Polyurethane resin composition, artificial leather, synthetic leather, and leather surface treatment agent

Abstract

This polyurethane resin composition contains an isocyanate group-terminated urethane prepolymer (E) or a reaction product of the isocyanate group-terminated urethane prepolymer (E) and a chain extender (G), and a neutralizing agent (F), the isocyanate group-terminated urethane prepolymer (E) having an ester bond and including a reaction product of an organic acid (C), polyisocyanate (D), and a polyol (A1) including a polycarbonate polyol (B1) having an average number of hydroxyl functional groups exceeding 2, and the content of the polycarbonate polyol (B1) or the content of a urea group derived from the chain extender (G) satisfying specific conditions.

Description

Polyurethane resin composition, artificial leather, synthetic leather, and leather surface treatment agent

[0001] The present disclosure relates to a polyurethane resin composition, an artificial leather, a synthetic leather, and a surface treatment agent for leather.

[0002] Polycarbonate-based polyurethane resin compositions are advantageous in terms of hydrolysis resistance, heat resistance, abrasion resistance, chemical resistance, etc., and are therefore used in artificial leather, synthetic leather, natural leather, etc.

[0003] Patent Document 1 discloses a method for producing a polyurethane emulsion for an aqueous one-component coating agent, which comprises reacting an organic diisocyanate (a1), a high molecular weight polyol (a2) having a carbonate skeleton, and a carboxyl group-containing low molecular weight glycol (a3) ​​to produce a carboxyl group-containing isocyanate group-terminated urethane prepolymer (A), mixing this with a nonionic polar group-containing polyisocyanate (B), neutralizing the carboxyl groups in the system with a neutralizer (C), and then emulsifying the mixture in water and subjecting it to a chain extension reaction with water.

[0004] Japanese Patent Application Laid-Open No. 2005-247897

[0005] However, the polyurethane emulsion disclosed in Patent Document 1 does not provide balanced mechanical properties compared to solvent-based polyurethane resins, and an improvement in the 100% modulus is desired. Furthermore, the polyurethane emulsion disclosed in Patent Document 1 has insufficient shape stability when exposed to a high-temperature environment.

[0006] Therefore, one aspect of the present disclosure is directed to providing a polyurethane resin composition, artificial leather, synthetic leather, and a surface treatment agent for leather, which have a low 100% modulus and a high softening temperature.

[0007] Each aspect of the present disclosure includes the following embodiments: (1) A polyurethane resin composition comprising a reaction product of an isocyanate group-terminated urethane prepolymer (E) and a chain extender (G), and a neutralizing agent (F), wherein the isocyanate group-terminated urethane prepolymer (E) comprises a reaction product of a polyol (A1) comprising a polycarbonate polyol (B1) having an ester bond and having an average hydroxyl functionality of more than 2, an organic acid (C), and a polyisocyanate (D), or a reaction product of a polyol (A2), a multifunctional polyol (B2) different from the polyol (A2), the organic acid (C), and the polyisocyanate (D), wherein the multifunctional polyol (B2) is a polycarbonate polyol having an ester bond and having an average hydroxyl functionality of more than 2; the polyurethane resin composition, wherein the content of the urea group derived from the chain extender (G) is 0.05 to 1.00 mmol / g relative to the total mass of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G). (2) The polyurethane resin composition according to (1), comprising: a reaction product of an isocyanate-terminated urethane prepolymer (E) and a chain extender (G); and a neutralizing agent (F), wherein the isocyanate-terminated urethane prepolymer (E) comprises a reaction product of a polyol (A2), a multifunctional polyol (B2) different from the polyol (A2), an organic acid (C), and a polyisocyanate (D), wherein the multifunctional polyol (B2) is a polycarbonate polyol having an ester bond and an average number of hydroxyl functional groups exceeding 2, and wherein the content of urea groups derived from the chain extender (G) in the polyurethane resin composition is 0.05 to 1.00 mmol / g relative to the sum of the mass of the isocyanate-terminated urethane prepolymer (E) and the mass of the chain extender (G).(3) The polyurethane resin composition according to (1) or (2), wherein the chain extender (G) is one or more selected from the group consisting of an amine compound having one or more primary or secondary amino groups, and water. (4) The polyurethane resin composition according to any one of (1) to (3), wherein the chain extender (G) comprises an amine compound having one or more primary or secondary amino groups, and the content of urea groups derived from the amine compound in the polyurethane resin composition is more than 0 mmol / g and 0.95 mmol / g or less relative to the sum of the mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G). (5) The polyurethane resin composition according to any one of (1) to (4), wherein the chain extender (G) comprises an amine compound having one or more primary or secondary amino groups, and the content of urea groups derived from the amine compound in the polyurethane resin composition is more than 0 mol% and not more than 99 mol% relative to the content of urea groups derived from the chain extender (G). (6) The polyurethane resin composition according to any one of (1) to (5), wherein the chain extender (G) comprises water, and the content of urea groups derived from water in the polyurethane resin composition is more than 0 mmol / g and not more than 0.95 mmol / g relative to the sum of the mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G). (7) The polyurethane resin composition according to any one of (1) to (6), further comprising a curing agent (X). (8) The polyurethane resin composition according to any one of (1) to (7), wherein the content of the polycarbonate polyol (B1) is 5 to 99% by mass relative to the content of the polyol (A1), or the content of the multifunctional polyol (B2) is 5 to 99% by mass relative to the total content of the polyol (A2) and the multifunctional polyol (B2).(9) A polyurethane resin composition comprising an isocyanate group-terminated urethane prepolymer (E) and a neutralizing agent (F), wherein the isocyanate group-terminated urethane prepolymer (E) is a reaction product of a polyol (A1) containing a polycarbonate polyol (B1) having an ester bond and having an average hydroxyl functionality of more than 2, an organic acid (C), and a polyisocyanate (D), or a reaction product of a polyol (A2), a multifunctional polyol (B2) different from the polyol (A2), the organic acid (C), and the polyisocyanate (D), wherein the multifunctional polyol (B2) is a polycarbonate polyol having an ester bond and having an average hydroxyl functionality of more than 2, wherein the content of the polycarbonate polyol (B1) is 40 to 99 mass% based on the content of the polyol (A1). (10) The polyurethane resin composition according to (9), comprising: an isocyanate group-terminated urethane prepolymer (E); and a neutralizing agent (F), wherein the isocyanate group-terminated urethane prepolymer (E) comprises a reaction product of a polyol (A2), a multifunctional polyol (B2) different from the polyol (A2), an organic acid (C), and a polyisocyanate (D), wherein the multifunctional polyol (B2) is a polycarbonate polyol having an ester bond and an average number of hydroxyl functional groups exceeding 2, and wherein the content of the multifunctional polyol (B2) is 40 to 99 mass% of the total content of the polyol (A2) and the multifunctional polyol (B2). (11) The polyurethane resin composition according to any one of (1) to (10), wherein the polyol (A1) containing the polycarbonate polyol (B1) has an average hydroxyl value of 30 to 150 mgKOH / g, or the polyol (A2) and the multifunctional polyol (B2) have an average hydroxyl value of 30 to 150 mgKOH / g.(12) The polyurethane resin composition according to any one of (1) to (11), wherein the polycarbonate polyol (B1) or the multifunctional polyol (B2) comprises a transesterification product of a polycarbonate polyol (b-1) and a polyester polyol (b-2) having an average hydroxyl functionality of 3 or more, or a transesterification product of a polycarbonate polyol (b-1), a polyester polyol (b-2) having an average hydroxyl functionality of 3 or more, and a polyester polyol (b-3) having an average hydroxyl functionality of 2 or more but less than 3. (13) The polycarbonate polyol (B1) or the polyfunctional polyol (B2) has an average hydroxyl functionality of 2.1 to 3.5, the polycarbonate polyol (B1) or the polyfunctional polyol (B2) has a hydroxyl value of 40 to 500 mgKOH / g, and the polycarbonate polyol (B1) or the polyfunctional polyol (B2) has a number average molecular weight of 400 to 4,000 g / mol. The polyurethane resin composition according to any one of (1) to (13), wherein the mass ratio of the polycarbonate polyol (b-1) to the polyester polyol (b-2) ([mass of (b-1)] / [mass of (b-2)]) is 90 / 10 to 10 / 90, or the mass ratio of the polycarbonate polyol (b-1) to the sum of the polyester polyol (b-2) and the polyester polyol (b-3) ([mass of (b-1)] / ([mass of (b-2)]+[mass of (b-3)])) is 95 / 5 to 5 / 95. (14) The polyurethane resin composition according to any one of (1) to (13), wherein the ester group concentration of the polycarbonate polyol (B1) or the multifunctional polyol (B2) is 10 to 90 mass%. (15) The polyurethane resin composition according to any one of (1) to (14), wherein the organic acid (C) is a dimethylol fatty acid. (16) The polyurethane resin composition according to any one of (1) to (15), wherein the neutralizing agent (F) is a basic neutralizing agent.(17) The polyurethane resin composition according to any one of (1) to (16), wherein the polyol (A1) contains a diol (A-2) and / or a tri- or higher functional polyhydric alcohol (A-3), or the polyol (A2) contains a diol (A-2) and / or a tri- or higher functional polyhydric alcohol (A-3). (18) A cured product obtained by curing the polyurethane resin composition according to any one of (1) to (17). (19) An artificial leather or synthetic leather comprising the cured product according to (18). (20) A leather surface treatment agent comprising the polyurethane resin composition according to any one of (1) to (18).

[0008] According to one aspect of the present disclosure, it is possible to provide a polyurethane resin composition, an artificial leather, a synthetic leather, and a surface treatment agent for leather, which have a low 100% modulus and a high softening temperature.

[0009] Exemplary embodiments for carrying out each aspect of the present disclosure will be described in further detail below, although the present disclosure is not limited to the following embodiments.

[0010] In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. Furthermore, the upper and lower limit values ​​described individually can be combined in any way.

[0011] A polyurethane resin composition according to a first aspect of the present disclosure comprises: a reaction product of an isocyanate-group-terminated urethane prepolymer (E) and a chain extender (G); and a neutralizing agent (F), wherein the isocyanate-group-terminated urethane prepolymer (E) comprises a reaction product of a polyol (A1) having an ester bond and including a polycarbonate polyol (B1) having an average hydroxyl group functionality of more than 2; an organic acid (C); and a polyisocyanate (D), wherein the content of urea groups derived from the chain extender (G) in the polyurethane resin composition is 0.05 to 1.00 mmol / g relative to the sum of the mass of the isocyanate-group-terminated urethane prepolymer (E) and the mass of the chain extender (G).

[0012] A polyurethane resin composition according to a modified example of the first aspect of the present disclosure includes: a reaction product of an isocyanate-group-terminated urethane prepolymer (E) and a chain extender (G); and a neutralizing agent (F), wherein the isocyanate-group-terminated urethane prepolymer (E) includes a reaction product of a polyol (A2), a multifunctional polyol (B2) different from the polyol (A2), an organic acid (C), and a polyisocyanate (D), wherein the multifunctional polyol (B2) is a polycarbonate polyol having an ester bond and an average number of hydroxyl functional groups exceeding 2, and wherein the content of urea groups derived from the chain extender (G) in the polyurethane resin composition is 0.05 to 1.00 mmol / g relative to the sum of the mass of the isocyanate-group-terminated urethane prepolymer (E) and the mass of the chain extender (G).

[0013] A polyurethane resin composition according to a second aspect of the present disclosure comprises an isocyanate group-terminated urethane prepolymer (E) and a neutralizing agent (F), wherein the isocyanate group-terminated urethane prepolymer (E) comprises a reaction product of a polyol (A1) containing a polycarbonate polyol (B1) having an ester bond and having an average hydroxyl functional group number of more than 2, an organic acid (C), and a polyisocyanate (D), and the content of the polycarbonate polyol (B1) is 40 to 99 mass% based on the content of the polyol (A1).

[0014] A polyurethane resin composition according to a modified example of the second aspect of the present disclosure comprises an isocyanate group-terminated urethane prepolymer (E) and a neutralizing agent (F), wherein the isocyanate group-terminated urethane prepolymer (E) comprises a reaction product of a polyol (A2), a multifunctional polyol (B2) different from the polyol (A2), an organic acid (C), and a polyisocyanate (D), wherein the multifunctional polyol (B2) is a polycarbonate polyol having an ester bond and an average number of hydroxyl functional groups exceeding two, and the content of the multifunctional polyol (B2) is 40 to 99 mass% of the total content of the polyol (A2) and the multifunctional polyol (B2).

[0015] In the following description, when simply referred to as a "polyurethane resin composition," this "polyurethane resin composition" includes both the polyurethane resin composition according to the first embodiment and its modified examples, and the polyurethane resin composition according to the second embodiment and its modified examples.

[0016] Components (A) to (F) and (G) of the polyurethane resin composition, as well as other components that may be contained therein, will be described below.

[0017] <Polyol (A1), Polyol (A2)> The polyol (A1) contains a polycarbonate polyol (B1) having an ester bond and an average number of hydroxyl functional groups exceeding 2. Examples of polyols other than the polycarbonate polyol (B1) contained in the polyol (A1) include polyester polyols, polyether polyols, polycarbonate polyols (excluding the polycarbonate polyol (B1)), polyolefin polyols, and polyols (A-1) formed from any combination of two or more of these.

[0018] Examples of the polyol (A2) include polyester polyols, polyether polyols, polycarbonate polyols (however, different from the polyfunctional polyol (B2)), polyolefin polyols, and polyols (A-1) consisting of any combination of two or more of these.

[0019] Preferred polyester polyols include polyester polyols (polyester diols) obtained from a diol and a dicarboxylic acid and / or anhydride thereof, polyester polyols (polyester diols) obtained by ring-opening addition polymerization of a cyclic ester compound such as a lactone using a diol as an initiator, polyester polyols obtained from a tri- or higher functional polyhydric alcohol, a diol, and a dicarboxylic acid and / or anhydride thereof, or polyester polyols obtained by ring-opening addition polymerization of a cyclic ester compound such as a lactone using a tri- or higher functional polyhydric alcohol and, if necessary, a diol as an initiator, and combinations of any two or more of these.

[0020] Examples of diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, diol dimer acid, ethylene oxide or propylene oxide adducts of bisphenol A, bis(β-hydroxyethyl)benzene, low molecular weight polyols such as xylylene glycol, and combinations of any two or more thereof.

[0021] Examples of trifunctional or higher polyhydric alcohols include trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, dipentaerythritol, sorbitol, and combinations of any two of these. Among these, trimethylolpropane, trimethylolethane, and pentaerythritol are preferred.

[0022] Examples of dicarboxylic acids and / or anhydrides thereof include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, hydrogenated dimer fatty acid, tartaric acid, and the like, and anhydrides thereof, as well as combinations of any two or more thereof.

[0023] Examples of cyclic ester compounds include β-propiolactone, β-butyrolactone, γ-butyrolactone, β-valerolactone, γ-valerolactone, δ-valerolactone, α-caprolactone, β-caprolactone, γ-caprolactone, δ-caprolactone, ε-caprolactone, α-methyl-ε-caprolactone, β-methyl-ε-caprolactone, 4-methylcaprolactone, γ-caprylolactone, ε-caprylolactone, ε-palmitolactone, and the like, as well as combinations of any two or more of these. Among these, ring-opening addition polymers of ε-caprolactone using ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, or the like as an initiator are preferred from the viewpoints of stability during polymerization and economy.

[0024] Examples of polyether polyols include polyethylene glycol, polypropylene ether polyol, polytetramethylene ether polyol, and combinations of any two or more of these.

[0025] Examples of polycarbonate polyols include the following polycarbonate polyols (α), (β), and (γ), the following polycarbonate polyols (α') and (β'), and any combination of two or more of these. Note that the polycarbonate polyol contained in polyol (A-1) is different from polycarbonate polyol (B1) and polyfunctional polyol (B2). (α) A polycarbonate polyol obtained from a diol (a-1) and a carbonate ester (a-2) (hereinafter also referred to as "polycarbonate polyol (α)"). (β) A polycarbonate polyol obtained from a diol (a-1), a carbonate ester (a-2), and a cyclic ester compound (a-3) such as a lactone (hereinafter also referred to as "polycarbonate polyol (β)"). (γ) A polycarbonate polyol obtained from a polycarbonate polyol (a-4) and a polyester polyol (a-5) (hereinafter also referred to as "polycarbonate polyol (γ)"). (α') A polycarbonate polyol which is a transesterification reaction product of a diol (a-1), a polyhydric alcohol (a-6) having three or more functional groups, and a carbonate ester (a-2) (hereinafter also referred to as "polycarbonate polyol (α')"). (β') A polycarbonate polyol (hereinafter also referred to as "polycarbonate polyol (β')") which contains a polyhydric alcohol (a-6) having three or more functional groups and an optional diol (a-1), and is a transesterification product with a polycarbonate polyol (a-7).

[0026] Examples of the diol (a-1) include the same diols as those mentioned in the description of the polyester polyol, among which ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, and 2-methyl-1,8-octanediol are preferred.

[0027] Examples of the carbonate ester (a-2) include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; alkylene carbonates such as ethylene carbonate and propylene carbonate; diaryl carbonates such as diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, diphenanthryl carbonate, diindanyl carbonate and tetrahydronaphthyl carbonate; and combinations of any two or more of these.

[0028] Examples of the cyclic ester compound (a-3) include the same cyclic ester compounds as those listed in the description of the polyester polyol.

[0029] Examples of the polycarbonate polyol (a-4) include the same ones as those mentioned in the description of the polycarbonate polyol (α).

[0030] Examples of the polyester polyol (a-5) include the same polyester polyols (polyester diols) as those mentioned in the description of the polyester polyol.

[0031] Examples of the polyhydric alcohol (a-6) include the same polyhydric alcohols as those listed in the description of the polyester polyol, among which trimethylolpropane, trimethylolethane, and pentaerythritol are preferred.

[0032] The polycarbonate polyol (a-7) is a polycarbonate polyol having two or more functional groups, and may be a polycarbonate polyol (a-7-1) having two functional groups, a polycarbonate polyol (a-7-2) having three or more functional groups, or a combination of two or more selected from the polycarbonate polyol (a-7-1) and the polycarbonate polyol (a-7-2).

[0033] Examples of the polycarbonate polyol (a-7-1) include the same ones as those mentioned in the description of the polycarbonate polyol (α).

[0034] Examples of the polycarbonate polyol (a-7-2) include the same ones as those mentioned in the description of the polycarbonate polyol (α').

[0035] Examples of polyolefin polyols include hydroxyl-terminated polybutadiene and its hydrogenated products, hydroxyl-containing chlorinated polyolefins, and combinations of any two or more of these.

[0036] In consideration of various durability and adhesion of the coating obtained from the polyurethane resin composition, the polyol (A-1) preferably contains a polycarbonate polyol, and more preferably contains a polycarbonate diol.

[0037] The number average molecular weight of the polyol (A-1) is preferably 300 to 10,000, and may be 500 to 7,000, 800 to 5,000, or 1,000 to 3,000. Details of the method for measuring the number average molecular weight may be as described in the examples below.

[0038] The average hydroxyl value of the polyol (A-1) is preferably 30 to 500 mgKOH / g, more preferably 40 to 400 mgKOH / g, and even more preferably 50 to 300 mgKOH / g. When the average hydroxyl value is 30 mgKOH / g or more, the urethane group concentration in the polyurethane resin does not become too low, and the strength at break in a tensile test is further improved. When the average hydroxyl value is 500 mgKOH / g or less, the urethane group concentration does not become too high, and the elongation at break in a tensile test is further improved.

[0039] The polyol (A1) may contain, as a polyol other than the polycarbonate polyol (B1), a diol (A-2) and / or a tri- or higher functional polyhydric alcohol (A-3) in addition to or instead of the polyol (A-1).

[0040] The polyol (A2) may contain a diol (A-2) and / or a tri- or higher functional polyhydric alcohol (A-3) in addition to or instead of the polyol (A-1). The diol (A-2) and the polyhydric alcohol (A-3) are different from the polyol (A-1).

[0041] Examples of the diol (A-2) include the same diols as those mentioned in the description of the polyester polyol, among which ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, and 2-methyl-1,8-octanediol are preferred.

[0042] Examples of the polyhydric alcohol (A-3) include the same polyhydric alcohols as those mentioned in the description of the polyester polyol, among which, from an economical viewpoint, trimethylolpropane, trimethylolethane, and pentaerythritol are preferred.

[0043] The molar ratio of the polyol (A-1) to the diol (A-2) and / or polyhydric alcohol (A-3) in the polyol (A1) and polyol (A2) [polyol (A-1) / (diol (A-2) and / or polyhydric alcohol (A-3)] is preferably 10 / 0 to 1 / 20, more preferably 10 / 0 to 1 / 10, and even more preferably 7 / 1 to 1 / 5. By adjusting the ratio within this range, a polyurethane resin composition having an even lower 100% modulus and an even higher softening temperature can be obtained.

[0044] <Polycarbonate polyol (B1), multifunctional polyol (B2)> In the first and second aspects, the polycarbonate polyol (B1) is a polycarbonate polyol having an ester bond and an average number of hydroxyl functional groups exceeding 2. The polycarbonate polyol (B1) is included in the polyol (A1).

[0045] In the modified example of the first embodiment and the modified example of the second embodiment, the multifunctional polyol (B2) is different from the polyol (A2) and is a polycarbonate polyol having an ester bond and an average number of hydroxyl functional groups exceeding two.

[0046] Examples of the polycarbonate polyol (B1) and the polyfunctional polyol (B2) include the following copolymer polyols (α") and (β"), and combinations of any two or more of these. (α") A copolymer polyol (hereinafter also referred to as "polycarbonate polyol (α")) which is a transesterification reaction product of polycarbonate polyol (b-1) and polyester polyol (b-2) having an average number of hydroxyl functional groups of 3 or more. (β") A copolymer polyol (hereinafter also referred to as "polycarbonate polyol (β")) which is a transesterification reaction product of polycarbonate polyol (b-1), polyester polyol (b-2) having an average number of hydroxyl functional groups of 3 or more, and polyester polyol (b-3) having an average number of hydroxyl functional groups of 2 or more but less than 3. Copolymer polyols not only achieve both high strength and high elongation mechanical properties, but also improve solubility in solvents and handleability by liquefying at room temperature.

[0047] Examples of the polycarbonate polyol (b-1) include the same ones as those mentioned in the description of the polycarbonate polyol (a-7).

[0048] Examples of the polyester polyol (b-2) include the following polyester polyols (δ) to (ε), and any combination of two or more of these. (δ) A polyester polyol obtained from a diol (b-2-1), a dicarboxylic acid and / or anhydride thereof (b-2-2), and a polyhydric alcohol (b-2-3) having an average number of hydroxyl functional groups of 3 or more (hereinafter also referred to as "polyester polyol (δ)"). (ε) A polyester polyol obtained by ring-opening addition polymerization of a cyclic ester compound (b-2-4) such as a lactone using a polyhydric alcohol (b-2-3) having an average number of hydroxyl functional groups of 3 or more and an optional difunctional alcohol (b-2-5) as an initiator (hereinafter also referred to as "polyester polyol (ε)").

[0049] Examples of the diol (b-2-1), dicarboxylic acid and / or anhydride thereof (b-2-2), and cyclic ester compound (b-2-4) include the same diols, dicarboxylic acid and / or anhydride thereof, and cyclic ester compounds as those mentioned in the description of the polyester polyol.

[0050] Examples of the polyhydric alcohol (b-2-3) include the same trifunctional or higher polyhydric alcohols as those mentioned in the description of the polyester polyol. As long as the desired effect is achieved, a bifunctional alcohol (b-2-5) such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexamethylene glycol, dipropylene glycol, or trimethylene glycol may be used as an initiator in combination with the polyhydric alcohol (b-2-3). In other words, the polyester polyol (ε) may be a polyester polyol having a moiety derived from the polyhydric alcohol (b-2-3) and a moiety derived from the cyclic ester compound (b-2-4), or may further include a polyester polyol having a moiety derived from the bifunctional alcohol (b-2-5) and a moiety derived from the cyclic ester compound (b-2-4).

[0051] (Catalyst) When preparing the polycarbonate polyol (B1) and the polyfunctional polyol (B2), it is preferable to use a catalyst. Examples of the catalyst include known transesterification catalysts, such as metal alkoxides such as lithium methoxide, sodium methoxide, sodium ethoxide, potassium methoxide, and potassium ethoxide; metal enolates such as lithium acetylacetonate, aluminum acetylacetonate, and zirconium acetylacetonate; metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; metal carboxylates such as lithium acetate, sodium acetate, and potassium acetate; trimethylamine, triethylamine, diisopropylethylamine, tributylamine, and the like. tertiary alkylamines such as amines; cyclic azines such as pyridine, pyrazine, and quinoline; tertiary cyclic amines such as N-methylpyrrolidine, N-methylpiperidine, N,N'-dimethylpiperazine, N-methylmorpholine, diazabicycloundecene, 1,4-diazabicyclo[2.2.2]octane, and 1,8-diazabicyclo[5.4.0]undecene; t-butyliminotris(dimethylamino)phosphorane (P1-t-Bu), t-butyliminotri(pyrrolidino)phosphorane, t-octyliminotris(dimethylamino)phosphorane (P1-t-Oct), and 1-t-butyl-2,2,4,4,4-pentakis(dimethylamino)-2λ ５ , 4λ ５ - Catenadi(phosphazene) (P2-t-Bu), 1-ethyl-2,2,4,4,4-pentakis(dimethylamino)-2λ ５ , 4λ ５ - Catenadi(phosphazene), 1-t-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phosphoranylideneamino]-2λ ５ , 4λ ５ - Catenadi(phosphazene) (P4-t-Bu), 1-tert-octyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phosphoranylideneamino]-2λ ５ , 4λ ５-catenadi(phosphazene) (P4-t-Oct); and combinations of any two or more of these. Among these, potassium hydrogen carbonate, sodium hydrogen carbonate, lithium acetate, lithium acetylacetonate, diazabicycloundecene, and P4-t-Bu are preferred in terms of high yield.

[0052] In the case of a two-component system of (b-1) and (b-2) (polycarbonate polyol (α")), the mass ratio of the polycarbonate polyol (b-1) to the polyester polyol (b-2) having an average number of hydroxyl functional groups of 3 or more ([mass of (b-1)] / [mass of (b-2)]) is preferably 90 / 10 to 10 / 90, more preferably (b-1) / (b-2)=80 / 20 to 20 / 80, even more preferably 70 / 30 to 30 / 70, and particularly preferably 60 / 40 to 40 / 60. In the case of a three-component system of (b-1), (b-2), and (b-3) (polycarbonate polyol (β")), The mass ratio of the polycarbonate polyol (b-1), to the polyester polyol (b-2) having an average number of hydroxyl functional groups of 3 or more and the polyester polyol (b-3) having an average number of hydroxyl functional groups of 2 or more but less than 3 ([mass of (b-1)] / ([mass of (b-2)]+[mass of (b-3)])) is preferably 95 / 5 to 5 / 95, more preferably 90 / 10 to 10 / 90, still more preferably 80 / 20 to 20 / 80, even more preferably 70 / 30 to 30 / 70, and particularly preferably 60 / 40 to 40 / 60.

[0053] When the mass ratio is within these ranges, an aqueous polyurethane resin emulsion composition having high strength and high elongation mechanical properties can be obtained due to the balance between the cohesive force of the polycarbonate polyol (b-1), the urethane group concentration, and the content of the polyester polyol (b-2), or the content of the polyester polyol (b-2) and the polyester polyol (b-3).

[0054] The average number of hydroxyl functional groups in the polycarbonate polyol (B1) and the polyfunctional polyol (B2) is preferably 2.1 to 3.5, more preferably 2.2 to 3.0, even more preferably 2.3 to 2.9, and particularly preferably 2.4 to 2.8. When the average number of hydroxyl functional groups is 3.5 or less, the elongation at break in a tensile test tends to be further improved, and when the average number of hydroxyl functional groups is 2.1 or more, the strength at break in a tensile test tends to be further improved.

[0055] The average hydroxyl value of the polycarbonate polyol (B1) and the polyfunctional polyol (B2) is preferably 40 to 500 mgKOH / g, more preferably 50 to 300 mgKOH / g. When the average hydroxyl value is 40 mgKOH / g or more, the urethane group concentration in the polyurethane resin does not become too low, and the strength at break in a tensile test is further improved. When the average hydroxyl value is 500 mgKOH / g or less, the urethane group concentration does not become too high, and the elongation at break in a tensile test is further improved.

[0056] The number average molecular weight of the polycarbonate polyol (B1) and the polyfunctional polyol (B2) is preferably 400 to 4,000 g / mol, more preferably 500 to 3,000 g / mol. If the number average molecular weight is 400 g / mol or more, the urethane group concentration in the polyurethane does not become too high, the initial modulus is suppressed, and flexibility is further improved. If the number average molecular weight is 4,000 g / mol or less, the urethane group concentration in the polyurethane resin does not become too low, and strength at break in a tensile test is further improved.

[0057] The ester group concentration of the polycarbonate polyol (B1) and the polyfunctional polyol (B2) is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, even more preferably 20 to 70% by mass, and particularly preferably 25 to 60% by mass. When the ester group concentration is 10% by mass or more, a polyurethane resin having excellent low-temperature properties tends to be obtained. When the ester group concentration is 90% by mass or less, a polyurethane resin having excellent long-term durability such as moist heat resistance tends to be obtained.

[0058] Considering ease of synthesis and ease of handling, the number average molecular weight of the polycarbonate polyol (b-1) is preferably 400 to 5,000 g / mol, and more preferably 500 to 3,000 g / mol.

[0059] (Method for producing polycarbonate polyol (B1) and polyfunctional polyol (B2)) The polycarbonate polyol (B1) and the polyfunctional polyol (B2) can be produced by transesterification of a polycarbonate polyol (b-1), a polyester polyol (b-2) having an average hydroxyl functionality of 3 or more, and, if necessary, a polyester polyol (b-3) having an average hydroxyl functionality of 2 or more but less than 3. In this case, it is preferable to use a catalyst, and the amount of the catalyst used is 0.0001 to 1 mass%, preferably 0.001 to 0.1 mass%, of the total mass of the polycarbonate polyol (b-1) and the polyester polyol (b-2) having an average hydroxyl functionality of 3 or more, or, when polyester polyol (b-3) is included, of the total mass of the polycarbonate polyol (b-1), the polyester polyol (b-2) having an average hydroxyl functionality of 3 or more, and the polyester polyol (b-3). When the amount of catalyst is equal to or greater than the lower limit, the reaction time can be further prevented from becoming long, and the resulting polycarbonate polyol is further prevented from becoming discolored.When the amount of catalyst is equal to or less than the upper limit, the turbidity can be further suppressed.

[0060] The reaction temperature for the transesterification reaction is preferably 70 to 250°C, more preferably 80 to 220°C.

[0061] (Contents of Polycarbonate Polyol (B1) and Polyfunctional Polyol (B2)) In the first aspect, the content of the polycarbonate polyol (B1) is preferably 5 to 99% by mass, more preferably 10 to 90% by mass, even more preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass, relative to the content of the polyol (A1) in the polyurethane resin composition. When the content of the polycarbonate polyol (B1) is within the above range, when used as a polyurethane film, a polyurethane film having particularly good 100% modulus and heat resistance is likely to be obtained. Furthermore, when the content of the polycarbonate polyol (B1) is 99% by mass or less, a polyurethane dispersion having particularly excellent handleability is likely to be obtained, and a polyurethane film having particularly excellent 100% modulus is likely to be obtained. In addition, when the content of the polycarbonate polyol (B1) is 5% by mass or more, a polyurethane film having particularly excellent heat resistance is likely to be obtained.

[0062] In the modified example of the first embodiment, the content of the multifunctional polyol (B2) is the same as the content of the polycarbonate polyol (B1) in the first embodiment, except that "with respect to the content of the polyol (A1) in the polyurethane resin composition" should be read as "with respect to the sum of the content of the polyol (A2) and the content of the multifunctional polyol (B2) in the polyurethane resin composition."

[0063] In the second aspect, the content of the polycarbonate polyol (B1) is preferably 40 to 99 mass%, more preferably 45 to 90 mass%, still more preferably 50 to 80 mass%, and particularly preferably 55 to 70 mass%, relative to the content of the polyol (A1) in the polyurethane resin composition. When the content of the polycarbonate polyol (B1) is within the above range, a polyurethane resin that is particularly excellent in softening temperature and that satisfies both 100% modulus, strength at break, and elongation at break is likely to be obtained when used as a polyurethane film.

[0064] In the modified example of the second embodiment, the content of the polyfunctional polyol (B2) is the same as the content of the polycarbonate polyol (B1) in the second embodiment, except that "with respect to the content of the polyol (A1) in the polyurethane resin composition" should be read as "with respect to the sum of the content of the polyol (A2) and the content of the polyfunctional polyol (B2) in the polyurethane resin composition."

[0065] (Average Hydroxyl Value of Polyol (A1) / Average Hydroxyl Value of Polyol (A2) and Polyfunctional Polyol (B2)) The average hydroxyl value of polyol (A1) in the first and second embodiments, and the average hydroxyl value when polyol (A2) and polyfunctional polyol (B2) are mixed in the modified first embodiment and the modified second embodiment, are preferably 30 to 150 mg KOH, more preferably 40 to 130 mg KOH, even more preferably 50 to 120 mg KOH, and particularly preferably 60 to 110 mg KOH. When the average hydroxyl value is within the above range, when used as a polyurethane film, a polyurethane film that is particularly good in both 100% modulus and heat resistance tends to be obtained. Furthermore, when the average hydroxyl value is 130 mg KOH or less, a polyurethane film that is particularly excellent in 100% modulus tends to be obtained.

[0066] (Crosslink Density) The crosslink density of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G) contained as needed is preferably 0.02 to 0.30, more preferably 0.05 to 0.25, and even more preferably 0.10 to 0.20. When the crosslink density is within the above range, when used as a polyurethane film, a polyurethane film that is particularly good in both 100% modulus and heat resistance is likely to be obtained. Furthermore, when the crosslink density is 0.30 or less, a polyurethane film that is particularly excellent in 100% modulus is likely to be obtained.

[0067] <Organic Acid (C)> The organic acid (C) may be, for example, a hydrophilic group-containing monomer that can impart hydrophilicity to the isocyanate group-terminated urethane prepolymer (E) obtained by reaction with the polyisocyanate (D), thereby making the final resin composition aqueous.

[0068] Examples of the organic acid (C) include those having one or more active hydrogen groups. Examples of organic acids include carboxylic acids, sulfonic acids, phosphoric acids, phosphonic acids, phosphinic acids, thiosulfonic acids, etc., and combinations of any two or more of these. These groups may be introduced independently or may be associated with each other like a chelate. Among these, dimethylol fatty acids having a carboxy group (—COOH) are more preferred.

[0069] The dimethylol fatty acid may be, for example, a compound represented by the following formula (c):

[0070]

[0071] In formula (c), R ｃ represents an aliphatic hydrocarbon group. ｃ The number of carbon atoms in the aliphatic hydrocarbon group represented by R may be, for example, 1 or more, 10 or less, 6 or less, or 3 or less. ｃ The aliphatic hydrocarbon group represented by R may be linear or branched. ｃ The aliphatic hydrocarbon group represented by the formula: ３ , -CH ２ CH ３ , -CH ２ CH ２ CH ３ , or C.H. ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ It may be.

[0072] Examples of dimethylol fatty acids include dimethylolalkanoic acids such as dimethylolpropionic acid (e.g., 2,2-dimethylolpropanoic acid), dimethylolbutanoic acid, dimethylolpentanoic acid, and dimethylolnonanoic acid, and combinations of any two or more of these.

[0073] The content of the organic acid (C) may be 0.01 mmol / g or more, 0.10 mmol / g or more, 0.20 mmol / g or more, or 0.30 mmol / g or more, and may be 0.80 mmol / g or less, 0.70 mmol / g or less, 0.60 mmol / g or less, 0.50 mmol / g or less, or 0.40 mmol / g or less, based on the sum of the mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G) in the polyurethane resin composition.

[0074] <Polyisocyanate (D)> The polyisocyanate (D) is a compound having two or more isocyanate groups (—N═C═O). The number of isocyanate groups in the polyisocyanate (D) may be, for example, 6 or less, 4 or less, or 3 or less. The number of isocyanate groups in the polyisocyanate (D) may be, for example, 2 to 3, or may be 2. The polyisocyanate (D) may be, for example, a compound having a plurality of isocyanate groups and a hydrocarbon group connecting the plurality of isocyanate groups.

[0075] The polyisocyanate (D) is not particularly limited, and examples thereof include various conventionally known polyisocyanates. For example, aliphatic isocyanates such as hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, and lysine diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylene diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylether diisocyanate, and 2- Examples of the diisocyanate include aromatic isocyanates such as nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate; aromatic aliphatic diisocyanates such as xylylene-1,4-diisocyanate and xylylene-1,3-diisocyanate; allophanate-modified polyisocyanates obtained by reacting these organic polyisocyanates with alcohols; and combinations of any two or more of these.

[0076] The polyisocyanate (D) is preferably an aliphatic diisocyanate or an alicyclic diisocyanate, more preferably an alicyclic diisocyanate, and further preferably isophorone diisocyanate or hydrogenated diphenylmethane diisocyanate.

[0077] In the first and second aspects, the ratio of the total number of moles of hydroxyl groups in the polyol (A1) excluding the polycarbonate polyol (B1) to the total number of moles of isocyanate groups in the polyisocyanate (D) (hydroxyl groups / isocyanate groups) may be, for example, 0.200 or more, 0.300 or more, or 0.400 or more, and may be 1.000 or less, 0.950 or less, 0.900 or less, or 0.800 or less.

[0078] In the modified example of the first embodiment and the modified example of the second embodiment, the ratio (hydroxyl groups / isocyanate groups) is the same as the ratio (hydroxyl groups / isocyanate groups) in the first embodiment and the second embodiment, except that "the total number of moles of hydroxyl groups in the polyol (A1) excluding the polycarbonate polyol (B1)" is read as "the total number of moles of hydroxyl groups in the polyol (A2)."

[0079] <One Embodiment of Isocyanate Group-Terminated Urethane Prepolymer (E)> One embodiment of the isocyanate group-terminated urethane prepolymer (E) may include, for example, a reaction product of a polyol (A1) containing a polycarbonate polyol (B1) having an ester bond and having an average hydroxyl functional group number of more than 2, an organic acid (C), and a polyisocyanate (D).

[0080] A modified example of one embodiment of the isocyanate group-terminated urethane prepolymer (E) may include, for example, a reaction product of a polyol (A2), a multifunctional polyol (B2), an organic acid (C), and a polyisocyanate (D).

[0081] <Neutralizing Agent (F)> The neutralizing agent (F) is preferably a basic neutralizing agent. Examples of the neutralizing agent (F) include organic amines such as ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-ethyl-1-propanol, and higher alkyl-modified morpholine; alkali metals such as lithium, potassium, and sodium; inorganic alkalis such as sodium hydroxide and potassium hydroxide; and combinations of any two or more of these. Furthermore, from the viewpoint of improving the durability and smoothness of the coating film, highly volatile neutralizing agents that dissociate upon heating, such as ammonia, trimethylamine, and triethylamine, are preferred.

[0082] The neutralizing agent may be a trialkylamine, such as trimethylamine, triethylamine, triisopropylamine, or tributylamine.

[0083] In order to improve the aqueous dispersion stability of the polyurethane resin composition, the neutralizing agent (F) may further contain an anionic polar group compound and a cationic polar group-containing compound.

[0084] The anionic polar group-containing compound may be, for example, a compound consisting of an organic acid having one or more active hydrogen groups and a neutralizing agent.

[0085] Organic acids include carboxylates, sulfonates, phosphates, phosphonates, phosphinates, thiosulfonates, etc., and combinations of any two or more thereof. These groups may be introduced independently or may be associated, such as in a chelate.

[0086] Examples of the cationic polar group-containing compound include a compound comprising a tertiary amine having one or more active hydrogen groups and one or more agents selected from the group consisting of neutralizing agents for inorganic acids and organic acids and quaternizing agents.

[0087] Examples of tertiary amines having one or more active hydrogen groups include N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dipropylethanolamine, N,N-diphenylethanolamine, N-methyl-N-ethylethanolamine, N-methyl-N-phenylethanolamine, N,N-dimethylpropanolamine, N-methyl-N-ethylpropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-methyldipropanolamine, N-phenyldiethanolamine, N-phenyldipropanolamine, N-hydroxyethyl-N-hydroxypropyl-methylamine, N,N'-dihydroxyethylpiperazine, triethanolamine, trisisopropanolamine, N-methyl-bis-(3-aminopropyl)-amine, N-methyl-bis-(2-aminopropyl)-amine, and the like; ammonia, primary amines such as methylamine, secondary amines such as dimethylamine to which alkylene oxide has been added; and combinations of any two or more of these.

[0088] Examples of inorganic acids and organic acids include hydrochloric acid, acetic acid, lactic acid, cyanoacetic acid, phosphoric acid, sulfuric acid, and the like, as well as combinations of any two or more of these acids.

[0089] Examples of the quaternizing agent include dimethyl sulfate, benzyl chloride, bromoacetamide, chloroacetamide, alkyl halides such as ethyl bromide, propyl bromide, and butyl bromide, and combinations of any two or more of these.

[0090] Other examples of the cationic polar group-containing compound include cationic compounds such as primary amine salts, secondary amine salts, tertiary amine salts, and pyridinium salts.

[0091] The content of the neutralizing agent may be 0.01 mmol / g or more, 0.10 mmol / g or more, 0.20 mmol / g or more, or 0.30 mmol / g or more, and may be 0.80 mmol / g or less, 0.70 mmol / g or less, 0.60 mmol / g or less, 0.50 mmol / g or less, or 0.40 mmol / g or less, based on the sum of the mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G) in the polyurethane resin composition.

[0092] (Organic Solvent) During synthesis of the isocyanate group-terminated urethane prepolymer (E), it may be diluted to any solid content with an organic solvent that is inactive to isocyanate groups. Examples of the organic solvent include aromatic solvents such as toluene, xylene, Swazol (an aromatic hydrocarbon solvent manufactured by Maruzen Petrochemical Co., Ltd.), and Solvesso (an aromatic hydrocarbon solvent manufactured by ExxonMobil Corporation); aliphatic hydrocarbon solvents such as hexane; alicyclic hydrocarbon solvents such as cyclohexane and isophorone; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, and isobutyl acetate; glycol ether ester solvents such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol-3-methyl-3-methoxybutyl acetate, and ethylene glycol ethyl-3-ethoxypropionate; glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dibutyl ether, propylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; ether solvents such as tetrahydrofuran and dioxane; and combinations of any two or more of these.

[0093] The organic solvent is preferably an ester-based solvent such as ethyl acetate, butyl acetate, or isobutyl acetate, which can be easily removed during desolvation and can be heated to 50 to 100°C during formation of the isocyanate group-terminated urethane prepolymer (E), and particularly preferably a ketone-based solvent such as acetone, methyl ethyl ketone, or methyl isobutyl ketone.

[0094] <Method for Producing Isocyanate-Terminated Urethane Prepolymer (E)> In the first and second embodiments, first, polyisocyanate (D), polyol (A1), and organic acid (C) are reacted, if necessary in a diluent solvent, under conditions such that the number of moles of isocyanate groups is in excess of the number of moles of hydroxyl groups to produce an isocyanate-terminated prepolymer before neutralization. A known urethane catalyst may be used in this reaction. The reaction temperature is preferably 0 to 100°C, and particularly preferably 20 to 90°C.

[0095] In the modified example of the first embodiment and the modified example of the second embodiment, "polyol (A1)" is to be read as "polyol (A2), multifunctional polyol (B2)."

[0096] <Chain extender (G)> The chain extender (G) is a compound that reacts with the isocyanate group-terminated urethane prepolymer (E) to form a polyurethane resin. Examples of the chain extender include a compound having a primary amino group (—NH ２ a compound having a functional group capable of reacting with an isocyanate group, such as a secondary amino group (—NH—) or a hydroxy group (—OH), or water (H ２ O) can be mentioned.

[0097] The chain extender (G) is preferably at least one selected from the group consisting of an amine compound having one or more primary or secondary amino groups and water.

[0098] The amine compound as the chain extender (G) may be an amine compound having two or more amino groups selected from the group consisting of primary amino groups and secondary amino groups, or may be a compound having one amino group selected from the group consisting of primary amino groups and secondary amino groups and one or more hydroxyl groups (—OH).

[0099] The amine compound is more preferably at least one selected from the group consisting of aliphatic diamines and alicyclic diamines. ２ N-R ｇ -NH ２ In formula (g1), R ｇrepresents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.

[0100] Examples of the amine compound include ethylenediamine, hexamethylenediamine, xylylenediamine, isophoronediamine, diethylenetriamine, N-aminoethyl-N-ethanolamine, monoethanolamine, and the like, as well as combinations of any two or more of these.

[0101] During the chain extension reaction, a curing catalyst (polymerization catalyst) may be used as needed. Examples of the curing catalyst include metal-based catalysts such as dioctyltin dilaurate, zinc naphthenate, and bismuth compounds, and conventional curing catalysts such as amine-based catalysts such as triethylenediamine and N-methylmorpholine. The use of a curing catalyst can further lower the reaction temperature.

[0102] The equivalent ratio (active hydrogen groups / isocyanate groups) of the active hydrogen groups (amino groups and hydroxyl groups) of the amine compound of the chain extender (G) to the isocyanate groups of the isocyanate group-terminated urethane prepolymer (E) is, for example, preferably 0 to 1.1, more preferably 0.05 to 1.05, even more preferably 0.10 to 1.00, and particularly preferably 0.2 to 0.8. When this ratio is within the above range, a polyurethane resin having excellent 100% modulus and heat resistance is likely to be formed.

[0103] <Method for producing polyurethane resin composition> The polyurethane resin composition can be produced, for example, by a method including a step of neutralizing an isocyanate group-terminated urethane prepolymer (E) with a neutralizing agent (F) to obtain a neutralized product of the isocyanate group-terminated urethane prepolymer (E), and a step of emulsifying the neutralized product of the isocyanate group-terminated urethane prepolymer (E) with water and reacting it with a chain extender (G) to obtain a polyurethane resin composition.

[0104] Examples of a method for carrying out a chain extension reaction between the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G) include a method in which the chain extender (G) is dissolved in water in advance, and the isocyanate group-terminated urethane prepolymer (E) is added to this aqueous solution of the chain extender (G) to emulsify and carry out a chain extension reaction, and a method in which the isocyanate group-terminated urethane prepolymer (E) is emulsified in water, and then the chain extender (G) or an aqueous solution of the chain extender (G) is added to carry out a chain extension reaction.

[0105] (Content of Urea Groups Derived from Chain Extender (G) (Concentration of Urea Groups Derived from Chain Extender (G))) The lower limit of the content of urea groups derived from the chain extender (G) relative to the sum of the mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G) in the polyurethane resin composition may be, for example, 0.05 mmol / g or more, 0.07 mmol / g or more, 0.10 mmol / g or more, 0.13 mmol / g or more, 0.15 mmol / g or more, 0.20 mmol / g or more, or 0.25 mmol / g or more. The upper limit of the content of urea groups derived from the chain extender (G) relative to the sum of the mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G) in the polyurethane resin composition may be, for example, 1.00 mmol / g or less, 0.95 mmol / g or less, 0.90 mmol / g or less, 0.80 mmol / g or less, 0.75 mmol / g or less, 0.70 mmol / g or less, 0.60 mmol / g or less, 0.55 mmol / g or less, 0.50 mmol / g or less, or 0.45 mmol / g or less. The content of urea groups derived from the chain extender (G) relative to the sum of the mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G) in the polyurethane resin composition may be, for example, 0.05 mmol / g to 1.00 mmol / g, 0.07 mmol / g to 0.90 mmol / g, 0.10 mmol / g to 0.80 mmol / g, 0.13 mmol / g to 0.70 mmol / g, or 0.15 mmol / g to 0.60 mmol / g. When the content of urea groups derived from the chain extender (G) is within the above range, when used as a polyurethane film, a polyurethane film with even better 100% modulus and heat resistance is likely to be obtained. Furthermore, when the content of urea groups derived from the chain extender (G) is 1.00 mmol / g or less, a polyurethane film with even better 100% modulus is likely to be obtained.

[0106] When the chain extender (G) does not contain anything other than an amine compound having one or more primary or secondary amino groups and water (i.e., when the chain extender contains only an amine compound having one or more primary or secondary amino groups and water), the content of urea groups derived from the chain extender (G) is equal to the sum of the content of urea groups derived from the amine compound and the content of urea groups derived from water.

[0107] (Amine Compound-Derived Urea Group Content (Amine Compound-Derived Urea Group Concentration)) The chain extender (G) may contain an amine compound having one or more primary or secondary amino groups. In this case, the lower limit of the amine compound-derived urea group content relative to the sum of the mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G) in the polyurethane resin composition may be, for example, more than 0 mmol / g, 0.01 mmol / g or more, 0.02 mmol / g or more, 0.03 mmol / g or more, 0.05 mmol / g or more, 0.10 mmol / g or more, 0.13 mmol / g or more, 0.15 mmol / g or more, 0.20 mmol / g or more, or 0.25 mmol / g or more. The upper limit of the content of urea groups derived from the amine compound, relative to the sum of the mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G) in the polyurethane resin composition, may be, for example, 0.95 mmol / g or less, 0.90 mmol / g or less, 0.80 mmol / g or less, 0.70 mmol / g or less, 0.60 mmol / g or less, 0.60 mmol / g or less, 0.50 mmol / g or less, 0.48 mmol / g or less, 0.45 mmol / g or less, 0.40 mmol / g or less, 0.34 mmol / g or less, 0.30 mmol / g or less, 0.25 mmol / g or less, or 0.23 mmol / g or less. The content of the urea group derived from the amine compound, relative to the sum of the mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G) in the polyurethane resin composition, may be, for example, more than 0 mmol / g to 0.95 mmol / g, 0.01 mmol / g to 0.9 mmol / g, 0.02 mmol / g to 0.80 mmol / g, 0.05 mmol / g to 0.70 mmol / g, 0.10 mmol / g to 0.60 mmol / g, 0.13 mmol / g to 0.50 mmol / g, 0.15 mmol / g to 0.40 mmol / g, 0.20 mmol / g to 0.34 mmol / g, or 0.25 mmol / g to 0.30 mmol / g. When the content of the urea group derived from the amine compound is within the above range, a polyurethane film having even better 100% modulus and heat resistance is likely to be obtained when used as a polyurethane film.Furthermore, when the content of urea groups derived from the amine compound is 0.95 mmol / g or less, a polyurethane film having an even more excellent 100% modulus is likely to be obtained.

[0108] (Content of Urea Groups Derived from Water (Concentration of Urea Groups Derived from Water)) The chain extender (G) may contain water.

[0109] The lower limit of the content of urea groups derived from water, relative to the sum of the mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G) in the polyurethane resin composition, may be, for example, more than 0 mmol / g, 0.01 mmol / g or more, 0.02 mmol / g or more, 0.03 mmol / g or more, 0.05 mmol / g or more, 0.07 mmol / g or more, 0.10 mmol / g or more, 0.13 mmol / g or more, 0.15 mmol / g or more, 0.20 mmol / g or more, or 0.25 mmol / g or more. The upper limit of the content of urea groups derived from water may be, for example, 0.95 mmol / g or less, 0.90 mmol / g or less, 0.80 mmol / g or less, 0.70 mmol / g or less, 0.60 mmol / g or less, 0.60 mmol / g or less, 0.50 mmol / g or less, 0.40 mmol / g or less, 0.30 mmol / g or less, or 0.25 mmol / g or less, relative to the sum of the mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G) in the polyurethane resin composition. The content of water-derived urea groups relative to the sum of the mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G) in the polyurethane resin composition may be, for example, more than 0 mmol / g to 0.95 mmol / g, 0.01 mmol / g to 0.9 mmol / g, 0.02 mmol / g to 0.80 mmol / g, 0.05 mmol / g to 0.70 mmol / g, 0.10 mmol / g to 0.60 mmol / g, 0.13 mmol / g to 0.50 mmol / g, 0.15 mmol / g to 0.40 mmol / g, 0.20 mmol / g to 0.34 mmol / g, or 0.25 mmol / g to 0.30 mmol / g. When the content of water-derived urea groups is within the above range, a polyurethane film having even better 100% modulus and heat resistance is likely to be obtained when used as a polyurethane film. Furthermore, when the content of urea groups derived from water is 0.95 mmol / g or less, a polyurethane film having an even better 100% modulus is likely to be obtained.

[0110] (Ratio of the content of urea groups derived from the amine compound to the content of urea groups derived from the chain extender (G)) The ratio of the content of urea groups derived from the amine compound to the content of urea groups derived from the chain extender (G) (amine compound-derived urea group ratio) can be calculated by dividing the concentration of urea groups derived from the amine compound by the concentration of urea groups derived from the chain extender (G), and the lower limit may be, for example, more than 0 mol%, 1 mol% or more, 3 mol% or more, 5 mol% or more, 10 mol% or more, 15 mol% or more, 20 mol% or more, 25 mol% or more, or 30 mol% or more. The upper limit of the amine compound-derived urea group ratio may be, for example, 99 mol% or less, 97 mol% or less, 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, 75 mol% or less, 70 mol% or less, or 65 mol% or less. The ratio of urea groups derived from the amine compound may be, for example, more than 0 mol% to 99 mol% or less, 5 mol% to 95 mol%, 10 mol% to 90 mol%, 15 mol% to 80 mol%, or 20 mol% to 70 mol%. When the ratio of urea groups derived from the amine compound is within the above range, when used as a polyurethane film, a polyurethane film with even better 100% modulus and heat resistance is likely to be obtained. Furthermore, when the ratio of urea groups derived from the amine compound is 99 mol% or less, a polyurethane film with even better 100% modulus is likely to be obtained.

[0111] The content of urea groups derived from the chain extender (G), the content of urea groups derived from the amine compound, the content of urea groups derived from water, and the content of urea groups derived from the amine compound relative to the content of urea groups derived from the chain extender (G) (amine compound-derived urea group ratio) are １ It can also be calculated using H-NMR measurement.

[0112] <Curing Agent (X)> The polyurethane resin composition may further contain a curing agent (X).

[0113] The curing agent (X) cures the reaction product of the isocyanate-terminated urethane prepolymer (E) and the chain extender (G) to form a polyurethane resin. When the polyurethane resin composition contains the curing agent (X), the curing agent (X) is one component of a two-component system. Specific examples of the curing agent (X) include urethane-modified, urea-modified, allophanate-modified, biuret-modified, uretdione-modified, and isocyanurate-modified organic diisocyanates. Among these, trimers and adducts of hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) are preferred.

[0114] <Other Components> In order to further improve physical properties or to impart various physical properties, the polyurethane resin composition may contain various additives, such as a film-forming agent, a viscosity modifier, an antigelling agent, a flame retardant, a plasticizer, an antioxidant, an ultraviolet absorber, an antibacterial agent, a filler, an internal mold release agent, a reinforcing material, a matting agent, an electrical conductivity imparting agent, a charge control agent, an antistatic agent, a lubricant, a dye, a pigment, and other processing aids.

[0115] The polyurethane resin composition may be an emulsion obtained by neutralizing an isocyanate group-terminated urethane prepolymer (E) with a neutralizing agent (F).

[0116] The polyurethane resin composition thus obtained is preferably used as an aqueous polyurethane resin emulsion. By curing this aqueous polyurethane resin emulsion, molded articles such as coatings and films that are tough, have a reduced 100% modulus (good texture), and have a high softening temperature can be obtained, and these articles can be suitably used for leather applications such as artificial leather and synthetic leather, as well as for leather surface treatment agents. The 100% modulus is an index that quantifies the moist, elastic, and luxurious feel experienced when touching synthetic leather, and when the value is within a certain range, the polyurethane resin will have good properties.

[0117] The polyurethane resin composition may be of either a one-component type or a two-component type, but is preferably of a one-component type.

[0118] [Artificial or Synthetic Leather] One embodiment of the artificial or synthetic leather includes a cured product of a polyurethane resin composition and a substrate. The artificial or synthetic leather according to one embodiment can be produced, for example, by a method including forming a cured product of the polyurethane resin composition on a substrate. The artificial or synthetic leather according to one embodiment can also be produced by a method including impregnating the substrate with the polyurethane resin composition and curing the polyurethane resin composition. In the artificial leather, the substrate may be, for example, a base fabric such as a knitted fabric or a woven fabric. In the synthetic leather, the substrate may be a nonwoven fabric.

[0119] [Leather surface treatment agent] The leather surface treatment agent is an agent used to treat the surface of leather or leather materials. The leather to which the leather surface treatment agent is applied may be, for example, synthetic leather, artificial leather, or natural leather.

[0120] Examples of the present invention will be described below, but the present invention is not limited to these examples. In the examples, % and parts are by mass unless otherwise specified.

[0121] <Calculation method for each composition in each example> (Concentration of urea groups derived from chain extender (G)) It is known that the reaction rate between an isocyanate group and a chain extender (G) is much higher than the reaction rate between an isocyanate group and a hydroxy group of a polyol component. Therefore, in the polyurethane resin composition, the content of urea groups derived from the chain extender (G) relative to the sum of the mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G) (the concentration of urea groups derived from the chain extender (G)) is equal to the content of unreacted isocyanate groups in the isocyanate group-terminated prepolymer (E). From the above, the concentration of urea groups derived from the chain extender (G) is defined by the following formula: Concentration (mmol / g) of urea groups derived from chain extender (G) = Content (mmol / g) of unreacted isocyanate groups in isocyanate group-terminated prepolymer (E) × ((Charged amount (g) of polyol (A1) + Charged amount (g) of organic acid (C) (dimethylol fatty acid) + Charged amount (g) of polyisocyanate (D) + Charged amount (g) of organic solvent before isocyanate group measurement) / (Charged amount (g) of polyol (A1) + Charged amount (g) of organic acid (C) (dimethylol fatty acid) + Charged amount (g) of polyisocyanate (D) + Charged amount (g) of chain extender (G)). In the case of each of the above-mentioned modified examples, "Charged amount (g) of polyol (A1)" is to be read as "Charged amount (g) of polyol (A2) + Charged amount (g) of polyfunctional polyol (B2)."

[0122] (Concentration of urea groups derived from amine compounds) In the polyurethane resin composition, the content of urea groups derived from amine compounds relative to the total mass of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G) (the concentration of urea groups derived from amine compounds) was determined from the amount of amine calculated from the amount of the amine compounds charged. Therefore, the concentration of urea groups derived from amine compounds is defined by the following formula: Concentration of urea groups derived from amine compound (mmol / g)=charged amount of amine compound (g) / molecular weight of chain extender (G) (amine compound) (g / mol)×number of amino groups per molecule / (charged amount of polyol (A1) (g)+charged amount of organic acid (C) (dimethylol fatty acid) (g)+charged amount of polyisocyanate (D) (g)+charged amount of chain extender (G) (g))×1000. In the case of each of the above-mentioned modified examples, "charged amount of polyol (A1) (g)" is to be read as "charged amount of polyol (A2) (g)+charged amount of polyfunctional polyol (B2) (g)."

[0123] In one embodiment of the present disclosure, water is used as a solvent, and therefore urea groups derived from amine compounds and urea groups derived from water are simultaneously generated. The reaction rate of urea groups derived from amine compounds is much higher than that of urea groups derived from water, and it can be said that all amines derived from amine compounds exist as urea groups.

[0124] (Concentration of urea groups derived from water) In the polyurethane resin composition, the content of urea groups derived from water (concentration of urea groups derived from water) relative to the sum of the mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G) was calculated by subtracting the concentration of urea groups derived from the chain extender (G) by the concentration of urea groups derived from the amine compound. Therefore, the concentration of urea groups derived from water is defined by the following formula: Concentration of urea groups derived from water (mmol / g) = Concentration of urea groups derived from chain extender (G) (mmol / g) - Concentration of urea groups derived from amine compound (mmol / g)

[0125] (Ratio of urea groups derived from amine compound) The content of urea groups derived from the amine compound relative to the content of urea groups derived from the chain extender (G) (ratio of urea groups derived from the amine compound) was calculated by dividing the concentration of urea groups derived from the amine compound by the concentration of urea groups derived from the chain extender (G). Therefore, the content of urea groups derived from the amine compound relative to the content of urea groups derived from the chain extender (G) is defined by the following formula: Content of urea groups derived from the amine compound relative to the content of urea groups derived from the chain extender (G) (ratio of urea groups derived from the amine compound) (mol %) = Concentration of urea groups derived from the amine compound (mmol / g) / Concentration of urea groups derived from the chain extender (G) (mmol / g) × 100

[0126] (Average hydroxyl value of polyol (A1) / average hydroxyl value of polyol (A2) and multifunctional polyol (B2)) - First and second embodiments The average hydroxyl value of polyol (A1) was calculated from the hydroxyl values ​​of the polyol components in polyol (A1) when mixed. Therefore, the average hydroxyl value is defined by the following formula: Average hydroxyl value (mg KOH / g) of polyol (A1) = (average hydroxyl value (mg KOH / g) of polyols other than polycarbonate polyol (B1) × charged amount (g) of polyols other than polycarbonate polyol (B1) + average hydroxyl value (mg KOH / g) of polycarbonate polyol (B1) × charged amount (g) of polycarbonate polyol (B1)) / (charged amount (g) of polyol (A1)) - In the case of modified example of first embodiment and modified example of second embodiment The average hydroxyl value of polyol (A2) and multifunctional polyol (B2) was calculated from the hydroxyl value when polyol (A2) and multifunctional polyol (B2) were mixed. Therefore, the average hydroxyl value is defined by the following formula. Average hydroxyl value (mg KOH / g) of polyol (A2) + multifunctional polyol (B2) = (average hydroxyl value (mg KOH / g) of polyol (A2) × charge amount (g) of polyol (A2) + average hydroxyl value (mg KOH / g) of multifunctional polyol (B2) × charge amount (g) of multifunctional polyol (B2)) / (charge amount (g) of polyol (A2) + charge amount (g) of multifunctional polyol (B2))

[0127] (Crosslink Density) The crosslink density for the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G) was calculated as follows: - In the case of the first and second embodiments, it was calculated from the amount of crosslinks derived from each of the following components: polycarbonate polyol (B1), a polyol in polyol (A1) having an average number of hydroxyl functional groups exceeding 2 (excluding polycarbonate polyol (B1)), and a tri- or higher functional polyhydric alcohol. - In the case of the modified example of the first embodiment and the modified example of the second embodiment, it was calculated from the amount of crosslinks derived from each of the following components: multifunctional polyol (B2), a polyol in polyol (A2) having an average number of hydroxyl functional groups exceeding 2, and a tri- or higher functional polyhydric alcohol.

[0128] Therefore, the crosslink density is defined by the following formula. When there are other components that form crosslinks, the crosslink density can be calculated in the same way by replacing the "polycarbonate polyol (B1)", "multifunctional polyol (B2)", and "polyhydric alcohol" in the molecules in the formula with the other components. However, when the average hydroxyl value is known, it can be calculated by substituting "polycarbonate polyol (B1)" and "multifunctional polyol (B2)", and when the true number average molecular weight (absolute molecular weight) is known, it can be calculated by substituting "polyhydric alcohol".

[0129] [In the case of polycarbonate polyol (B1)] Crosslink density (mmol / g)=(feed amount (g) of polycarbonate polyol (B1))×(average hydroxyl value (mg KOH / g) of polycarbonate polyol (B1)) / 56.11 (g KOH / g) / 1000 / (number of functional groups in polycarbonate polyol (B1))×(number of functional groups in polycarbonate polyol (B1)−2) / (feed amount (g) of polyol (A1)+(feed amount (g) of organic acid (C) (dimethylol fatty acid))+(feed amount (g) of polyisocyanate (D))+(feed amount (g) of chain extender (G))×1000 [In the case of multifunctional polyol (B2)] Crosslink density (mmol / g)=(g) of charged polyfunctional polyol (B2)×(mg KOH / g) of average hydroxyl value of polyfunctional polyol (B2) / 56.11(g KOH / g) / 1000 / (number of functional groups in polyfunctional polyol (B2)×(number of functional groups in polyfunctional polyol (B2)−2) / ((g) of charged polyol (A2)+(g) of charged polyfunctional polyol (B2)+(g) of charged organic acid (C) (dimethylol fatty acid)+(g) of charged polyisocyanate (D)+(g) of charged chain extender (G))×1000 [in the case of a tri- or higher functional polyhydric alcohol (or a polyol having an average number of hydroxyl functional groups exceeding 2)] Crosslink density (mmol / g) = charge amount (g) of polyol (or polyol having an average number of hydroxyl group functionalities exceeding 2) / molecular weight (g / mol) of polyol (or polyol having an average number of hydroxyl group functionalities exceeding 2) × (number of functional groups of polyol (or polyol having an average number of hydroxyl group functionalities exceeding 2) - 2) / (charge amount (g) of polyol (A1) + charge amount (g) of organic acid (C) (dimethylol fatty acid) + charge amount (g) of polyisocyanate (D) + charge amount (g) of chain extender (G)) × 1000. In the case of each of the above-mentioned modified examples, "charge amount (g) of polyol (A1)" is to be read as "charge amount (g) of polyol (A2) + charge amount (g) of polyfunctional polyol (B2)."

[0130] (Polycarbonate polyol (B1) content, multifunctional polyol (B2) content) In the first and second embodiments, the content of polycarbonate polyol (B1) in the polyurethane resin was calculated from the mass ratio when polycarbonate polyol (B1) and polyol (A1) other than polycarbonate polyol (B1) were mixed. Therefore, the polycarbonate polyol (B1) content is defined by the following formula: Polycarbonate polyol (B1) content (mass%) = Charge amount (g) of polycarbonate polyol (B1) / Charge amount (g) of polyol (A1) × 100 In the modified examples of the first and second embodiments, the content of multifunctional polyol (B2) in the polyurethane resin was calculated from the mass ratio when polyol (A2) and multifunctional polyol (B2) were mixed. Therefore, the content of the polyfunctional polyol (B2) is defined by the following formula: Content of the polyfunctional polyol (B2) (% by mass) = Charge amount of the polyfunctional polyol (B2) (g) / (Charge amount of the polyol (A2) (g) + Charge amount of the polyfunctional polyol (B2) (g)) × 100

[0131] The method for producing the polycarbonate polyols (polycarbonate diols) used in the examples and comparative examples is described below.

[0132] Synthesis Example 1: Polyol Production 1 826 g of 1,6-hexanediol, 787 g of diethyl carbonate, and 0.05 g of tetrabutyl titanate were mixed in a 2 L two-necked glass reactor equipped with a stirrer, thermometer, heater, and cooler, and reacted at 100 to 190°C for 8 hours under normal pressure while removing low-boiling components. The reaction temperature was then increased to 190°C, the pressure in the flask was reduced to 1 kPa, and the reaction was continued for another 8 hours to obtain a polycarbonate polyol (polycarbonate diol (PCD-1)).

[0133] Synthesis Example 2: Polyol Production 2 830 g of 1,6-hexanediol, 771 g of diethyl carbonate, and 0.05 g of tetrabutyl titanate were mixed in a 2 L two-necked glass reactor equipped with a stirrer, thermometer, heating device, and cooler, and reacted at 100 to 190°C for 8 hours under normal pressure while removing low-boiling components. The reaction temperature was then increased to 190°C, the pressure in the flask was reduced to 1 kPa, and the reaction was continued for another 8 hours to obtain a polycarbonate polyol (polycarbonate diol (PCD-2)).

[0134] Synthesis Example 3: Polyol Production 3 266.2 g of 1,6-hexanediol, 272.7 g of trimethylolpropane, 461.2 g of diethyl carbonate, and 0.05 g of potassium hydrogen carbonate were mixed in a 2 L two-necked glass reactor equipped with a stirrer, thermometer, heater, and cooler, and the mixture was reacted at 100 to 190°C for 8 hours under normal pressure while removing low-boiling components. The reaction temperature was then increased to 150°C, the pressure in the flask was reduced to 1 kPa, and the reaction was continued for another 8 hours to obtain polycarbonate polyol (PCP-α).

[0135] Synthesis Example 4: Polyol Production 4 Into a 1 L four-necked glass reactor equipped with a stirrer, a thermometer, a heating device, and a cooler, 575 g of the polycarbonate diol (PCD-1) obtained in Polyol Production 1, 400 g of polycaprolactone triol (PLACCEL 305), 25 g of polycaprolactone diol (PLACCEL 210), and 0.03 g of potassium hydrogen carbonate were charged, and a transesterification reaction was carried out at 190°C for 5 hours to obtain polyol (PCP-1).

[0136] Synthesis Example 5: Polyol Production 5 Into a 1 L four-necked glass reactor equipped with a stirrer, a thermometer, a heating device, and a cooler, 674 g of the polycarbonate diol (PCD-2) obtained in Polyol Production 2, 326 g of polycaprolactone triol (Placcel 305), and 0.03 g of potassium hydrogen carbonate were charged, and a transesterification reaction was carried out at 190°C for 5 hours to obtain polyol (PCP-2).

[0137] Synthesis Example 6: Polyol Production 6 Into a 1 L four-neck glass reactor equipped with a stirrer, a thermometer, a heating device, and a cooler, 678.1 g of the polycarbonate diol (PCD-1) obtained in Polyol Production 1, 85.7 g of polycaprolactone triol (PLACCEL 305), 236.2 g of polycaprolactone diol (PLACCEL 210), and 0.03 g of potassium hydrogen carbonate were charged, and a transesterification reaction was carried out at 190°C for 5 hours to obtain polyol (PCP-3).

[0138] Synthesis Example 7: Production of Polyol 7 Into a 1 L four-necked glass reactor equipped with a stirrer, a thermometer, a heating device, and a cooler, 50 g of the polycarbonate diol (PCD-1) obtained in the production of polyol, 249.9 g of polycaprolactone triol (PLACCEL 320), 199.9 g of polycaprolactone diol (PLACCEL 220), and 0.03 g of potassium hydrogen carbonate were charged, and a transesterification reaction was carried out at 190°C for 5 hours to obtain polyol (PCP-4).

[0139] Synthesis Example 8: Polyol Production 8 Into a 1 L four-necked glass reactor equipped with a stirrer, a thermometer, a heating device, and a cooler, 288.7 g of the polycarbonate diol (PCD-1) obtained in Polyol Production 1, 125.9 g of the polycarbonate polyol (PCP-α) obtained in Polyol Production 3, 85.3 g of polycaprolactone diol (Placcel 220), and 0.03 g of potassium hydrogen carbonate were charged, and a transesterification reaction was carried out at 190°C for 5 hours to obtain polyol (PCP-5).

[0140] (Average Number of Hydroxyl Functional Groups) The average number of hydroxyl functional groups of the polycarbonate polyol (B1) and the polyfunctional polyol (B2) was calculated using the following formula based on the nominal number of functional groups of the polyols contained in the polycarbonate polyol (B1) and the polyfunctional polyol (B2). The results are shown in Table 1. Average Number of Hydroxyl Functional Groups = ((Number of functional groups of polycarbonate polyol (b-1) × number of moles) + (Number of functional groups of polyester polyol (b-2) × number of moles) + (Number of functional groups of polyester polyol (b-3) × number of moles)) / ((Number of moles of polycarbonate polyol (b-1)) + (Number of moles of polyester polyol (b-2)) + (Number of moles of polyester polyol (b-3))). Note that the number of moles in the above formula can be calculated by dividing the charged amount by the molecular weight. Number of moles of compound in reaction system (number of moles) = amount of compound charged (g) / molecular weight of compound (g / mol)

[0141] (Number of hydroxyl functional groups of PCP-α) When the average number of hydroxyl functional groups could not be calculated from the charged amount, the number average molecular weight obtained by GPC measurement was used to calculate the average number of hydroxyl functional groups. The results are shown in Table 1. Average number of hydroxyl functional groups of PCP-α = 56.11 (mg KOH / g) × 1000 / number average molecular weight calculated by GPC measurement (g / mol) / average hydroxyl value (mg KOH / g)

[0142] (Ester Group Concentration) The content (ester group concentration) of polyester polyol (b-2) and polyester polyol (b-3) relative to the total of polycarbonate polyol (b-1), polyester polyol (b-2), and polyester polyol (b-3) in polycarbonate polyol (B1) and multifunctional polyol (B2) was calculated from the charged amounts of the raw polycarbonate compound and polyester compound. The ester group concentration is defined by the following formula. The results are shown in Table 1. Ester group concentration (mass%) = (charged amount (g) of polyester polyol (b-2) + charged amount (g) of polyester polyol (b-3)) / (charged amount (g) of polycarbonate polyol (b-1) + charged amount (g) of polyester polyol (b-2) + charged amount (g) of polyester polyol (b-3)) × 100

[0143] (Analysis and Evaluation) [Measurement of Number Average Molecular Weight] The resulting composition was subjected to GPC analysis under the following conditions to measure the number average molecular weight of the composition. The results are shown in Table 1.

[0144] -Conditions- (1) Measuring instrument: HLC-8420 (manufactured by Tosoh Corporation) (2) Column: TSKgel (manufactured by Tosoh Corporation) G3000H-XL G3000H-XL G2000H-XL G2000H-XL (3) Mobile phase: THF (tetrahydrofuran) (4) Detector: RI (refractive index) detector (attached to HLC-8420) (5) Temperature: 40°C (6) Flow rate: 1,000 ml / min (7) Calibration curve: A calibration curve was obtained using the following commercial products (all bifunctional polyoxypropylene polyols manufactured by Sanyo Chemical Industries, Ltd.).・"SANNIX PP-200" (number average molecular weight = 200, average number of hydroxyl functional groups: 2) ・"SANNIX PP-400" (number average molecular weight = 400, average number of hydroxyl functional groups: 2) ・"SANNIX PP-1000" (number average molecular weight = 1000, average number of hydroxyl functional groups: 2) ・"SANNIX PP-2000" (number average molecular weight = 2000, average number of hydroxyl functional groups: 2) ・"SANNIX PP-3000" (number average molecular weight = 3200, average number of hydroxyl functional groups: 2) ・"SANNIX PP-4000" (number average molecular weight = 4160, average number of hydroxyl functional groups: 2) (8) Approximation formula of calibration curve: cubic equation (9) Concentration of sample solution: 0.5 mass% THF solution

[0145] [Measurement of Hydroxyl Value (OHv)] The hydroxyl value of the composition obtained by a method using an acetylating reagent was measured in accordance with JIS K1557-1. The results are shown in Table 1.

[0146] [Evaluation of Properties] The resulting composition was used as a sample, and the sample was heated at 80°C for 1 hour and then left at 25°C for 3 days. The state of the sample after leaving it was visually inspected, and if it had even a slight fluidity at the above temperature, it was rated as a liquid, and if it had no fluidity, it was rated as a solid. The results are shown in Table 1.

[0147]

[0148] 1,6-Hexanediol: BASF JAPAN Trimethylolpropane: Tokyo Chemical Industry Co., Ltd. Diethyl carbonate: Sigma-Aldrich Tetrabutyl titanate: Tokyo Chemical Industry Co., Ltd. Potassium hydrogen carbonate: Fujifilm Wako Pure Chemical Industries, Ltd. PLACCEL 305: Polycaprolactone triol (molecular weight = 550, hydroxyl value = 305, number of functional groups = 3) manufactured by Daicel Corporation PLACCEL 320: Polycaprolactone triol (molecular weight = 2000, hydroxyl value = 84.2, number of functional groups = 3) manufactured by Daicel Corporation PLACCEL 210: Polycaprolactone diol (molecular weight = 1000, hydroxyl value = 112, number of functional groups = 2) manufactured by Daicel Corporation Placcel 220: Polycaprolactone diol (molecular weight = 2000, hydroxyl value = 56.1, number of functional groups = 2) manufactured by Daicel Corporation

[0149] Example 1: Preparation of aqueous polyurethane resin emulsion 1 A 2 L reactor (hereinafter referred to as reactor A) equipped with a stirrer, thermometer, nitrogen seal tube, and condenser was charged with 139.4 g of N-980N (manufactured by Tosoh Corporation: number average molecular weight 2000; hydroxyl value 56.11 mg KOH / g; 1,6-hexanediol-based polycarbonate diol), 6.2 g of 1,6-hexanediol, 62.4 g of PCP-1, 150 g of acetone, 10.6 g of 2,2-dimethylolpropanoic acid, and 69.3 g of isophorone diisocyanate, heated to 60°C, stirred at the same temperature for 30 minutes, then 0.24 g of U-600 was added, and the reaction was carried out for 5 hours. The unreacted isocyanate group content at the end of urethanization was 0.323 mmol / g relative to the amount charged. Next, 8.0 g of triethylamine was added to neutralize the carboxyl groups, and then 640 g of water was added with stirring and emulsified. After emulsification, 0.36 g of KL-245 was added, and within 30 minutes, amine water (60 g of water and 4.0 g of isophoronediamine) was added, and the amine chain extension reaction was carried out at 40°C for 12 hours. When the presence of isocyanate groups was no longer confirmed by FT-IR, stirring was stopped. The reaction solution was then transferred to a 2 L eggplant flask and distilled under reduced pressure to remove 150 g of acetone and 100 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-1).

[0150] Example 2: Preparation of polyurethane resin emulsion 2 Reactor A was charged with 114.4 g of N-980N, 3.0 g of 1,6-hexanediol, 93.6 g of PCP-1, 150 g of acetone, 10.6 g of 2,2-dimethylolpropanoic acid, and 69.3 g of isophorone diisocyanate, and the mixture was heated to 60°C and stirred at the same temperature for 30 minutes. Then, 0.24 g of U-600 was added and the mixture was allowed to react for 5 hours. The unreacted isocyanate group content at the end of urethanization was 0.305 mmol / g relative to the amount charged. Next, emulsification and post-emulsification procedures were carried out in the same manner as in Example 1, to obtain an aqueous polyurethane resin emulsion composition (PUD-2).

[0151] Example 3: Production of polyurethane resin emulsion 3. 110.3 g of N-980N, 4.1 g of 1,6-hexanediol, 93.6 g of PCP-2, 150 g of acetone, 10.6 g of 2,2-dimethylolpropanoic acid, and 69.3 g of isophorone diisocyanate were charged into reactor A, heated to 60°C, and stirred at the same temperature for 30 minutes. Then, 0.24 g of U-600 was added and the reaction was carried out for 5 hours. The unreacted isocyanate group content at the end of urethanization was 0.312 mmol / g relative to the amount charged. Next, emulsification and post-emulsification procedures were carried out in the same manner as in Example 1, to obtain an aqueous polyurethane resin emulsion composition (PUD-3).

[0152] Example 4: Production of polyurethane resin emulsion 4 Reactor A was charged with 59.4 g of N-980N, 145.3 g of PCP-1, 150 g of acetone, 10.6 g of 2,2-dimethylolpropanoic acid, and 72.7 g of isophorone diisocyanate, and the mixture was heated to 60°C and stirred at the same temperature for 30 minutes. After that, 0.24 g of U-600 was added and the mixture was allowed to react for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.260 mmol / g relative to the amount charged. Next, emulsification and post-emulsification operations were performed in the same manner as in Example 1, to obtain an aqueous polyurethane resin emulsion composition (PUD-4).

[0153] (Example 5: Production of polyurethane resin emulsion 5) 103.1 g of N-980N, 6.6 g of 1,6-hexanediol, 109.7 g of PCP-3, 150 g of acetone, 10.6 g of 2,2-dimethylolpropanoic acid, and 59.9 g of isophorone diisocyanate were charged into reactor A, heated to 60°C, and stirred at the same temperature for 30 minutes. After that, 0.24 g of U-600 was added and the reaction was carried out for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.114 mmol / g relative to the amount charged. Next, 8.0 g of triethylamine was charged to neutralize the carboxyl groups, and then 640 g of water was charged with stirring to emulsify. After emulsification, 0.36 g of KL-245 was added, and within 30 minutes, amine water (60 g of water and 2.0 g of isophoronediamine) was added, and the amine chain extension reaction was carried out at 40°C for 12 hours. Stirring was stopped when the presence of isocyanate groups was no longer confirmed by FT-IR. The reaction solution was then transferred to a 2-L recovery flask and distilled under reduced pressure to remove 150 g of acetone and 100 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-5).

[0154] Example 6: Production of Polyurethane Resin Emulsion 6 Reactor A was charged with 49.1 g of N-980N, 5.8 g of 1,6-hexanediol, 164.6 g of PCP-3, 150 g of acetone, 10.6 g of 2,2-dimethylolpropanoic acid, and 59.9 g of isophorone diisocyanate, and the mixture was heated to 60°C and stirred at the same temperature for 30 minutes. Then, 0.24 g of U-600 was added and the mixture was allowed to react for 5 hours. The unreacted isocyanate group content at the end of urethanization was 0.112 mmol / g relative to the amount charged. Next, emulsification and post-emulsification procedures were carried out in the same manner as in Example 5, yielding an aqueous polyurethane resin emulsion composition (PUD-6).

[0155] Example 7: Production of polyurethane resin emulsion 7 Reactor A was charged with 5.0 g of 1,6-hexanediol, 214.5 g of PCP-3, 150 g of acetone, 10.6 g of 2,2-dimethylolpropanoic acid, and 59.9 g of isophorone diisocyanate, and the mixture was heated to 60°C and stirred at the same temperature for 30 minutes. After that, 0.24 g of U-600 was added and the reaction was carried out for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.112 mmol / g relative to the amount charged. Next, emulsification and post-emulsification operations were carried out in the same manner as in Example 5, to obtain an aqueous polyurethane resin emulsion composition (PUD-7).

[0156] Example 8: Production of polyurethane resin emulsion 8 Reactor A was charged with 101.0 g of N-980N, 6.5 g of 1,6-hexanediol, 107.5 g of PCP-3, 150 g of acetone, 10.6 g of 2,2-dimethylolpropanoic acid, and 62.3 g of isophorone diisocyanate, and the mixture was heated to 60°C and stirred at the same temperature for 30 minutes. Then, 0.24 g of U-600 was added and the mixture was allowed to react for 5 hours. The unreacted isocyanate group content at the end of urethanization was 0.208 mmol / g relative to the amount charged. Next, emulsification and post-emulsification procedures were carried out in the same manner as in Example 1, to obtain an aqueous polyurethane resin emulsion composition (PUD-8).

[0157] Example 9: Production of Polyurethane Resin Emulsion 9 Reactor A was charged with 48.1 g of N-980N, 5.6 g of 1,6-hexanediol, 161.2 g of PCP-3, 150 g of acetone, 10.6 g of 2,2-dimethylolpropanoic acid, and 62.3 g of isophorone diisocyanate, and the mixture was heated to 60°C and stirred at the same temperature for 30 minutes. Then, 0.24 g of U-600 was added and the mixture was allowed to react for 5 hours. The unreacted isocyanate group content at the end of urethanization was 0.169 mmol / g relative to the amount charged. Next, emulsification and post-emulsification procedures were carried out in the same manner as in Example 1, to obtain an aqueous polyurethane resin emulsion composition (PUD-9).

[0158] Example 10: Production of polyurethane resin emulsion 10 Reactor A was charged with 4.8 g of 1,6-hexanediol, 210.2 g of PCP-3, 150 g of acetone, 10.6 g of 2,2-dimethylolpropanoic acid, and 62.3 g of isophorone diisocyanate, and the mixture was heated to 60°C and stirred at the same temperature for 30 minutes. After that, 0.24 g of U-600 was added and the reaction was carried out for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.182 mmol / g relative to the amount charged. Next, emulsification and post-emulsification operations were carried out in the same manner as in Example 1, to obtain an aqueous polyurethane resin emulsion composition (PUD-10).

[0159] Example 11: Production of polyurethane resin emulsion 11 Reactor A was charged with 112.7 g of N-980N, 112.7 g of PCP-3, 150 g of acetone, 10.6 g of 2,2-dimethylolpropanoic acid, and 51.8 g of isophorone diisocyanate, and the mixture was heated to 60°C and stirred at the same temperature for 30 minutes. After that, 0.24 g of U-600 was added and the reaction was carried out for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.234 mmol / g relative to the amount charged. Next, emulsification and post-emulsification operations were carried out in the same manner as in Example 1, to obtain an aqueous polyurethane resin emulsion composition (PUD-11).

[0160] Example 12: Preparation of polyurethane resin emulsion 12 Reactor A was charged with 56.0 g of N-980N, 167.9 g of PCP-3, 150 g of acetone, 10.6 g of 2,2-dimethylolpropanoic acid, and 53.4 g of isophorone diisocyanate, and the mixture was heated to 60°C and stirred at the same temperature for 30 minutes. After that, 0.24 g of U-600 was added and the mixture was allowed to react for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.213 mmol / g relative to the amount charged. Next, emulsification and post-emulsification operations were performed in the same manner as in Example 1, to obtain an aqueous polyurethane resin emulsion composition (PUD-12).

[0161] Example 13: Preparation of polyurethane resin emulsion 13 Reactor A was charged with 167.4 g of N-980N, 9.4 g of 1,6-hexanediol, 31.2 g of PCP-1, 150 g of acetone, 10.6 g of 2,2-dimethylolpropanoic acid, and 69.3 g of isophorone diisocyanate, and the mixture was heated to 60°C and stirred at the same temperature for 30 minutes. After that, 0.24 g of U-600 was added and the reaction was carried out for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.278 mmol / g relative to the amount charged. Next, emulsification and post-emulsification operations were carried out in the same manner as in Example 1, to obtain an aqueous polyurethane resin emulsion composition (PUD-13).

[0162] Example 14: Production of polyurethane resin emulsion 14. Reactor A was charged with 50.5 g of PLACCEL 220, 3.3 g of 1,6-hexanediol, 53.7 g of PCP-3, 75 g of acetone, 5.3 g of 2,2-dimethylolpropanoic acid, and 31.2 g of isophorone diisocyanate, and the mixture was heated to 60°C and stirred at the same temperature for 30 minutes. Then, 0.12 g of U-600 was added and the mixture was reacted for 5 hours. The content of unreacted isocyanate groups at the end of the urethanization reaction was 0.129 mmol / g relative to the amount charged. Next, 4.0 g of triethylamine was charged to neutralize the carboxyl groups, and then 320 g of water was charged with stirring to emulsify the mixture. After emulsification, 0.18 g of KL-245 was added, and within 30 minutes, amine water (30 g of water and 2.0 g of isophoronediamine) was added, and the amine chain extension reaction was carried out at 40°C for 12 hours. Stirring was stopped when the presence of isocyanate groups was no longer confirmed by FT-IR. The reaction solution was then transferred to a 2-L recovery flask and distilled under reduced pressure to remove 75 g of acetone and 50 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-14).

[0163] Example 15: Production of polyurethane resin emulsion 15. 50.5 g of N-980N, 3.3 g of 1,6-hexanediol, 53.7 g of PCP-4, 75 g of acetone, 5.3 g of 2,2-dimethylolpropanoic acid, and 31.2 g of isophorone diisocyanate were charged into reactor A, heated to 60°C, and stirred at the same temperature for 30 minutes. Then, 0.12 g of U-600 was added and the reaction was carried out for 5 hours. The unreacted isocyanate group content at the end of urethanization was 0.127 mmol / g relative to the amount charged. Next, emulsification and post-emulsification operations were carried out in the same manner as in Example 14 to obtain an aqueous polyurethane resin emulsion composition (PUD-15).

[0164] Example 16: Production of polyurethane resin emulsion 16 Reactor A was charged with 53.0 g of N-980N, 0.7 g of 1,6-hexanediol, 53.7 g of PCP-5, 75 g of acetone, 5.3 g of 2,2-dimethylolpropanoic acid, and 31.2 g of isophorone diisocyanate, and the mixture was heated to 60°C and stirred at the same temperature for 30 minutes. After that, 0.12 g of U-600 was added and the reaction was carried out for 5 hours. The unreacted isocyanate group content at the end of urethanization was 0.140 mmol / g relative to the amount charged. Next, emulsification and post-emulsification operations were carried out in the same manner as in Example 14, to obtain an aqueous polyurethane resin emulsion composition (PUD-16).

[0165] Comparative Example 1: Production of Polyurethane Resin Emulsion 17 Reactor A was charged with 206.9 g of N-980N, 8.2 g of 1,6-hexanediol, 150 g of acetone, 10.6 g of 2,2-dimethylolpropanoic acid, and 62.3 g of isophorone diisocyanate, and the mixture was heated to 60°C and stirred at the same temperature for 30 minutes. Then, 0.24 g of U-600 was added and the mixture was allowed to react for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.197 mmol / g relative to the amount charged. Next, emulsification and post-emulsification procedures were carried out in the same manner as in Example 1, yielding an aqueous polyurethane resin emulsion composition (PUD-17).

[0166] (Comparative Example 2: Production of Polyurethane Resin Emulsion 18) 198.2 g of N-980N, 7.8 g of 1,6-hexanediol, 150 g of acetone, 10.6 g of 2,2-dimethylolpropanoic acid, and 67.2 g of isophorone diisocyanate were charged into reactor A, heated to 60°C, and stirred at the same temperature for 30 minutes. After that, 0.24 g of U-600 was added and the reaction was carried out for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.263 mmol / g relative to the amount charged. Next, 8.0 g of triethylamine was charged to neutralize the carboxyl groups, and then 640 g of water was charged with stirring to emulsify. After emulsification, 0.36 g of KL-245 was added, and within 30 minutes, amine water (60 g of water and 8.0 g of isophoronediamine) was added, and the amine chain extension reaction was carried out at 40°C for 12 hours. Stirring was stopped when the presence of isocyanate groups was no longer confirmed by FT-IR. The reaction solution was then transferred to a 2-L recovery flask and distilled under reduced pressure to remove 150 g of acetone and 100 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-18).

[0167] Comparative Example 3: Production of Polyurethane Resin Emulsion 19 Reactor A was charged with 193.9 g of N-980N, 7.6 g of 1,6-hexanediol, 150 g of acetone, 10.6 g of 2,2-dimethylolpropanoic acid, and 69.7 g of isophorone diisocyanate, and the mixture was heated to 60°C and stirred at the same temperature for 30 minutes. After that, 0.24 g of U-600 was added and the mixture was reacted for 5 hours. The content of unreacted isocyanate groups at the end of the urethanization reaction was 0.275 mmol / g relative to the amount charged. Next, 8.0 g of triethylamine was charged to neutralize the carboxyl groups, and then 640 g of water was charged with stirring to emulsify the mixture. After emulsification, 0.36 g of KL-245 was added, and within 30 minutes, amine water (60 g of water and 9.9 g of isophoronediamine) was added, and the amine chain extension reaction was carried out at 40°C for 12 hours. Stirring was stopped when the presence of isocyanate groups was no longer confirmed by FT-IR. The reaction solution was then transferred to a 2-L recovery flask and distilled under reduced pressure to remove 150 g of acetone and 100 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-19).

[0168] Comparative Example 4: Production of Polyurethane Resin Emulsion 20 Reactor A was charged with 202.3 g of N-980N, 7.1 g of 1,6-hexanediol, 4.3 g of trimethylolpropane, 150 g of acetone, 10.9 g of 2,2-dimethylolpropanoic acid, and 71.2 g of isophorone diisocyanate, and the mixture was heated to 60°C and stirred at the same temperature for 30 minutes. Then, 0.24 g of U-600 was added and the mixture was reacted for 5 hours. The content of unreacted isocyanate groups at the end of the urethanization reaction was 0.328 mmol / g relative to the amount charged. Next, 8.0 g of triethylamine was charged to neutralize the carboxyl groups, and then 640 g of water was charged with stirring to emulsify the mixture. After emulsification, 0.36 g of KL-245 was added, and within 30 minutes, amine water (60 g of water and 4.1 g of isophoronediamine) was added, and the amine chain extension reaction was carried out at 40°C for 12 hours. Stirring was stopped when the presence of isocyanate groups was no longer confirmed by FT-IR. The reaction solution was then transferred to a 2-L recovery flask and distilled under reduced pressure to remove 150 g of acetone and 100 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-20).

[0169] (Comparative Example 5: Production of Polyurethane Resin Emulsion 21) 203.7 g of N-980N, 1.4 g of 1,6-hexanediol, 8.6 g of trimethylolpropane, 150 g of acetone, 10.9 g of 2,2-dimethylolpropanoic acid, and 71.2 g of isophorone diisocyanate were charged into reactor A, heated to 60°C, and stirred at the same temperature for 30 minutes. After that, 0.24 g of U-600 was added and the reaction was carried out for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.305 mmol / g relative to the amount charged. Next, 8.0 g of triethylamine was charged to neutralize the carboxyl groups, and then 640 g of water was charged with stirring to emulsify. After emulsification, 0.36 g of KL-245 was added, and within 30 minutes, amine water (60 g of water and 4.1 g of isophoronediamine) was added, and the amine chain extension reaction was carried out at 40°C for 12 hours. Stirring was stopped when the presence of isocyanate groups was no longer confirmed by FT-IR. The reaction solution was then transferred to a 2-L recovery flask and distilled under reduced pressure to remove 150 g of acetone and 100 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-21).

[0170] (Example 17: Production of polyurethane resin emulsion 22) 48.8 g of N-980N, 3.2 g of 1,6-hexanediol, 52.0 g of PCP-3, 75 g of acetone, 5.3 g of 2,2-dimethylolpropanoic acid, and 35.4 g of isophorone diisocyanate were charged into reactor A, heated to 60°C, and stirred at the same temperature for 30 minutes. After that, 0.12 g of U-600 was added and the reaction was carried out for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.374 mmol / g relative to the amount charged. Next, 4.0 g of triethylamine was charged to neutralize the carboxyl groups, and then 320 g of water was charged with stirring to emulsify. After emulsification, 0.18 g of KL-245 was added, and within 30 minutes, amine water (30 g of water and 0.62 g of isophoronediamine) was added, and the amine chain extension reaction was carried out at 40°C for 12 hours. Stirring was stopped when the presence of isocyanate groups was no longer confirmed by FT-IR. The reaction solution was then transferred to a 2-L recovery flask and distilled under reduced pressure to remove 75 g of acetone and 50 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-22).

[0171] (Example 18: Production of polyurethane resin emulsion 23) 48.1 g of N-980N, 3.2 g of 1,6-hexanediol, 51.2 g of PCP-3, 75 g of acetone, 5.3 g of 2,2-dimethylolpropanoic acid, and 36.8 g of isophorone diisocyanate were charged into reactor A, heated to 60°C, and stirred at the same temperature for 30 minutes. After that, 0.12 g of U-600 was added and the reaction was carried out for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.423 mmol / g relative to the amount charged. Next, 4.0 g of triethylamine was charged to neutralize the carboxyl groups, and then 320 g of water was charged with stirring to emulsify. After emulsification, 0.18 g of KL-245 was added, and within 30 minutes, amine water (30 g of water and 0.75 g of isophoronediamine) was added, and the amine chain extension reaction was carried out at 40°C for 12 hours. Stirring was stopped when the presence of isocyanate groups was no longer confirmed by FT-IR. The reaction solution was then transferred to a 2-L recovery flask and distilled under reduced pressure to remove 75 g of acetone and 50 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-23).

[0172] (Example 19: Production of polyurethane resin emulsion 24) Reactor A was charged with 46.6 g of N-980N, 3.1 g of 1,6-hexanediol, 49.7 g of PCP-3, 75 g of acetone, 5.3 g of 2,2-dimethylolpropanoic acid, and 39.5 g of isophorone diisocyanate, and the mixture was heated to 60°C and stirred at the same temperature for 30 minutes. After that, 0.12 g of U-600 was added and the mixture was allowed to react for 5 hours. The content of unreacted isocyanate groups at the end of the urethanization reaction was 0.523 mmol / g relative to the amount charged. Next, 4.0 g of triethylamine was charged to neutralize the carboxyl groups, and then 320 g of water was charged with stirring to emulsify the mixture. After emulsification, 0.18 g of KL-245 was added, and within 30 minutes, amine water (30 g of water and 0.99 g of isophoronediamine) was added, and the amine chain extension reaction was carried out at 40°C for 12 hours. Stirring was stopped when the presence of isocyanate groups was no longer confirmed by FT-IR. The reaction solution was then transferred to a 2-L recovery flask and distilled under reduced pressure to remove 75 g of acetone and 50 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-24).

[0173] (Example 20: Production of polyurethane resin emulsion 25) Reactor A was charged with 60.0 g of N-980N, 2.2 g of 1,6-hexanediol, 41.5 g of PCP-1, 75 g of acetone, 5.3 g of 2,2-dimethylolpropanoic acid, and 34.6 g of isophorone diisocyanate, and the mixture was heated to 60°C and stirred at the same temperature for 30 minutes. After that, 0.12 g of U-600 was added and the mixture was allowed to react for 5 hours. The unreacted isocyanate group content at the end of urethanization was 0.244 mmol / g relative to the amount charged. Next, 4.0 g of triethylamine was charged to neutralize the carboxyl groups, and then 350 g of water was charged with stirring and emulsified. After emulsification, 0.18 g of KL-245 was added, and the amine chain extension reaction was carried out at 40°C for 12 hours. When the presence of isocyanate groups was no longer confirmed by FT-IR, stirring was stopped. The reaction solution was then transferred to a 2 L recovery flask and distilled under reduced pressure to remove 75 g of acetone and 50 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-25).

[0174] (Example 21: Production of Polyurethane Resin Emulsion 26) An isocyanate-terminated urethane prepolymer was obtained in reactor A in the same manner as in Example 20. The unreacted isocyanate group content at the end of urethanization was 0.222 mmol / g relative to the amount charged. Next, 4.0 g of triethylamine was charged to neutralize the carboxyl groups, and then 320 g of water was charged with stirring to emulsify. After emulsification, 0.18 g of KL-245 was added, and within 30 minutes, amine water (containing 30 g of water and 0.83 g of isophoronediamine) was charged, and an amine chain extension reaction was carried out at 40°C for 12 hours. By performing the same operations as in Example 20, an aqueous polyurethane resin emulsion composition (PUD-26) was obtained.

[0175] (Example 22: Production of Polyurethane Resin Emulsion 27) An isocyanate-terminated urethane prepolymer was obtained in reactor A in the same manner as in Example 20. The unreacted isocyanate group content at the end of urethanization was 0.253 mmol / g relative to the amount charged. Next, 4.0 g of triethylamine was charged to neutralize the carboxyl groups, and then 320 g of water was charged with stirring to emulsify. After emulsification, 0.18 g of KL-245 was added, and within 30 minutes, amine water (containing 30 g of water and 1.88 g of isophorone diamine) was charged, and an amine chain extension reaction was carried out at 40°C for 12 hours. By performing the same operations as in Example 20, an aqueous polyurethane resin emulsion composition (PUD-27) was obtained.

[0176] Example 23: Production of polyurethane resin emulsion 28 An isocyanate-terminated urethane prepolymer was prepared in reactor A in the same manner as in Example 20. The unreacted isocyanate group content at the end of urethanization was 0.257 mmol / g relative to the amount charged. Next, 4.0 g of triethylamine was charged to neutralize the carboxyl groups, and then 320 g of water was charged with stirring to emulsify. After emulsification, 0.18 g of KL-245 was added, and within 30 minutes, amine water (containing 30 g of water and 3.83 g of isophoronediamine) was charged, and an amine chain extension reaction was carried out at 40°C for 12 hours. This was followed by the same procedures as in Example 20 to obtain an aqueous polyurethane resin emulsion composition (PUD-28).

[0177] (Example 24: Production of polyurethane resin emulsion 29) An isocyanate-terminated urethane prepolymer was obtained in reactor A in the same manner as in Example 20. The unreacted isocyanate group content at the end of urethanization was 0.241 mmol / g relative to the amount charged. Next, 4.0 g of triethylamine was charged to neutralize the carboxyl groups, and then 320 g of water was charged with stirring to emulsify. After emulsification, 0.18 g of KL-245 was added, and within 30 minutes, amine water (containing 30 g of water and 4.04 g of isophoronediamine) was charged, and an amine chain extension reaction was carried out at 40°C for 12 hours. By performing the same operations as in Example 20, an aqueous polyurethane resin emulsion composition (PUD-29) was obtained.

[0178] (Example 25: Production of Polyurethane Resin Emulsion 30) An isocyanate-terminated urethane prepolymer was prepared in reactor A in the same manner as in Example 20. The unreacted isocyanate group content at the end of urethanization was 0.259 mmol / g relative to the amount charged. Next, 4.0 g of triethylamine was charged to neutralize the carboxyl groups, and then 320 g of water was charged with stirring to emulsify. After emulsification, 0.18 g of KL-245 was added, and within 30 minutes, amine water (containing 30 g of water and 4.83 g of isophorone diamine) was charged, and an amine chain extension reaction was carried out at 40°C for 12 hours. By performing the same operations as in Example 20, an aqueous polyurethane resin emulsion composition (PUD-30) was obtained.

[0179] Comparative Example 6: Production of Polyurethane Resin Emulsion 31 An isocyanate-terminated urethane prepolymer was prepared in reactor A in the same manner as in Example 20. The unreacted isocyanate group content at the end of urethanization was 0.675 mmol / g relative to the amount charged. Next, 4.0 g of triethylamine was charged to neutralize the carboxyl groups, and then 320 g of water was charged with stirring to emulsify. After emulsification, 0.18 g of KL-245 was added, and within 30 minutes, amine water (containing 30 g of water and 1.18 g of isophorone diamine) was charged, and an amine chain extension reaction was carried out at 40°C for 12 hours. This was followed by the same procedures as in Example 20 to obtain an aqueous polyurethane resin emulsion composition (PUD-31).

[0180] (Example 26: Production of polyurethane resin emulsion 32) 10.3 g of N-980N, 4.8 g of 1,6-hexanediol, 191.3 g of PCP-3, 150 g of acetone, 10.6 g of 2,2-dimethylolpropanoic acid, and 67.3 g of isophorone diisocyanate were charged into reactor A, heated to 60°C, and stirred at the same temperature for 30 minutes. After that, 0.24 g of U-600 was added and the reaction was carried out for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.342 mmol / g relative to the amount charged. Next, 8.0 g of triethylamine was charged to neutralize the carboxyl groups, and then 640 g of water was charged with stirring to emulsify. After emulsification, 0.36 g of KL-245 was added, and within 30 minutes, amine water (a blend of 60 g of water, 4.0 g of isophoronediamine, and 3.6 g of monoethanolamine) was added, and the amine chain extension reaction was carried out at 40°C for 12 hours. Stirring was stopped when the presence of isocyanate groups was no longer confirmed by FT-IR. The reaction solution was then transferred to a 2-L recovery flask and distilled under reduced pressure to remove 150 g of acetone and 100 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-32).

[0181] (Comparative Example 7: Production of Polyurethane Resin Emulsion 33) 204.1 g of N-980N, 8.0 g of 1,6-hexanediol, 150 g of acetone, 10.9 g of 2,2-dimethylolpropanoic acid, and 69.2 g of isophorone diisocyanate were charged into reactor A, heated to 60°C, and stirred at the same temperature for 30 minutes. After that, 0.24 g of U-600 was added and the reaction was carried out for 5 hours. The content of unreacted isocyanate groups at the end of the urethanization was 0.356 mmol / g relative to the amount charged. Next, 8.2 g of triethylamine was charged to neutralize the carboxyl groups, and then 640 g of water was charged with stirring to emulsify. After emulsification, 0.36 g of KL-245 was added, and within 30 minutes, amine water (60 g of water, 4.1 g of isophoronediamine, and 3.7 g of monoethanolamine) was added, and the amine chain extension reaction was carried out at 40°C for 12 hours. Stirring was stopped when the presence of isocyanate groups was no longer confirmed by FT-IR. The reaction solution was then transferred to a 2-L recovery flask and distilled under reduced pressure to remove 150 g of acetone and 100 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-33).

[0182] (Comparative Example 8: Production of Polyurethane Resin Emulsion 34) 206.1 g of N-980N, 6.0 g of trimethylolpropane, 150 g of acetone, 10.9 g of 2,2-dimethylolpropanoic acid, and 69.2 g of isophorone diisocyanate were charged into reactor A, heated to 60°C, and stirred at the same temperature for 30 minutes. After that, 0.24 g of U-600 was added and the reaction was carried out for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.361 mmol / g relative to the amount charged. Next, 8.2 g of triethylamine was charged to neutralize the carboxyl groups, and then 640 g of water was charged with stirring to emulsify. After emulsification, 0.36 g of KL-245 was added, and within 30 minutes, amine water (60 g of water, 4.1 g of isophoronediamine, and 3.7 g of monoethanolamine) was added, and the amine chain extension reaction was carried out at 40°C for 12 hours. When the presence of isocyanate groups was no longer confirmed by FT-IR, stirring was stopped. The reaction solution was then transferred to a 2-L recovery flask and distilled under reduced pressure to remove 150 g of acetone and 100 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-34).

[0183] The compositions of the resulting aqueous polyurethane resin emulsion compositions are shown in Tables 2 to 5. In Tables 2 to 5, the isocyanate group-terminated urethane prepolymer (E) is abbreviated as "prepolymer (E)."

[0184]

[0185]

[0186]

[0187]

[0188] Trimethylolpropane: Sigma-Aldrich; 1,6-Hexanediol: BASF-JAPAN; 2,2-Dimethylolpropionic acid: Tokyo Chemical Industry Co., Ltd.; Isophorone diisocyanate: Evonik; Acetone: KH Neochem; Triethylamine: Kishida Chemical Co., Ltd.; Isophorone diamine: Tokyo Chemical Industry Co., Ltd.; Monoethanolamine: Fujifilm Wako Pure Chemical Industries, Ltd.; Neostan U-600: Nitto Kasei Co., Ltd.; KL-245: Evonik; Water: City water

[0189] <Method for preparing a film for tensile property testing> 14.0 parts of dipropylene glycol dimethyl ether was added to 100 parts of the aqueous polyurethane resin emulsion compositions PUD-1 to PUD-31 obtained in Examples 1 to 25 and Comparative Examples 1 to 6, and the mixture was mixed to obtain a base resin. The base resin was applied to a dry film thickness of approximately 100 μm, and cured by drying at 25°C for 2 days and at 80°C for 2 hours. The physical properties of this cured product were evaluated. The results are shown in Tables 6 to 8.

[0190] [Evaluation Tests] [Tensile Properties] The tensile properties of the obtained cured products were measured in accordance with JIS K6251 (100% modulus, strength at break, elongation at break). Testing equipment: Tensilon UTA-500 (manufactured by A&D Co., Ltd.) Measurement conditions: 25°C x 50% RH Head speed: 200 mm / min No. 4 dumbbell

[0191] [Softening Temperature] A test piece was obtained from the obtained film using a dumbbell, and a 2 cm gauge line was marked on the test piece, and the thickness at the center of the gauge line was measured. A weight of a predetermined weight was attached to one grip of the test piece, and the other grip was clamped with a double clip. The test piece was hung in a dryer with the clip facing up, and the temperature inside the dryer was increased and the distance between the gauge lines was observed. The temperature when the distance between the gauge lines reached 4 cm was read as the softening temperature. - Processing device: constant temperature air dryer DRK633DA (manufactured by Advantec Co., Ltd.) - Weight: thickness at the center of the gauge line (μm) × 0.05 g - Dumbbell No. 2 (based on JIS K6251) - Heating rate: 5°C / min

[0192] [Evaluation criteria: one-component type] The physical properties of 100% modulus, strength at break, elongation at break, and softening temperature were evaluated as A, B, C, or D (A: very good, B: good, C: fair, D: poor). Furthermore, the overall evaluation was evaluated as A, B, or D (A: very good, B: good, D: poor). <100% Modulus> A: 2.7 MPa or more and 4.5 MPa or less B: Less than 2.7 MPa, or more than 4.5 MPa and less than 5.0 MPa D: 5.0 MPa or more <Strength at break> A: 35 MPa or more C: Less than 35 MPa <Elongation at break> A: 350 MPa or more C: Less than 350 MPa <Softening temperature> A: 120°C or more B: Less than 120°C and 85°C or more D: Less than 85°C <Overall evaluation> A: Each physical property was evaluated as A only B: No physical property was evaluated as D, and at least one physical property was evaluated as B or C D: Each physical property was evaluated as D

[0193]

[0194]

[0195]

[0196] Furthermore, PUD-32 to PUD-34, which are the polyol components obtained in Example 26 and Comparative Examples 7 and 8, the curing agent (X), which is the polyisocyanate component, and the film-forming aid were charged into a 200 ml glass bottle in the amounts shown in Table 9 and mixed to obtain a liquid mixture. The liquid mixture was applied to release paper so that the dry film thickness was approximately 100 μm, and a cured product was produced by drying at 25°C for 2 days and at 80°C for 2 hours. The physical properties of this cured product were evaluated. The results are shown in Table 9. The units of charge in the table are in grams. Dipropylene glycol dimethyl ether: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Aquanate 200: manufactured by Tosoh Corporation (nonionic water-dispersible polyisocyanate, NCO content = 11.9%)

[0197] [Evaluation criteria: two-component type] The physical properties of 100% modulus, strength at break, elongation at break, and softening temperature were evaluated as A, B, C, or D (A: very good, B: good, C: fair, D: poor). Furthermore, the overall evaluation was evaluated as A, B, or D (A: very good, B: good, D: poor). <100% Modulus> A: 2.0 MPa or more and 3.5 MPa or less B: Less than 2.0 MPa, or more than 3.5 MPa and less than 4.0 MPa D: 4.0 MPa or more <Strength at break> A: 30 MPa or more C: Less than 30 MPa <Elongation at break> A: 300 MPa or more C: Less than 300 MPa <Softening temperature> A: 190°C or more D: Less than 190°C <Overall evaluation> A: Each physical property was evaluated as A only B: Each physical property was evaluated as not D, and at least one of B or C was included D: Each physical property was evaluated as D

[0198]

Claims

1. a reaction product of an isocyanate group-terminated urethane prepolymer (E) and a chain extender (G); A polyurethane resin composition comprising: The isocyanate group-terminated urethane prepolymer (E) is a polyol (A1) containing a polycarbonate polyol (B1) having an ester bond and an average hydroxyl functional group number of more than 2; an organic acid (C); a reaction product of Polyol (A2), a multifunctional polyol (B2) different from the polyol (A2); and an organic acid (C); and a polyisocyanate (D), The polyfunctional polyol (B2) is a polycarbonate polyol having an ester bond and an average hydroxyl group functionality of more than 2, the content of the polycarbonate polyol (B1) is 10 to 99% by mass relative to the content of the polyol (A1), the content of the polyfunctional polyol (B2) is 10 to 99 mass% based on the total content of the polyol (A2) and the content of the polyfunctional polyol (B2), a crosslinking density of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G) is 0.02 to 0.35; In the polyurethane resin composition, the content of the urea group derived from the chain extender (G) is 0.05 to 1.00 mmol / g relative to the total mass of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G), the chain extender (G) contains an amine compound having one or more primary or secondary amino groups, the polyurethane resin composition, wherein the content of the urea group derived from the amine compound is more than 0 mmol / g and 0.95 mmol / g or less, relative to the total mass of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G).

2. The polyurethane resin composition a reaction product of an isocyanate group-terminated urethane prepolymer (E) and a chain extender (G); A polyurethane resin composition comprising: The isocyanate group-terminated urethane prepolymer (E) is Polyol (A2), a multifunctional polyol (B2) different from the polyol (A2); and an organic acid (C); and a polyisocyanate (D), the multifunctional polyol (B2) is a polycarbonate polyol having an ester bond and an average number of hydroxyl functional groups exceeding 2, 2. The polyurethane resin composition according to claim 1, wherein the content of the urea group derived from the chain extender (G) in the polyurethane resin composition is 0.05 to 1.00 mmol / g, relative to the total mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G).

3. 2. The polyurethane resin composition according to claim 1, wherein the chain extender (G) is an amine compound having one or more primary or secondary amino groups and water.

4. the chain extender (G) contains an amine compound having one or more primary or secondary amino groups, 2. The polyurethane resin composition according to claim 1, wherein a content of urea groups derived from the amine compound in the polyurethane resin composition is more than 0 mol % and 99 mol % or less relative to a content of urea groups derived from the chain extender (G).

5. the chain extender (G) contains water, 2. The polyurethane resin composition according to claim 1, wherein a content of the water-derived urea group in the polyurethane resin composition is more than 0 mmol / g and 0.95 mmol / g or less, relative to the total mass of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G).

6. The polyurethane resin composition according to claim 1, further comprising a curing agent (X).

7. The polyol (A1) containing the polycarbonate polyol (B1) has an average hydroxyl value of 30 to 150 mgKOH / g, or 2. The polyurethane resin composition according to claim 1, wherein the polyol (A2) and the multifunctional polyol (B2) have an average hydroxyl value of 30 to 150 mgKOH / g.

8. The polycarbonate polyol (B1) or the polyfunctional polyol (B2) is or comprising a transesterification product of a polycarbonate polyol (b-1) and a polyester polyol (b-2) having an average hydroxyl functionality of 3 or more; 2. The polyurethane resin composition according to claim 1, comprising a transesterification reaction product of a polycarbonate polyol (b-1), a polyester polyol (b-2) having an average number of hydroxyl functional groups of 3 or more, and a polyester polyol (b-3) having an average number of hydroxyl functional groups of 2 or more but less than 3.

9. the polycarbonate polyol (B1) or the multifunctional polyol (B2) has an average hydroxyl functionality of 2.1 to 3.5; the hydroxyl value of the polycarbonate polyol (B1) or the multifunctional polyol (B2) is 40 to 500 mgKOH / g; the number average molecular weight of the polycarbonate polyol (B1) or the multifunctional polyol (B2) is 400 to 4,000 g / mol; 9. The polyurethane resin composition according to claim 8, wherein the mass ratio of the polycarbonate polyol (b-1) to the polyester polyol (b-2) ([mass of (b-1)] / [mass of (b-2)]) is 90 / 10 to 10 / 90, or the mass ratio of the polycarbonate polyol (b-1) to the sum of the polyester polyol (b-2) and the polyester polyol (b-3) ([mass of (b-1)] / ([mass of (b-2)]+[mass of (b-3)])) is 95 / 5 to 5 / 95.

10. 2. The polyurethane resin composition according to claim 1, wherein the polycarbonate polyol (B1) or the multifunctional polyol (B2) has an ester group concentration of 10 to 90 mass%.

11. The polyurethane resin composition according to claim 1 , wherein the organic acid (C) is a dimethylol fatty acid.

12. The polyurethane resin composition according to claim 1 , wherein the neutralizing agent (F) is a basic neutralizing agent.

13. The polyol (A1) contains a diol (A-2) and / or a tri- or higher functional polyhydric alcohol (A-3), or 2. The polyurethane resin composition according to claim 1, wherein the polyol (A2) comprises a diol (A-2) and / or a tri- or higher functional polyhydric alcohol (A-3).

14. A cured product obtained by curing the polyurethane resin composition according to any one of claims 1 to 13.

15. An artificial or synthetic leather comprising the cured product according to claim 14.

16. A surface treatment agent for leather, comprising the polyurethane resin composition according to any one of claims 1 to 13.