CN109722918B - Polyurethane resin composition, coating film, and synthetic leather - Google Patents
Polyurethane resin composition, coating film, and synthetic leather Download PDFInfo
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- CN109722918B CN109722918B CN201811256346.2A CN201811256346A CN109722918B CN 109722918 B CN109722918 B CN 109722918B CN 201811256346 A CN201811256346 A CN 201811256346A CN 109722918 B CN109722918 B CN 109722918B
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Abstract
The present invention addresses the problem of providing a polyurethane resin composition having excellent oil resistance, low-temperature flexibility, and mechanical strength. The present invention provides a polyurethane resin composition containing a polyurethane resin containing a polyol (X), a chain extender (Y) having an amino group, and a polyisocyanate (Z) as essential raw materials, wherein the polyol (X) contains 1 to 50 mass% of a polycarbonate polyol (A) which is produced from a diol having 8 to 11 carbon atoms. In addition, the present invention provides: a coating film formed using the polyurethane resin composition; and a synthetic leather characterized by having the coating film. The polyurethane resin composition of the present invention can be suitably used as a material used for producing synthetic leather, clothing, a support pad, a polishing pad, and the like, and is particularly suitable as a material for synthetic leather.
Description
Technical Field
The present invention relates to a polyurethane resin composition.
Background
Polyurethane resins are widely used in various fields such as synthetic leathers and sheets for molding. In particular, when the resin composition is used for a member used for a long period of time such as synthetic leather for a vehicle interior material, higher durability is required.
The durability is evaluated in various items, including heat resistance, moist heat resistance, light resistance, chemical resistance, abrasion resistance, and the like, and particularly, in recent years, chemical resistance such as oil resistance, acid resistance, and sunscreen resistance is required for synthetic leather parts that frequently come into contact with the human body. As the material having excellent resistance to oil and acid, for example, a resin composition containing a polycarbonate-based urethane resin, a polyether-based urethane resin, and an acrylic resin is disclosed (for example, see patent document 1).
However, as a material for synthetic leather, not only the above oil and acid resistance, but also a level required for improving low-temperature bendability in consideration of use in cold regions is required, and further, excellent mechanical strength for obtaining excellent abrasion resistance is required. However, no material having these characteristics has been found.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2012 and 1693
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a polyurethane resin composition having excellent oil and acid resistance, low-temperature flexibility, and mechanical strength.
Means for solving the problems
The present invention provides a polyurethane resin composition containing a polyurethane resin containing a polyol (X), a chain extender (Y) having an amino group, and a polyisocyanate (Z) as essential raw materials, wherein the polyol (X) contains 1 to 50 mass% of a polycarbonate polyol (A) which is produced from a diol having 8 to 11 carbon atoms.
In addition, the present invention provides: a coating film formed using the polyurethane resin composition; and a synthetic leather characterized by having the coating film.
ADVANTAGEOUS EFFECTS OF INVENTION
The polyurethane resin composition of the present invention is excellent in resistance to oil acidity, low-temperature flexibility and mechanical strength.
Therefore, the polyurethane resin composition of the present invention can be suitably used as a material used for producing synthetic leather, clothing, a support pad, a polishing pad, and the like, and can be particularly suitably used as a material for synthetic leather.
Detailed Description
The polyurethane resin composition of the present invention contains a polyurethane resin containing a polyol (X), a chain extender (Y) having an amino group, and a polyisocyanate (Z) as essential raw materials, wherein the polyol (X) contains 1 to 50 mass% of a polycarbonate polyol (A) which is produced from a diol having 8 to 11 carbon atoms.
The polycarbonate polyol (a) is an essential component for obtaining excellent low-temperature flexibility. The amount of the polycarbonate polyol (A) used is necessarily 1 to 50% by mass based on the polyol (X). If the amount of the polycarbonate polyol (a) used is less than 1% by mass of the polyol (X), the required low-temperature flexibility cannot be obtained, and if it exceeds 50% by mass, the oil-resistant acid cannot be obtained although sufficient low-temperature flexibility can be obtained. The amount of the polycarbonate polyol (a) used is more preferably in the range of 3 to 40% by mass in the polyol (X) from the viewpoint of sufficiently obtaining more excellent low-temperature bending properties and oil and acid resistance.
Examples of the diol having 8 to 11 carbon atoms as a raw material of the polycarbonate polyol (a) include: diols having 8 to 9 carbon atoms such as 2, 4-dimethyl-1, 5-pentanediol, 2, 3-dimethyl-1, 5-pentanediol, 2-ethyl-1, 5-pentanediol, 2-methyl-1, 6-hexanediol, 3-methyl-1, 6-hexanediol, 1, 7-nonanediol, 2-ethyl-1, 6-hexanediol, 2-methyl-1, 7-nonanediol, 3-methyl-1, 7-nonanediol, 4-methyl-1, 7-nonanediol, 1, 8-octanediol, 2-methyl-1, 8-octanediol, and 1, 9-nonanediol; and diols having 10 to 11 carbon atoms such as 2-methyl-1, 8-octanediol, 3-methyl-1, 8-octanediol, 4-methyl-1, 8-octanediol, 1, 10-decanediol, 2-methyl-1, 10-decanediol, 3-methyl-1, 10-decanediol, 4-methyl-1, 10-decanediol, and 1, 11-undecanediol. These diols may be used alone, or 2 or more of them may be used in combination.
Among the above, from the viewpoint of obtaining more excellent oil resistance, low-temperature bending resistance and mechanical strength, it is preferable to use a diol having a straight chain structure and a diol having a branched structure in combination as the raw material of the polycarbonate polyol (a).
The molar ratio of the linear diol to the diol having a branched structure [ (C8-C11 linear)/(C8-C11 branched) ] is preferably in the range of 10/90 to 90/10, and more preferably in the range of 10/90 to 70/30, from the viewpoint of obtaining more excellent oil resistance, low-temperature flexibility and mechanical strength.
Specifically, the polycarbonate polyol (a) may be obtained by reacting the diol having 8 to 11 carbon atoms with a carbonate and/or phosgene by a known method. Further, the diol may be a diol having 2 to 7 carbon atoms in combination as necessary. The proportion of the diol having 8 to 11 carbon atoms is preferably 80% by mass or more, more preferably 90% by mass or more, of the total diols.
Examples of the carbonate include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate. These compounds may be used alone, or 2 or more of them may be used in combination.
The number average molecular weight of the polycarbonate polyol (a) is preferably in the range of 1500 to 3500 from the viewpoint of obtaining more excellent mechanical strength and low-temperature flexibility. The number average molecular weight of the polycarbonate polyol (a) is a value measured by a Gel Permeation Chromatography (GPC) method.
The polyol (X) contains the polycarbonate polyol (a) as an essential component, but may contain other polyols as necessary.
As the other polyols, for example, there can be used: polycarbonate polyols, polyether polyols, polyester polyols, polyacrylic polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, and the like other than the above (a). These polyols may be used alone, or 2 or more kinds may be used in combination. Among them, polycarbonate polyols other than the above (a) are preferably used from the viewpoint of obtaining more excellent resistance to oil and acid, low-temperature bending properties, and mechanical strength by using them in combination with the above (a).
The polycarbonate polyols other than the polycarbonate polyol (a) are not particularly limited as long as they have a carbonate structure, and for example, polycarbonate polyols obtained from diols having 4 to 6 carbon atoms such as propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, 3-methyl-1, 5-pentanediol, and neopentyl glycol are preferably used from the viewpoint of obtaining more excellent oil resistance, low-temperature bending properties, and mechanical strength. In the polycarbonate polyol, other diols may be used in combination as the diol component, but the proportion of the diol having 4 to 6 carbon atoms is preferably 80% by mass or more, more preferably 90% by mass or more of the diols.
The amount of the polycarbonate polyol other than (a) used is preferably in the range of 30 to 95% by mass, and more preferably in the range of 55 to 90% by mass in the polyol (X), from the viewpoint of obtaining more excellent resistance to oil acids, low-temperature bending properties, and mechanical strength.
The number average molecular weight of the other polyol is preferably in the range of 600 to 50000 from the viewpoint of obtaining good mechanical strength of the coating film, and in the case where a polycarbonate polyol other than the polyol (a) is used as the other polyol, the number average molecular weight is preferably in the range of 1500 to 3500 from the viewpoint of obtaining more excellent resistance to oil acidity, low-temperature bending properties and mechanical strength. The number average molecular weight of the other polyols is a value measured by a Gel Permeation Chromatography (GPC) method.
The chain extender (Y) having an amino group is an essential component from the viewpoint of obtaining excellent mechanical strength and oil and acid resistance.
The number average molecular weight of the chain extender (Y) having an amino group is 50 to 550, and for example, the following can be used: ethylenediamine, 1, 2-propylenediamine, 1, 6-hexamethylenediamine, piperazine, 2, 5-dimethylpiperazine, isophoronediamine, 1, 2-cyclohexanediamine, 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine, 4 ' -dicyclohexylmethanediamine, 3 ' -dimethyl-4, 4 ' -dicyclohexylmethanediamine, hydrazine, and the like. These chain extenders may be used alone, or 2 or more kinds may be used in combination. Among them, from the viewpoint of obtaining more excellent mechanical strength and oil and acid resistance, a chain extender having an alicyclic structure is preferably used.
The amount of the chain extender (Y) used is preferably in the range of 1 to 15 mass%, more preferably in the range of 3 to 10 mass% of the total mass of the polyol (X), the chain extender (Y) and the polyisocyanate (Z) from the viewpoint of obtaining excellent mechanical strength and oil and acid resistance.
As the polyisocyanate (Z), for example, there can be used: 1, 3-and 1, 4-phenylene diisocyanates, 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-4, 6-phenylene diisocyanate, 1, 4-dimethyl-2, 5-phenylene diisocyanate, diethylbenzene diisocyanate, and mixtures thereof, Diisopropylbenzene diisocyanate, 1-methyl-3, 5-diethylbenzene diisocyanate, 3-methyl-1, 5-diethylbenzene-2, 4-diisocyanate, 1,3, 5-triethylbenzene-2, 4-diisocyanate, naphthalene-1, 5-diisocyanate, 1-methyl-naphthalene-1, 5-diisocyanate, naphthalene-2, 6-diisocyanate, naphthalene-2, 7-diisocyanate, 1-dinaphthyl-2, 2 '-diisocyanate, biphenyl-2, 4' -diisocyanate, biphenyl-4, 4 '-diisocyanate, 3' -dimethylbiphenyl-4, aromatic polyisocyanates such as 4 ' -diisocyanate, 4 ' -diphenylmethane diisocyanate, 2 ' -diphenylmethane diisocyanate, and diphenylmethane-2, 4-diisocyanate; 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, aliphatic or alicyclic polyisocyanates such as 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4-dicyclohexylmethane diisocyanate, 2,4 '-dicyclohexylmethane diisocyanate, 2' -dicyclohexylmethane diisocyanate and 3,3 '-dimethyl-4, 4' -dicyclohexylmethane diisocyanate. These polyisocyanates may be used alone, or 2 or more kinds may be used in combination.
The polyisocyanate (Z) is preferably contained in an amount of 10 mass% or more, more preferably 10 to 50 mass%, and still more preferably 13 to 40 mass%, from the viewpoint of satisfying both excellent low-temperature flexibility and coatability of the polyurethane resin composition. In addition, it is preferable to use an aliphatic polyisocyanate and an alicyclic polyisocyanate in combination from the viewpoint of satisfying both of more excellent low-temperature flexibility and coatability of the polyurethane resin composition as the polyisocyanate (Z).
The amount of the polyisocyanate (Z) used is preferably in the range of 7 to 60 mass%, more preferably in the range of 10 to 45 mass% of the total mass of the polyol (X), the chain extender (Y) and the polyisocyanate (Z) from the viewpoint of obtaining excellent mechanical strength and reactivity.
Examples of the method for producing the polyurethane resin include: the method for producing the polyester resin composition is a method of collectively charging and reacting the polyol (X), the chain extender (Y) and the polyisocyanate (Z), and the reaction is preferably carried out at a temperature of 30 to 100 ℃ for 3 to 10 hours, for example. The reaction may be carried out in a solvent described later.
The molar ratio [ (isocyanate group)/(hydroxyl group and amino group) ] of the isocyanate group of the polyisocyanate (Z) to the hydroxyl group of the polyol (X) and the amino group of the chain extender (Y) is preferably in the range of 0.6 to 2, and more preferably in the range of 0.8 to 1.2.
The number average molecular weight of the polyurethane resin obtained by the above method is preferably 5000 to 1000000, more preferably 10000 to 500000, from the viewpoint of further improving the mechanical strength and flexibility of the coating film. The number average molecular weight of the polyurethane resin is a value measured by a Gel Permeation Chromatography (GPC) method.
The polyurethane resin composition contains the polyurethane resin as an essential component, but may contain other components as needed.
As the other components, for example, there can be used: solvents, pigments, flame retardants, plasticizers, softeners, stabilizers, waxes, antifoaming agents, dispersants, penetrants, surfactants, fillers, mildewcides, antibacterial agents, ultraviolet absorbers, antioxidants, weather-resistant stabilizers, fluorescent brighteners, anti-aging agents, thickeners, and the like. These components can be used alone, also can be used in combination of 2 or more.
As the solvent, for example, there can be used: ketone solvents such as water, N-dimethylformamide, 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, sec-butyl acetate, and the like; alcohol solvents such as methanol, ethanol, isopropanol, and butanol. These solvents may be used alone, or 2 or more of them may be used in combination.
The content of the solvent is preferably in the range of 30 to 90% by mass in the polyurethane resin composition from the viewpoint of workability and viscosity.
The polyurethane resin composition of the present invention is applied to a substrate and dried to obtain a coating film.
As the substrate, for example, a fibrous substrate including a nonwoven fabric, a woven fabric, a knitted fabric, and the like; resin films, and the like. As the substance constituting the fibrous base material, for example, there can be used: chemical fibers such as polyester fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, polylactic acid fibers, and the like; cotton, hemp, silk, wool, their blend fibers, and the like.
As the resin film, for example, there can be used: polyethylene terephthalate film, polycarbonate film, acrylic resin film, COP (cycloolefin polymer) film, TAC (triacetyl cellulose) film, and the like.
The surface of the base material may be subjected to antistatic treatment, mold release treatment, water repellent treatment, water absorbing treatment, antibacterial/deodorant treatment, bacteriostatic treatment, ultraviolet blocking treatment, or the like as required.
Examples of the method for applying the polyurethane resin composition of the present invention to the substrate include: a coating method using a coater, a bar coater, a blade coater, a T-die coater, a roll coater, or the like.
The method for drying the coated polyurethane resin composition includes, for example, a method of drying the composition at a temperature of 50 to 140 ℃ for 30 seconds to 10 minutes.
The thickness of the obtained coating is appropriately determined depending on the application, and is, for example, in the range of 0.001 to 10 mm.
When the film is used for a leather-like sheet, the 100% modulus obtained in a tensile test under a crosshead speed of 10 mm/sec is preferably 9MPa or more, and more preferably in the range of 11 to 20MPa, from the viewpoint of obtaining more excellent abrasion resistance. The method for measuring the 100% modulus value of the coating film is described in examples.
In the case of obtaining a synthetic leather using the above coating film, the coating film is preferably used as a skin layer or a top coat layer of the synthetic leather.
Examples of the method for producing the synthetic leather include: a method of bonding the surface-treated layer formed on the release paper and the coating film by a known method. Examples of the material for forming the surface-treated layer include solvent-based urethane resins, aqueous urethane resins, and aqueous acrylic resins. In addition, a known adhesive may be used for the bonding as needed.
As described above, the polyurethane resin composition of the present invention is excellent in resistance to oil acidity, low-temperature flexibility and mechanical strength. Therefore, the polyurethane resin composition of the present invention can be suitably used as a material used for producing synthetic leather, clothing, a support pad, a polishing pad, and the like, and can be particularly suitably used as a material for synthetic leather.
Examples
The present invention will be described in more detail below with reference to examples.
[ example 1]
10 parts by mass of a polycarbonate diol (starting from 1, 9-nonanediol (C9 straight chain) and 2-methyl-1, 8-octanediol (C9 branched chain) in a nitrogen-substituted 4-neck flask equipped with a stirrer, a reflux condenser and a thermometer, [ C9 straight chain/C9 branched chain ] (hereinafter referred to as a molar ratio): 65/35, number average molecular weight: 2000, hereinafter referred to simply as "PC 1"), polycarbonate diol (obtained by using 1, 4-butanediol (C4) and 1, 6-hexanediol (C6) as raw materials, [ C4/C6] (hereinafter, referred to as a molar ratio): 90/10, number average molecular weight: 2000, hereinafter, referred to simply as "other PC 1") 180 parts by mass, and polytetramethylene glycol (number average molecular weight: 2000, hereinafter, referred to simply as "PTMG") 10 parts by mass were dehydrated at 120 to 130 ℃ under a reduced pressure of 0.095 MPa. After dehydration, 130 parts by mass of N, N-dimethylformamide (hereinafter abbreviated as "DMF") was added thereto while cooling to 50 ℃ and sufficiently stirred. After stirring, 33 parts by mass of 4, 4' -dicyclohexylmethane diisocyanate (hereinafter abbreviated as "H12 MDI"), 9 parts by mass of hexamethylene diisocyanate (hereinafter abbreviated as "HDI") and 0.1 part by mass of stannous octoate were added and reacted at 75 ℃. Next, 328 parts by mass of DMF and 153 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, and then, the mixture was cooled to 35 ℃, and 12 parts by mass of isophorone diamine (hereinafter abbreviated as "IPDA") was added thereto and stirred and mixed, thereby stretching the polyurethane resin. Next, 1 part by mass of N, N-dibutylamine and 153 parts by mass of isopropyl alcohol were added and mixed to obtain a polyurethane resin composition.
[ example 2]
A4-neck flask substituted with nitrogen and equipped with a stirrer, a reflux condenser and a thermometer was charged with 39 parts by mass of polycarbonate diol (1, 9-nonanediol (C9 straight chain) and 2-methyl-1, 8-octanediol (C9 branched chain) as raw materials, [ C9 straight chain/C9 branched chain ] (hereinafter referred to as a molar ratio): 15/85, number average molecular weight: 2000, hereinafter referred to simply as "PC 2"), and the other parts by mass of PC 1156, and dehydrated at 120 to 130 ℃ under a reduced pressure of 0.095 MPa. After dehydration, 128 parts by mass of DMF was added while cooling to 50 ℃, and sufficiently stirred. After stirring, 37 parts by mass of H12MDI, 6 parts by mass of HDI, and 0.1 part by mass of stannous octoate were added and reacted at 75 ℃. Next, 324 parts by mass of DMF and 151 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, cooled to 35 ℃, and 12 parts by mass of IPDA was added and stirred and mixed to elongate the polyurethane resin. Next, 1 part by mass of N, N-dibutylamine and 151 parts by mass of isopropyl alcohol were added and mixed to obtain a polyurethane resin composition.
[ example 3]
A4-neck flask with a stirrer, a reflux condenser and a thermometer and replaced by nitrogen was charged with 2167 parts by mass of PC and 1124 parts by mass of other PC, and dehydrated at 120 to 130 ℃ under a reduced pressure of 0.095 MPa. After dehydration, while cooling to 50 ℃, 124 parts by mass of DMF was added and sufficiently stirred. After stirring, 34 parts by mass of isophorone diisocyanate (hereinafter abbreviated as "IPDI"), 6 parts by mass of HDI, and 0.1 part by mass of stannous octoate were added and reacted at 75 ℃. Next, 325 parts by mass of DMF and 150 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, and the mixture was cooled to 35 ℃, and 18 parts by mass of 4, 4' -dicyclohexylmethanediamine (hereinafter abbreviated as "H12 MDA") was added thereto and stirred and mixed to elongate the urethane resin. Next, 1 part by mass of N, N-dibutylamine and 150 parts by mass of isopropyl alcohol were added and mixed to obtain a polyurethane resin composition.
[ example 4]
In a nitrogen-substituted 4-neck flask equipped with a stirrer, a reflux condenser and a thermometer, 170 parts by mass of PC (1, 6-hexanediol (C6) (100 [ [ C6] ], number average molecular weight: 2000, hereinafter abbreviated as "other PC 2") was charged, and dehydration was carried out at 120 to 130 ℃ under a reduced pressure of 0.095 MPa. After dehydration, DMF 131 parts by mass was added while cooling to 50 ℃ and sufficiently stirred. After stirring, 32 parts by mass of H12MDI, 13 parts by mass of HDI, and 0.1 part by mass of stannous octoate were added and reacted at 75 ℃. Next, 331 parts by mass of DMF and 154 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, and then the mixture was cooled to 35 ℃, 13 parts by mass of IPDA was added thereto and stirred and mixed to elongate the polyurethane resin. Next, 1 part by mass of N, N-dibutylamine and 154 parts by mass of isopropyl alcohol were added and mixed to obtain a polyurethane resin composition.
[ example 5]
A4-neck flask with a stirrer, a reflux condenser and a thermometer and purged with nitrogen was charged with 129 parts by mass of PC and 164 parts by mass of polycarbonate diol [ C4/C6] (hereinafter referred to as a molar ratio) 70/30, number average molecular weight: 2000 and hereinafter referred to simply as "other PC 3], as raw materials [ 1, 4-butanediol (C4) and 1, 6-hexanediol (C6) ], and dehydrated at 120 to 130 ℃ under a reduced pressure of 0.095 MPa. After dehydration, 125 parts by mass of DMF was added while cooling to 50 ℃ and sufficiently stirred. After stirring, 30 parts by mass of IPDI, 10 parts by mass of HDI, and 0.1 part by mass of stannous octoate were added and reacted at 75 ℃. Next, 330 parts by mass of DMF and 152 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, and then cooled to 35 ℃, 19 parts by mass of H12MDA was added thereto, and the mixture was stirred and mixed to elongate the urethane resin. Next, 1 part by mass of N, N-dibutylamine and 152 parts by mass of isopropyl alcohol were added and mixed to obtain a polyurethane resin composition.
[ example 6]
228 parts by mass of PC and 3159 parts by mass of another PC were charged into a nitrogen-substituted 4-neck flask equipped with a stirrer, a reflux condenser and a thermometer, and dehydration was carried out at 120 to 130 ℃ under a reduced pressure of 0.095 MPa. After dehydration, 122 parts by mass of DMF was added while cooling to 50 ℃, and sufficiently stirred. After stirring, 31 parts by mass of IPDI, 8 parts by mass of HDI, and 0.1 part by mass of stannous octoate were added and reacted at 75 ℃. Next, 320 parts by mass of DMF and 147 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, and then the mixture was cooled to 35 ℃, 18 parts by mass of H12MDA was added thereto, and the mixture was stirred and mixed to elongate the polyurethane resin. Next, 1 part by mass of N, N-dibutylamine and 147 parts by mass of isopropyl alcohol were added and mixed to obtain a polyurethane resin composition.
Comparative example 1
A4-neck flask with a stirrer, a reflux condenser and a thermometer and replaced by nitrogen was charged with 1118 parts by mass of PC and 378 parts by mass of another PC, and dehydrated at 120 to 130 ℃ under a reduced pressure of 0.095 MPa. After dehydration, while cooling to 50 ℃, 127 parts by mass of DMF was added and sufficiently stirred. After stirring, 31 parts by mass of IPDI, 8 parts by mass of HDI, and 0.1 part by mass of stannous octoate were added and reacted at 75 ℃. Next, DMF 329 parts by mass and ethyl acetate 152 parts by mass were added to the organic solvent solution of the urethane prepolymer, and cooled to 35 ℃, H12MDA 17 parts by mass was added thereto, and stirred and mixed, thereby elongating the polyurethane resin. Next, 1 part by mass of N, N-dibutylamine and 152 parts by mass of isopropyl alcohol were added and mixed to obtain a polyurethane resin composition.
Comparative example 2
In a 4-neck flask substituted with nitrogen gas and equipped with a stirrer, a reflux condenser and a thermometer, 2 parts by mass of other PC was charged, and dehydration was carried out at 120 to 130 ℃ under a reduced pressure of 0.095 MPa. After dehydration, while cooling to 50 ℃, 127 parts by mass of DMF was added and sufficiently stirred. After stirring, 40 parts by mass of H12MDI, 6 parts by mass of HDI, and 0.1 part by mass of stannous octoate were added and reacted at 75 ℃. Next, 325 parts by mass of DMF and 151 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, cooled to 35 ℃, 14 parts by mass of IPDA was added, and stirred and mixed to elongate the polyurethane resin. Next, 1 part by mass of N, N-dibutylamine and 151 parts by mass of isopropyl alcohol were added and mixed to obtain a polyurethane resin composition.
Comparative example 3
A polyurethane resin composition was obtained in the same manner as in example 1, except that IPDA was not used.
[ method for measuring number average molecular weight ]
The number average molecular weight of the polyol and the like used in examples and comparative examples represents a value measured by a Gel Permeation Chromatography (GPC) method under the following conditions.
Measurement device: high-speed GPC apparatus (HLC-8220 GPC, manufactured by Tosoh corporation)
Column: the following columns manufactured by Tosoh corporation were connected in series and used.
"TSKgel G5000" (7.8 mmI.D.. times.30 cm). times.1 roots
"TSKgel G4000" (7.8mm I.D.. times.30 cm). times.1 roots
"TSKgel G3000" (7.8 mmI.D.. times.30 cm). times.1 roots
"TSKgel G2000" (7.8 mmI.D.. times.30 cm). times.1 roots
A detector: RI (differential refractometer)
Column temperature: 40 deg.C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Injection amount: 100 μ L (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: the calibration curve was prepared using the following standard polystyrene.
(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 "
[ method for measuring mechanical Strength ]
A coating film was produced by applying a solution prepared by mixing 40 parts by mass of DMF with 100 parts by mass of the polyurethane resin compositions obtained in examples and comparative examples to a flat release paper (manufactured by Lintec corporation, "EK-100D") so that the film thickness after drying was 30 μm, drying at 90 ℃ for 2 minutes, and further drying at 120 ℃ for 2 minutes. The obtained coating film was cut into a short strip having a width of 5mm and a length of 50mm, and the strip was stretched at a crosshead speed of 10 mm/sec in an atmosphere at a temperature of 23 ℃ by using a tensile tester "AUTOGRAPH AG-I" (manufactured by Shimadzu corporation), and the 100% modulus (MPa) of the test piece was measured. The distance between the chucks at this time was set to 40 mm. From the obtained 100% modulus value, the mechanical strength was evaluated as follows.
"A": 5MPa or more
"B": less than 5MPa
[ measurement method of oil resistance and acidity ]
A coating was produced in the same manner as in the above-described [ method for measuring mechanical strength ]. Then, the film was cut into a short strip having a width of 5mm and a length of 50mm to prepare a test piece, which was immersed in oleic acid at room temperature for 24 hours and then taken out, and the oleic acid adhering to the surface was gently wiped off with a paper wipe. Then, the test piece was stretched at a crosshead speed of 10 mm/sec and a chuck-to-chuck distance of 40mm in an atmosphere at a temperature of 23 ℃ by using a tensile tester "AUTOGRAPH AG-I" (manufactured by Shimadzu corporation), and the stress at which the test piece was stretched by 100% was measured. The oil resistance was evaluated as follows, taking the value obtained by dividing the stress by the 100% modulus value measured in the above [ method for measuring mechanical strength ] as the retention ratio of the 100% modulus value.
"A": the retention rate is 40% or more
"B": the retention rate is more than 30 percent and less than 40 percent
"C": the retention rate is less than 30 percent
[ method of measuring Low-temperature flexibility ]
A coating film was formed on a release paper by applying a mixture of 100 parts by mass of the polyurethane resin compositions obtained in examples and comparative examples, 40 parts by mass of DMF, 30 parts by mass of methyl ethyl ketone, and 20 parts by mass of a colorant "ダイラック L-1770S" manufactured by DIC corporation, to a release paper so that the film thickness after drying became 30 μm, drying at 90 ℃ for 2 minutes, and further drying at 120 ℃ for 2 minutes. Then, a mixture of 100 parts by mass of polyurethane resin "CRISPON TA-205 FT" manufactured by DIC and 60 parts by mass of DMF, 12 parts by mass of polyisocyanate crosslinking agent "Burnock DN-950" manufactured by DIC and 1 part by mass of tin catalyst "Accel T-81E" manufactured by DIC was applied to the film so that the film thickness after drying became 60 μm, and the film was dried at 100 ℃ for 1 minute. Then, the polyester base fabric was placed on the base fabric, and the base fabric was pressure-bonded using a 120 ℃ laminator, then cured at 40 ℃ for 3 days, and the release paper was peeled off to obtain a synthetic leather.
The synthetic leather was subjected to a bending test (30 ℃ C., 100 cycles/min) using a deflectometer (manufactured by ANTIAN Seisaku-Sho K.K.; "deflectometer with a cold trap"), and the number of times until the surface of the synthetic leather was broken was measured, and evaluated as follows.
"A": more than 20000 times
"B": 10000 times or more and less than 20000 times
"C": less than 10000 times
[ Table 1]
[ Table 2]
The abbreviations in tables 1 to 2 are explained.
"Mn": number average molecular weight
"NCO": polyisocyanates
Therefore, the following steps are carried out: the polyurethane resin compositions of examples 1 to 6 of the present invention are excellent in resistance to oil acidity, low-temperature flexibility and mechanical strength. In particular, although the low-temperature flexibility is a very severe test at-30 ℃, the synthetic leather having a coating film of the polyurethane resin composition of the present invention is not apt to be cracked.
On the other hand, in comparative example 1, the polycarbonate polyol (a) was used in an amount outside the range defined in the present invention, and the mechanical strength and the oil and acid resistance were poor.
In comparative example 2, the polycarbonate polyol (a) was not used, and the resistance to oil acidity and low-temperature bending was insufficient.
In comparative example 3, the chain extender (Y) having an amino group was not used, and the mechanical strength and the oil resistance and the acid resistance were poor.
Claims (4)
1. A polyurethane resin composition comprising a polyurethane resin essentially containing a polyol (X) containing 1 to 50 mass% of a polycarbonate polyol (A) produced from a diol having 8 to 11 carbon atoms, a chain extender (Y) having an amino group, and a polyisocyanate (Z), wherein,
the diol in the polycarbonate polyol (A) includes a linear diol and a diol having a branched structure,
the molar ratio of the linear diol to the diol having a branched structure, i.e., (C8-C11 linear)/(C8-C11 branched) is in the range of 10/90 to 90/10,
the polyol (X) further contains a polycarbonate polyol (B) which is produced from a diol having 4 to 6 carbon atoms,
the polyisocyanate (Z) contains 10% by mass or more of an aliphatic polyisocyanate.
2. The polyurethane resin composition according to claim 1, wherein the polycarbonate polyol (A) has a number average molecular weight in the range of 1500 to 3500.
3. A coating film formed by using the polyurethane resin composition according to claim 1 or 2.
4. A synthetic leather characterized by having the coating film according to claim 3.
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| WO2021084955A1 (en) * | 2019-10-28 | 2021-05-06 | Dic株式会社 | Urethane resin composition, adhesive, and synthetic leather |
| WO2022097333A1 (en) * | 2020-11-05 | 2022-05-12 | Dic株式会社 | Laminate and synthetic leather |
| WO2022097332A1 (en) * | 2020-11-05 | 2022-05-12 | Dic株式会社 | Laminate and synthetic leather |
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