TW201922831A - Urethane resin composition, coating film and synthetic leather - Google Patents

Abstract

The problem to be solved by the present invention is to provide a urethane resin composition that exhibits excellent oleic acid resistance, low temperature flexibility and mechanical strength. The present invention provides a urethane resin composition characterized by containing: (Y) a polyisocyanate; and (Z) a urethane resin obtained by using, as essential raw materials, (X) a polyol which contains (A), a polycarbonate polyol obtained using butane diol and hexane diol as raw materials, and (B) at least one type of glycol compound selected from the group consisting of a monocyclic aliphatic glycol (b-1), a spiro ring-containing glycol (b-2), and an aromatic glycol (b-3). The present invention also provides: a coating film characterized by being formed from the urethane resin composition; and a synthetic leather characterized by having the coating film.

Description

Urethane resin composition, film, and synthetic leather

The present invention relates to a urethane resin composition.

Urethane resins are widely used in various fields, such as synthetic leather and sheets for molding. In particular, when used for a long-term member such as synthetic leather for vehicle interior materials, higher durability is required.

The aforementioned durability evaluation items involve various aspects, including heat resistance, humidity and heat resistance, light resistance, chemical resistance, and abrasion resistance. Especially in recent years, synthetic leather members that have frequent contact with the human body require oil resistance. Chemical resistance such as acidity or sunscreen resistance. As the excellent materials such as the above-mentioned oil and acid resistance, there is disclosed a resin composition composed of a polycarbonate-based polyurethane resin, a polyether-based polyurethane resin, and an acrylic resin (for example, refer to Patent Literature 1).

However, as a material for synthetic leather, not only the aforementioned oil and acid resistance, but also the need to imagine that the requirements for low-temperature bendability also increase when used in cold areas. Furthermore, in order to obtain excellent abrasion resistance, Excellent mechanical strength is required. However, materials that have all these characteristics have not been discovered.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2012-1693

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

The present invention provides a urethane resin composition, which is characterized by containing a urethane resin (Z) using a polyol (X) and a polyisocyanate (Y) as essential raw materials, and the polyol (X) Polycarbonate polyol (A) using butanediol and hexanediol as raw materials, and selected from the group consisting of monocyclic aliphatic diol (b-1), spiro ring diol (b-2), and aromatic two One or more diol compounds (B) in the group consisting of alcohol (b-3).

The present invention also provides a coating film, which is formed from the urethane resin composition, and a synthetic leather, which is provided with the coating film.

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

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

[Mode for Carrying Out the Invention]

The urethane resin composition of the present invention contains a urethane resin (Z) using a polyol (X) and a polyisocyanate (Y) as essential raw materials. The polyol (X) includes butanediol and Polycarbonate polyol (A) with hexanediol as raw material and selected from monocyclic aliphatic diol (b-1), spiro ring diol (b-2) and aromatic diol (b-3) One or more diol compounds (B) in the group to be composed.

The polycarbonate polyol (A) is required to use butanediol and hexanediol as raw materials in order to obtain very excellent mechanical strength while maintaining excellent oil resistance and low-temperature bendability.

Examples of the butanediol include 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol. These butanediols can be used alone or in combination of two or more. Among these, from the viewpoint of obtaining more excellent mechanical strength, 1,4-butanediol is preferably used.

As the hexanediol, for example, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2 , 3-hexanediol, 2,4-hexanediol, 3,4-hexanediol, and the like. These hexanediol systems may be used alone or in combination of two or more. Among these, from the viewpoint of obtaining more excellent mechanical strength, 1,6-hexanediol is preferably used.

From the viewpoint of obtaining more excellent mechanical strength, the molar ratio [C4 / C6] of the aforementioned butanediol (C4) and hexanediol glycol (C6) is preferably in the range of 60/40 to 95/5. A more preferable range is 65/35 to 93/7.

Specifically, the polycarbonate diol (A) may be a one obtained by reacting the butanediol and hexanediol with a carbonate and / or phosgene by a known method.

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

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

From the viewpoint of obtaining more excellent oil and acid resistance, low-temperature bending resistance, and mechanical strength, the use amount of the polycarbonate polyol (A) is preferably 30% by mass or more, more preferably 40% of the polyol (X). A range of ~ 99% by mass, particularly preferably a range of 50 ~ 95% by mass.

As the polyol (X) used in the present invention, it must be selected from the group consisting of a monocyclic aliphatic diol (b-1), a diol having a spiro ring (b-2), and an aromatic diol (b-3). One or more diol compounds (B) in this group. By using this specific diol compound (B) and the polycarbonate polyol (A) in combination, it is possible to achieve excellent coexistence of oil resistance to acidic acid, low-temperature bendability, and mechanical strength.

Examples of the monocyclic aliphatic diol (b-1) include cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, and hydrogenated bisphenol A; and alkylene oxide adducts thereof. . These diols can be used alone or in combination of two or more. Among these, from the viewpoint of obtaining more excellent oil and acid resistance, low-temperature bending resistance, and mechanical strength, it is preferably used. One or more diols selected from the group consisting of cyclohexanedimethanol, hydrogenated bisphenol A, and alkylene oxide adducts of hydrogenated bisphenol A.

As the spiro diol (b-2), 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) -2,4,8,10-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 and the like. These diols can be used alone or in combination of two or more. Among these, 3,9-bis (1,1-dimethyl-2-hydroxyethyl)-is preferably used from the viewpoint of obtaining more excellent oil acid resistance, low-temperature bending resistance, and mechanical strength. 2,4,8,10-tetraoxaspiro [5,5] undecane.

As the aromatic diol, for example, bisphenol A, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylphosphonium, and hydroquinone can be used; These alkylene oxide adducts and the like. These diols can be used alone or in combination of two or more.

From more excellent oil acid resistance, low temperature bending resistance and From the viewpoint of mechanical strength, the content ratio of the diol compound (B) is preferably less than 10% by mass in the polyol (X), more preferably in the range of 1 to 9% by mass, and even more preferably 2 to 7% by mass. % Range.

The polyol (X) contains the polycarbonate polyol (A) and the diol compound (B) as essential components, but may further contain other polyols if necessary.

As the other polyol, for example, polycarbonate polyols, polyether polyols, polyester polyols, polyacrylic polyols, polybutadiene polyols, and hydrogenated polybutadiene polyols other than the above (A) can be used. Alcohol and so on. These polyols can be used alone or in combination of two or more. Among these, it is preferable to use a polymer other than the above-mentioned (A) from the viewpoint of obtaining more excellent oil and acid resistance, low-temperature bendability, and mechanical strength by using it in combination with the polycarbonate polyol (A). Carbonate polyol.

The polycarbonate polyol other than the above (A) is not particularly limited as long as it has a carbonate structure. For example, propylene glycol, butanediol, pentanediol, hexanediol, decanediol, and caprolactone can be used. , Polycarbonate polyols such as cyclohexanedimethanol, 3-methyl-1,5-pentanediol, neopentyl glycol, isosorbide, etc. as raw materials. These raw materials may be used alone as a raw material having a hydroxyl group, or two or more of them may be used in combination.

From the viewpoint of obtaining more excellent oil acid resistance, low-temperature bending resistance, and mechanical strength, the use amount of polycarbonate polyols other than the aforementioned (A) is preferably less than 40% by mass in the polyol (X). The range is more preferably 1 to 35% by mass, and even more preferably 3 to 33% by mass.

In the aforementioned polyol (X), other Chain elongating agent (a number average molecular weight of 40 to 550).

As the other chain extender, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and hexamethylene glycol can be used. Methylene glycol, trimethylolpropane, glycerin and other chain extenders with hydroxyl groups; ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine 2-methylpiperazine 2,5-dimethylpiperazine , Isophorone diamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine Chain extenders with amine groups such as 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, ethylenediamine, and ethylenediamine. These chain elongating agents may be used alone or in combination of two or more kinds. Among these, from the viewpoint of easily suppressing discoloration of the film with time, it is preferable to use a chain elongator having an amine group, and more preferably to use a chain elongator having an amine group and an alicyclic structure.

From the viewpoint of easily inhibiting the discoloration of the film over time, the amount of use of the other chain elongating agent is preferably in the range of 1 to 50 parts by mass relative to 100 parts by mass of the polyol (X). More preferably, it is in the range of 3 to 20 parts by mass.

Examples of the polyisocyanate (Y) include 1,3- and 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, and 1-methyl-2,6-phenylene. Phenyl 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 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 Aromatic polyisocyanates such as diisocyanate, 2,2'-diphenylmethane diisocyanate, diphenylmethane-2,4-diisocyanate; tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate , 1,6-hexamethylene diisocyanate, dodecyl diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopentyl diisocyanate, 1,3-cyclohexyl diisocyanate , 1,4-cyclohexyl diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate (Ester methyl) cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-di Aliphatic or alicyclic polyisocyanates, such as cyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate, and the like. These polyisocyanates can be used alone or in combination of two or more. Among these, from the viewpoint of obtaining more excellent durability and improving light resistance, oleic acid resistance, and low-temperature bending resistance, it is preferable to use an aliphatic and / or alicyclic polyisocyanate, and more preferably Aliphatic polyisocyanate and alicyclic polyisocyanate are used together.

As the combined use of the aforementioned aliphatic polyisocyanate and alicyclic polyisocyanate The mass ratio [aliphatic NCO / alicyclic NCO] at the time of isocyanate is preferably expressed by its mass ratio [aliphatic NCO / alicyclic NCO] from the viewpoint of obtaining more excellent oil resistance and low-temperature bendability. The range is 5/95 to 60/40, more preferably 10/90 to 50/50, and even more preferably 15/85 to 45/55.

From the viewpoint of obtaining excellent mechanical strength and reactivity, the amount of the polyisocyanate (Y) used is preferably within a range of 10 to 60% by mass of the total mass of the polyol (X) and the polyisocyanate (Y). A more preferable range is 15 to 45 mass%.

Examples of the method for producing the urethane resin (Z) include a method in which the polyol (X) and the polyisocyanate (Y) are added together and reacted to produce the reaction. It is preferably performed at a temperature of 30 to 100 ° C for 3 to 10 hours. The above reaction may be performed in a solvent described later.

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

From the viewpoint of further improving the mechanical strength and flexibility of the film, 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, more preferably 10,000 to 500,000 range. The number average molecular weight of the urethane resin (Z) indicates a value measured by a gel permeation chromatography (GPC) method.

The urethane resin composition contains the urethane The ester resin (Z) is an essential component, but may contain other components as needed.

As the other components, for example, solvents, pigments, flame retardants, plasticizers, softeners, stabilizers, waxes, defoamers, dispersants, penetrants, surfactants, fillers, antifungal agents, and antibacterial agents can be used. , UV absorber, antioxidant, weather stabilizer, fluorescent whitening agent, anti-aging agent, tackifier, etc. These components may be used alone or in combination of two or more.

Examples of the solvent include water, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, and methyl. Ketone solvents such as n-propyl ketone, acetone, methyl isobutyl ketone, etc .; methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, isopropyl acetate Ester solvents such as butyl ester, second butyl acetate, etc .; alcohol solvents such as methanol, ethanol, isopropanol, and butanol. These solvents may be used alone or in combination of two or more.

From the viewpoint of operability and viscosity, the content of the solvent is preferably in a range of 30 to 90% by mass in the urethane resin composition.

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

As the substrate, for example, a fibrous substrate composed of a nonwoven fabric, a woven fabric, a knitted fabric, or the like; a resin film, or the like can be used. As the fibrous substrate, chemical fibers such as polyester fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, and polylactic acid fibers can be used; cotton, hemp, etc. , Silk, wool, These blended fibers and so on.

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

On the surface of the aforementioned substrate, if necessary, treatments such as antistatic processing, demolding processing, water repellent processing, water absorption processing, antibacterial deodorization processing, bacteriostatic processing, and ultraviolet blocking processing may be applied.

Examples of the method for applying the urethane resin composition of the present invention to the aforementioned substrate include a coating method using an applicator, a bar coater, a blade coater, a T-die coater, or a roll coater. .

Examples of a method for drying the coated urethane resin composition include a method of drying at a temperature of 50 to 140 ° C. for 30 seconds to 10 minutes.

The thickness of the obtained film is appropriately determined depending on the application to be used, but is, for example, in the range of 0.001 to 10 mm.

When the aforementioned film is used for a leather-like sheet, from the viewpoint of obtaining more excellent abrasion resistance, the 100% modulus obtained by a tensile test at a crosshead speed of 10 mm / sec is preferably 9 MPa or more. A more preferable range is 11 to 20 MPa. The method for measuring the 100% modulus value of the film is described in Examples.

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

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

As described above, the urethane resin composition of the present invention is excellent in oil acid resistance, low-temperature bendability, and mechanical strength. Therefore, the urethane resin composition of the present invention can be suitably used as a material used in the production of synthetic leather, clothing, support pads, polishing pads, and the like, and particularly suitable as a material for synthetic leather.

[Example]

Hereinafter, the present invention will be described in more detail using examples.

[Example 1]

In a nitrogen-replaced 4-necked flask equipped with a stirrer, a reflux cooling tube, and a thermometer, 117 parts by mass of polycarbonate diol (with 1,4-butanediol and 1,6-hexanediol as raw materials, [C4 / C6] (hereinafter, Molar ratio) = 70/30, number average molecular weight: 2,000, hereinafter referred to as "PC1"), 14 parts by mass of polycarbonate diol (using 1,6-hexanediol as a raw material) ([C6] = 100, number average molecular weight: 2,000, hereinafter referred to as "other PC1"), and dehydration was performed at 120 to 130 ° C under a reduced pressure of 0.095 MPa. After dehydration, while cooling to 50 ° C, 101 parts by mass of N, N-dimethylformamide (hereinafter referred to as "DMF") and 7 parts by mass of hydrogenated bisphenol A (hereinafter referred to as "HBPA") were added. ), Stir well. After stirring, 33 parts by mass of isophorone diisocyanate (hereinafter referred to as "IPDI"), 17 parts by mass of hexamethylene diisocyanate (hereinafter referred to as "HDI") and 0.1 part by mass of octanoic acid were added. Tin, reacted at 75 ° C, An organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular terminal is obtained. Next, by adding 243 parts by mass of DMF and 110 parts by mass of ethyl acetate to the organic solvent solution of the aforementioned urethane prepolymer, cooling to 35 ° C, and adding 21 parts by mass of isophorone diamine (Hereinafter, referred to as "IPDA"), and agitate and mix to extend the polyurethane resin. Subsequently, 0.3 parts by mass of N, N-dibutylamine and 110 parts by mass of isopropanol were added and mixed to obtain a urethane resin composition.

[Example 2]

In a nitrogen-replaced 4-neck flask equipped with a stirrer, a reflux cooling tube, and a thermometer, 117 parts by mass of PC1 and 8 parts by mass of other PC1 were added, and dehydration was performed at 120 to 130 ° C. at a reduced pressure of 0.095 MPa. After dehydration, while cooling to 50 ° C., 97 parts by mass of DMF and 5 parts by mass of cyclohexanedimethanol (hereinafter, referred to as “CHDM”) were added and stirred well. After stirring, 38 parts by mass of IPDI, 12 parts by mass of HDI and 0.1 parts by mass of stannous octoate were added and reacted at 75 ° C to obtain a urethane prepolymer having an isocyanate group at the molecular terminal. Organic solvent solution. Next, by adding 199 parts by mass of DMF and 89 parts by mass of ethyl acetate to the organic solvent solution of the aforementioned urethane prepolymer, cooling to 35 ° C., and adding 21 parts by mass of 4,4′-bis Cyclohexylmethanediamine (hereinafter referred to as "H12MDA") is stirred and mixed to extend the polyurethane resin. Subsequently, 0.8 parts by mass of N, N-dibutylamine and 89 parts by mass of isopropyl alcohol were added and mixed to obtain a urethane resin composition.

[Example 3]

In a nitrogen-replaced 4-necked flask equipped with a stirrer, a reflux cooling tube, and a thermometer, 117 parts by mass of polycarbonate diol (with 1,4-butanediol and 1,6-hexanediol as raw materials, [C4 / C6] = 90/10, number-average molecular weight: 2,000, hereinafter referred to as "PC2"), 21 parts by mass of other PC1, and dehydrated at 120-130 ° C under a reduced pressure of 0.095 MPa. After dehydration, while cooling to 50 ° C., 101 parts by mass of DMF and 7 parts by mass of an ethylene oxide 1 mol adduct of hydrogenated bisphenol A (hereinafter referred to as “POEBA”) were added and stirred well. After stirring, 30 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (hereinafter referred to as "H12MD1"), 19 parts by mass of HDI and 0.1 parts by mass of stannous octoate were added, and the reaction was performed at 75 ° C. To obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular terminal. Next, by adding 225 parts by mass of DMF and 89 parts by mass of ethyl acetate to the organic solvent solution of the aforementioned urethane prepolymer, cooling to 35 ° C, adding 18 parts by mass of IPDA, and stirring and mixing, The polyurethane resin is stretched. Subsequently, 0.6 parts by mass of N, N-dibutylamine and 102 parts by mass of isopropanol were added and mixed to obtain a urethane resin composition.

[Example 4]

In a nitrogen-replaced 4-neck flask equipped with a stirrer, a reflux cooling tube, and a thermometer, 91 parts by mass of PC2 and 42 parts by mass of (using 1,3-propanediol and 1,4-butanediol as raw materials, [ C3 / C4] = 50/50, Number average molecular weight: 2,000, hereinafter referred to as "other PC2"), and dehydrated at a pressure of 0.095 MPa at 120 to 130 ° C. After dehydration, while cooling to 50 ° C, 100 parts by mass of DMF and 7 parts by mass of spirodiol (manufactured by Mitsubishi Gas Chemical Co., Ltd., hereinafter referred to as "SPG") were added and stirred well. After stirring, by adding 32 parts by mass of IPDI and 13 parts by mass of HDI and 0.1 parts by mass of stannous octoate, and reacting them at 75 ° C., a urethane prepolymer having an isocyanate group at the molecular terminal was obtained. Organic solvent solution. Next, by adding 261 parts by mass of DMF and 118 parts by mass of ethyl acetate to the organic solvent solution of the aforementioned urethane prepolymer, cooling to 35 ° C., adding 24 parts by mass of H12MDA, and stirring and mixing, The polyurethane resin is stretched. Subsequently, 0.3 parts by mass of N, N-dibutylamine and 118 parts by mass of isopropanol were added and mixed to obtain a urethane resin composition.

[Example 5]

In a nitrogen-replaced 4-neck flask equipped with a stirrer, a reflux cooling tube, and a thermometer, 102 parts by mass of PC1 and 29 parts by mass of other PC1 were added, and dehydration was performed at 120 to 130 ° C. at a reduced pressure of 0.095 MPa. After dehydration, while cooling to 50 ° C., 98 parts by mass of DMF and 5 parts by mass of SPG were added, and the mixture was thoroughly 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 were added and reacted at 75 ° C to obtain a urethane prepolymer having an isocyanate group at the molecular terminal. Organic solvent solution. Next, by adding 233 to the organic solvent solution of the aforementioned urethane prepolymer, Part by mass of DMF and 105 parts by mass of ethyl acetate were cooled to 35 ° C, 22 parts by mass of H12MDA was added, and the mixture was stirred and mixed to extend the polyurethane resin. Subsequently, 0.9 parts by mass of N, N-dibutylamine and 105 parts by mass of isopropanol were added and mixed to obtain a urethane resin composition.

[Example 6]

To a 4-neck flask replaced with nitrogen with a stirrer, a reflux cooling tube, and a thermometer, 120 parts by mass of PC1 and 7 parts by mass of those using 1,4-butanediol and 1,10-decanediol as raw materials were added. [C4 / C10] = 90/10, number-average molecular weight: 3,000, hereinafter referred to as "other PC3"), and dehydrated at 120 ~ 130 ° C under a reduced pressure of 0.095 MPa. After dehydration, while cooling to 50 ° C., 100 parts by mass of DMF and 7 parts by mass of HBPA were added and thoroughly stirred. After stirring, 36 parts by mass of H12MDI and 15 parts by mass of HDI and 0.1 parts by mass of stannous octoate were added and reacted at 75 ° C to obtain a urethane prepolymer having an isocyanate group at the molecular terminal. Organic solvent solution. Next, by adding 214 parts by mass of DMF and 97 parts by mass of ethyl acetate to the organic solvent solution of the aforementioned urethane prepolymer, cooling to 35 ° C, adding 17 parts by mass of IPDA, and stirring and mixing, The polyurethane resin is stretched. Subsequently, 0.5 parts by mass of N, N-dibutylamine and 97 parts by mass of isopropanol were added and mixed to obtain a urethane resin composition.

[Comparative Example 1]

In a nitrogen-replaced 4-neck flask equipped with a stirrer, a reflux cooling tube, and a thermometer, 109 parts by mass of PC2 and 26 parts by mass of other PC1 were added, and dehydration was performed at 120 to 130 ° C. at 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, referred to as “EG”) were added and stirred well. After stirring, 38 parts by mass of H12MDI and 11 parts by mass of HDI and 0.1 parts by mass of stannous octoate were added and reacted at 75 ° C to obtain a urethane prepolymer having an isocyanate group at the molecular terminal. Organic solvent solution. Next, by adding 271 parts by mass of DMF and 124 parts by mass of ethyl acetate to the organic solvent solution of the aforementioned urethane prepolymer, cooling to 35 ° C, adding 20 parts by mass of IPDA, and stirring and mixing, The polyurethane resin is stretched. Subsequently, 0.7 part by mass of N, N-dibutylamine and 124 parts by mass of isopropanol were added and mixed to obtain a urethane resin composition.

[Comparative Example 2]

In a nitrogen-replaced 4-neck flask equipped with a stirrer, a reflux cooling tube, and a thermometer, 88 parts by mass of PC2 and 59 parts by mass of other PC1 were added, and dehydration was performed at 120 to 130 ° C. at a reduced pressure of 0.095 MPa. After dehydration, while cooling to 50 ° C., 101 parts by mass of DMF was added and stirred sufficiently. After stirring, 34 parts by mass of IPDI and 6 parts by mass of HDI and 0.1 parts by mass of stannous octoate were added and reacted at 75 ° C to obtain a urethane prepolymer having an isocyanate group at the molecular terminal. Organic solvent solution. Next, 278 parts by mass of DMF was added to the organic solvent solution of the urethane prepolymer. 126 parts by mass of ethyl acetate was cooled to 35 ° C, 23 parts by mass of H12MDA was added, and the mixture was stirred and mixed to extend the polyurethane resin. Subsequently, by adding 0.3 parts by mass of N, N-dibutylamine and 126 parts by mass of isopropanol, a urethane resin composition was obtained.

[Method for measuring number average molecular weight]

The number average molecular weights of the polyhydric alcohols and the like used in the examples and comparative examples represent values measured by a gel permeation chromatography (GPC) method under the following conditions.

Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)

Tubular string: It is used by connecting the following tubular columns made by Tosoh Corporation in series.

`` TSKgel G5000 '' (7.8mmI.D. × 30cm) × 1

`` TSKgel G4000 '' (7.8mmI.D. × 30cm) × 1

`` TSKgel G3000 '' (7.8mmI.D. × 30cm) × 1

`` TSKgel G2000 '' (7.8mmI.D. × 30cm) × 1

Detector: RI (differential refractometer)

Column temperature: 40 ℃

Eluent: tetrahydrofuran (THF)

Flow rate: 1.0mL / min

Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)

Standard sample: Use the following standard polystyrene to make a calibration curve.

(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" made by Tosoh Corporation

"TSKgel Standard Polystyrene F-288" made by Tosoh Corporation

"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[Measurement method of mechanical strength]

40 parts by mass of DMF was added to 100 parts by mass of the urethane resin composition obtained in the examples and comparative examples, and the dried solution was applied on a flat surface so that the film thickness after drying became 30 micrometers. Paper ("EK-100D" manufactured by Lintec Co., Ltd.), dried at 90 ° C Dry for 2 minutes, and then dry at 120 ° C for 2 minutes to make a film. Next, the obtained film was cut into a strip shape with a width of 5 mm and a length of 50 mm, and a tensile tester "Autograph AG-I" (manufactured by Shimadzu Corporation) was used in a crosshead at a temperature of 23 ° C. The test piece was stretched at a rate of 10 mm / second, and the 100% modulus (MPa) of the test piece was measured. The distance between chucks at this time was set to 40 mm. From the obtained 100% modulus value, the mechanical strength was evaluated as follows.

"A": 11MPa or more and less than 20MPa

"B": 9MPa or more and less than 11MPa

"C": less than 9MPa

[Determination method of oil resistance to acidity]

A film was produced in the same manner as in the above [Method for Measuring Mechanical Strength]. Next, this film was cut into a strip-shaped test piece having a width of 5 mm and a length of 50 mm. After being immersed in oleic acid at normal temperature for 24 hours, the film was taken out, and the oleic acid attached to the surface was gently wiped with a paper cloth. Then, using a tensile tester "Autograph AG-I" (manufactured by Shimadzu Corporation) under a temperature of 23 ° C, the cross head was stretched at a speed of 10 mm / sec and the distance between the chucks was measured. The stress at 100% extension of the test piece. The value obtained by dividing this stress by the 100% modulus value measured in the aforementioned [Method for Measuring Mechanical Strength] was regarded as the retention rate of the 100% modulus value, and the oil acid resistance was evaluated as follows.

"A": Retention rate above 40%

"B": retention rate is more than 30% and less than 40%

"C": retention rate is less than 30%

[Method for measuring low-temperature bendability]

In 100 parts by mass of the urethane resin composition obtained in the 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 manufactured by DIC Corporation were incorporated. Dilac L-1770S "is blended with a coating so that the film thickness after drying becomes 30 microns, coated on release paper, dried at 90 ° C for 2 minutes, and further dried at 120 ° C for 2 minutes, and on the release paper Make a film. Next, 100 parts by mass of a urethane resin "Crysbon TA-205FT" manufactured by DIC Corporation, 60 parts by mass of DMF, and 12 parts by mass were coated on the film so that the film thickness after drying became 60 microns. Part of a blending solution of polyisocyanate cross-linking agent "Burnock DN-950" made by DIC Corporation, and 1 part by mass of a tin catalyst "Axel T-81E" made by DIC Corporation, dried at 100 ° C for 1 minute . Next, a polyester base cloth was placed and pressure-bonded with a laminator at 120 ° C, and then matured at 40 ° C for 3 days, and the release paper was peeled to obtain a synthetic leather.

For this synthetic leather, a bending test (-10 ° C, 100 times per minute) of a deflection meter ("deflection meter with a low temperature tank" manufactured by Yasuda Seiki Seisakusho Co., Ltd. was performed, and it was measured that the synthetic leather occurred on the surface The number of times until rupture was evaluated as follows.

"A": 20,000 times or more

"B": 10,000 times or more and less than 20,000 times

"C": less than 10,000 times

The abbreviations in Tables 1 to 2 are explained.

"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

It can be seen that Examples 1 to 6 of the urethane resin composition of the present invention are excellent in oil acid resistance, low-temperature bending resistance, and mechanical strength.

On the other hand, Comparative Example 1 was a case where ethylene glycol was used instead of the diol compound (B), and the oil acid resistance was poor.

In Comparative Example 2, the diol compound (B) and its substitutes were not used, and the mechanical strength and oil and acid resistance were poor.

Claims (8)

A urethane resin composition, comprising: a urethane resin (Z) containing a polyol (X) and a polyisocyanate (Y) as essential raw materials; the polyol (X) containing butyl Polycarbonate polyol (A) using diol and hexanediol as raw materials, and selected from monocyclic aliphatic diol (b-1), spiro ring diol (b-2), and aromatic diol (b -3) one or more types of diol compounds (B) in the group consisting of. The urethane resin composition according to claim 1, wherein the content of the diol compound (B) in the polyol (X) is less than 10% by mass. For example, the urethane resin composition of claim 1 or 2, wherein the number average molecular weight of the polycarbonate polyol (A) is in a range of 1,500 to 3,500. The urethane resin composition according to any one of claims 1 to 3, wherein the molar ratio of butanediol (C4) to hexanediol (C6) in the polycarbonate polyol (A) is [ C4 / C6] is in the range of 60/40 ~ 95/5. 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. For example, the film of claim 6 has a 100% modulus obtained by a tensile test at a crosshead speed of 10 mm / sec. Which is 9 MPa or more. A synthetic leather characterized by having a film as claimed in claim 6 or 7.