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

Abstract

To provide a polyurethane resin composition capable of achieving both excellent water resistance and heat resistance, and to provide artificial leather or synthetic leather containing a cured product of the polyurethane resin, and a surface treatment agent for leather.SOLUTION: A polyurethane resin composition comprising a polyurethane resin and a curing agent, a reaction product of an isocyanate group-terminated urethane prepolymer (E) containing a reaction product of a polyol (A), a specific antibacterial agent (B), an organic acid (C), and a polyisocyanate (D), and a chain extender (F) which may contain the specific antibacterial agent (B); Or a reaction product of (E) containing the reaction product of (A), (C), and (D) and (F) containing (B), and (G) a neutralizing agent, wherein the content of the antibacterial agent (B) is 0.2 to 7.5 mass%, the curing agent is a polyisocyanate compound, and the content of the curing agent is 0.1 to 100 parts by mass. SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Polyurethane resin compositions have traditionally been used exclusively as compositions containing organic solvents, and because they have high adhesion to various materials and various excellent physical properties, they have been widely used as coating agents, paints, adhesives, printing inks, etc.

[0003] In recent years, from the viewpoint of environmental conservation, work safety, and other social and industrial demands, there has been a demand for aqueous (water-based) polyurethane resin compositions (aqueous polyurethane resin compositions) that do not use organic solvents.

[0004] The properties of aqueous polyurethane resin compositions can be improved by changing the various components, and various aqueous polyurethane resin compositions have been proposed. For example, Patent Document 1 proposes a polyurethane resin composition that uses a polycarbonate polyol to achieve both a low 100% modulus and high heat resistance. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2022 / 244850 Summary of the Invention [Problem to be solved by the invention]

[0006] However, when quaternary ammonium salts are fixed to the polyurethane resin skeleton to impart antibacterial properties to the polyurethane resin, problems arise in that the resin absorbs water and turns white, and its heat resistance decreases due to its low molecular weight.

[0007] An object of one aspect of the present disclosure is to provide a polyurethane resin composition that can achieve both excellent water resistance and heat resistance.An object of another aspect of the present disclosure is to provide an artificial leather or synthetic leather, and a leather surface treatment agent, each of which includes a cured product of the polyurethane resin. [Means for solving the problem]

[0008] Each aspect of the present disclosure provides at least the following (1) to (17). (1): A polyurethane resin composition comprising a polyurethane resin and a curing agent, The polyurethane resin is a reaction product of an isocyanate-terminated urethane prepolymer (E) comprising a reaction product of a polyol (A), an antimicrobial agent (B) which is a quaternary ammonium salt represented by formula (1), an organic acid (C), and a polyisocyanate (D), and a chain extender (F) which may contain the antimicrobial agent (B) which is a quaternary ammonium salt represented by formula (1); or a reaction product of an isocyanate-terminated urethane prepolymer (E) comprising a reaction product of a polyol (A), an organic acid (C), and a polyisocyanate (D), and a chain extender (F) which contains the antimicrobial agent (B) which is a quaternary ammonium salt represented by formula (1); a neutralizing agent (G), the content of the antibacterial agent (B) is 0.2 mass% or more and 7.5 mass% or less relative to the total mass of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (F) in the polyurethane resin composition; the curing agent is a polyisocyanate compound, A polyurethane resin composition, wherein the content of the curing agent is 0.1 parts by mass or more and 100 parts by mass or less relative to 100 parts by mass of the polyurethane resin. (R 1 ) a (R 2 ) b (R 3 ) c N + X - (1) (In formula (1), R1 is an aliphatic hydrocarbon group in which at least one hydrogen atom is substituted with a hydroxy group, R 1 The number of carbon atoms in If only one hydrogen atom is substituted with a hydroxy group, the number is 4 to 11. When two or more hydrogen atoms are replaced by hydroxy groups, the number is 3 to 11. R 2 is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, R 3 is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, X - is the conjugate base of the acid, a represents 1 or 2, b represents 1, c represents 1 or 2, and a+b+c=4 is satisfied; and R 1 , R 2 and R 3 The total number of carbon atoms in the aliphatic hydrocarbon group represented by the formula (I) is 15 or more and 23 or less, When a or c is 2, multiple R 1 or R 3 may be the same or different.) (2) The polyurethane resin composition according to (1), wherein the curing agent is at least one selected from the group consisting of urethane-modified, urea-modified, allophanate-modified, biuret-modified, uretdione-modified, and isocyanurate-modified organic diisocyanates. (3) The polyurethane resin composition according to (1) or (2), wherein the curing agent is at least one selected from the group consisting of trimers and adducts of hexamethylene diisocyanate or isophorone diisocyanate. (4) The polyurethane resin composition according to any one of (1) to (3), wherein the antibacterial agent (B) is a quaternary ammonium salt represented by formula (2).

[0009] [ka]

[0010] (In formula (2), m represents an integer of 6 to 11, n represents an integer of 10 to 14, and m+n=16 to 21 is satisfied; X - represents a halide ion.)

[0011] (5): The polyurethane resin composition according to any one of (1) to (3), wherein the antibacterial agent (B) is a quaternary ammonium salt represented by formula (3).

[0012] [ka]

[0013] (In formula (3), n represents an integer of 12 to 14, and X - represents a halide ion.)

[0014] (6): The polyurethane resin composition according to (5), wherein the antibacterial agent (B) is a quaternary ammonium salt represented by formula (3), and n is 12. (7): The polyol (A) contains a polyol (A-1) and a multifunctional polyol (A-2), the polyol (A-1) is at least one selected from the group consisting of polyester diols, polyether diols, polycarbonate diols, and polyolefin diols; The polyurethane resin composition according to any one of (1) to (6), wherein the multifunctional polyol (A-2) is one or more selected from the group consisting of polyester polyols (A-2-1), polyether polyols (A-2-2), polyolefin polyols (A-2-3), and polycarbonate polyols (A-2-4), each having three or more hydroxy groups in one molecule. (8): The polyurethane resin composition according to (7), wherein the multifunctional polyol (A-2) contains the polycarbonate polyol (A-2-4). (9): The polyol (A) contains a polyol (A-1) and a polyhydric alcohol (A-3), the polyol (A-1) is at least one selected from the group consisting of polyester diols, polyether diols, polycarbonate diols, and polyolefin diols; The polyurethane resin composition according to any one of (1) to (6), wherein the polyhydric alcohol (A-3) has three or more hydroxy groups in one molecule and a molecular weight of 300 or less. (10): The polyol (A) is a polyfunctional polyol (A-2) and a diol (A-4), or A composition comprising a polyol (A-1), a multifunctional polyol (A-2), and a diol (A-4), the polyol (A-1) is at least one selected from the group consisting of polyester diols, polyether diols, polycarbonate diols, and polyolefin diols; the multifunctional polyol (A-2) is one or more selected from the group consisting of polyester polyols (A-2-1), polyether polyols (A-2-2), polyolefin polyols (A-2-3), and polycarbonate polyols (A-2-4), each having three or more hydroxy groups in one molecule; The polyurethane resin composition according to any one of (1) to (6), wherein the diol (A-4) is a diol other than polyester diol, polyether diol, polycarbonate diol, and polyolefin diol. (11): The polyol (A) comprises a polyol (A-1), a polyhydric alcohol (A-3), and a diol (A-4), the polyol (A-1) is at least one selected from the group consisting of polyester diols, polyether diols, polycarbonate diols, and polyolefin diols; the polyhydric alcohol (A-3) has three or more hydroxy groups in one molecule and a molecular weight of 300 or less; The polyurethane resin composition according to any one of (1) to (6), wherein the diol (A-4) is a diol other than polyester diol, polyether diol, polycarbonate diol, and polyolefin diol. (12): The polyurethane resin composition according to any one of (1) to (11), wherein the organic acid (C) is a dimethylol fatty acid. (13): The polyurethane resin composition according to any one of (1) to (12), wherein the chain extender (F) comprises an amine compound having one or more primary or secondary amino groups. (14): The polyurethane resin composition according to any one of (1) to (13), wherein the neutralizing agent (G) is a basic neutralizing agent. (15): The 100% modulus of the cured product of the polyurethane resin composition measured by the following method is 10 MPa or less; The polyurethane resin composition according to any one of (1) to (14), which has a softening temperature of 100° C. or higher. [100% modulus measurement method] A No. 4 dumbbell-shaped test piece, 50 μm thick, is stretched at a tension speed of 200 mm / min using a tensile tester in an environment of 25°C and 50% RH, and the stress at 100% elongation is defined as the 100% modulus. (16): An artificial leather or synthetic leather comprising a cured product of the polyurethane resin composition according to any one of (1) to (15). (17): A surface treatment agent for leather, comprising the polyurethane resin composition according to any one of (1) to (15). [Effects of the Invention]

[0015] According to one aspect of the present disclosure, there is provided a polyurethane resin composition that can achieve both excellent water resistance and heat resistance. According to another aspect of the present disclosure, there is provided an artificial leather or synthetic leather containing a cured product of the polyurethane resin composition, and a leather surface treatment agent. DETAILED DESCRIPTION OF THE INVENTION

[0016] 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.

[0017] In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the Examples. Furthermore, the upper and lower limits described individually can be combined arbitrarily. In this specification, "cured product" includes (1) the form of a cured film, and (2) both a product cured by crosslinking or the like and a product cured by volatilization of the solvent and solidification.

[0018] [Polyurethane resin composition] The polyurethane resin composition according to one embodiment of the present disclosure comprises: A polyurethane resin and a curing agent are included, The polyurethane resin is a reaction product of an isocyanate-terminated urethane prepolymer (E) comprising a reaction product of a polyol (A), an antimicrobial agent (B) which is a quaternary ammonium salt represented by formula (1), an organic acid (C), and a polyisocyanate (D), and a chain extender (F) which may contain the antimicrobial agent (B) which is a quaternary ammonium salt represented by formula (1); or a reaction product of an isocyanate-terminated urethane prepolymer (E) comprising a reaction product of a polyol (A), an organic acid (C), and a polyisocyanate (D), and a chain extender (F) which contains the antimicrobial agent (B) which is a quaternary ammonium salt represented by formula (1); a neutralizing agent (G), the content of the antibacterial agent (B) is 0.2 mass% or more and 7.5 mass% or less relative to the total mass of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (F) in the polyurethane resin composition; the curing agent is a polyisocyanate compound, A polyurethane resin composition, wherein the content of the curing agent is 0.1 parts by mass or more and 100 parts by mass or less relative to 100 parts by mass of the polyurethane resin. (R 1 ) a (R 2 ) b (R 3 ) c N + X - (1) (In formula (1), R 1 is an aliphatic hydrocarbon group in which at least one hydrogen atom is substituted with a hydroxy group, R 1 The number of carbon atoms in If only one hydrogen atom is substituted with a hydroxy group, the number is 4 to 11. When two or more hydrogen atoms are replaced by hydroxy groups, the number is 3 to 11. R 2 is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, R 3 is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, X - is the conjugate base of the acid, a represents 1 or 2, b represents 1, c represents 1 or 2, and a+b+c=4 is satisfied; and R 1 , R 2 and R 3 The total number of carbon atoms in the aliphatic hydrocarbon group represented by the formula (I) is 15 or more and 23 or less, When a or c is 2, multiple R 1 or R 3 may be the same or different.)

[0019] Components that may be contained in the polyurethane resin composition will be described below.

[0020] <Isocyanate group-terminated urethane prepolymer (E)> A first embodiment of the isocyanate group-terminated urethane prepolymer (E) is a case in which the chain extender (F) does not contain the antibacterial agent (B), but contains a reaction product of a polyol (A), an antibacterial agent (B), an organic acid (C), and a polyisocyanate (D). A second embodiment of the isocyanate group-terminated urethane prepolymer (E) is a case in which the chain extender (F) contains an antibacterial agent (B), and may contain either [1] a reaction product of a polyol (A), an antibacterial agent (B), an organic acid (C), and a polyisocyanate (D), or [2] a reaction product of a polyol (A), an organic acid (C), and a polyisocyanate (D).

[0021] <Polyol (A)> In any embodiment of the isocyanate group-terminated urethane prepolymer (E), the polyol (A) may optionally contain one or more of polyol (A-1), multifunctional polyol (A-2), polyhydric alcohol (A-3), and diol (A-4). Such polyol (A) may include one containing either one of the multifunctional polyol (A-2) and the polyhydric alcohol (A-3), one containing both, one further containing polyol (A-1), or one further containing diol (A-4). More specifically, those containing a polyol (A-1) and a multifunctional polyol (A-2); those containing a polyol (A-1) and a polyhydric alcohol (A-3); those containing a multifunctional polyol (A-2) and a diol (A-4); a composition comprising a polyol (A-1), a multifunctional polyol (A-2), and a diol (A-4); those containing a polyol (A-1), a polyhydric alcohol (A-3), and a diol (A-4); Examples include:

[0022] (Polyol (A-1)) The polyol (A) may contain, for example, polyol (A-1) which is at least one selected from the group consisting of polyester diols, polyether diols, polycarbonate diols, and polyolefin diols.

[0023] The polyester diol is preferably a polyester diol obtained from a diol and a dicarboxylic acid and / or anhydride thereof, or a polyester diol obtained by ring-opening addition polymerization of a cyclic ester compound such as a lactone using a diol as an initiator.

[0024] Examples of diols include low molecular weight polyols 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, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, diol dimer acid, ethylene oxide or propylene oxide adducts of bisphenol A, bis(β-hydroxyethyl)benzene, and xylylene glycol, as well as combinations of any two or more of these.

[0025] Examples of dicarboxylic acids and / or anhydrides thereof include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, hydrogenated dimer fatty acid, tartaric acid, and the like, and anhydrides thereof, as well as combinations of any two or more thereof.

[0026] Examples of cyclic ester compounds include β-propiolactone, β-butyrolactone, γ-butyrolactone, β-valerolactone, γ-valerolactone, δ-valerolactone, α-caprolactone, β-caprolactone, γ-caprolactone, δ-caprolactone, ε-caprolactone, α-methyl-ε-caprolactone, β-methyl-ε-caprolactone, 4-methylcaprolactone, γ-caprylolactone, ε-caprylolactone, ε-palmitolactone, and the like, as well as combinations of any two or more of these. Among these, ring-opening addition polymers of ε-caprolactone using ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, or the like as an initiator are preferred from the standpoints of stability during polymerization and economy.

[0027] Examples of polyether diols include polyethylene glycol, polypropylene ether diol, polytetramethylene ether diol, and the like, as well as combinations of any two or more of these.

[0028] The polycarbonate diol may contain an ester bond. Examples thereof include the following polycarbonate diols (α), (β), and (γ), and combinations of any two or more of these. (α) Polycarbonate diol obtained from diol (a-1) and carbonate ester (a-2) (hereinafter also referred to as "polycarbonate diol (α)") (β) A polycarbonate diol obtained from a diol (a-1), a carbonate ester (a-2), and a cyclic ester compound (a-3) such as a lactone (hereinafter also referred to as "polycarbonate diol (β)"). (γ) Polycarbonate diol obtained from polycarbonate diol (a-4) and polyester diol (a-5) (hereinafter also referred to as "polycarbonate diol (γ)")

[0029] Examples of the diol (a-1) include the same diols as those mentioned in the description of the polyester diol, 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.

[0030] Examples of the carbonate ester (a-2) include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; alkylene carbonates such as ethylene carbonate and propylene carbonate; diaryl carbonates such as diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, diphenanthryl carbonate, diindanyl carbonate and tetrahydronaphthyl carbonate; and combinations of any two or more of these.

[0031] Examples of the cyclic ester compound (a-3) include the same cyclic ester compounds as those mentioned in the description of the polyester diol.

[0032] Examples of the polycarbonate diol (a-4) include the same ones as those mentioned in the description of the polycarbonate diol (α).

[0033] Examples of the polyester diol (a-5) include the same as those mentioned in the description of the polyester diol.

[0034] Examples of polyolefin diols include hydroxyl-terminated polybutadiene and hydrogenated products thereof, hydroxyl-containing chlorinated polyolefins, and combinations of any two or more of these.

[0035] In consideration of various durability and adhesion of the coating film obtained from the polyurethane resin composition, the polyol (A-1) preferably contains a polycarbonate diol.

[0036] The number average molecular weight of the polyol (A-1) is preferably 300 to 10,000, and may be 500 to 7,000, 800 to 5,000, or 1,000 to 3,000. Details of the method for measuring the number average molecular weight may be as described in the examples below.

[0037] The average hydroxyl value of the polyol (A-1) is preferably 30 to 500 mgKOH / g, more preferably 40 to 400 mgKOH / g, and even more preferably 50 to 300 mgKOH / g. When the average hydroxyl value is 30 mgKOH / g or more, the urethane group concentration in the polyurethane resin does not become too low, and the strength at break in a tensile test is further improved. When the average hydroxyl value is 500 mgKOH / g or less, the urethane group concentration does not become too high, and the elongation at break in a tensile test is further improved.

[0038] (Multifunctional polyol (A-2)) The polyol (A) may contain one or more multifunctional polyols (A-2) having three or more hydroxy groups in one molecule, selected from the group consisting of polyester polyols (A-2-1), polyether polyols (A-2-2), polyolefin polyols (A-2-3), and polycarbonate polyols (A-2-4). The polycarbonate polyols (A-2-4) having three or more hydroxy groups in one molecule may have an ester bond.

[0039] As the polyester polyol (A-2-1) having three or more hydroxy groups in one molecule, polyester polyols obtained from a trifunctional or higher polyhydric alcohol, a diol, and a dicarboxylic acid and / or anhydride, or polyester polyols obtained by ring-opening addition polymerization of a cyclic ester compound such as a lactone using a polyhydric alcohol and, if necessary, a diol as an initiator, are preferred.

[0040] Examples of trifunctional or higher polyhydric alcohols include trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, dipentaerythritol, sorbitol, and combinations of any two or more of these. Among these, trimethylolpropane, trimethylolethane, and pentaerythritol are preferred.

[0041] Examples of the diol, dicarboxylic acid and / or anhydride thereof, and cyclic ester compound include the same diol, dicarboxylic acid and / or anhydride thereof, and cyclic ester compound as those mentioned in the description of the polyester diol.

[0042] Examples of the polyether polyol (A-2-2) having three or more hydroxy groups in one molecule include polyethylene glycol, polypropylene ether polyol, polytetramethylene ether polyol, etc., each having three or more hydroxy groups in one molecule, and any combination of two or more of these.

[0043] Examples of the polyolefin polyol (A-2-3) having three or more hydroxy groups in one molecule include hydroxy-terminated polybutadienes and hydrogenated products thereof, hydroxy-containing chlorinated polyolefins, and combinations of any two or more of these, all of which have three or more hydroxy groups in one molecule.

[0044] Among the polycarbonate polyols (A-2-4) having three or more hydroxy groups in one molecule, examples of polyfunctional polycarbonate polyols having no ester bond include the following polycarbonate polyols (α') and (β'), and any combination of two or more of these. (α') A polycarbonate polyol (hereinafter also referred to as "polycarbonate polyol (α')") which is a transesterification reaction product of a diol (a-6), a polyhydric alcohol (a-7) having three or more functional groups, and a carbonate ester (a-8). (β') A polycarbonate polyol (hereinafter also referred to as "polycarbonate polyol (β')") which contains a polyhydric alcohol (a-7) having three or more functional groups and an optional diol (a-6), and is a transesterification product with a polycarbonate polyol (a-9).

[0045] Examples of the diol (a-6) include the same diols as those mentioned in the description of the polyester diol, 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.

[0046] Examples of the polyhydric alcohol (a-7) include the same tri- or higher functional polyhydric alcohols as those described in the description of the polyester polyol (A-2-1). Among these, trimethylolpropane, trimethylolethane, and pentaerythritol are preferred.

[0047] Examples of the carbonate ester (a-8) include the same carbonate ester (a-2) as those mentioned in the description of the polycarbonate diols (α) and (β).

[0048] The polycarbonate polyol (a-9) is a polycarbonate polyol having two or more hydroxy groups in one molecule, and may be a polycarbonate polyol (a-9-1) having two hydroxy groups in one molecule (i.e., a polycarbonate diol), or a polycarbonate polyol (a-9-2) having three or more hydroxy groups in one molecule, or a combination of two or more selected from the polycarbonate polyols (a-9-1) and polycarbonate polyols (a-9-2).

[0049] Examples of the polycarbonate polyol (a-9-1) include the same ones as those mentioned in the description of the polycarbonate diol (α).

[0050] Examples of the polycarbonate polyol (a-9-2) include the same ones as those mentioned in the description of the polycarbonate polyol (α').

[0051] Among the polycarbonate polyols (A-2-4) having three or more hydroxy groups in one molecule, examples of polyfunctional polycarbonate polyols having an ester bond include the following copolymer polyols (α") and (β"), and any combination of two or more of these. (α") A copolymer polyol (hereinafter also referred to as "polycarbonate polyol (α")"), which is an ester exchange reaction product between a polycarbonate polyol (a-10) and a polyester polyol (a-11) having three or more hydroxy groups in one molecule. (β") A copolymer polyol (hereinafter also referred to as "polycarbonate polyol (β")") which is a transesterification reaction product of a polycarbonate polyol (a-10), a polyester polyol (a-11) having three or more hydroxy groups in one molecule, and a polyester polyol (a-12) having two or more but less than three hydroxy groups in one molecule. Copolymer polyols combine high strength and high elongation mechanical properties, and also improve solubility in solvents and ease of handling due to their liquid state at room temperature.

[0052] Examples of the polycarbonate polyol (a-10) include the same ones as those mentioned in the description of the polycarbonate polyol (a-9).

[0053] Examples of the polyester polyol (a-11) include the following polyester polyols (δ) to (ε) and any combination of two or more of these. (δ) A polyester polyol obtained from a diol (a-11-1), a dicarboxylic acid and / or its anhydride (a-11-2), and a polyhydric alcohol (a-11-3) having three or more functional groups (hereinafter also referred to as "polyester polyol (δ)"). (ε) A polyester polyol (hereinafter also referred to as "polyester polyol (ε)") obtained by ring-opening addition polymerization of a cyclic ester compound (a-11-4) such as a lactone using a polyhydric alcohol (a-11-3) having three or more functional groups and a difunctional alcohol (a-11-5), which is used as needed, as an initiator.

[0054] Examples of the diol (a-11-1), dicarboxylic acid and / or its anhydride (a-11-2), and cyclic ester compound (a-11-4) include the same diols, dicarboxylic acid and / or its anhydride, and cyclic ester compounds as those listed in the description of the polyester diol.

[0055] Examples of the polyhydric alcohol (a-11-3) include the same trifunctional or higher polyhydric alcohols as those mentioned in the description of the polyester polyol (A-2-1). As long as the desired effect is achieved, a bifunctional alcohol (a-11-5) such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexamethylene glycol, dipropylene glycol, or trimethylene glycol may be used as an initiator in combination with the polyhydric alcohol (a-11-3). In other words, the polyester polyol (a-11) may be a polyester polyol having a moiety derived from the polyhydric alcohol (a-11-3) and a moiety derived from the cyclic ester compound (a-11-4), or may further include a polyester polyol having a moiety derived from the bifunctional alcohol (a-11-5) and a moiety derived from the cyclic ester compound (a-11-4).

[0056] In consideration of various durability and adhesion of the coating film obtained from the polyurethane resin composition, the multifunctional polyol (A-2) preferably contains a polycarbonate polyol (A-2-4).

[0057] The lower limit of the average functionality of the multifunctional polyol (A-2) may be, for example, 1.80 or more, 1.90 or more, 2.00 or more, 2.10 or more, 2.20 or more, 2.30 or more, 2.40 or more, or 2.50 or more. The upper limit of the average functionality of the multifunctional polyol (A-2) 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 average functionality is 2.00 to 3.90, and may be, for example, 2.10 to 3.80, 2.20 to 3.70, 2.30 to 3.50, or 2.50 to 3.40. When the average functionality is 3.90 or less, the elongation at break in a tensile test is further improved, and when the average functionality is 1.80 or more, the strength at break and softening temperature in a tensile test tend to be further improved.

[0058] The average number of functional groups is defined by the following formula. Average functionality = (average hydroxyl value (mg KOH / g) of multifunctional polyol (A-2) × number average molecular weight (g / mol) calculated from the PPG calibration curve obtained by GPC measurement of multifunctional polyol (A-2)) / (56.11 (g KOH / mol) × 1,000)

[0059] The average hydroxyl value of the multifunctional polyol (A-2) is preferably 30 to 500 mgKOH / g, more preferably 40 to 400 mgKOH / g, and even more preferably 50 to 300 mgKOH / g. When the average hydroxyl value is 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.

[0060] The average hydroxyl value is a hydroxyl value measured by a method using an acetylating reagent in accordance with JIS K1557-1. Details of the measurement method are as described in the examples below.

[0061] The number average molecular weight of the polyfunctional polyol (A-2) is preferably 400 to 4,000 g / mol, more preferably 500 to 3,000 g / mol. When the number average molecular weight is 400 g / mol 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 4,000 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.

[0062] (Polyhydric alcohol (A-3)) The polyhydric alcohol (A-3) is an alcohol having three or more hydroxy groups in one molecule and a molecular weight of 300 or less. Examples of the polyhydric alcohol include the same tri- or higher functional polyhydric alcohols as those described in the description of the polyester polyol (A-2-1). Examples of the polyhydric alcohol include trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, dipentaerythritol, sorbitol, etc., and combinations of any two or more of these. Among these, trimethylolpropane, trimethylolethane, and pentaerythritol are preferred.

[0063] (Diol (A-4)) The polyol (A) may contain a diol (A-4) other than the polyol (A-1), the polyfunctional polyol (A-2), and the polyhydric alcohol (A-3). That is, the diol (A-4) is a polyester diol, a polyether diol, a polycarbonate diol, or a polyolefin diol, or a diol having three or more hydroxy groups per molecule other than the polyester polyol (A-2-1), the polyether polyol (A-2-2), the polyolefin polyol (A-2-3), the polycarbonate polyol (A-2-4), and the polyhydric alcohol (A-3). Examples of the diol (A-4) include the same diols as those listed in the description of the polyester diol. The diol (A-4) preferably includes 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.

[0064] (Content of multifunctional polyol (A-2)) The content of the polyfunctional polyol (A-2) relative to the total mass of the polyol (A) and the antibacterial agent (B) in the polyurethane resin composition may be 5.0 mass% or more, 7.0 mass% or more, 10.0 mass% or more, 20.0 mass% or more, or 30.0 mass% or more, and may be 100 mass% or less, 90 mass% or less, 80 mass% or less, 70 mass% or less, or 60 mass% or less, since this enables the formation of a cured product with a higher softening temperature. The content of the polyfunctional polyol (A-2) relative to the total mass of the polyol (A) and the antibacterial agent (B) in the polyurethane resin composition 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%. When the content of the polyfunctional polyol (A-2) is within the above range, when used as a polyurethane film, a polyurethane film with even better 100% modulus and heat resistance is likely to be obtained. Furthermore, when the content of the polyfunctional polyol (A-2) is 100% by mass or less, a polyurethane dispersion with even better handleability is likely to be obtained. Furthermore, when the content of the polyfunctional polyol (A-2) is 100% by mass or less, a polyurethane film with even better 100% modulus is likely to be obtained.

[0065] (Polyhydric alcohol (A-3) content) The content of the polyhydric alcohol (A-3) may be 0.1 mass% or more, 0.2 mass% or more, 0.3 mass% or more, 0.4 mass% or more, or 0.5 mass% or more, and may be 10 mass% or less, 9 mass% or less, 8 mass% or less, 7 mass% or less, 6 mass% or less, 5 mass% or less, or 4 mass% or less, based on the total mass of the polyol (A) and the antibacterial agent (B) in the polyurethane resin composition. When the content of the polyhydric alcohol (A-3) is 0.1 mass% or more, a polyurethane film with excellent heat resistance is easily obtained. Furthermore, when the content of the polyhydric alcohol (A-3) is 10 mass% or less, a polyurethane dispersion with good handleability is easily obtained.

[0066] (Diol (A-4) content) The content of diol (A-4) in polyol (A) is preferably 0 to 95 mol%, more preferably 1 to 50 mol%, even more preferably 2 to 20 mol%, and even more preferably 3 to 10 mol%. By adjusting the content within this range, a polyurethane resin composition having a lower 100% modulus and a higher softening temperature can be obtained.

[0067] The diol (A-4) is preferably used in combination with other polyols such as the polyol (A-1), the polyfunctional polyol (A-2), and the polyhydric alcohol (A-3).

[0068] <Antibacterial agent (B) which is a quaternary ammonium salt represented by formula (1)> The antibacterial agent (B) may be, for example, a quaternary ammonium salt that imparts antibacterial activity to the isocyanate-terminated urethane prepolymer (E) obtained by reaction with the polyisocyanate (D), thereby imparting antibacterial activity to the polyurethane resin composition obtained as a result. The antibacterial agent (B) may be, for example, a quaternary ammonium salt that imparts antibacterial activity to the polyurethane resin obtained by reaction with the isocyanate-terminated urethane prepolymer (E), thereby imparting antibacterial activity to the polyurethane resin composition obtained as a result. The present inventors speculate that the whitening of the resin occurs due to the water absorption of the antibacterial agent (B), which is a quaternary ammonium salt.

[0069] The antibacterial agent (B) is represented by the formula (1): (R 1 ) a (R 2 ) b (R 3 ) c N + X - (1) (In formula (1), R 1 is an aliphatic hydrocarbon group in which at least one hydrogen atom is substituted with a hydroxy group, R 1 The number of carbon atoms in If only one hydrogen atom is substituted with a hydroxy group, the number is 4 to 11. When two or more hydrogen atoms are replaced by hydroxy groups, the number is 3 to 11. R 2 is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, R 3 is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, X - is the conjugate base of the acid, a represents 1 or 2, b represents 1, c represents 1 or 2, and a+b+c=4 is satisfied; and R 1 , R 2 and R 3 The total number of carbon atoms in the aliphatic hydrocarbon group represented by the formula (I) is 15 or more and 23 or less, When a or c is 2, multiple R 1 or R 3 may be the same or different.) It is a quaternary ammonium salt represented by the formula:

[0070] In formula (1), R 3 R is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and may be linear or branched, saturated or unsaturated, but is preferably an alkyl group, and particularly preferably a linear alkyl group. Without such an aliphatic hydrocarbon group having 1 to 3 carbon atoms, the quaternary ammonium cation becomes less accessible to bacteria, resulting in a decrease in antibacterial activity and alcohol-cleaning resistance. 3 Examples of R include a methyl group, an ethyl group, and a propyl group, and among these, a methyl group is preferred from the viewpoint that antibacterial activity and resistance to alcohol washing tend to be further improved. 3 The number (c) of R is 1 or 2, and from the viewpoint that the antibacterial activity and the alcohol-cleaning resistance tend to be further improved, c is preferably 2. 3 When a plurality of groups are present in one molecule, they may be the same or different.

[0071] In formula (1), R 2R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, and may be linear or branched, saturated or unsaturated, but is preferably an alkyl group, and is particularly preferably a linear alkyl group, as this enhances antibacterial activity. 2 The number of carbon atoms in R is 10 to 18, specifically 10, 11, 12, 13, 14, 15, 16, 17, or 18, and may be within a range with any two of the numerical values ​​exemplified here as upper and lower limits. 2 The inventors speculate that R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, which provides sufficient hydrophobicity and exhibits antibacterial properties based on its action on cell membranes, resulting in excellent antibacterial activity. 2 Examples of R include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group. 2 The number (b) is 1.

[0072] In formula (1), R 1 is an aliphatic hydrocarbon group in which at least one hydrogen atom is substituted with a hydroxy group, and such aliphatic hydrocarbon group may be linear or branched, saturated or unsaturated, but is preferably an alkyl group, and particularly preferably a linear alkyl group, because it enhances antibacterial activity. By introducing a hydroxy group into at least one aliphatic hydrocarbon group in this way, when an antibacterial agent is added to a production process for a resin such as urethane, the hydroxy group reacts with a functional group in the resin raw material and is fixed to the resin by a bond such as a covalent bond (preferably a covalent bond), thereby improving the alcohol cleaning resistance of the antibacterial activity.

[0073] And, R in Equation (1) 1 However, when R has one substituted hydroxy group, it must be an aliphatic hydrocarbon group having 4 to 11 carbon atoms. The hydrocarbon chain, which is a linker between the cationic moiety and the hydroxy group, affects the antibacterial activity, and when there is one substituted hydroxy group, if the aliphatic hydrocarbon group has less than 4 carbon atoms or more than 11 carbon atoms, the antibacterial activity decreases. 1has one substituted hydroxy group, R 1 The number of carbon atoms in R is 4 to 11, and may be 5 to 11, or 6 to 10, specifically 4, 5, 6, 7, 8, 9, 10, or 11, and may be within a range with any two of the numerical values ​​exemplified here as upper and lower limits. 1 The hydroxyl group is preferably a hydroxyalkyl group having 4 to 11 carbon atoms, and examples include a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, a hydroxyoctyl group, a hydroxynonyl group, a hydroxydecyl group, a hydroxyundecyl group, etc. The position at which the hydroxyl group is bonded to the aliphatic hydrocarbon group is not particularly limited, but it is preferable that the hydroxyl group be bonded to a terminal carbon atom, from the viewpoint that when added to a resin, it becomes more likely to react with the functional groups of the resin, and the alcohol cleaning resistance of the antibacterial activity tends to be further improved.

[0074] Furthermore, R in formula (1) 1 However, when there are two or more substituted hydroxy groups, the aliphatic hydrocarbon group must have 3 to 11 carbon atoms. The hydrocarbon chain, which is the linker between the cationic moiety and the hydroxy group, affects the antibacterial activity, and when there are two or more substituted hydroxy groups, if the aliphatic hydrocarbon group has less than 3 carbon atoms or more than 11 carbon atoms, the antibacterial activity decreases. R in formula (1) 1 has two or more substituted hydroxy groups, R 1 The number of carbon atoms in R is 3 to 11, specifically 3, 4, 5, 6, 7, 8, 9, 10, or 11, and may be within a range with any two of the numerical values ​​exemplified here as upper and lower limits. 1Examples of R include dihydroxypropyl, dihydroxybutyl, dihydroxypentyl, dihydroxyhexyl, dihydroxyheptyl, dihydroxyoctyl, dihydroxynonyl, dihydroxydecyl, dihydroxyundecyl, trihydroxypropyl, trihydroxybutyl, trihydroxypentyl, trihydroxyhexyl, trihydroxyheptyl, trihydroxyoctyl, trihydroxynonyl, trihydroxydecyl, and trihydroxyundecyl groups. From the viewpoint of suppressing the formation of unnecessary crosslinks when added to a resin production process and further improving the mechanical properties of the resin, the number of substituted hydroxy groups is preferably three or less, and more preferably two. Such R 1 As the hydroxyl group, a dihydroxyalkyl group having 3 to 11 carbon atoms is preferred. The position at which the hydroxyl group is bonded to the aliphatic hydrocarbon group is not particularly limited, but from the viewpoint that when added to a resin, it becomes more likely to react with the functional group of the resin and the alcohol cleaning resistance of the antibacterial activity tends to be further improved, when there are two or more substituted hydroxyl groups, it is preferred that the hydroxyl group be bonded to each of the terminal carbon atom and the second carbon atom from the terminal.

[0075] Also, R 1 The number (a) of R is 1 or 2, and a+b+c=4 must be satisfied. From the viewpoint that antibacterial activity tends to be further improved, a is preferably 1. In addition, R 1 When a plurality of groups are present in one molecule, they may be the same or different.

[0076] Furthermore, R in one molecule of the quaternary ammonium salt represented by formula (1) 1 , R 2 and R 3 The total number of carbon atoms in the aliphatic hydrocarbon group (R 1 ~R 3The total number of carbon atoms in R 1 also affects the antibacterial activity. If the total number of carbon atoms is less than 15, the antibacterial activity decreases, whereas if the total number of carbon atoms exceeds 23, the antibacterial activity decreases. 1 , R 2 and R 3 The total number of carbon atoms in the aliphatic hydrocarbon group represented by the formula (I) is 15 or more and 23 or less, specifically 15, 16, 17, 18, 19, 20, 21, 22, or 23, and may be within a range with any two of the numerical values ​​exemplified here as the upper and lower limits.

[0077] In addition, X in formula (1) - is a conjugate base of an acid, preferably a conjugate base of a strong acid. By combining the specific quaternary ammonium cation and the conjugate base (anion) of a strong acid and using the resulting salt, the salt functions as an antibacterial agent with excellent antibacterial activity, and when added to a resin to form an antibacterial resin composition, the antibacterial activity tends to be improved. On the other hand, the conjugate base of a weak acid such as a carboxylate ion tends not to sufficiently improve the antibacterial activity. Examples of conjugate bases of strong acids include halide ions such as bromine (Br), chlorine (Cl), fluorine (F), and iodine (I), as well as nitrate ions, sulfate ions, phosphate ions, and perchlorate ions. Among these, halide ions are preferred, with bromide ions and chloride ions being particularly preferred, as they tend to further improve antibacterial activity.

[0078] Next, a quaternary ammonium salt, which is one embodiment of the antibacterial agent (B), which is a quaternary ammonium salt represented by formula (1), will be described. The first quaternary ammonium salt, which is one embodiment of the antibacterial agent (B), is represented by formula (2):

[0079] [ka]

[0080] (In formula (2), m represents an integer of 6 to 11, n represents an integer of 10 to 14, and m+n=16 to 21 is satisfied; X - represents a halide ion.) It is a quaternary ammonium salt represented by the formula:

[0081] Among the quaternary ammonium salts represented by formula (2), those in which m is 6 and n is an integer from 12 to 14 are preferred, and such quaternary ammonium salts are represented by formula (3):

[0082] [ka]

[0083] (In formula (3), n represents an integer of 12 to 14, and X - represents a halide ion.) Among the quaternary ammonium salts represented by formula (3), those in which n is 12 are more preferred.

[0084] Furthermore, a second quaternary ammonium salt, which is one embodiment of the quaternary ammonium salt represented by formula (1), is represented by formula (4):

[0085] [ka]

[0086] (In formula (4), n represents an integer from 12 to 16, and X - represents a halide ion.) It is expressed as:

[0087] The content of the antibacterial agent (B) may be 0.2% by mass or more, 0.3% by mass or more, 0.4% by mass or more, 0.6% by mass or more, 0.8% by mass or more, or 1.5% by mass or more, based on the sum of the mass of the isocyanate group-terminated urethane prepolymer (E) and the mass of the chain extender (F) in the polyurethane resin composition, and may be 7.5% by mass or less, 7.0% by mass or less, 6.5% by mass or less, 6.0% by mass or less, 5.0% by mass or less, or 4.0% by mass or more. When the content of the antibacterial agent (B) is within the above range, a polyurethane resin that exhibits both excellent antibacterial activity and film-forming properties tends to be easily obtained. Furthermore, when the content of the antibacterial agent (B) is 7.5% by mass or less, a polyurethane resin that exhibits even better film-forming properties tends to be easily obtained. Furthermore, when the content of the antibacterial agent (B) is 0.2% by mass or more, a polyurethane resin that exhibits even better antibacterial activity tends to be easily obtained.

[0088] <Organic acid (C)> The organic acid (C) may be, for example, a hydrophilic group-containing monomer that can impart hydrophilicity to the isocyanate group-terminated urethane prepolymer (E) obtained by reaction with the polyisocyanate (D), thereby making the final resin composition aqueous.

[0089] Examples of the organic acid (C) include those having one or more active hydrogen groups. Examples of the organic acid include carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acid, phosphinic acid, thiosulfonic acid, etc., and combinations of any two or more of these. These organic acids (C) may be introduced independently or may be associated with each other, such as in a chelate. Among them, dimethylol fatty acid having a carboxy group (-COOH) is more preferred.

[0090] The dimethylol fatty acid may be, for example, a compound represented by the following formula (c):

[0091] [ka]

[0092] In formula (c), R c represents an aliphatic hydrocarbon group.c The number of carbon atoms in the aliphatic hydrocarbon group represented by R may be, for example, 1 or more, or 10 or less, 6 or less, or 3 or less. c The aliphatic hydrocarbon group represented by R may be linear or branched. c The aliphatic hydrocarbon group represented may be, for example, -CH3, -CH2CH3, -CH2CH2CH3, or CH2CH2CH2CH2CH2CH2CH2CH3.

[0093] Examples of dimethylol fatty acids include dimethylolalkanoic acids such as dimethylolpropionic acid (such as 2,2-dimethylolpropanoic acid), dimethylolbutanoic acid, dimethylolpentanoic acid, and dimethylolnonanoic acid, and combinations of any two or more of these.

[0094] 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 (F) in the polyurethane resin composition.

[0095] <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.

[0096] The polyisocyanate (D) is not particularly limited, and various conventionally known polyisocyanates can be used. 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, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylmethane diisocyanate, aromatic isocyanates such as phenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate; aralkyl diisocyanates such as xylylene-1,4-diisocyanate and xylylene-1,3-diisocyanate; allophanate-modified polyisocyanates obtained by reacting these organic polyisocyanates with alcohols; nurate-modified polyisocyanates obtained by reacting these organic polyisocyanates; and combinations of any two or more of these.

[0097] The polyisocyanate (D) is preferably an aliphatic diisocyanate or an alicyclic diisocyanate, more preferably an alicyclic diisocyanate, and even more preferably isophorone diisocyanate or hydrogenated diphenylmethane diisocyanate.

[0098] The ratio of the total number of moles of hydroxy groups in the polyol (A) to the total number of moles of isocyanate groups in the polyisocyanate (D) (hydroxy 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.

[0099] <One embodiment of isocyanate group-terminated urethane prepolymer (E)> One embodiment of the isocyanate group-terminated urethane prepolymer (E) may be, for example, a reaction product of a polyol (A), an antibacterial agent (B), an organic acid (C), and a polyisocyanate (D). In addition, when the chain extender (F) contains the antibacterial agent (B), the isocyanate group-terminated urethane prepolymer (E) may be a reaction product of a polyol (A), an organic acid (C), and a polyisocyanate (D).

[0100] <Method for producing isocyanate group-terminated urethane prepolymer (E)> The isocyanate-terminated urethane prepolymer (E) can be produced, for example, by reacting polyisocyanate (D), polyol (A), antibacterial agent (B), and organic acid (C) when the chain extender (F) does not contain antibacterial agent (B); or by reacting polyisocyanate (D), polyol (A), and organic acid (C), and optionally antibacterial agent (B), when the chain extender (F) contains antibacterial agent (B), in a diluent solvent, if necessary, under conditions such that the number of moles of isocyanate groups exceeds the number of moles of hydroxyl groups. A known urethane catalyst may be used in this process. The reaction temperature is preferably 0 to 100°C, and particularly preferably 20 to 90°C.

[0101] <Chain extender (F)> The chain extender (F) is a compound that reacts with the isocyanate-terminated urethane prepolymer (E) to form a polyurethane resin. Examples of the chain extender (F) include compounds having a functional group that can react with an isocyanate group, such as a primary amino group (-NH), a secondary amino group (-NH-), or a hydroxy group (-OH), or water (HO).

[0102] The chain extender (F) is preferably at least one selected from the group consisting of an amine compound having at least one primary amino group or secondary amino group and water.

[0103] The amine compound as the chain extender (F) 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 hydroxy groups (—OH).

[0104] 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 (f): H2N-R f -NH2(f) In formula (f), R f represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.

[0105] Examples of the amine compound include ethylenediamine, hexamethylenediamine, xylylenediamine, isophoronediamine, diethylenetriamine, N-aminoethyl-N-ethanolamine, monoethanolamine, and the like, as well as combinations of any two or more of these.

[0106] The chain extender (F) may have a hydroxy group (-OH), may contain an antibacterial agent (B), may use an antibacterial agent (B), or may use an aliphatic glycol as the chain extender (F). When the isocyanate-terminated urethane prepolymer (E) contains a reaction product of a polyol (A), an antibacterial agent (B), an organic acid (C), and a polyisocyanate (D), the chain extender (F) may or may not contain an antibacterial agent (B); however, when the isocyanate-terminated urethane prepolymer (E) contains a reaction product of a polyol (A), an organic acid (C), and a polyisocyanate (D), the chain extender (F) should contain an antibacterial agent (B).

[0107] Examples of the antibacterial agent (B) include the same as those listed in the explanation of the antibacterial agent (B).

[0108] Examples of aliphatic glycols include the same diols as those mentioned in the description of polyester diols, among which 1,4-butanediol is preferred in terms of flexibility, durability, and processability.

[0109] The content of the chain extender (F) may be 0.01 mmol / g or more, 0.05 mmol / g or more, 0.1 mmol / g or more, or 0.3 mmol / g or more, and may be 1.00 mmol / g or less, 0.80 mmol / g or less, 0.70 mmol / g or less, 0.60 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 (F) in the polyurethane resin composition.

[0110] The urea group in the polyurethane resin is generated by the amino group of the chain extender (F).

[0111] The urea group concentration, based on the sum of the mass of the isocyanate-terminated urethane prepolymer (E) and the mass of the chain extender (F) in the polyurethane resin composition, may be greater than 0 mmol / g, 0.01 mmol / g or greater, 0.05 mmol / g or greater, 0.1 mmol / g or greater, or 0.3 mmol / g or greater, and may be 1.00 mmol / g or less, 0.80 mmol / g or less, 0.70 mmol / g or less, 0.60 mmol / g or less, or 0.50 mmol / g or less. A urea group concentration of greater than 0 mmol / g tends to provide a polyurethane resin with even better 100% modulus. Additionally, a urea group concentration of 1.00 mmol / g or less tends to provide a polyurethane resin with even better heat resistance.

[0112] During the chain extension reaction, a curing catalyst (polymerization catalyst) may be used as needed. Examples of the curing catalyst include metal catalysts such as dioctyltin dilaurate, zinc naphthenate, and bismuth compounds, and conventional curing catalysts such as amine catalysts such as triethylenediamine and N-methylmorpholine. The use of a curing catalyst can further increase the reaction rate and lower the reaction temperature.

[0113] The equivalent ratio (active hydrogen groups / isocyanate groups) of the active hydrogen groups (amino groups and hydroxy groups) in the chain extender (F) to the isocyanate groups in the isocyanate-terminated urethane prepolymer (E) is, for example, preferably 0 to 1.3, more preferably 0.05 to 1.0, and even more preferably 0.10 to 0.9. When this ratio is within the above range, a polyurethane resin with excellent mechanical properties and film-forming properties is likely to be formed.

[0114] <Neutralizer (G)> The neutralizing agent (G) is preferably a basic neutralizing agent. Examples of the neutralizing agent (G) include organic amines such as ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-ethyl-1-propanol, and higher alkyl-modified morpholine; alkali metals such as lithium, potassium, and sodium; inorganic alkalis such as sodium hydroxide and potassium hydroxide; and combinations of any two or more of these. Furthermore, from the viewpoint of improving the durability and smoothness of the coating film, highly volatile neutralizing agents that dissociate upon heating, such as ammonia, trimethylamine, and triethylamine, are preferred.

[0115] The neutralizing agent (G) may be a trialkylamine, and preferred examples of the trialkylamine include trimethylamine, triethylamine, triisopropylamine, and tributylamine.

[0116] In order to further improve the aqueous dispersion stability of the polyurethane resin composition, the neutralizing agent (G) may further contain an anionic polar group compound and a cationic polar group-containing compound.

[0117] Examples of anionic polar group-containing compounds include organic acid salts composed of an organic acid having one or more active hydrogen groups and a neutralizing agent. Examples of organic acid salts include carboxylates, sulfonates, phosphates, phosphonates, phosphinates, thiosulfonates, etc., and combinations of any two or more of these. These organic acid salts may be introduced independently or may be associated with each other, such as in a chelate.

[0118] Examples of cationic polar group-containing compounds include those comprising a primary or secondary amine having one or more active hydrogen groups and one or more agents selected from neutralizing agents for inorganic and organic acids and quaternizing agents.

[0119] 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; addition products of alkylene oxide to ammonia, primary amines such as methylamine, and secondary amines such as dimethylamine; and combinations of any two or more of these.

[0120] Examples of inorganic acids and organic acids include hydrochloric acid, acetic acid, lactic acid, cyanoacetic acid, phosphoric acid, sulfuric acid, and the like, as well as combinations of any two or more of these acids.

[0121] 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.

[0122] Other examples of the cationic polar group-containing compound include cationic compounds such as primary amine salts, secondary amine salts, tertiary amine salts, and pyridinium salts.

[0123] The content of the neutralizing agent (G) 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 (F) in the polyurethane resin composition.

[0124] <Organic solvents> During synthesis of the isocyanate group-terminated urethane prepolymer (E), it may be diluted to any solid content with an organic solvent that is inactive to isocyanate groups. Examples of the organic solvent include aromatic solvents such as toluene, xylene, Swazol (an aromatic hydrocarbon solvent manufactured by Maruzen Petrochemical Co., Ltd.), and Solvesso (an aromatic hydrocarbon solvent manufactured by ExxonMobil Corporation); aliphatic hydrocarbon solvents such as hexane; alicyclic hydrocarbon solvents such as cyclohexane and isophorone; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, and isobutyl acetate; glycol ether ester solvents such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol-3-methyl-3-methoxybutyl acetate, and ethylene glycol ethyl-3-ethoxypropionate; glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dibutyl ether, propylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; ether solvents such as tetrahydrofuran and dioxane; and combinations of any two or more of these.

[0125] The organic solvent is preferably an ester-based solvent such as ethyl acetate, butyl acetate, or isobutyl acetate, which can be easily removed during desolvation and can be heated to 50 to 100°C during formation of the isocyanate group-terminated urethane prepolymer (E), and particularly preferably a ketone-based solvent such as acetone, methyl ethyl ketone, or methyl isobutyl ketone.

[0126] <Method of producing polyurethane resin composition> The polyurethane resin composition can be produced, for example, by a method including the steps of neutralizing an isocyanate group-terminated urethane prepolymer (E) with a neutralizing agent (G) to obtain a neutralized product of the isocyanate group-terminated urethane prepolymer (E), and emulsifying the neutralized product of the isocyanate group-terminated urethane prepolymer (E) with water and reacting it with a chain extender (F) to obtain a polyurethane resin composition.

[0127] Examples of methods for carrying out the chain extension reaction between the isocyanate group-terminated urethane prepolymer (E) and the chain extender (F) include a method in which the chain extender (F) is dissolved in water in advance, and then the isocyanate group-terminated urethane prepolymer (E) is added to this aqueous solution of the chain extender (F) to emulsify and carry out the chain extension reaction, and a method in which the isocyanate group-terminated urethane prepolymer (E) is emulsified in water, and then an aqueous solution of the chain extender (F) is added to carry out the chain extension reaction.

[0128] When the chain extender (F) contains the antimicrobial agent (B), the isocyanate-terminated urethane prepolymer (E) may be a reaction product of a polyol (A), an organic acid (C), and a polyisocyanate (D).

[0129] <Curing agent> The polyurethane resin composition includes a polyurethane resin and a curing agent. The curing agent is a polyisocyanate compound. The curing agent forms a cured product together with the polyurethane resin, such as a coating, a film, or a surface treatment agent for synthetic leather.

[0130] Specific examples of the curing agent include urethane-modified, urea-modified, allophanate-modified, biuret-modified, uretdione-modified, and isocyanurate-modified organic diisocyanates. Among these, trimers or adducts of hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI) are preferred.

[0131] The content of the curing agent is 0.1 parts by mass or more and 100 parts by mass or less, and may be 1 part by mass or more, 5 parts by mass or more, or 20 parts by mass or more, and may be 80 parts by mass or less, 60 parts by mass or less, or 40 parts by mass or less, relative to 100 parts by mass of the polyurethane resin. When the content is 0.1 parts by mass or more, a cured polyurethane resin product having excellent water resistance and heat resistance is likely to be obtained. When the content is 100 parts by mass or less, a cured polyurethane resin product having excellent elongation at break in a tensile test is likely to be obtained.

[0132] <Other ingredients> To further improve the physical properties or to impart various other properties, the polyurethane resin composition may contain various additives, such as film-forming agents, viscosity modifiers, antigelling agents, flame retardants, plasticizers, antioxidants, ultraviolet absorbers, antibacterial agents, fillers, internal release agents, reinforcing materials, matting agents, conductivity-imparting agents, charge control agents, antistatic agents, lubricants, dyes, pigments, and other processing aids.

[0133] 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 (F) with a neutralizing agent (G).

[0134] The polyurethane resin composition thus obtained is preferably used as an aqueous polyurethane resin emulsion. By curing this aqueous polyurethane resin emulsion, the 100% modulus is reduced (the texture is good), and molded articles such as coatings and films with excellent antibacterial activity and film-forming properties can be obtained. These articles are suitable for leather applications such as artificial leather and synthetic leather, and as leather surface treatment agents. The 100% modulus is an index that quantifies the moist, luxurious feel experienced when touching synthetic leather; the lower the value, the better the polyurethane resin's properties.

[0135] <100% modulus of cured product> The 100% modulus of the cured product of the polyurethane resin composition, measured by the following method, is preferably 10 MPa or less, and more preferably 9.5 MPa or less. When the 100% modulus is 10 MPa or less, a cured product of the polyurethane resin with a good texture is likely to be obtained.

[0136] [100% modulus measurement method] A No. 4 dumbbell-shaped test piece, 50 μm thick, is stretched at a tension speed of 200 mm / min using a tensile tester in an environment of 25°C and 50% RH, and the stress at 100% elongation is defined as the 100% modulus.

[0137] <Softening temperature> The softening temperature of the cured product of the polyurethane resin composition is preferably 100° C. or higher, and more preferably 110° C. or higher. When the softening temperature is 100° C. or higher, a cured polyurethane resin product with excellent heat resistance is likely to be obtained.

[0138] [Method for measuring softening temperature] After obtaining a test piece from the polyurethane resin film using a dumbbell, mark a 2cm gauge on the test piece and measure the thickness at the center of the gauge. A weight of a specified weight is attached to one grip of the test piece, and the other grip is clamped with a double clip. After hanging the test piece in a dryer with the clip on the upper side, the temperature inside the dryer is increased and the distance between the gauge lines is observed. The temperature when the distance between the gauge lines reaches 4cm is taken as the softening temperature. Processing equipment: Constant temperature blower dryer DRK633DA (manufactured by Advantech) Weight: gauge center thickness (μm) x 0.05g Dumbbell No. 2 (JIS K6251 compliant) Heating rate: 5℃ / min

[0139] [Artificial leather or synthetic leather] One 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 one embodiment can be produced, for example, by a method including forming a cured product of the polyurethane resin composition on a substrate. The artificial leather or synthetic leather according to one embodiment can also be produced by a method including impregnating the substrate with the polyurethane resin composition and curing the polyurethane resin composition. In the artificial leather, the substrate may be, for example, a base fabric such as a knitted fabric or a woven fabric. In the synthetic leather, the substrate may be a nonwoven fabric.

[0140] [Leather surface treatment agent] The leather surface treatment agent contains a polyurethane resin composition and is 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. [Example]

[0141] Examples of the present invention will be described below, but the present invention is not limited to these examples. In the examples, % and parts are by mass unless otherwise specified.

[0142] <Polyol property evaluation method> (Measurement of number average molecular weight) The polyol was subjected to GPC analysis under the following conditions to measure the number average molecular weight of the polyol. -conditions- (1) Measuring instrument: HLC-8420 (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: 1,000, average number of functional groups: 2) Sannix PP-2000 (number average molecular weight: 2,000, average number of functional groups: 2) Sannix PP-3000 (number average molecular weight: 3,200, average number of functional groups: 2) Sannix PP-4000 (number average molecular weight: 4,160, average number of functional groups: 2) (8) Approximation of the calibration curve: cubic equation (9) Sample solution concentration: 0.5% by mass THF solution

[0143] (Average number of functional groups) The average functionality of the multifunctional polyol (A-2) was calculated from the number average molecular weight and hydroxyl value obtained by GPC (Gel Permeation Chromatography). Here, the number average molecular weight of the multifunctional polyol (A-2) is the number average molecular weight calculated as a bifunctional polyoxypropylene polyol, measured using GPC (Gel Permeation Chromatography) with the entire multifunctional polyol (A-2) as the measurement object. Normally, the average functionality is calculated from the true number average molecular weight and the average hydroxyl value, but since it is difficult to calculate the true number average molecular weight of the multifunctional polyol (A-2), the number average molecular weight converted from the PPG calibration curve in GPC measurement was used, and the assumed average functionality calculated using the following formula was defined as the average functionality of the multifunctional polyol (A-2). Average functionality = (average hydroxyl value (mg KOH / g) of multifunctional polyol (A-2) × number average molecular weight (g / mol) calculated from the PPG calibration curve obtained by GPC measurement of multifunctional polyol (A-2)) / (56.11 (g KOH / mol) × 1,000)

[0144] (Measurement of hydroxyl value (OHv)) The hydroxyl value of the polyol obtained by a method using an acetylation reagent was measured in accordance with JIS K1557-1.

[0145] (Property evaluation) The obtained polyol was used as a sample, and the sample was heated at 80° C. for 1 hour and then left to stand at 25° C. for 3 days. 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.

[0146] <Calculation method for each composition> (Antibacterial agent (B) content) The content of the antibacterial agent (B) was calculated from the amount of the antibacterial agent (B) charged, and was therefore defined by the following formula. Content (mass%) of antibacterial agent (B) = Amount (g) of antibacterial agent (B) / [Amount (g) of polyol (A) + Amount (g) of antibacterial agent (B) + Amount (g) of organic acid (C) + Amount (g) of polyisocyanate (D) + Amount (g) of chain extender (F)] × 100

[0147] (Structural analysis of antibacterial agents) The structure of each antibacterial agent was determined by NMR spectroscopy. Using deuterated chloroform (manufactured by Ambridge Isotope Laboratories, Inc., hereinafter referred to as CDCl3) or deuterated dimethyl sulfoxide (manufactured by Ambridge Isotope Laboratories, Inc., hereinafter referred to as DMSO-d6) with tetramethylsilane (TMS) added as the chemical shift standard, each antibacterial agent was dissolved at a concentration of 1% by mass and analyzed using a nuclear magnetic resonance spectrometer (manufactured by Bruker, "AVANCE II") at 400 MHz ( 1 The frequency of the NMR spectrum was measured using 1H-NMR.

[0148] [Production of antibacterial agents 1] (Synthesis of N-dodecyl-N-(6-hydroxyhexyl)-N,N-dimethylammonium bromide) A 500 mL three-necked round-bottom flask equipped with a reflux condenser and a thermometer was charged with a stirrer, 6-dimethylamino-1-hexanol (36.31 g, 250 mmol), acetonitrile (125 mL), and 1-bromododecane (62.31 g, 250 mmol), and the mixture was stirred under reflux (82°C) for 5 hours. After cooling, the acetonitrile was distilled off under reduced pressure. The resulting crude product was washed with ethyl acetate and then dried under reduced pressure to obtain a colorless viscous product of N-dodecyl-N-(6-hydroxyhexyl)-N,N-dimethylammonium bromide (yield: 93.75 g, 95%) (antibacterial agent-1). The NMR analysis results of the obtained antibacterial agent-1 are as follows. 1 H-NMR(400MHz,DMSO-d6):δ4.38(m,1H),3.43-3.36(m,2H),3.26-3.18(m,4 H),2.99(s,6H),1.70-1.58(m,4H),1.49-1.18(m,24H),0.89-0.82(m,3H).

[0149] 6-Dimethylamino-1-hexanol: Kao Corporation 1-Bromododecane: manufactured by Tokyo Chemical Industry Co., Ltd. Acetonitrile: Fujifilm Wako Pure Chemical Industries, Ltd.

[0150] [Synthesis Example 1: Production of Polyol 1] 826 g of 1,6-hexanediol, 787 g of diethyl carbonate, and 0.05 g of tetrabutyl titanate were mixed in a 2 L, two-necked glass reactor (hereafter referred to as Reactor A) equipped with a stirrer, thermometer, heater, and condenser. The mixture was reacted at 100-190°C for 8 hours under atmospheric pressure while removing low-boiling components. The reaction temperature was then increased to 190°C, the pressure inside the flask was reduced to 1 kPa, and the reaction was continued for another 8 hours to obtain polycarbonate polyol (PCD-1). The physical properties of this polyol were evaluated according to the methods described above. The results are shown in Table 1.

[0151] [Synthesis Example 2: Production of Multifunctional Polycarbonate Polyol 1] A 1L four-neck glass reactor equipped with a stirrer, thermometer, heater, and condenser was charged with 575 g of the polyol (PCD-1) obtained in Polyol Production 1, 400 g of polycaprolactone triol (PLACCEL 305), 25 g of polycaprolactone diol (PLACCEL 210), and 0.03 g of potassium bicarbonate, and the transesterification reaction was carried out at 190°C for 5 hours to obtain a multifunctional polycarbonate polyol (PCP-1). The physical properties of this polyol were evaluated according to the methods described above. The results are shown in Table 1.

[0152] [Table 1]

[0153] 1,6-Hexanediol: BASF JAPAN Diethyl carbonate: Sigma-Aldrich Plaxel 305: Polycaprolactone triol (molecular weight = 550, hydroxyl value = 305, number of functional groups = 3) manufactured by Daicel Corporation Plaxel 210: Polycaprolactone diol (molecular weight = 1,000, hydroxyl value = 112, number of functional groups = 2) manufactured by Daicel Corporation Tetrabutyl titanate: Tokyo Chemical Industry Co., Ltd. Potassium bicarbonate: Fujifilm Wako Pure Chemical Industries, Ltd.

[0154] [Synthesis Example 3: Production of Polyurethane Resin Emulsion 1] A 1 L reactor (hereinafter referred to as reactor B) equipped with a stirrer, a thermometer, a nitrogen seal tube, and a condenser was charged with 89.9 g of N-980N (manufactured by Tosoh Corporation: number average molecular weight 2,000; hydroxyl value 56.11 mgKOH / g; 1,6-hexanediol-based polycarbonate diol), 1.0 g of trimethylolpropane, 4.4 g of 1,6-hexanediol, 4.4 g of antibacterial agent-1, 75 g of acetone, 5.3 g of 2,2-dimethylolpropanoic acid, and 37.0 g of isophorone diisocyanate, heated to 60°C, and stirred at the same temperature for 30 minutes. After that, 0.16 g of Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.: inorganic bismuth catalyst) was added, and the mixture was allowed to react for 9 hours. Next, 4.0 g of triethylamine was added to neutralize the carboxyl groups, and then 320 g of water was added with stirring to emulsify. Within 30 minutes, amine water (30 g of water mixed with 4.0 g of isophorone diamine) was added, and the amine chain extension reaction was carried out at 40°C for 12 hours. Stirring was stopped when the presence of isocyanate groups was no longer confirmed by FT-IR. The reaction solution was then transferred to a 2-L 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-1). The composition is shown in Table 2.

[0155] [Synthesis Example 4: Production of Polyurethane Resin Emulsion 2] Reactor B was charged with 53.5 g of N-980N, 39.9 g of PCP-1, 1.9 g of 1,6-hexanediol, 4.4 g of Antibacterial Agent-1, 75 g of acetone, 5.3 g of 2,2-dimethylolpropanoic acid, and 37.0 g of isophorone diisocyanate. The mixture was heated to 60°C and stirred at the same temperature for 30 minutes. Then, 0.16 g of Neostan U-600 was added and the mixture was allowed to react for 11.5 hours. The emulsification and post-emulsification procedures were the same as in Synthesis Example 3, resulting in an aqueous polyurethane resin emulsion composition (PUD-2). The composition is shown in Table 2.

[0156] [Synthesis Example 5: Production of Polyurethane Resin Emulsion 3] Reactor B was charged with 93.8 g of N-980N, 1.0 g of trimethylolpropane, 4.9 g of 1,6-hexanediol, 75 g of acetone, 5.3 g of 2,2-dimethylolpropanoic acid, and 37.0 g of isophorone diisocyanate, heated to 60°C, and stirred at that temperature for 30 minutes. Then, 0.16 g of Neostan U-600 was added and the mixture was allowed to react for 7 hours. The emulsification and post-emulsification procedures were the same as in Synthesis Example 3, yielding an aqueous polyurethane resin emulsion composition (PUD-3). The composition is shown in Table 2.

[0157] N-980N: Tosoh Corporation, 1,6-hexanediol-based polycarbonate diol Trimethylolpropane: Sigma-Aldrich 1,6-Hexanediol: BASF JAPAN 2,2-Dimethylolpropionic acid: Tokyo Chemical Industry Co., Ltd. Isophorone diisocyanate: Evonik Acetone: KH Neochem Triethylamine: manufactured by Kishida Chemical Co., Ltd. Isophoronediamine: manufactured by Tokyo Chemical Industry Co., Ltd. Neostan U-600: Inorganic bismuth catalyst manufactured by Nitto Kasei Co., Ltd. ·Water: Purified water

[0158] (Example 1: Preparation of polyurethane resin film 1) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-1 obtained in Synthesis Example 3, 1 part Aquanate-200 (manufactured by Tosoh Corporation), 101 parts water, 23.8 parts dipropylene glycol dimethyl ether, and 0.5 parts BYK-3456 (manufactured by BYK) were added to obtain a liquid blend. The liquid blend was applied to a dry film thickness of 50 μm and dried at 25°C for 2 days and then at 80°C for 2 hours to produce a cured product (polyurethane resin film). The physical properties of this cured product were evaluated. The results are shown in Table 3.

[0159] (Example 2: Preparation of polyurethane resin film 2) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-1 obtained in Synthesis Example 3, 5 parts of Aquanate-200, 117 parts of water, 26.6 parts of dipropylene glycol dimethyl ether, and 0.5 parts of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. The physical properties of this film were evaluated. The results are shown in Table 3.

[0160] (Example 3: Preparation of polyurethane resin film 3) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-1 obtained in Synthesis Example 3, 10 parts of Aquanate-200, 143 parts of water, 30.1 parts of dipropylene glycol dimethyl ether, and 0.6 parts of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. The physical properties of this film were evaluated. The results are shown in Table 3.

[0161] (Example 4: Preparation of polyurethane resin film 4) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-1 obtained in Synthesis Example 3, 15 parts of Aquanate-200, 177 parts of water, 34.8 parts of dipropylene glycol dimethyl ether, and 0.7 parts of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. This film was used to evaluate its physical properties. The results are shown in Table 3.

[0162] (Example 5: Preparation of polyurethane resin film 5) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-1 obtained in Synthesis Example 3, 20 parts of Aquanate-200, 195 parts of water, 37.7 parts of dipropylene glycol dimethyl ether, and 0.7 parts of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. The physical properties of this film were evaluated. The results are shown in Table 3.

[0163] (Example 6: Preparation of polyurethane resin film 6) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-1 obtained in Synthesis Example 3, 30 parts of Aquanate-200, 250 parts of water, 45.2 parts of dipropylene glycol dimethyl ether, and 0.9 parts of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. The physical properties of this film were evaluated. The results are shown in Table 3.

[0164] (Example 7: Preparation of polyurethane resin film 7) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-2 obtained in Synthesis Example 4, 1 part of Aquanate-200, 101 parts of water, 23.8 parts of dipropylene glycol dimethyl ether, and 0.5 parts of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. The physical properties of this film were evaluated. The results are shown in Table 3.

[0165] (Example 8: Preparation of polyurethane resin film 8) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-2 obtained in Synthesis Example 4, 5 parts of Aquanate-200, 117 parts of water, 26.6 parts of dipropylene glycol dimethyl ether, and 0.5 parts of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. The physical properties of this film were evaluated. The results are shown in Table 3.

[0166] (Example 9: Preparation of polyurethane resin film 9) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-2 obtained in Synthesis Example 4, 10 parts of Aquanate-200, 143 parts of water, 30.1 parts of dipropylene glycol dimethyl ether, and 0.6 parts of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. The physical properties of this film were evaluated. The results are shown in Table 3.

[0167] (Example 10: Preparation of polyurethane resin film 10) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-2 obtained in Synthesis Example 4, 15 parts of Aquanate-200, 177 parts of water, 34.8 parts of dipropylene glycol dimethyl ether, and 0.7 parts of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. The physical properties of this film were evaluated. The results are shown in Table 3.

[0168] (Example 11: Preparation of polyurethane resin film 11) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-2 obtained in Synthesis Example 4, 20 parts of Aquanate-200, 195 parts of water, 37.7 parts of dipropylene glycol dimethyl ether, and 0.7 parts of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. The physical properties of this film were evaluated. The results are shown in Table 3.

[0169] (Example 12: Preparation of polyurethane resin film 12) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-2 obtained in Synthesis Example 4, 30 parts of Aquanate-200, 250 parts of water, 45.2 parts of dipropylene glycol dimethyl ether, and 0.9 parts of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. The physical properties of this film were evaluated. The results are shown in Table 3.

[0170] (Comparative Example 1: Preparation of polyurethane resin film 13) To 100 parts of the aqueous polyurethane resin emulsion composition of PUD-3 obtained in Synthesis Example 5, 90 parts of water, 22.6 parts of dipropylene glycol dimethyl ether, and 0.4 parts of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. The physical properties of this film were evaluated. The results are shown in Table 3. Since the PUD-3 obtained in Synthesis Example 5 did not contain an antibacterial agent, Comparative Example 1 is a test example used as a reference example.

[0171] (Comparative Example 2: Preparation of polyurethane resin film 14) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-1 obtained in Synthesis Example 3, 90 parts of water, 22.6 parts of dipropylene glycol dimethyl ether, and 0.4 parts of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. The physical properties of this film were evaluated. The results are shown in Table 3.

[0172] (Comparative Example 3: Preparation of polyurethane resin film 15) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-1 obtained in Synthesis Example 3, 40 parts of Aquanate-200, 307 parts of water, 52.6 parts of dipropylene glycol dimethyl ether, and 1.0 part of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. The physical properties of this film were evaluated. The results are shown in Table 3.

[0173] (Comparative Example 4: Preparation of polyurethane resin film 16) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-1 obtained in Synthesis Example 3, 50 parts of Aquanate-200, 353 parts of water, 59.5 parts of dipropylene glycol dimethyl ether, and 1.1 parts of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. The physical properties of this film were evaluated. The results are shown in Table 3.

[0174] (Comparative Example 5: Preparation of polyurethane resin film 17) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-2 obtained in Synthesis Example 4, 90 parts of water, 22.6 parts of dipropylene glycol dimethyl ether, and 0.4 parts of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. The physical properties of this film were evaluated. The results are shown in Table 3.

[0175] (Comparative Example 6: Preparation of polyurethane resin film 18) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-2 obtained in Synthesis Example 4, 40 parts of Aquanate-200, 307 parts of water, 52.6 parts of dipropylene glycol dimethyl ether, and 1.0 part of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. The physical properties of this film were evaluated. The results are shown in Table 3.

[0176] (Comparative Example 7: Preparation of polyurethane resin film 19) To 100 parts of the aqueous polyurethane resin emulsion composition PUD-2 obtained in Synthesis Example 4, 50 parts of Aquanate-200, 353 parts of water, 59.5 parts of dipropylene glycol dimethyl ether, and 1.1 parts of BYK-3456 were added to obtain a blended solution. The subsequent operations were the same as in Example 1, and a polyurethane resin film was produced. The physical properties of this film were evaluated. The results are shown in Table 3.

[0177] [Evaluation test] (water resistance) The polyurethane resin films obtained in Examples 1 to 12 and Comparative Examples 1 to 7 were cut into 5 cm squares. 0.4 mL of water was dropped onto the center of the film, which was then sandwiched between 4 cm squares of polyethylene film and left at room temperature for 24 hours. The water was then wiped off, and the film appearance was evaluated by visual observation. Evaluation was based on whether the film showed no change in appearance (5), whether it showed slight whitening (4), whether it was whitened but still transparent (3), whether it was whitened but still slightly transparent (2), and whether it was whitened and completely transparent (1).

[0178] (Tensile properties) The tensile properties of the polyurethane resin films obtained in Examples 1 to 12 and Comparative Examples 1 to 7 were measured in accordance with JIS K7321. (100% modulus: M100, strength at break: TB, elongation at break: EB) Testing equipment: Tensilon UTA-500 (manufactured by A&D) Measurement conditions: 25°C x 50% RH Head speed: 200mm / min Dumbbell No. 4

[0179] (Softening temperature) Test specimens were obtained from the polyurethane resin films obtained in Examples 1 to 12 and Comparative Examples 1 to 7 using dumbbells. A 2-cm gauge was then marked on the test specimen, and the thickness at the center of the gauge was measured. A weight of a predetermined weight was attached to one grip of the test specimen, and the other grip was clamped with a double clip. The specimen was then hung in a dryer with the clip facing up. The temperature inside the dryer was then increased, and the gauge length was measured. The temperature at which the gauge length reached 4 cm was recorded as the softening temperature. In Table 3, ">270" indicates a softening temperature greater than 270°C, meaning that the gauge length did not reach 4 cm at the upper limit of the dryer temperature of 270°C. Processing equipment: Constant temperature blower dryer DRK633DA (manufactured by Advantech) Weight: gauge center thickness (μm) x 0.05g Dumbbell No. 2 (JIS K6251 compliant) Heating rate: 5℃ / min

[0180] [Table 2]

[0181] [Table 3]

[0182] Aquanate-200: Tosoh Corporation (nonionic water-dispersible polyisocyanate, NCO content = 11.9%) Dipropylene glycol dimethyl ether: Fujifilm Wako Pure Chemical Industries, Ltd. BYK-3456: BYK

[0183] The curing agent content in each example is the number of parts contained relative to 100 parts of polyurethane resin, and can be calculated using the following formula: Here, the solid content of PUD1 to 3 is 30 mass %. Hardener content (parts) = Hardener amount (g) / [PUD amount (g) x 0.30] x 100

Claims

1. A polyurethane resin composition comprising a polyurethane resin and a curing agent, The polyurethane resin is a reaction product of an isocyanate-terminated urethane prepolymer (E) comprising a reaction product of a polyol (A), an antimicrobial agent (B) which is a quaternary ammonium salt represented by formula (1), an organic acid (C), and a polyisocyanate (D), and a chain extender (F) which may contain the antimicrobial agent (B) which is a quaternary ammonium salt represented by formula (1); or a reaction product of an isocyanate-terminated urethane prepolymer (E) comprising a reaction product of a polyol (A), an organic acid (C), and a polyisocyanate (D), and a chain extender (F) which contains the antimicrobial agent (B) which is a quaternary ammonium salt represented by formula (1); a neutralizing agent (G), the content of the antibacterial agent (B) is 0.2 mass% or more and 7.5 mass% or less, based on the total mass of the isocyanate group-terminated urethane prepolymer (E) and the chain extender (F) in the polyurethane resin composition; the curing agent is a polyisocyanate compound, The polyurethane resin composition, wherein the content of the curing agent is 0.1 parts by mass or more and 100 parts by mass or less relative to 100 parts by mass of the polyurethane resin. (R １ ) ａ (R ２ ) ｂ (R ３ ) ｃ N ＋ ・X － (1) (In formula (1), R １ is an aliphatic hydrocarbon group in which at least one hydrogen atom is substituted with a hydroxy group, R １ The number of carbon atoms in If only one hydrogen atom is replaced by a hydroxy group, it is 4 to 11. If two or more hydrogen atoms are replaced by hydroxy groups, the number is 3 to 11. R ２ is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, R ３ is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, X － is the conjugate base of the acid, a represents 1 or 2, b represents 1, c represents 1 or 2, and a+b+c=4 is satisfied; and R １ , R ２ and R ３ The total number of carbon atoms in the aliphatic hydrocarbon groups represented by the formula (I) is 15 or more and 23 or less, When a or c is 2, a plurality of R １ or R ３ may be the same or different.)

2. 2. The polyurethane resin composition according to claim 1, wherein the curing agent is at least one selected from the group consisting of urethane-modified, urea-modified, allophanate-modified, biuret-modified, uretdione-modified, and isocyanurate-modified organic diisocyanates.

3. 3. The polyurethane resin composition according to claim 2, wherein the curing agent is at least one selected from the group consisting of a trimer and an adduct of hexamethylene diisocyanate or isophorone diisocyanate.

4. The polyurethane resin composition according to claim 1, wherein the antibacterial agent (B) is a quaternary ammonium salt represented by formula (2): 【Chemistry 1】 (In formula (2), m represents an integer of 6 to 11, n represents an integer of 10 to 14, and m+n=16 to 21 is satisfied; X － represents a halide ion.)

5. The polyurethane resin composition according to claim 1, wherein the antibacterial agent (B) is a quaternary ammonium salt represented by formula (3): 【Chemistry 2】 (In formula (3), n represents an integer of 12 to 14, and X － represents a halide ion.)

6. The polyurethane resin composition according to claim 5, wherein the antibacterial agent (B) is a quaternary ammonium salt represented by formula (3), and n is 12.

7. the polyol (A) contains a polyol (A-1) and a multifunctional polyol (A-2), the polyol (A-1) is at least one selected from the group consisting of polyester diols, polyether diols, polycarbonate diols, and polyolefin diols; 2. The polyurethane resin composition according to claim 1, wherein the multifunctional polyol (A-2) is one or more selected from the group consisting of polyester polyols (A-2-1), polyether polyols (A-2-2), polyolefin polyols (A-2-3), and polycarbonate polyols (A-2-4), each having three or more hydroxy groups in one molecule.

8. The polyurethane resin composition according to claim 7, wherein the multifunctional polyol (A-2) includes the polycarbonate polyol (A-2-4).

9. the polyol (A) contains a polyol (A-1) and a polyhydric alcohol (A-3), the polyol (A-1) is at least one selected from the group consisting of polyester diols, polyether diols, polycarbonate diols, and polyolefin diols; 2. The polyurethane resin composition according to claim 1, wherein the polyhydric alcohol (A-3) has three or more hydroxy groups in one molecule and a molecular weight of 300 or less.

10. The polyol (A) is a polyfunctional polyol (A-2) and a diol (A-4), or The composition comprises a polyol (A-1), a multifunctional polyol (A-2), and a diol (A-4), the polyol (A-1) is at least one selected from the group consisting of polyester diols, polyether diols, polycarbonate diols, and polyolefin diols; the polyfunctional polyol (A-2) is one or more selected from the group consisting of polyester polyols (A-2-1), polyether polyols (A-2-2), polyolefin polyols (A-2-3), and polycarbonate polyols (A-2-4), each having three or more hydroxy groups in one molecule; 2. The polyurethane resin composition according to claim 1, wherein the diol (A-4) is a diol other than polyester diols, polyether diols, polycarbonate diols, and polyolefin diols.

11. the polyol (A) contains a polyol (A-1), a polyhydric alcohol (A-3), and a diol (A-4); the polyol (A-1) is at least one selected from the group consisting of polyester diols, polyether diols, polycarbonate diols, and polyolefin diols; the polyhydric alcohol (A-3) has three or more hydroxy groups in one molecule and a molecular weight of 300 or less; 2. The polyurethane resin composition according to claim 1, wherein the diol (A-4) is a diol other than polyester diols, polyether diols, polycarbonate diols, and polyolefin diols.

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

13. The polyurethane resin composition according to claim 1, wherein the chain extender (F) comprises an amine compound having one or more primary or secondary amino groups.

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

15. the 100% modulus of a cured product of the polyurethane resin composition measured by the following method is 10 MPa or less; The polyurethane resin composition according to claim 1, which has a softening temperature of 100°C or higher. [Method for measuring 100% modulus] A No. 4 dumbbell-shaped test piece having a thickness of 50 μm is stretched at a tension speed of 200 mm / min using a tensile tester in an environment of 25°C and 50% RH, and the stress at 100% stretch is defined as the 100% modulus.

16. An artificial leather or synthetic leather comprising a cured product of the polyurethane resin composition according to any one of claims 1 to 15.

17. A surface treatment agent for leather, comprising the polyurethane resin composition according to any one of claims 1 to 15.

Images