA-B80E, MF-B60B, MF-K60B, SBB-70P, SBN-70D, E402-B80B, WB40-100, WT30-100, WT31-100, WB40-80D, WT20-100, WL70-100, WE50-100, WA21-100, WM44-L70G, etc.

[0051] The content of the isocyanate compound can be appropriately adjusted according to the molar amount of the hydroxyl group of the polyol that is the main component.Specifically, the molar ratio (NCO / OH) of the isocyanate group of the isocyanate compound to the hydroxyl group of the polycarbonate polyol composition can be, for example, 0.2 or more and 5.0 or less, for example, 0.4 or more and 3.0 or more, for example, 0.5 or more and 2.0 or less.When NCO / OH is above the lower limit, the hardness of the coating film tends to be high and the chemical resistance tends to be high.On the other hand, when NCO / OH is below the upper limit, the smoothness of the coating film tends to be further improved.

[0052] <Chain Extender> The chain extender used when producing the polyurethane resin of the present embodiment is not particularly limited, but examples thereof include ordinary polyols and polyamines.

[0053] The polyol is not particularly limited, but examples thereof include linear diols, branched diols, cyclic diols, and diols having an aromatic ring.

[0054] The linear diol is not particularly limited, but examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol.

[0055] The branched diol is not particularly limited, but examples thereof include 2-methyl-1,8-octanediol, neopentyl glycol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, and 2,4-diethyl-1,5-pentanediol.

[0056] The cyclic diol is not particularly limited, but examples thereof include 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2-bis(4-hydroxycyclohexyl)-propane.

[0057] The diol having an aromatic ring is not particularly limited, but examples thereof include p-xylene diol, p-tetrachloroxylene diol, 1,4-bis(hydroxyethoxy)benzene, and 2,2-bis[(4-hydroxyethoxy)phenyl]propane.

[0058] The polyamine is not particularly limited, but examples thereof include hydroxyamines and polyamines. The hydroxyamine is not particularly limited, but examples thereof include N-methylethanolamine and N-ethylethanolamine. The polyamine is not particularly limited, but examples thereof include ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4,4'-diphenylmethanediamine, methylenebis(o-chloroaniline), xylylenediamine, diphenyldiamine, tolylenediamine, hydrazine, piperazine, and N,N'-diaminopiperazine. These chain extenders may be used alone or in combination of two or more.

[0059] <Coating Composition> The coating composition of this embodiment contains the polycarbonate polyol composition described above. The coating composition of this embodiment may also contain the isocyanate compound. By containing the polycarbonate polyol composition described above, the coating composition of this embodiment can form a coating film that is excellent in drying properties, appearance, hardness, chemical resistance, and extensibility.

[0060] The method for producing the coating composition using the polycarbonate polyol composition is not particularly limited, and known production methods can be used.For example, the two-component solvent-based coating composition can be produced by mixing the main component obtained from the polycarbonate polyol composition and the curing agent etc. made of isocyanate compound just before coating; the one-component solvent-based coating composition can be produced by reacting the above-mentioned polycarbonate polyol composition with the isocyanate compound and the urethane prepolymer with an isocyanate terminal group; the one-component solvent-based coating composition can be produced by reacting the polycarbonate polyol composition, the isocyanate compound and the polyurethane resin obtained, and the one-component solvent-based coating composition can be produced by previously mixing the main component and the curing agent etc. made of blocked isocyanate compound.

[0061] <Organic Solvent> The coating composition of this embodiment can contain an organic solvent in an amount of 1% by mass or more and 95% by mass or less, as needed, to adjust workability during application. The content of the organic solvent is more preferably 15% by mass or more and 80% by mass or less, and even more preferably 30% by mass or more and 70% by mass or less. The organic solvent used is not particularly limited, but is preferably an organic solvent that is substantially inactive to the isocyanate compound and does not contain active hydrogen. The solvent may be either a hydrophilic solvent or a hydrophobic solvent.

[0062] The hydrophobic solvent is not particularly limited, but examples thereof include mineral spirits, solvent naphtha, LAWS (Low Aromatic White Spirit), HAWS (High Aromatic White Spirit), toluene, xylene, cyclohexane, etc.; esters such as ethyl acetate and butyl acetate; and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.

[0063] The hydrophilic solvent is not particularly limited, but examples thereof include alcohols such as methanol, ethanol, propanol, isopropanol, and 2-ethylhexanol; ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; and esters of ether alcohols such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and dipropylene glycol monomethyl ether acetate. These can be used alone or in combination. Among these, C1-8 alcohols such as 2-ethylhexanol and di-C1-4 alkylene glycol di-C1-3 alkyl ethers such as dipropylene glycol dimethyl ether are preferred.

[0064] <Antioxidant> The coating composition of the present embodiment may further contain an antioxidant in addition to the polycarbonate polyol composition. The antioxidant may be added at the stage of producing the coating composition, or may be added to the polycarbonate polyol composition in advance. Furthermore, the antioxidant may be used alone or in combination of two or more.

[0065] The antioxidant is not particularly limited, but examples thereof include substances having antioxidant properties that are used as light stabilizers, heat stabilizers, etc.

[0066] The antioxidant used as the light resistance stabilizer is not particularly limited, but examples thereof include hindered amine-based antioxidants, benzophenone-based antioxidants, benzotriazole-based antioxidants, triazine-based antioxidants, and cyanoacrylate-based antioxidants.

[0067] The hindered amine antioxidant is not particularly limited, but examples thereof include ADK STAB LA-52 (trade name), ADK STAB LA-68 (trade name), ADK STAB LA-77Y (trade name), ADK STAB LA-81 (trade name) (each manufactured by ADEKA CORPORATION), TINUVIN 622 (trade name), TINUVIN 765 (trade name), TINUVIN 770 (trade name), TINUVIN 791 (trade name) (each manufactured by BASF).

[0068] The benzophenone-based antioxidant is not particularly limited, but examples thereof include Chimassorb 81 (trade name) (manufactured by BASF).

[0069] The benzotriazole-based antioxidant is not particularly limited, but examples thereof include Tinuvin P (trade name) and Tinuvin 234 (trade name) (both manufactured by BASF).

[0070] The triazine-based antioxidant is not particularly limited, but examples thereof include Tinuvin 1577ED (trade name) and Tinuvin 400 (trade name) (manufactured by BASF).

[0071] The cyanoacrylate antioxidant is not particularly limited, but examples thereof include Uvinul 3035 (trade name) (manufactured by BASF Corporation).

[0072] The antioxidant used as the heat stabilizer is not particularly limited, but examples thereof include hindered phenol-based antioxidants, phosphorus-containing antioxidants, sulfur-containing antioxidants, vitamin E-based antioxidants, and hydroxyamine-based antioxidants.

[0073] The hindered phenol-based antioxidant is not particularly limited, but examples thereof include dibutylhydroxytoluene (hereinafter, may be abbreviated as "BHT"), Irganox 1010 (trade name), Irganox 1135 (trade name), Irganox 1330 (trade name), Irganox 3114 (trade name), Irganox 565 (trade name), Irganox 1520L (trade name) (each manufactured by BASF Corporation), Adekastab AO-20 (trade name), Adekastab AO-30 (trade name), Adekastab AO-50 (trade name), Adekastab AO-60 (trade name), Adekastab AO-80 (trade name) (each manufactured by ADEKA Corporation).

[0074] The phosphorus-containing antioxidant is not particularly limited, but examples thereof include ADK STAB PEP-8 (trade name), ADK STAB HP-10 (trade name), ADK STAB 1178 (trade name), ADK STAB C (trade name) (each manufactured by ADEKA CORPORATION), Irgafos 168, Irgafos 38 (trade name) (manufactured by BASF SE), and Sumilizer GP (trade name) (manufactured by Sumitomo Chemical Co., Ltd.).

[0075] The sulfur-containing antioxidant is not particularly limited, but examples thereof include Irganox PS800FL (trade name) (manufactured by BASF).

[0076] The vitamin E-based antioxidant is not particularly limited, but examples thereof include Irganox E201 (trade name) (manufactured by BASF).

[0077] The hydroxyamine-based antioxidant is not particularly limited, but examples thereof include Irgastab FS042 (trade name) (manufactured by BASF).

[0078] Among these, the antioxidant is preferably at least one selected from the group consisting of hindered phenol antioxidants, hindered amine antioxidants, triazine antioxidants, sulfur-containing antioxidants, and phosphorus-containing antioxidants. Furthermore, the antioxidant is more preferably at least one selected from the group consisting of Tinuvin 765 (trade name), Adekastab LA-52 (trade name), Adekastab LA-81 (trade name), BHT, Irganox 565 (trade name), Adekastab C (trade name), and Sumilizer GP (trade name).

[0079] <Additives> The coating composition of this embodiment may further contain additives that are generally added to paints as needed. Examples of such additives include, but are not limited to, inorganic pigments, organic pigments, extender pigments, urethane beads, silane coupling agents, titanium coupling agents, organic phosphates, organic phosphites, thickeners, leveling agents, thixotropic agents, antifoaming agents, freeze stabilizers, matting agents, crosslinking reaction catalysts (catalysts for promoting curing), antiskinning agents, dispersants, wetting agents, fillers, plasticizers, lubricants, reducing agents, preservatives, antifungal agents, deodorizers, anti-yellowing agents, UV absorbers, antistatic agents or charge control agents, anti-settling agents, colorants, and color inhibitors. These additives may be contained alone or in combination of two or more.

[0080] <Polyol> The polyurethane resin of the present embodiment may contain other polyols in addition to the polycarbonate polyol composition. The other components are not particularly limited, but examples thereof include curable compositions, polyhydric alcohol compounds, and polyols such as polyester polyols, acrylic polyols, polyether polyols, polyolefin polyols, and fluorine polyols described in JP 2018-012769 A.

[0081] <Adhesive Composition> The adhesive composition of this embodiment contains the polycarbonate polyol composition. The adhesive composition of this embodiment may also contain the isocyanate compound. Applications of the adhesive composition of this embodiment are not particularly limited, and examples include automobiles, building materials, home appliances, woodworking, and solar cell laminates. Since sufficient adhesiveness is required for laminating various adherends, this is a preferred example of the use of the adhesive composition of this embodiment.

[0082] Examples of adherends for which the adhesive composition of the present embodiment can be used include, but are not limited to, glass; various metals such as aluminum, iron, galvanized steel sheet, copper, and stainless steel; porous materials such as wood, paper, mortar, and stone; materials coated with fluorine paint, urethane paint, acrylic urethane paint, or the like; cured sealant products such as silicone-based cured products, modified silicone-based cured products, and urethane-based cured products; rubbers such as vinyl chloride, natural rubber, and synthetic rubber; leathers such as natural leather and artificial leather; fibers such as plant fibers, animal fibers, carbon fibers, and glass fibers; nonwoven fabrics, and films and plates made of resins such as polyester, acrylic, polycarbonate, triacetyl cellulose, and polyolefin; and inks such as ultraviolet-curable acrylic resin layers, printing inks, and UV inks.

[0083] <Aqueous Polyurethane Dispersion> The aqueous polyurethane dispersion of this embodiment is an aqueous polyurethane dispersion obtained by dispersing a polyurethane resin containing the above-mentioned polycarbonate polyol composition in water. The water-dispersible polyurethane resin of this embodiment is obtained, for example, from the polycarbonate polyol composition, the isocyanate compound, and a carboxyl group- and / or sulfonic acid group-containing polyol or a salt thereof.

[0084] The carboxyl group- and / or sulfonic acid-containing polyol or its salt used in the aqueous polyurethane dispersion of this embodiment is a component used to introduce carboxylate or sulfonic acid groups for the purposes of self-emulsifying the water-dispersible polyurethane in water and imparting dispersion stability to the aqueous polyurethane dispersion. Examples of carboxyl group-containing polyols include, but are not limited to, 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid, and 2,2-dimethyloloctanoic acid. Examples of sulfonic acid-containing polyols include diol sulfonate (3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid) and diol sulfamate (N,N-bis(2-hydroxyl)sulfamic acid) and alkylene oxide adducts thereof. The salts of these carboxyl group- and / or sulfone group-containing polyols are not particularly limited, but examples include ammonium salts, amine salts [salts of primary amines having 1 to 12 carbon atoms (primary monoamines, for example, methylamine, ethylamine, propylamine, and octylamine), salts of secondary monoamines (dimethylamine, diethylamine, and dibutylamine), salts of tertiary monoamines (aliphatic tertiary monoamines such as trimethylamine, triethylamine, triethanolamine, N-methyldiethanolamine, and N,N-methylethanolamine; heterocyclic tertiary monoamines such as N-methylpiperidine and N-methylmorpholine; aromatic ring-containing tertiary monoamines such as benzyldimethylamine, α-methylbenzyldimethylamine, and N-dimethylaniline)], alkali metal (sodium, potassium, and lithium cation) salts, and combinations of two or more thereof.

[0085] Among the salts, amine salts are preferred, aliphatic tertiary monoamine salts are more preferred, and triethylamine salts are particularly preferred.

[0086] When the polyol is not a salt but a polyol containing carboxyl and / or sulfonic groups, the carboxyl and / or sulfonic groups can be neutralized using a neutralizing agent to form carboxylate and / or sulfonate groups.

[0087] The neutralizing agent is not particularly limited, and examples thereof include alkaline compounds that form the cations listed above as counter ions. Specific examples thereof include, but are not particularly limited to, ammonia, amines [primary amines having 1 to 12 carbon atoms (primary monoamines, for example, methylamine, ethylamine, propylamine, and octylamine), secondary monoamines (dimethylamine, diethylamine, and dibutylamine), tertiary monoamines (aliphatic tertiary monoamines such as trimethylamine, triethylamine, triethanolamine, N-methyldiethanolamine, and N,N-dimethylethanolamine; heterocyclic tertiary monoamines such as N-methylpiperidine and N-methylmorpholine; aromatic ring-containing tertiary monoamines such as benzyldimethylamine, α-methylbenzyldimethylamine, and N-dimethylaniline], alkali metals (sodium, potassium, and lithium cations), alkali metal hydroxides, and combinations of two or more thereof.

[0088] Of these, amines are preferred, aliphatic tertiary monoamines are more preferred, and triethylamine is particularly preferred.

[0089] The amount of carboxyl group- and / or sulfone group-containing polyol or its salt used is preferably an amount that results in 0.01 to 10 mol% of carboxyl groups and / or sulfone groups relative to the water-dispersible polyurethane resin. The ratio of carboxyl groups and / or sulfone groups relative to the water-dispersible polyurethane resin is more preferably 0.1 to 7 mol%, and even more preferably 0.5 to 5 mol%. When the carboxyl group and / or sulfone group content is 0.01 mol% or more, dispersion stability tends to be better. Furthermore, when the content is 10 mol% or less, the water resistance of the resulting coating film tends to be better.

[0090] The aqueous polyurethane dispersion of this embodiment may also contain a surfactant. The surfactant is not particularly limited, but examples thereof include anionic surfactants such as higher fatty acids, resin acids, acidic fatty alcohols, sulfates, higher alkyl sulfonates, alkylaryl sulfonates, sulfonated castor oil, and sulfosuccinates, and nonionic surfactants such as known reaction products of ethylene oxide with long-chain fatty alcohols or phenols.

[0091] <Method for Producing Aqueous Polyurethane Dispersion> The method for producing the aqueous polyurethane dispersion of this embodiment is not particularly limited, and examples thereof include the following: In the presence or absence of an organic solvent not containing an active hydrogen-containing group in the molecule (e.g., acetone, methyl ethyl ketone, tetrahydrofuran, N,N-dimethylformamide, etc.), the isocyanate compound containing two or more isocyanate groups per molecule, the polycarbonate polyol composition, and a carboxyl group- and / or sulfone group-containing polyol or a salt thereof are subjected to a urethanization reaction by a one-shot method or a multi-stage method at an (NCO group / OH group) equivalent ratio of preferably 0.5 to 1.5, more preferably 0.8 to 1.2, and even more preferably 0.9 to 1.1 to synthesize a polyurethane resin, and then neutralize the polyurethane resin with a neutralizing agent as needed. After that, water is added dropwise to the resulting reaction solution while vigorously stirring, and the solvent is removed as needed after the dropwise addition to obtain an aqueous polyurethane dispersion. Alternatively, the reaction solution obtained above can be added to and dispersed in water with stirring, and then the solvent can be removed as necessary to obtain an aqueous polyurethane dispersion.

[0092] By having an (NCO group / OH group) equivalent ratio of 0.5 or more, the molecular weight of the resulting polyurethane can be increased, and a more stable aqueous polyurethane dispersion tends to be obtained, and furthermore, the strength and flexibility of the coating film formed by an aqueous coating composition containing the aqueous polyurethane dispersion as a constituent component tends to be superior. Similarly, by having an (NCO group / OH group) equivalent ratio of 1.5 or less, the molecular weight of the resulting polyurethane can be increased, and a more stable aqueous polyurethane dispersion tends to be obtained, and furthermore, the strength and flexibility of the coating film formed by an aqueous coating composition containing the aqueous polyurethane dispersion as a constituent component tends to be superior.

[0093] Furthermore, as a method for producing the aqueous polyurethane dispersion of the present embodiment, a prepolymer may be synthesized in advance from the isocyanate compound, the polycarbonate polyol composition, and a carboxyl group- and / or sulfone group-containing polyol or a salt thereof under conditions of excess isocyanate, and the prepolymer may be dispersed in water, followed by adding a chain extender to form an aqueous polyurethane dispersion.

[0094] The chain extender is not particularly limited, but examples thereof include water, short-chain diols such as ethylene glycol, 1,3-propanediol, and 1,4-butanediol, and polyamines such as hydrazine, ethylenediamine, diethyltriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, hexamethylenediamine, and cyclohexylenediamine. The amount of chain extender added is usually 0 to 1.2 mol, and preferably 0.1 to 0.6 mol, per mol of isocyanate groups in the urethane prepolymer.

[0095] In the process of producing the aqueous polyurethane dispersion of this embodiment, a known urethanization catalyst can be used as needed. The urethanization catalyst is not particularly limited, but examples thereof include amine catalysts (e.g., triethylamine, N-ethylmorpholine, triethylenediamine, etc.), tin-based catalysts (e.g., dibutyltin dilaurate, dioctyltin dilaurate, tin octoate, etc.), and titanium-based catalysts (e.g., tetrabutyl titanate, etc.).

[0096] The solids content of the aqueous polyurethane dispersion of this embodiment is preferably 10 to 70% by mass, and more preferably 20 to 60% by mass.

[0097] The particle size of the polyurethane in the aqueous polyurethane dispersion of this embodiment is preferably 500 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less. A polyurethane particle size of 500 nm or less is preferred because the appearance and film strength of the coating film of the aqueous coating composition containing the aqueous polyurethane dispersion tend to be better.

[0098] <Method for Producing Polycarbonate Polyol Composition> Specific examples of the method for producing the polycarbonate polyol composition of the present embodiment are not particularly limited, but include a method of producing a polycarbonate polyol composition from a polyhydric alcohol using alkylene oxide, carbonate, and diol as raw materials through a transesterification reaction as described in H. Schnell, Polymer Reviews, Vol. 9 (published by Interscience Publishers, USA, in 1964), pages 9-20, etc. Further specific production methods include the following methods: (1) A method of obtaining a polycarbonate polyol composition containing the alkylene ether structure, the alkyl chain structure, and the polycarbonate structure from a polyhydric alcohol through an addition reaction or transesterification reaction between an alkylene oxide and a carbonate compound or a diol compound. (2) A method of obtaining a polycarbonate polyol composition by addition reaction of an alkylene oxide with a polyhydric alcohol, and then transesterification and / or depolymerization of the alkylene oxide group-containing polyhydric alcohol containing the alkylene ether structure and the alkyl chain structure with a polycarbonate polyol precursor containing a polycarbonate structure obtained by reaction of a carbonate with a diol compound. (3) A method of obtaining a polycarbonate polyol composition by transesterification and / or depolymerization of a polyhydric alcohol, an alkylene oxide, and the polycarbonate polyol precursor described in (2). Among the above, (2) is more preferred in terms of ease of production, resistance to discoloration, and low viscosity.

[0099] The method for producing the polycarbonate polyol composition of the present embodiment preferably includes a step of subjecting a polycarbonate polyol precursor derived from the following general formula (III) and an alkylene oxide group-containing alcohol derived from the following general formulas (I) and (II) to a transesterification reaction and / or depolymerization reaction in the presence of a transesterification reaction catalyst: (In general formula (I), R １１ is a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having from 2 to 20 carbon atoms, R １２ is any one of the polycarbonate structure represented by general formula (III), a hydrogen group, or a hydrocarbon residue which may contain an ether group, a carboxyl group, or a carbonate group. １２ is a polycarbonate structure represented by general formula (III). １１ The hydrocarbon group may be of one type or of multiple types. n11 is an integer of 1 or more and 10 or less, and * represents a bond to the alkyl chain structure represented by general formula (II). (In general formula (II), R ２１ , R ２２ , R ２３ and R ２４ is a group selected from the group consisting of an alkylene ether structure represented by general formula (I), a hydrogen group, a hydroxyl group, and a residue bonded via a divalent hydrocarbon group having from 1 to 20 carbon atoms, and the hydrocarbon group is a linear, branched, or cyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and may contain a hydroxyl group, an amino group, a sulfide group, an ether group, a carbonyl group, a carboxyl group, or a carbonate group. ２１ , R ２２ , R ２３ and R ２４ At least one of R is an alkylene ether structure represented by general formula (I). ２１ , R ２２ , R ２３ , R ２４ The hydrocarbon group may be of one type or of multiple types. (In general formula (III), R ３１R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having from 2 to 15 carbon atoms. ３１ There are at least two types of hydrocarbon groups. n31 is any integer.

[0100] <Method for Producing Alkylene Oxide Group-Containing Polyhydric Alcohol> In the method for producing a polycarbonate polyol composition of the present embodiment, the alkylene oxide group-containing polyhydric alcohol can be produced, for example, by adding an alkaline compound to the polyhydric alcohol alone or a mixture thereof having a hydrocarbon group bonded to a hydroxyl group, and then adding alkylene oxide to the polyhydric alcohol under pressure in a sealed environment.

[0101] As a method for imparting the alkyl chain structure represented by the general formula (II), R ２１ , R ２２ , R ２３ , R ２４However, it is preferable to use a polyhydric alcohol containing a structure in which at least one group selected from a hydrogen group, a hydroxyl group, a hydrocarbon group, and a hydrocarbon group to which a hydroxyl group is bonded, and in which the average number of hydroxyl groups per molecule is 3 or more. Furthermore, from the viewpoint of production stability, a polyhydric alcohol containing the hydrocarbon group to which a hydroxyl group is bonded is more preferable.Compounds that satisfy these requirements are not particularly limited, but examples thereof include 1,2,3-propanetriol (also known as glycerin), 2-hydroxymethyl-1,2,3-propanetriol, 2-hydroxymethyl-1,2,4-butanetriol, 2-hydroxymethyl-1,2,3-butanetriol, 2,2-bis(hydroxymethyl)-1,4-butanediol, 2,2-bis(hydroxymethyl)-1,3-butanediol, 3-hydroxymethyl-3-methyl-1,2,4-butanetriol, 2,2-bis(hydroxymethyl)-1,4-butanediol, 2,2-bis(hydroxymethyl)-1,6-hexanediol, 2,2-bis(hydroxymethyl)-1,3-pentanediol, 3,3-bis(hydroxymethyl)-1,5-pentanediol, 2,2-bis(hydroxymethyl)-1,5-pentanediol, 3,3-bis(2-hydroxyethyl)-1,5-pentanediol, 2,2-bis(hydroxymethyl)-1,3-heptanediol, 2,2-bis(hydroxymethyl)-1,3-propanediol (also known as pentaerythritol), 2-hydroxymethyl- 2-Methylpropane-1,3-diol (also known as trimethylolethane), 2-hydroxymethyl-2-ethylpropane-1,3-diol (also known as trimethylolpropane), 3,3-dimethyl-1,2,4-butanetriol, 2-hydroxymethyl-2-methyl-1,3-butanediol, 2-hydroxymethyl-2-propyl-1,3-propanediol, 2-ethyl-2-hydroxymethyl-1,4-butanediol, 2-ethyl-1,2,3-propanetriol, 2-ethyl-2-hydroxymethyl butyl-1,3-butanediol, 2-hydroxymethyl-2-methyl-1,3-pentanediol, 2-butyl-2-hydroxymethyl-1,3-propanediol, 3-(2-hydroxymethyl)-3-methyl-1,5-pentanediol, 3-ethyl-3-hydroxymethyl-1,5-pentanediol, 2-hydroxymethyl-2-propyl-1,4-butanediol, 3-ethyl-(2-hydroxyethyl)1,5-pentanediol, dipentaerythritol, and ditrimethylolpropane.Among these, trimethylolpropane or pentaerythritol is preferred because it is easily available, has high reactivity, can produce a polycarbonate polyol composition with the desired number of functional groups, and becomes liquid at 25°C, and pentaerythritol is even more preferred because it has high hardness as a polyurethane composition. These may be used alone or in combination of two or more. The quaternary carbon contained in the compound is １３ This can be confirmed by the presence of a peak between 40 ppm and 50 ppm in C-NMR. It can also be calculated by the calculation method described in the Examples below using the hydroxyl value described in the Examples below and the number average molecular weight determined by GPC.

[0102] When a solvent is used in the alkylene oxide addition, it is not particularly limited, and examples thereof include polar protic solvents such as methanol, ethanol, and 1-propanol; polar aprotic solvents such as acetone, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, and dimethyl sulfoxide; nonpolar solvents such as hexane, toluene, ethyl acetate, and chloroform; and water.

[0103] The alkaline compound is not particularly limited, but examples thereof include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, and barium hydroxide; amines such as dimethylamine, trimethylamine, and triethylamine; and quaternary ammonium salts such as tetramethylammonium hydroxide and benzyltrimethylammonium hydroxide. These may be used alone or in combination of two or more. The state of the alkaline compound is not particularly limited, and may be, for example, a solid, liquid, aqueous solution, or alcohol solution. The amount of the alkaline compound added is preferably 0.001% by mass to 1% by mass, more preferably 0.01% by mass to 0.5% by mass, relative to 100% by mass of the polyhydric alcohol.

[0104] The alkylene oxide is not particularly limited, but examples thereof include ethylene oxide, propylene oxide, etc. The amount of alkylene oxide added is preferably 0.1 equivalents or more and 10.0 equivalents or less per equivalent of the hydroxyl group of the polyhydric alcohol.

[0105] The reaction temperature is preferably 60° C. or higher and 200° C. or lower, more preferably 80° C. or higher and 150° C. or lower, in order to allow the reaction to proceed efficiently.

[0106] The reaction pressure is preferably 0.5 MPa or less in that the reaction can be easily controlled.

[0107] After the reaction is complete, for example, the product salt and remaining alkaline compounds are neutralized with an acid or removed from the reaction solution. Next, for example, the reaction solution is heated under normal pressure or reduced pressure to remove the remaining solvent and excess alkylene oxide from the reaction solution, and the alkylene oxide group-containing polyhydric alcohol is recovered. The alkylene oxide group-containing polyhydric alcohol produced by these methods preferably has a raw material polyhydric alcohol content of less than 10% by mass. By keeping the polyhydric alcohol content within the above range, the produced polycarbonate polyol composition tends to be less cloudy in appearance and have a lower viscosity.

[0108] <Polycarbonate Polyol Precursor> The polycarbonate polyol precursor that may be used in the method for producing the polycarbonate polyol composition of the present embodiment preferably has the structural unit represented by general formula (III) above, and both ends of the molecule are hydroxyl groups.

[0109] The number average molecular weight of the polycarbonate polyol precursor that may be used in the method for producing the polycarbonate polyol composition of the present embodiment is not particularly limited, but is preferably 500 or more and 5,000 or less, and more preferably 1,000 or more and 3,000 or less.

[0110] When the number average molecular weight of the polycarbonate polyol precursor is equal to or greater than the lower limit, the performance of the polyurethane resin composed of the polycarbonate polyol composition tends to be further improved. On the other hand, when the number average molecular weight of the polycarbonate polyol precursor is equal to or less than the upper limit, it is preferable in terms of handling during production of the polycarbonate polyol composition. The polycarbonate polyol precursor containing a structure represented by general formula (III) used as a raw material for producing the polycarbonate polyol composition of this embodiment is not particularly limited, and known methods can be used. For example, it can be obtained by reacting a carbonate compound and a diol compound in the presence of a transesterification catalyst.

[0111] <Carbonate Compound> When a carbonate compound is used in the method for producing a polycarbonate polyol composition of the present embodiment, examples of the carbonate compound include, but are not limited to, alkylene carbonate, dialkyl carbonate, diaryl carbonate, etc. Examples of alkylene carbonate include, but are not limited to, ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 1,2-pentylene carbonate, etc. Examples of dialkyl carbonate include, but are not limited to, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, etc. Examples of diaryl carbonate include, but are not limited to, diphenyl carbonate, etc. Among these, the carbonate compound used in the method for producing a polycarbonate polyol of the present embodiment is preferably ethylene carbonate, dimethyl carbonate, diethyl carbonate, or diphenyl carbonate, and more preferably ethylene carbonate.

[0112] <Diol Compound> The diol compound used in the method for producing a polycarbonate polyol composition of this embodiment is not limited to the following. Examples include linear diols, branched diols, cyclic diols, and diols having an aromatic ring. The linear diol is not particularly limited, but examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nanodiol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol. Examples of branched diols include, but are not limited to, 2-methyl-1,8-octanediol, neopentyl glycol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, and 2,4-diethyl-1,5-pentanediol. Examples of cyclic diols include, but are not limited to, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2-bis(4-hydroxycyclohexyl)propane. Examples of diols having an aromatic ring include, but are not limited to, p-xylenediol, p-tetrachloroxylenediol, 1,4-bis(hydroxyethoxy)benzene, and 2,2-bis[(4-hydroxyethoxy)phenyl]propane. Among the above diol compounds, linear or branched diols having 3 to 10 carbon atoms are preferred, and 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol are preferred, with 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol being more preferred.

[0113] <Catalyst> In producing the polycarbonate polyol composition or the polycarbonate polyol precursor, a transesterification catalyst can be used. The catalyst can be selected from ordinary transesterification catalysts.

[0114] The transesterification catalyst is not particularly limited, but examples thereof include metal alcoholates, hydrides thereof, oxides thereof, amides thereof, hydroxides thereof, and salts thereof.

[0115] The transesterification catalyst is preferably at least one metal selected from the group consisting of metals of Groups 4, 5, 6, 7, 8, 9, 10, and 11 of the long periodic table, as well as salts, alcoholates, and organic compounds containing the metal. Among these, one or more metals selected from the group consisting of lithium, magnesium, calcium, titanium, manganese, ytterbium, tin, zinc, and zirconium are more preferred, as they allow the transesterification reaction and / or depolymerization reaction to obtain the polycarbonate polyol to proceed more smoothly, resulting in less coloration and suppressed turbidity of the composition. One or more metals selected from the group consisting of lithium, magnesium, calcium, titanium, manganese, and ytterbium are even more preferred, and one or more metals selected from the group consisting of magnesium, titanium, zirconium, tin, lead, and manganese are particularly preferred, with one or more metals selected from the group consisting of titanium and manganese being extremely preferred.

[0116] The organic magnesium compound is not particularly limited, but examples thereof include magnesium acetate, magnesium(II) acetylacetonate, and 2,2,6,6-tetramethyl-3,5-heptanedionatomagnesium(II) dihydrate.

[0117] The organic compound containing titanium is not particularly limited, but examples thereof include titanium tetra-n-butoxide, titanium tetra-n-propoxide, and titanium tetraisopropoxide.

[0118] The organic compound of zirconium is not particularly limited, but examples thereof include zirconium(IV) acetylacetone, zirconium(IV) tetrapropoxide, zirconium(IV) tetrabutoxide, and zirconium(IV) acetylacetonate.

[0119] The organic tin compound is not particularly limited, but examples thereof include tin oxalate, di-n-butyltin dimaleate, di-n-butyltin dilaurate, di-n-butyltin oxide, di-n-butyltin diacetate, and di-n-octyltin dilaurate.

[0120] The organic lead compound is not particularly limited, but examples thereof include lead acetate trihydrate, tetraphenyl lead, and lead stearate.

[0121] The organic manganese compound is not particularly limited, but examples thereof include manganese(II) acetate and manganese(II) acetylacetonate.

[0122] The transesterification catalyst may further comprise a transesterification catalyst containing at least one metal selected from the group consisting of metals of Groups 1 and 2 of the long periodic table. The metal contained in the transesterification catalyst is not particularly limited, but examples include lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, and radium. Among these, lithium, sodium, potassium, magnesium, and calcium are preferred, as they allow for better transesterification and / or depolymerization reactions to obtain the polycarbonate polyol composition.

[0123] The organic lithium compound is not particularly limited, but examples thereof include lithium hydroxide, lithium methylate (lithium methoxide), lithium ethylate (lithium ethoxide), lithium propoxide, and lithium butoxide.

[0124] The organic compound of sodium is not particularly limited, but examples thereof include sodium hydroxide, sodium methylate (sodium methoxide), sodium ethylate (sodium ethoxide), sodium propoxide, and sodium butoxide.

[0125] The organic potassium compound is not particularly limited, but examples thereof include potassium hydroxide, potassium methylate (potassium methoxide), potassium ethylate (potassium ethoxide), potassium propoxide, and potassium butoxide.

[0126] The organic compound of magnesium is not particularly limited, but examples thereof include calcium hydroxide, dimethoxycalcium, diethoxycalcium, dipropoxycalcium, and dibutoxycalcium.

[0127] The organic calcium compound is not particularly limited, but examples thereof include magnesium hydroxide, dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, and dibutoxy magnesium.

[0128] These transesterification catalysts can be used alone or in combination of two or more.

[0129] The amount of the transesterification catalyst used is preferably 0.00001% by mass or more and 0.2% by mass or less, and more preferably 0.0001% by mass or more and 0.1% by mass or less, based on the total mass of the raw materials.

[0130] The transesterification catalyst used in the transesterification reaction and / or depolymerization reaction remains without being consumed even after the production of the polycarbonate polyol composition. Therefore, the amount of metal in the transesterification catalyst can be calculated based on the amount of the transesterification catalyst used. When a commercially available polycarbonate diol is used, the amount of metal in the transesterification catalyst contained in the polycarbonate diol can be determined by measuring it using ICP (Inductively Coupled Plasma) emission spectroscopy.

[0131] <Catalyst Deactivator> The polycarbonate polyol composition or polycarbonate polyol precursor of this embodiment may contain a catalyst deactivator, such as a phosphoric acid ester compound, added to deactivate the transesterification catalyst used during its production. The amount of catalyst deactivator added is preferably 0.8 to 5.0 times the molar amount of the transesterification catalyst used, and more preferably 1.0 to 3.0 times the molar amount. When a catalyst deactivator is used in an amount equal to or greater than the lower limit, the transesterification catalyst is sufficiently deactivated. When the resulting polycarbonate polyol composition is used as, for example, a raw material for producing a polyurethane resin, the reactivity of the polycarbonate polyol composition with isocyanate groups tends to be sufficiently reduced. Furthermore, when a catalyst deactivator is used in an amount equal to or less than the upper limit, discoloration of the resulting polycarbonate polyol composition can be suppressed, and when used as a raw material for producing a polyurethane resin, polyurethane polymerization tends to proceed smoothly. Furthermore, the mixture may be heated and stirred to ensure the deactivation of the transesterification catalyst.

[0132] The catalyst deactivator used is not particularly limited, and examples thereof include inorganic phosphoric acids such as phosphoric acid and phosphorous acid, organic phosphoric acid esters such as mono(or di)ethyl phosphate, mono(or di)propyl phosphate, mono(or di)butyl phosphate, mono(or di)butoxyethyl phosphate, mono(or di)2-ethylhexyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, and triphenyl phosphite, sulfonic acids, sulfonate esters, etc. These may be used alone or in combination of two or more.

[0133] When a polycarbonate polyol precursor that may be used as a raw material for the polycarbonate polyol composition of this embodiment contains a catalyst deactivator for the transesterification catalyst used in its production, the transesterification reaction and / or depolymerization reaction between the polycarbonate polyol and the alkylene oxide group-containing polyhydric alcohol usually tends to proceed more slowly. Therefore, when producing the polycarbonate polyol composition of this embodiment, a required amount of the transesterification catalyst can be newly added.

[0134] On the other hand, when the polycarbonate polyol precursor does not contain a catalyst deactivator for the transesterification catalyst, the transesterification reaction and / or depolymerization reaction of this embodiment usually tends to proceed easily. However, when it is desired to further lower the reaction temperature or shorten the reaction time in the production process of the polycarbonate polyol composition of this embodiment, a necessary amount of a new transesterification catalyst can be added. In this case, the same transesterification catalyst as used in the production of the polycarbonate polyol precursor can be used.

[0135] <Production Conditions for Polycarbonate Polyol Composition and Polycarbonate Polyol Precursor> In the production of the polycarbonate polyol composition and polycarbonate polyol precursor of the present embodiment, a method of stirring while heating is preferred.

[0136] The temperature during stirring is not particularly limited, but is preferably 120°C or higher and 200°C or lower, and more preferably 130°C or higher and 180°C or lower.

[0137] By setting the reaction temperature to the above lower limit or higher, reactions such as transesterification and depolymerization can be carried out in a shorter time, which tends to be economical. By setting the reaction temperature to the above upper limit or lower, the acid value of the resulting polycarbonate polyol composition can be controlled within a specific range, which tends to more effectively prevent discoloration.

[0138] It is also preferable to keep the oxygen concentration in the reaction vessel during production at 0.5% or less. There are no particular limitations on the method for keeping the oxygen concentration at 0.5% or less, but examples include replacing 1.5 times or more of the reaction vessel with nitrogen and then stirring while flowing nitrogen, or reducing the pressure to 0.1 kPa or less, replacing with nitrogen, and stirring under slightly reduced pressure. By keeping the oxygen concentration at 0.5% or less, the generation of peroxides is suppressed, and coloration of the resulting polycarbonate polyol composition tends to be prevented.

[0139] In order to keep the oxygen concentration at 0.5% or less, the nitrogen flow rate is preferably 0.1 L / min to 50 L / min, more preferably 0.2 L / min to 30 L / min. A nitrogen flow rate of at least the lower limit mentioned above is preferred because it can prevent oxygen from being mixed in, and a nitrogen flow rate of at most the upper limit mentioned above tends to prevent the volatilization of the raw material diol and keep the hydroxyl value of the resulting polycarbonate diol composition constant.

[0140] <Applications> The polycarbonate polyol composition of this embodiment can be used as a raw material for polyurethane resins to be reacted with isocyanate compounds. Polyurethane resins obtained using this polycarbonate polyol composition have excellent chemical resistance, heat resistance, and weather resistance, and therefore can be widely used in foams, elastomers, paints, coating agents, pressure-sensitive adhesives, adhesives, inks, casting agents, heat dissipation materials, optical components, extrusion-molded films, cast films, artificial leather, synthetic leather, various surface treatment agents, and the like. Furthermore, the polycarbonate polyol composition can be used as a modifier added to polyester, polyimide, polypropylene, polycarbonate, epoxy resin, and the like, and as a raw material for active energy ray-curable compounds such as urethane (meth)acrylate.

[0141] The coating composition of the present embodiment has excellent drying properties, chemical resistance, and weather resistance, and has high hardness, and therefore can be suitably used in a wide range of fields, such as coating exterior or interior materials for automobiles, buses, railway vehicles, construction machinery, agricultural machinery, etc., floors, walls, and roofs of buildings, metal products, mortar and concrete products, woodworking products, plastic products, ceramic building materials such as calcium silicate boards and gypsum boards, films, etc.

[0142] The fields of use of the polycarbonate polyol composition of this embodiment when used as an adhesive composition or pressure-sensitive adhesive composition are not particularly limited, and examples include automobiles, building materials or home appliances, woodworking, and laminates for solar cells. Among these, optical components for liquid crystal displays of home appliances such as televisions, personal computers, digital cameras, and mobile phones exhibit various functions, so it is preferable to laminate films and plates of various adherends. Since sufficient adhesion, bonding properties, and high film strength are required between the films and plates of various adherends, this is a preferred example of using the polycarbonate polyol composition of this embodiment as a pressure-sensitive adhesive composition or adhesive composition.

[0143] The synthetic leather of this embodiment contains a polyurethane resin containing the polycarbonate polyol composition described above. The synthetic leather of this embodiment is, for example, a synthetic leather in which a base fabric, an adhesive layer, an intermediate layer, and a surface layer are laminated in this order, and preferably contains a polyurethane resin made from the polycarbonate polyol composition. In the synthetic leather of this embodiment, the polyurethane resin is preferably contained in the adhesive layer and / or the intermediate layer, and the synthetic leather of this embodiment preferably contains the polyurethane resin described above because it makes it possible to reduce the amount of organic solvent used during production.

[0144] The adherend for which the polyurethane resin of the present embodiment can be used is not particularly limited, and examples thereof include various metals such as glass, aluminum, iron, galvanized steel plate, copper, and stainless steel; porous materials such as wood, paper, mortar, and stone; materials coated with fluorine paint, urethane paint, acrylic urethane paint, and the like; cured products of silicone-based, modified silicone-based, and urethane-based sealants; rubbers such as vinyl chloride, natural rubber, and synthetic rubber; leathers such as natural leather and artificial leather; fibers such as plant-based, animal-based, carbon fiber, and glass fiber; nonwoven fabrics; films and plates of resins such as polyester, acrylic, polycarbonate, triacetyl cellulose, and polyolefin; active energy ray-curable resin layers; and inks such as printing ink and UV ink.

[0145] The present invention will be explained in more detail below by way of examples and comparative examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention.

[0146] In the examples and comparative examples, the physical properties and evaluations of the polyisocyanate compositions were measured as follows. Unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass." The physical properties of the polycarbonate polyol compositions obtained here can be considered to be equivalent to those of polycarbonate polyols.

[0147] <Measurement method>

[0148] [Physical Property 1: Melt Viscosity] After preheating the polycarbonate polyol composition to 50°C, the melt viscosity was measured at 50°C using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., TVE-22HT, rotor: 1°34' x R24). The rotation speed was as follows:

[0149] (Rotation speed) 100 rpm (for less than 512 mPa・s) 50 rpm (for 512 mPa・s or more but less than 1,024 mPa・s) 20 rpm (for 1,024 mPa・s or more but less than 2,560 mPa・s) 10 rpm (for 2,560 mPa・s or more but less than 5,120 mPa・s) 5 rpm (for 5.12 Pa・s or more but less than 10.24 Pa・s) 2.5 rpm (for 10.24 Pa・s or more but less than 20.48 Pa・s) 1.0 rpm (When the viscosity is 20.48 Pa·s or more and less than 51.20 Pa·s) 0.5 rpm (When the viscosity is 51.20 Pa·s or more and less than 102.4 Pa·s)

[0150] [Physical Property 2: Measurement of Hydroxyl Value (OHV)] An acetylation reagent was prepared by adding pyridine to 12.5 g of acetic anhydride in a volumetric flask to make a 50 mL solution. 1.0 to 10.0 g of sample was precisely weighed and placed in a 100 mL recovery flask. 5 mL of acetylation reagent and 10 mL of toluene were added to the recovery flask using a volumetric pipette to obtain a solution. A condenser was then attached to the recovery flask, and the solution was heated and stirred at 100°C for 1 hour. 2.5 mL of distilled water was added to the recovery flask using a volumetric pipette, and the resulting solution was heated and stirred for an additional 10 minutes. After cooling the solution for 2 to 3 minutes, 12.5 mL of ethanol was added to the recovery flask. After adding 2 to 3 drops of phenolphthalein as an indicator, the solution was titrated with 0.5 mol / L ethanolic potassium hydroxide. 5 mL of the acetylation reagent, 10 mL of toluene, and 2.5 mL of distilled water were placed in a 100 mL recovery flask and heated and stirred for 10 minutes. The resulting solution was then titrated in the same manner (blank test). Based on this result, the hydroxyl value (OHV) was calculated using the following formula (i): hydroxyl value (mg KOH / g) = {(b - a) × 28.05 × f} / e (i) In formula (i), a represents the titration volume (mL) of the sample, b represents the titration volume (mL) of the blank test, e represents the sample weight (g), and f represents the titrant factor.

[0151] [Physical Property 3: Molecular Weight Measurement (GPC)] The number average molecular weight (Mn) of the polycarbonate polyol composition was measured by GPC using the following method: The polycarbonate polyol compositions obtained in the examples and comparative examples described below were prepared with tetrahydrofuran (hereinafter also referred to as "THF") to a concentration of 0.5% by mass, and the number average molecular weight (Mn) was measured at 22.0 to 36.5 min in terms of standard polystyrene using the following GPC apparatus. GPC device: HLC-8320 manufactured by Tosoh Corporation Analytical columns: 1 TSKgel G4000H, 1 G3000H, 2 G2000H Guard column: TSKgel guard column HXL-L Reference column: TSKgel Super H-RC Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Column temperature: 40°C RI detector: RI (built into the device HLC-8320) Calibration curve: Standard polystyrene (manufactured by Tosoh Corporation)

[0152] [Physical Property 4: Average Number of Hydroxyl Groups] The average number of hydroxyl groups (n) per molecule of polycarbonate polyol was calculated using the number average molecular weight (Mn) calculated in terms of standard polystyrene obtained by the method in Physical Property 3 and the hydroxyl value obtained by the method in Physical Property 2, using the following formula (ii): Average number of hydroxyl groups (n) = (Mn) × ([OHV] × 10 －３ / 56.1) ...(ii)

[0153] [Physical Property 5: Hazen Color Index (APHA)] In accordance with JIS K0071-1 (2017), the APHA of the polycarbonate polyol compositions obtained in the examples and comparative examples described below was measured by comparing with a standard solution placed in a colorimetric tube. The reagent used was a 1000 degree color standard solution (Fujifilm Wako Pure Chemical Industries, Ltd.). Solutions were prepared in increments of 5 up to APHA 30 and evaluated.

[0154] [Physical Property 6: １３C-NMR Measurement] The molar ratio (carbonate group / quaternary carbon group) of the carbonate group derived from the polycarbonate structure represented by the following general formula (III) to the quaternary carbon group derived from the alkyl chain structure represented by the following general formula (II) was calculated as follows: (In general formula (II), R ２１ , R ２２ , R ２３ and R ２４ is a group selected from the group consisting of an alkylene ether structure represented by general formula (I), a hydrogen group, a hydroxyl group, and a residue bonded via a divalent hydrocarbon group having from 1 to 20 carbon atoms, and the hydrocarbon group is a linear, branched, or cyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and may contain a hydroxyl group, an amino group, a sulfide group, an ether group, a carbonyl group, a carboxyl group, or a carbonate group. ２１ , R ２２ , R ２３ and R ２４ At least one of R is an alkylene ether structure represented by general formula (I). ２１ , R ２２ , R ２３ , R ２４ The hydrocarbon group may be of one type or of multiple types. (In general formula (III), R ３１ R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having from 2 to 15 carbon atoms. ３１ The hydrocarbon group of formula (I) is at least two kinds. n31 is any integer.) The integral values ​​of the carbonate group derived from the polycarbonate structure and the quaternary carbon group derived from the alkyl chain structure were measured by the following nuclear magnetic resonance (NMR). NMR apparatus: JEOL-ECZ500 Observation nucleus: １３ C Sample concentration: 50 mass / volume % Accumulation: 5,000 times Solvent: DMSO-d Measurement temperature: 30°C Chemical shift reference: TMS 0.00 ppm

[0155] [Physical Property 7: Molar Ratio of Carbonate Groups to Quaternary Carbon Groups] １３C-NMR was measured as in Physical Properties 6. １３ In C-NMR, the ratio (integral value (B) / integral value (A)) of the integral value of the signal derived from the carbonate group at 150 to 160 ppm to the integral value (A) of the signal derived from the quaternary carbon at 40 to 50 ppm was calculated, and this ratio was defined as the molar ratio (carbonate group / quaternary carbon group) of the carbonate group derived from the polycarbonate structure to the quaternary carbon group derived from the alkyl chain structure.

[0156] [Physical Property 8: Molar Fraction of Diol Compound (Excluding Alkylene Oxide Group-Containing Polyhydric Alcohol)] Hydrolysis of the polycarbonate polyol compositions obtained in the examples and comparative examples described below was carried out by the following method. 1 g of the sample was placed in a 100 mL recovery flask, followed by 30 g of ethanol and 4 g of potassium hydroxide, and the mixture was reacted at 100°C for 1 hour. After cooling to room temperature, 2 to 3 drops of phenolphthalein were added to the recovery flask as an indicator, and the mixture was neutralized with hydrochloric acid. The recovery flask was cooled in a refrigerator for at least 1 hour, and the precipitated salt was removed by filtration to obtain a filtrate.

[0157] The filtrate obtained by hydrolysis was analyzed by gas chromatography. A calibration curve was prepared in advance using each known diol compound as a standard substance, and the mass fraction was calculated from the area ratio obtained by gas chromatography (GC). The analysis was performed using a gas chromatograph GC-2014 (Shimadzu Corporation) equipped with a DB-WAX (J&W) column and a flame ionization detector (FID) as the detector. The column temperature profile was as follows: 60°C was maintained for 5 minutes, and then the temperature was increased to 250°C at a rate of 10°C / min. The molar ratio of the diol compound (excluding polyhydroxy compounds having an oxyethylene structure) was calculated from the mass fraction obtained by gas chromatography and the molecular weight of each diol compound.

[0158] [Physical Property 9: Metal Species of Transesterification Catalyst] The metal species of the transesterification catalyst in the polycarbonate polyol composition was confirmed by ICP-MS (inductively coupled plasma mass spectrometry).

[0159] [Physical Property 10: Structures (I) to (III) of Polycarbonate Polyol] In the polycarbonate polyol, the alkylene ether structure represented by the general formula (I) is １ The presence of an alkyl group adjacent to the ether group was confirmed by H-NMR, and the alkyl chain structure represented by general formula (II) was １３ The presence of quaternary carbon was confirmed by C-NMR, and the polycarbonate structure represented by general formula (III) was １３ The presence of a carbonate structure by C-NMR, １ This was confirmed by H-NMR by the presence of an alkyl group adjacent to the carbonate group.

[0160] <Evaluation Method> [Evaluation 1: Appearance of Polycarbonate Polyol Composition] The polycarbonate polyol composition synthesized in the Synthesis Example was placed in a 20 mL glass bottle, heated at 80° C., and stored at 23° C. for 7 days, after which the appearance was visually observed. [Evaluation Criteria] ○: No turbidity was observed in the composition (transparent) △: Slight turbidity was observed in the composition ×: Turbidity was observed in the composition

[0161] [Evaluation 2: Appearance (Transmittance) of Polycarbonate Diol Composition] The transmittance of the polycarbonate diol compositions synthesized in the Synthesis Examples was measured at 23°C using an ultraviolet-visible spectrophotometer, and evaluated according to the following criteria. <Measurement conditions> Apparatus: JASCO V-65, JASCO Corporation Measurement wavelength: 550 nm Cell length: 20 mm [Evaluation criteria] ○: Transmittance is 80% or more △: Transmittance is 50% or more but less than 80% ×: Transmittance is less than 50%

[0162] Preparation Example 1: Production of Coating Composition The polycarbonate polyol composition obtained in Examples 1 to 21 or the Comparative Example and polyisocyanate (product name: Duranate TPA-100, manufactured by Asahi Kasei Corporation, isocyanate content: 23.1% by mass) were weighed out so that the NCO / OH ratio was 1.00. Butyl acetate was then added so that the solids content was 50% by mass, and the mixture was stirred using a propeller blade at 600 rpm for 10 minutes to obtain a coating composition.

[0163] [Preparation Example 2: Production of aqueous coating composition] The polycarbonate polyol composition obtained in Example 22 was dissolved in propylene glycol monomethyl ether acetate to a solid content of 70% by mass to obtain a solution. The solution was added to pure water to a solid content of 20% by mass, and the mixture was stirred using a propeller blade at 1000 rpm for 10 minutes to obtain an aqueous dispersion. To this aqueous dispersion was added an isocyanate compound (product name: Duranate WT31-100, manufactured by Asahi Kasei Corporation, isocyanate content: 17.4% by mass) so that the NCO / OH ratio was 1.25, and further a leveling agent (BYK-331, manufactured by BYK) and a crosslinking reaction catalyst (Borchers LH10, ​​manufactured by OMG Borchers) were added in amounts of 0.3% by mass and 3.0% by mass, respectively, based on the total of the polycarbonate polyol composition and the isocyanate compound, and water was adjusted to a solids content of 35% by mass. The mixture was stirred with a propeller blade at 1000 rpm for 10 minutes to obtain an aqueous coating composition.

[0164] [Evaluation 3: Appearance of coating film] The coating composition prepared in Preparation Example was applied to a glass plate so that the resin film thickness was 50 μm. After drying at 60° C. for 30 minutes and aging at 23° C. / 50% RH for 7 days, the appearance was visually observed. [Evaluation criteria] ○: No turbidity was observed in the coating film △: Slight turbidity was observed in the coating film ×: Turbidity was observed in the coating film

[0165] [Evaluation 4: Coating film appearance (haze value)] The coating composition prepared in each preparation example was applied to a cationic electrodeposited plate (JIS G3141: SPCC-SD) so that the resin film thickness was 50 μm. The coating was dried at 60°C for 30 minutes and aged at 23°C / 50% RH for 7 days. Thereafter, the 20° reflected haze value of the resulting coating film was measured using a Haze-Gloss (manufactured by BYK Gardnar). [Evaluation criteria] ○: Haze value is 0.5% or less △: Haze value is more than 0.5% and 2.0% or less ×: Haze value is greater than 2.0% or is ineligible for evaluation

[0166] [Evaluation 5: Curability] The coating composition prepared in Preparation Example was applied to a polypropylene plate so that the resin film thickness was 50 μm. After drying at 60° C. for 30 minutes, the plate was aged at 23° C. / 50% RH for 1.3 days. The coating film was peeled off and its mass was measured. The peeled coating film (film) was immersed in acetone at 23° C. for 24 hours, and then dried at 105° C. for 60 minutes, and its mass was measured. The ratio of the mass after immersion to the mass before immersion was defined as the gel fraction (mass%) to evaluate the curability. [Evaluation Criteria] ○: Gel fraction exceeds 80 mass% △: Gel fraction is 50 mass% or more and 80 mass% or less ×: Gel fraction is less than 50 mass%

[0167] [Evaluation 6: Drying] The coating composition prepared in Preparation Example was applied to a glass plate to a film thickness of 50 μm. After drying at 60° C. for 30 minutes, curing was started at 23° C. / 50% RH. After 28 hours, a cotton ball (cylindrical, 2.5 cm in diameter, 2.0 cm in height) was placed on the coating film, and a 100 g weight was placed on top of it for 60 seconds. The weight and cotton were then removed, and the cotton marks remaining on the coating film were observed. [Evaluation Criteria] ○: No cotton marks were visible △: A slight cotton mark remained ×: A clear cotton mark remained

[0168] [Evaluation 7: Hardness] The coating composition prepared in Preparation Example was applied to a glass plate to a film thickness of 40 μm. After drying at 60° C. for 30 minutes, the plate was stored at 23° C. / 50% RH. After one week, the coating film was measured for Konig hardness (cycles) using a Konig hardness tester (manufactured by BYK Garder, trade name "Pendulum hardness tester"). [Evaluation criteria] ○: 80 cycles or more △: 50 cycles or more but less than 80 cycles ×: Less than 50 cycles

[0169] [Evaluation 8: Film Strength] The coating composition prepared in Preparation Example was applied to a polypropylene plate so that the resin film thickness was 60 μm. After drying at 60°C for 30 minutes, the film was aged at 23°C / 50% RH for 7 days. The coating film was peeled off, and the breaking elongation of the resulting cured resin film was measured using a Tensilon RTE-1210 (trade name) manufactured by A&D. The strength of the coating film was evaluated according to the following evaluation criteria based on the stress value when the coating film was stretched 50%. The results are shown in Tables 1 to 5. The stress value was measured under the following conditions: Tensile speed: 10 mm / min; Sample dimensions: Length 20 mm x Width 10 mm x Thickness 60 μm; Measurement environment: Temperature 23°C, humidity 50% RH [Evaluation criteria] ○: Stress value is 5 MPa or more; △: Stress value is 3 MPa or more but less than 5 MPa; ×: Stress value is less than 3 MPa

[0170] [Evaluation 9: Chemical resistance of coating film (resistance to oleic acid)] The coating composition prepared in Preparation Example was applied to a glass plate to a film thickness of 50 μm. After drying at 60° C. for 30 minutes, it was stored at 23° C. / 50% RH for 1 week. A cotton ball impregnated with oleic acid was left on the surface of the coating film for 1 minute, and the appearance was visually observed. [Evaluation criteria] ○: No abnormalities were observed in the appearance. △: Marks were observed around the cotton ball. ×: Marks of sagging were observed on the surface of the cotton ball.

[0171] Synthesis of Polycarbonate Polyol Precursor Synthesis Example 1 Synthesis of Polycarbonate Polyol Precursor A-1 230 g of 1,5-pentanediol, 250 g of 1,6-hexanediol, and 400 g of ethylene carbonate were charged into a glass flask (hereinafter also referred to as the "reactor") equipped with a rectification column filled with structured packing and a stirrer, followed by the addition of 0.0468 g of titanium tetra-n-butoxide as a catalyst. The reactor was immersed in an oil bath, and the reaction was carried out at 165°C for 12 hours while removing a portion of the distillate. The reactor was then directly connected to a condenser, and the temperature of the oil bath was raised to 180°C. The pressure was then gradually reduced, and the reaction was carried out for an additional 6 hours, yielding Polycarbonate Polyol Precursor A-1, which was a liquid at room temperature. The resulting Polycarbonate Polyol Precursor A-1 had a hydroxyl value of 55.2 mgKOH / g and a number average molecular weight of 2,030.

[0172] Synthesis Example 2 (Synthesis of Polycarbonate Polyol Precursor A-2) 458 g of 1,5-pentanediol, 500 g of 1,6-hexanediol, and 760 g of ethylene carbonate were charged into a reactor similar to that used in Synthesis Example 1, followed by the addition of 0.086 g of titanium tetra-n-butoxide as a catalyst. The reactor was immersed in an oil bath, and the reaction was carried out at 165°C for 12 hours while removing a portion of the distillate. The reactor was then directly connected to a condenser, and the temperature of the oil bath was raised to 180-190°C. The pressure was then gradually reduced, and the reaction was carried out for an additional 3 hours, yielding Polycarbonate Polyol Precursor A-2, which was a liquid at room temperature. The resulting Polycarbonate Polyol Precursor A-2 had a hydroxyl value of 110.0 mgKOH / g and a number average molecular weight of 1,020.

[0173] Synthesis Example 3 Synthesis of Polycarbonate Polyol Precursor A-3 400 g of 1,4-butanediol, 200 g of 1,6-hexanediol, and 540 g of ethylene carbonate were charged into a reactor similar to that used in Synthesis Example 1, followed by the addition of 0.15 g of titanium tetra-n-butoxide as a catalyst. The reactor was immersed in an oil bath, and the reaction temperature was gradually increased from 150°C to 180°C. The reaction was carried out for 20 hours while distilling off the resulting mixture of ethylene glycol and ethylene carbonate. The pressure was then gradually reduced, and the reaction was carried out for an additional 10 hours at 185°C while distilling off the diol and ethylene carbonate, yielding Polycarbonate Polyol Precursor A-3. The resulting Polycarbonate Polyol A-3 had a hydroxyl value of 55.4 mgKOH / g and a number average molecular weight of 2,020.

[0174] Synthesis Example 4 Synthesis of Polycarbonate Polyol Precursor A-4 250 g of 1,4-butanediol, 270 g of 1,6-hexanediol, and 445 g of ethylene carbonate were charged into a reactor similar to that used in Synthesis Example 1, followed by the addition of 0.096 g of titanium tetra-n-butoxide as a catalyst. The reactor was immersed in an oil bath, and the reaction was carried out at 160°C for 20 hours while removing a portion of the distillate. The reactor was then directly connected to a condenser, and the temperature of the oil bath was raised to 180°C. The pressure was then gradually reduced, and the reaction was carried out for an additional 8 hours, yielding Polycarbonate Polyol Precursor A-4, which was a liquid at room temperature. The resulting Polycarbonate Polyol Precursor A-4 had a hydroxyl value of 55.8 mgKOH / g and a number average molecular weight of 2,010.

[0175] Synthesis Example 5 Synthesis of Polycarbonate Polyol Precursor A-5 550 g of 2-methyl-1,3-propanediol, 423 g of 1,4-butanediol, and 952 g of ethylene carbonate were charged into a reactor similar to that used in Synthesis Example 1, followed by the addition of 0.1925 g of titanium tetra-n-butoxide as a catalyst. The reactor was immersed in an oil bath, and the reaction was carried out at 155°C for 25 hours while removing a portion of the distillate. The reactor was then directly connected to a condenser, and the temperature of the oil bath was raised to 170°C. The pressure was then gradually reduced, and the reaction was carried out for an additional 5 hours, yielding Polycarbonate Polyol Precursor A-5, which was a liquid at room temperature. The resulting Polycarbonate Polyol Precursor A-5 had a hydroxyl value of 53.0 mgKOH / g and a number average molecular weight of 2,117.

[0176] Synthesis Example 6 Synthesis of Polycarbonate Polyol Precursor A-6 346 g of 1,3-propanediol, 40 g of 1,6-hexanediol, and 430 g of ethylene carbonate were charged into a reactor similar to that used in Synthesis Example 1, followed by the addition of 0.08 g of titanium tetra-n-butoxide as a catalyst. The reactor was immersed in an oil bath, and the reaction was carried out at 160 to 170°C for 12 hours while removing a portion of the distillate. The reactor was then directly connected to a condenser, and the temperature of the oil bath was raised to 180°C. The pressure was then gradually reduced, and the reaction was further carried out to obtain Polycarbonate Polyol Precursor A-6, which was a liquid at room temperature. The resulting Polycarbonate Polyol A-6 had a hydroxyl value of 56.2 mgKOH / g and a number average molecular weight of 1,997.

[0177] Synthesis Example 7 Synthesis of Polycarbonate Polyol Precursor A-7 335 g of 1,4-butanediol, 195 g of 1,10-decanediol, and 405 g of dimethyl carbonate were charged into a reactor similar to that used in Synthesis Example 1, followed by the addition of 0.0936 g of titanium tetra-n-butoxide as a catalyst. The reactor was immersed in an oil bath, and the reaction was carried out at 160°C for 10 hours while removing a portion of the distillate. The reactor was then directly connected to a condenser, and the temperature of the oil bath was raised to 185°C. The pressure was then gradually reduced, and the reaction was carried out for an additional 2 hours, yielding Polycarbonate Polyol Precursor A-7, which was waxy at room temperature. The resulting Polycarbonate Polyol Precursor A-7 had a hydroxyl value of 56.3 mgKOH / g and a number average molecular weight of 1,992.

[0178] Synthesis Example 8 Synthesis of Polycarbonate Polyol Precursor A-8 230 g of 1,5-pentanediol, 250 g of 1,6-hexanediol, and 400 g of ethylene carbonate were charged into a reactor similar to that used in Synthesis Example 1, followed by the addition of 19.6 mg of manganese (II) acetate tetrahydrate and 4.8 mg of lithium methoxide as catalysts. The reactor was immersed in a heated oil bath, and polycondensation was carried out by transesterification for 3 hours at an internal flask temperature of 150°C and a vacuum of 4 kPa while a portion of the distillate was withdrawn. The reaction was then switched to simple distillation, and the pressure was gradually reduced to 0.5 kPa while the reaction was carried out for 1 hour at an internal flask temperature of 160-170°C, and the monomer was distilled off to obtain Polycarbonate Diol Precursor A-8. The resulting Polycarbonate Diol Precursor A-8 had a hydroxyl value of 56.2 mg KOH / g and a number average molecular weight of 1,996.

[0179] Synthesis Example 9 (Synthesis of Polycarbonate Polyol Precursor A-9) Mn(OAc) was used as a catalyst. ２ ・4H ２ Polycarbonate diol precursor A-9 was obtained in the same manner as in Synthesis Example 8, except that 19.6 mg of O and 2.1 mg of a 28% methanol solution of sodium methoxide were added. The hydroxyl value of the obtained polycarbonate diol precursor A-9 was 56.4 mg KOH / g, and the number average molecular weight was 1,989.

[0180] Synthesis Example 10 Synthesis of Polycarbonate Polyol Precursor A-10 536 g of 1,6-hexanediol and 400 g of ethylene carbonate were charged into a reactor similar to that used in Synthesis Example 1, followed by the addition of 0.0475 g of titanium tetra-n-butoxide as a catalyst. The reactor was immersed in an oil bath, and the reaction was carried out at 165°C for 12 hours while removing a portion of the distillate. The reactor was then directly connected to a condenser, and the temperature of the oil bath was raised to 180°C. The pressure was then gradually reduced, and the reaction was carried out for an additional 3 hours, yielding Polycarbonate Polyol Precursor A-10, which was solid at room temperature. The resulting Polycarbonate Polyol Precursor A-10 had a hydroxyl value of 55.2 mgKOH / g and a number average molecular weight of 2,033.

[0181] Synthesis Example 11 (Synthesis of Polycarbonate Polyol Precursor A-11) 230 g of 1,5-pentanediol, 250 g of 1,6-hexanediol, and 400 g of ethylene carbonate were charged into a reactor similar to that used in Synthesis Example 1, followed by the addition of 0.0468 g of titanium tetra-n-butoxide as a catalyst. The reactor was immersed in an oil bath, and the reaction was carried out at 165°C for 12 hours while removing a portion of the distillate. The reactor was then directly connected to a condenser, and the temperature of the oil bath was raised to 180°C. The pressure was then gradually reduced, and the reaction was carried out for an additional 12 hours to obtain Polycarbonate Polyol Precursor A-11, which was a liquid at room temperature. The resulting polycarbonate polyol A-11 had a hydroxyl value of 37.5 mgKOH / g and a number average molecular weight of 2,992.

[0182] Synthesis Example 12 Synthesis of Polycarbonate Polyol Precursor A-12 Polycarbonate polyol precursor A-12 was obtained by synthesis in the same manner as in Synthesis Example 1, except that 0.20 g of a 28% methanol solution of sodium methoxide was used as the catalyst instead of titanium tetra-n-butoxide. The hydroxyl value of the obtained polycarbonate polyol A-12 was 55.2 mgKOH / g and the number average molecular weight was 2,000.

[0183] <Synthesis and Evaluation of Polycarbonate Polyol Composition> [Example 1] A 1 L four-neck flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel was conditioned with a nitrogen atmosphere, and 500.0 g of the polycarbonate polyol precursor A-1 produced in Synthesis Example 1 and 292.9 g of a pentaerythritol-ethylene oxide (hereinafter abbreviated as EO) adduct (hydroxyl value: 716 mg KOH / g, manufactured by Nippon Nyukazai Co., Ltd., hereinafter abbreviated as B-1) were charged as raw materials, and the temperature inside the reactor was maintained at 150°C, and the mixture was stirred for 6 hours. The refractive index of the reaction solution was measured over time, and it was confirmed that the refractive index value had not changed. Thereafter, 85% phosphoric acid was added in an amount 2.0 times the molar ratio of phosphoric acid to titanium tetra-n-butoxide, and the reactor was heat-treated at 110°C for 3 hours to obtain polycarbonate polyol composition C-1. The various physical properties and evaluation results of the obtained polycarbonate polyol composition C-1 are shown in Table 1.

[0184] [Example 2] Polycarbonate polyol composition C-2 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-1 and 209.0 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The various physical properties and evaluation results of the obtained polycarbonate polyol composition C-2 are shown in Table 1.

[0185] [Example 3] Polycarbonate polyol composition C-3 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-1 and 138.0 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The various physical properties and evaluation results of the obtained polycarbonate polyol composition C-3 are shown in Table 1.

[0186] [Example 4] Polycarbonate polyol composition C-4 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-1 and 115.7 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The various physical properties and evaluation results of the obtained polycarbonate polyol composition C-4 are shown in Table 1.

[0187] [Example 5] Polycarbonate polyol composition C-5 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-1 and 85.5 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-5 are shown in Table 1.

[0188] [Example 6] Polycarbonate polyol composition C-6 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-1 and 37.5 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-6 are shown in Table 1.

[0189] Example 7 Polycarbonate polyol composition C-7 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-2 produced in Synthesis Example 2 and 193.2 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-7 are shown in Table 1.

[0190] [Example 8] Polycarbonate polyol composition C-8 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-2 and 123.7 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The various physical properties and evaluation results of the obtained polycarbonate polyol composition C-8 are shown in Table 2.

[0191] [Example 9] Polycarbonate polyol composition C-9 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-2 and 50.0 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-9 are shown in Table 2.

[0192] Example 10 Polycarbonate polyol composition C-10 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-3 produced in Synthesis Example 3 and 211.2 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-10 are shown in Table 2.

[0193] [Example 11] Polycarbonate polyol composition C-11 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-3 and 116.5 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The various physical properties and evaluation results of the obtained polycarbonate polyol composition C-11 are shown in Table 2.

[0194] Example 12 Polycarbonate polyol composition C-12 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-4 produced in Synthesis Example 4 and 115.9 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-12 are shown in Table 2.

[0195] Example 13 Polycarbonate polyol composition C-13 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-5 produced in Synthesis Example 5 and 211.4 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-13 are shown in Table 2.

[0196] Example 14 Polycarbonate polyol composition C-14 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-6 produced in Synthesis Example 6 and 204.9 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-14 are shown in Table 2.

[0197] Example 15 Polycarbonate polyol composition C-15 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-7 produced in Synthesis Example 7 and 114.3 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-15 are shown in Table 3.

[0198] Example 16 Polycarbonate polyol composition C-16 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-1 and 327.2 g of trimethylolpropane-EO adduct (hydroxyl value: 420 mgKOH / g, manufactured by Nippon Nyukazai Co., Ltd., hereinafter abbreviated as B-2) were charged as raw materials. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-16 are shown in Table 3.

[0199] Example 17 Polycarbonate polyol composition C-17 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-1 and 172.6 g of trimethylolpropane-EO adduct B-2 were charged as raw materials. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-17 are shown in Table 3.

[0200] Example 18 Polycarbonate polyol composition C-18 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-1 and 171.4 g of trimethylolpropane-EO adduct (hydroxyl value: 618 mgKOH / g, manufactured by Nippon Nyukazai Co., Ltd., hereinafter abbreviated as B-3) were charged as raw materials. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-18 are shown in Table 3.

[0201] Example 19 Polycarbonate polyol composition C-19 was obtained by synthesis in the same manner as in Example 3, except that the stirring temperature was set to 200°C and the amount of pentaerythritol-EO adduct B-1 was set to 137.1 g. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-19 are shown in Table 3.

[0202] Example 20 Polycarbonate polyol composition C-20 was obtained by synthesizing in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-1 produced in Synthesis Example 1, 173.9 g of pentaerythritol-propylene oxide adduct (hydroxyl value: 609 mgKOH / g, manufactured by Nippon Nyukazai Co., Ltd., hereinafter abbreviated as B-4) and 0.10 g of titanium tetra-n-butoxide were charged as raw materials into a reactor similar to that of Example 1, the temperature inside the reactor was maintained at 170°C, and the mixture was stirred for 12 hours. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-20 are shown in Table 3.

[0203] Example 21 A reactor similar to that used in Synthesis Example 1 was charged with 230 g of 1,5-pentanediol, 250 g of 1,6-hexanediol, 400 g of ethylene carbonate, and 102 g of pentaerythritol-EO adduct B-1, followed by the addition of 0.0600 g of titanium tetra-n-butoxide as a catalyst. The reactor was immersed in an oil bath, and the reaction was carried out at 165°C for 12 hours while removing a portion of the distillate. The reactor was then directly connected to a condenser, and the temperature of the oil bath was raised to 180°C. The pressure was then gradually reduced, and the reaction was carried out for an additional 6 hours, yielding polycarbonate polyol composition C-21, which is a liquid at room temperature. The various physical properties and evaluation results of the resulting polycarbonate polyol composition C-21 are shown in Table 3. The resulting polycarbonate polyol composition C-21 had a hydroxyl value of 265.3 mgKOH / g and a number average molecular weight of 800.

[0204] Example 22 Polycarbonate polyol composition C-22 was obtained by synthesis in the same manner as in Example 1, except that 435.0 g of polycarbonate polyol precursor A-1 produced in Synthesis Example 1, 100.5 g of pentaerythritol-EO adduct B-1, and 65.0 g of polyethylene glycol (trade name: Polyethylene Glycol 1000, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were charged as raw materials into the same reactor as in Example 1. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-22 are shown in Table 3.

[0205] Polycarbonate polyol composition C-23 was obtained by synthesis in the same manner as in Example 4, except that 22.0 mg of a 28% methanol solution of sodium methoxide was added as the catalyst. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-23 are shown in Table 4.

[0206] [Example 24] Polycarbonate polyol composition C-24 was obtained by synthesis in the same manner as in Example 4, except that 6.2 mg of calcium acetate monohydrate was added as the catalyst. The various physical properties and evaluation results of the obtained polycarbonate polyol composition C-24 are shown in Table 4.

[0207] [Example 25] Polycarbonate polyol composition C-25 was obtained by synthesis in the same manner as in Example 22, except that 85% phosphoric acid was not added. The various physical properties and evaluation results of the obtained polycarbonate polyol composition C-25 are shown in Table 4.

[0208] Example 26 Polycarbonate polyol composition C-26 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-8 produced in Synthesis Example 8 and 115.5 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-26 are shown in Table 4.

[0209] Example 27 Polycarbonate polyol composition C-27 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-9 produced in Synthesis Example 9 and 115.3 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-27 are shown in Table 4.

[0210] Example 28 Polycarbonate polyol composition C-28 was obtained by synthesis in the same manner as in Example 4, except that 1.84 g of Tinuvin 765 (trade name, manufactured by BASF) was added as an antioxidant. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-28 are shown in Table 4.

[0211] Example 29 Polycarbonate polyol composition C-29 was obtained by synthesis in the same manner as in Example 4, except that 1.84 g of Adekastab LA-52 (trade name, manufactured by ADEKA Corporation) was added as an antioxidant. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-29 are shown in Table 4.

[0212] Example 30 Polycarbonate polyol composition C-30 was obtained by synthesis in the same manner as in Example 4, except that 1.84 g of Adekastab LA-81 (trade name, manufactured by ADEKA Corporation) was added as an antioxidant. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-30 are shown in Table 4.

[0213] Example 31 Polycarbonate polyol composition C-31 was obtained by synthesis in the same manner as in Example 4, except that 1.23 g of Tinuvin 765 (trade name, manufactured by BASF) and 1.23 g of Tinuvin 400 (trade name, manufactured by BASF) were added as antioxidants. The physical properties and evaluation results of the obtained polycarbonate polyol composition C-31 are shown in Table 4.

[0214] In the polycarbonate polyol compositions of Examples 1 to 31, the polycarbonate polyol contained an alkylene ether structure represented by general formula (I), an alkyl chain structure represented by general formula (II), and a polycarbonate structure represented by general formula (III).

[0215] Comparative Example 1 Polycarbonate polyol composition D-1 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-10 synthesized in Synthesis Example 10 and 134.3 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The physical properties and evaluation results of the obtained polycarbonate polyol composition D-1 are shown in Table 5.

[0216] Comparative Example 2 Polycarbonate polyol composition D-2 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-1 and 50.1 g of pentaerythritol were charged as raw materials. The various physical properties and evaluation results of the obtained polycarbonate polyol composition D-2 are shown in Table 5.

[0217] Comparative Example 3 Polycarbonate polyol composition D-3 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-1 and 68.5 g of trimethylolpropane were charged as raw materials. The various physical properties and evaluation results of the obtained polycarbonate polyol composition D-3 are shown in Table 5.

[0218] Comparative Example 4 Polycarbonate polyol composition D-4 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-11 and 30.6 g of pentaerythritol-EO adduct B-1 were charged as raw materials. The physical properties and evaluation results of the obtained polycarbonate polyol composition D-4 are shown in Table 5.

[0219] Comparative Example 5 Polycarbonate polyol composition D-5 was obtained by synthesis in the same manner as in Example 1, except that 500.0 g of polycarbonate polyol precursor A-12 and 138.0 g of pentaerythritol-EO adduct B-1 were charged. The various physical properties and evaluation results of the obtained polycarbonate polyol composition D-5 are shown in Table 5.

[0220] Comparative Example 6 500.0 g of diethylene glycol, 31.2 g of trimethylolpropane-EO adduct B-3, 470.7 g of dimethyl carbonate, and 2.00 g of a 28% methanol solution of sodium methoxide as a catalyst were charged into the same reactor as in Synthesis Example 1. The mixture was heated in an oil bath set to 175°C, and the flask's internal temperature was maintained at 150°C for 4 hours, and the resulting methanol was removed. The distillation column was then replaced with a simple distillation apparatus, and the mixture was heated in an oil bath set to 165°C. Stirring was continued for 8 hours at an internal flask temperature of 150-155°C and a vacuum of 0.7 kPa, removing the diethylene glycol from the flask. Polycarbonate polyol composition D-6 was obtained through this reaction. The physical properties and evaluation results of the resulting polycarbonate polyol composition D-6 are shown in Table 6.

[0221] Comparative Example 7 Polycarbonate polyol composition D-7 was obtained by synthesis in the same manner as in Comparative Example 6, except that 0.28 g of titanium tetra-n-butoxide was used as the catalyst instead of the 28% methanol solution of sodium methoxide. The physical properties and evaluation results of the obtained polycarbonate polyol composition D-7 are shown in Table 6.

[0222] Comparative Example 8 Evaluation was carried out using polycarbonate polyol precursor A-2. The evaluation results are shown in Table 6.

[0223] Comparative Example 9 Evaluation was carried out using pentaerythritol-EO adduct B-1. The evaluation results are shown in Table 6.

[0224] Comparative Example 10 Evaluation was carried out using pentaerythritol. The evaluation results are shown in Table 6.

[0225] [Comparative Example 11] Polycarbonate polyol composition D-8 was obtained by mixing 500.0 g of polycarbonate polyol precursor A-1 and 138.0 g of pentaerythritol-EO adduct B-1 used in Example 3. The various physical properties and evaluation results of the obtained polycarbonate polyol composition D-8 are shown in Table 6.

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232] This application is based on a Japanese patent application (Patent Application No. 2024-102180) filed on June 25, 2024, the contents of which are incorporated herein by reference.

[0233] According to the present invention, it is possible to provide a liquid polycarbonate polyol composition that is low in viscosity, low in color, and does not generate turbidity. Furthermore, when used as a raw material for polyurethane resins, the polycarbonate polyol composition of the present invention exhibits excellent drying properties, appearance, hardness, chemical resistance, and film strength. Furthermore, the polycarbonate polyol composition of the present invention can be widely used in foams, elastomers, paints, coating agents, pressure-sensitive adhesives, adhesives, artificial leather, synthetic leather, aqueous polyurethane paints, etc.

Claims

1. A polycarbonate polyol composition comprising: a polycarbonate polyol having an alkylene ether structure represented by the following general formula (I), an alkyl chain structure represented by the following general formula (II), and a polycarbonate structure represented by the following general formula (III), wherein the average number of hydroxyl groups per molecule is 2.5 to 5.0; and a transesterification catalyst containing at least one metal selected from the group consisting of metals of Groups 4, 5, 6, 7, 8, 9, 10, and 11 of the long form periodic table; said polycarbonate polyol composition being liquid at 23°C and having a viscosity at 50°C of 500 mPa·s to 10,000 mPa·s. (In general formula (I), R １１ is a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having from 2 to 20 carbon atoms, R １２ is any one of the polycarbonate structure represented by general formula (III), a hydrogen group, or a hydrocarbon residue which may contain an ether group, a carboxyl group, or a carbonate group. １２ is a polycarbonate structure represented by general formula (III). １１ The hydrocarbon group may be of one type or of multiple types. n11 is an integer of 1 or more and 10 or less, and * represents a bond to the alkyl chain structure represented by general formula (II). (In general formula (II), R ２１ , R ２２ , R ２３ and R ２４ is a group selected from the group consisting of an alkylene ether structure represented by general formula (I), a hydrogen group, a hydroxyl group, and a residue bonded via a divalent hydrocarbon group having from 1 to 20 carbon atoms, and the hydrocarbon group is a linear, branched, or cyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and may contain a hydroxyl group, an amino group, a sulfide group, an ether group, a carbonyl group, a carboxyl group, or a carbonate group. ２１ , R ２２ , R ２３ and R ２４ At least one of R is an alkylene ether structure represented by general formula (I). ２１ , R ２２ , R ２３ , R ２４ The hydrocarbon group may be of one type or of multiple types. (In general formula (III), R ３１ R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having from 2 to 15 carbon atoms. ３１ There are at least two types of hydrocarbon groups. n31 is any integer.

2. R in the polycarbonate structure represented by the general formula (III) ３１ The polycarbonate polyol composition according to claim 1, wherein each of the groups is at least two of linear or branched hydrocarbon groups having 3 to 6 carbon atoms.

3. The polycarbonate polyol composition according to claim 1 or 2, wherein the mass ratio of the polycarbonate structure represented by general formula (III) in the polycarbonate polyol composition is 60 mass % or more and 90 mass % or less.

4. The polycarbonate polyol composition according to claim 1 or 2, wherein the molar ratio of carbonate groups derived from the polycarbonate structure represented by general formula (III) to quaternary carbon groups derived from the alkyl chain structure represented by general formula (II) (carbonate groups / quaternary carbon groups) is 10 or more and 50 or less.

5. The polycarbonate polyol composition according to claim 1 or 2, which is transparent at 23°C.

6. The polycarbonate polyol composition according to claim 1 or 2, having a Hazen color number (APHA) value of 100 or less.

7. The polycarbonate polyol composition according to claim 1 or 2, further comprising a transesterification catalyst containing at least one metal selected from the group consisting of metals of Groups 1 and 2 of the long form periodic table.

8. The polycarbonate polyol composition according to claim 1 or 2, wherein the alkyl chain structure represented by general formula (II) is an alkyl chain structure derived from a polyhydric alcohol, and the polyhydric alcohol is at least one selected from the group consisting of trimethylolpropane and pentaerythritol.

9. R in the alkylene ether structure represented by the general formula (I) １１ The polycarbonate polyol composition according to claim 1 or 2, wherein is a linear, branched, or cyclic aliphatic hydrocarbon group having from 2 to 3 carbon atoms.

10. The polycarbonate polyol composition according to claim 1 or 2, having a hydroxyl value of 50 mg KOH / g or more and 270 mg KOH / g or less.

11. The polycarbonate polyol composition according to claim 1 or 2, wherein the polycarbonate structure represented by general formula (III) further contains a polyoxyethylene structure represented by the following general formula (IV): (In general formula (IV), n41 is a number of 3 or more and 50 or less.) 12. A polyurethane resin comprising a reaction product of the polycarbonate polyol composition according to claim 1 or 2 and an isocyanate compound.

13. A coating composition comprising the polycarbonate polyol composition of claim 1 or 2.

14. An adhesive composition comprising the polycarbonate polyol composition of claim 1 or 2.

15. An aqueous polyurethane dispersion obtained by dispersing a polyurethane resin containing the polycarbonate polyol composition according to claim 1 or 2 in water.

16. Synthetic leather comprising a polyurethane resin containing the polycarbonate polyol composition according to claim 1 or 2.

17. A method for producing the polycarbonate polyol composition according to claim 1 or 2, comprising a step of transesterification and / or depolymerization of a polycarbonate polyol precursor derived from the following general formula (III) with an alkylene oxide group-containing alcohol derived from the following general formulas (I) and (II) in the presence of a transesterification catalyst: (In general formula (I), R １１ is a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having from 2 to 20 carbon atoms, R １２ is any one of the polycarbonate structure represented by general formula (III), a hydrogen group, or a hydrocarbon residue which may contain an ether group, a carboxyl group, or a carbonate group. １２ is a polycarbonate structure represented by general formula (III). １１ The hydrocarbon group may be of one type or of multiple types. n11 is an integer of 1 or more and 10 or less, and * represents a bond to the alkyl chain structure represented by general formula (II). (In general formula (II), R ２１ , R ２２ , R ２３ and R ２４ is a group selected from the group consisting of alkylene ether structures represented by general formula (I) or residues bonded via a hydrogen group, a hydroxyl group, and a divalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is a linear, branched, or cyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and may contain a hydroxyl group, an amino group, a sulfide group, an ether group, a carbonyl group, a carboxyl group, or a carbonate group. ２１ , R ２２ , R ２３ and R ２４ At least one of R is an alkylene ether structure represented by general formula (I). ２１ , R ２２ , R ２３ , R ２４ The hydrocarbon group may be of one type or of multiple types. (In general formula (III), R ３１ R is a divalent linear, branched, or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having from 2 to 15 carbon atoms. ３１ There are at least two types of hydrocarbon groups. n31 is any integer.

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