Wet film-forming material

Abstract

To solve the problem, the present application provides a wet film-forming material using a bio-based raw material and having excellent wet film-forming properties and hydrolysis resistance. The wet film-forming material of the present application is a wet film-forming material containing a polyurethane resin composition of a polyurethane resin (X) using a polyol (A) and a polyisocyanate (B) as raw materials, and an organic solvent (Y). The polyol (A) contains a bio-based polyester polyol (A-1) and a bio-based polyether polyol (A-2), and the polyisocyanate (B) contains an aromatic polyisocyanate, and the bio-based polyester polyol (A-1) is a polyester polyol using a bio-based diethylene glycol and a bio-based sebacic acid as raw materials.

Description

TECHNICAL FIELD

[0001] The present application relates to a wet film-forming material of a polyurethane resin composition. BACKGROUND

[0002] A polyurethane resin composition has been used for various applications such as adhesives or coating agents, molding materials, and the like, because it forms a film having good flexibility and strength. Among them, the polyurethane resin composition is preferably used for manufacturing porous bodies used in clothes or moisture-permeable waterproof materials, polishing pads, and the like, represented by intermediate layers or skin layers of leather-like sheets, because it has a good soft feel.

[0003] As a method for manufacturing porous bodies using the polyurethane resin composition, a wet method in which an organic solvent is easily recovered is known from the viewpoint of reducing environmental load. For example, a method for manufacturing a waterproof processing cloth in which a resin formulation liquid containing a urethane resin for moisture-permeable waterproof processing, dimethylformamide, and a crosslinking agent, and the like is applied to a base material, and is coagulated by being immersed in a 10% aqueous solution of dimethylformamide is known (for example, see Patent Literature 1). As a wet film-forming urethane resin composition, a urethane resin composition using a urethane resin obtained by reacting a polyol containing an aliphatic polyester polyol with a polyisocyanate containing an aromatic polyisocyanate, and further containing a carbodiimide compound and an organic solvent is disclosed (for example, see Patent Literature 2).

[0004] On the other hand, against the background of global warming and depletion of oil resources, the demand for environmental load reduction materials using bio-based raw materials such as plants is increasing worldwide. By using bio-based raw materials, the use amount of fossil resources such as oil can be reduced, and in this regard, it is possible to contribute to the formation of a sustainable society. Among them, the demand for the development of sustainable products is increasing, and the development of products using bio-based raw materials is also required in synthetic leather. However, the current situation is that a wet film-forming material using bio-based raw materials has not yet been developed.

[0005] [Prior Art Documents]

[0006] [Patent Literature]

[0007] [Patent Literature 1] Japanese Patent Laid-Open No. 2007-169486

[0008] [Patent Literature 2] Japanese Patent Laid-Open No. 2012-102182 SUMMARY

[0009] [Problems to be Solved by the Invention]

[0010] The present application provides a wet film-forming material using a bio-based raw material and having excellent wet film-forming properties and hydrolysis resistance.

[0011] [Technical means for solving the problem]

[0012] The present application provides the following embodiments.

[0013] [1] A wet film-forming material, which is a wet film-forming material of a polyurethane resin composition containing a polyurethane resin (X) using a polyol (A) and a polyisocyanate (B) as raw materials, and an organic solvent (Y),

[0014] wherein

[0015] the polyol (A) contains a bio-based polyester polyol (A-1) and a bio-based polyether polyol (A-2),

[0016] the polyisocyanate (B) contains an aromatic polyisocyanate,

[0017] the bio-based polyester polyol (A-1) uses a diol compound and a bio-based sebacic acid as raw materials,

[0018] the diol compound contains a bio-based diethylene glycol.

[0019] [2] The wet film-forming material according to [1], wherein the content of the bio-based diethylene glycol in the diol compound is 15% by mass or more and 100% by mass or less.

[0020] [3] The wet film-forming material according to [1] or [2], wherein the mass ratio [(A-1) / (A-2)] of the bio-based polyester polyol (A-1) to the bio-based polyether polyol (A-2) is 90:10 to 10:90.

[0021] [4] The wet film-forming material according to any one of [1] to [3], wherein the bio-based polyether polyol (A-2) is a bio-based polytetramethylene ether glycol.

[0022] [5] The wet film-forming material according to any one of [1] to [4], wherein the raw materials of the polyurethane resin (X) further contain a chain extender.

[0023] [6] The wet film-forming material according to [5], wherein the chain extender is at least one selected from the group consisting of ethylene glycol, 1,4-butanediol, and 1,3-propanediol.

[0024] [7] The wet film-forming material according to any one of [1] to [6], wherein the polyisocyanate (B) is diphenylmethane diisocyanate.

[0025] [Effects of the Invention]

[0026] The wet film-forming material of the present application uses a polyurethane resin composition using a bio-based raw material as a raw material, and is an environmentally friendly material. In addition, the polyurethane resin composition has excellent wet film-forming properties and hydrolysis resistance.

[0027] Therefore, the polyurethane resin composition of the present application can be preferably used as a material used in the production of synthetic leather, clothing, support pads, polishing pads, and the like, and can be particularly preferably used as a material for synthetic leather. DETAILED DESCRIPTION

[0028] (Explanation of Terms)

[0029] In the present specification, "bio-based" means being produced from plant raw materials such as sugarcane, corn, or castor oil.

[0030] (Wet film-forming material)

[0031] The wet film-forming material of the present embodiment is a wet film-forming material of the polyurethane resin composition of the present embodiment.

[0032] [Polyurethane resin composition]

[0033] The polyurethane resin composition of the present embodiment contains the polyurethane resin (X) of the present embodiment and an organic solvent (Y).

[0034] [Polyurethane resin (X)]

[0035] The polyurethane resin (X) of the present embodiment is a polyurethane resin using a polyol (A) and a polyisocyanate (B) as raw materials. That is, it is a polyurethane resin obtained by reacting a polyol (A) and a polyisocyanate (B). The polyurethane resin (X) of the present embodiment is preferably a polyurethane resin using a polyol (A), a chain extender, and a polyisocyanate (B) as raw materials. That is, it is preferably a polyurethane resin obtained by reacting a polyol (A), a chain extender, and a polyisocyanate (B).

[0036] The polyol (A) of the present embodiment contains a bio-based polyester polyol (A-1) using a diol compound and a bio-based sebacic acid as raw materials, the diol compound containing a bio-based diethylene glycol.

[0037] [Polyol (A)]

[0038] The polyol (A) of the present embodiment contains a bio-based polyester polyol (A-1) and a bio-based polyether polyol (A-2).

[0039] The total content of the bio-based polyester polyol (A-1) and the bio-based polyether polyol (A-2) in the polyol (A) is preferably in the range of 10 to 100% by mass, more preferably in the range of 20 to 100% by mass, from the viewpoint of further excellent wet film formability and hydrolysis resistance.

[0040] The total content of the bio-based polyester polyol (A-1) and the bio-based polyether polyol (A-2) in the raw material of the polyurethane resin (X) is preferably in the range of 10 to 95% by mass, more preferably in the range of 20 to 95% by mass, from the viewpoint of further excellent wet film formability and hydrolysis resistance.

[0041] The mass ratio [(A-1) / (A-2)] of the bio-based polyester polyol (A-1) to the bio-based polyether polyol (A-2) is preferably in the range of 90 / 10 to 10 / 90, more preferably in the range of 70 / 30 to 30 / 70, from the viewpoint of further excellent wet film formability and hydrolysis resistance.

[0042] "Bio-based polyester polyol (A-1)"

[0043] The bio-based polyester polyol (A-1) of the present embodiment is a polyester polyol obtained by using a diol compound and a bio-based sebacic acid as raw materials. That is, it is a polyester polyol obtained by reacting a diol compound with a bio-based sebacic acid. The diol compound contains a bio-based diethylene glycol.

[0044] As the bio-based polyester polyol (A-1) using the diol compound as a raw material, for example, a polyol obtained by subjecting a diol compound containing a bio-based diethylene glycol to a publicly known esterification reaction with a bio-based sebacic acid can be used. As the bio-based diethylene glycol of the present embodiment, for example, a substance obtained by using a waste molasses of sugar cane or the like as a raw material using a publicly known method or the like can be used.

[0045] As a specific example of the bio-based diethylene glycol, for example, "Bio DEG" manufactured by India Glycols can be cited.

[0046] As the diol compound other than the bio-based diethylene glycol, for example, bio-based ethylene glycol, bio-based 1,3-propanediol, petroleum-derived diethylene glycol, petroleum-derived ethylene glycol, propylene glycol, petroleum-derived 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, trimethylolpropane, trimethylolethane, glycerol, ε-caprolactone, and the like can be used. These compounds can be used alone or in combination of two or more. Among them, bio-based ethylene glycol and bio-based 1,3-propanediol are particularly preferable.

[0047] The diol compound containing the bio-based diethylene glycol is preferably bio-based diethylene glycol.

[0048] In the case where the bio-based diethylene glycol is used in combination with the other diol compound, the bio-based diethylene glycol is preferably used in an amount of 5 mol% or more, more preferably 7 mol% or more, and further preferably 10 mol% or more, based on the total amount of the diol compound. Alternatively, the content of the bio-based diethylene glycol in the diol compound is preferably 15 mass% or more and 100 mass% or less, more preferably 30 mass% or more and 100 mass% or less, and further preferably 50 mass% or more and 100 mass% or less.

[0049] In addition to the bio-based sebacic acid of the present embodiment, as the other polybasic acid, for example, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, maleic anhydride, fumaric acid, 1,3-cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, anhydrides of these acids, and the like can be used. These polybasic acids can be used alone or in combination of two or more.

[0050] The other polybasic acid is preferably a bio-based polybasic acid. As the bio-based polybasic acid, succinic acid, dimer acid, 2,5-furandicarboxylic acid, and the like can be used. These compounds can be used alone or in combination of two or more.

[0051] As the bio-based sebacic acid of the present embodiment, for example, a bio-based sebacic acid obtained by performing a publicly known cleavage reaction with a caustic on a vegetable oil such as castor oil, and the like can be used. As the bio-based succinic acid, for example, a bio-based succinic acid obtained by fermenting corn, sugar cane, cassava, sago, and the like using a publicly known method, and the like can be used. As the bio-based dimer acid, for example, a bio-based dimer acid obtained by dimerizing an unsaturated fatty acid derived from a natural oil fatty acid of a plant using a publicly known method, and the like can be used. As the bio-based 2,5-furandicarboxylic acid, for example, a bio-based 2,5-furandicarboxylic acid using fructose as a raw material; a bio-based 2,5-furandicarboxylic acid obtained by a publicly known method using furan carboxylic acid, which is a furfural derivative, and carbon dioxide.

[0052] As a specific example of the bio-based sebacic acid, for example, "Bio Seb" manufactured by Hokuetsu Pharcos Co., Ltd. can be mentioned.

[0053] As the number average molecular weight of the bio-based polyester polyol (A-1), in terms of obtaining further superior wet film formability and hydrolysis resistance, it is preferable to be in the range of 400 to 6000, more preferable to be in the range of 500 to 5000, and further preferable to be in the range of 700 to 3000. Furthermore, the number average molecular weight of the bio-based polyester polyol (A-1) represents a value determined by a gel permeation chromatography (GPC) method.

[0054] As the bio-based polyester polyol (A-1) which is preferable, for example, a reaction product of "Bio DEG" manufactured by India Glycols Ltd. and "Bio Seb" manufactured by Hokuetsu Pharcos Co., Ltd. can be mentioned.

[0055] "Bio-based polyether polyol (A-2)"

[0056] As the bio-based polyether polyol (A-2) of the present embodiment, for example, a polyoxyethylene glycol, a polyoxypropylene glycol, a polyoxytetramethylene glycol, a polyoxyethylene polyoxypropylene glycol, a polyoxyethylene polyoxytetramethylene glycol, a polyoxypropylene polyoxytetramethylene glycol, and the like can be used. These polyether polyols can be used alone, or two or more kinds thereof can be used in combination. Among these, in terms of obtaining further higher wet film formability and hydrolysis resistance by reducing the crystalline structure of the polymer, it is preferable to use a bio-based polyoxytetramethylene glycol (bio-based polytetramethylene ether glycol (PTMG)).

[0057] As the bio-based polytetramethylene ether glycol of the present embodiment, for example, a bio-based polytetramethylene ether glycol or the like obtained by a publicly known method such as ring-opening polymerization of tetrahydrofuran derived from a plant-derived material such as corn can be used.

[0058] As a specific example of the bio-based polytetramethylene ether glycol, for example, "Bio PTMG" manufactured by Mitsubishi Chemical Corporation can be cited.

[0059] As the number average molecular weight of the bio-based polyether polyol (A-2), from the viewpoint of further higher wet film formability and hydrolysis resistance, it is preferable to be in the range of 500 to 5,000, and more preferable to be in the range of 700 to 3,000. Further, the number average molecular weight of the bio-based polyether polyol (A-2) is a value determined in the same manner as the number average molecular weight of the bio-based polyester polyol (A-1).

[0060] "Other polyols"

[0061] As the polyol (A), in addition to the bio-based polyester polyol (A-1) and the bio-based polyether polyol (A-2), other polyols can also be used in combination. As the other polyols, for example, polycarbonate diols, polybutadiene polyols, polyester polyols other than the bio-based polyester polyol (A-1), polyether polyols other than the bio-based polyether polyol (A-2), and the like can be used. These polyols can be used alone, or two or more can be used in combination.

[0062] As the number average molecular weight of the other polyols, from the viewpoint of obtaining further excellent wet film formability and hydrolysis resistance, it is preferable to be in the range of 200 to 100,000, and more preferable to be in the range of 300 to 10,000. Further, the number average molecular weight of the other polyols is a value determined by a gel permeation chromatography (GPC) method.

[0063] 〔Chain extender〕

[0064] In the polyol (A), as needed, a chain extender (a) having a molecular weight in the range of 50 to 450 can be used in combination.

[0065] As the chain extender (a), for example, a chain extender having a hydroxyl group such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, trimethylolpropane, glycerol, and the like; a chain extender having an amino group such as ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophorone diamine, 4,4'-dicyclohexylmethane diamine, 3,3'-dimethyl-4,4'-dicyclohexylmethane diamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, triethylenetetramine, and the like can be used. These chain extenders can be used alone or in combination of two or more. Among these, in terms of further improving the wet film formability and the hydrolysis resistance, the chain extender having a hydroxyl group is preferable, and ethylene glycol, 1,3-propanediol, 1,4-butanediol are more preferable. As the ethylene glycol, 1,3-propanediol, bio-based ethylene glycol, bio-based 1,3-propanediol can be used.

[0066] As the amount of use when the chain extender (a) is used, in terms of further improving the wet film formability and the hydrolysis resistance, it is preferable to be in the range of 0.1 to 50% by mass, and more preferably in the range of 1 to 30% by mass, based on the total mass of the raw materials constituting the polyurethane resin (X).

[0067] 〔Polyisocyanate〕

[0068] As the polyisocyanate (B), an aromatic polyisocyanate is included in view of obtaining excellent wet film formability. As the aromatic polyisocyanate, for example, 1,3-phenylene diisocyanate 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, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, 1-methyl-3,5-diethylphenylene 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-2,4-diisocyanate, and the like can be used. These compounds can be used alone or in combination of two or more. Among these, in view of obtaining further excellent wet film formability, hydrolysis resistance, and the like, 4,4'-diphenylmethane diisocyanate is preferred.

[0069] The content of the aromatic polyisocyanate in the polyisocyanate (B) is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.

[0070] In the polyisocyanate (B), other polyisocyanates can be used as necessary. As the other polyisocyanates, for example, tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate, and the like aliphatic or alicyclic polyisocyanates can be used. These polyisocyanates can be used alone or in combination of two or more.

[0071] As the use amount of the polyisocyanate (B), in terms of further improving the wet film-forming property, hydrolysis resistance, and the like, it is preferably in the range of 10 to 60% by mass, and more preferably in the range of 15 to 45% by mass, based on the total mass of the raw materials for the polyurethane resin (X).

[0072] In particular, in the case where the aromatic polyisocyanate contained in the polyisocyanate (B) is diphenylmethane diisocyanate, the content of diphenylmethane diisocyanate in the raw materials for the polyurethane resin (X) of the present embodiment is preferably 10% by mass or more and 60% by mass or less, and more preferably 10% by mass or more and 55% by mass or less.

[0073] [Method for producing polyisocyanate resin]

[0074] As the method for producing the polyurethane resin (X), for example, a method in which the polyol (A), the chain extender as necessary, and the polyisocyanate (B) are all charged at once and allowed to react can be exemplified. The reaction is preferably performed at a temperature of 30 to 100°C for 3 to 10 hours, for example. In addition, the reaction can be performed in the organic solvent (Y) described later.

[0075] As the number average molecular weight of the polyurethane resin (X) obtained by the above method, in terms of further improving the abrasion resistance, the acid resistance, the low-temperature flexibility, the mechanical strength and the softness of the film, it is preferably in the range of 5,000 to 1,000,000, and more preferably in the range of 10,000 to 500,000. Note that the number average molecular weight of the polyurethane resin (X) indicates a value measured by a gel permeation chromatography (GPC) method.

[0076] As the content of the polyurethane resin (X), it is preferable in the range of 10 to 90 mass% in the polyurethane resin composition, and more preferable in the range of 15 to 80 mass%.

[0077] [Organic solvent]

[0078] As the organic solvent (Y) of the present embodiment, for example, the following can be used: a ketone solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, methyl n-propyl ketone, acetone, methyl isobutyl ketone, and the like; an ester solvent such as methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, sec-butyl acetate, and the like; an alcohol solvent such as methanol, ethanol, isopropanol, butanol, and the like; and the like. These organic solvents can be used alone or in combination of two or more.

[0079] As the content of the organic solvent (Y), it is preferable in the range of 20 to 90 mass% in the polyurethane resin composition from the viewpoint of workability and viscosity, and more preferable in the range of 40 to 80 mass%.

[0080] [Other components]

[0081] The polyurethane resin composition contains the polyurethane resin (X) and the organic solvent (Y) as essential components, but can contain other components as necessary.

[0082] As the other components, for example, the following can be used: a pigment, a flame retardant, a plasticizer, a softener, a stabilizer, a wax, an antifoaming agent, a dispersant, a penetrant, a surfactant, a filler, a mildew-proof agent, an antibacterial agent, an ultraviolet absorber, an antioxidant, a weather-resistant stabilizer, an optical brightener, an anti-aging agent, an adhesion-improving agent, and the like. These components can be used alone or in combination of two or more.

[0083] [Method for producing polyurethane resin composition]

[0084] As the method for producing the polyurethane resin composition of the present embodiment, for example, the following can be listed: a method in which the polyurethane resin composition is not separated from the solution of the polyurethane resin produced, and is used directly in the solution state, and an organic solvent (Y) is added as necessary to produce a polyurethane resin composition having a prescribed composition, and the like. The organic solvent (Y) added to the polyurethane resin composition can be the same as or different from the organic solvent used when the polyurethane resin is produced. The organic solvent (Y) added to the polyurethane resin composition is preferably the same as the organic solvent used when the polyurethane resin is produced.

[0085] [Method for producing wet film-forming material (porous body)]

[0086] Next, a method of producing a wet film-forming product (porous body) of the present embodiment by a wet film-forming method using the polyurethane resin composition will be described.

[0087] The wet film-forming method refers to a method of coating or impregnating the polyurethane resin composition on a surface of a substrate, and then contacting water or water vapor or the like with the coated or impregnated surface, thereby solidifying the polyurethane resin (A) to produce a porous body.

[0088] As the substrate on which the polyurethane resin composition is coated, for example, a substrate including nonwoven fabric, woven fabric, knitted fabric; a resin film or the like can be used. As the material constituting the substrate, for example, chemical fibers such as polyester fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber; cotton, hemp, silk, wool, blended fibers thereof or the like can be used.

[0089] As for the surface of the substrate, an antistatic treatment, a release treatment, a water-repellent treatment, a water-absorbing treatment, an antibacterial and deodorant treatment, a bacterium-preventing treatment, an ultraviolet-shielding treatment or the like can be optionally performed.

[0090] As the method of coating or impregnating the polyurethane resin composition on the surface of the substrate, for example, gravure coating, blade coating, pipe coating, and a bar coater method can be listed. At this time, in order to adjust the viscosity of the polyurethane resin composition to improve the coating workability, the amount of the organic solvent (Y) can be optionally adjusted.

[0091] As the film thickness of the coating film containing the polyurethane resin composition coated or impregnated by the method, a range of 0.5 mm to 5 mm is preferred, and a range of 0.5 mm to 3 mm is more preferred.

[0092] As the method of contacting water or water vapor with the coated or impregnated surface of the polyurethane resin composition, for example, a method of immersing a substrate provided with a coated or impregnated layer containing the polyurethane resin composition in a water bath, a method of spraying water on the coated surface using a spray or the like, or the like can be listed. The immersion is preferably performed in a water bath at 5°C to 60°C for about 2 minutes to 20 minutes.

[0093] As for the wet film-forming product obtained by the method, the surface thereof is preferably washed using water at room temperature or warm water to extract and remove the organic solvent (Y), and then dried. The washing is preferably performed using water at 5°C to 60°C for about 20 minutes to 120 minutes, and the water used in the washing is preferably changed once or more or continuously changed using running water. The drying is preferably performed using a drying machine or the like adjusted to 80°C to 120°C for about 10 minutes to 60 minutes.

[0094] [Example]

[0095] Hereinafter, the present embodiment will be described in more detail using examples.

[0096] [Synthesis Example 1]

[0097] [Synthesis of Bio-based Polyester Polyol]

[0098] In a four-necked flask including a thermometer, a stirrer, an inert gas inlet, and a reflux cooler, 187 parts by mass of bio-based sebacic acid (Bio Seb), 113 parts by mass of bio-based diethylene glycol (Bio DEG) were put, and 0.01% of tetraisopropyl titanate as an esterification catalyst was added with respect to the total amount of the raw materials, and the reaction was performed at 220°C for 15 hours to obtain a bio-based polyester polyol PA1.

[0099] The acid value of the obtained bio-based polyester polyol was 0.54 mgKOH / g, and the hydroxyl value was 55.6 mgKOH / g. The results are shown in Table 1.

[0100] Further, the acid value of the bio-based polyester polyol was a value obtained by measurement according to Japanese Industrial Standards (JIS) K1557-5. The hydroxyl value of the bio-based polyester polyol was a value obtained by measurement according to JIS K0070.

[0101] [Synthesis Examples 2 to 4]

[0102] Bio-based polyester polyols PA2 to PA4 were obtained using the same method as in Synthesis Example 1 based on the raw materials and blending ratios (unit: parts by mass) shown in Table 1. In addition, the acid value and the hydroxyl value of the bio-based polyester polyols were evaluated using the same evaluation method. The results are shown in Table 1.

[0103] [Table 1]

[0104]

[0105] Explanation of symbols in Table 1:

[0106] Bio DEG: Bio-based diethylene glycol (manufactured by India Glycols)

[0107] Bio 1,3-PDO: Bio-based 1,3-propanediol (manufactured by Dupont) Bio EG: Bio-based ethylene glycol (manufactured by India Glycols) Bio Seb: Bio-based sebacic acid (manufactured by Toyokuni Seiyu)

[0108] [Example 1]

[0109] <Preparation of polyurethane resin composition>

[0110] In a four-necked flask including a stirrer, a reflux cooling tube, a thermometer, and a nitrogen gas blowing tube, under a nitrogen gas stream, the bio-based polyester polyol PA1 (number average molecular weight 2000) obtained in the Synthesis Example 1, 140 parts by mass, the bio-based polytetramethylene ether glycol (MW = 1000) (Bio PTMG1K), 140 parts by mass, ethylene glycol (EG), 18 parts by mass, N,N-dimethylformamide, 970 parts by mass were mixed with sufficient stirring. After the stirring and mixing, methylene diphenyl diisocyanate (MDI), 125 parts by mass was added, and reacted at 80°C for 3 hours, to obtain a polyurethane resin solution having a solid content of 30% and a viscosity of 800 dPa.s, as a polyurethane resin composition.

[0111] <Preparation of wet film-forming material>

[0112] A formulation solution obtained by diluting the obtained polyurethane resin composition with N,N-dimethylformamide (DMF), 60 parts by mass was applied to a polyethylene terephthalate film with a gap of 1 mm, and then immersed in water at 25°C for 10 minutes, washed with warm water at 40°C for 1 hour, and dried with a 100°C drying machine for 30 minutes, to obtain a wet film-forming material.

[0113] The wet film-forming material obtained was evaluated for wet film-forming properties and hydrolysis resistance using the evaluation methods described below. The results are shown in Table 2.

[0114] [Example 2]

[0115] In a four-necked flask including a stirrer, a reflux cooling tube, a thermometer, and a nitrogen gas blowing tube, under a nitrogen gas stream, the bio-based polyester polyol PA2 (number average molecular weight 2000) obtained in the Synthesis Example 2, 140 parts by mass, the bio-based polytetramethylene ether glycol (MW = 1000) (Bio PTMG1K), 140 parts by mass, ethylene glycol (EG), 18 parts by mass, N,N-dimethylformamide, 970 parts by mass were mixed with sufficient stirring. After the stirring and mixing, methylene diphenyl diisocyanate (MDI), 125 parts by mass was added, and reacted at 80°C for 3 hours, to obtain a polyurethane resin solution having a solid content of 30% and a viscosity of 700 dPa.s, as a polyurethane resin composition.

[0116] <Preparation of wet film-forming material>

[0117] In addition to using the obtained polyurethane resin composition, a wet film-forming material was produced by the same method as in Example 1, and the obtained wet film-forming material was evaluated by the same method as in Example 1. The results thereof are shown in Table 2.

[0118] [Example 3]

[0119] In a four-necked flask including a stirrer, a reflux cooling tube, a thermometer, and a nitrogen blowing tube, under a nitrogen stream, 140 parts by mass of the bio-based polyester polyol PA3 (number average molecular weight 2000) obtained in Synthesis Example 3, 140 parts by mass of a bio-based polytetramethylene ether glycol (MW = 1000) (Bio PTMG1K), 18 parts by mass of ethylene glycol (EG), and 970 parts by mass of N,N-dimethylformamide were mixed with stirring. After the mixing with stirring, 125 parts by mass of diphenylmethane diisocyanate (MDI) was added, and the mixture was reacted at 80°C for 3 hours, to obtain a polyurethane resin solution having a solid content of 30% and a viscosity of 900 dPa.s, as a polyurethane resin composition.

[0120] <Production of wet film-forming material>

[0121] In addition to using the obtained polyurethane resin composition, a wet film-forming material was produced by the same method as in Example 1, and the obtained wet film-forming material was evaluated by the same method as in Example 1. The results thereof are shown in Table 2.

[0122] [Example 4]

[0123] In a four-necked flask including a stirrer, a reflux cooling tube, a thermometer, and a nitrogen blowing tube, under a nitrogen stream, 140 parts by mass of the bio-based polyester polyol PA1 (number average molecular weight 2000) obtained in Synthesis Example 1, 140 parts by mass of a bio-based polytetramethylene ether glycol (MW = 1000) (Bio PTMG1K), 18 parts by mass of bio-based ethylene glycol (Bio EG), and 970 parts by mass of N,N-dimethylformamide were mixed with stirring. After the mixing with stirring, 125 parts by mass of diphenylmethane diisocyanate (MDI) was added, and the mixture was reacted at 80°C for 3 hours, to obtain a polyurethane resin solution having a solid content of 30% and a viscosity of 800 dPa.s, as a polyurethane resin composition.

[0124] <Production of wet film-forming material>

[0125] In addition to using the obtained polyurethane resin composition, a wet film-forming material was produced by the same method as in Example 1, and the obtained wet film-forming material was evaluated by the same method as in Example 1. The results thereof are shown in Table 2.

[0126] [Example 5]

[0127] In a four-necked flask including a stirrer, a reflux cooling tube, a thermometer, and a nitrogen blowing tube, under a stream of nitrogen, 70 parts by mass of the bio-based polyester polyol PA1 (number average molecular weight 2000) obtained in Synthesis Example 1, 140 parts by mass of bio-based polytetramethylene ether glycol (MW = 1000) (Bio PTMG2K), 18 parts by mass of bio-based 1,3-propanediol (Bio 1,3-PDO), and 780 parts by mass of N,N-dimethylformamide were mixed with stirring. After the mixing with stirring, 99 parts by mass of diphenylmethane diisocyanate (MDI) was added, and the mixture was reacted at 80°C for 3 hours to obtain a polyurethane resin solution having a solid content of 30% and a viscosity of 900 dPa.s, as a polyurethane resin composition.

[0128] <Manufacture of wet film-forming material>

[0129] A wet film-forming material was manufactured by the same method as in Example 1, except that the obtained polyurethane resin composition was used, and the obtained wet film-forming material was evaluated by the same method as in Example 1. The results are shown in Table 2.

[0130] [Example 6]

[0131] In a four-necked flask including a stirrer, a reflux cooling tube, a thermometer, and a nitrogen blowing tube, under a stream of nitrogen, 70 parts by mass of the bio-based polyester polyol PA1 (number average molecular weight 2000) obtained in Synthesis Example 1, 140 parts by mass of bio-based polytetramethylene ether glycol (MW = 1000) (Bio PTMG2K), 18 parts by mass of bio-based 1,3-propanediol (Bio 1,3-PDO), and 780 parts by mass of N,N-dimethylformamide were mixed with stirring. After the mixing with stirring, 99 parts by mass of diphenylmethane diisocyanate (MDI) was added, and the mixture was reacted at 80°C for 3 hours to obtain a polyurethane resin solution having a solid content of 30% and a viscosity of 900 dPa.s, as a polyurethane resin composition.

[0132] <Manufacture of wet film-forming material>

[0133] A wet film-forming material was manufactured by the same method as in Example 1, except that the obtained polyurethane resin composition was used, and the obtained wet film-forming material was evaluated by the same method as in Example 1. The results are shown in Table 2.

[0134] [Comparative Example 1]

[0135] <Preparation of polyurethane resin composition>

[0136] In a four-necked flask including a stirrer, a reflux cooling tube, a thermometer, and a nitrogen blowing tube, under a stream of nitrogen, the bio-based polyester polyol PA1 (number average molecular weight 2000) obtained in Synthesis Example 1, 210 parts by mass, ethylene glycol (EG) 18 parts by mass, and N,N-dimethylformamide 770 parts by mass were mixed with stirring. After the mixing with stirring, diphenylmethane diisocyanate (MDI) 99 parts by mass was added, and the mixture was reacted at 80°C for 3 hours to obtain a polyurethane resin solution having a solid content of 30% and a viscosity of 900 dPa-s, as a polyurethane resin composition.

[0137] <Manufacture of wet film>

[0138] A wet film was manufactured by the same method as in Example 1, except that the obtained polyurethane resin composition was used, and the obtained wet film was evaluated by the same method as in Example 1. The results are shown in Table 2.

[0139] [Comparative Example 2]

[0140] <Manufacture of polyurethane resin composition>

[0141] In a four-necked flask including a stirrer, a reflux cooling tube, a thermometer, and a nitrogen blowing tube, under a stream of nitrogen, the bio-based polyester polyol PA2 (number average molecular weight 2000) obtained in Synthesis Example 2, 210 parts by mass, ethylene glycol (EG) 18 parts by mass, and N,N-dimethylformamide 770 parts by mass were mixed with stirring. After the mixing with stirring, diphenylmethane diisocyanate (MDI) 99 parts by mass was added, and the mixture was reacted at 80°C for 3 hours to obtain a polyurethane resin solution having a solid content of 30% and a viscosity of 900 dPa-s, as a polyurethane resin composition.

[0142] <Manufacture of wet film>

[0143] A wet film was manufactured by the same method as in Example 1, except that the obtained polyurethane resin composition was used, and the obtained wet film was evaluated by the same method as in Example 1. The results are shown in Table 2.

[0144] [Comparative Example 3]

[0145] <Manufacture of polyurethane resin composition>

[0146] In a four-necked flask including a stirrer, a reflux cooling tube, a thermometer, and a nitrogen blowing tube, under a stream of nitrogen, 210 parts by mass of the bio-based polyester polyol PA3 (number average molecular weight 2000) obtained in Synthesis Example 3, 18 parts by mass of ethylene glycol (EG), and 770 parts by mass of N,N-dimethylformamide were mixed with stirring. After the mixing with stirring, 99 parts by mass of diphenylmethane diisocyanate (MDI) was added, and the mixture was reacted at 80°C for 3 hours to obtain a polyurethane resin solution having a solid content of 30% and a viscosity of 700 dPa.s, as a polyurethane resin composition.

[0147] [Production of wet film]

[0148] A wet film was produced by the same method as in Example 1 except that the obtained polyurethane resin composition was used, and the obtained wet film was evaluated by the same method as in Example 1. The results are shown in Table 2.

[0149] [Comparative Example 4]

[0150] [Production of polyurethane resin composition]

[0151] In a four-necked flask including a stirrer, a reflux cooling tube, a thermometer, and a nitrogen blowing tube, under a stream of nitrogen, 210 parts by mass of bio-based polytetramethylene ether glycol (MW = 2000) (Bio PTMG2K), 18 parts by mass of ethylene glycol (EG), and 770 parts by mass of N,N-dimethylformamide were mixed with stirring. After the mixing with stirring, 99 parts by mass of diphenylmethane diisocyanate (MDI) was added, and the mixture was reacted at 80°C for 3 hours to obtain a polyurethane resin solution having a solid content of 30% and a viscosity of 900 dPa.s, as a polyurethane resin composition.

[0152] [Production of wet film]

[0153] A wet film was produced by the same method as in Example 1 except that the obtained polyurethane resin composition was used, and the obtained wet film was evaluated by the same method as in Example 1. The results are shown in Table 2.

[0154] [Method for measuring number average molecular weight]

[0155] The number average molecular weight of the polyol and the like used in the examples and comparative examples represents a value determined by a gel permeation chromatography (GPC) method under the following conditions.

[0156] Measurement device: high-speed GPC device ("HLC-8220 GPC" manufactured by Tosoh Corporation)

[0157] Column: A column manufactured by TOSOH CORPORATION described below was used by connecting in series.

[0158] "TSKgel G5000" (7.8 mm I.D. x 30 cm) x 1

[0159] "TSKgel G4000" (7.8 mm I.D. x 30 cm) x 1

[0160] "TSKgel G3000" (7.8 mm I.D. x 30 cm) x 1

[0161] "TSKgel G2000" (7.8 mm I.D. x 30 cm) x 1

[0162] Detector: RI (differential refractometer)

[0163] Column temperature: 40°C

[0164] Eluent: Tetrahydrofuran (THF)

[0165] Flow rate: 1.0 mL / min

[0166] Injection amount: 100 μL (sample concentration: 0.4 mass% in tetrahydrofuran)

[0167] Standard sample: A calibration curve was prepared using the following standard polystyrenes.

[0168] (Standard polystyrenes)

[0169] "TSKgel Standard Polystyrene A-500" manufactured by TOSOH CORPORATION

[0170] "TSKgel Standard Polystyrene A-1000" manufactured by TOSOH CORPORATION

[0171] "TSKgel Standard Polystyrene A-2500" manufactured by TOSOH CORPORATION

[0172] "TSKgel Standard Polystyrene A-5000" manufactured by TOSOH CORPORATION

[0173] "TSKgel Standard Polystyrene F-1" manufactured by TOSOH CORPORATION

[0174] "TSKgel Standard Polystyrene F-2" manufactured by TOSOH CORPORATION

[0175] "TSKgel Standard Polystyrene F-4" manufactured by TOSOH CORPORATION

[0176] "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation

[0177] "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation

[0178] "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation

[0179] "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation

[0180] "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation

[0181] "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation

[0182] "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[0183] [Method for evaluating wet film-forming property]

[0184] The wet film-forming product obtained in the Examples and Comparative Examples was visually observed using a scanning electron microscope "SU3500" (magnification 500x) manufactured by Hitachi High Technology Co., Ltd. to confirm whether or not a porous body was formed. The case where a uniform shape of a porous body was confirmed was evaluated as "O", and the case where a non-uniform porous body was confirmed was evaluated as "X".

[0185] [Method for evaluating hydrolysis resistance]

[0186] The obtained wet film-forming product (synthetic leather) was cured under a hygrothermal condition of 70°C, 95% for 5 weeks. The case where there was no abnormality in appearance was evaluated as "O", and the case where gloss change + tackiness was generated in the appearance was evaluated as "X".

[0187]

[0188] Explanation of symbols in Table 2:

[0189] (A): Polyol

[0190] (A-1): Bio-based polyester polyol

[0191] (A-2): Bio-based polyether polyol

[0192] (B): Polyisocyanate

[0193] Chex: Chain extender

[0194] Bio EG: Bio-based ethylene glycol (manufactured by India Glycols) EG: Ethylene glycol (manufactured by Mitsubishi Chemical)

[0195] MDI: Diphenylmethane diisocyanate (manufactured by Tosoh)

[0196] DMF: N,N-dimethylformamide (manufactured by Mitsubishi Gas Chemical)

[0197] Bio PTMG1K: Bio-based polytetramethylene ether glycol (Mw = 1000) (manufactured by Mitsubishi Chemical)

[0198] Bio PTMG2K: Bio-based polytetramethylene ether glycol (Mw = 2000) (manufactured by Mitsubishi Chemical)

[0199] It is understood that the wet film formability and hydrolysis resistance of Examples 1 to 6, which are wet film formers of the present embodiment, are excellent.

[0200] On the other hand, Comparative Examples 1 to 3 are not a method including bio-based polytetramethylene ether glycol, but the hydrolysis resistance is poor. Comparative Example 4 is a method using a polyol (A) including only bio-based polytetramethylene ether glycol, but the wet film formability is poor.

Claims

1. A wet film-forming material, which is a wet film-forming material of a polyurethane resin composition, said polyurethane resin composition containing a polyurethane resin (X) made from a polyol (A) and a polyisocyanate (B), and an organic solvent (Y), The wet film-forming material is characterized in that... The polyol (A) contains a bio-based polyester polyol (A-1) and a bio-based polyether polyol (A-2). The polyisocyanate (B) contains an aromatic polyisocyanate. The bio-based polyester polyol (A-1) is made from diol compounds and bio-based sebacic acid. The diol compound includes bio-based diethylene glycol. The bio-based polyether polyol (A-2) comprises bio-based polytetramethylene ether diol.

2. The wet film-forming material according to claim 1, wherein, In the diol compound, the content of the bio-based diethylene glycol is 15% by mass or more and 100% by mass or less.

3. The wet film-forming material according to claim 1 or 2, wherein, The mass ratio (A-1) / (A-2) of the bio-based polyester polyol (A-1) to the bio-based polyether polyol (A-2) is 90:10 to 10:

90.

4. The wet film-forming material according to claim 1 or 2, wherein, The bio-based polyether polyol (A-2) is bio-based polytetramethylene ether diol.

5. The wet film-forming material according to claim 1 or 2, wherein, The raw materials for the polyurethane resin (X) also include chain elongating agents.

6. The wet film-forming material according to claim 5, wherein, The chain elongating agent is at least one selected from the group consisting of ethylene glycol, 1,4-butanediol, and 1,3-propanediol.

7. The wet film-forming material according to claim 1 or 2, wherein, The polyisocyanate (B) is diphenylmethane diisocyanate.

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