Polyurethane resin composition, coating, and synthetic leather

Abstract

To provide a polyurethane resin composition using a biomass raw material which is excellent in abrasion resistance, oleic acid resistance and low temperature flexibility.SOLUTION: A polyurethane resin composition contains a polyurethane resin (X) containing polyol (A), polyisocyanate (B) and a chain extender (C) as raw materials, and an organic solvent (Y). The polyol (A) contains polycarbonate polyol (A-1) containing biomass-derived decane diol as a raw material, and polycarbonate polyol (A-2) containing a biomass-derived dihydroxy compound having a cyclic ether structure as a raw material. A film is formed of the polyurethane resin composition, and artificial leather has the film.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polyurethane resin composition, a coating, and an artificial leather. [Background technology]

[0002] In the context of global warming and the depletion of petroleum resources, there is a growing global demand for environmentally friendly materials made from biomass materials such as plants. The use of biomass materials can contribute to the creation of a sustainable society by reducing the use of fossil resources such as petroleum.

[0003] Polyurethane resins are widely used in the manufacture of synthetic leather, artificial leather, films, and the like. Higher durability is required for components that are used for a long period of time, such as synthetic leather for vehicle interior materials. Evaluation items for such durability are wide-ranging, and include heat resistance, moist heat resistance, light resistance, chemical resistance, and abrasion resistance (see, for example, Patent Document 1). In particular, in recent years, synthetic leather components that frequently come into contact with the human body are required to have chemical resistance to oleic acid, and the required level of flexibility at low temperatures is also increasing in anticipation of use in cold regions. However, the current situation is that a synthetic leather material that uses biomass raw materials and satisfies various durability requirements has not yet been developed. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP2016-222921A Summary of the Invention [Problem to be solved by the invention]

[0005] The problem to be solved by the present invention is to provide a polyurethane resin composition which uses a biomass raw material and has excellent abrasion resistance, oleic acid resistance, and low-temperature flexibility. [Means for solving the problem]

[0006] The present invention provides a polyurethane resin composition containing a polyurethane resin (X) made from a polyol (A), a polyisocyanate (B), and a chain extender (C) and an organic solvent (Y), wherein the polyol (A) contains a polycarbonate polyol (A-1) made from a biomass-derived decanediol and a polycarbonate polyol (A-2) made from a biomass-derived dihydroxy compound having a cyclic ether structure.

[0007] The present invention also provides a film formed from the polyurethane resin composition, and an artificial leather having the film. Effect of the Invention

[0008] The polyurethane resin composition of the present invention uses biomass raw materials and is an environmentally friendly material. The polyurethane resin composition also has excellent abrasion resistance, oleic acid resistance, and low-temperature flexibility.

[0009] Therefore, the polyurethane resin composition of the present invention can be suitably used as a material for producing synthetic leather, clothing, support pads, polishing pads, etc., and can be particularly suitably used as a material for synthetic leather. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The polyurethane resin composition of the present invention is a polyurethane resin composition containing a polyurethane resin (X) made from a specific polyol (A), a polyisocyanate (B), and a chain extender (C) as raw materials, and an organic solvent (Y).

[0011] In order to obtain excellent abrasion resistance, oleic acid resistance, and low-temperature flexibility, it is essential to use two types of polycarbonate polyols derived from biomass, namely, polycarbonate polyol (A-1) derived from decanediol derived from biomass and polycarbonate polyol (A-2) derived from a dihydroxy compound having a cyclic ether structure derived from biomass, as the polyol (A). If the polycarbonate polyol (A-1) is not used, the low-temperature flexibility is particularly poor, and if the polycarbonate polyol (A-2) is not used, the abrasion resistance is particularly poor.

[0012] The mass ratio of the polycarbonate polyol (A-1) to the polycarbonate polyol (A-2) [(A-1) / (A-2)] is preferably in the range of 98 / 2 to 40 / 60, and more preferably in the range of 95 / 5 to 60 / 40, in order to obtain even better abrasion resistance, oleic acid resistance, and low-temperature flexibility.

[0013] The total amount of the polycarbonate polyol (A-1) and the polycarbonate polyol (A-2) used in the polyol (A) is preferably 60% by mass or more, more preferably 80% by mass, further preferably 90% by mass, and particularly preferably 95% by mass.

[0014] Examples of polyols that can be used as the polyol (A) other than the polycarbonate polyols (A-1) and (A-2) include polyester polyols, polyether polyols, polybutadiene polyols, polycarbonate polyols other than the polycarbonate polyols (A-1) and (A-2), etc. These polyols may be used alone or in combination of two or more.

[0015] The polycarbonate polyol (A-1) made from the biomass-derived decanediol can be, for example, a reaction product of a glycol compound containing the biomass-derived decanediol with a carbonate ester and / or phosgene. Specifically, those described in JP 2018-127758 A and the like can be used.

[0016] As the decanediol, 1,10-decanediol is preferable since it provides even better resistance to oleic acid and low-temperature flexibility.

[0017] Examples of glycol compounds that can be used other than the decanediol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, trimethylolpropane, trimethylolethane, glycerin, ε-caprolactone, and neopentyl glycol. These compounds may be used alone or in combination of two or more. Among these, butanediol is preferably used, and 1,4-butanediol is more preferable, since it provides better oleic acid resistance and low-temperature flexibility.

[0018] When the biomass-derived decanediol and the butanediol are used in combination, the total amount used is preferably 50 mol % or more, more preferably 70 mol % or more, and even more preferably 80 mol % or more, of the glycol compound.

[0019] When the biomass-derived decanediol (C10) and butanediol (C4) are used in combination, the molar ratio [(C4) / (C10)] is preferably in the range of 50 / 50 to 98 / 2, and more preferably in the range of 75 / 25 to 95 / 5, in order to obtain even better oleic acid resistance and low-temperature flexibility.

[0020] Examples of the carbonate ester that can be used include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. These compounds may be used alone or in combination of two or more kinds.

[0021] The number average molecular weight of the polycarbonate diol (A-1) is preferably in the range of 500 to 100,000, more preferably in the range of 700 to 10,000, and further preferably in the range of 1,500 to 4,000, from the viewpoint of obtaining even better oleic acid resistance and low-temperature flexibility. The number average molecular weight of the polycarbonate diol (A-1) is a value measured by gel permeation chromatography (GPC).

[0022] As the preferable polycarbonate polyol (A-1), for example, "Benebiol NL-3010DB" manufactured by Mitsubishi Chemical Corporation and the like can be obtained as a commercially available product.

[0023] The polycarbonate polyol (A-2) made from the biomass-derived dihydroxy compound having a cyclic ether structure can be, for example, a reaction product of a glycol compound containing a biomass-derived dihydroxy compound having a cyclic ether structure with a carbonate ester and / or phosgene. Specifically, those described in JP 2017-133024 A and the like can be used.

[0024] As the dihydroxy compound having a cyclic ether structure, isosorbide, isomannide, isoidet, etc. can be used. These compounds can be used alone or in combination of two or more. Among these, isosorbide is preferred because it provides even better abrasion resistance.

[0025] Examples of glycol compounds that can be used other than the dihydroxy compounds include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, trimethylolpropane, trimethylolethane, glycerin, ε-caprolactone, and neopentyl glycol. These compounds may be used alone or in combination of two or more. Among these, butanediol is preferred, and 1,4-butanediol is more preferred, in that even more excellent abrasion resistance can be obtained.

[0026] When the biomass-derived dihydroxy compound having a cyclic ether structure and the butanediol are used in combination, the total amount used is preferably 50 mol % or more, more preferably 70 mol % or more, and even more preferably 80 mol % or more, of the glycol compound.

[0027] Also, The biomass-derived dihydroxy compound having a cyclic ether structure (ISB)When butanediol (C4) is used in combination, the molar ratio [(C4) / (ISB)] is preferably in the range of 30 / 70 to 90 / 10, more preferably in the range of 40 / 60 to 80 / 20, and even more preferably in the range of 50 / 50 to 70 / 30, in order to obtain even better oleic acid resistance and low-temperature flexibility.

[0028] Examples of the carbonate ester that can be used include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. These compounds may be used alone or in combination of two or more kinds.

[0029] The number average molecular weight of the polycarbonate diol (A-2) is preferably in the range of 400 to 100,000, more preferably in the range of 450 to 5,000, and further preferably in the range of 500 to 2,000, from the viewpoint of obtaining even more excellent abrasion resistance. The number average molecular weight of the polycarbonate diol (A-2) is a value measured by gel permeation chromatography (GPC).

[0030] As the preferable polycarbonate polyol (A-2), for example, "Benebiol HS0830B", "Benebiol HS0840B", "Benebiol HS0840H", "Benebiol HS0850H" and the like manufactured by Mitsubishi Chemical Corporation are available as commercially available products.

[0031] Examples of the polyisocyanate (B) include 1,3- and 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-2,5-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3-dimethyl-2,4-phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1-methyl-3,5-diethyl Aromatic polyisocyanates such as benzene diisocyanate, 3-methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5-triethylbenzene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 1-methyl-naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 1,1-dinaphthyl-2,2'-diisocyanate, biphenyl-2,4'-diisocyanate, biphenyl-4,4'-diisocyanate, 3-3'-dimethylbiphenyl-4,4'-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, and diphenylmethane-2,4-diisocyanate;Aliphatic or alicyclic polyisocyanates such as tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-di(isocyanatemethyl)cyclohexane, 1,4-di(isocyanatemethyl)cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, and 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, it is preferable to use aliphatic and / or alicyclic polyisocyanates, since they can further improve light resistance, abrasion resistance, oleic acid resistance, and low-temperature bending property.

[0032] The amount of the polyisocyanate (B) used is preferably in the range of 10 to 60 mass %, more preferably 15 to 45 mass %, of the total mass of the raw materials constituting the polyurethane resin (A), in terms of obtaining even better mechanical strength and reactivity.

[0033] Examples of the chain extender (C) include hydroxyl group-containing chain extenders such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, trimethylolpropane, and glycerin; and amino group-containing chain extenders such as ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, and triethylenetetramine. These chain extenders may be used alone or in combination of two or more. Among these, it is preferable to use a chain extender having an amino group, and it is more preferable to use a chain extender having an amino group and an alicyclic structure, because this makes it easier to inhibit discoloration of the coating over time and can further improve abrasion resistance, oleic acid resistance, and low-temperature flexibility.

[0034] The amount of the chain extender (C) used is preferably in the range of 1 to 50 mass %, more preferably 2 to 30 mass %, of the total mass of the raw materials constituting the polyurethane resin (A), from the viewpoint of achieving even better abrasion resistance, oleic acid resistance, and low-temperature flexibility.

[0035] The polyurethane resin (X) can be produced, for example, by charging the polyol (A), the polyisocyanate (B), and the chain extender (C) all at once and reacting them, and the reaction is preferably carried out, for example, at a temperature of 30 to 100° C. for 3 to 10 hours. The reaction may also be carried out in an organic solvent (Y) described later.

[0036] The molar ratio of the hydroxyl groups in the polyol (A) and the sum of the hydroxyl groups and amino groups in the chain extender (C) to the isocyanate groups in the polyisocyanate (Y) [(isocyanate groups) / (hydroxyl groups and amino groups)] is preferably in the range of 0.6 to 2, and more preferably in the range of 0.7 to 1.1.

[0037] The number average molecular weight of the polyurethane resin (X) obtained by the above method is preferably in the range of 5,000 to 1,000,000, more preferably in the range of 10,000 to 500,000, from the viewpoint of further improving abrasion resistance, oleic acid resistance, low-temperature bending property, and mechanical strength and flexibility of the coating. The number average molecular weight of the polyurethane resin (X) is a value measured by gel permeation chromatography (GPC).

[0038] The content of the polyurethane resin (X) in the polyurethane resin composition is preferably in the range of 10 to 90% by mass, and more preferably in the range of 15 to 80% by mass.

[0039] Examples of the organic solvent (B) that can be used include ketone solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, methyl-n-propyl ketone, acetone, and methyl isobutyl ketone; ester solvents such as methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, isobutyl acetate, and sec-butyl acetate; and alcohol solvents such as methanol, ethanol, isopropyl alcohol, and butanol. These organic solvents may be used alone or in combination of two or more.

[0040] The content of the organic solvent (B) is preferably within a range of 20 to 90% by mass in the polyurethane resin composition from the viewpoints of workability and viscosity.

[0041] The polyurethane resin composition contains the polyurethane resin (X) and the organic solvent (Y) as essential components, but may contain other components as necessary.

[0042] Examples of the other components that can be used include pigments, flame retardants, plasticizers, softeners, stabilizers, waxes, defoamers, dispersants, penetrants, surfactants, fillers, antifungal agents, antibacterial agents, UV absorbers, antioxidants, weathering stabilizers, fluorescent brighteners, antiaging agents, thickeners, etc. These components may be used alone or in combination of two or more.

[0043] The polyurethane resin composition of the present invention can be applied to a substrate and dried to obtain a coating.

[0044] The substrate may be, for example, a fibrous substrate made of nonwoven fabric, woven fabric, knitted fabric, etc.; a resin film, etc. The fibrous substrate may be, for example, a chemical fiber such as polyester fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, etc.; cotton, hemp, silk, wool, or a blend of these fibers.

[0045] Examples of the resin film that can be used include a polyethylene terephthalate film, a polycarbonate film, an acrylic resin film, a COP (cycloolefin polymer) film, and a TAC (triacetyl cellulose) film.

[0046] The surface of the substrate may be subjected to treatments such as antistatic treatment, release treatment, water repellency treatment, water absorption treatment, antibacterial and deodorizing treatment, bacteriostatic treatment, and ultraviolet blocking treatment, if necessary.

[0047] Examples of a method for applying the polyurethane resin composition of the present invention to the substrate include application methods using an applicator, a bar coater, a knife coater, a T-die coater, a roll coater, and the like.

[0048] The applied polyurethane resin composition can be dried, for example, at a temperature of 50 to 140° C. for 30 seconds to 10 minutes.

[0049] The thickness of the resulting coating is appropriately determined depending on the application, but is, for example, in the range of 0.001 to 10 mm.

[0050] When producing synthetic leather using the film, it is preferable to use the film as a surface layer or a top coat layer of the synthetic leather.

[0051] The synthetic leather can be produced, for example, by laminating a surface treatment layer formed on a release paper to the coating by a known method. Examples of materials that can be used to form the surface treatment layer include solvent-based urethane resins, water-based urethane resins, water-based acrylic resins, etc. Furthermore, a known adhesive can be used for laminating the materials, if necessary.

[0052] As described above, the polyurethane resin composition of the present invention uses biomass raw materials and is an environmentally friendly material. The polyurethane resin composition also has excellent abrasion resistance, oleic acid resistance, and low-temperature flexibility. EXAMPLES

[0053] The present invention will now be described in more detail with reference to examples.

[0054] [Example 1] In a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 202 parts by mass of polycarbonate diol made from 1,4-butanediol and biomass-derived 1,10-decanediol (molar ratio [(C4) / (C10)]=90 / 10, number average molecular weight: 3,000, hereinafter abbreviated as "Bio PC (1)") and 101 parts by mass of polycarbonate diol made from 1,4-butanediol and biomass-derived isosorbide (molar ratio [(C4) / (ISB)]=60 / 40, number average molecular weight: 800, hereinafter abbreviated as "Bio PC (5)") were added, and dehydration was performed at 120°C to 130°C under a reduced pressure of 0.095 MPa. After dehydration, 310 parts by mass of N,N-dimethylformamide (hereinafter abbreviated as "DMF") was added while cooling to 50°C and thoroughly stirred and mixed. After stirring and mixing, 67 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (hereinafter abbreviated as "H12MDI") and 0.2 parts by mass of stannous octylate were added and reacted at 75°C to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end. Next, 862 parts by mass of DMF was added to the organic solvent solution of the urethane prepolymer, and the solution was cooled to 35°C to obtain an isophorone. Nji To the mixture was added 15 parts by mass of IPDA, and the polyurethane resin was chain-extended by stirring and mixing. Next, 1.5 parts by mass of N,N-dibutylamine was added and mixed to obtain a polyurethane resin composition with a nonvolatile content of 25% by mass and a viscosity of 300 dPa s.

[0055] [Example 2] In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 240 parts by mass of Bio PC (1) and 59 parts by mass of Bio PC (5) were added, and dehydration was performed at 120°C to 130°C under a reduced pressure of 0.095 MPa. After dehydration, 116 parts by mass of DMF was added while cooling to 50°C, and thoroughly stirred and mixed. After stirring and mixing, 43 parts by mass of isophorone diisocyanate (hereinafter abbreviated as "IPDI") and 0.2 parts by mass of stannous octylate were added, and reacted at 75°C to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end. Next, 980 parts by mass of DMF was added to the organic solvent solution of the urethane prepolymer, and cooled to 35°C, and 16 parts by mass of 4,4'-dicyclohexylmethanediamine (hereinafter abbreviated as "H12MDA") was added, and the polyurethane resin was chain-elongated by stirring and mixing. Next, 1.5 parts by mass of N,N-dibutylamine was added and mixed to obtain a polyurethane resin composition with a nonvolatile content of 25% by mass and a viscosity of 300 dPa·s.

[0056] [Example 3] In a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 265 parts by mass of polycarbonate diol (molar ratio [(C4) / (C10)]=80 / 20, number average molecular weight: 3,000, hereinafter abbreviated as "Bio PC (2)") made from 1,4-butanediol and biomass-derived 1,10-decanediol as raw materials, and 29 parts by mass of Bio PC (5) were added, and dehydration was performed at 120°C to 130°C under a reduced pressure of 0.095 MPa. After dehydration, 115 parts by mass of DMF was added while cooling to 50°C, and the mixture was thoroughly stirred and mixed. After stirring and mixing, 41 parts by mass of IPDI, 8 parts by mass of hexane diisocyanate (hereinafter abbreviated as "HDI"), and 0.2 parts by mass of stannous octylate were added, and the mixture was reacted at 75°C to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end. Next, 967 parts by mass of DMF was added to the organic solvent solution of the urethane prepolymer, cooled to 35°C, and 15 parts by mass of H12MDA was added and stirred and mixed to extend the chain of the polyurethane resin. Next, 1.5 parts by mass of N,N-dibutylamine was added and mixed to obtain a polyurethane resin composition with a nonvolatile content of 25% by mass and a viscosity of 300 dPa s.

[0057] [Example 4] In a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 225 parts by mass of Bio PC (2) and 56 parts by mass of Bio PC (5) were added, and dehydration was performed at 120°C to 130°C under a reduced pressure of 0.095 MPa. After dehydration, 117 parts by mass of DMF was added while cooling to 50°C, and the mixture was thoroughly stirred and mixed. After stirring and mixing, 69 parts by mass of H12MDI and 0.2 parts by mass of stannous octylate were added, and the mixture was reacted at 75°C to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end. Next, 980 parts by mass of DMF was added to the organic solvent solution of the urethane prepolymer, and the mixture was cooled to 35°C, and 15 parts by mass of H12MDA was added, and the polyurethane resin was chain-extended by stirring and mixing. Next, 1.5 parts by mass of N,N-dibutylamine was added and mixed to obtain a polyurethane resin composition with a non-volatile content of 25% by mass and a viscosity of 300 dPa·s.

[0058] [Example 5] In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 200 parts by mass of Bio PC (2) and 86 parts by mass of Bio PC (5) were added, and dehydration was performed at 120°C to 130°C under a reduced pressure of 0.095 MPa. After dehydration, 118 parts by mass of DMF was added while cooling to 50°C, and the mixture was thoroughly stirred and mixed. After stirring and mixing, 70 parts by mass of IPDI and 0.2 parts by mass of stannous octylate were added, and the mixture was reacted at 75°C to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end. Next, 990 parts by mass of DMF was added to the organic solvent solution of the urethane prepolymer, and the mixture was cooled to 35°C, and 13 parts by mass of IPDA was added and stirred and mixed to extend the chain of the polyurethane resin. Next, 1.5 parts by mass of N,N-dibutylamine was added and mixed to obtain a polyurethane resin composition with a non-volatile content of 25% by mass and a viscosity of 300 dPa·s.

[0059] [Example 6] In a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 203 parts by mass of polycarbonate diol (molar ratio [(C4) / (C10)]=90 / 10, number average molecular weight: 2,000, hereinafter abbreviated as "Bio PC (3)") made from 1,4-butanediol and biomass-derived 1,10-decanediol as raw materials, and 49 parts by mass of Bio PC (5) were added, and dehydration was performed at 120°C to 130°C under a reduced pressure of 0.095 MPa. After dehydration, 110 parts by mass of DMF was added while cooling to 50°C and thoroughly stirred and mixed. After stirring and mixing, 77 parts by mass of H12MDI and 0.2 parts by mass of stannous octylate were added and reacted at 75°C to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end. Next, 916 parts by mass of DMF was added to the organic solvent solution of the urethane prepolymer, cooled to 35°C, and 12 parts by mass of IPDA was added and stirred and mixed to extend the chain of the polyurethane resin. Next, 1.5 parts by mass of N,N-dibutylamine was added and mixed to obtain a polyurethane resin composition with a nonvolatile content of 25% by mass and a viscosity of 300 dPa s.

[0060] [Example 7] In a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 201 parts by mass of polycarbonate diol (molar ratio [(C4) / (C10)]=80 / 20, number average molecular weight: 2,000, hereinafter abbreviated as "Bio PC (4)") made from 1,4-butanediol and biomass-derived 1,10-decanediol as raw materials, and 48 parts by mass of Bio PC (5) were added, and dehydration was performed at 120°C to 130°C under a reduced pressure of 0.095 MPa. After dehydration, 109 parts by mass of DMF was added while cooling to 50°C and thoroughly stirred and mixed. After stirring and mixing, 76 parts by mass of H12MDI and 0.2 parts by mass of stannous octylate were added, and the mixture was reacted at 75°C to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end. Next, 908 parts by mass of DMF was added to the organic solvent solution of the urethane prepolymer, cooled to 35°C, and 15 parts by mass of H12MDA was added and stirred and mixed to extend the chain of the polyurethane resin. Next, 1.5 parts by mass of N,N-dibutylamine was added and mixed to obtain a polyurethane resin composition with a nonvolatile content of 25% by mass and a viscosity of 300 dPa s.

[0061] [Comparative Example 1] In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 370 parts by mass of Bio PC (1) was added, and dehydration was performed at 120°C to 130°C under a reduced pressure of 0.095 MPa. After dehydration, 143 parts by mass of DMF was added while cooling to 50°C, and the mixture was thoroughly stirred and mixed. After stirring and mixing, 59 parts by mass of H12MDI and 0.2 parts by mass of stannous octylate were added, and the mixture was reacted at 75°C to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end. Next, 1200 parts by mass of DMF was added to the organic solvent solution of the urethane prepolymer, and the mixture was cooled to 35°C, and 16 parts by mass of IPDA was added and stirred and mixed to extend the chain of the polyurethane resin. Next, 1.5 parts by mass of N,N-dibutylamine was added and mixed to obtain a polyurethane resin composition with a non-volatile content of 25% by mass and a viscosity of 300 dPa·s.

[0062] [Comparative Example 2] In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 200 parts by mass of Bio PC (5) was added, and dehydration was performed at 120°C to 130°C under a reduced pressure of 0.095 MPa. After dehydration, 106 parts by mass of DMF was added while cooling to 50°C, and the mixture was thoroughly stirred and mixed. After stirring and mixing, 112 parts by mass of H12MDI and 0.2 parts by mass of stannous octylate were added, and the mixture was reacted at 75°C to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end. Next, 889 parts by mass of DMF was added to the organic solvent solution of the urethane prepolymer, and the mixture was cooled to 35°C, and 10 parts by mass of IPDA was added and stirred and mixed to extend the chain of the polyurethane resin. Next, 1.5 parts by mass of N,N-dibutylamine was added and mixed to obtain a polyurethane resin composition with a non-volatile content of 25% by mass and a viscosity of 300 dPa·s.

[0063] [Comparative Example 3] In a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 300 parts by mass of polycarbonate polyol (polycarbonate polyol made from hexanediol derived from petroleum resources, number average molecular weight: 2,000, hereinafter referred to as "petroleum-based PC") was added, and dehydration was performed at 120°C to 130°C under a reduced pressure of 0.095 MPa. After dehydration, 124 parts by mass of DMF was added and thoroughly stirred and mixed while cooling to 50°C. After stirring and mixing, 75 parts by mass of H12MDI and 0.2 parts by mass of stannous octylate were added and reacted at 75°C to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end. Next, 1040 parts by mass of DMF was added to the organic solvent solution of the urethane prepolymer, cooled to 35°C, 14 parts by mass of IPDA was added, and the polyurethane resin was chain-extended by stirring and mixing. Next, 1.5 parts by mass of N,N-dibutylamine was added and mixed to obtain a polyurethane resin composition with a nonvolatile content of 25% by mass and a viscosity of 300 dPa·s.

[0064] [Method for measuring number average molecular weight] The number average molecular weights of polyols and the like used in the examples and comparative examples are values ​​measured by gel permeation chromatography (GPC) under the following conditions.

[0065] Measurement equipment: High-speed GPC equipment (Tosoh Corporation "HLC-8220GPC") Column: The following columns manufactured by Tosoh Corporation were used, connected in series. "TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000" (7.8mm I.D. x 30cm) x 1 "TSKgel G3000" (7.8mm I.D. x 30cm) x 1 "TSKgel G2000" (7.8mmI.D. x 30cm) x 1 Detector: RI (differential refractometer) Column temperature: 40℃ Eluent: tetrahydrofuran (THF) Flow rate: 1.0mL / min Injection volume: 100 μL (sample concentration 0.4% by mass in tetrahydrofuran solution) Standard sample: A calibration curve was prepared using the following standard polystyrene.

[0066] (Standard polystyrene) "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[0067] [Method of measuring abrasion resistance] A mixture of 100 parts by mass of the polyurethane resin composition obtained in each of the Examples and Comparative Examples, 40 parts by mass of DMF, and 20 parts by mass of a colorant "Dilac L-1770S" manufactured by DIC Corporation was applied onto a release paper (DE-73M ​​manufactured by Ajinomoto Trading Co., Ltd.) so that the solid film thickness was 30 microns, and the mixture was dried at 90°C for 2 minutes and then at 120°C for 2 minutes to prepare a polyurethane resin film. Next, a mixture consisting of 100 parts by mass of polyurethane resin adhesive "Crisbon TA-205FT (manufactured by DIC Corporation, solid content 70%), 60 parts by mass of DMF, 12 parts by mass of polyisocyanate crosslinking agent "Burnock DN-950" (manufactured by DIC Corporation), and 1 part by mass of catalyst "Accel T-81E" (manufactured by DIC Corporation) was applied onto the polyurethane resin film to a solid film thickness of 60 microns, and then dried at 100°C for 1 minute. Next, a polyester base fabric was placed on the surface and pressed with a laminator at 120°C, and then the surface was aged at 40°C for 3 days, after which the release paper was peeled off to obtain synthetic leather. This synthetic leather was subjected to a Taber abrasion test (JIS L 1096:2010, abrasion wheel: CS-10, load: 1 kg, rotation speed: 70 rpm, number of tests: 1,000), and the surface of the synthetic leather was observed and evaluated as follows. "A"; no tears. "B": There are some tears on the surface. "C": There is a large tear exposing the fabric.

[0068] [Method for measuring resistance to oleic acid] Synthetic leather was prepared in the same manner as in the above [Method of measuring abrasion resistance]. Four drops of oleic acid were then dropped onto the surface of the synthetic leather, and the leather was left to stand at 80°C for 24 hours, after which it was removed. The oleic acid adhering to the surface was lightly wiped off, and the change in appearance was visually confirmed and evaluated as follows. "A": No change in appearance. "B": There was some swelling. "C": Largely swollen.

[0069] [Method for measuring low temperature flexibility] Synthetic leather was produced in the same manner as in the above [Method of measuring abrasion resistance]. Next, this synthetic leather was subjected to a bending test (-10°C, 100 times / min) using a flexometer (Yasuda Seiki Seisakusho Co., Ltd.'s "Flexiometer with low temperature bath") to measure the number of times the synthetic leather was bent until cracks appeared on the surface, and was evaluated as follows. "A": 60,000 times or more "B": 30,000 to less than 60,000 times "C": Less than 30,000 times

[0070] [Table 1]

[0071] [Table 2]

[0072] The abbreviations in Tables 1 and 2 are as follows. "C4": 1,4-butanediol derived from petroleum resources "C10": 1,10-decanediol derived from biomass "ISB": Biomass-derived isosorbide "C6": Hexanediol derived from petroleum resources "Mole ratio": mole ratio of glycol feedstock "Mn"; number average molecular weight

[0073] It was found that Examples 1 to 7, which are polyurethane resin compositions of the present invention, were excellent in abrasion resistance, oleic acid resistance, and low-temperature flexibility.

[0074] On the other hand, the comparative example 1 is In this embodiment, polycarbonate polyol (A-2) was not used, but the abrasion resistance was poor.

[0075] Comparative Example 2 is an embodiment in which the polycarbonate polyol (A-1) was not used, and the low-temperature flexibility was poor.

[0076] Comparative Example 3 is an embodiment in which a petroleum-based polycarbonate polyol was used instead of the polycarbonate polyols (A-1) and (A-2), but the abrasion resistance and oleic acid resistance were poor.

Claims

1. A polyurethane resin composition comprising a polyurethane resin (X) made from a polyol (A), a polyisocyanate (B), and a chain extender (C) having an amino group, and an organic solvent (Y), wherein the polyol (A) is A polyurethane resin composition comprising: a polycarbonate polyol (A-1) made from a biomass-derived decanediol; and a polycarbonate polyol (A-2) made from a biomass-derived dihydroxy compound having a cyclic ether structure.

2. The polyurethane resin composition according to claim 1, wherein the polycarbonate polyol (A-1) and the polycarbonate polyol (A-2) are further made from butanediol as a raw material.

3. The molar ratio [(C4) / (C10)] of the butanediol (C4) to the biomass-derived decanediol (C10) in the polycarbonate polyol (A-1) is in the range of 50 / 50 to 98 / 2. The polyurethane resin composition according to claim 2.

4. The polyurethane resin composition according to claim 2 or 3, wherein the molar ratio [(C4) / (ISB)] of the butanediol (C4) to the biomass-derived dihydroxy compound having a cyclic ether structure (ISB) in the polycarbonate polyol (A-2) is in the range of 30 / 70 to 90 / 10.

5. The polyurethane resin composition according to any one of claims 1 to 4, wherein the biomass-derived dihydroxy compound having a cyclic ether structure is biomass-derived isosorbide.

6. A coating formed from the polyurethane resin composition according to any one of claims 1 to 5.

7. 7. Synthetic leather comprising the coating according to claim 6.

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