Polyurethane resin composition, cured product, artificial leather, synthetic leather and surface treatment agent for leather

Abstract

To provide a polyurethane resin composition capable of forming a cured product having a low 100% modulus and a high softening temperature.SOLUTION: There is provided a polyurethane resin composition comprising an isocyanate group-terminated urethane prepolymer (E) and a neutralizer. The isocyanate group-terminated urethane prepolymer (E) contains a reaction product of a polyol (A) including a polycarbonate polyol (B) having an average hydroxyl group functional group number of more than 2, an organic acid (C) and a polyisocyanate (D), the total content of urea groups in the polyurethane resin composition is 0.01 to 0.80 mmol / g based on the total sum of the mass of the isocyanate-terminated urethane prepolymer (E) and the mass of a chain extender (G) and the deemed average functional group number of the polycarbonate polyol (B) is 2.0 to 3.90.SELECTED DRAWING: None

Description

[Technical field]

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

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

[0003] Here, 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 polymer 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. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2005-247897 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, the polyurethane emulsion disclosed in Patent Document 1 does not provide well-balanced mechanical properties compared to solvent-based polyurethane resins, and there is a need to improve the 100% modulus. Also, the polyurethane emulsion disclosed in Patent Document 1 has room for improvement in terms of shape stability when exposed to a high-temperature environment.

[0006] Therefore, an object of one embodiment of the present disclosure is to provide a cured product having a low 100% modulus and a high softening temperature, and a polyurethane resin composition capable of forming the cured product.An object of one embodiment of the present disclosure is to provide an artificial leather or synthetic leather, and a surface treatment agent for leather, each of which includes a cured product of the polyurethane resin composition. [Means for solving the problem]

[0007] Each aspect of the present disclosure includes the following embodiments. (1) a reaction product of an isocyanate-terminated urethane prepolymer (E) and a chain extender (G); A polyurethane resin composition comprising: The isocyanate group-terminated urethane prepolymer (E) A polyol (A) containing a polycarbonate polyol (B) having an average hydroxyl functionality of more than 2; An organic acid (C); and a polyisocyanate (D), the total content of urea groups in the polyurethane resin composition is 0.01 to 0.80 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); A polyurethane resin composition, wherein the polycarbonate polyol (B) has a deemed average functionality of 2.0 to 3.90. (2) The chain extender (G) is an amine compound having one or more primary or secondary amino groups, and and water. (3) The chain extender (G) comprises an amine compound having one or more primary or secondary amino groups, The polyurethane resin composition according to (1) or (2), wherein a content of the urea group derived from the amine compound in the polyurethane resin composition is more than 0 mmol / g and 0.480 mmol / g or less, based on the total mass of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G). (4) The chain extender (G) comprises an amine compound having one or more primary or secondary amino groups, The polyurethane resin composition according to any one of (1) to (3), wherein the content of the urea group derived from the amine compound in the polyurethane resin composition is more than 0 mol % and 95 mol % or less, based on the total content of the urea groups. (5) The chain extender (G) contains water, The polyurethane resin composition according to any one of (1) to (4), wherein a content of the urea group derived from water in the polyurethane resin composition is more than 0 mmol / g and 0.80 mmol / g or less, based on the total mass of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G). (6) The polyurethane resin composition according to any one of (1) to (5), wherein the content of the polycarbonate polyol (B) is 5.0 mass % or more based on the total content of the polyol (A). (7) The polyurethane resin composition according to any one of (1) to (6), wherein the polyol (A) has an average hydroxyl value of 30 to 150 mgKOH / g. (8) The polycarbonate polyol (B) is or a transesterification product of a diol (b-1), a polyhydric alcohol (b-2), and a carbonate ester (b-3), The polyurethane resin composition according to any one of (1) to (7), comprising an ester exchange reaction product of a diol (b-1), a polyhydric alcohol (b-2), and a polycarbonate polyol (b-4). (9) The polyurethane resin composition according to any one of (1) to (8), wherein the polycarbonate polyol (B) has a hydroxyl value of 40 to 500 mgKOH / g. (10) The polyurethane resin composition according to any one of (1) to (9), wherein the polycarbonate polyol (B) has a number average molecular weight of 400 to 4,000 g / mol. (11) The polyurethane resin composition according to any one of (1) to (10), wherein the organic acid (C) is a dimethylol fatty acid. (12) The polyurethane resin composition according to any one of (1) to (11), wherein the neutralizing agent (F) is a basic neutralizing agent. (13) The polyurethane resin composition according to any one of (1) to (12), wherein the polyol (A) contains a diol (a-1). (14) The polyurethane resin composition according to any one of (1) to (13), which is a one-component type. (15) The polyurethane resin composition according to any one of (1) to (13), further comprising a curing agent (X). (16) The polyurethane resin composition according to (15), which is of a two-component type. (17) A cured product of a polyurethane resin composition comprising a reaction product of an isocyanate group-terminated urethane prepolymer (E) and a chain extender (G), The isocyanate group-terminated urethane prepolymer (E) A polyol (A) containing a polycarbonate polyol (B) having an average hydroxyl functionality of more than 2; An organic acid (C); and a polyisocyanate (D), the total content of urea groups in the polyurethane resin composition is 0.01 to 0.80 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); A cured product, wherein the polycarbonate polyol (B) has a deemed average functionality of 2.0 to 3.90. (18) An artificial leather or a synthetic leather comprising a cured product of the polyurethane resin composition according to any one of (1) to (17). (19) A surface treatment agent for leather, comprising a cured product of the polyurethane resin composition according to any one of (1) to (17). Effect of the Invention

[0008] According to one aspect of the present disclosure, it is possible to provide a cured product having a low 100% modulus and a high softening temperature, and a polyurethane resin composition capable of forming the cured product. According to one aspect of the present disclosure, it is possible to provide an artificial leather or synthetic leather containing the cured product of the polyurethane resin composition, and a surface treatment agent for leather. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[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 the present specification, the numerical range indicated by "~" indicates a range including the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in the present specification, the upper limit or lower limit of the numerical range may be replaced with a value shown in the Examples. In addition, the upper limit and lower limit values ​​described individually can be arbitrarily combined. In the present specification, the "cured product" includes the form of a cured film. In addition, in the present specification, the "cured product" includes both a product cured by crosslinking or the like and a product cured by volatilization of the solvent to solidify.

[0011] The polyurethane resin composition according to the embodiment of the present disclosure includes a reaction product of an isocyanate-terminated urethane prepolymer (E) and a chain extender (G), and a neutralizing agent (F). The isocyanate-terminated urethane prepolymer (E) includes a reaction product of a polyol (A), an organic acid (C), and a polyisocyanate (D). In the polyurethane resin composition, the total content of urea groups is 0.01 to 0.80 mmol / g relative to the sum of the mass of the isocyanate-terminated urethane prepolymer (E) and the mass of the chain extender (G), and the deemed average number of functional groups of the polycarbonate polyol (B) is 2.0 to 3.90. The polyurethane resin composition according to the embodiment of the present disclosure may further include a curing agent.

[0012] Components that may be contained in the polyurethane resin composition will be described below.

[0013] [Isocyanate-terminated urethane prepolymer (E)] The isocyanate-terminated urethane prepolymer (E) contains a reaction product of a polyol (A), an organic acid (C), and a polyisocyanate (D).

[0014] <Polyol (A)> The polyol (A) contains a polycarbonate polyol (B) having an average hydroxyl group functionality of more than 2. The polyol (A) may contain a polycarbonate polyol (B) and a polyol (B') different from the polycarbonate polyol (B), or may contain only the polycarbonate polyol (B).

[0015] (Polycarbonate polyol (B)) Examples of the polycarbonate polyol (B) include the following polycarbonate polyols (α) to (β) and any combination of two or more of these. (α) A polycarbonate polyol which is an ester exchange reaction product of a diol (b-1), a polyhydric alcohol (b-2), and a carbonate ester (b-3) (hereinafter, also referred to as "polycarbonate polyol (α)"). (β) A polycarbonate polyol which is an ester exchange reaction product of a diol (b-1), a polyhydric alcohol (b-2), and a polycarbonate polyol (b-4) (hereinafter, also referred to as "polycarbonate polyol (β)").

[0016] Examples of the diol (b-1) include aliphatic diols such as 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, and dimer acid diols, and aromatic diols such as ethylene oxide and propylene oxide adducts of bisphenol A, bis(β-hydroxyethyl)benzene, and xylylene glycol, and combinations of any two of these. Among these, diols having 2 to 9 carbon atoms are preferred. Moreover, aliphatic diols are preferred, and 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,9-nonanediol are more preferred. These may be used alone or in combination of two or more kinds.

[0017] Examples of the polyhydric alcohol (b-2) having three or more hydroxyl functional groups include trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, dipentaerythritol, sorbitol, and combinations of any two of these. Among these, trimethylolpropane, trimethylolethane, and pentaerythritol are preferred.

[0018] Examples of the carbonate ester (b-3) include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, and dibutyl carbonate; cyclic 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. From the viewpoints of availability and ease of setting polymerization reaction conditions, it is preferable to use dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate, and ethylene carbonate.

[0019] The polycarbonate polyol (b-4) is a polycarbonate polyol having two or more hydroxyl functional groups, and may be a polycarbonate polyol (b-4-1) (i.e., a polycarbonate diol) having two hydroxyl functional groups, or a polycarbonate polyol (b-4-2) having three or more hydroxyl functional groups, or a combination of two or more selected from the polycarbonate polyol (b-4-1) and the polycarbonate polyol (b-4-2).

[0020] Examples of the polycarbonate polyol (b-4-1) include those obtained by reacting a carbonate ester with a diol.

[0021] Examples of the carbonate esters include the same ones as those mentioned above in the description of the carbonate esters.

[0022] Examples of the diol include the same as those mentioned above in the description of the diol. Among them, 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.

[0023] The polycarbonate polyol (b-4-2) may be, for example, one obtained by reacting a carbonate ester with a diol and a polyhydric alcohol having 3 or more hydroxyl functional groups. The carbonate ester may, for example, be the same as those mentioned in the description of the carbonates above.

[0024] Examples of glycols include those mentioned above in the description of diols, 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.

[0025] Examples of polyhydric alcohols having three or more hydroxyl functional groups include trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, sorbitol, and combinations of any two or more of these.

[0026] Considering ease of synthesis and ease of handling, the number average molecular weight of the polycarbonate polyol (b-4) is preferably 400 to 5,000 g / mol, more preferably 500 to 3,000 g / mol. The details of the method for measuring the number average molecular weight may be as described in the examples below.

[0027] The molar ratio of the diol (b-1) to the polyhydric alcohol (b-2) having 3 or more hydroxyl functional groups (diol (b-1) / polyhydric alcohol (b-2)) is preferably 1 / 5 to 60 / 1, more preferably 1 / 3 to 40 / 1. By using the polyhydric alcohol having 3 or more hydroxyl functional groups at the above upper limit or less, gelation due to crosslinking during the polymerization reaction of polycarbonate is more likely to be suppressed. In addition, by using the polyhydric alcohol (b-2) at the above upper limit or less, texture tends to be further improved. By setting the molar ratio of the diol (b-1) to the polyhydric alcohol (b-2) having 3 or more hydroxyl functional groups in the above range, polycarbonate polyol (B) can be efficiently obtained, and when it is made into polyurethane, texture, mechanical strength, and high softening temperature tend to be compatible.

[0028] The mixing ratio of the total of the diol (b-1) and the polyhydric alcohol (b-2) to the carbonate ester (b-3) is not particularly limited, but the molar ratio of (the total of the diol (b-1) and the polyhydric alcohol (b-2)):carbonate ester (b-3) is preferably 1:3 to 3:1, and more preferably 1:2.5 to 2.5:1. By using the above mixing ratio, the desired polycarbonate polyol can be obtained more efficiently.

[0029] The mixing ratio of the total of the diol (b-1) and the polyhydric alcohol (b-2) to the polycarbonate polyol (b-4) is not particularly limited, but the molar ratio of (the total of the diol (b-1) and the polyhydric alcohol (b-2)):polycarbonate polyol (b-1) is preferably 1:50 to 50:1, and more preferably 1:30 to 30:1. By using the above mixing ratio, the desired polycarbonate polyol can be obtained more efficiently.

[0030] (catalyst) It is preferable to use a catalyst when preparing the polycarbonate polyol (α). Examples of the catalyst include known transesterification catalysts. Examples of the catalyst include 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; and tertiary alkylamines such as trimethylamine, triethylamine, diisopropylethylamine, and tributylamine. 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), 1-t-butyl-2,2,4,4,4-pentakis(dimethylamino)-2λ 5 ,4λ 5 -Catenazi(phosphazene)(P2-t-Bu), 1-ethyl-2,2,4,4,4-pentakis(dimethylamino)-2λ 5 , 4λ 5 -Catenazi(phosphazene), 1-t-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phosphoranylideneamino]-2λ 5 ,4λ 5 -Catenazi(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, or P4-t-Bu is preferred because it further improves the yield of polycarbonate polyol.

[0031] The content of the transesterification catalyst in the mixed solution may be 0.0001 to 0.1 parts by mass, or 0.0005 to 0.01 parts by mass, based on 100 parts by mass of the diol (b-1), the polyhydric alcohol (b-2), and the carbonate ester (b-3) in the mixed solution, from the viewpoint of easily controlling the reaction temperature appropriately and further suppressing an increase in the color number of the reaction product. The content of the transesterification catalyst is preferably as small as possible, based on the viewpoint of further facilitating control of the reactivity of the urethanization reaction. When the content of the transesterification catalyst is increased, the reactivity of the urethanization reaction tends to increase. The content of the transesterification catalyst in the mixed solution is preferably 0.001 parts by mass or more, more preferably 0.002 parts by mass or more, and even more preferably 0.003 parts by mass or more, based on 100 parts by mass of the polyhydric alcohol (b-2), the diol (b-1), and the carbonate ester (b-3) in the mixed solution, from the viewpoint of further facilitating control of the urethanization reaction. From the viewpoint of further suppressing the increase in the color number of the reaction product, the content of the transesterification catalyst in the mixed solution is preferably 0.050 parts by mass or less, more preferably 0.040 parts by mass or less, and even more preferably 0.030 parts by mass or less, relative to 100 parts by mass of the total amount of the polyhydric alcohol (b-2), the diol (b-1), and the carbonate ester (b-3) in the mixed solution. From these viewpoints, the content of the transesterification catalyst in the mixed solution is preferably 0.001 to 0.050 parts by mass, more preferably 0.002 to 0.040 parts by mass, and even more preferably 0.003 to 0.030 parts by mass, relative to 100 parts by mass of the total amount of the polyhydric alcohol (b-2), the diol (b-1), and the carbonate ester (b-3) in the mixed solution.

[0032] The heating temperature (reaction temperature) of the mixed liquid may be, for example, 80 to 250°C, or 100 to 220°C. When the reaction temperature is 80°C or higher, the transesterification reaction is more likely to proceed, and the desired polycarbonate polyol is more likely to be obtained. When the reaction temperature is 250°C or lower, the number of colors of the obtained polycarbonate polyol and the composition containing the polycarbonate polyol is further reduced. In addition, the transesterification reaction may be carried out while keeping the temperature constant, or may be carried out while increasing the temperature stepwise or continuously depending on the reaction progress. At this time, the reaction progress can be accelerated by distilling off the generated alcohol or diol.

[0033] The mixture can be heated under normal pressure, but in the latter half of the reaction, it can also be heated under reduced pressure (for example, under a pressure of 101 to 0.1 kPa). This can increase the distillation rate of the distillate produced, and can accelerate the progress of the reaction. In this specification, normal pressure means a pressure of 101.325 kPa ± 20.000 kPa. From the viewpoint of easily obtaining a desired polycarbonate polyol, it is preferable that the mixture is heated under a pressure of 101.325 kPa ± 20.000 kPa (first heating) and then heated under a reduced pressure of 10.000 kPa or less (second heating).

[0034] (catalyst) It is preferable to use a catalyst when preparing the polycarbonate polyol (β). Examples of the catalyst include the same catalysts as those described in the preparation of the polycarbonate polyol (α). Among them, potassium hydrogen carbonate, sodium hydrogen carbonate, lithium acetate, lithium acetylacetonate, or P4-t-Bu is preferable because it further improves the yield of the polycarbonate polyol.

[0035] The amount of the catalyst used may be 0.0001 to 1 mass% of the total mass of the diol (b-1), the polyhydric alcohol (b-2), and the polycarbonate polyol (b-4), and is preferably 0.001 to 0.1 mass%. When the amount of the catalyst is equal to or greater than the lower limit, the reaction time can be further prevented from being prolonged, so that the resulting polycarbonate polyol is further prevented from being colored. When the amount of the catalyst is equal to or less than the upper limit, the turbidity tends to be further suppressed.

[0036] The reaction temperature for the transesterification reaction is preferably from 70 to 250°C, and more preferably from 80 to 220°C.

[0037] The lower limit of the deemed average functionality of the polycarbonate polyol (B) may be, for example, 2.0 or more, 2.1 or more, 2.2 or more, 2.3 or more, 2.4 or more, or 2.5 or more. The upper limit of the deemed average functionality of the polycarbonate polyol (B) may be, for example, 3.90 or less, 3.80 or less, 3.70 or less, 3.60 or less, 3.50 or less, or 3.40 or less. The deemed average functionality is 2.0 to 3.90, and may be, for example, 2.1 to 3.80, 2.2 to 3.70, 2.3 to 3.50, or 2.5 to 3.40. When the deemed average functionality is 3.90 or less, the elongation at break in the tensile test is further improved, and when the deemed average functionality is 2.0 or more, the strength at break and the softening temperature in the tensile test tend to be further improved.

[0038] The deemed average functionality is defined by the following formula. Deemed average functionality=(average hydroxyl value (mg KOH / g) of polycarbonate polyol (B) × number average molecular weight (g / mol) calculated from the PPG calibration curve obtained by GPC measurement of polycarbonate polyol (B)) / (56.11 (KOHg / mol) × 1000)

[0039] The average hydroxyl value of the polycarbonate polyol (B) is preferably 40 to 500 mgKOH / g, more preferably 50 to 450 mgKOH / g, and even 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.

[0040] The average hydroxyl value is a hydroxyl value measured by a method using an acetylation reagent in accordance with JIS K1557-1. Details of the measurement method are as described in the Examples below.

[0041] The number average molecular weight of the polycarbonate polyol (B) is preferably 400 to 4,000 g / mol, more preferably 500 to 3000 g / mol. When the number average molecular weight is 400 or more, the urethane group concentration in the polyurethane does not become too high, and the 100% modulus tends to be further improved. When the number average molecular weight is 4000 g / mol or less, the urethane group concentration in the polyurethane resin does not become too low, and the breaking strength in a tensile test is further improved. Details of the method for measuring the number average molecular weight obtained by GPC (Gel Permeation Chromatography) measurement are as described in the examples below.

[0042] (Polycarbonate polyol (B) content) The content of the polycarbonate polyol (B) may be 5.0 mass% or more, 7.0 mass% or more, 10.0 mass% or more, 15.0 mass% or more, or 20.0 mass% or more, and may be 100 mass% or less, 95 mass% or less, 90 mass% or less, 85 mass% or less, or 80 mass% or less, relative to the content of the polyol (A) in the polyurethane resin composition (or the sum of the mass of the polyol (B') and the mass of the polycarbonate polyol (B)), since it is possible to form a cured product having a higher softening temperature. The content of the polycarbonate polyol (B) is preferably 5.0 to 100 mass%, 8.0 to 95 mass%, or 10 to 90 mass%, more preferably 15 to 80 mass%, and even more preferably 20 to 70 mass%, relative to the content of the polyol (A) in the polyurethane resin composition (or the sum of the mass of the polyol (B') and the mass of the polycarbonate polyol (B)). When the content of polycarbonate polyol (B) is within the above range, when used as a polyurethane film, it is easy to obtain a polyurethane film having better 100% modulus and heat resistance. When the content of polycarbonate polyol (B) is 100% by mass or less, it is easy to obtain a polyurethane dispersion having better handling properties. When the content of polycarbonate polyol (B) is 100% by mass or less, it is easy to obtain a polyurethane film having better 100% modulus.

[0043] (Polyol (B')) Examples of polyols (B') different from polycarbonate polyol (B) include polyester polyols, polyether polyols, polycarbonate polyols (excluding compounds corresponding to polycarbonate polyol (B)), polyolefin polyols, and combinations of any two or more of these.

[0044] As the polyester polyol, a polyester polyol obtained from a glycol and a dicarboxylic acid, or a polyol obtained by ring-opening addition polymerization of a cyclic ester compound such as a lactone using a glycol as an initiator is preferable.

[0045] Examples of glycols 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 adduct of bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, low molecular weight polyols such as pentaerythritol, and combinations of any two or more of these.

[0046] Examples of dicarboxylic acids include polybasic acids such as oxalic acid, malonic acid, maleic acid, adipic acid, tartaric acid, pimelic acid, sebacic acid, phthalic acid, and terephthalic acid, and combinations of any two or more of these.

[0047] Examples of cyclic ester compounds such as lactones 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, and combinations of any two or more of these.

[0048] Examples of polyether polyols include polyethylene glycol, polypropylene ether polyol, polytetramethylene ether polyol, and the like, as well as combinations of any two or more of these.

[0049] The polycarbonate polyol may be, for example, one obtained by reacting a carbonate with a glycol. The carbonate and the glycol may be the same compounds as those exemplified above.

[0050] Examples of polyolefin polyols include hydroxyl-terminated polybutadiene and hydrogenated products thereof, hydroxyl-containing chlorinated polyolefins, and combinations of any two or more of these.

[0051] The polyol (B') may be one type selected from the above-mentioned polyols, or a combination of two or more types.

[0052] Considering various durability and adhesion of the coating film obtained from the polyurethane resin composition, the polyol (B') preferably contains a polycarbonate polyol, and more preferably contains a polycarbonate diol.

[0053] The number average molecular weight of the polyol (B') is preferably 300 to 10,000, and may be 500 to 7,000, 800 to 5,000, or 1000 to 3,000. Details of the method for measuring the number average molecular weight may be as described in the examples below.

[0054] The polyol (B') may contain a diol (a-1). Examples of the diol (a-1) include the same glycols as those mentioned in the description of the polyester polyol. The diol (a-1) preferably contains at least one selected from the group consisting of 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.

[0055] The molar ratio of polyol (B') to diol (a-1) [polyol (B') / diol (a-1)] is preferably 10 / 0 to 1 / 20, and more preferably 10 / 0 to 1 / 10. By adjusting the ratio within this range, a polyurethane resin composition having a lower 100% modulus and a higher softening temperature can be obtained.

[0056] (Average hydroxyl value of polyol (A)) The average hydroxyl value of the polyol (A) is preferably 30 to 150 mgKOH, more preferably 50 to 130 mgKOH, and even more preferably 60 to 120 mgKOH. When the average hydroxyl value is within the above range, when used as a polyurethane film, a polyurethane film having both better 100% modulus and better heat resistance tends to be obtained. In addition, when the average hydroxyl value is 150 mgKOH or less, a polyurethane film having better 100% modulus is easily obtained. The average hydroxyl value of the polyol (A) is calculated from the hydroxyl values ​​of each of the components contained in the polyol (A). The specific method for calculating the average hydroxyl value of the polyol (A) is described in detail in the examples below.

[0057] (Crosslink density) The crosslink density of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G) is preferably 0.02 to 0.47, more preferably 0.03 to 0.40, and more preferably 0.05 to 0.35. When the crosslink density is within the above range, when the polyurethane film is used, a polyurethane film having both better 100% modulus and better heat resistance tends to be obtained. When the crosslink density is 0.47 or less, a polyurethane film having better 100% modulus is easily obtained.

[0058] <Organic acid (C)> The organic acid (C) may be, for example, a hydrophilic group-containing monomer that can impart hydrophilicity to the isocyanate-terminated prepolymer (E) obtained by reaction with the polyisocyanate (D) and make the final resin composition aqueous.

[0059] The organic acid (C) may, for example, have one or more active hydrogen groups. Examples of the organic acid include carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acid, phosphinic acid, thiosulfonic acid, and the like, 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 them, dimethylol fatty acid having a carboxy group (-COOH) is more preferred.

[0060] The dimethylol fatty acid may be, for example, a compound represented by the following formula (c): [ka] In formula (c), R c R 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, and may be 10 or less, 6 or less, or 3 or less. c The aliphatic hydrocarbon group represented by the formula (I) may be linear or branched. c The aliphatic hydrocarbon group represented by may be, for example, -CH3, -CH2CH3, -CH2CH2CH3, or CH2CH2CH2CH2CH2CH2CH3.

[0061] Examples of dimethylol fatty acids include dimethylol propionic acid (such as 2,2-dimethylol propanoic acid), dimethylol butanoic acid, dimethylol pentanoic acid, dimethylol nonanoic acid, and other dimethylol alkanoic acids, and combinations of any two or more of these.

[0062] The content of the organic acid (C) may be 0.01 mmol / g or more or 0.10 mmol / g or more, and may be 0.80 mmol / g or less, or 0.50 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.

[0063] <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.

[0064] The polyisocyanate (D) is not particularly limited, and may be any of various conventionally known polyisocyanates. For example, aliphatic isocyanates such as hexamethylene 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-nitrodiphenyl-4 aromatic isocyanates such as 1,4-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, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate; aromatic aliphatic diisocyanates such as xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate; allophanate-modified polyisocyanates obtained by reacting these organic polyisocyanates with alcohols; and combinations of any two or more of these.

[0065] The polyisocyanate (D) is preferably an aliphatic diisocyanate or an alicyclic diisocyanate, more preferably an alicyclic diisocyanate, and further preferably isophorone diisocyanate.

[0066] The ratio of the total number of moles of hydroxyl groups in the polyol (A) 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 0.950 or less, 0.900 or less, or 0.800 or less.

[0067] <One embodiment of isocyanate group-terminated prepolymer (E)> One embodiment of the isocyanate group-terminated prepolymer (E) includes, for example, a reaction product of polyol (B'), a polyol different from the polyol (B'), an organic acid (C), and a polyisocyanate (D), where the polyol different from the polyol (B') may be a polycarbonate polyol (B) having an average hydroxyl group functionality of more than 2.

[0068] <Method for producing isocyanate-terminated prepolymer (E)> The isocyanate-terminated prepolymer (E) can be produced, for example, by a method including reacting a polyisocyanate (D), a polyol (A) and an organic acid (C) in a diluting solvent as necessary under conditions in which the number of moles of isocyanate groups is in excess of the number of moles of hydroxyl groups. At this time, a known urethane catalyst may be used. The reaction temperature is preferably 0 to 100°C, particularly preferably 20 to 90°C.

[0069] [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 the like, and combinations of any two or more of these. In addition, 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.

[0070] The neutralizing agent may be a trialkylamine, such as trimethylamine, triethylamine, triisopropylamine, or tributylamine.

[0071] In order to further improve the water 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.

[0072] Examples of anionic polar group-containing compounds include those consisting of an organic acid having one or more active hydrogen groups and a neutralizing agent. The organic acid includes carboxylates, sulfonates, phosphates, phosphonates, phosphinates, thiosulfonates, etc., and combinations of any two or more of these. These groups may be introduced independently or may be associated with each other, such as a chelate.

[0073] Examples of the cationic polar group-containing compound include A primary or secondary amine having one or more active hydrogen groups, and at least one selected from the group consisting of neutralizing agents for inorganic acids and organic acids, and quaternizing agents.

[0074] Examples of primary or secondary 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, a primary amine such as methylamine, a secondary amine such as dimethylamine, and an alkylene oxide are added thereto; and combinations of any two or more of these.

[0075] 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.

[0076] 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.

[0077] Other examples of cationic polar group-containing compounds include cationic compounds such as primary amine salts, secondary amine salts, tertiary amine salts, and pyridinium salts.

[0078] The content of the neutralizing agent may be 0.01 mmol / g or more or 0.10 mmol / g or more, and may be 0.80 mmol / g or less, or 0.50 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.

[0079] (Organic solvent) During synthesis of the isocyanate-terminated prepolymer (E), the prepolymer 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 (aromatic hydrocarbon solvent manufactured by Maruzen Petrochemical Co., Ltd.), and Solvesso (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.

[0080] The organic solvent is preferably an ester-based solvent such as ethyl acetate, butyl acetate, isobutyl acetate, etc., 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 is particularly preferably a ketone-based solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.

[0081] [Chain extender (G)] The chain extender is a compound that reacts with the isocyanate-terminated urethane prepolymer (E) to form a polyurethane resin. Examples of the chain extender include a compound having a functional group that can react with an isocyanate group, such as a primary amino group (-NH2), a secondary amino group (-NH-), or a hydroxyl group (-OH), or water (H2O).

[0082] The chain extender (G) is preferably one or more members selected from the group consisting of amine compounds having one or more primary or secondary amino groups and water.

[0083] 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).

[0084] The amine compound is more preferably at least one selected from the group consisting of aliphatic diamines and alicyclic diamines. The amine compound is, for example, a compound represented by the formula (g1): H2N-R g In the formula (g1), R g represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.

[0085] Examples of the amine compound include ethylenediamine, hexamethylenediamine, xylylenediamine, isophoronediamine, diethylenetriamine, N-aminoethyl-N-ethanolamine, monoethanolamine, and the like, and combinations of any two or more of these.

[0086] In the chain extension reaction, a curing catalyst (polymerization catalyst) may be used as necessary. Examples of the curing catalyst include metal catalysts such as dioctyltin dilaurate, zinc naphthenate, and bismuth compounds, and amine catalysts such as triethylenediamine and N-methylmorpholine. By using the curing catalyst, the reaction speed can be further increased and the reaction temperature can be further reduced.

[0087] The equivalent ratio (active hydrogen group / isocyanate group) of the active hydrogen group (amino group and hydroxyl group) of the amine compound to the isocyanate group of the isocyanate group-terminated prepolymer (E) is, for example, preferably 0 to 1.3, more preferably 0.05 to 1.1, and even more preferably 0.10 to 0.9. When this ratio is within the above range, a polyurethane resin having excellent 100% modulus and heat resistance is easily formed.

[0088] <Method of producing polyurethane resin composition> The polyurethane resin composition can be produced, for example, by a method including a step of neutralizing an isocyanate-terminated prepolymer (E) with a neutralizing agent (F) to obtain a neutralized product of the isocyanate-terminated prepolymer (E), and a step of emulsifying the neutralized product of the isocyanate-terminated prepolymer (E) with water and reacting it with a chain extender (G) to obtain a polyurethane resin composition.

[0089] Examples of a method for carrying out a chain extension reaction between the isocyanate-terminated prepolymer (E) and the chain extender (G) include a method in which the chain extender (G) is dissolved in water in advance, and then the isocyanate-terminated prepolymer (E) is charged into the aqueous solution of the chain extender (G) to carry out emulsification and chain extension reaction, and a method in which the isocyanate-terminated prepolymer (E) is emulsified in water, and then an aqueous solution of the chain extender (G) is charged to carry out the chain extension reaction.

[0090] (total urea group content) The lower limit of the total content of urea groups is 0.01 mmol / g or more, for example, 0.02 mmol / g or more, 0.05 mmol / g or more, 0.10 mmol / g or more, 0.13 mmol / g or more, or 0.15 mmol / g or more, 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. The upper limit of the total content of urea groups is 0.80 mmol / g or less, for example, 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, 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. The total content of urea groups is 0.01 to 0.80 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), and may be, for example, 0.05 mmol / g or more and 0.75 mmol / g or less, 0.07 mmol / g or more and 0.70 mmol / g or less, 0.13 mmol / g or more and 0.60 mmol / g or less, or 0.15 mmol / g or more and 0.55 mmol / g or less. When the total content of urea groups is within the above range, when used as a polyurethane film, a polyurethane film having both better 100% modulus and better heat resistance is easily obtained. In addition, when the total content of urea groups is 0.80 mmol / g or less, a polyurethane film having better 100% modulus is easily obtained.

[0091] 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 total content of urea groups 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.

[0092] (Amine compound-derived urea group content) The chain extender (G) may contain an amine compound having one or more primary or secondary amino groups. In this case, the content of the urea group derived from the amine compound in the polyurethane resin composition may be, for example, 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, or 0.15 mmol / g or more, based on the total mass of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G). The upper limit of the content of the urea group derived from the amine compound may be, for example, 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, based on the sum of the mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G). The content of the urea group derived from the amine compound may be, for example, 0 mmol / g or more and 0.480 mmol / g or less, 0.01 mmol / g or more and 0.400 mmol / g or less, 0.05 mmol / g or more and 0.340 mmol / g or less, or 0.130 mmol / g or more and 0.300 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). When the concentration of urea groups derived from the amine compound is within the above range, a polyurethane film having better 100% modulus and heat resistance is easily obtained when used as a polyurethane film. Also, when the concentration of urea groups derived from the amine compound is 0.480 mmol / g or less, a polyurethane film having better 100% modulus is easily obtained.

[0093] (Content of urea groups derived from water) The chain extender (G) may contain water. The lower limit of the content of urea groups derived from water may be, for example, 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, or 0.15 mmol / g or more, 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. The upper limit of the content of urea groups derived from water may be 0.80 mmol / g or less, for example, 0.70 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, 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. The content of the urea group derived from water may be, for example, 0.01 mmol / g or more and 0.80 mmol / g or less, 0.05 mmol / g or more and 0.70 mmol / g or less, 0.10 mmol / g or more and 0.60 mmol / g or less, or 0.15 mmol / g or more and 0.50 mmol / g or less, based on the total mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (G). When the concentration of the urea group derived from water is within the above range, when used as a polyurethane film, a polyurethane film having both a better 100% modulus and heat resistance is easily obtained. In addition, when the concentration of the urea group derived from water is 0.80 mmol / g or less, a polyurethane film having a better 100% modulus is easily obtained.

[0094] (Amine compound-derived urea group content relative to total urea group content) The lower limit of the content of urea groups derived from amine compounds (amine compound-derived urea group ratio) may be, for example, 0 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, based on the total content of urea groups. The upper limit of the content of urea groups derived from amine compounds relative to the total content of urea groups may be, for example, 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 content of urea groups derived from amine compounds relative to the total content of urea groups may be, for example, 0 to 95 mol%, 5 to 90 mol%, 10 to 85 mol%, 15 to 80 mol%, or 20 to 70 mol% relative to the total content of urea groups. When the content of urea groups derived from amine compounds relative to the total content of urea groups is within the above range, a polyurethane film having better 100% modulus and heat resistance is easily obtained when used as a polyurethane film. Also, when the concentration of urea groups derived from amine compounds is 100 mol% or less, a polyurethane film having better softening temperature is easily obtained.

[0095] <Hardening agent (X)> The polyurethane resin composition may further contain a curing agent (X). 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) constitutes one component of the two-component system. When the polyurethane resin composition does not contain the curing agent (X), the polyurethane resin composition is suitable as a one-component system.

[0096] Specific examples of the curing agent (X) include urethane-modified, urea-modified, allophanate-modified, biuret-modified, uretdione-modified, isocyanurate-modified organic diisocyanates, etc. Among these, a trimer or adduct of hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI) is preferred.

[0097] <Other ingredients> In order to further improve the physical properties and 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 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.

[0098] The polyurethane resin composition may be an emulsion obtained by neutralizing a reaction product of an isocyanate group-terminated urethane prepolymer (E) and a chain extender (G) with a neutralizing agent (F).

[0099] The polyurethane resin composition thus obtained is preferably used as an aqueous polyurethane resin emulsion. By curing this aqueous polyurethane resin emulsion, a molded product such as a coating film or film that is tough, has a reduced 100% modulus (good texture), and has a high softening temperature can be obtained, and can be suitably used for leather applications such as artificial leather and synthetic leather, or as a surface treatment agent for leather. The 100% modulus is one of the indices that quantify the moist and luxurious feeling when touching synthetic leather, and the lower the value, the better the polyurethane resin has the above characteristics. In addition, the polyurethane resin composition may be of a one-component type or a two-component type, but is preferably of a one-component type.

[0100] [Cured product] One embodiment of the cured product is a cured product of a polyurethane resin composition including a reaction product of an isocyanate group-terminated urethane prepolymer (E) and a chain extender (G), The isocyanate group-terminated urethane prepolymer (E) A polyol (A) containing a polycarbonate polyol (B) having an average hydroxyl functionality of more than 2; An organic acid (C); and a polyisocyanate (D), the total content of urea groups in the polyurethane resin composition is 0.01 to 0.80 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); The polycarbonate polyol (B) has a deemed average functionality of 2.0 to 3.90. The cured product according to one embodiment is obtained by curing the above-mentioned polyurethane resin composition, and is obtained, for example, by removing part or all of the neutralizing agent (F) and part or all of the water from the composition.

[0101] [Artificial or synthetic leather] An embodiment of the artificial leather or synthetic leather includes a cured product of the polyurethane resin composition and a substrate. The artificial leather or synthetic leather according to an embodiment can be produced, for example, by a method including forming a cured product of the polyurethane resin composition on a substrate. The artificial leather or synthetic leather according to an embodiment can be produced by a method including impregnating a substrate with a polyurethane resin composition and curing the polyurethane resin composition. In the artificial leather, the substrate can be, for example, a base fabric such as a knitted fabric or a woven fabric. In the synthetic leather, the substrate can be a nonwoven fabric.

[0102] [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. EXAMPLES

[0103] 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 weight unless otherwise specified.

[0104] <Calculation method for each composition> (Deemed average number of functional groups) The deemed average functionality of polycarbonate polyol (B) was calculated from the number average molecular weight and hydroxyl value obtained by GPC (Gel Permeation Chromatography) measurement. Normally, the average functionality is calculated from the true number average molecular weight and average hydroxyl value, but since it is difficult to calculate the true number average molecular weight of polycarbonate polyol (B), the number average molecular weight converted from the PPG calibration curve in GPC measurement is used and defined as the deemed average functionality. The deemed average functionality is defined by the following formula. Deemed average functionality=(average hydroxyl value (mg KOH / g) of polycarbonate polyol (B) × number average molecular weight (g / mol) calculated from the PPG calibration curve obtained by GPC measurement of polycarbonate polyol (B)) / (56.11 (KOHg / mol) × 1000)

[0105] (total urea group content) The urea group in the polyurethane resin composition is formed by the reaction of the isocyanate group in the isocyanate-terminated prepolymer (E) with the amine compound and / or water contained as the chain extender (G). It is known that the reaction rate between the isocyanate group and the chain extender (G) is much higher than the reaction rate between the isocyanate group and the hydroxyl group of the polyol component. Therefore, the total content of the urea group is equal to the content of the unreacted isocyanate group in the isocyanate-terminated prepolymer (E). From the above, the total content of the urea group relative to the sum of the mass of the isocyanate-terminated urethane prepolymer (E) and the mass of the chain extender (G) is defined by the following formula. Total content of urea groups (mmol / g) = content of urea groups derived from water (mmol / g) + content of urea groups derived from amine compounds (mmol / g)

[0106] In one embodiment of the present disclosure, since water is used as a solvent, urea groups derived from amine compounds and urea groups derived from water are generated simultaneously. The reaction rate of the urea groups derived from amine compounds is much higher than that of the urea groups derived from water, and it can be said that all of the amines derived from the amine compounds exist as urea groups.

[0107] The total urea group content can also be expressed as 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).

[0108] (Amine compound-derived urea group content) The content of the urea group derived from the amine compound was determined from the amount of amine calculated from the amount of the amine compound charged. Therefore, the content of the urea group derived from the amine compound relative to the total mass of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G) is defined by the following formula. Content of urea groups derived from amine compound (mmol / g) = Amount of amine compound (g) / Molecular weight of amine compound (g / mol) × Number of amino groups per molecule / (Amount of polyol (B') (g) + Amount of polycarbonate polyol (B) (g) + Amount of organic acid (dimethylol fatty acid) (C) (g) + Amount of polyisocyanate (D) (g) + Amount of chain extender (G) (g)) × 1000

[0109] Urea groups derived from water are produced through a multi-step reaction. First, water reacts with the isocyanate of the isocyanate-terminated prepolymer (E) to form carbamic acid, which then undergoes decarbonation to become a primary amine. Next, the primary amine produced reacts with the isocyanate of another isocyanate-terminated prepolymer (E) to produce a urea group. Thus, the urea group produced by water consumes two isocyanates.

[0110] (Content of urea groups derived from water) 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) is defined by the following formula. Content of urea groups derived from water (mmol / g) = [Content of unreacted isocyanate groups in isocyanate-terminated prepolymer (E) (mmol / g) × ((Feed amount of polyol (B') (g) + Feed amount of polycarbonate polyol (B) (g) + Feed amount of organic acid (dimethylol fatty acid) (C) (g) + Feed amount of polyisocyanate (D) (g) + Feed amount of organic solvent before isocyanate group measurement (g)) / (Feed amount of polyol (B') (g) + Feed amount of polycarbonate polyol (B) (g) + Feed amount of organic acid (dimethylol fatty acid) (C) (g) + Feed amount of polyisocyanate (D) (g) + Feed amount of chain extender (G) (g)) - Concentration of urea groups derived from amine compounds (mmol / g)] / 2

[0111] The amount of organic solvent charged before the measurement of the isocyanate group is the mass of the organic solvent contained at the time of measuring the amount of isocyanate groups in the isocyanate group-terminated prepolymer (E).

[0112] (Amine compound-derived urea group content relative to total urea group content) The content of urea groups derived from amine compounds relative to the total content of urea groups (amine compound-derived urea group ratio) was calculated by dividing the content of urea groups derived from amine compounds by the total content of urea groups. Therefore, the content of urea groups derived from amine compounds relative to the total content of urea groups is defined by the following formula: Content of urea groups derived from amine compounds relative to the total content of urea groups (mol%) = Content of urea groups derived from amine compounds (mmol / g) / Total content of urea groups (mmol / g) × 100

[0113] The total content of urea groups, the content of urea groups derived from amine compounds, the content of urea groups derived from water, and the content of urea groups derived from amine compounds relative to the total content of urea groups (the ratio of urea groups derived from amine compounds) are 1 It can also be calculated using H-NMR measurement.

[0114] (Average hydroxyl value) The average hydroxyl value was calculated from the hydroxyl value when the polyol (B') and the polycarbonate polyol (B) were mixed together. Therefore, the average hydroxyl value is defined by the following formula. Average hydroxyl value (mg KOH / g) = (average hydroxyl value (mg KOH / g) of polyol (B') × charge amount (g) of polyol (B') + average hydroxyl value (mg KOH / g) of polycarbonate polyol (B) × charge amount (g) of polycarbonate polyol (B)) / (charge amount (g) of polyol (B') + charge amount (g) of polycarbonate polyol (B))

[0115] (Crosslink density) The crosslink density for the isocyanate-terminated urethane prepolymer (E) and the chain extender (G) was calculated from the amount of crosslinks derived from the polyhydric alcohol with three or more functional groups, the polycarbonate polyol (B) or the polyol (B'). Therefore, the crosslink density is defined by the following formula. If there is another component that forms a crosslink, the crosslink density can be calculated in the same way by replacing the "polycarbonate polyol (B)" and "polyhydric alcohol" in the molecule in the formula with the other component.

[0116] ((In the case of polycarbonate polyol (B)) Crosslink density (mmol / g) = charge amount (g) of polycarbonate polyol (B) × average hydroxyl value of polycarbonate polyol (B) (mgKOH / g) / 56.11 / 1000 / number of functional groups of polycarbonate polyol (B) × (number of functional groups of polycarbonate polyol (B) - 2) / (charge amount (g) of polyol (B') + charge amount (g) of polycarbonate polyol (B) + charge amount (g) of organic acid (dimethylol fatty acid) (C) + charge amount (g) of polyisocyanate (D) + charge amount (g) of chain extender (G)) × 1000

[0117] ((In the case of polyhydric alcohol)) Crosslink density (mmol / g) = amount of polyhydric alcohol (g) / molecular weight of polyhydric alcohol (g / mol) × (number of functional groups of polyhydric alcohol - 2) / (amount of polyol (B') (g) + amount of polycarbonate polyol (B) (g) + amount of organic acid (dimethylol fatty acid) (C) (g) + amount of polyisocyanate (D) (g) + amount of chain extender (G) (g)) × 1000

[0118] (Polycarbonate polyol (B) content) The content of the polycarbonate polyol (B) in the polyurethane resin composition was calculated from the mass ratio when the polyol (B') and the polycarbonate polyol (B) were mixed together. Therefore, the content of the polycarbonate polyol (B) is defined by the following formula.

[0119] Content of polycarbonate polyol (B) (% by mass)=Charge amount of polycarbonate polyol (B) (g) / (Charge amount of polyol (B') (g)+Charge amount of polycarbonate polyol (B) (g))×100

[0120] (Analysis and Evaluation) [Content of unreacted isocyanate groups in isocyanate-terminated prepolymer (E)] The content of unreacted isocyanate groups in the isocyanate-terminated prepolymer (E) was measured in accordance with JIS-K6806.

[0121] [Measurement of number average molecular weight] The composition thus obtained 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.

[0122] -conditions- (1) Measuring instrument: HLC-8420 (manufactured by Tosoh Corporation) (2) Column: TSKgel (Tosoh Corporation) G3000H-XL G3000H-XL G2000H-XL G2000H-XL (3) Mobile phase: THF (tetrahydrofuran) (4) Detector: RI (refractive index) detector (accessory for HLC-8420) (5) Temperature: 40℃ (6)Flow rate: 1.000ml / min (7) Calibration curve: A calibration curve was obtained using the following products (all bifunctional polyoxypropylene polyols manufactured by Sanyo Chemical Industries, Ltd.). "Sannix PP-200" (number average molecular weight = 200, average number of functional groups: 2) "Sannix PP-400" (number average molecular weight = 400, average number of functional groups: 2) "Sannix PP-1000" (number average molecular weight = 1000, average number of functional groups: 2) "Sannix PP-2000" (number average molecular weight = 2000, average number of functional groups: 2) "Sannix PP-3000" (number average molecular weight = 3200, average number of functional groups: 2) "Sannix PP-4000" (number average molecular weight = 4160, average number of functional groups: 2) (8) Approximation of calibration curve: Cubic equation (9) Sample solution concentration: 0.5% by mass in THF solution

[0123] [Measurement of hydroxyl value (OHv)] The hydroxyl value of the composition obtained was measured by a method using an acetylating agent in accordance with JIS K1557-1, and the results are shown in Table 1.

[0124] [Characteristics evaluation] The obtained composition was used as a sample, which was heated at 80° C. for 1 hour and then left to stand for 3 days at 25° C. The state of the sample after standing was visually confirmed, 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.

[0125] [Synthesis of polycarbonate polyol 1] 31.3g of trimethylolpropane, 413.8g of 1,6-hexanediol, 454.9g of diethyl carbonate, and 0.045g of lithium acetylacetonate were mixed in a 1L two-neck glass reactor (hereinafter referred to as reactor A) equipped with a stirrer, thermometer, heating device, and cooler, and reacted at 100 to 150°C for 8 hours under normal pressure while removing low boiling point 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 a polycarbonate polyol (PCP-1A).

[0126] [Synthesis of polycarbonate polyol 2] All operations were carried out in the same manner as in Synthesis 1 of polycarbonate polyol to obtain polycarbonate polyol (PCP-1B).

[0127] [Synthesis of polycarbonate polyol 3] All operations were carried out in the same manner as in Synthesis 1 of polycarbonate polyol to obtain polycarbonate polyol (PCP-1C).

[0128] [Synthesis of polycarbonate polyol 4] All operations were carried out in the same manner as in Synthesis 1 of polycarbonate polyol to obtain polycarbonate polyol (PCP-1D).

[0129] [Synthesis of polycarbonate polyol 5] All operations were carried out in the same manner as in Synthesis 1 of polycarbonate polyol to obtain polycarbonate polyol (PCP-1E).

[0130] [Synthesis of polycarbonate polyol 6] In reactor A, 74.4 g of trimethylolpropane, 393.2 g of 1,6-hexanediol, 432.4 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate were mixed and reacted at 100 to 150°C for 8 hours under normal pressure while removing low boiling point 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-2A).

[0131] [Synthesis of polycarbonate polyol 7] In reactor A, 35.2 g of trimethylolpropane, 298.5 g of 1,6-hexanediol, 468.8 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate were mixed and reacted at 100 to 150°C for 8 hours under normal pressure while removing low boiling point 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-3).

[0132] [Synthesis of polycarbonate polyol 8] In reactor A, 0.82 g of trimethylolpropane, 199.1 g of 1,6-hexanediol, 200.1 g of diethyl carbonate, and 0.020 g of lithium acetylacetonate were mixed and reacted at 100 to 150°C for 8 hours under normal pressure while removing low boiling point 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-4).

[0133] [Synthesis of polycarbonate polyol 9] In reactor A, 3.31 g of trimethylolpropane, 196.81 g of 1,6-hexanediol, 199.9 g of diethyl carbonate, and 0.020 g of lithium acetylacetonate were mixed and reacted at 100 to 150°C for 8 hours under normal pressure while removing low boiling point 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-5).

[0134] [Synthesis of polycarbonate polyol 10] In reactor A, 8.08 g of trimethylolpropane, 192.2 g of 1,6-hexanediol, 199.8 g of diethyl carbonate, and 0.020 g of lithium acetylacetonate were mixed and reacted at 100 to 150°C for 8 hours under normal pressure while removing low boiling point 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-6).

[0135] [Synthesis of polycarbonate polyol 11] In reactor A, 20.53 g of trimethylolpropane, 180.3 g of 1,6-hexanediol, 199.2 g of diethyl carbonate, and 0.020 g of lithium acetylacetonate were mixed and reacted at 100 to 150°C for 8 hours under normal pressure while removing low boiling point 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-7).

[0136] [Synthesis of polycarbonate polyol 12] In reactor A, 24.82 g of trimethylolpropane, 176 g of 1,6-hexanediol, 199.2 g of diethyl carbonate, and 0.020 g of lithium acetylacetonate were mixed and reacted at 100 to 150°C for 8 hours under normal pressure while removing low boiling point 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-8).

[0137] [Synthesis of polycarbonate polyol 13] In reactor A, 30.43 g of trimethylolpropane, 170.3 g of 1,6-hexanediol, 199.2 g of diethyl carbonate, and 0.020 g of lithium acetylacetonate were mixed and reacted at 100 to 150°C for 8 hours under normal pressure while removing low boiling point 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-9).

[0138] [Synthesis of polycarbonate polyol 14] In reactor A, 44.63 g of trimethylolpropane, 156.2 g of 1,6-hexanediol, 199.2 g of diethyl carbonate, and 0.020 g of lithium acetylacetonate were mixed and reacted at 100 to 150°C for 8 hours under normal pressure while removing low boiling point 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 a polycarbonate polyol (PCP-10).

[0139] [Table 1]

[0140] 1,6-Hexanediol: BASF JAPAN 1,4-Butanediol: Fujifilm Wako Pure Chemical Industries, Ltd. Trimethylolpropane: Sigma-Aldrich Diethyl carbonate: Sigma-Aldrich Lithium acetylacetonate: Sigma-Aldrich

[0141] (Example 1: Production of polyurethane resin emulsion 1) A 1L reactor (hereinafter referred to as reactor B) equipped with a stirrer, a thermometer, a nitrogen seal tube, and a cooler was charged with 77.6g of N-980N (manufactured by Tosoh Corporation: number average molecular weight 2000; hydroxyl value 56.11mgKOH / g; 1,6-hexanediol-based polycarbonate diol), 3.04g of 1,6-hexanediol, 26.9g of PCP-1A, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 31.2g of isophorone diisocyanate, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The unreacted isocyanate group content at the end of urethanization was 0.286mmol / g relative to the amount charged. Next, 3.99 g of triethylamine was charged to neutralize the carboxyl group, and then 320 g of water was charged while stirring to emulsify. After emulsification, 0.18 g of KL-245 was added, and within 30 minutes, amine water (30 g of water and 1.99 g of isophorone diamine) was charged, 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, the stirring was stopped. Then, the reaction solution was transferred to a 2L eggplant flask and distilled under reduced pressure to remove 75 g of acetone and 50 g of water, and an aqueous polyurethane resin emulsion composition (PUD-1) was obtained.

[0142] (Example 2: Production of polyurethane resin emulsion 2) Into reactor B, 51.8g of N-980N, 1.99g of 1,6-hexanediol, 53.8g of PCP-1A, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 31.2g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.268mmol / g relative to the amount charged. Next, emulsification and operations after emulsification were performed in the same manner as in Example 1 to obtain an aqueous polyurethane resin emulsion composition (PUD-2).

[0143] (Example 3: Production of polyurethane resin emulsion 3) Into reactor B, 25.9g of N-980N, 0.95g of 1,6-hexanediol, 80.6g of PCP-1A, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 31.2g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.270mmol / g relative to the amount charged. Next, emulsification and operations after emulsification were performed in the same manner as in Example 1 to obtain an aqueous polyurethane resin emulsion composition (PUD-3).

[0144] (Example 4: Production of polyurethane resin emulsion 4) Into a reactor B, 84.1g of N-980N, 4.32g of 1,6-hexanediol, 15.6g of PCP-2A, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 31.2g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.284mmol / g relative to the amount charged. Next, emulsification and operations after emulsification were performed in the same manner as in Example 1 to obtain an aqueous polyurethane resin emulsion composition (PUD-4).

[0145] (Example 5: Production of polyurethane resin emulsion 5) Into a reactor B, 70.4g of N-980N, 2.37g of 1,6-hexanediol, 31.2g of PCP-2A, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 34.7g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.280mmol / g relative to the amount charged. Next, emulsification and operations after emulsification were performed in the same manner as in Example 1 to obtain an aqueous polyurethane resin emulsion composition (PUD-5).

[0146] (Example 6: Production of polyurethane resin emulsion 6) Into reactor B, 56.8g of N-980N, 0.41g of 1,6-hexanediol, 46.8g of PCP-2A, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 34.7g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.355mmol / g relative to the amount charged. Next, emulsification and operations after emulsification were performed in the same manner as in Example 1 to obtain an aqueous polyurethane resin emulsion composition (PUD-6).

[0147] (Example 7: Production of polyurethane resin emulsion 7) Into reactor B, 78.9g of N-980N, 3.40g of 1,6-hexanediol, 27.4g of PCP-1B, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 29.9g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.170mmol / g relative to the amount charged. Next, 3.99g of triethylamine was charged to neutralize the carboxyl groups, and then 320g of water was charged while stirring to emulsify. After emulsification, 0.18 g of KL-245 was added, and within 30 minutes, amine water (30 g of water and 0.99 g of isophorone diamine) 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 2L eggplant flask and distilled under reduced pressure to remove 75 g of acetone and 50 g of water, obtaining an aqueous polyurethane resin emulsion composition (PUD-7).

[0148] (Example 8: Production of polyurethane resin emulsion 8) Into reactor B, 52.5g of N-980N, 2.42g of 1,6-hexanediol, 54.9g of PCP-1B, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 29.9g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.169mmol / g relative to the amount charged. Next, emulsification and post-emulsification operations were performed in the same manner as in Example 7 to obtain an aqueous polyurethane resin emulsion composition (PUD-8).

[0149] (Example 9: Production of polyurethane resin emulsion 9) Into reactor B, 75.7g of N-980N, 3.26g of 1,6-hexanediol, 26.3g of PCP-1B, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 32.4g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.266mmol / g relative to the amount charged. Next, 3.99g of triethylamine was charged to neutralize the carboxyl groups, and then 320g 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 2.99 g of isophorone diamine) 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 2L eggplant flask and distilled under reduced pressure to remove 75 g of acetone and 50 g of water, obtaining an aqueous polyurethane resin emulsion composition (PUD-9).

[0150] (Example 10: Production of polyurethane resin emulsion 10) Into reactor B, 50.3g of N-980N, 2.32g of 1,6-hexanediol, 52.6g of PCP-1B, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 32.4g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.263mmol / g relative to the amount charged. Next, emulsification and post-emulsification operations were performed in the same manner as in Example 9 to obtain an aqueous polyurethane resin emulsion composition (PUD-10).

[0151] (Example 11: Production of polyurethane resin emulsion 11) Into reactor B, 84.6g of N-980N, 28.2g of PCP-1B, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 25.9g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.238mmol / 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-11).

[0152] (Example 12: Production of polyurethane resin emulsion 12) Into reactor B, 55.5g of N-980N, 55.5g of PCP-1B, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 27.6g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.231mmol / 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).

[0153] (Example 13: Production of polyurethane resin emulsion 13) Into reactor B, 27.4g of N-980N, 82.3g of PCP-1B, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 29.0g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.242mmol / g relative to the amount charged. Next, emulsification and operations after emulsification were performed in the same manner as in Example 1 to obtain an aqueous polyurethane resin emulsion composition (PUD-13).

[0154] (Example 14: Production of polyurethane resin emulsion 14) Into reactor B, 98.2g of N-980N, 10.9g of PCP-1C, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 27.6g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, then 0.12g of U-600 was added, and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.322mmol / g relative to the amount charged. Next, 3.99g of triethylamine was charged to neutralize the carboxyl groups, and 320g of water was charged while stirring to emulsify. After emulsification, 0.18g of KL-245 was added, and amine water (30g of water and 3.98g of isophorone diamine) was charged within 30 minutes, 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 75 g of acetone and 50 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-14).

[0155] (Example 15: Production of polyurethane resin emulsion 15) Into reactor B, 76.9g of N-980N, 3.70g of 1,6-hexanediol, 26.9g of PCP-3, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 31.2g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.143mmol / g relative to the amount charged. Next, emulsification and operations after emulsification were performed in the same manner as in Example 1 to obtain an aqueous polyurethane resin emulsion composition (PUD-15).

[0156] (Example 16: Production of polyurethane resin emulsion 16) Into reactor B, 50.6g of N-980N, 3.11g of 1,6-hexanediol, 53.7g of PCP-3, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 31.2g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.223mmol / 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-16).

[0157] (Example 17: Production of polyurethane resin emulsion 17) Into reactor B, 54.6g of N-980N, 2.45g of 1,6-hexanediol, 57.1g of PCP-1D, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 24.5g of hexamethylene diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.192mmol / 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-17).

[0158] (Example 18: Production of polyurethane resin emulsion 18) Into a reactor B, 51.3 g of Plaxel 220 (manufactured by Daicel Corporation: number average molecular weight 2000; hydroxyl value 56.11 mg KOH / g; ε-caprolactone ring-opening polymerization type ester polyol; average number of functional groups 2), 2.44 g of 1,6-hexanediol, 53.7 g of PCP-1E, 75 g of acetone, 5.29 g of 2,2-dimethylolpropanoic acid, and 31.2 g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12 g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.251 mmol / g relative to the amount charged. Next, emulsification and operations after emulsification were performed in the same manner as in Example 1 to obtain an aqueous polyurethane resin emulsion composition (PUD-18).

[0159] (Comparative Example 1: Production of Polyurethane Resin Emulsion 19) Into reactor B, 103.4g of N-980N, 4.08g of 1,6-hexanediol, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 31.2g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.197mmol / 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-19).

[0160] (Comparative Example 2: Production of Polyurethane Resin Emulsion 20) Into reactor B, 99.1g of N-980N, 3.91g of 1,6-hexanediol, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 33.6g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.340mmol / g relative to the amount charged. Next, emulsification and post-emulsification operations were performed in the same manner as in Example 14 to obtain an aqueous polyurethane resin emulsion composition (PUD-20).

[0161] (Comparative Example 3: Production of Polyurethane Resin Emulsion 21) Into reactor B, 97.0g of N-980N, 3.82g of 1,6-hexanediol, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 34.8g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, then 0.12g of U-600 was added, and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.263mmol / g relative to the amount charged. Next, 3.99g of triethylamine was charged to neutralize the carboxyl groups, and 320g of water was charged while stirring to emulsify. After emulsification, 0.18g of KL-245 was added, and amine water (30g of water and 4.97g of isophorone diamine) was charged within 30 minutes, 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 75 g of acetone and 50 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-21).

[0162] (Comparative Example 4: Production of Polyurethane Resin Emulsion 22) Into a reactor B, 101.1g of N-980N, 3.56g of 1,6-hexanediol, 2.15g of trimethylolpropane, 75g of acetone, 5.43g of 2,2-dimethylolpropanoic acid, and 35.6g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.275mmol / g relative to the amount charged. Next, emulsification and operations after emulsification were performed in the same manner as in Comparative Example 5 to obtain an aqueous polyurethane resin emulsion composition (PUD-22).

[0163] (Comparative Example 5: Production of Polyurethane Resin Emulsion 23) Into reactor B, 101.9g of N-980N, 0.69g of 1,6-hexanediol, 4.29g of trimethylolpropane, 75g of acetone, 5.43g of 2,2-dimethylolpropanoic acid, and 35.6g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.328mmol / g relative to the amount charged. Next, emulsification and post-emulsification operations were performed in the same manner as in Comparative Example 5 to obtain an aqueous polyurethane resin emulsion composition (PUD-23).

[0164] (Comparative Example 6: Production of Polyurethane Resin Emulsion 24) Into reactor B, 106.8g of N-980N, 1.59g of 1,6-hexanediol, 2.06g of trimethylolpropane, 75g of acetone, 5.43g of 2,2-dimethylolpropanoic acid, and 32.0g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.305mmol / g relative to the amount charged. Next, emulsification and post-emulsification operations were performed in the same manner as in Comparative Example 5 to obtain an aqueous polyurethane resin emulsion composition (PUD-24).

[0165] [Table 2] [Table 3]

[0166] [Table 4]

[0167] The content of urea groups derived from water is calculated from the results of measuring the NCO content, and may be a negative value due to an error in the NCO content. In Table 4, the negative percentage of the content of urea groups derived from water is shown as "0.01", but this is rounded off to the third decimal place, and is actually about 0.005.

[0168] (Example 19: Production of polyurethane resin emulsion 25) Into reactor B, 50.2g of N-980N, 3.52g of 1,6-hexanediol, 53.7g of PCP-5, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 31.2g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.207mmol / 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-25).

[0169] (Example 20: Production of polyurethane resin emulsion 26) Into reactor B, 50.6g of N-980N, 3.16g of 1,6-hexanediol, 53.7g of PCP-6, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 31.2g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.229mmol / g relative to the amount charged. Next, emulsification and operations after emulsification were performed in the same manner as in Example 1 to obtain an aqueous polyurethane resin emulsion composition (PUD-26).

[0170] (Example 21: Production of polyurethane resin emulsion 27) Into reactor B, 52.6g of N-980N, 1.18g of 1,6-hexanediol, 53.7g of PCP-7, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 31.2g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.253mmol / g relative to the amount charged. Next, emulsification and operations after emulsification were performed in the same manner as in Example 1 to obtain an aqueous polyurethane resin emulsion composition (PUD-27).

[0171] (Example 22: Production of polyurethane resin emulsion 28) Into reactor B, 52.4g of N-980N, 1.31g of 1,6-hexanediol, 53.7g of PCP-8, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 31.2g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.268mmol / g relative to the amount charged. Next, emulsification and operations after emulsification were performed in the same manner as in Example 1 to obtain an aqueous polyurethane resin emulsion composition (PUD-28).

[0172] (Example 23: Production of polyurethane resin emulsion 29) Into reactor B, 53.5g of N-980N, 0.24g of 1,6-hexanediol, 53.7g of PCP-9, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 31.2g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.205mmol / g relative to the amount charged. Next, emulsification and operations after emulsification were performed in the same manner as in Example 1 to obtain an aqueous polyurethane resin emulsion composition (PUD-29).

[0173] (Comparative Example 7: Production of Polyurethane Resin Emulsion 30) Into reactor B, 50.0g of N-980N, 3.71g of 1,6-hexanediol, 53.7g of PCP-4, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 31.2g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.224mmol / 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-30).

[0174] (Comparative Example 8: Production of Polyurethane Resin Emulsion 31) Into reactor B, 56.8g of N-980N, 53.7g of PCP-10, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 31.2g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.186mmol / 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-31).

[0175] [Table 5]

[0176] (Example 24: Production of polyurethane resin emulsion 32) Into reactor B, 51.2g of N-980N, 53.7g of PCP-1D, 2.6g of 1,6-hexanediol, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 27.1g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.257mmol / g relative to the amount charged. Next, 3.99g of triethylamine was charged to neutralize the carboxyl groups, and then 320g 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 3.68 g of isophorone diamine) 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 2L eggplant flask and distilled under reduced pressure to remove 75 g of acetone and 50 g of water, obtaining an aqueous polyurethane resin emulsion composition (PUD-32).

[0177] (Example 25: Production of polyurethane resin emulsion 33) In the reactor B, an isocyanate group-terminated urethane prepolymer was obtained in the same manner as in Example 24. The content of unreacted isocyanate groups at the end of urethane formation was 0.241 mmol / g relative to the amount charged. Next, 3.99 g of triethylamine was charged to neutralize the carboxyl groups, and then 320 g of water was charged while 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 2.67 g of isophorone diamine) was charged, 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, the stirring was stopped. Then, the reaction solution was transferred to a 2L eggplant flask, and 75 g of acetone and 50 g of water were removed by vacuum distillation to obtain an aqueous polyurethane resin emulsion composition (PUD-33).

[0178] (Example 26: Production of polyurethane resin emulsion 34) In the reactor B, an isocyanate group-terminated urethane prepolymer was obtained in the same manner as in Example 24. The content of unreacted isocyanate groups at the end of urethanization was 0.268 mmol / g relative to the amount charged. Next, 3.99 g of triethylamine was charged to neutralize the carboxyl groups, and then 320 g of water was charged while stirring to emulsify. After emulsification, 0.18 g of KL-245 was added, and within 30 minutes, amine water (30 g of water and 1.99 g of isophorone diamine) was charged, 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, the stirring was stopped. Then, the reaction solution was transferred to a 2L eggplant flask, and 75 g of acetone and 50 g of water were removed by vacuum distillation to obtain an aqueous polyurethane resin emulsion composition (PUD-34).

[0179] (Example 27: Production of polyurethane resin emulsion 35) In the reactor B, an isocyanate group-terminated urethane prepolymer was obtained in the same manner as in Example 24. The content of unreacted isocyanate groups at the end of urethane formation was 0.259 mmol / g relative to the amount charged. Next, 3.99 g of triethylamine was charged to neutralize the carboxyl groups, and then 320 g of water was charged while stirring to emulsify. After emulsification, 0.18 g of KL-245 was added, and within 30 minutes, amine water (30 g of water and 0.97 g of isophorone diamine) was charged, 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, the stirring was stopped. Then, the reaction solution was transferred to a 2L eggplant flask, and 75 g of acetone and 50 g of water were removed by vacuum distillation to obtain an aqueous polyurethane resin emulsion composition (PUD-35).

[0180] (Example 28: Production of polyurethane resin emulsion 36) In the reactor B, an isocyanate group-terminated urethane prepolymer was obtained in the same manner as in Example 24. The content of unreacted isocyanate groups at the end of urethane formation was 0.258 mmol / g relative to the amount charged. Next, 3.99 g of triethylamine was charged to neutralize the carboxyl groups, and then 320 g of water was charged while 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 0.49 g of isophorone diamine) was charged, 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, the stirring was stopped. Then, the reaction solution was transferred to a 2L eggplant flask, and 75 g of acetone and 50 g of water were removed by vacuum distillation to obtain an aqueous polyurethane resin emulsion composition (PUD-36).

[0181] (Example 29: Production of polyurethane resin emulsion 37) In the reactor B, an isocyanate group-terminated urethane prepolymer was obtained in the same manner as in Example 24. The content of unreacted isocyanate groups at the end of urethane formation was 0.271 mmol / g relative to the amount charged. Next, 3.99 g of triethylamine was charged to neutralize the carboxyl groups, and then 350 g of water was charged while stirring to emulsify. After emulsification, 0.18 g of KL-245 was added, and the amine extension reaction was carried out at 40°C for 12 hours. When the presence of isocyanate groups was no longer confirmed by FT-IR, the stirring was stopped. Then, the reaction solution was transferred to a 2L eggplant flask, and 75 g of acetone and 50 g of water were removed by vacuum distillation to obtain an aqueous polyurethane resin emulsion composition (PUD-37).

[0182] (Example 30: Production of polyurethane resin emulsion 38) Into reactor B, 55.8g of N-980N, 55.8g of PCP-1D, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 27.1g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, then 0.12g of U-600 was added, and reacted for 2 hours and 45 minutes. The content of unreacted isocyanate groups at the end of urethanization was 0.399mmol / g relative to the amount charged. Next, 3.99g of triethylamine was charged to neutralize the carboxyl groups, and 320g of water was charged while stirring to emulsify. After emulsification, 0.18g of KL-245 was added, and amine water (30g of water and 3.20g of isophorone diamine) was charged within 30 minutes, 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 75 g of acetone and 50 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-38).

[0183] (Example 31: Production of polyurethane resin emulsion 39) Into reactor B, 55.8g of N-980N, 55.8g of PCP-1D, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 27.1g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, then 0.12g of U-600 was added, and reacted for 4 hours and 15 minutes. The content of unreacted isocyanate groups at the end of urethanization was 0.345mmol / g relative to the amount charged. Next, 3.99g of triethylamine was charged to neutralize the carboxyl groups, and 320g of water was charged while stirring to emulsify. After emulsification, 0.18g of KL-245 was added, and amine water (mixed with 30g of water and 2.77g of isophorone diamine) was charged within 30 minutes, 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 75 g of acetone and 50 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-39).

[0184] (Comparative Example 9: Production of Polyurethane Resin Emulsion 40) Into reactor B, 55.8g of N-980N, 55.8g of PCP-1D, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 27.1g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, then 0.12g of U-600 was added, and reacted for 1 hour and 20 minutes. The content of unreacted isocyanate groups at the end of urethanization was 0.780mmol / g relative to the amount charged. Next, 3.99g of triethylamine was charged to neutralize the carboxyl groups, and 320g of water was charged while stirring to emulsify. After emulsification, 0.18g of KL-245 was added, and amine water (mixed with 30g of water and 6.25g of isophorone diamine) was charged within 30 minutes, 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 75 g of acetone and 50 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-40).

[0185] [Table 6]

[0186] Trimethylolpropane: Sigma-Aldrich 1,6-Hexanediol: BASF JAPAN 2,2-Dimethylolpropionic acid: Tokyo Chemical Industry Co., Ltd. Isophorone diisocyanate: Evonik Hexamethylene diisocyanate: Tokyo Chemical Industry Co., Ltd. Acetone: KH Neochem Triethylamine: Kishida Chemical Co., Ltd. Isophoronediamine: manufactured by Tokyo Chemical Industry Co., Ltd. Neostan U-600: Manufactured by Nitto Kasei Co., Ltd. KL-245: Evonik ·Water: Purified water

[0187] <How to prepare film for tensile property test> 14.0 parts of dipropylene glycol dimethyl ether was added to 100 parts of the aqueous polyurethane resin emulsion composition PUD-1 to PUD-40 obtained in Examples 1 to 31 and Comparative Examples 1 to 9, and mixed to obtain a base material. The base material was applied so that the dry film thickness was about 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 were evaluated using this cured product. The results are shown in Tables 7 to 10.

[0188] [Evaluation test 1] [Tensile properties] The tensile properties of the obtained cured product were measured in accordance with JIS K7321 (100% modulus, strength at break, elongation at break). Test equipment: Tensilon UTA-500 (manufactured by A&D) Measurement conditions: 25℃×50%RH Head speed: 200mm / min Dumbbell No. 4

[0189] [Softening temperature] A test piece was obtained from the obtained film using a dumbbell, a 2 cm mark was drawn on the test piece, and the thickness at the center of the mark was measured. A weight of a specified weight was attached to one grip of the test piece, and the other grip was clamped with a double clip, and the test piece was hung in a dryer with the clip on the upper side. The temperature inside the dryer was then increased and the distance between the marks was observed. The temperature at which the distance between the marks reached 4 cm was read as the softening temperature. Processing equipment: constant temperature blower dryer DRK633DA (manufactured by Advantec) Weight: thickness of center of gauge line (μm) x 0.05g Dumbbell No. 2 (JIS K6251 compliant) Heating rate: 5℃ / min

[0190] [Evaluation Criteria] The physical properties of 100% modulus, strength at break, elongation at break, and softening temperature were rated as A, B, C, or D (A: very good, B: good, C: average, D: poor). Furthermore, the overall rating was A, B, or D (A: very good, B: good, D: poor).

[0191] <100% modulus> A: Less than 4.0MPa B: 4.0MPa or more and less than 5.0MPa D:5.0MPa or more <Strength at break> A:30MPa or more C: Less than 30MPa <Elongation at break> A:450MPa or more C: Less than 450MPa <Softening temperature> A: 120℃ or higher B: Less than 120℃ 90℃ or more D: Less than 90℃ <Overall rating> A: Each physical property is rated A only B: The evaluation of each physical property does not include D, and includes at least one B or C. D: The evaluation of each physical property value includes D.

[0192] [Table 7]

[0193] [Table 8]

[0194] [Table 9]

[0195] [Table 10]

[0196] [Production of polycarbonate polyol 2-1] 31.3g of trimethylolpropane, 413.8g of 1,6-hexanediol, 454.9g of diethyl carbonate, and 0.045g of lithium acetylacetonate were mixed in a 1L two-neck glass reactor equipped with a stirrer, thermometer, heating device, and cooler, and reacted at 100-150°C for 8 hours under normal pressure while removing low boiling point components. The reaction temperature was then increased to 150°C, the pressure in the flask was reduced to 1kPa, and the reaction was continued for another 8 hours to obtain polycarbonate polyol (PCP-1F).

[0197] [Production of polycarbonate polyol 2-2] 74.4g of trimethylolpropane, 393.2g of 1,6-hexanediol, 432.4g of diethyl carbonate, and 0.045g of lithium acetylacetonate were mixed in a 1L two-neck glass reactor equipped with a stirrer, thermometer, heating device, and cooler, and reacted at 100-150°C for 8 hours under normal pressure while removing low boiling point components. The reaction temperature was then increased to 150°C, the pressure in the flask was reduced to 1kPa, and the reaction was continued for another 8 hours to obtain polycarbonate polyol (PCP-2B).

[0198] Production of polycarbonate polyols 2-1 to 2-2 is shown in Table 11.

[0199] [Table 11]

[0200] 1,6-Hexanediol: BASF JAPAN Trimethylolpropane: Sigma-Aldrich Diethyl carbonate: Sigma-Aldrich Lithium acetylacetonate: Sigma-Aldrich.

[0201] (Example 63: Production of aqueous polyurethane resin emulsion 2-1) A 1L reactor (hereinafter referred to as reaction group A) equipped with a stirrer, a thermometer, a nitrogen seal tube, and a cooler was charged with 51.1g of N-980N (manufactured by Tosoh Corporation: number average molecular weight 2000; hydroxyl value 56.11mgKOH / g; 1,6-hexanediol-based polycarbonate diol), 3.07g of 1,6-hexanediol, 51.9g of PCP-1F, 75g of acetone, 5.43g of 2,2-dimethylolpropanoic acid, and 34.6g of isophorone diisocyanate, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.356mmol / g relative to the amount charged. Next, 4.10 g of triethylamine was charged to neutralize the carboxyl group, and then 320 g of water was charged while stirring to emulsify. After emulsification, 0.18 g of KL-245 was added, and within 30 minutes, amine water (30 g of water, 2.04 g of isophorone diamine, and 1.83 g of monoethanolamine) was charged, 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, the stirring was stopped. Then, the reaction solution was transferred to a 2L eggplant flask and distilled under reduced pressure to remove 75 g of acetone and 50 g of water, and an aqueous polyurethane resin emulsion composition (PUD-41) was obtained.

[0202] (Example 64: Production of aqueous polyurethane resin emulsion 2-2) Into reactor A, 26.6g of N-980N, 79.8g of PCP-1F, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 30.5g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, then 0.12g of U-600 was added, and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.349mmol / g relative to the amount charged. Next, 3.99g of triethylamine was charged to neutralize the carboxyl groups, and 320g of water was charged while stirring to emulsify. After emulsification, 0.18g of KL-245 was added, and amine water (30g of water, 1.99g of isophorone diamine, and 1.78g of monoethanolamine) was charged within 30 minutes, 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 75 g of acetone and 50 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-42).

[0203] (Example 65: Production of aqueous polyurethane resin emulsion 2-3) Into reactor A, 81.1g of N-980N, 4.33g of 1,6-hexanediol, 15.1g of PCP-2A, 75g of acetone, 5.29g of 2,2-dimethylolpropanoic acid, and 36.5g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.371mmol / g relative to the amount charged. Next, 3.99g of triethylamine was charged to neutralize the carboxyl groups, and then 320g 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, 1.99 g of isophorone diamine, and 1.43 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 2L eggplant flask and distilled under reduced pressure to remove 75 g of acetone and 50 g of water, obtaining an aqueous polyurethane resin emulsion composition (PUD-43).

[0204] (Comparative Example 19: Production of aqueous polyurethane resin emulsion 2-4) Into a reactor A, 103.1 g of N-980N, 3.00 g of trimethylolpropane, 75 g of acetone, 5.43 g of 2,2-dimethylolpropanoic acid, and 34.6 g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12 g of U-600 was added and reacted 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, 4.10 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, 2.04 g of isophorone diamine, and 1.83 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 2L eggplant flask and distilled under reduced pressure to remove 75 g of acetone and 50 g of water, obtaining an aqueous polyurethane resin emulsion composition (PUD-44).

[0205] (Comparative Example 20: Production of aqueous polyurethane resin emulsion 2-5) Into reactor A, 102.0g of N-980N, 4.02g of 1,6-hexanediol, 75g of acetone, 5.43g of 2,2-dimethylolpropanoic acid, and 34.6g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, and then 0.12g of U-600 was added and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.356mmol / g relative to the amount charged. Next, 4.10g of triethylamine was charged to neutralize the carboxyl groups, and then 320g 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, 2.04 g of isophorone diamine, and 1.83 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 2L eggplant flask and distilled under reduced pressure to remove 75 g of acetone and 50 g of water, obtaining an aqueous polyurethane resin emulsion composition (PUD-45).

[0206] (Comparative Example 21: Production of aqueous polyurethane resin emulsion 2-6) Into reactor A, 97.6g of N-980N, 3.85g of 1,6-hexanediol, 75g of acetone, 5.43g of 2,2-dimethylolpropanoic acid, and 37.1g of isophorone diisocyanate were charged, heated to 60°C, stirred at the same temperature for 30 minutes, then 0.12g of U-600 was added, and reacted for 5 hours. The content of unreacted isocyanate groups at the end of urethanization was 0.420mmol / g relative to the amount charged. Next, 4.10g of triethylamine was charged to neutralize the carboxyl groups, and 320g of water was charged while stirring to emulsify. After emulsification, 0.18g of KL-245 was added, and amine water (30g of water, 4.09g of isophorone diamine, and 1.83g of monoethanolamine) was charged within 30 minutes, 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 75 g of acetone and 50 g of water, yielding an aqueous polyurethane resin emulsion composition (PUD-46).

[0207] Examples 63 to 65 (PUDs 41 to 43) and Comparative Examples 19 to 21 (PUDs 44 to 46) are summarized in Table 12.

[0208] [Table 12]

[0209] 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. Isophoronediamine: manufactured by Tokyo Chemical Industry Co., Ltd. Monoethanolamine: Fujifilm Wako Pure Chemical Industries, Ltd. Neostan U-600: Manufactured by Nitto Kasei Co., Ltd. KL-245: Evonik ·Water: City water

[0210] Furthermore, the polyol components PUD-41 to PUD-46 obtained in Examples 63 to 65 and Comparative Examples 19 to 21, 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 13 and mixed to obtain a mixed solution. The mixed solution was applied onto release paper so that the dry film thickness was about 100 μm, and a cured product was produced by drying at 25° C. for 1 day and at 80° C. for 2 hours. The physical properties were evaluated using this cured product. The results are shown in Table 13. The unit of charge in the table is grams. Dipropylene glycol dimethyl ether: Fujifilm Wako Pure Chemical Industries, Ltd. Aquanate 200: Tosoh Corporation (nonionic water-dispersible polyisocyanate, NCO content = 11.9%)

[0211] [Evaluation Test 2-1] [Tensile properties] The tensile properties of the obtained cured product were measured in accordance with JIS K7321 (100% modulus, strength at break, elongation at break). Test equipment: Tensilon UTA-500 (manufactured by A&D) Measurement conditions: 25℃×50%RH Head speed: 200mm / min Dumbbell No. 4

[0212] [Softening temperature] A test piece was obtained from the obtained film using a dumbbell, a 2 cm mark was drawn on the test piece, and the thickness at the center of the mark was measured. A weight of a specified weight was attached to one grip of the test piece, and the other grip was clamped with a double clip, and the test piece was hung in a dryer with the clip on the upper side. The temperature inside the dryer was then increased and the distance between the marks was observed. The temperature at which the distance between the marks reached 4 cm was read as the softening temperature. Processing equipment: constant temperature blower dryer DRK633DA (manufactured by Advantec) Weight: thickness of center of gauge line (μm) x 0.05g Dumbbell No. 2 (JIS K6251 compliant) Heating rate: 5℃ / min

[0213] [Evaluation Criteria] The physical properties of 100% modulus, strength at break, elongation at break, and softening temperature were rated as A, B, C, or D (A: very good, B: good, C: average, D: poor). Furthermore, the overall rating was A, B, or D (A: very good, B: good, D: poor). <100% modulus> A: Less than 5.0MPa B: 5.0MPa or more and less than 6.5MPa D:6.5MPa or more <Strength at break> A:30MPa or more C: Less than 30MPa <Elongation at break> A:250MPa or more C: Less than 250MPa <Softening temperature> A: 230℃ or higher B: Less than 230℃ 210℃ or more D: Less than 210℃ <Overall rating> A: Each physical property is rated A only B: The evaluation of each physical property does not include D, and includes at least one B or C. D: The evaluation of each physical property value includes D.

[0214] [Table 13]

[0215] Aquanate 200: Tosoh Corporation (nonionic water-dispersible polyisocyanate, NCO content = 11.9%) Dipropylene glycol dimethyl ether: Fujifilm Wako Pure Chemical Industries, Ltd.

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 (A) containing a polycarbonate polyol (B) having an average hydroxyl functionality of more than 2; an organic acid (C); and a polyisocyanate (D), the content of the polycarbonate polyol (B) is 10.0 mass% or more relative to the total content of the polyol (A), the polycarbonate polyol (B) comprises a polycarbonate polyol (α) which is a transesterification product of a diol (b-1), a polyhydric alcohol (b-2) having three or more hydroxyl functional groups, and a carbonate ester (b-3), or a polycarbonate polyol (β) which is a transesterification product of a diol (b-1), a polyhydric alcohol (b-2) having three or more hydroxyl functional groups, and a polycarbonate polyol (b-4); the polyhydric alcohol (b-2) is at least one selected from the group consisting of trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, dipentaerythritol, and sorbitol; a crosslinking density of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G) is 0.02 to 0.47; the chain extender (G) comprises 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 0.400 mmol / g or less, relative to the total mass of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G).

2. A polyurethane resin composition as described in claim 1, wherein the content of urea groups derived from the amine compound in the polyurethane resin composition is more than 0 mol% and not more than 95 mol% relative to the total content of the urea groups.

3. The chain extender (G) contains water, 3. 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 0.80 mmol / g or less, relative to the total mass of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G).

4. A polyurethane resin composition according to claim 1 or 2, wherein the average hydroxyl value of the polyol (A) is 30 to 150 mg KOH / g.

5. The polyurethane resin composition according to claim 1, wherein the polycarbonate polyol (B) has a hydroxyl value of 40 to 500 mg KOH / g.

6. The polyurethane resin composition according to claim 1, wherein the polycarbonate polyol (B) has a number average molecular weight of 400 to 4,000 g / mol.

7. A polyurethane resin composition described in claim 1 or 2, wherein the organic acid (C) is a dimethylol fatty acid.

8. A polyurethane resin composition described in claim 1 or 2, wherein the neutralizing agent (F) is a basic neutralizing agent.

9. The polyurethane resin composition according to claim 1, wherein the polyol (A) comprises a diol (a-1).

10. A polyurethane resin composition described in claim 1 or 2, which is a one-component type.

11. The polyurethane resin composition according to claim 1 or 2, further comprising a curing agent (X).

12. A polyurethane resin composition described in claim 11, which is a two-component type.

13. A cured product of a polyurethane resin composition comprising a reaction product of an isocyanate group-terminated urethane prepolymer (E) and a chain extender (G), The isocyanate group-terminated urethane prepolymer (E) is a polyol (A) containing a polycarbonate polyol (B) having an average hydroxyl functionality of more than 2; an organic acid (C); and a polyisocyanate (D), the content of the polycarbonate polyol (B) is 10.0 mass% or more relative to the total content of the polyol (A), the polycarbonate polyol (B) comprises a polycarbonate polyol (α) which is a transesterification product of a diol (b-1), a polyhydric alcohol (b-2) having three or more hydroxyl functional groups, and a carbonate ester (b-3), or a polycarbonate polyol (β) which is a transesterification product of a diol (b-1), a polyhydric alcohol (b-2) having three or more hydroxyl functional groups, and a polycarbonate polyol (b-4); the polyhydric alcohol (b-2) is at least one selected from the group consisting of trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, dipentaerythritol, and sorbitol; a crosslinking density of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G) is 0.02 to 0.47; the chain extender (G) comprises an amine compound having one or more primary or secondary amino groups, a cured product, wherein the content of the urea group derived from the amine compound in the polyurethane resin composition is more than 0 mmol / g and 0.400 mmol / g or less, relative to the total mass of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (G).

14. Artificial leather or synthetic leather comprising a cured product of the polyurethane resin composition described in claim 1 or 2.

15. A surface treatment agent for leather, comprising a cured product of the polyurethane resin composition described in claim 1 or 2.