JP6528915B1 - Urethane resin composition, film, and synthetic leather - Google Patents

Abstract

The problem to be solved by the present invention is to provide a urethane resin composition excellent in oleic acid resistance, low temperature flexibility, and mechanical strength. The present invention provides a polycarbonate polyol (A) using butanediol and hexanediol as raw materials, a monocyclic aliphatic glycol (b-1), a glycol having a spiro ring (b-2), and an aromatic glycol (b-) 3) A polyol (X) containing at least one glycol compound (B) selected from the group consisting of 3), and a urethane resin (Z) containing polyisocyanate (Y) as an essential raw material It is intended to provide a urethane resin composition. Another object of the present invention is to provide a film formed of the above urethane resin composition, and a synthetic leather characterized by having the film.

Description

  The present invention relates to a urethane resin composition.

  Urethane resin is widely used in various fields such as synthetic leather and sheets for molding processing. However, higher durability is required particularly when used for long-term members such as synthetic leather for vehicle interior materials.

  The above-mentioned evaluation items of durability are various and include heat resistance, moist heat resistance, light resistance, chemical resistance, abrasion resistance and the like, and in particular, in recent years, synthetic leather members frequently in contact with the human body. Are required to have chemical resistance such as oleic acid resistance and sun oil resistance. As a material excellent in oleic acid resistance and the like, for example, a resin composition comprising a polycarbonate-based polyurethane resin, a polyether-based polyurethane resin, and an acrylic resin is disclosed (see, for example, Patent Document 1).

  However, as a material for synthetic leather, not only the above-mentioned oleic acid resistance, etc., but also the demand level of flexibility at low temperature is increased assuming use in cold regions, and furthermore, excellent abrasion resistance is obtained The excellent mechanical strength of is also needed. However, no material has yet been found that combines all of these properties.

JP, 2012-1693, A

  The problem to be solved by the present invention is to provide a urethane resin composition excellent in oleic acid resistance, low temperature flexibility, and mechanical strength.

  The present invention provides a polycarbonate polyol (A) using butanediol and hexanediol as raw materials, a monocyclic aliphatic glycol (b-1), a glycol having a spiro ring (b-2), and an aromatic glycol (b-) 3) A polyol (X) containing at least one glycol compound (B) selected from the group consisting of 3), and a urethane resin (Z) containing polyisocyanate (Y) as an essential raw material It is intended to provide a urethane resin composition.

  Another object of the present invention is to provide a film formed of the above urethane resin composition, and a synthetic leather characterized by having the film.

  The urethane resin composition of the present invention is excellent in oleic acid resistance, low temperature flexibility, and mechanical strength.

  Therefore, the urethane resin composition of the present invention can be suitably used as a material used for producing synthetic leather, clothing, support pads, polishing pads and the like, and particularly preferably used as a material of synthetic leather it can.

  The urethane resin composition of the present invention comprises a polycarbonate polyol (A) having butanediol and hexanediol as raw materials, a monocyclic aliphatic glycol (b-1), a glycol having a spiro ring (b-2), and an aroma A polyol (X) containing at least one glycol compound (B) selected from the group consisting of group glycols (b-3), and a urethane resin (Z) containing polyisocyanate (Y) as an essential raw material It is a thing.

  In order to obtain very excellent mechanical strength while maintaining excellent oleic acid resistance and low temperature flexibility, the polycarbonate polyol (A) is essential to use butanediol and hexanediol as raw materials.

  As the butanediol, for example, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol and the like can be used. These butanediols may be used alone or in combination of two or more. Among these, it is preferable to use 1,4-butanediol from the viewpoint of obtaining further excellent mechanical strength.

  Examples of the hexanediol include 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, and 2,3-hexanediol. 2,4-hexanediol, 3,4-hexanediol, etc. can be used. These hexanediols may be used alone or in combination of two or more. Among these, it is preferable to use 1,6-hexanediol from the viewpoint that much higher mechanical strength is obtained.

  The molar ratio [C4 / C6] of the butanediol (C4) and the hexanediol diol (C6) is in the range of 60/40 to 95/5 from the viewpoint of obtaining even more excellent mechanical strength. It is preferably in the range of 65/35 to 93/7.

  As the polycarbonate diol (A), specifically, one obtained by reacting the butanediol and hexanediol with a carbonate and / or phosgene according to a known method can be used.

  As said carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate etc. can be used, for example. These compounds may be used alone or in combination of two or more.

  The number average molecular weight of the polycarbonate diol (A) is preferably in the range of 1,500 to 3,500, from the viewpoint of obtaining even more excellent mechanical strength. The number average molecular weight of the polycarbonate polyol (A) is a value measured by gel permeation chromatography (GPC).

  The amount of the polycarbonate polyol (A) used is preferably 30% by mass or more in the polyol (X), from the viewpoint of obtaining even more excellent oleic acid resistance, low temperature flexibility and mechanical strength. The range of -99 mass% is more preferable, and the range of 50-95 mass% is further preferable.

  The polyol (X) used in the present invention is selected from the group consisting of a monocyclic aliphatic glycol (b-1), a glycol having a spiro ring (b-2), and an aromatic glycol (b-3) It is essential to use a glycol compound (B) of a kind or more. By using this specific glycol compound (B) in combination with the polycarbonate polyol (B), it is possible to achieve excellent compatibility between oleic acid resistance, low temperature flexibility and mechanical strength which are in a trade-off relationship.

  As the monocyclic aliphatic glycol (b-1), for example, cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, and alkylene oxide adducts of these, etc. can be used. These glycols may be used alone or in combination of two or more. Among these, cyclohexane dimethanol, hydrogenated bisphenol A, and an alkylene oxide adduct of hydrogenated bisphenol A are selected from the viewpoint that oleic acid resistance, low temperature flexibility and mechanical strength can be further improved. Preferably, one or more glycols are used.

  As the glycol (b-2) having a spiro ring, for example, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] Undecane, 3,9-bis (2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (1-methyl-2-hydroxyethyl) -2, 4,8,10-Tetraoxaspiro [5,5] undecane, 3,9-bis (1-ethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (1-ethyl-1-methyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (2-hydroxyethyl-2) -Methyl) -2,4,8, 0-tetraoxaspiro [5,5] undecane, 3,9-bis (1-methyl-2-hydroxy-2-methylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (1-ethyl-2-hydroxy-2-methylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (1,1-dimethyl-) 2-hydroxy-2-methylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (1-ethyl-1-methyl-2-hydroxy-2-methylethyl) ) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (2-hydroxypropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, etc. Can be used. These glycols may be used alone or in combination of two or more. Among these, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8, from the viewpoint that oleic acid resistance, low temperature flexibility and mechanical strength can be further improved. It is preferred to use 10-tetraoxaspiro [5,5] undecane.

  As the aromatic glycol, for example, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydroquinone, and alkylene oxide adducts thereof may be used. it can. These glycols may be used alone or in combination of two or more.

  The content of the glycol compound (B) is preferably less than 10% by mass in the polyol (X) from the viewpoint of obtaining even more excellent oleic acid resistance, low temperature flexibility and mechanical strength. The range of -9% by mass is more preferable, and the range of 2 to 7% by mass is more preferable.

  Although the said polyol (X) contains the said polycarbonate polyol (A) and the said glycol compound (B) as an essential component, you may further contain other polyols as needed.

  As said other polyol, polycarbonate polyol other than said (A), polyether polyol, polyester polyol, polyacryl polyol, a polybutadiene polyol, a hydrogenated polybutadiene polyol etc. can be used, for example. These polyols may be used alone or in combination of two or more. Among them, polycarbonate polyols other than the above (A) can be used from the viewpoint that even more excellent oleic acid resistance, low temperature flexibility and mechanical strength can be obtained by using in combination with the polycarbonate polyol (A). preferable.

  The polycarbonate polyols other than the above (A) are not particularly limited as long as they have a carbonate structure, but, for example, propanediol, butanediol, pentanediol, hexanediol, decanediol, caprolactone, cyclohexanedimethanol, 3-methyl-1 A polycarbonate polyol etc. which use 5-pentanediol, neopentyl glycol, isosorbide etc. as a raw material can be used. These raw materials may be used singly as a raw material having a hydroxyl group or in combination of two or more.

  The amount used when using polycarbonate polyols other than the above (A) is less than 40% by mass in the polyol (X) from the viewpoint of obtaining more excellent oleic acid resistance, low temperature flexibility and mechanical strength. The range of 1 to 35% by mass is more preferable, and the range of 3 to 33% by mass is further preferable.

  If necessary, other chain extenders (having a number average molecular weight of 40 to 550) may be used in combination with the polyol (X).

  Examples of the other chain extender include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and trimethylolpropane. , A chain extender having a hydroxyl group such as glycerol; ethylene diamine, 1,2-propane diamine, 1,6-hexamethylene diamine, piperazine, 2-methyl piperazine, 2,5-dimethyl piperazine, isophorone diamine, 4,4'- Dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethyl ethanolamine, hydrazine, diethylene oxide Amines, can be used a chain extender having an amino group such as triethylene tetramine. 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, from the viewpoint of easily suppressing the discoloration of the film over time.

  The amount of use of the other chain extender is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the polyol (X) from the viewpoint of easily suppressing the successive color change of the film. The range of 3 to 20 parts by mass is more preferable.

  As polyisocyanate (Y), for example, 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-diethylbenzene 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, diphenylmethane Aromatic polyisocyanates such as 2,4-diisocyanate; tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopentylene Isocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-di (isocyanatomethyl) cyclohexane, 1,4-di (isocyanatemethyl) cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4- Dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate And aliphatic or alicyclic polyisocyanates such as 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, aliphatic and / or alicyclic polyisocyanates are preferably used from the viewpoint of obtaining further excellent durability and improving light resistance, oleic acid resistance, and low temperature flexibility. It is preferable to use an aliphatic polyisocyanate and a cycloaliphatic polyisocyanate in combination.

  As mass ratio [aliphatic NCO / alicyclic NCO] in the case of using the aliphatic polyisocyanate and the alicyclic polyisocyanate in combination, further excellent oleic acid resistance and low temperature flexibility are obtained, The mass ratio [aliphatic NCO / alicyclic NCO] is preferably in the range of 5/95 to 60/40, more preferably in the range of 10/90 to 50/50, and 15/85 to 45/50. A range of 55 is more preferred.

  The amount of the polyisocyanate (Y) used is in the range of 10 to 60% by mass in the total mass of the polyol (X) and the polyisocyanate (Y), from the viewpoint of obtaining excellent mechanical strength and reactivity. Is preferable, and the range of 15 to 45% by mass is more preferable.

  Examples of the method for producing the urethane resin (Z) include a method in which the polyol (X) and the polyisocyanate (Y) are charged at one time and reacted, and the reaction is carried out, for example, It is preferable to carry out at a temperature of 100 ° C. for 3 to 10 hours. Also, the reaction may be carried out in a solvent described later.

  The molar ratio [(isocyanate group) / (hydroxy group and amino group)] between the hydroxyl group of the polyol (X) and the isocyanate group of the polyisocyanate (Y) is in the range of 0.6 to 2 Preferably, it is more preferably in the range of 0.8 to 1.2.

  The number average molecular weight of the urethane resin (Z) obtained by the above method is preferably in the range of 5,000 to 1,000,000 in that the mechanical strength and flexibility of the film can be further improved. The range of 10,000 to 500,000 is more preferable. In addition, the number average molecular weight of the said urethane resin (Z) shows the value measured by gel permeation chromatography (GPC) method.

  Although the said urethane resin composition contains the said urethane resin (Z) as an essential component, you may contain another component as needed.

  Examples of the other components include solvents, pigments, flame retardants, plasticizers, softeners, stabilizers, waxes, antifoaming agents, dispersants, penetrants, surfactants, fillers, mildewproofing agents, antibacterial agents, A UV absorber, an antioxidant, a weathering stabilizer, a fluorescent whitening agent, an antiaging agent, a thickener and the like can be used. These components may be used alone or in combination of two or more.

  Examples of the solvent include ketone solvents such as water, 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, ethyl acetate, isopropyl acetate, isobutyl acetate, isobutyl acetate and sec-butyl acetate; alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol can be used . These solvents may be used alone or in combination of two or more.

  The content of the solvent is preferably in the range of 30 to 90% by mass in the urethane resin composition from the viewpoint of workability and viscosity.

  The urethane resin composition of the present invention is coated on a substrate and dried to obtain a film.

  As said base material, the fibrous base material which consists of a nonwoven fabric, woven fabric, knitting etc., resin film etc. can be used, for example. Examples of the fibrous base material include chemical fibers such as polyester fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, etc .; cotton, hemp, silk, wool, etc. Blended fibers can be used.

  As the resin film, for example, a polyethylene terephthalate film, a polycarbonate film, an acrylic resin film, a COP (cycloolefin polymer) film, a TAC (triacetyl cellulose) film or the like can be used.

  The surface of the substrate may be subjected to treatments such as antistatic treatment, mold release treatment, water repellent treatment, water absorption treatment, antibacterial deodorizing treatment, antibacterial treatment, ultraviolet blocking treatment, etc., as necessary. .

  As a method of apply | coating the urethane resin composition of this invention to the said base material, the application method by an applicator, a bar coater, a knife coater, a T-die coater, a roll coater etc. is mentioned, for example.

  As a method of drying the applied urethane resin composition, for example, a method of drying at a temperature of 50 to 140 ° C. for 30 seconds to 10 minutes can be mentioned.

  The thickness of the obtained film is appropriately determined in accordance with the application to be used, 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 by the tensile test at a crosshead speed of 10 mm / sec is 9 MPa, from the viewpoint that even better abrasion resistance can be obtained. It is preferable that it is more than, and the range of 11-20 Mpa is more preferable. In addition, the measuring method of the said 100% modulus value of the said film is described in the Example.

  In order to obtain a synthetic leather using the film, it is preferable to use the film as the skin layer or top coat layer of the synthetic leather.

  Examples of the method for producing the synthetic leather include a method of bonding the surface treatment layer formed on a release paper and the film by a known method. As a material which forms the said surface treatment layer, solvent-type urethane resin, water-based urethane resin, water-based acrylic resin etc. can be used, for example. Moreover, you may use a well-known adhesive agent for the said bonding as needed.

  As described above, the urethane resin composition of the present invention is excellent in oleic acid resistance, low temperature flexibility, and mechanical strength. Therefore, the urethane resin composition of the present invention can be suitably used as a material used for producing synthetic leather, clothing, support pads, polishing pads and the like, and particularly preferably used as a material of synthetic leather it can.

  Hereinafter, the present invention will be described in more detail by way of examples.

Example 1
A polycarbonate diol (having 1,4-butanediol and 1,6-hexanediol as a raw material, [C4 / C6] (hereinafter, referred to as “C4 / C6”), was added to a nitrogen-substituted four-necked flask having a stirrer, a reflux condenser and a thermometer. Molar ratio: 70/30, number average molecular weight; 2,000, hereinafter abbreviated as "PC1") 117 parts by mass, polycarbonate diol (having 1,6-hexanediol as a raw material, [C6] = 100 Number average molecular weight; 2,000 (hereinafter abbreviated as "other PC 1") 14 parts by mass) was added, and dehydration was performed at 120 to 130 ° C at a degree of reduced pressure of 0.095 MPa. After dehydration, while cooling to 50 ° C., 101 parts by mass of N, N-dimethylformamide (hereinafter abbreviated as “DMF”) and 7 parts by mass of hydrogenated bisphenol A (hereinafter abbreviated as “HBPA”) Was thoroughly stirred. After stirring, 33 parts by mass of isophorone diisocyanate (hereinafter abbreviated as "IPDI"), 17 parts by mass of hexamethylene diisocyanate (hereinafter abbreviated as "HDI") and 0.1 parts by mass of stannous octoate are added. The reaction was conducted at 75 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular terminal. Subsequently, 243 parts by mass of DMF and 110 parts by mass of ethyl acetate are added to the organic solvent solution of the urethane prepolymer, cooled to 35 ° C., and 21 parts by mass of isophorone diamine (hereinafter abbreviated as “IPDA”) is added. The polyurethane resin was elongated by stirring and mixing. Then, a urethane resin composition was obtained by adding 0.3 parts by mass of N, N-dibutylamine and 110 parts by mass of isopropyl alcohol and mixing.

Example 2
117 parts by mass of PC1 and 8 parts by mass of other PC1 were added to a nitrogen-substituted four-necked flask having a stirrer, a reflux condenser and a thermometer, and dehydration was performed at 120 to 130 ° C. under a reduced pressure of 0.095 MPa. . After dehydration, 97 parts by mass of DMF and 5 parts by mass of cyclohexanedimethanol (hereinafter abbreviated as “CHDM”) were added while cooling to 50 ° C., and the mixture was sufficiently stirred. After stirring, 38 parts by mass of IPDI, 12 parts by mass of HDI, and 0.1 parts by mass of stannous octoate are added, and reacted at 75 ° C. to obtain an organic urethane prepolymer having an isocyanate group at its molecular end A solvent solution was obtained. Next, 199 parts by mass of DMF and 89 parts by mass of ethyl acetate are added to the organic solvent solution of the urethane prepolymer, cooled to 35 ° C., and abbreviated as 4,4′-dicyclohexylmethanediamine (hereinafter, “H12 MDA”). 21) The polyurethane resin was elongated by adding 21 parts by mass and stirring and mixing. Next, a urethane resin composition was obtained by adding and mixing 0.8 parts by mass of N, N-dibutylamine and 89 parts by mass of isopropyl alcohol.

[Example 3]
A polycarbonate diol (having 1,4-butanediol and 1,6-hexanediol as a raw material, [C4 / C6] = 90 /) in a nitrogen-substituted four-necked flask having a stirrer, a reflux condenser and a thermometer 10, number average molecular weight; 2,000, hereinafter abbreviated as "PC2") 117 parts by mass, 21 parts by mass of another PC 1 were added, and dehydration was performed at 120 to 130 ° C under a reduced pressure of 0.095 MPa. After dehydration, 101 parts by mass of DMF and 7 parts by mass of ethylene oxide 1 mol adduct of hydrogenated bisphenol A (hereinafter abbreviated as “POEBA”) were added while cooling to 50 ° C., and the mixture was sufficiently stirred. After stirring, 30 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (hereinafter abbreviated as "H12MDI"), 19 parts by mass of HDI and 0.1 parts by mass of stannous octoate are added, and the mixture is stirred at 75.degree. By making it react, the organic solvent solution of the urethane prepolymer which has an isocyanate group at the molecular terminal was obtained. Subsequently, 225 parts by mass of DMF and 89 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, cooled to 35 ° C., 18 parts by mass of IPDA were added, and the polyurethane resin was elongated by stirring and mixing. . Next, a urethane resin composition was obtained by adding 0.6 parts by mass of N, N-dibutylamine and 102 parts by mass of isopropyl alcohol and mixing.

Example 4
Into a nitrogen-substituted four-necked flask having a stirrer, a reflux condenser and a thermometer, 91 parts by mass of PC2 (using 1,3-propanediol and 1,4-butanediol as a raw material, [C3 / C4] = 50/50, number average molecular weight; 2,000, hereinafter 42 parts by mass of "other PC2" are added, and dehydration is performed at 120 to 130 ° C under a reduced pressure of 0.095 MPa. After dehydration, 100 parts by mass of DMF and 7 parts by mass of spiroglycol (Mitsubishi Gas Chemical Co., Ltd., hereinafter abbreviated as “SPG”) were added while cooling to 50 ° C., and the mixture was sufficiently stirred. After stirring, 32 parts by mass of IPDI, 13 parts by mass of HDI and 0.1 parts by mass of stannous octoate are added, and reacted at 75 ° C. to obtain an organic solvent solution of urethane prepolymer having isocyanate group at molecular terminal I got Subsequently, 261 parts by mass of DMF and 118 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, cooled to 35 ° C., 24 parts by mass of H12 MDA were added, and the polyurethane resin was elongated by stirring and mixing. . Next, a urethane resin composition was obtained by adding 0.3 parts by mass of N, N-dibutylamine and 118 parts by mass of isopropyl alcohol and mixing.

[Example 5]
102 parts by mass of PC1 and 29 parts by mass of other PC1 were added to a nitrogen-substituted four-necked flask having a stirrer, a reflux condenser and a thermometer, and dehydration was performed at 120 to 130 ° C. under a reduced pressure of 0.095 MPa. . After dehydration, 98 parts by mass of DMF and 5 parts by mass of SPG were added while cooling to 50 ° C., and the mixture was sufficiently stirred. After stirring, 39 parts by mass of IPDI, and 7 parts by mass of HDI and 0.1 parts by mass of stannous octoate are added, and reacted at 75 ° C. to obtain an organic solvent solution of urethane prepolymer having isocyanate group at molecular terminal I got Subsequently, 233 parts by mass of DMF and 105 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, cooled to 35 ° C., 22 parts by mass of H12 MDA was added, and the polyurethane resin was elongated by stirring and mixing. . Next, a urethane resin composition was obtained by adding 0.9 parts by mass of N, N-dibutylamine and 105 parts by mass of isopropyl alcohol and mixing.

[Example 6]
A nitrogen-substituted four-necked flask having a stirrer, a reflux condenser and a thermometer, and 120 parts by mass of PC1 (having 1,4-butanediol and 1,10-decanediol as a raw material, [C4 / C10] = 90/10, number average molecular weight; 3,000, hereinafter, 7 parts by mass of "other PC 3" are added, and dehydration is performed at 120 to 130 ° C under a reduced pressure of 0.095 MPa. After dehydration, 100 parts by mass of DMF and 7 parts by mass of HBPA were added while cooling to 50 ° C., and the mixture was sufficiently stirred. After stirring, 36 parts by mass of H12 MDI, and 15 parts by mass of HDI and 0.1 parts by mass of stannous octoate are added, and reacted at 75 ° C., thereby forming an organic urethane prepolymer having an isocyanate group at its molecular end A solvent solution was obtained. Subsequently, 214 parts by mass of DMF and 97 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, cooled to 35 ° C., 17 parts by mass of IPDA were added, and the polyurethane resin was elongated by stirring and mixing. . Next, 0.5 parts by mass of N, N-dibutylamine and 97 parts by mass of isopropyl alcohol were added and mixed to obtain a urethane resin composition.

Comparative Example 1
109 parts by mass of PC2 and 26 parts by mass of other PC1 were added to a nitrogen-replaced four-necked flask having a stirrer, a reflux condenser and a thermometer, and dehydration was performed at 120 to 130 ° C. under a reduced pressure of 0.095 MPa. . After dehydration, while cooling to 50 ° C., 100 parts by mass of DMF and 1 part by mass of ethylene glycol (hereinafter abbreviated as “EG”) were added and sufficiently stirred. After stirring, 38 parts by mass of H12MDI, 11 parts by mass of HDI and 0.1 parts by mass of stannous octoate are added, and reacted at 75 ° C., thereby forming an organic urethane prepolymer having an isocyanate group at its molecular end A solvent solution was obtained. Next, 271 parts by mass of DMF and 124 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, cooled to 35 ° C., 20 parts by mass of IPDA were added, and the polyurethane resin was elongated by stirring and mixing. . Next, 0.7 parts by mass of N, N-dibutylamine and 124 parts by mass of isopropyl alcohol were added and mixed to obtain a urethane resin composition.

Comparative Example 2
88 parts by mass of PC2 and 59 parts by mass of other PC1 were added to a nitrogen-substituted four-necked flask having a stirrer, a reflux condenser and a thermometer, and dehydration was performed at 120 to 130 ° C. under a reduced pressure of 0.095 MPa. . After dehydration, 101 parts by mass of DMF was added while cooling to 50 ° C., and the mixture was sufficiently stirred. After stirring, 34 parts by mass of IPDI, and 6 parts by mass of HDI and 0.1 parts by mass of stannous octoate are added, and reacted at 75 ° C. to obtain an organic urethane prepolymer having an isocyanate group at its molecular end A solvent solution was obtained. Subsequently, 278 parts by mass of DMF and 126 parts by mass of ethyl acetate were added to the organic solvent solution of the urethane prepolymer, cooled to 35 ° C., 23 parts by mass of H12 MDA was added, and the polyurethane resin was elongated by stirring and mixing. . Next, a urethane resin composition was obtained by adding 0.3 parts by mass of N, N-dibutylamine and 126 parts by mass of isopropyl alcohol and mixing.

[Method of measuring number average molecular weight]
The number average molecular weights of the polyol and the like used in Examples and Comparative Examples are values measured under the following conditions by gel permeation chromatography (GPC).

Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were used in series connection.
"TSKgel G5000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 4000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 3000" (7.8 mm ID × 30 cm) × 1 This "TSKgel G2000" (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

(Standard polystyrene)
Tosoh Corporation "TSKgel standard polystyrene A-500"
Tosoh Corporation "TSKgel standard polystyrene A-1000"
Tosoh Corporation "TSKgel standard polystyrene A-2500"
Tosoh Corporation "TSKgel standard polystyrene A-5000"
Tosoh Corporation "TSKgel standard polystyrene F-1"
Tosoh Corporation "TSKgel standard polystyrene F-2"
Tosoh Corporation "TSKgel standard polystyrene F-4"
Tosoh Corporation "TSKgel standard polystyrene F-10"
Tosoh Corporation "TSKgel standard polystyrene F-20"
Tosoh Corporation "TSKgel standard polystyrene F-40"
Tosoh Corporation "TSKgel standard polystyrene F-80"
Tosoh Corporation "TSKgel standard polystyrene F-128"
Tosoh Corporation "TSKgel standard polystyrene F-288"
Tosoh Corporation "TSKgel standard polystyrene F-550"

[Method of measuring mechanical strength]
100 parts by mass of the urethane resin composition obtained in Examples and Comparative Examples were mixed with 40 parts by mass of DMF and dried on a flat release paper ("EK-100D" manufactured by LINTEC Corporation). The coating was applied to 30 microns, dried at 90 ° C. for 2 minutes, and further dried at 120 ° C. for 2 minutes to prepare a film. Then, the obtained film is cut into strips of width 5 mm and length 50 mm, and a tensile tester “Autograph AG-I” (manufactured by Shimadzu Corporation) is used to cross at an atmosphere of temperature 23 ° C. The sample was pulled at a head speed of 10 mm / sec, and the 100% modulus (MPa) of the test piece was measured. The distance between chucks at this time was 40 mm. From the obtained 100% modulus value, mechanical strength was evaluated as follows.
"A": 11 MPa or more and less than 20 MPa "B": 9 MPa or more and less than 11 MPa "C": less than 9 MPa

[Method for measuring oleic acid resistance]
A film was produced in the same manner as the above-mentioned [Method of measuring mechanical strength]. Subsequently, the film was cut into strips of 5 mm in width and 50 mm in length, immersed in oleic acid at normal temperature for 24 hours and then taken out, and oleic acid adhering to the surface was lightly wiped off with a paper waste. Then, using a tensile tester “Autograph AG-I” (manufactured by Shimadzu Corporation), the specimen is pulled under the conditions of a crosshead speed of 10 mm / sec and a chuck distance of 40 mm under an atmosphere of temperature 23 ° C. The stress at 100% elongation was measured. The oleic acid resistance was evaluated as follows using the value obtained by dividing this stress by the 100% modulus value measured in the above-mentioned [Method for measuring mechanical strength] as the retention of the 100% modulus value.
"A": retention rate is 40% or more "B": retention rate is 30% or more and less than 40% "C": retention rate is less than 30%

[Method of measuring low temperature flexibility]
100 parts by mass of the urethane resin composition 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 coloring agent “Dylac L-1770S” manufactured by DIC Corporation Were coated on a release paper so that the film thickness after drying was 30 microns, dried at 90 ° C. for 2 minutes, and further dried at 120 ° C. for 2 minutes to prepare a film on release paper. Then, on this film, 100 parts by mass of a urethane resin “Kurisbon TA-205FT” manufactured by DIC Corporation, 60 parts by mass of DMF, and 12 parts by mass of polyisocyanate crosslinking agent “Burnock DN-950” manufactured by DIC Corporation A mixed solution consisting of 1 part by mass of a tin catalyst "Accel T-81E" manufactured by DIC Corporation was applied so that the film thickness after drying would be 60 microns, and dried at 100 ° C for 1 minute. Next, a polyester base was placed thereon and pressure-bonded with a 120 ° C. laminator, and then aged at 40 ° C. for 3 days, and the release paper was peeled off to obtain a synthetic leather.
This synthetic leather is subjected to a flexibility test (-10 ° C, 100 times / minute) with a flexometer (“low temperature bath-equipped flexiometer” manufactured by Yasuda Seiki Co., Ltd.) until the surface of the synthetic leather is cracked The number of times was measured and evaluated as follows.
"A": 20,000 or more "B": 10,000 or more and less than 20,000 "C": less than 10,000

The abbreviations in Tables 1 and 2 will be described.
"Mn"; number average molecular weight "C3"; 1,3-propanediol "C4"; 1,4-butanediol "C10": 1, 10-decanediol "C6": 1, 6-hexanediol "C5" : 1,5-pentanediol

  Examples 1 to 6, which are the urethane resin compositions of the present invention, were found to be excellent in oleic acid resistance, low temperature flexibility, and mechanical strength.

  On the other hand, Comparative Example 1 was an embodiment in which ethylene glycol was used instead of the glycol compound (B), but oleic acid resistance was poor.

  Although the comparative example 2 is an aspect which does not use a glycol compound (B) and its substitute, either, mechanical strength and oleic acid resistance were inferior.

Claims (8)

Polycarbonate polyol (A) having butanediol and hexanediol as raw materials, and polycarbonate polyols other than the above (A) (polycarbonate polyols having 1,6-hexanediol as raw materials, 1,3-propanediol and 1,4-butane Polycarbonate polyol having diol as a raw material, or polycarbonate polyol (excluding aromatic polycarbonate polyol) having 1,4-butanediol and 1,10-decanediol as raw materials, and monocyclic aliphatic glycol (b-1) A polyol (X) comprising a glycol (b-2) having a spiro ring, and at least one glycol compound (B) selected from the group consisting of an aromatic glycol (b-3), and a polyisocyanate Urethane resin (Y) is an essential raw material ( ) Containing the (amount of polycarbonate polyol other than A) is a urethane resin composition, wherein the der Rukoto in less than 40 wt% polyol (X).
The urethane resin composition according to claim 1, wherein the content of the glycol compound (B) in the polyol (X) is less than 10% by mass. The urethane resin composition according to claim 1 or 2, wherein the number average molecular weight of the polycarbonate polyol (A) is in the range of 1,500 to 3,500. The molar ratio [C4 / C6] of butanediol (C4) and hexanediol (C6) in the polycarbonate polyol (A) is in the range of 60/40 to 95/5. The urethane resin composition of description. The urethane resin composition according to any one of claims 1 to 4, wherein the polyisocyanate (Y) contains an aliphatic polyisocyanate and an alicyclic polyisocyanate. A film formed by the urethane resin composition according to any one of claims 1 to 5. The film according to claim 6, wherein the 100% modulus obtained by the tensile test under the condition of the cross head speed of 10 mm / sec is 9 MPa or more. A synthetic leather characterized by having the film according to claim 6 or 7.